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7th International Conference on Engineering Research, Innovation and Education

January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 007

Optimization of Ultrasound-assisted Extraction of Mucilage from


Taro (Colocasia esculenta) Corm by Response Surface
Methodology
Saydul Md Safwa*, Md. Akib Bin Kabir, Md. Rahmatuzzaman Rana

Shahjalal University of Science and Technology, Sylhet-3114, Bangladesh.

Email:saydulsafwa@gmail.com, akib.djp@gmail.com, rzaman-fet@sust.edu

*Corresponding author [Saydul Md Safwa]

Abstract: The taro (Colocasia esculenta) corm has been documented as a


Keywords:
potential source of mucilage, depending on the method of extraction. The
● Colocasia objective was to optimize the Ultrasound-assisted extraction (UAE) conditions
for extracting mucilage from taro corm by using response surface
esculenta; methodology (RSM). Firstly, to derive a statistical model for optimizing the
● Ultrasound UAE extraction conditions a Box-Behnken design was applied to ultrasonic
assisted temperature (40 to 60 °C), time (15 to 45 min), water to solid ratio (3 to 7).
A second-order polynomial model was used for predicting the responses, and
extraction; the model was verified statistically with analysis of variance (ANOVA). The
● Mucilage; ANOVA results revealed that UAE extraction temperature, time, and water
● Optimization; to solid ratio had a significant (p < 0.01) influence on the mucilage yield. For
mucilage yield, the R2 values were 0.9908, indicating that the models
● Response developed based on second-order polynomials were satisfactory for
Surface analyzing interactions between parameters. Again, under optimum conditions
Methodology; which were ultra-sonication temperature, sonication time and water–to–solid
ratio is 60 °C, 45 min and 5 respectively, and the predicted value of the yield
is 4.22 % and the experimental value of the yield was 4.31 % with residual
standard error values below 0.02%, which is close to the predicted value.
Moreover, the composite desirability is 0.9764 which is close to 1 and
reflects the model validity. The experimental outcomes matched the
predicted values, demonstrating the model's suitability and RSM's
effectiveness in enhancing the extraction conditions. This optimized
extraction method may be successful in the industrial extraction procedure
with further experiments.

1. Introduction
Mucilage is a naturally occurring complex polymeric carbohydrate molecule with a highly branched
structure (Golalikhani et al. 2014) and the capacity to change the rheology of a solution (De los Santos-
Santos et al. 2020). There are several uses for mucilage in food systems, including thickening, gelling,
modifying texture, and stabilizing (Tosif et al. 2021). Having an excellent

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capacity of holding water and oil as well as adequate emulsion and foaming properties make them ideal
as food additives for enhancing the appearance, texture, and shelf life of various foods (Quinzio et al.
2018). Mucilage may be found in all types of plants, in diverse plant sections, and very modest amounts in
most of the species (Hadley 2020). Taro (Colocasia esculenta), a plant of the Araceae family, has been
reported as a potential source of about 3 to 19% mucilage and 70 to 80% starch, depending upon the
extraction method (Ribeiro Pereira et al. 2020). In the past, conventional extraction procedures were used
to obtain mucilage from plant sources. However, most of these methods rely on the extraction power of
different solvents, heat, and long extraction time. These methods can cause the antioxidant activity and
total phenolic content to be lost because of oxidation, hydrolysis, and ionization, making it essential to look
for better alternative methods (Rasheed et al. 2018). non-thermal processing approaches have been
researched as complete or partial replacements for traditional heat treatment throughout the previous two
decades (Char et al. 2010). The extraction efficiency of mucilage can be affected by ultrasonic extraction
cycles, ultrasonic duration, ultrasonic temperature, solvent concentration, solvent acidity, and solvent type
employed in the UAE (Sun et al. 2019). When many independent variables impact the responding factors
during the extraction process, there is a possibility that the variables which will be selected for the
operation will interact and influence one another's effects on the response (Cui et al. 2018). Therefore,
finding an optimum conditions is vital through optimization procedure is necessary. Response surface
methodology can be an effective tool to optimize the process. Even though there is a lot of research on
UAE, the optimization of UAE conditions on taro corm has not been investigated. Thus, the main objective
of the present work was to optimize the effect of extraction ultrasonic temperature, ultrasonic time, and
water-to-solid ratio on the ultrasound extraction yield of mucilage extracted from taro using Response
surface methodology.

2. Materials and methods

2.1 Sample preparation

Taro (Colocasia esculenta) corm was purchased from a local market in Sylhet, Bangladesh. Thecorms were
carefully cleaned to remove any foreign matter such as dust or dirt, after which they were wrapped in plastic
bags and sealed before being stored in a dry and cool place to be used infuture experiments.

2.2 Ultrasonic assisted extraction (UAE)

The mucilage were extracted from taro corm following Babamoradi, Yousefi, and Ziarati (2018) method
with some modification, where after peeling and slicing 15- g of sample was taken for each experiment
following the Box-Behnken experimental design (Table 1 and Table 2). The samples were immersed in di-
ionized water for 24 hours and extracted using an ultra-sonication bath (Model- GT Sonic VGT-1990QT).
After this treatment, the sample was retained for 30 min to cool down. After filtering the sample by using a
muslin cloth, the resultant liquid portion was centrifuged at 4000 rpm for 10min. After centrifugation, the
supernatant was collected; this completed the maceration process and started the precipitation process. In
precipitation, 99.5% ethanol was added at the rate of three volumes of the supernatant. The precipitate was
collected and dried for about 18 hours at 50°C. After drying, dried mucilage was ground by using the
grinder, and finally, by completing the sieving process, the extraction process was complete

Table 1: Coded values of the independent variables used in the ultrasound-assisted extraction of mucilage

Coded levels
Medium components Symbols
-1 0 1
Temperature (°C) X1 40 50 60
Time (min) X2 15 30 45
Water to solid ratio X3 3 5 7

Table 2: BBD with responses for optimization of ultrasound-assisted extraction of mucilage

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Trial Number Temperature Time (min) Water-to-
(°C) solid ratio

1 40 15 5
2 60 15 5
3 50 45 3
4 50 30 5
5 60 30 7
6 50 30 5
7 40 45 5
8 50 30 5
9 50 45 7
10 60 45 5
11 60 30 3
12 40 30 7
13 50 15 7
14 50 15 3
15 40 30 3

2.3 Analysis of the extraction yield

After collecting and weighting the dried mucilage powder, by using equation (1) the yield of mucilage
extraction was estimated.
Dried mucilage extraction weight(g)
Mucilage extraction yield (% w/w) = (1)
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑇𝑎𝑟𝑜 𝑐𝑜𝑟𝑚

2.4 Experimental design and statistical analysis


The present study used a BBD for each independent variable to evaluate the effects and a total of 15 runs
were performed (Table 2). After collecting data, RSM was also used to find out the optimum condition for
three independent variables to extract mucilage. To evaluate the effect of three parameter a second-order
polynomial equation, which obtained from RSM, was applied. The equation is given below:
𝑌 = 𝑏0 + 𝑏1𝑥1 + 𝑏2𝑥2 + 𝑏3𝑥3 + 𝑏11𝑥2 + 𝑏22𝑥2 + 𝑏33𝑥2 + 𝑏12𝑥1𝑥2 + 𝑏13𝑥1𝑥3 + 𝑏23𝑥2𝑥3 + ℇ
1 2 3
The coefficients of the polynomial were represented by b0 (constant term), b1, b2, and b3 (linear effects), b11,
b22, and b33 (quadratic effect s), and b12, b13, and b23 (interaction effects). Design- Expert® (version 12.0.3)
and Minitab® (version 14) statistical software was used for the experimental design and the analysis of
variance (ANOVA) to determine the effects of significantinteractions in the model (p < 0.01).
3. Result and Discussions
Three variables, which was ultrasonic temperature, time and water to solid ratio, for this particularstudy were
chosen as well as the selection of the minimum and maximum values were based on the previous
experiments done on the extraction of polysaccharides from various plant materials (K. Wang et al. 2021).

3.1 Fitting the model and analysis of variance


Using RSM with BBD, the present study examined the effects of ultrasound time, temperature, and water to
solid ratio on the extraction of mucilage by taro corm. Table 3 summarizes each run'sresponses (extraction of
mucilage).

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By using multiple regression analysis to evaluate the experimental data, it was found that a second-order
polynomial model might appropriately represent the acquired data. After calculating the regression
coefficients, we were able to derive the following equation for predicting extraction yield:
𝑌 = 1.63+0.9876𝑋1 + 0.4083𝑋2 − 0.0141𝑋3 − 0.1477𝑋1𝑋2 − 0.4305𝑋1𝑋3 + 0.2368𝑋2𝑋3
+ 0.4876𝑋12 + 0.8388𝑋22 − 0.4139𝑋32
The equation in terms of coded factors can be used to make predictions about the response for given levels
of each factor. By default, the high levels of the factors are coded as +1 and the low levels are coded as -1.
The coded equation is useful for identifying the relative impact of the factors by comparing the factor
coefficients (Ahmed et al. 2021). Generally, coefficients with a positive sign in the fitted model imply that
the variable can enhance the response. In contrast, a negative sign suggests a variable's ability to lower the
response. The coefficient table demonstrated that ultrasonic temperature influence the most among other
interactions due to the highest amount of coefficient comparing to other linear interactions. Moreover, in
the case of binary interactions, the interaction between UAE extraction time and water to solid ratio had the
highest positive effects on extracting mucilage. Specifically, ultrasound time demonstrated the most potent
positive effects on the yield. Based on an analysis of variance (ANOVA) (Table 4), P-values less than 0.05
indicate model terms are significant. Adjusted 𝑅2 indicates how well the regression models describe the
data when many variables are included and evaluating the model's adequacy. In this study, the value of
Adjusted 𝑅2 was found to be acceptable. Moreover, Figure 1 demonstrates similarities between predicted
and actual values, which conclude that the model is accurate and satisfactory.

Figure 1: Diagnostic plot for model adequacy. Correlation between predicted and experimental values of mucilage
yield

Table 3: Box-Behnken design with responses for Table 4: Analysis of variance of the
optimization of ultrasound-assisted extraction of experimental results of the BBD.
mucilage
Trial Temperature Time Water- Yield Source Sum of F- p-value
Number (°C) (min) to- solid (%) squares value
ratio Prob>F
1 40 15 5 1.297 Model 14.42 59.65 0.0001
2 60 15 5 3.693 X1 <
3 50 45 3 2.134 7.80 290.50 0.0001
4 50 30 5 1.483 X2 1.33 49.64 0.0009
5 60 30 7 2.133 X3 0.0016 0.0594 0.8171
6 50 30 5 1.812 X1X2 0.0873 3.25 0.1313
7 40 45 5 2.520 X1X3 0.7413 27.60 0.0033
8 50 30 5 1.602 X2X3 0.2242 8.35 0.0342
9 50 45 7 2.686 X
1
2 0.8778 32.68 0.0023
10 60 45 5 4.325 2 2
X 2.60 96.72 0.0002
11 60 30 3 3.129 3 2
X 0.6326 23.55 0.0047
12 40 30 7 1.144 Residual 0.1343
13 50 15 7 1.507 CV% 7.73
14 50 15 3 1.902 R2 0.9908
15 40 30 3 0.418 Adjusted R2 0.9742
Predicted
0.9048
R2

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3.3. Response surface analysis of the extraction of mucilage
1
To demonstrate the main effects and interaction3effects of the variables response surface
2 3
plots (figure 2 and
3) were used in mucilage extraction from Taro corm. The positive effects of variables and their interactions
were ranked as follows: Temperature (X1) > Time × Time (X 2)> Time (X2) > Temperature 2 ×
2
Temperature (X ) > Temperature × Water to solid ratio (X1X3)>Water to solid ratio × Water to solid
ratio(X 2) > Time × Water to solid ratio (X X ).The contour plots in Figure 4 (a-f) depict the effects of
extraction temperature, time, and water to ratio, with the yield of mucilage as the response. Figures 4a, 4b
visualized that increasing of temperature with the lower amount of water to solid ratio produce high amount
of yield but it lessen down gradually when the ratio was increased. In the case of the UAE, some authors
report Similar results where increasing the temperature from 20°C to 70°C has a superior result when
compared to non-sonicated extractions (Shirsath et al. 2012). However, figures 4c and 4d demonstrate that
with the escalating temperature and time, the yield was proliferated, which is the complete opposite trend to
the previous case. At a constant condition (Samavati and Manoochehrizade 2013) experienced the yield of
polysaccharides from Malva Sylvestris; the extraction yield rose as the extraction period increased from 1
to 4 h. An interesting case was seen in figures 4e and 4f, where after a gradual rise, a steady fall was
displayed as the water to solid ratio was increased. On the contrary, enlarging extraction time showed a
complete opposite scenario and again yellow zone was barely exhibited which was considered to be
unlikely than other combinations. Increasing the water-to-raw-material ratio enhances polysaccharide
extraction yield substantially because there is more driving force for the polysaccharide mass transfer
(Koocheki et al. 2010). However, further increment of water to solid ratio from 5:1 to 7:1 showed reduction
in the mucilage yield. It might be the result of a bid loss during the product collect

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Polysaccharides that were overly dissolved in water hampered the buildup of extraction products and might
waste solvent and energy (Chao et al. 2013).

Figure 2: Half normal plot of standardized


effects of variables.

Figure 3: Pareto chart of the variables on


mucilage extraction.

Figure 4 : Three-dimensional (3D) and two-dimensional (2D) response surface plots showing the combinedeffects of
(a) temperature (X1) and time (X2) (b) temperature (X1) and Water to solid ratio (X3) (c) time (X2) and Water to
solid ratio (X3) on the mucilage yield.

3.4. Optimization of extraction parameters and models validation

One of the primary objectives of the present study was to determine the optimal process parameters of
the UAE for taro corm mucilage. The data given in Table 5, under optimum conditions which are
extraction temperature, time and water to solid ratio is 60°C, 45 min and 5 respectively the predicted
value of the yield is 4.233% and experimental value of the yield was 4.315% which is close to the
predicted value. The composite desirability is 0.9764 which is closeto 1. So, the model is valid.

Table 5: Optimized condition for ultrasound assisted extraction of taro corm mucilage

Temperatur Time Water to Target Predicte Experimental Composite


e (°C) (min) solid ratio d Yield desirability
Yield (%) (Out of 1)
X1 X2 X3 (%)
60.00 45.00 5 Max. 4.233 4.315± 0.015 0.9764

(Wu et al. 2015) obtained similar results when extracting polysaccharides, where the extraction yield was
4.81% under optimal conditions (temperature was 70 °C, time was 54 min, and water to solid ratio was 9)
and (Niknam et al. 2020) extracted gum from Barhang seeds and found 3.7%optimum extraction yield under
optimal conditions (temperature, time, and water to solid ratio were 32.5 o C, 30 min, and 20 respectively).

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4. Conclusion
RSM was successfully applied to optimize the extraction process and analyze the effects of extraction
temperature, time, and water to solid ratio and their interactions. However, these models can be employed
further to obtain desired responses with increasing efficacy. Overall, this study should be considered a first
step for the extraction, separation, and analysis of polysaccharides, contributing to the further research of
taro corm as a health food.

Acknowledgment
This study received financial support from the promotional research grant (Project ID: S/2021/1/28) by the
Shahjalal University of Science and Technology (SUST) research center. The authors acknowledge with
thanks for the technical assistance and other supports received from the Department of Food Engineering
and tea Technology of Shahjalal University of Science andTechnology, Sylhet, Bangladesh.

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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 008

Effect of Discharge current on the capacity of lead acid


Battery

Md. Kamrul Hasan*, Golam Kibria

Rajshahi University of Engineering & Technology, Rajshahi-6204, Bangladesh

*Corresponding author [Md. Kamrul Hasan]

Keywords:
Abstract: The lead-acid battery has been widely used in the fields of electric
● Lead acid battery; vehicles, IPS, Solar Power Station etc. In this study, 60 pieces of lead- acid
battery were adopted to explore the effects of discharge current on the
● Constant current
capacity of lead acid battery. Batteries were classified into three samples
discharge method; according to the mass of active materials and sizes of the plates. In every
● Constant current samples, there were 20 pieces similar batteries of similar plates and active
materials. The batteries were charged according to the constant current
charge method;
charging method. After that capacity of the batteries were measured using
● Capacity of constant current discharging method. Comparing the data found from the
battery; research, the data were displayed in graphs to show the gradual changes of
capacity with changes of discharge current and discharge time.
● Discharge current;

1. Introduction
Battery cost, battery capacity and efficiency of the battery are main factors determining whether electric
vehicles would be used widely [1]. The price of batteries is more than fuel, and mileage is also limited
which restricts the usage of electric vehicle. These problems should be resolved especially efficiency of the
batteries. Having a high energy density, lithium-ion battery can be used to improve the range of mileage of
electric vehicles but the price of lithium-ion battery is very high. Therefore, research of electric vehicle
focuses on decreasing the cos of battery and increasing the efficiency of lead acid batteries simultaneously.
Although the energy density of lead-acid battery is lower than that of lithium-ion battery, the cost of lead-
acid battery is less. Again the source of renewable energy is decreasing day by day. So usage of electricity
produced from solar power should be increased.

The research findings have shown the intermittent current discharge method is able to release more
capacity than constant current [3-5]. As the available battery capacity is subject to the load current size, the
releasable capacity varies under different discharge currents. For instance, while a larger discharge current
implies a smaller battery released capacity, a smaller discharge current implies a larger battery released
capacity. Such phenomena are especially obvious in lead.

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When current flows through the cell there is a voltage drop due to the internal resistance of the cell.
Internal resistance decreases the terminal voltage of the cell at the time of discharging and increases the
voltage needed to charge the cell. Thus internal resistance reduces capacity as well as decreases its
charge/discharge efficiency of the cell. Higher discharge rates produce higher internal resistance and it
creates higher internal voltage drops. Spiral construction of the electrodes is mainly used to decrease
internal impedance. This reduces heat generation and permits increases charge and discharge rates.

The internal resistance influences the capacity of a cell. The higher the internal resistance, the higher the
losses while charging and discharging, especially at higher currents. So for high discharge rates the
available capacity of the cell will be lower. Conversely, if the discharge current is lower, the capacity will
be higher.
2. Experimental
2.1 Sample preparation
2.4% antimonial lead was melted in the furnace and grids were produced in the grid casting machine.
Grids of positive plates were covered by a set of tubes made of synthetic cloth called gauntlet. Then these
tubes were filled by red oxide, grey oxide and other materials. After completing tube filling the plates were
dipped into dilute sulfuric acid of 1.140 gm/cc specific gravity [7]. After completing sulphation process,
the tubular plates were washed by DM water until the pH of water reaches to 7.0. After that positive plates
were dried to the drying chamber at 500 celsius for 4 hours [9].

Paste of chemicals were made by mixing the required amount of chemicals. All flat grids were filled with
the paste chemicals in pasting machine. Raw materials for the pasting were lead oxide (grey), sulfuric acid,
fiber flock, indulin AT, barium sulfate, carbon black etc. After completing pasting process, these plates
were cured in the curing chamber. Negative plate curing process was completed in two steps: curing and
drying. Negative plates were cured at 450 celsius and 95% humidity. After that cured negative plates were
dried at 650 celsius. So the negative plates are dried unless its moister content is downed up to 1% [8].

2.2 Materials
In this research three samples were prepared and every samples was prepared by 20 pieces of batteries. The size of
plates and raw materials of making plates for the samples are also different. Jinfan rectifier (50A, 415V) is used to
apply the constant discharge method on the samples to measure the discharge time.

Table 1 Dimension of the positive plates


Plate dimension Plate Thickness
Sample type Positive plate type
(mm*mm) (mm)
Sample 1 ET180TP 180*150 5
Sample 2 ET175TP 175*150 5
Sample 3 ET160TP 160*150 5

Table 2 Dimension of the negative plates


Plate dimension Plate Thickness
Sample type Negative plate type (mm*mm) (mm)
Sample 1 ET180F(2.3) 180*150 2.3
Sample 2 ET175F(2.3) 175*150 2.3
Sample 3 ET160F(2.3) 160*150 2.3

Page | 965
Table 3 Number of plates in the samples
Positive
Sample type Positive plate type Negative plate type plate/cell Negative plate /cell
Sample 1 ET180TP ET180F(2.3) 4 5
Sample 2 ET175TP ET175F(2.3) 4 5
Sample 3 ET160TP ET160F(2.3) 3 4

Table 4 Mass of active materials of plates in the sample


Mass of active material/ positive Mass of active material / negative plate
Sample type plate (gm) (gm)
Sample 1 365.1 207.6
Sample 2 351.8 199.12
Sample 3 310 191.6

Table 5 Mass of active materials per cell in the sample


Mass of active material / Negative
Mass of active material/ Positive cell (gm)
Sample type cell (gm)
Sample 1 1460.4 1038
Sample 2 1407.2 995.6
Sample 3 930 766.4

Table 6 Theoretical capacity of the samples


Sample type Active material weight /Cell(g) Theoretical capacity (Ah)
Sample 1 1038 268.49
Sample 2 995.6 257.52
Sample 3 766.4 198.24

2.3 Experimental procedure


The plates were assembled and every cell was separated by the separators [5]. After that the batteries were filled with
1.070 gravity acid and a circuit of 20 batteries were formed by connecting them in a seriesconnection for every sample.
Then the circuit was connected with rectifier and the batteries were charged according to charging program. Normally
current supply is constant at the time of charging and for this theprocedure is called constant current charging method
[4]. After completing the charging process, the samples were filled with 1.280 gravity acid. The charging processes
were described at the table of 7, 8, and9.

Page | 966
Table 7 Charging program for sample 1
Step Condition Current(A) Duration(H)
1 Charge 5 1
2 Charge 10 1
3 Charge 25 21
4 Charge 22 11
5 Discharge 20 1
Change of 1.070 gravity acid and filled
6 Interrupt
with
1.280 gravity acid
7 Charge 17 8
8 Charge 14 3
9 Discharge 20 4
10 Charge 17 7
11 Charge 14 6

Table 8 Charging program for sample 2


Step Condition Current(A) Duration(H)
1 Charge 5 1
2 Charge 10 1
3 Charge 22 11
4 Charge 20 21
5 Discharge 20 1
Change of 1.070 gravity acid and filled
6 Interrupt
with
1.280 gravity acid
7 Charge 17 8
8 Charge 14 3
9 Discharge 20 4
10 Charge 17 7
11 Charge 14 6

Table 9 Charging program for sample 3


Duration(Hours
Step Condition Current(A) )
1 Charge 5 1
2 Charge 10 1
3 Charge 19 11
4 Charge 17.5 21
5 Discharge 17.5 1

Change of 1.070 gravity acid and filled with


6 Interrupt
1.280 gravity acid

7 Charge 16 8
8 Charge 12 3
9 Discharge 17.5 4

Page | 967
10 Charge 16 7
11 Charge 12 6

Batteries coneected in series connection Rectifier


Fig. 1. Experimental set up
Then discharge process was conducted at constant current process on every circuit to calculate the discharge time of
the samples. The discharged current was varied from 10A to 30A for every sample. Discharge process was continued
till the terminal voltage of circuit reached at 210V. The cut-off-voltagewas 10.5V for every battery. Every sample has
20 pieces batteries. So cut-off voltage for every sample was fixed at 210V [6]. Then the capacity was calculated by
multiplying the discharge ampere with the discharge time which was got from the discharge process [8].

3. Theory/calculation
Theoretical Capacity of the lead-acid battery is the ratio of mass of negative or positive plate toelectrochemical
equivalent weight of respective plate [3].
Electrochemical equivalent weight of negative plate (GNAM) is 3.866 g.Pb/Ah.So theoretical
capacity for Negative plate, CTheoretical(NAM)=MNAM/GNAM
Where “MNAM”is the mass of active material of negative plates/Cell [4] Electrochemical
equivalent weight of positive plate (GPAM) is 4.463 g.PbO2/AhSo theoretical capacity for
positive plate, CTheoretical(PAM)=MPAM/GPAM

Page | 968
Where “MPAM” is the mass of active material of negative plates/Cell [4] The Lowest
Value of CTheoretical(NAM) and CTheoretical(PAM) is taken as CTheoretical

Peukert Equation shows how the available capacity of a battery changes with the change of discharge rate[5].
Peukert Equation, C = InT
Where "C" is the theoretical capacity (Ah), "I" is the current (A), "T" is time, and "n" is the Peukert constant.The equation
shows that at higher currents, there is less available energy in the battery. The Peukert constantis directly related with the
internal resistance of the battery. At higher currents, there will be more losses and available capacity will be lower [4].

4. Result and Discussions


In this research, it was found that with the increase of discharge current the capacity of battery decreasesfor every
samples. There is a little effect of peukart constant on the change of discharge current for a specific sample. The result
data from the research are shown on the tables.

Table 10 Actual capacity for different discharge current for sample 1


Discharge Cut off voltage/ Circuit Actual capacity Peukert
Discharge time(H)
current(A) (V) (Ah) constant
3.95 30 210 118.5 1.24
4.95 25 210 123.75 1.24
6.50 20 210 130 1.24
9.30 15 210 139.5 1.24
12.15 12 210 145.8 1.245
15.20 10 210 152 1.246

Table 11 Actual capacity for different discharge current for sample 2


Discharge Cut off voltage/ Actual capacity Peukert
Discharge time (H)
current(A) Circuit (V) (Ah) constant
3.75 30 210 112.5 1.243
4.75 25 210 118.75 1.24
6.20 20 210 124 1.243
8.80 15 210 132 1.246
11.65 12 210 139.8 1.245
14.60 10 210 146 1.246

Table 10 Actual capacity for different discharge current for sample 3


Discharge Cut off voltage/ Actual capacity Peukert
Discharge time(H)
current(A) Circuit (V) (Ah) constant
3.00 30 210 90 1.23
3.90 25 210 97.5 1.22
5.15 20 210 103 1.21
7.15 15 210 107.25 1.21
9.40 12 210 112.8 1.22
11.85 10 210 118.5 1.226

Page | 969
Actual capacity vs Discharge
1 time
6
0
1
capacity(Ah)
5
0
Actual

1
4
0
1 2 4 6.00 10.00 12.00 14.00
3 . . 16.00
0 0 8.00 Discharge time
0 (H)
0 0
1
2Figure 2 Figure 3 the graph of actual capacity vs discharge time for sample 1
0
1
1
0
Actual capacity vs Discharge
1
10 time
50
0
1
capacity(Ah)

4
0
Actual

1
3
0 2 4 6 8 10.00 12.00 14.00
. . . . 16.00
1 0 0 0 Discharge
0 time
2 0 0 0 (H)0
0
Figure 3 Figure 3 the graph of actual capacity vs discharge time for sample 2
1
1
0
1
0
0

Page | 970
Actual capacity vs Discharge
1 time
3
0

capacity(Ah)
2
0
Actual
1
1
0
2 4 6 8 1 1 1
1 . . . . 0 2 4
0 0 0 Discharge
0 time . . .
0 0 0 0 (H) 0 0 0 0
0 0 0 0
9
Figure 3 the graph of actual capacity vs discharge time for sample 3
0

8
0
Actual capcity vs Discharge
1
current
6
0
1
Actual capacity

5
0
1
4
(Ah)

0
1
3
0 5 1 1 20 2 3 3
0 5 5 0 5
1 Discharge current(A)
2
0 Sam Sam Sam
ple 3 ple 2 ple 3
1
1
0 Figure 2 the graph of actual capacity vs discharge current
1 the actual capacity for every sample decreases with increase of discharge current but the capacity
From the figures,
0 increase of discharge time.
increases with the
0
9
0
5. Conclusion 8
0
It is clear that if all other variable, responsible for the change of capacity variation, are constant, Actual Capacity
of lead acid battery will be changed with change of discharge current and discharge time. In this research, there is a
gradual increase of actual capacity with the increase of discharge current and peukart constant almost constant for
each sample

Page | 971
References
1. Yow-Chy Liu, Battery management system for Improving Battery efficient in Electric Vehivles,WEVJ,
Vol. 4,ISSN 2032-6653,2010
2. UG. Pragnesh B. Gohil, UG. Digvijay P. Jadav, UG. Chirag N. Solar Battery Charger, ISSN: 2321-9939,
IJEDR, 2017
3. D. Pavlov, Lead-Acid Batteries: Science and Technology -2nd Edition, Elseiver, ISBN 978044495522,2017
4. D. Pavlov; P. Nikolov, Rogachev, T. Influence of carbons on the structure of the negative activematerial
of lead-acid batteries and on battery performance. J. Power Sources 2011, 196, 5155–5167.
5. D. Pavlov, A. Kirchev, M. Stoycheva, B. Monahov, Power Sources 137 (2004) 288.
6. P. Ruetschi, J. Power Sources 113 (2003) 363.
7. W. F. Gillian, A. M. Hardman, R. Kiessling, D.W. H. Lambert. Technical and research aspects oflead/acid
battery production,1989,217-235
8. J. M. Stevenson and A. T. Kuhn, in L. J. Pearce (ed.), Power Sources 10, Int. Power Sources Symposium
Committee, Leatherhead, 1984, pp. 555 – 567.
9. Md. Kamrul Hasan, Investigation of the effect of active materials of solar battery on active mass utilization
co-efficient, Saudi Journal of Engineering and Technology,2022, 10.36348/sjet.2022.v07i08.00

Page | 972
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 021

Effect of Temperature on Anaerobic Co-Digestion of Tannery


Waste with locally available substrates

Nisha N.M., A., Islam A.N.M.N., B., Basak S.R.*, C. and Kabir M. I., D.

Department of Civil and Environmental Engineering,

Shahjalal University ofScience and Technology, Sylhet 3114,

Email: nushratmumatin7@gmail.com, anmislam17@gmail.com, shilpy_basak@yahoo.com,


imran.kabir-cee@sust.edu

*Corresponding Author- [Shilpi Rani Basak]

Abstract: The quantity and characteristics of solid waste produced at different unit
Keywords:
operations of the tanning process vary greatly. Fleshing is a type of animal tissue waste
produced in greater amounts during the preparatory leather processing stage than other
● Reactor; kinds of solid waste in the tanning industry. Basically, the fleshing portion is a kind of
● Fleshing; biodegradable volatile solid. To manage this solid waste, anaerobic co-digestion is one of
the best environment-friendly options. Anaerobic digestion is a complicated process that
● Anaerobic
digests organic compounds and converts them to biogas. It depends on a number of critical
Digestion;
operating factors, including temperature. This research adopted batch anaerobic co-
● Inoculum; digestion using tannery waste fleshing as a substrate at various temperatures. This study
● Substrate; aims to determine how different temperatures affect tannery waste batch anaerobic co-
digestion. Four anaerobic reactors (R1, R2, R3, R4) were operational under temperatures
● Gas
(45±1)°C, (40±1)°C, (35±1)°C, and (32±2)°C (Room Temperature) respectively.
Production Moreover, this study's specific objective is to examine the biodegradability of substrates.
Anaerobic co-digestion of tannery solid waste has been evaluated in terms of volatile solid
Rate;
reduction, COD reduction, gas generation rate, and cumulative gas generation. The
anaerobic digestion period for the study was 35 days. In a conclusion, the R1 reactor which
was functional under thermophilic temperature (45°C) demonstrated the best result among
all the reactors with the highest cumulative gas production of 3850mL, the highest
percentage of volatile solids reduction of 40%, and a COD reduction of 65.6%.

1. Introduction
One of today's most difficult challenges is waste management. Converting solid waste into sustainable
energy is one of the modern solid waste management technologies. The leather industry, one of
Bangladesh's oldest industries, plays an important role in the national economy. But in manufacturing
processes, it produces a considerable amount of solid waste (332.2 t/d) that

Page | 973
It's essential to evaluate the most appropriate methods and/or technologies for effective energy recovery
from waste. Anaerobic digestion is a better way to treat tannery wastes. It is a biologicalmechanism in which
anaerobic bacteria break down complex organic substances in the absence of oxygen. Organic molecules
are converted to biogas in anaerobic digestion [3]. Anaerobic co- digestion is the simultaneous digestion of
two or more organic substances. It has various advantages over conventional anaerobic digestion, such as
improved digestibility, increased biogas production/methane yield due to the availability of additional
nutrients, and more efficient equipment usage and cost-sharing. Temperature, pH, mixing ratio, C/N ratio,
and other parameters are important in anaerobic digestion. There are three temperature ranges for anaerobic
digestion.
Some studies were conducted on higher temperature effects on anaerobic digestion. For instance, a study
found that the thermophilic temperature range produces faster reaction rates than the mesophilic
temperature range [4]. Thus, this study aims to determine the effect of different temperatures on biogas
production and to analyze the biodegradability of substrates.
2. Experimental
Among the four steps in this research, the first step was a site visit to get a complete picture of the study
area which is BSCIC Tannery Industrial Estate, Dhaka. In the second stage, samples were gathered and
their various properties were analyzed at the same time. The preparation of thesubstrate came next. A small-
scale anaerobic digestion unit had been experimentally set up. Finally, the procedure was analyzed through
continuous monitoring and data collection.
2.1 Sample preparation
A mixture of cow dung and water was kept for 5 days before being used as inoculum. The substrate
(fleshing and cow dung), inoculum (cow dung water), sewage water, and distilled water were mixed in all
reactors. A meat grinder was used to grind the fleshing for using it as a substrate. The fleshing, sewage water,
and cow dung were mixed in a 1:1:1 ratio. After mixing the above components, the inoculum was applied
to the substrate in a 1:1 inoculum-to-substrate ratio. Finally, the substrate was diluted with distilled water in
a 1:1 ratio in all reactors.
2.2 Materials
Fleshing, which is generated as solid waste in tanneries, is a viable waste for anaerobic digestion.It is mostly
of lipids and fats. They are produced by preparing animal skin for the tanning process. Sewage water will
provide a source of different microorganisms required for the various stages of the anaerobic digestion
cycle. As the C/N ratio of fleshing material was too low to be utilized directly as a medium for gas
production, the value was increased by mixing cow dung with fleshing in varied proportions throughout the
digestion phase. However, Cow dung not only increases the C/N value of the substrate but also acts as a
buffering medium during the digestionprocess [5]. Inoculum is pre-digested material that contains all of the
necessary microorganisms for the various processes of anaerobic digestion.
2.3 Experimental procedure
In this study, a batch reactor experimental setup was used. Three bottles were used, which were labeled as
1, 2, and 3no. The no.1 bottle was a sample bottle containing the substrate. The no.2 bottle was a gas bottle
with a scale for measuring the volume of gas. The no.2 and no.3 bottles were filled with water. Pipes
were used to connect the three bottles. Applying the water. displacement method, the generated gas
was collected in the second bottle, and the scaling of the second bottle was used to estimate the rate of gas
production. By measuring how much water was displaced, the volume of gas was determined. R1 was kept
at (45±1)°C, R2 at (40±1)°C, R3 at (35±1)°C, and R4 at (32±2)°C, which is room temperature. The
temperature-controlling device was set to control the following temperature ranges: (35°C), (40°C), and
(45°C). Daily gas production was monitored; when the gas bottle was full, a stop cork released the gas.
Room temperature, pH, COD reduction, VS (volatile solids) reduction, and gas production were observed
regularly during the digestion period of 35 days (25 September–30 October).

Page | 974
3. Theory
Anaerobic digestion consists of several steps, including hydrolysis, acidogenesis, acetogenesis, and
methanogenesis, that are carried out by various groups of microbes, some of which are syntrophic and rely
on diverse environmental needs [6]. The digestion process starts with bacterial hydrolysis of the input
materials, which decomposes insoluble organic polymers like carbohydrates, lipids, and proteins and
makes them susceptible to bacteria ([7];[8]). The organisms consume the original feedstock, which
undergoes a variety of various processes that convert it to intermediate molecules such as sugars, hydrogen,
and acetic acid before being turned into biogas [9]. In an anaerobic system, the methanogenic bacteria
releases most of the chemical energy contained within the starting material as methane [10]. However,
decomposing any organic materials in an anaerobic system covers two fields which are waste management
and theproduction of renewable energy known as biogas. Temperature is one of the essential parametersthat
influence the effectiveness of anaerobic digestion. Anaerobic digestion can occur at three different
temperatures: psychrophilic (below 25°C), mesophilic (25°C-45°C), and thermophilic (45°C -70°C) [11].
Temperature fluctuations can have an impact on microbial development and significantly decrease biogas
generation [12]. Hence, this study attempts to identify the influences of mesophilic temperatures and
thermophilic temperatures on the anaerobic digestion of tannery waste through gas production, COD
reduction, and Volatile solid reduction.
4. Result and Discussions
4.1 Characteristics of Raw Materials
The proportion of different materials was the same for the R1, R2, R3, and R4 reactors. Table 1 shows the
characteristics of raw materials. In this table, the pH of the fleshing is extremely high for its liming effect
and that is 10.4. On the other hand, sewage water has a pH of 7.3
Table 1: Characteristics of raw materials
Material Total solid (%) Volatile solid (%) COD (mg/L) pH
Sewage water 0.664 0.404 980 7.5
Inoculum 3.4125 2.4913 1410 7.3
Fleshing 14.47 10.89 - 10.4
Cow dung 11.12 8.25 - 8.5
4.2 Biogas generation
4.2.1 Daily biogas production
The figure-1 shows the daily gas production of four reactors over a period of 35 days. From the
graph, the gas generation phase is 16-33 days. On the 28th day, the maximum gas generation was observed
at the R1 (700mL), R2 (550mL), and R3 (400mL) reactors. At the R4 reactor, the maximum gas of 150mL
generation occurred on the 17th day. The gas generation decreases after the maximum production.

Page | 975
8

Biogas Production
0
0 R1
R2

(ml)
6
0 R3
0 R
4
4 0
0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36
0 Time (Day)

2 Figure 1: Daily gas production at different reactors


0
4.2.2Cumulative
0
gas production
Figure 2 represents the cumulative gas generation. The proportion of substrate in all reactors was the
same. But there were huge differences in cumulative gas production among the four reactors due to the
different levels of reduction of the volatile solid. Because of the higher VS reduction at R1, the gas
generation was also higher than in other reactors. The cumulative gas production at R1, R2, R3, and R4
were respectively 3850 ml, 3050 ml, 2900 ml, and 800 ml at the end of the5th week.

5000
4000
3000
Production(
Cumulitive

R1
2000
R2
1000 R3
0
Gas

R4
ml)

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
34 36

Time (day)

Figure 2: Cumulative gas production

4.3 Other
parameters
Figure 4 represents the change in volatile solids in R1, R2, R3, and R4 reactors at one-week intervals.
The percentage of volatile solid reduction at R1, R2, R3, and R4 were 40%, 35.5%, 22.6%, and 11.3%
respectively. The VS reduction is higher at R1 among all the reactors. The reduction of volatile solids
depends on temperature. The gas production rate depends on the reduction of volatile solids. In figure 5,
The percentages of COD destruction at R1, R2, R3, and R4 were 65.5%, 58.8%, 53.8%, and 21.7%. The
rate of COD decrease is higher at high temperatures than at room temperatures [13]. Here, high COD
reduction is observed in the R1 reactor.

6 2
R1 5 R1
4 0
R2 R2
0
(mg/L)

2
(g/L)

COD

R3 2 R
VS

0 0 3R
0 7 14 21 28 35 R 0 7 14 21 28 35
4 0 4
Time(Day) 0 Time(Day)
1
5
Figure-4: Change in Volatile solid with time 0
Figure-5: Change in COD with time
0
1
0
0
0
5
0
0

Page | 976
pH which is another essential parameter has the ideal range of 6.5-8.0 for anaerobic digestion and the
highest gas yield was observed in the range of 7.5-8.0 by the Chengdu Research Institute [14]. In our
study, initial pH values in R1, R2, R3, and R4 had decreased. Then while transforming into methane and
carbon dioxide, the pH level increased once more. During the last two weeks, all of the reactors' pH
values were between 7.6 and 8.
5. Conclusion
The major purpose of this study has been to examine how temperature influenced the anaerobic
digestion of tannery waste. An extensive laboratory analysis shows that tannery waste fleshing contains
a significant amount of volatile solids that are biodegradable. From the experiment, it was inferred that
the maximum level of cumulative gas production, 3850mL and maximum level of volatile solids
reduction and COD destruction, 40%, and 65.5% respectively, were obtained at 45℃ (Thermophilic
temperature). Within the digestion period, the pH values of R1 were in the range of 7.4 to 8. The best
outcomes were obtained at thermophilic temperatures.
Acknowledgment
The authors acknowledge the assistance of “Water Supply Lab,” Shahjalal University of Science and
Technology, Sylhet. They are also thankful to Naim Ali & Joy Chowdhury, students of the Department
of Electrical & Electronics Engineering, Shahjalal University of Science and Technology, Sylhet.
References
1. S.R.Basak., A.S.Mita., M.J.B.Alam.,“Solid Waste Management in the Leather Sector of
Bangladesh” , March 2020, Journal of Scientific and Engineering Research
https://www.researchgate.net/publication/340090805_Solid_Waste_Management_in_the
2. _Leather_Sector_of_Bangladesh
3. H. L. Paul., A.P.M. Antunes., A. D. Covington. et al., “Bangladeshi Leather Industry: An
Overview of Recent Sustainable Developments”, Journal- Society of Leather Technologists and
Chemists. 2013
4. R. M. Jingura., and R. Matengaifa., “Optimization of biogas production by anaerobic digestion for
sustainable energy development in Zimbabwe,” Renewable and Sustainable Energy Reviews, Jun.
2009, vol. 13, no. 5, pp. 1116–1120, http://dx.doi.org/10.1016/J.RSER.2007.06.015.
5. J. K. Kim., B. R. Oh., Y. N. Chun. et al., “Effects of temperature and hydraulic retention time on
anaerobic digestion of food waste,” Journal of Bioscience and Bioengineering, Oct. 2006, vol.
102, no. 4, pp. 328–332, http://dx.doi.org/10.1263/JBB.102.328.
6. M. Rouf., P. Bajpai., and C. Jotshi., “Optimization of Biogas Generation from Press Mud in
Batch Reactor,” Bangladesh Journal of Scientific and Industrial Research, Jan. 2010, vol. 45, no.
4, pp. 371–376, http://dx.doi.org/10.3329/BJSIR.V45I4.7383.
7. P. Weiland, “Biogas production: Current state and perspectives,” Applied Microbiology
Biotechnology, Sep. 2010, vol. 85, no. 4, pp. 849–860, http://dx.doi.org/10.1007/S00253-009-
2246-7/FIGURES/4.
8. M. Lesteur., V. Bellon-Maurel., C.Gonzalezc. et al., “Alternative methods for determining
anaerobic biodegradability: A review,” Process Biochemistry, Apr. 2010,vol. 45, no. 4, pp. 431–
440, http://dx.doi.org/10.1016/J.PROCBIO.2009.11.018.
9. F. Ali Shah., Q. Mahmood., M. Maroof Shah. et al.,, “Microbial ecology of anaerobic digesters:
The key players of anaerobiosis,” The Scientific World Journal, 2014,
http://dx.doi.org/10.1155/2014/183752.

Page | 977
10. E. J. I and A. K. E, “Studies on the microbial spectrum in anaerobic biomethannization of cow
dung in 10 m 3 fixed dome biogas digester,” International Journal of the Physical Sciences, vol. 5,
no. 8, pp. 1331–1337, 2010,
11. Available: http://www.academicjournals.org/IJPS
12. E. Kwietniewska and J. Tys, “Process characteristics, inhibition factors and methane yields of
anaerobic digestion process, with particular focus on microalgal biomass
13. fermentation,” Renewable and Sustainable Energy Reviews, Jun. 2014, vol. 34, pp. 491– 500,
http://dx.doi.org/10.1016/J.RSER.2014.03.041.
14. “The-biogas-handbook-Science-production-and-applications.”
https://www.yumpu.com/de/document/view/63141881/the-biogas-handbook-science-
production-and-applications.
15. S. Wang., F. Ma., W. Ma. et al., “Influence of Temperature on Biogas Production Efficiency
and Microbial Community in a Two-Phase Anaerobic Digestion System,” Water 2019, Vol. 11,
Page 133, vol. 11, no. 1, p. 133,
16. http://dx.doi.org/ 10.3390/W11010133.
17. H. O. Pörtner., B Berdal., R Blust. et al., “Climate induced temperature effects on growth
performance, fecundity and recruitment in marine fish: developing a hypothesis for cause and
effect relationships in Atlantic cod (Gadus morhua) and common eelpout (Zoarces viviparus),”
Continental Shelf Research. 1975–1997, Dec. 2001, vol. 21, no. 18–19, pp,
http://dx.doi.org/10.1016/S0278-4343(01)00038-3.
18. W. Mussoline., G. Esposito., A. Giordano. et al., “The Anaerobic Digestion of Rice Straw: A
Review”, Critical Reviews in Environmental Science and Technology. Jan.2013, vol. 43, no. 9,
pp. 895–915, http://dx.doi.org/10.1080/10643389.2011.627018

Page | 978
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 028

Optimization of charging parameters for supercapacitor


MD. Habibur Rahman *, Md. Mostafizur Rahman, Md, Minhazur Rahman,
M. Mastabur Rahman.

Chemical Engineering and Polymer Science,

Shahjalal University of Science andTechnology, Sylhet.

Email: habibcep201644@gmail.com, mostafizur.cep@gmail.com,


minhazurrahmancep@gmail.com, mrahman-cep@sust.edu

*Corresponding author [Md. Habibur Rahman]

Abstract: The continual depletion of fossil fuels necessitates the development of


Keywords:
environmentally friendly and cost-effective energy storage systems. In terms of power
density, cycle stability, and charge/discharge speed, supercapacitors are promising energy
● Supercapacitor; storage devices. Charging time, applied voltage and current density have significant
● Conductive impact on the performance of a newly produced supercapacitor. In the construction of
supercapacitor, activated carbon was employed as the negative electrode, whereas
Polymer; conductive polymer composites were used as the positive electrode. Two current collectors
● Charging acted as terminals for charging and discharging the complete system, and a micro-porous
separator was used to separate the anode and cathode. DC power supply was used to charge
● Performance of the supercapacitor, and a DC load bank was used to discharge the supercapacitor. Different
Supercapacitor; voltage was applied in the beginning with a constant current density to find the optimized
one. The optimized voltage was found 4V at the current density of 2.5A for a single cell.
● Specific For optimization of charging time, the fabricated asymmetric supercapacitor cell was
Capacitance; overcharged for 22 minutes, and the specific capacitance found in the first cycle is 204.15
F/g, but in the fourth cycle, it was dropped to 19.13 F/g, with a discharge time of 3
● Cyclic seconds. The highest coloumbic efficiency in the second cycle was 8.84%, with an energy
Retention. density of 13.81 Wh/Kg. On the other hand, after 7 minutes of charging the cell, the
specific capacitance in the first cycle was found 113 F/g and the sp. capacitance in the 7th
cycle was 55.71F/g, with a discharge time was 21 seconds, and coloumbic efficiency was
found at 21% in the 4th cycle. Overcharging a supercapacitor affects its performance
including a reduction in cyclic retention and efficiency as well as cycle life. It was found
that overcharging results deactivation of active materials. Low charging time results
higher Coloumbic efficiency. Finally, it can be concluded that optimum charging time
considerably boosts the overall performance, hence it is crucial to develop an efficient
supercapacitor.

1. Introduction
Conductive polymers and their composites have been receiving special attention in many widespread
applications due to their unique properties such as thermal stability, photocatalytic activity, electrical
conductivity, etc. [1]. Because of their high conductivity in a doped condition, high charge storage capacity,
low cost, and environmental friendliness, conducting polymers have been a hotspot for research as
electrode materials for supercapacitors[2]. Conducting polymer-based electrodes can undergo a quick and
reversible redox reaction, allowing them to store high-density charges and produce
Page | 979
large faradic capacitances [3-6]. However, conducting polymers may swell and shrink during the
electrochemical redox process, resulting in limited cycle life and capacitance degradation after long-term
charge and discharge cycles [7-9]. As a result, increasing the cyclic stability of conducting polymer
electrodes has become a promising issue. In general, conductive polymer composites prepared with a
combination of metal oxides, metal hydroxides, or metal sulfides can buffer volume change during
repeated redox cycles while also improving mechanical stability and specific capacitance. [10-12]
Polyaniline (PANI) is a widely used polymer among conductive families, with unique properties such as
high thermal, electrical, and environmental/chemical stability, as well as reasonable cost. PANI, on the other
hand, has several drawbacks, including low cycle stability, low power density, slower electron mobility, and
a short lifespan. To overcome it's shortcomings, a composite of PANI with metal oxides, carbonaceous
materials, 2D materials such as graphene, Boron nitride (BN), transition metal dichalcogenides, and other
materials is required [13-14]. It shows a conjugated structure that brings about conductivity in a doped state,
where the dopants are usually acids endowing conductivity to PANI. However, in high-technology
applications, PANI should be armed with advanced materials due to its brittle structure and weak
performance in counter ion insertion/deinsertion and charge/discharge cycle life. Graphene (G), due to its
high electron mobility, mechanical/thermal stability, high surface area volume (2675m2/g), and capacitance
(550F/g), has been utilized in various applications.[15] The combination of graphene oxide (GO) and PANI
exhibits an attractive character in comparison with pristine PANI. PANI unhands conductivity because of
dopant migration (e.g., HCl is a small molecule that migrates to the surface over time); on the other hand, a
PANI/GO oxide composite, because of the Graphene oxide acidic groups, remains conductive for a long time
and no migration occurs in composites Polyaniline/Graphene oxide and PANI exhibit synergistic effects
[16]. A unit cell test (two-electrode system), a half-cell test (three-electrode system), and an impedance test
are all methods for determining specific capacitance. The unit cell and half-cell tests are mainly used to
determine the specific capacitance of the supercapacitor. In the two-electrode system, there is a special type
is called Asymmetric hybrid supercapacitor which is a couple of both a faradaic Pseudocapacitor electrode
and a no faradaic EDLC electrode. For faradaic electrode conductive polymer, metal oxide (e.g. Ru 2O,
MnO2, Co3O4) is used.[17] In a non-faradaic process, supercapacitor stores charge electrostatically whereas
faradaic electrode store charges electrochemically by transfer of charge between electrode and electrolyte
same as the battery. 'Pseudo capacitors' are systems in which the capacitance arises from redox processes,
and the accompanying capacitance is known as pseudocapacitance. [18] This capacitance is accomplished
through underpotential deposition, reduction-oxidation reaction & intercalation process.
In this study, conductive polymer composites PANI/GO and PANI/hBN (hBN) were synthesized, and used
as electrode materials in the fabrication of supercapacitor. The supercapacitor device was evaluated in terms
of capacitance, energy density, and charging parameters (applied voltage, discharge time etc.) were
optimized.

2. Experimental
2.1 Materials
Oxalic Acid (C2H2O4), Sodium Sulfate (Na2SO4), Activated Carbon, ammonium peroxidisulphide (APS),
Cobalt Oxide (Co3O4) were used to fabricate the asymmetric hybrid supercapacitor. Cu sheet was used as a
current collector (98% pure), and Heavy Duty Paper Towel was used as separator. All the chemicals were
collected from Merck, Germany. A battery load bank model EBC-A20 manufactured by ZKE TECH and EB
tester software, version 1.8.5, a dedicated software for the battery load bank, and DC Power Supply,
Brand:Vantek, Model:DPS 3305P were used.

Page | 980
2.2 Preparation of asymmetric supercapacitor (ASD)
The asymmetric supercapacitor device was fabricated with binary electrode sections comprising of anode
and cathode materials separated with microporous separator. The whole system was squeezed between two
current collectors which functioned as terminals while charging and discharging. The current collectors work
as a transporting medium of current from current source to the electrode, and electrode to external load.
Copper sheet of 0.5mm thickness and 30 cm2 area was used as current collector in this study. The conductive
polymer composite material was mixed with cobalt oxide and APS and pasted onto the current collector by
brush. On the other current collector, activated charcoal was mixed with electrolyte (1 M Sodium sulfate
solution), and pasted onto another current collector by brush(Fig 1A). Thereafter the electrode was left to dry
properly. Then the separator was placed between the electrodes and Na 2SO4 (1M) was added dropwise so
that we can keep the amount of electrolyte constant for every single trial. After preparing the cell, the whole
setup was connected with a DC power supply for charging, and also connected with DC load bank for
constant current discharge (Fig 1B). The supercapacitor was evaluated based on electrochemical properties
(e.g., specific capacitance (F/g), energy density (Wh/kg) and power density (W/kg), cyclic retention %, and
Coloumbic Efficiency %).

Fig 1. Fabrication of supercapacitor (A), and Experimental setup (B)

2.5 Theory/calculation
The following equations are used to find out the effect of different parameters in the performance of newly
fabricated supercapacitors . Mahato et al.[19] Mitchell et al.[20] also used these equations to calculate
specific energy, energy density, power density, Columbia efficiency, and capacitive retention.

Page | 981
It
C= ……………………………………………… (1)
m∆V

Where C denotes capacitance in F/g, I represents current, t indicates discharge time in second, ∆V denotes voltage
difference, and m is the weight of materials. I, t and ∆V were found from DC load bank, and sp. capacitance was
calculated following equation (1).

E = 1 CV2............................................................... (2)
2

Where E stands for the energy density (Wh/kg), and V stands for voltage. Power density (W/kg) is calculated
following the equation (3).

E........................................................
P= (3)
t

The coloumbic efficiency (CE) of a supercapacitor is calculated by the following equation [21]
𝐈disscharge × tdischarge ...............................................................
CE= 𝐐𝐝 = Icharge × tcharge
(4) [21]
𝐐𝐜

Where Q represents the amount of charge, or capacity. For constant current operation Q=It. Where I
representcurrent and t represents time.
Cyclic retention of supercapacitor is calculated by this equation
th cycle
Cyclic retention % after nth cycle=Specific capacitance at n × 100 ........... (5)
Specific capacitance at 1stcycle

2. Result and Discussions


Applied voltage optimization
Different voltages were applied to find out the effective results. The voltage was applied using a DC
voltage/power supplier. Specific capacitance, Energy density, Power density, Cyclic retention of the cell was
evaluated for every applied voltage. All other parameters remained unchanged.
Table 1. Electrochemical properties of supercapacitor when charged at different applied voltage.
2V 3.7V 4V 4.3V 5V 6V

Sp. Capacitance, F/g 185.07 198.1 204.72 153.06 145.4 142.14

Energy Density, Wh/Kg 22.5 22.08 21.37 18.425 14.32 15.88

Power Density, W/Kg 1250 1119.8 1083 1163.68 1052.44 1121.2


5 3
Cyclic Retention, % (5 cycles) 38 25.17 63.11 64 38 45

Table 1 shows that supercapacitor cell at applied voltage of 4V showed highest specific capacitance with
a high energy density and cyclic retention. Power Density is very stable and almost similar for all PANI-
based supercapacitor. Hence, 4V is the optimum voltage for this Polyaniline based Supercapacitor.

Page | 982
Optimization of applied current density
For this part of the experiment, PANI/h-BN was taken as electrode material and all other parameters were
kept unchanged. Different current density was applied by using a DC power supply. The applied voltage
was 4V which is the optimized applied voltage found in the previous experiments. Three asymmetric
hybrid-type supercapacitors were fabricated, and they were charged at different current densities. For
every applied current density Specific capacitance, Energy density, Power density, Cyclic retention of
the cell was evaluated using DC Load Bank and findings are presented in the Table 2.
Table 2. Electrochemical properties of ASD at different current density
Current Specific Capacitance Energy Power Coloumbic Cyclic
Density (F/g) density density retention after
(Wh/Kg) (W/Kg) Efficiency (%) 5 cycles(%)

1 A/g 103.6 8.051 935 25.78 25.78

2.5 A/g 342.6 25.84 921.1 27 64

4 A/g 150 18.72 1182.5 11.33 31.04

Table 2 shows how the performance of the same supercapacitor varies because of the change of applied
current density. 2.5 A/g (2.5 ampere per gm of active electrode material i.e. PANI/h-BN for this part of
the experiment) shows the highest specific capacitance, cyclic retention, energy density, and Coloumbic
efficiency. So, 2.5 A/g is the optimized applied current density.

Figure 2. Variation of voltage as a function of time of ASD at different current density(A), Variation of
Specific Capacitance at different current density.
In figure 2, 2.5 A/g applied current density showed highest discharge time compared to other two applied
current density. Though higher current density increases the voltage of the cell but it can not store more
charge which is clear from this figure.
Optimization of charging time
While fabricating a new supercapacitor for testing, all other parameters were kept constant so that we can
only see the effect of charging time. In this part of the experiment, optimized applied voltage and current
density was used which was found from previous experiments. Which are 4V and 2.5 A/gm. In this part,
PANI-GO (weight ratio of PANI 97% and Graphene Oxide 3%) was used as electrode material.

Page | 983
15 22 7 Current
1.4 minute minute minut (A) 0
s s es .
1.2 8
1 0
0.8 .
7
Voltag

Curren
0.6
e, V

t, A
0
0.4 .
6
0.2
0
0 .
0 10 20 30 4 5 6 5
Discharge time, sec 0 0 0
0
.
Figure 3. Variation of voltage as a function of time of supercapacitor charged for different time.
4
Figure 3 represents discharge time and variation of voltage of as a function of time of 1st cycle
0 of all 3
supercapacitors charged for different duration of time. This figure clearly shows that high charging
. time
increases the charge storing capacity significantly. It also decreases the voltage of the cell.3 As we are
pushing the capacitor beyond its capacity, something interesting happens. It loses its ability 0 to store
charge and loses its ability to gain voltage in every single cycle. But if we consider other. important
properties like cyclic retention and coloumbic efficiency, long charging time shows poor results
2 in cyclic
behavior. 0
Table 3. Electrochemical properties of supercapacitor charged for 7 minutes. .
1
Properties cycle cycle 2 cycle cycle cycle cycle 0 cycle
1 3 4 5 6 7

Specific capacitance, F/g 113 65.98 55.87 49.57 50.5 57.71 55.71

Energy Density, Wh/Kg 15.7 9.59 8.21 7.72 7.57 9.4 8.24
5
Power Density W/Kg 126 1278.7 1286 1323 1298 1353.7 1290
0 5
Coloumbic Efficiency (%) 11.25 14.74 21 16.15 12.95 13.77

This table shows the cyclic behavior of supercapacitor which was charged for 7 minutes. From the table,
we can see the capacitive retention after 7 cycles were 49.3%. Energy density, power density, and
coloumbic efficiency are also calculated. And 1st supercapacitor showed the best results. The amount of
charge stored here are less i.e. the discharge time because the charging time was less. The same thing is
also reported in literature [22].
From the table, specific capacitance and discharge time is stabilizing as we are approaching for more
cycles.

Page | 984
Figure 4 shows discharge time
for different cycles. Also, the
cell took less time to reach up to
a certain voltage while charging
it for the next cycles. And the
starting voltage is also
stabilizing for the next cycles.
More significantly, the voltage
of the capacitor was almost the
same as the previous cycles.

Figure 4. Variation of voltage as a function of time of supercapacitor charged for 7 minutes.


Table 4. Electrochemical properties of supercapacitor charged for 15 minutes.
Properties cycle 1 cycle 2 cycle 3 cycle 4 cycle 5

Specific capacitance, F/g 159.93 75.48 42.3 33.5 25.77

Energy Density, Wh/Kg 17.63 7.18 2.48 1.266 0.303

Power Density, W/Kg 1113.68 1035 812.5 651.25 363.75

Coloumbic Efficiency, % 19.23 14.66 8.75 4.287

This table shows the electrochemical properties of the supercapacitor charged for 15 minutes and its
cyclic behavior. Specific capacitance in the 1st cycle is higher than the 7 minutes charged capacitor, but
the cyclic behavior is poor than the 1st capacitor. Capacitive retention is 16.11% which is lower and the
quantitative value for 2nd capacitor is 25.77 whereas in trial 1 it was 50.5 in the 5th cycle which is almost
double. The reduction in energy density in every single cycle is also quiet more than 1st capacitor.
Figure 5 displays the variation of
discharge time in a different cycle.
We can see that this is very low and
reduces to 3 seconds in the 5th
cycle. This is maybe the reason for
the deactivation of active materials
which store charges. Also, the
initial voltage is decreasing for a
new cycle.

Figure 5. Variation of voltage as a function of time of supercapacitor charged for 15 minutes.


Table 5. Electrochemical properties of ASD charged for 22 minutes.

Cycle cycle 1 cycle 2 cycle 3 cycle 4

Specific capacitance,F/g 204.15 50.38 28.409 19.13

Page | 985
Energy Density, Wh/Kg 13.81 2.911 0.76 0.408

Power Density, W/Kg 875.5 806.25 550 490

Coloumbic Efficiency, % 8.84 4.67 6.52

This table shows the electrochemical properties of the supercapacitor charged for 22 minutes and its
cyclic behavior. Specific capacitance in the 1st cycle is higher than the 7 minutes and 15 minutes charged
capacitors, but the cyclic behavior is poor than the 1st & 2nd capacitors. Capacitive retention is 9.37%
which is lower other two capacitors. And this one didn’t even show the 5th cycle and lost its ability to
store charge completely to show a continuous discharge duration. The reduction in energy density in
every single cycle is also quiet more than other two trials.
Figure 6 shows the discharge time
when the supercapacitor was charged
and discharged cyclically. It shows
the discharge time for the same
constant current discharge is
decreasing meaning that the ability of
the capacitor to store charge for this
applied voltage and current is
decreasing and the voltage gain for a
new cycle is lower than the previous
cycles.
Figure 6. Variation of voltage as a function of time of supercapacitor charged for 22 minutes.

Figure 7. Discharge time as a function of cycle (A), Variation of Energy Density at different cycles for

Page | 986
different charging time (B), Variation of Specific Capacitance at different cycles for different charging
time.
Cyclic analysis of supercapacitor charged for different period of time shows that, supercapacitor charged
for 7 minutes stabilizes its charge storing properties (i.e. Sp, capacitnce, Energy and Discharge time)
whereas overcharged supercapacitors are losing its cyclic property. Figure 7 is a clear indication of that.

Conclusion
In this study, the applied voltage, charging time and current density are optimized to improve the
capacitive performance of the Polyanniline based supercapacitors. The optimized voltage was found 4V
at the current density of 2.5A which signifies that the supercapacitor cell at applied voltage of 4V showed
highest specific capacitance with a high energy density and cyclic retention. And the power Density is
very stable and similar for all Polyanniline based supercapacitor. From the cyclic analysis result it shows
that a lower charging time shows more cyclic stability than a long charging time. But long charging time
can store more charge in the 1st cycle, but it loses its ability to store charge in later cycles resulting in a
low discharge time. But supercapacitor which is not overcharged (charged for 7 minutes) showed
excellent cyclic stability. It conserved its ability to store charge and discharge it when connected to the
DC load bank for constant current discharge. This was also found in our experiment that low charging
time leads to higher Coloumbic Efficiency. Several times the cell was charged for less than 10 sec and
the Coloumbic Efficiency was 100% for all the cases. High charging time increases the charge storing
capacity significantly but it decreases the voltage of the cell. These findings are particularly intriguing
from the standpoint of hybrid capacitor development and practical application.

Acknowledgment
The authors are thankful for the financial support from the Grant for Advanced Research in
Education, the Ministry of Education, Government of the People’s Republic of Bangladesh
(Research grant 2020-2022, Project code: PS20191250). We also acknowledge grant from SUST
research center (AS/2021/1/09).
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Page | 988
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 066

Impact of different cooking conditions on the formation of polycyclic


aromatic hydrocarbons and their health risk assessment in chicken meat
products

Nazmul Islam, S M Nahid Hasan, Emon Das, Farzana Yasmin, Iftekhar Ahmad and Wahidu
Zzaman*

Department of Food Engineering and Tea Technology,

Shahjalal University of Science and Technology, Sylhet-3114, Bangladesh

Email: nazmul.sust.fet@gmail.com, munnanahidhasan@gmail.com, itsmeimon@gmail.com,


farzanayasmin119@gmail.com, iftekharfet.sust@yahoo.com, wahidanft@yahoo.com*

*Corresponding author [Dr. Wahiduzzaman, wahid-ttc@sust.edu, Tel: 880-821-713491]

Abstract: Carcinogenic Polycyclic Aromatic Hydrocarbons (naphthalene, fluorine,


Keywords:
phenanthrene, anthracene, Benzo[a]anthracene, pyrene, chrysene, benzo[a]pyrene, etc.)
may be present in the foods that are cooked at high temperatures. This study aimed to
● Polycyclic aromatic quantify the PAHs level in conditionally cooked chicken meat samples. Another objective
hydrocarbons; was to determine carcinogenic risk and non-carcinogenic risk for each method of cooking.
For this work, green tea-marinated raw chicken meats were cooked in a microwave oven
● Benzo[a] pyrene; for 13 discrete temperatures and duration of cooking, arrayed by response surface
methodology. Then, the samples were hydrolyzed, extracted, and then analyzed by a GC-
● Response surface MS machine. The GC-MS report showed, as the cooking time and/or temperature
methodology; increased, so did the residue of carcinogenic PAHs. At 220°C and 90 minutes of cooking,
the highest value of the total PAHs was found at 179.78 µg/kg; otherwise, at 180°C and 75
● Carcinogenic risk; minutes of cooking, the lowest value of total PAHs was found at 56.42µg/kg. Among the
● Non-carcinogenic PAHs the marker PAH, Benzo[a]pyrene (BaP) was found in all samples, ranging from 1.83
risk; to 5.22µg/kg. Ten of the thirteen cooked samples exceeded the level of BaP (2.0 µg/kg)
established by the European Union for smoked meat and smoked meat products (EC,
● GC-MS; 2011). The carcinogenic and hazard risk values were calculated, ranging from 4.0×10 -6 to
1.14×10-5 and 1.93×10-3 to 5.46×10-3 respectively assuming daily chicken intaking of a 60
kg person for 70 years.
● Chicken meat

1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are vast molecules comprising two or more fused benzene rings. PAHs
are common environmental contaminants synthesized by incomplete combustion or pyrolysis of organic
compounds (Ishizaki et al., 2010).
About15 PAHs have been identified,suchas Fluorene(Fle), Anthracene(Ant), Pyrene(Pyr), Phenanthrene(Phe),
Naphthalene(Nap), Chrysene(Chr), Benzo[a]anthracene(BaA), Benzo[a]pyrene(BaP), etc (Kamankesh et al.,
2015). The PAHs are lipophilic, semi-volatile, and have a long shelf life. These are widely present in the
environment because of their hydrophobic properties. As a result, both plants and animals have the potential to
incorporate environmental PAHs into the food chain. Inhalation, dermal contact, and eating of contaminated
foods, are the three main ways humans are exposed to PAHs. Diet is the usual means which account for| 989
Page 88–98%
of such contamination that people are exposed (Tareq et al., 2020). PAHs are on the priority pollutant lists of
European Union (EU) and the Environmental Protection Agency (EPA). These can cause cancer. BaP can be used
as a marker for the presence and effect of carcinogenic PAHs in food, as stated by the European Food Safety
Authority (EFSA) in 2008(Alexander et al., 2008). According to EU, the maximum level for Bap is 2 µg/kg(EC,
2011). Several researchers investigated the presence of the PAHs in food samples. (Garvin, n.d.) first found that
BaP and other related PAHs were present in charcoal-broiled beef. (Chung et al., 2011) revealed that, the kind of
heat source and cooking technique is highly correlated with PAH levels. (Tareq et al., 2020) reported that popular
ways to cook chicken at home (using a microwave, pan-frying after boiling, and using a gas grill both directly and
indirectly) can lead to the formation of PAHs in the meat. (Singh et al., 2016) stated that PAH concentration
depends on elements like distance from the heat source, fuel utilized, level of processing, cooking durations and
procedures. (Weisburger et al., 2002) stated that applying tea polyphenols to beef before cooking stops the
formation of the mutagens in a dose-dependent way. Traditionally roasting and grilling of meat is done by wood
fire. Nowadays, many people use microwave ovens where they can cook the meat at a controlled pre-set
temperature. However, most people are unaware of how temperature influences the formation of PAH levels.
Here, chicken meat samples were marinated with green tea extracts, and the samples were prepared at 13 different
temperatures and cooking times using the response surface methodology (RSM). Thus, the objective was to
quantify the level of PAHs in every time-temperature of cooking. Besides, our purpose was to determine the
carcinogenic risk and non-carcinogenic risk from the dietary intake of chicken in a specific cooking condition.
This study will form a basis for possible future research on the effect of tea marination on the formation of PAH
levels.
2. Experimental
2.1 Materials
Pieces of raw chicken meat were bought from a HACCP-certified meat shop in the Sylhet area of Bangladesh.
The pieces of meat had no bone but flesh only. For marination purposes, green tea was also collected from the
Sylhet area of Bangladesh.
2.2 Sample preparation
Chicken meats presented a uniform weight (approximately 40 g). No other elements but Green tea brewed water
was used to marinate chicken meats for 4 hours in the ratio of 1gm:1ml, according to(Wang et al., 2019). The
marinated samples were then cooked at 13 cooking conditions varying in time and temperature, provided by RSM,
shown in Table 1. All the cooked samples were brought out at normal room temperature and stored at 60°C for 48
hours. With a mortar and pestle, the dry samples were ground into powder. About 5g of meat from each sample
was weighed and then placed in the individual round-bottom flask that had been thoroughly cleaned.
2.3 Preparation for GC-MS Analysis
Preparation for GC-MS analysis was done according to(Tareq et al., 2020).At first, fat was removed from samples
by hydrolysis with 100 mL of 2 M methanolic KOH solution. The mixture was shaken for 30 minutes, then
refluxed at 60°C for 2.5 hrs and cooled. Then PAHs of these samples were extracted with 40 mL of cyclohexane.
The flask was sealed and left in the dark overnight. The transparent top cyclohexane layer was collected by
centrifuging, and residual water was eliminated by anhydrous sodium sulfate. The cleanup column was prepared
with cotton, cotton layers, sodium sulfate, and silica gel, and the column was washed with 5 ml dichloromethane.
The color of the extracted sample was reduced by passing nitrogen gas through the cleanup column. The pre-
concentrated solution was then passed through a C18 cartridge. For the standard solution, a known quantity of
standards was dissolved in a predetermined volume of dichloromethane with concentrations of 0.5, 1, 2, and 4
mg/kg for calibration.
2.4 Analysis in GC-MS
A Varian GC (Model: Varian CP 3800, USA) and MS (Model: Varian Saturn 2200) with a VF-5 fused silica
capillary column were used for PAHs analysis according to(Tareq et al., 2020). As a carrier gas, helium flowed at
1 mL/min. For GC-MS detection, a 70 eV selected ion storage was used. Injector, transfer line, and manifold,
temperatures were 275°C, 280°C, 40°C. All analytical instruments and settings were equal; however, oven
temperature, SIS mode, and total run duration for measuring PAHs were varied. Diluted 1 mL solutions were
manually injected for each standard and sample solution. Target compounds in pre-concentrated samples were
identified using chromatogram retention durations and mass spectrometry with standards. Blank reagent
measurements calibrated the instrument.
3. Theory/calculation
Page | 990
3.1 Dietary exposure(Ed) for PAHs: Ed was calculated as the following equation based on (Xia et al., 2010)
Ed = ∑𝑛𝑖=1 BEC × IRi …………………(i)
where, CPAH= concentration of an individual PAH compound in meat; TEF= Toxic equivalence factor; BEC=B[a]
equivalent concentration in meat; IRi=Ingestion rate of chicken meat per day.
3.2 Carcinogenic Risk (CR) for PAHs: CR of PAHs was measured based on(Xia et al., 2010) method,
CR= (Ed×Efr×ED×SF×Cf) / (BW×AT)…………….. (ii)
where, Efr=Exposure frequency; ED=Exposure duration; SF=slope factor; Cf =Conversion factor; BW=Body
weight; AT=Average time for non carcinogens.
3.3 Non-carcinogenic risk calculation: NCR of PAHs was measured according to the method given by (Li et
C ×IR×Cf×ED×EF
al., 2016); NCR = iBW×AT×RfDo …………………………(iii)
where, RfDo = Oral ingestion reference dose of PAHs (mg/kg/day) according to USEPA, 2012.
4. Result and Discussion
The correlation coefficients (R²) for the time-temperature of cooking versus PAHs formation, BaP formation,
carcinogenic risk, and non-carcinogenic risk in RSM were 98.58%, 91.85%, 92.39%, and 92.94%, respectively.
Each RSM result had a Variance Inflation Factor (VIF) of greater than 1 and a lack of fit greater than 0.05. This
data suggests that the RSM model fits the information well. The determined carcinogenic and non-carcinogenic
risk values of PAHs are summarized separately in Table 1. At 220°C and 90 minutes of cooking, the maximum
value of total PAHs was 179.78µg/kg, whereas the minimum value was 56.42µg/kg at 180°C and 75 minutes of
cooking (Table 1). The interaction plot (Fig 1) showed the relationship between cooking time temperature and
PAHs generation. Benzo[a]pyrene, the carcinogenic marker PAHs, was detected in every sample, ranging from
1.83 to 5.22 µg/kg(Ta. The contour plot (Fig 2) showed the generation of Benzo[a]pyrene with time-temperature.
Fig 1 and Fig 2 showed that, as the cooking time temperature increased, so did the BaP level and the total PAHs
level. The maximum level of BaP is 2.0 µg/kg for smoked meat and meat products by the EU(EC, 2011). Among
the thirteen samples, ten samples exceeded that limit. The current study observed the maximum carcinogenic risk
(1.14×10-5) and non-carcinogenic risk (5.46×10-3) among the 13 samples when cooked for 90 minutes at 220°C.
The calculation was done assuming a person weighs 60 kg and consumes chicken meat at an ingestion rate of 17.4
g/day daily with a lifespan of 70 years. The lowest CR (4.0×10-6) and NCR (1.93×10-3) were obtained by cooking
at 180 °C for 60 minutes. Generally, CR values below 10-6 are negligible, above 10-4 are unacceptable, and
between 10-6 and 10-4 are acceptable(Tareq et al., 2020). In our study, the CR values of all 13 samples of cooked
chicken meat were found to be within acceptable ranges. In all 13 samples, the CR and NCR values were
gradually enhanced with cooking time and temperature, as shown in Figures 3 and 4.

4.1 Figures and tables


Table 1: Effect of different time-temperature of cooking on PAHs generation, Carcinogenic Risk and Non-Carcinogenic Risk

Time ΣPAHs Carcinogenic Non-


Sample Temperature(⁰C) (min) Risk Carcinogenic
(µg/kg)
No Risk
1 220 60 148.47 5.50E-06 2.73E-03
2 220 75 151.24 7.08E-06 3.43E-03
3 220 90 179.78 1.14E-05 5.46E-03
4 200 60 95.5 4.30E-06 2.08E-03
5 200 75 101.86 4.49E-06 2.17E-03
6 200 90 111.43 5.62E-06 2.70E-03
7 180 60 63.6 4.00E-06 1.93E-03
8 180 75 56.42 4.44E-06 2.12E-03
9 180 90 79.18 5.75E-06 2.73E-03
10 200 75 84.09 5.41E-06 2.58E-03
11 200 75 91.06 4.53E-06 2.15E-03
12 200 75 88.72 4.67E-06 2.23E-03
13 200 75 96.85 4.06E-06 1.97E-03

Page | 991
Figure 1: PAHs generation at different Figure 2: Benzo[a]pyrene formation at
time-temperature of cooking different time-temperature of cooking

Carcinogenic Risk
1.20E-05

1.00E-05

8.00E-06

6.00E-06

4.00E-06

2.00E-06

0.00E+00
60 min 75 min 90 min 60 min 75 min 90 min 60 min 75 min 90 min
180°C 200°C 220°C

Figure 3: Carcinogenic Risk at different time-temperature of cooking

Non-Carcinogenic Risk
6.00E-03
5.00E-03
4.00E-03
3.00E-03
2.00E-03
1.00E-03
0.00E+00
60 min 75 min 90 min 60 min 75 min 90 min 60 min 75 min 90 min
180°C 200°C 220°C

Figure 4: Non-Carcinogenic Risk at different time-temperature of cooking

5. Conclusion
This study concludes that the higher the cooking duration and temperature, the higher the PAHs level. BaP, the
marker PAH level below the standard (2.0 µg/kg), was found in sample 4 (200°-60min), sample 7 (180°C-60min),
and sample 13 (200°C-75min). Both the highest CR (1.14×10-5) and the highest NCR (5.46×10-3) were found at
220°C for 90 minutes of cooking, which was the maximum value of temperature and time. The CRPage values
| 992for all
the samples were found within the acceptable limit (between 10-4 and 10-6). To get a lower risk, it is recommended
to cook chicken below the range of 200°C-75min. The marination of green tea extracts might impact on reducing
the risk. Further research should be done to determine the effect of green tea marination.
References
1. Alexander, J., Benford, D., Cockburn, A., Cravedi, J., Dogliotti, E., Domenico, A. Di, Fernández-cruz, M. L.,
Fink-gremmels, J., Fürst, P., Galli, C., Grandjean, P., Gzyl, J., Heinemeyer, G., Johansson, N., Mutti, A.,
Schlatter, J., Leeuwen, R. Van, Peteghem, C. Van, & Verger, P. (2008). Polycyclic Aromatic Hydrocarbons in
Food - Scientific Opinion of the Panel on Contaminants in the Food Chain. EFSA Journal, 6(8), 1–114.
https://doi.org/10.2903/j.efsa.2008.724
2. Chung, S. Y., Yettella, R. R., Kim, J. S., Kwon, K., Kim, M. C., & Min, D. B. (2011). Effects of grilling and
roasting on the levels of polycyclic aromatic hydrocarbons in beef and pork. Food Chemistry, 129(4), 1420–
1426. https://doi.org/10.1016/j.foodchem.2011.05.092
3. EC. (2011). COMMISSION REGULATION (EU) No 835/2011 of 19 August 2011. Official Journal of the
European Union, L 215(835), 4–8.
4. Garvin, J. E. (n.d.). Benzo ( a ) pyrene and Other Polynuclear Hydrocarbons in. 2, 53–55.
5. Ishizaki, A., Saito, K., Hanioka, N., Narimatsu, S., & Kataoka, H. (2010). Determination of polycyclic
aromatic hydrocarbons in food samples by automated on-line in-tube solid-phase microextraction coupled
with high-performance liquid chromatography-fluorescence detection. Journal of Chromatography A,
1217(35), 5555–5563. https://doi.org/10.1016/j.chroma.2010.06.068
6. Kamankesh, M., Mohammadi, A., Hosseini, H., & Modarres Tehrani, Z. (2015). Rapid determination of
polycyclic aromatic hydrocarbons in grilled meat using microwave-assisted extraction and dispersive liquid-
liquid microextraction coupled to gas chromatography-mass spectrometry. Meat Science, 103, 61–67.
https://doi.org/10.1016/j.meatsci.2015.01.001
7. Li, J., Dong, H., Li, X., Han, B., Zhu, C., & Zhang, D. (2016). Ecotoxicology and Environmental Safety
Quantitatively assessing the health risk of exposure to PAHs from intake of smoked meats. Ecotoxicology and
Environmental Safety, 124, 91–95. https://doi.org/10.1016/j.ecoenv.2015.10.007
8. Singh, L., Varshney, J. G., & Agarwal, T. (2016). Polycyclic aromatic hydrocarbons’ formation and
occurrence in processed food. Food Chemistry, 199(December), 768–781.
https://doi.org/10.1016/j.foodchem.2015.12.074
9. Tareq, A. R. M., Afrin, S., Hossen, M. S., Hashi, A. S., Quraishi, S. B., Nahar, Q., Begum, R., & Ullah, A. K.
M. A. (2020). Gas Chromatography–Mass Spectrometric (GC-MS) Determination of Polycyclic Aromatic
Hydrocarbons in Smoked Meat and Fish Ingested by Bangladeshi People and Human Health Risk
Assessment. Polycyclic Aromatic Compounds, 0(0), 1–11. https://doi.org/10.1080/10406638.2020.1790017
10. Wang, H., Wang, C., Li, C., Xu, X., & Zhou, G. (2019). Effects of phenolic acid marinades on the formation
of polycyclic aromatic hydrocarbons in charcoal-grilled chicken wings. Journal of Food Protection, 82(4),
684–690. https://doi.org/10.4315/0362-028X.JFP-18-420
11. Weisburger, J. H., Veliath, E., Larios, E., Pittman, B., Zang, E., & Hara, Y. (2002). Tea polyphenols inhibit
the formation of mutagens during the cooking of meat. Mutation Research - Genetic Toxicology and
Environmental Mutagenesis, 516(1–2), 19–22. https://doi.org/10.1016/S1383-5718(01)00351-5
12. Xia, Z., Duan, X., Qiu, W., Liu, D., Wang, B., Tao, S., Jiang, Q., Lu, B., Song, Y., & Hu, X. (2010). Health
risk assessment on dietary exposure to polycyclic aromatic hydrocarbons (PAHs) in Taiyuan, China. Science
of the Total Environment, 408(22), 5331–5337. https://doi.org/10.1016/j.scitotenv.2010.08.008

Page | 993
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 089

Development of Instant Green Tea by Foam mat drying and


quality assessment based on antioxidant properties

Nazmul Islam, S M Nahid Hasan, Iftekhar Ahmad and Wahidu Zzaman*

Department of Food Engineering and Tea Technology,

Shahjalal University of Science andTechnology, Sylhet-3114, Bangladesh

Email: nazmul.sust.fet@gmail.com, munnanahidhasan@gmail.com,


iftekharfet.sust@yahoo.com

*Corresponding author [Dr. Wahiduzzaman, wahid-ttc@sust.edu, Tel: 880-821-713491]

Keywords:
Abstract: Foam mat drying is an economical alternative to drum, spray, and freeze-
drying, where a liquid is turned into a stable foam, and then it goes through air
● Foam mat drying; drying. A high-quality food powder can be obtained by a proper selection of foaming
methods, foaming agents, foam stabilizers, and the time taken for foaming. This study
● Green tea; aimed at developing instant green tea powder through foam mat drying from green tea
extracts and focused on investigating the antioxidant levels in both green tea and made
● Instant green tea instant green tea powder. For making instant green tea, 1.0% Carboxymethyl cellulose
(CMC) as emulsifiers and 5% egg albumin as foaming agents were incorporated into
● Total phenolic green tea extracts, whipped for 5 minutes, and dried at 40ºC temperature until gaining
content ; a consistent weight. Thereafter both green tea and instant-made green tea samples
were prepared using methanolic extraction. Then, the total phenolic content (TPC),
● Total antioxidant total antioxidant activity (TAC), and diphenyl-picrylhydrazyl (DPPH) scavenging
activity; activity of both samples were determined by spectrophotometer at 765nm, 695nm,
and 517nm, respectively. In making instant green tea powder by foam mat drying
● DPPH radical process, total antioxidant capacity was reduced by 0.406 mg AAE/g (from 0.809 mg
scavenging activity; AAE/g to 0.403 mgAAE/g), and total phenolic content was decreased by 7.79 mg
GAE/g (from 10.45 mg GAE/g to 2.66 mg GAE/g) and DPPH radical scavenging
activity percentage reduced by 33.9% (from
62.20% to 28.3%) from green tea extracts.

1. Introduction
Drying is an essential processing step in preserving foods. From the ancient days, drying has
been an excellent example of food preservation(Hardy & Jideani, 2017). In general, drying reduces water
activity in food to a specific level, making it difficult for microorganisms to survive and thus increasing
shelf life(M. A. Hossain et al., 2021) Consequently, applying suitable drying conditions is crucial to the
quality of the final product so that it should be easier to rehydrate a product without changing its taste,
smell, or nutritional value(Maciel et al., 2021). Spray drying, freeze drying, drum drying, tray drying,
solar drying, and foam mat drying can be used for drying(Hertzendorf et al., 1970). Freeze and spray
drying produce high-quality products in terms of rehydration and color, but both have considerable
operating and set-up costs. Hot air drying is

Page | 994
the easiest and cheapest drying process, but the dried product quality is relatively low (Affandi et al.,
2017). The revised foam mat drying is significantly less expensive than spray-drying and freeze-drying
due to its faster drying at lower temperatures despite nutritional quality retention and ease of
reconstitution (Benkovi et al., 2018). Foam-mat drying is a simple way to dry liquid- solid foods by
mixing them with a stabilizing agent and/or a foaming agent to make a stable foam and drying them at 50
to 80 °C (Febrianto et al., 2012). The higher interfacial area of foamed materials results in a faster drying
rate than non-foamed materials because the air trap is formed in foam, which increases the surface
area of the food. Thus, a short temperature can easily remove the water molecules from food (A.
Wilson et al., 2012). The use of foam-mat drying makes it feasible to generate a powder that does not
stick to the walls of the dryer(Ratti & Kudra, 2006). Compared to non-foam dried powder, foam mat dried
powder has a significantly higher concentration of biological components. In terms of color, flavor, and
taste, powder from foam- mat drying is nearly identical to a fresh sample. Foam mat drying is becoming
more popular andis commercially used to dry liquids that produce high-quality concentrates, such as milk,
fruit juices, coffee, and Tea (Bag et al., 2011). Developing instant tea production can be a good
application of foam mat drying. Instant tea is a fully soluble dried tea powder. Instant tea being ready to
reconstitute into a cup of tea, it has become a fast-growing product in the world(Someswararao &
Srivastav, 2012).This study aimed to develop instant green tea by foam mat drying and assess the quality
based on their antioxidant properties.

2. Experimental
2.1 Materials
Green tea was collected from the local market of the Sylhet region of Bangladesh.

2.2 Experimental procedure

2.2.1 Development of instant green Tea


At first, the green tea was extracted in hot water (1 g per 15 ml) for 10 minutes and cooled. After that, 5%
of egg albumin was added as a foaming agent, and 1.0% of Carboxymethyl cellulose (CMC) was added
as a foam stabilizer. For foam formation, the mixture was whipped well for 5 minutes. Foam density and
foam expansion volume were determined according to (Shaari et al., 2018).

mass of the foam(g)


Foam density = Volume of the foam(ml)
….................... (i)
V1−V0
Foam Expansion (%) = V0
….………………… (ii)

Where V0= Initial Volume of tea foam(cm³); V1= Final Volume of the foam(cm³)
The foam was then spread on parchment paper laid trays for a larger surface area, and the trays were kept
in oven drier at 40°C until the mass transfer was stopped. After getting a consistent weight, the dried tea
foam was removed from the dryer and crushed by a grinder. This was the foam mat-dried instant green
tea sample.

Page | 995
2.2.2 Methanolic extraction
Both raw green tea samples and foam mat-dried instant green tea samples underwent the following
procedure (M. S. Hossain et al., 2021). One gram of each tea sample was mixed with 25ml of methanol.
The mixture was then homogenized in a shaking incubator for 90 minutes at 20ºC. After that, the crude
extract was centrifuged for 15 minutes at a speed of 3000 rpm. The centrifuged is the sample for TPC,
TAC, and DPPH scavenging percentage measurement.

2.2.3 Determination of total phenolic content


The total phenolic content of the two samples was measured according to (Zzaman et al., 2021). Tea
extracts of 1 ml was mixed with 5 mL of Folin–Ciocalteu solution (1:10 v/v) and 4 mL of 7.5% sodium
carbonate, and the mixture was vortexed for 15 s. To product color it was kept dark at 40◦C for 30 min.
At 765 nm wavelength, the absorbance was measured using a spectrophotometer, and the blank was read
against a series of standard gallic acid solutions. The total phenolic content was calculated as the
equivalent of gallic acid per gram using a standard gallic acid calibration curve.
y = 0.0903x + 0.0540; (R² = 0.9998) ................... (i)
The total phenolic content was expressed in milligrams of equivalent gallic acid (GAE) per gram of dry
extract, a standard reference chemical.

2.2.4 Determination of total antioxidant capacity


TAC reagent was prepared by 0.6 M Sulphuric acid, 0.028 M sodium phosphate, and 0.004 M ammonium
molybdate mixed in a ratio of 4:2:4, and after that, 3 mL of this TAC reagent was applied with 0.3 mL of
each tea extract. It was then incubated at 95 ◦C for 90 min, followed by (M. S. Hossain et al., 2021). At
695 nm wavelength, the absorbance was measured against a blank using a spectrophotometer. L-ascorbic
acid was used to create a standard curve, and the results were reported as mg of ascorbic acid equivalent
per gram.
y = 2.3570x + 0.3683; (R² = 0.9998).................. (iii)

2.2.5 Determination of DPPH radical scavenging activity


By using 80%(v/v) of methanol, 0.16 µL of DPPH methanol solution was prepared. 2 mL of the DPPH
solution was then added to 2 mL of each tea extract solution and the mixture was then vortexed for 30 s
according to ((M. S. Hossain et al., 2021). To product color, it was kept in adark place for 30 minutes.
At 517 nm wavelength, the absorbance was measured using a spectrophotometer.
Scavenging of DPPH = [(Ac - As) / Ac] × 100 ………(iv)
Where Ac denotes the absorbance of the control (100 µL of methanol solvent with 100 µL of theDPPH
solution) and As denotes the absorbance of the sample.

Page | 996
3. Results and Discussion
Calculated by equations 1 and 2, the expansion volume of the foam was found to be 133.3%, and the
foam density was found to be 0.55 g/cm3. As the foam density ranges from 0.2 to 0.6 g/cm3 the , foam
density of that green tea was suitable for foam mat drying, according to (Azizpour et al., 2014). From the
Gallic and ascorbic acid calibration curve, the R2 values were found to be 0.9998 for both TPC and TAC
measurements. So these curve fitted well for equation- (iii) & (iv). Fig-1, Fig-2, and Fig-3, respectively,
showed the change of the samples' TAC, TPC, and DPPH scavenging activity. The total antioxidant
capacity of raw green tea was calculated 0.809 mg AAE/g (milligram of Ascorbic acid equivalents per
gram), and after foam mat drying, in instant tea, the total antioxidant capacity was found 0.403 mg AAE/g
shown in Fig-1. The total phenolic content of raw green tea was calculated 10.45 mg GAE/g (milligram
of Gallic acid equivalents per gram) and after foam mat drying, in instant tea, the total phenolic
content was found to be 2.66 mg GAE/g shown in Fig-2. The DPPH radical scavenging activity of raw
green tea was calculated 62.2% and after foam mat drying, in instant tea, the DPPH radical scavenging
activity was found 28.3% shown in Fig-3. This data indicated that due to foam mat drying, the TAC was
reduced by 7.79 mg GAE/g, the TPC was reduced by 0.406 mg AAE/g, and the scavenging activity of
DPPH was reduced by 33.9%

3.1 Figures

1 12 10.45
0
0.8 . 10
8 8
0.6 0 0.403 6
0.4 9
4 2.66
0.2
TAC (mg TPC (mg
0 AAE/g) 2
GAE/g)
Raw green Instant green 0
tea tea Raw green Instant
tea green tea

Fig -1: Total Antioxidant Capacity Fig -2: Total Phenolic Content (TPC)
(TAC)

80
6
60 2.
2
40 % 2
8.
20 3 DPPH
%
0 Scavenging
Raw green Instant activity(%)
tea green tea

Fig -3: DPPH Scavenging activity (%)

Page | 997
4. Conclusion
The bioactive compounds of raw green tea were decreased when instant green tea is produced by the foam
mat drying process, while the foam was formed with the addition of 5% egg albumin, 1% CMC and 5
minutes of whipping and drying at 40°C. From the results, it can be shown that the total antioxidant
capacity, total phenolic content, and scavenging activity of instant green tea were reduced by 49%,
25.5%, and 45.49%, respectively, from the raw green tea. So the production of instant green tea using the
foam mat drying process is inefficient. Again, the foam- forming ingredients and their concentration
might impact on the antioxidant properties. Further research should be done on the effect of foam foaming
ingredients on the antioxidant properties of green tea.

References
1. A. Wilson, R., M. Kadam, D., Chadha, S., & Sharma, M. (2012). Foam Mat Drying
Characteristics of Mango Pulp. International Journal of Food Science and Nutrition Engineering,
2(4), 63–69. https://doi.org/10.5923/j.food.20120204.03
2. Affandi, N., Zzaman, W., Yang, T. A., & Easa, A. M. (2017). Production of nigella sativa
beverage powder under foam mat drying using egg albumen as a foaming agent. Beverages, 3(1).
https://doi.org/10.3390/beverages3010009
3. Azizpour, M., Mohebbi, M., Hossein Haddad Khodaparast, M., & Varidi, M. (2014).
Optimization of Foaming Parameters and Investigating the Effects of Drying Temperature on the
Foam-Mat Drying of Shrimp (Penaeus indicus). Drying Technology, 32(4), 374–384.
https://doi.org/10.1080/07373937.2013.794829
4. Bag, S. K., Srivastav, P. P., & Mishra, H. N. (2011). Optimization of Process Parameters for
Foaming of Bael (Aegle marmelos L.) Fruit Pulp. Food and Bioprocess Technology, 4(8), 1450–
1458. https://doi.org/10.1007/s11947-009-0243-6
5. Benkovi, M., Janutis, L., & Morkunaite, M. (2018). Production of cocoa and carob- based drink
powders by foam mat drying. May, 1–11. https://doi.org/10.1111/jfpe.12825
6. Febrianto, A., Kumalaningsih, S., & Aswari, A. W. (2012). Process Engineering of Drying Milk
Powder with Foam Mat Drying Method, A Study of the Effect of the Concentration and Types of
Filler. J. Basic. Appl. Sci. Res, 2(4), 3588–3592. www.textroad.com
7. Hardy, Z., & Jideani, V. A. (2017). Foam-mat drying technology: A review. Critical Reviews in
Food Science and Nutrition, 57(12), 2560–2572. https://doi.org/10.1080/10408398.2015.1020359
8. Hertzendorf, M. S., Moshy, R. J., & Seltzer, E. (1970). Foam Drying In The Food Industry. C R C
Critical Reviews in Food Technology, 1(1), 25–70. https://doi.org/10.1080/10408397009527099
9. Hossain, M. A., Mitra, S., Belal, M., & Zzaman, W. (2021). Effect of foaming agent
concentration and drying temperature on biochemical properties of foam mat dried tomato
powder. Food Research, 5(1), 291–297. https://doi.org/10.26656/fr.2017.5(1).372
10. Hossain, M. S., Sifat, S. A. din, Hossain, M. A., Salleh, S., Hossain, M., Akter, S., & Hossain, M.
B. (2021). Comparative assessment of bioactive compounds, antioxidant capacity and nutritional
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11. Maciel, K. S., José, L., Teixeira, Q., Maria, S., & Lucia, D. (2021). Optimization of foam mat
drying for instant coffee processing and its effect on drying kinetics and quality characteristics.
Drying Technology, 0(0), 1–15.
https://doi.org/10.1080/07373937.2021.1887210
12. Ratti, C., & Kudra, T. (2006). Drying of foamed biological materials: Opportunities and
challenges. Drying Technology, 24(9), 1101–1108.
https://doi.org/10.1080/07373930600778213
13. Shaari, N. A., Sulaiman, R., Rahman, R. A., & Bakar, J. (2018). Production of pineapple fruit
(Ananas comosus) powder using foam mat drying: Effect of whipping time and egg albumen
concentration. Journal of Food Processing and Preservation, 42(2), 1–10.
https://doi.org/10.1111/jfpp.13467
14. Someswararao, C., & Srivastav, P. P. (2012). A novel technology for production of instant tea
powder from the existing black tea manufacturing process. Innovative Food Science and
Emerging Technologies, 16, 143–147.
https://doi.org/10.1016/j.ifset.2012.05.005
15. Zhang, Q., Achal, V., Xu, Y., & Xiang, W. N. (2014). Aquaculture wastewater quality
improvement by water spinach (Ipomoea aquatica Forsskal) floating bed and ecological benefit
assessment in ecological agriculture district. Aquacultural Engineering, 60, 48– 55.
https://doi.org/10.1016/j.aquaeng.2014.04.002
16. Zzaman, W., Biswas, R., & Hossain, M. A. (2021). Application of immersion pre- treatments and
drying temperatures to improve the comprehensive quality of pineapple (Ananas comosus)
slices. Heliyon, 7(1), e05882.
https://doi.org/10.1016/j.heliyon.2020.e05882

Page | 999
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 091

Molecular Modeling of H-bonded Liquid Hydrogen Chalcogenide


in Chemistry and Biology
M. Shahriar1, N. A. N. Rafi2, A. Sarder3, Sheikh I. Hossain4, T. Ahmed5,6, and K. S. Salem7,*

Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Dhaka,


1,2,7

Bangladesh
3
Biotechnology and Genetic Engineering Discipline, Khulna University, Khulna, Bangladesh
4School of Chemistry, University of Sydney, NSW, Australia
5School of Engineering, University of Newcastle, NSW, Australia
6
Department of Nuclear Engineering, North Carolina State University, NC, USA

Email: 1mshahriar79@gmail.com, 2nabidalniazr@gmail.com, 3amit_sarder@ku.ac.bd,


4sheikh.hossain@sydney.edu.au, 5,6tanvir.ahmed@uon.edu.au, 7,*samaher.salem@du.ac.bd

* Corresponding author: [K. S. Salem]

Abstract: Water (H2O) and hydrogen sulfide (H2S) are the most important polar triatomic liquids in the
hydrogen chalcogenide series and the simplest hydrogen bonded capable molecules. Both liquids differ
from ideality and are thus of great interest from a fundamental standpoint. Liquid H2S is encountered in
various industrial processes, including the extraction and refining of oil and natural gas, pulp and paper
manufacturing, sewage treatment plants, manure-handling plants, tanneries, and coke oven plants whereas
water is widely used in numerous chemical and biological processes. Although liquid water is well studied,
due to the toxicity of liquid H2S, the molecular structure and dynamics are little known. In this
investigation, we set out to develop a computational protocol to capture the inner representation of liquid
H2O and H2S.

These models are based on rigid polarizable model (J. Phys. Chem. B 2013, 117, 17, 5222-5229) for liquid
H2S and SWM4-NDP (Chem. Phys. Lett. 2006, 418, 1-3, 245-249) model for liquid water. Both models
contain a massless charge and a drude induced dipole to capture the intermolecular interaction, which
produces the hydrogen bond between the molecules. In LAMMPS, both rigid models are developed with
1000 molecules in a system considering 12-6 Lennard Jones (LJ), and Coulombic potential energy. The
initial positions for the simulation are produced by fftool and PACMOL. The system is equilibrated for
0.25 ns using NPT simulation. After equilibration, the simulation is carried out for additional 5 ns to
generate the radial distribution functions, angular distribution functions, and self-diffusion coefficient of
H2O and H2S. The modeling protocol is developed at standard pressure using the LAMMPS simulation
engine, which is capable of capturing the structure and dynamics of H2O at room temperature and H2S at
212 K.
The radial distribution functions, angular distribution functions, and self-diffusion coefficient are
calculated from H2O and H2S models. The obtained results are in good agreement with experimental and
previous simulated data and can capture the hydrogen bonded clustering. Despite their characteristic
simplifications, these two molecular models are presented to open the door meaningfully for experimental
efforts to capture the properties of pure liquids by molecular dynamics simulation for chemistry and
biology.
Keywords: Liquid hydrogen chalcogenide; Molecular modeling; Drude model; Structure anddynamics;
LAMMPS

Page | 1000
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 096

A Simple, Highly Selective Spectrophotometric Method for the


Simultaneous Determination of Arsenic (III) & Arsenic (V)) at Nano-
trace Levels in some Groundwater, Real, Biological, Food and Soil
Samples Using 2-Hydroxy-1- napthaldehyde-orthoaminophenol

1, 2
Ayesha Afrin, 1M. Imran Hossain Mollah, 1M. Jamaluddin Ahmed

1Laboratoryof Analytical Chemistry,2 Department of Chemistry, University of Chittagong,


Chottogram, Bangladesh
2Department of Applied Chemistry and Chemical Engineering, University of Chittagong,
Chottogram, Bangladesh.

Email: aafrin.aec@cu.ac.bd

Corresponding Author: [Ayesha Afrin]

Abstract
A new spectrophotometric reagent 2-Hydroxy-1-napthaldehyde-orthoaminophenol has been
synthesized and characterized. A very simple, ultra-sensitive, highly selective and non-
extractive new spectrophotometric method for the simultaneous determination of arsenic (III)
and arsenic (V) at nano-trace levels using 2-Hydroxy-1-napthaldehyde-orthoaminophenol(HNA-
OAP)has been developed. HNA-OAP has been proposed as a new analytical reagent for the
direct non-extractive spectrophotometric determination of arsenic (III&V). This novel
spectrophotometric reagent reacts in a slightly acidic (0.00016-0.0004 M H2SO4) aqueous
solution with arsenic(III) in 20% N,N-dimethylformamide (DMF) to produce highly absorbent
red chelate with has an absorption maximum at 505 nm. The absorbance intensity of the metal-
chelate reaches a constant value (after heating for 5 min at (45±5) 0C within 15 min and remains
stable over 24 h. The average molar absorption coefficient and Sandell’s sensitivity were found
to be 2.46×104 L mol-1cm-1 and 5-ng cm-2. Linear calibration graphs were obtained for 0.01 – 60-
mgL-1 of As, having a detection limit of 1-ngmL-1; the quantification limit of the reaction system
was found to be 10-ngmL-1 and the RSD was 0-3%. The stoichiometric composition of the
chelate is 3:2 (As : HNA-OAP). A large excess of over 60 cations, anions and complexion agents
(like, chloride, phosphate, azide, tartrate, oxalate, SCN- etc.) do not interfere in the
determination. The developed method was successfully used in the determination of total arsenic
Page | 1001
in several certified reference materials (alloys, steels, ores, human urine, hair, nails, bovine liver
and sediments) as well as in some biological fluids (human blood, urine, hair, nail and milk), soil
samples, food samples (vegetables, fruits, rice, corn and wheat), solutions containing both
arsenic(III) and arsenic(V) speciation and complex synthetic mixtures. The results of the
proposed method for assessing groundwater, biological, food and soil samples were comparable
with both ICP-OES & AHG-AAS and were found to be in excellent agreement. The method has
high precision and accuracy (s = ± 0.01 for 0.5 mg L-1).

Keywords: Spectrophotometry; arsenic-determination; 2-hydroxy-1-napthaldehyde-

orthoaminophenol; groundwater, real; biological, soil and food samples.

Methodology
To 0.1-1.0-mL of a neutral aqueous (pH 6) solution containing 0.1 – 600-μg of arsenic (III) in a
10-mL calibrated flask was mixed with a 1:200 - 1:700 fold molar excess (preferably 1- mL of

3.8×10-3 M) of the 2-hydroxy-1-napthaldehyde–orthoaminophenol (HNA-OAP) reagent solution


followed by the addition of 0.8 -2.0-mL (preferably 1-mL) of 0.0002 M of sulfuric acid. Then, 2-
mL of N, N-dimethylformamide (DMF) was added and the mixture was diluted to the mark with
de-ionized water. After heating for 5 min at (45±5)oC then cooled at room temperature
(25±5)oCfor 15 min, then absorbance was measured at 495 nm against a corresponding reagent
blank. The arsenic content in an unknown sample was determined using a concurrently prepared
calibration graph.

Results

The absorption spectra of the As (III)- HNA-OAP in 0.0002 M sulfuric acid medium was
recorded using a spectrophotometer. The absorption spectra of the As(III)-HNA-OAP are a
symmetric curve with maximum absorbance at 495 nm; an average molar absorption coefficient
of 2.46×104 L mol–1 cm-1. HNA-OAP did not show any absorbance. In all instances,
measurements were made at 495 nm against a reagent blank.

Conclusion

The proposed method using HNA-OAP in aqueous solutions not only is one of the most sensitive
methods for the determination of arsenic but also is excellent in terms of selectivity and
simplicity. Therefore, this method will be successfully applied to the monitoring of nano-trace
(ng g-1) amounts of arsenic in real, environmental, biological, soil and food sample.

Page | 1002
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 097

Physicochemical and Sensory Properties of Composite Flour


Biscuits Prepared from Wheat, Germinated Sorghum, and
Jackfruit Seed
Abonti Biswas, Md. Rahmatuzzaman Rana*

Shahjalal University of Science and Technology, Sylhet-3114, Bangladesh.


Email: abontibiswas1812@gmail.com, rzaman-fet@sust.edu
*Corresponding author: [Md. Rahmatuzzaman Rana]

Keywords: Abstract: Researchers have developed composite flour-based baked items with
reduced gluten. The project aimed to make gluten-free biscuits from sorghum,
● Wheat;
jackfruit, and wheat flour. Proximate and functional features of five flour
● Germinated
formulations were studied. Except for fat, the nutritional composition (moisture,
sorghum;
protein, ash, fiber) of jackfruit seed flour was marginally greater than that of
● Jackfruit seed;
germinated sorghum flour. Fat is prominent in sorghum flour (3.89
● Composite flour
± 0.08). Sorghum flour has higher functional qualities such as foaming (7.9±.12),
biscuits;
swelling (10.12±0.05), and water holding capacity (137.28±0.52). However,
● Functional
jackfruit seed flour had a higher oil retention capacity (107.57± .32) and bulk density
Properties;
(0.88±.05). Biscuits made using the blended flours (5% to 20% GSF–5% JSF) with
WF appeared to have the highest moisture, protein, fat, carbohydrate; while the
biscuits with the best diameter and thickness were SF20% -WF80%t -JSF5%.
Control sample (WF100 percent) biscuits had the lowest water-holding capacity
(WHC) and oil-holding capacity (OHC). At thesame time, they were high in SF-JSF
composite flour cookies (p ≤ .05). Though the control biscuit (100 percent WF) had
the highest spread ratio (8.92±0.21), the composite flour biscuit (SF20% -WF80% -
5% JSF) had the most desirable spread ratio (8.25±0.43). The evaluations of every
variety of biscuits regarding each sensory attribute (color, flavor, taste, texture)
were allhigher than the minimum required score of 5.

1. Introduction

Biscuits are readily accessible baked goods that are ready to eat, come in a variety of sizes and forms, are
inexpensive, and have a high nutritional content(Asif-Ul-Alam et al., 2014). They are the most often consumed
baked goods across all age groups in many nations because they have a very palatable flavor and a lengthy
longevity(Islam et al., 2012a). Wheat (Triticum aestivum) is a common cereal that plays a vital role as a global
commodity due to its gluten-forming proteins, which have the elasticity and rigidity required for bakery items
and pasta(Inyang et al., 2018) Wheat includes 78.10% carbohydrate, 14.70% protein, 2.10% fat, 2.10%
minerals, and significant amounts of vitamins (thiamine and vitamin-B) (Topping, 2007). In recent years,
consumer interest in wheat-free foods has increased to reduce the risk of celiac disease (CD). In gluten-sensitive
patients, celiac disease causes damage to the small intestinal mucosa. Researchers claimed eliminating gluten
can treat celiac disease. People with celiac disease can't eat breads, baked goods, and other wheat-based
foods(Jothi et al., 2014). In January 2007, the FDA suggested the rule for labeling gluten-free products to meet

Page | 1003
the demand for high-quality gluten-free cookies/breads. Wheat alternatives like sorghum, millet, jackfruit,
pigeon flour etc. should ideally have more nutritional value than wheat, especially in developing countries
where malnutrition is widespread. (Okpala et al., 2013). The most popular bakery product in Bangladesh's
urban and suburban areas is the composite flour biscuit. In many affluent nations, including Bangladesh, the
consumption of leavened wheat baked goods has increased considerably due to changing dietary preferences,
rising population, and urbanization. On the other hand, many emerging nations are unable to produce wheat
appropriate for making baked goods due to climate factors. Therefore,research may focus on making alternative
cookies without wheat or partially replacing wheat flour with flour from local crops(Islam et al., 2012b).
Creating composite flour typically has the goal of creating something better which refers to enhanced features
or capabilities, or in some circumstances, enhanced economies(Okpala et al., 2013).
Legumes and cereals are both excellent sources of protein, and their amino acid profiles complement one
another. The nutritional value of these grains has been said to be enhanced by traditional processing techniques
like fermentation and germination. Germination causes a rise in the amount of free limiting amino acids with
altered functional characteristics of seed components(Hallén et al., 2004). Fermentation of grains enhances the
composition of aminoacids and vitamin content boosts the availability of protein and carbohydrates and reduces
levels of anti-nutrients. Therefore, it is anticipated that composite flour made from fermented legumes and
germinated grains will have the benefit of enhancing total nutrition. Sorghum (Sorghum bicolor L. Moench) is a
staple food throughout Africa and Asia, providing proteins, calories, and minerals. Sorghum, rich in
phytochemicals (de Morais Cardoso et al., 2017 )is an attractive element in gluten-free formulations (Schober et
al., 2005);(Renzetti et al., 2008), but its usage as a food source in industrialized nations is underutilized.
Understanding the physicochemical properties of germinated sorghum flour can largely determine the optimum
applications for it in the food industry. Antinutritional elements are present in all cereals and are not exclusive
to sorghum. The bioavailability of other nutrients in cereals and legumes can be improved by processing
techniques including germination and fermentation, which can reduce antinutritional effects(Arouna et al.,
2020). The functional qualities of the flour were significantly influenced by the germination of the sorghum
grain. In addition to using germinated sorghum flour as a functional ingredient in manufactured foods like
weaning foods and baked goods, it appears to be able to build some new foods based on germinated sorghum
for people with celiac disease(Ojha et al., 2018).
Jackfruit (Artocarpus heterophyllus) is a Moraceae fruit. It grows across Bangladesh, especially in Chittagong,
Sylhet, Gazipur, Mymensingh, Tangail, Comilla, and Jessore. Jackfruit seeds comprise 15% of a fruit's weight
(Akter & Haque, 2018a). Studies show that jackfruit seed is rich in carbohydrates, protein, and minerals(F. C. K.
Ocloo et al., 2010) This flour can be combined with other grain flours to make cake, bread, and biscuits without
compromising their functional and sensory qualities. Literature suggests jackfruit seeds have many
benefits(Akter & Haque, 2018b). Jacalin, a key protein found in jackfruit seeds, has been shown to be
beneficial for enhancing the immune system's response(Hossain et al., 2014). The health advantages of
jackfruit seeds include anticancer, antihypertensive, antiaging, antioxidant, antiulcer, and many others. Jackfruit
seeds also contain phytonutrients,lignins, saponins, and isoflavones (Kushwaha et al., 2021). Jackfruit seeds are
typically not used on an industrial scale and are instead thrown away, boiled and consumed as a snack, or used
in specific regional recipes at the household level.

For flour to be used successfully and profitably in food compositions, detailed information on its nutrient
content, functional characteristics, and historical usage data is needed.With the above thought, the present study
was conducted to evaluate the physicochemical, functional, properties of germinated sorghum flour and
jackfruit seed flour; and to develop a dietary fiber-enriched baked product by incorporating germinated
sorghum & jackfruit seed flour with wheat flour in the formulation. Then, the investigation examined
germinated sorghum flour's effect on biscuit production and sensory panel acceptability.

2. Materials and methods

2.1.1 Raw materials


The sorghum and jackfruit seed samples were collected from Bangladesh Agricultural Development
Corporation (BADC) Agro Service Center, Kumargaon, Sylhet. Visually discolored, diseased, damaged
samples were removed to minimize biological variability.

Page | 1004
2.2 Sample Preparetion
2.2.1 Preparation of germinated sorghum flour
Sorghum (Sorghum bicolor) seeds were germinated according to the method described by (Elkhalifa &
Bernhardt, 2010) with modification. Sorghum seeds (400 g) were soaked in distilled water
overnight to remove dirt, weed seeds, husk and others. The wet seeds were subsequently
sanitized with 0.07% sodium hypochlorite at a ratio of 1:4 (w/v) for 30 min to retard any mold
growth during germination. The soaked grains were then washed with distilled water until
neutral pH obtained. The hydrated seeds were spread out on trays, and moistened and covered
with muslin cloth. The grains were moistened with water when necessary. The germination
process was done at room temperature in the dark for 36-48 h and the germination evaluated by
the percentage of germinated seeds. The sprouted seeds were collected and hot air dried (OF-
21E, Jeio Tech, Korea) at 45 °C for desired moisture content (about 5%). To obtain
homogeneous flours grains were grounded using a grinder (IKA M 20, Universal Mill,
Germany) and sieved through a 0.5mm sieve and stored in high-density polyethene bags at 4 °C
until further analysis.
2.2.2 Preparation of jackfruit seed flour
Jackfruit seed flour were prepared according to a method described by (Meethal et al., 2017) with
modification. Jackfruit seeds were cleaned manually to remove all foreign materials and white
aril (seed coats). Seeds were then lye peeled with 5% NaOH for 2 min to remove the thin
brown endosperm covers the fleshy white cotyledon, and washed thrice with distilled water to
remove residual lye. Then, seeds were cut into small pieces, and dried to constant weight in a
hot air oven at 45 °C for desired moisture content. Dried seeds were ground using a laboratory
grinder and sieved using a 0.5 mm mesh to obtain equallyfine flour

2.2.3 Blending of flour


The procedure that was implemented can be found in (Ohizua et al., 2017)

2.2.4 Biscuit development


With a few minor alterations, biscuits were made in accordance with AACC method no. 10-50 (AACC,
2000).Wheat flour was replaced with germinated sorghum flour (GSF) in four proportions 5,10,15, and
20% and same amount of jackfruit seed flour (5%) in all treatments which were designated in B1, B2,
B3 and B4 respectively, whereas Bo (without germinated sorghum and jackfruit seed flour was not
supplemented) considered as control. Table 1 illustratesthe basic formulations used to prepare biscuits.

Page | 1005
Table 1. Formulation of biscuits
Ingredients Quantity (g/100 g)
Bo B1 B2 B3 B4
Wheat flour 100 95 90 85 80
Germinated sorghum seed -- 5 10 15 20
flour
Jackfruit seed flour -- 5 5 5 5
Vegetable oil 40 40 40 40 40
Sugar 40 40 40 40 40
Salt (NaCl) 0.5 0.5 0.5 0.5 0.5
Powder milk 5 5 5 5 5
Ammonium bicarbonate 5 5 5 5 5
Water 20 20 20 20 20

2.3 Characterization of flour


2.3.1 Functional properties of flour
2.3.1.1 Bulk density
The bulk density was determined according to the method described by (Oladele & Aina, 2007)with
modifications.
2.3.1.2 Water and oil absorption capacity
The method of (Chandra et al., 2015) was used to determine water and oil absorption capacity.
2.3.1.3 Swelling capacity
The method of (Okaka & Potter, 1977) with some modifications was used or determining the swelling
capacity.
2.3.1.4 Foaming capacity
Foaming capacity was determined as described by (Narayana & Narasinga Rao, 1982) with slight
modifications.
2.3.1.5 Emulsifying activity
Emulsifying activity was determined as described by.(Yasumatsu et al., 1972a) with modifications.

2.4 Profile analysis of Biscuits


2.4.1 Proximate analysis
Prepared composite flour and biscuits were analyzed for moisture, protein (micro-Kjeldahl, N × 6.25),
fat (solvent extraction), crude fiber and ash were determined according to method described in AOAC
(2010). The carbohydrate content was calculated by subtraction method.
2.4.2 Evaluation of physical properties of biscuits
The biscuits weight was calculated as a mean of three single biscuits with a digital balance meter. The
biscuit diameter was calculated by putting three biscuit edge to edge horizontally in a row, and a vernier
Caliper used to measure the diameter (cm) with an average value of 0.01 mm accuracy. Thickness was
determined after three biscuits were placed on each other, and the mean thickness (cm) was taken into
consideration. The spread ratio was determined by comparing the mean diameter with mean thickness of
the biscuit.
2.4.3 Chemical Analysis
Page | 1006
2.4.3.1 Proximate composition of Biscuits
According to the formula, the percentages of moisture, crude fat, crude protein, and ash in the cookies
were as follows: (AOAC, 2003). The difference approach was utilized in order to determine the total
carbohydrates.
2.4.4 Sensory evaluation
The sensory evaluation of biscuits was conducted by 15 semi-trained testers who frequently consumed
biscuits and were experienced with the sensory quality attributes of biscuits. The test was performed
using 09-point hedonic numbering from 1 (disliked extremely) to 9 (liked extremely). Three-digit
random numbers have been encoded and displayed in identical containers. Every sample was rated for
color, texture, flavor, and overall acceptability.
2.5 Statistical analysis
A one-way variance analysis (ANOVA) was performed on the triplicate data using SPSS software (SPSS
version 15.0 SPSS Inc. Chicago, Illinois, U.S.A). All values were represented as a percentage and mean
± SD, and statistically significant differences among samples were determined with DMRT test at p ˂
0.05 considerat.
3. Results And Discussions
3.1 Effect of Germination on Sorghum Seed flour
The findings revealed a statistically significant difference (p ≤ .05) between wheat flour (WF) and
composite flour made up of varying amounts of germinated sorghum and jackfruit seed flours( Table
02). Non-germinated sorghum moisture is 11.030±09 (Table 2). After germination, numbers dropped.
11.030±0.09 became 6.520±0.08. Our results may change due to the sorghum cultivars and germination
procedure employed—non-germinated sorghum seed protein content 8.08±0.45. By germination, fat
content increased from 3.11±0.15 to 3.89±0.08. Compared to non- germinated sorghum, germinated
sorghum has significantly less ash. Our results may change due to the sorghum cultivars and germination
procedure employed. Amylase activity is 3.89±0.08 to 31.8234±0.53 in sprouted sorghum flour. This is
because the effect of enzyme of germinating seeds is activated at this time (Elkhalifa & Bernhardt,
2010).

Page | 1007
Table 2: Proximate composition of germinated and ungerminated sorghum seed flour and
jackfruit seed flour
Component Ungerminated Germinated sorghum Jackfruit
sorghum seed
Moisture (%) 11.03 ± 0.09 6.52 ± 0.08 6.70
±0.20
Protein (%) 8.08 ± 0.45 9.23 ± 0.59 13.02±0.
46
Fat (%) 3.11 ± 0.15 3.89 ± 0.08 1.39±.04
Ash (%) 1.54 ± 0.02 1.08 ± 0.01 2.57±0.0
4
Fiber (%) - 3.76±0.0
4
Carbohydrate 71.12 ± .25 28.18 ± 0.35 82.64±.1
(%) 6
Alpha amylase 3.89±0.08 31.8234±.53 --
activity
Data are mean±SD
Starch digestion by -amylase results in the production of maltose (Elemo et al., 2010). Furthermore, the
findings of this study more or less agree with the outcome of those reported by (Phattanakulkaewmorie
et al., 2011).
3.2 Functional properties of Germinated Sorghum Flour
Water absorption capacity, oil absorption capacity, swelling capacity, foaming capacity, emulsifying
activity, and bulk density are all functional qualities of flour, as given in the Table
03. Baking relies heavily on these flour characteristics. Our findings on the water-absorbing capacity of
germinated sorghum seed flour were quite similar to those of a study by (Elkhalifa & Bernhardt, 2010),
137.28%. The mouthfeel is enhanced, and the flavor is preserved because of the oil-holding capability.
Sorghum flour had an oil retention capacity of 107.57%, close to the 110% published in the journal
(Elkhalifa & Bernhardt, 2010). One indicator of a powder's ability to absorb water is its swelling
capacity. However, the value reported by(J et al., 2018) for the swelling capacity of germinated sorghum
flour was 10.12%.Assessment of qualities for foaming is thought to depend on how protein molecules
are arranged. Flexible proteins can foam well, whereas highly organized globular molecules have poor
foaming properties .Water dispersible nitrogen has been linked to foam stability and expansion. Bakery
items can use food ingredients with good foaming capability and stability(Islam et al., 2012a). In
contrast, highly organized globular molecules have a low power for foaming. Researchers have shown
that adding water- dispersible nitrogen to a foam increases its volume and ability to resist
collapse(Yasumatsu et al., 1972b). The 7.9% foaming capacity of sorghum flour was very close to the
figure (Elkhalifa & Bernhardt, 2010). Values for bulk density and emulsifying capacity of the sorghum
flour were 77% and 60.34%, respectively, almost identical to those reported in the journal (Elkhalifa &
Bernhardt, 2010).
Table 3: Functional Properties of Germinated Sorghum seed flours
Property Germinated sorghum Jackfruit
seed
Water absorption capacity (%) 137.28±0.52 201.78±.67
Oil holding capacity (%) 93.33± 1.37 107.57±
.32
Swelling capacity (%) 10.12±0.05 4.96±.12

Page | 1008
Foaming capacity (%) 7.9±.12 25.75±.10
Bulk density (g\ml) 0.77±0.09 .88±.05
Emulsifying activity (%) 60.34±.47 50.17±0.23
Data are mean±SD
3.3 Functional Properties of jackfruit seed flour
Table 03 shows jackfruit seed flour's functional properties: water absorption, oil absorption, swelling,
foaming, emulsifying activity, and bulk density. These flour qualities are significant for baking.JSF had a
201.78% water absorption rate. (Zhang et al., 2021) reported similar water absorption capacity. 93.33%
oil absorption. Oil absorption capacity is vital as fat is inevitable for the improvement of flavor and
texture in baked goods. Kinsella et al. Similar to this report (A Roy Chowdhury et al., 2012). Table 14
shows swelling capacity. It was reported in a literature somewhat increased swelling capacity(F. Ocloo
et al., 2010a). Water retention in inflated starch granules affects food quality (Asaoka et al., 1992). JSF
foamed at 25.75 percent. Higher foaming capacity than reported (F. Ocloo et al., 2010b). Protein
configuration affects foaming ability. Flexible proteins froth well, but globular molecules don't (Islam et
al., 2012b). Particle size affects bulk density. Study found.88g/cm3. Odeoemelan, 2005 reported a lower
bulk density.
3.4 Chemical composition of biscuits
Table 4 displays the findings of an estimated analysis of the biscuits' composition and .The biscuits were
manufactured with a variety of flours. Biscuits made with a composite flour made up of WF-80%-GSF-
20%-JSF-5% had the highest moisture, protein, and fat content levels. Biscuits made with groups of
GSF in a blended flour made up of WF-90%-GSF-10%-JSF-5% had the lowest levels of moisture,
protein, and fat content (p .05). Biscuits made with pure wheat flour (WF100%) had the lowest levels of
fat content (p <0.05)

Table 4 Chemical Composition of the biscuits with germinated sorghum flour and
jackfruit seed flour

Control Biscuit containing germinated sorghum flour and jackfruitseed


Parameter flour

B0 B1 B2 B3 B4
Moisture (%) 2.71±0.0 2.51±0.1 2.00 ±0.1 2.15±0.2 3.22 ± 0.2
Protein (%) 9.23±0.2 9.55±0.01 9.03±0.1 9.78±0.2 9.98±0.4
Fat (%) 20.5±0.1 21.09±0.15 21.54±0.0 21.71±0.08 21.85±0.1
4
Ash (%) 1.55±0.01 1.42±0.04 1.18±0.3 1.10±0.2 1.09±0.08
Fiber (%) 0.97±0.01 1.01±0.05 1.39±0.04 1.71±0.1 1.86±0.16
Carbohydrate 66.31±0.1 68.38±0.01 68.99±0.3 70.33±0.17 71.64±0.2
(%)
Data are mean±SD
The biscuitss prepared with 100% wheat flour had a high ash concentration. In contrast, thosecreated
using composite flours had the lowest ash content (WF-90% -GSF-10%-JSF-5%, WF-

Page | 1009
85%-GSF-15%-JSF-5%, and WF-90%-GSF-20%-JSF-5%, respectively). Biscuits were made using
blended flour (WF-80%-GSF-20%-JSF-5%), which had a higher carbohydrate content than the control
biscuit sample made with 100% WF, had a lower carbohydrate content. Variances in the chemical
composition of the raw materials may be responsible for the variations in the chemical composition of
the cookies produced using various types of flour. In a similar vein, earlier research has demonstrated
that biscuits made using a variety of flours have distinct variations in their chemical make-up (Giuberti et
al., 2018a),(Jan et al., 2015),(Yildiz & Gocmen,2021).
3.5 Physical and functional properties of biscuits
When comparing the biscuits' diameter and thickness among samples, we found no statistically
significant changes between those prepared with a higher percentage of GSF in the composite flour (WF
80%-GSF 20%-JSF 5%) and those made with WF100% (Table 5). Biscuits baked with 100% WF spread
at a high rate. The actual fiber content of the SF likely accounts for the larger diameter and thicker
biscuits produced by utilizing a higher proportion of GSF in the mix than fine wheat flour. The high oil
content in the flour, as the whole flour was used, which retained the germ, and the large particle size of
the entire sorghum and jackfruit seed flour compared to fine wheat flour may explain the enhanced
spread ratio of cookies created with a high level of WF(Belorio et al., 2019),(Paesani et al., 2020).
In comparison to biscuits made with control flour (WF100%), those made with GSF and JSF flour in
combinations with varying percentages of wheat flour had significantly higher water-holding capacity
(WHC) and oil-holding capacity (OHC) (p≤0 .05). In biscuits with high levels of GSF (WF 80%-GSF
20%-JSF 5%), the values of these functional attributes were marginally higher than in biscuits with
lower levels of GSF, indicating that GSF affected these variables. Whole flour of germinated sorghum
and jackfruit seed flour, which contain the bran that is rich in fiber and protein, and are known to bind
more water and oil in their structure, may account for the high WHC and OHC in cookies made using
GSF and JSF flour in combinations with different percentages of wheat flour. It matches the findings by
(Jan et al., 2015) (Sharma et al., 2016).
Table 5: Physical and functional properties of biscuits

Control Biscuit with Germinated Sorghum seed flour and Jackfruit


Parame seed flour
ter

B0 B1 B2 B3 B4
Physical
Properties

Diameter(cm) 5.18±0.16 5.21±0.06 5.28±0.03 5.20±0.18 5.56±0.01


Thickness(cm) 0.55±0.15 0.53±0.04 0.55±0.07 0.57±0.02 0.59±0.02
Weight(g) 4.25±0.08 4.58±0.59 5.87±0.60 6.03±0.38 6.25±0.49
Spread ratio 8.92±0.21 8.25±0.75 8.19±0.62 7.86±0.12 8.25±0.43

Functional
Properties

Water Holding 1.72 ± 0.01b 2.14 ± 0.04a 2.16 ± 0.10a 2.21 ± 0.04a 2.25 ± 0.05a
Capacity
Oil Holding 1.75 ± 0.03b 1.80 ± 0.10ab 1.78 ± 0.02ab 1.88 ± 0.03a 1.88 ± 0.03a
Capacity

Page | 1010
Different letters in a row indicate a significant difference at p < 0.05. Data are mean±SD
3.6 Sensory attributes of cookies
The biscuits that were generated with 0, 5, 10, 15, 20% germinated sorghum flour and consistently 5%
jackfruit seed flour, with the exception of the control, were evaluated by a panel of ten tasters for their
sensory qualities. Table 06 illustrates the sensory characteristics of cookies that were crafted with whole
wheat flour (WF) and composite flour that contained varying proportions of sorghum and jackfruit seed
flours.
Table 6: Sensory Profile of Biscuits

Samples/Parameters Color Flavor Taste Texture Overall


Acceptability
Bo 6.750 6.850 6.900 7.250 7.350
B1 7.250 7.250 7.300 7.150 7.500
B2 7.800 8.100 7.800 7.250 8.400
B3 7.000 7.050 7.250 6.800 7.100
B4 6.200 6.100 6.450 6.500 6.200

According to the results of a one-way analysis of variance, all of these sensory attributes of the various
biscuits were significantly (P≤0.05) different from one another. As a consequence, the samples of
biscuits showed varying degrees of acceptability in terms of color, flavor, texture, and overall
acceptability. The biscuits that contained 10% SGF and 5% JSF were given the finest grade possible for
their color, flavor, textural quality, and overall acceptance. Similar to this, prior research found that
biscuits manufactured with gluten-free flours had sensory scores that were higher than the threshold
score for all of their sensory qualities (Giuberti et al., 2018b); (Hussain et al., 2020). In another study,
the cookies created using gluten-free flours did not differ significantly from those made with traditional
flours in terms of their sensory qualities (Paesaniet al., 2020).
4. Conclusion
Biscuits made with flour mixes containing jackfruit seed and germinated sorghum can achieve a level of
physical and nutritional quality that is satisfactory. Sorghum and jackfruit seed flour was incorporated to
the biscuit formulation, which improved the cookies' physicochemical properties,nutritional value as well
as sensory quality. The newly developed gluten-free cookies may be a useful source of nourishment for
people who are gluten intolerant and for those who are on a restricted budget. Furthermore, further
investigation into the nutritional features of gluten-free biscuits prepared from jackfruit seed flour and
germinated sorghum flour is strongly advised.

Page | 1011
Acknowledgement
The authors would like to express their gratitude to the Department of Food Engineering and Tea
Technology at Shahjalal University of Science and Technology in Sylhet, Bangladesh, for providing
technical aid and additional supports during the research experiment.

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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 106

Effect of Storage on Physicochemical Properties and Antioxidant


Activity of Pumpkin Powder and its Products

Anwara Akter Khatun*, B. Md. Abdul Halim, and C. N. H. M. Rubel Mozumder

Department of Food Science and Nutrition, Faculty of Engineering,


Hajee Mohammad Danesh Science and Technology University, Dinajpur, Bangladesh,
Email: anwarakhatun@gmail.com, halim1507060hstu@gmail.com, rubel.infs@gmail.com
*Corresponding author [Anwara Akter Khatun]

Abstract

The aim of this study was to produce and analyze pumpkin powder and drink powder to evaluate their nutritional and
efficacy potential for the development of healthy products. The powders were formulated and evaluated based on their
physical properties, proximal compositions, phenolic compounds and antioxidant activity. Drinks powdered were made
with a mixture of ingredients that were substituted with pumpkin powder in the proportions of 10%, 20%, 30% and
40%. A sensory evaluation was carried out to select the most accepted combination. The most accepted product was
subjected to nutritional analysis and storage studies, which were taken as criteria for good quality. The dehydrated
pumpkin powder showed a good amount of protein, fat, fiber and ash. Pumpkin powder contains sufficient amount of
beta- carotene and vitamin C. It shows higher DPPH scavenging activity and FRAP. On the other hand, pumpkin pulp
powder shows low antioxidant activity in terms of ABTS. The nutritional profile of beverages based on 20% and 30%
pumpkin powder had a sufficient amount of nutritional value and antioxidant activity. During storage, a significant
increase in total sugars was observed, while an insignificant increase in the immediate composition was observed.
Carotenoids, vitamin C, and antioxidant properties showed significant decreases during long-term storage at ambient
temperature. Pumpkin powder can be successfully incorporated into powdered drinks or other traditional products.
Because of its nutritional potential, it is recognized as an excellent food source to meet daily nutritional needs.

Keywords: pumpkin powder; physicochemical properties; product development; storage stability;sensory


evaluation

1. INTRODUCTION

Pumpkin is an important vegetable crop in Bangladesh due to its great economic importance as well as its
nutritional value and year-round availability. It is a very popular and one of the most important vegetable
crops grown extensively in tropical and subtropical countries. Due to its high nutrient content and
lucrative market price, squash can be considered a high value crop. [1].

Page | 1015
Pumpkins are fruits of several plants belonging to the Cucurbita genus and the Cucurbitaceae family.
Cucarbita moschota, Cucarbita maxima & Cucarbita pepo are three of the most commonly grown
species worldwide. Cucurbita is one of the most commercially valuable genera of vegetable crops [2].
Pumpkins are grown in different parts of the world for their pulp and seeds for human consumption, either
for direct use or to formulate other ingredients such as syrups, jellies, jams and purees [3-4]. Pumpkin
pulp has the dietary and health importance of proteins, polysaccharides such as pectin, carotene, mineral
salts, minerals (potassium, phosphorus, magnesium, iron and selenium), vitamins (vitamin A, riboflavin,
vitamin B6, vitamin C, vitamin K, vitamin E) and some substances such as phenolic compounds
(flavonoids & phenolic acids), amino acids and terpenoids [5-7].

Carotenoids, particularly Beta-carotene, have been described as the coloring agent responsible for the
yellowish appearance of squash. Carotenoids offer protection against cell destruction by free radicals and
thus reduce the risk of cancer. β-Carotene is also a vital source of vitamin A [10].Vitamin A is considered
a powerful natural antioxidant and is important for protecting the health of skin and mucous membranes,
as well as being the essential vitamin for healthy vision [12].With these beneficial effects of pumpkin, it
can be incorporated into various value-added products. Most parts of the squash are edible, from the
fleshy parts to the seeds, and are eaten in a variety of ways.

Drying is a food preservation technique that removes water from food to the point where oxidation
reactions are reduced. It is also more durable, requires less storage space and is easier to transport. This
makes it an excellent opportunity to make pumpkin flour [21]. One of the challenges of plant breeding is
to balance nutrient quality with good industrial yields and reduce post-harvest losses. Thus, the present
study was undertaken with the following objectives: To evaluate nutritional composition, bioactive
compounds and antioxidant activity, sensory qualities and storage stability of pumpkin powder & its
product.

2. MARERIALS AND METHODS

2.1. Preparation of pumpkin powder


Good quality mature pumpkin (Cucurbita maxima) bought in ripe stage from local market in Dinajpur.
The pumpkin was washed, cut into large pieces, its seeds were removed, and its downy part was peeled
off and shredded into small shreds with a shredder. The ground squash was dried in a laboratory scale
multi-purpose universal cabinet drier at 60-65°C for 18 hours. The dried pumpkin shreds were ground to a
fine powder using a kitchen grinder and sieved through a 300 mesh screen. The produced pumpkin pulp
powder was stored in an airtight container at 4°C in a cooled state for further examination.

2.2. Preparation of drinks powder

The basic recipe for the preparation of drink powder was standardized by using ingredients such as fine
pumpkin pulp and seed powder, milk powder, icing sugar, salt, peanut powder and germinated wheat
powder. After all the ingredients were properly measured, they were mixed very well. We used this
mixture as a drinks powder. The prepared mixture powder was stored in an airtight container at ambient
temperature conditions for further study.

Page | 1016
Table 1: Formulation of the drink powder produced with different concentration pumpkin pulp
powder

Ingredient Standard (S1) (S2) (S3) (S4)


Pumpkin pulp powder (g) 100 20 30 40
Germinated wheat powder (g) 0 30 20 10
Pumpkin seed powder (g) 0 10 10 10
Milk powder(g) 0 10 10 10
Icing sugar (g) 0 10 10 10
Peanut powder (g) 0 20 20 20
Salt (g) 0 0.2 0.2 0.2
Here, (S1) pumpkin powder, (S2), (S3) and (S4) 20%, 30%, 40% pumpkin powder-based drinks respectively.

2.3. Chemical Analysis of pumpkin powder and its products

2.3.1. Physical properties and proximate nutrient analysis


The physical properties and proximate composition analyses of pumpkin powder & its product were
carried out according to the methodology by Anderson [24] & AOAC (2012) respectively. 2.8.3.
Determination bioactive compounds and antioxidant activity

The total phenol, flavonoid content, DPPH, ABTS and Ferric reducing anti-oxidant power radical
scavenging capacity of each sample was determined according to the method described by Singleton and
Rossi, Madhujith and Shahidi , Re et al. [39].and Saikia respectively.

2.3.2. Statistical analysis

All the experiments for each sample were done in triplicates. Results are presented as means ± standard
deviation. Statistical analysis was performed (SPSS for windows version 22.0) by one way analysis of
variance (ANOVA). Mean comparison were performed using Duncan’s multiple range tests for
significant effect at p≤ 0.05.

3. RESULTS AND DISCUSSION

3.1. Physicochemical properties of pumpkin powder and its products

3.1.1. Bulk density

Pumpkin powder (S1) had a bulk density of 0.75 g/cm3, while sample S3 had a bulk density of
0.780g/cm3. Table 1 shows that as additional pumpkin powder was added to the composite flour, the bulk
density of the composite flour increased. Bulk density is a significant component in both science and
economics, second only to moisture. The bulk density is influenced by the particle size and density of the
flour, making it a critical factor in deciding the type of packaging material needed, as well as material
handling and application in the food sector.

3.1.2. Water absorption index (WAI) and water solubility index (WSI)

Table 2 shows the functional characteristics of the S1, S2 and S3 samples. The WAI 8 g/g pumpkin pulp
powder and other samples (8.34 to 8.74 g/g) were found to be relatively high. Noor and Komathi [43]
defined a lower WAI for unpeeled pumpkin pulp flour (2.5 g/g) and peeled flour (1.52 g/g). Previously, it
Page | 1017
was found that high WAC depends on the amount of soluble fiber (SF), which includes some components
in plant tissue materials that can hold water.

3.1.3. Milk absorption index (MAI) and milk solubility index (MSI)

The milk absorption capacity for the pumpkin powder was low (9.4 g/g), indicating less affinity to milk
when compared to the values observed in Ferreira et al. [47] study utilizing broken rice grain flour (11.68
g/g). The milk absorption showed the same low-value trend as the MAI, indicating that it should not be
used to design food products that do not require heating or instant foods. The milk solubility was higher
than the water solubility in this investigation, indicating that the might pumpkin pulp powder be used in
sweets and milk-based goods for consumption.

Table 2: Physicochemical properties of pumpkin pulp powder and its products

Properties S1 S2 S3
Bulk density (g/cm3) 0.75 ±0.034a 0.77±.0063a 0.78±0.005a
Water absorption capacity (g/g) 8.00 ±308a 8.39±0.78a 8.74±0.78a
Water solubility capacity (g/g) 16.33 ±1.53b 22.00±2.00a 21.66±0.57a
Milk absorption capacity (g/g) 9.41±0.06b 10.8±0.146a 10.81±0.047a
Milk solubility capacity (g/g) 22.74±1.08a 21.03±1.40a
21.11±1.10a

Here, each value is expressed as mean ± SD of each sample. (S1) pumpkin powder, (S2) 20% and (S3) 30% pumpkin powder-
based drinks powder. Values having the same superscript letter in a row are significant (p ≤0.05).

3.2.1 Storage studies of physicochemical characteristics and antioxidant activity of pumpkin


powder and its products

3.2.2 Antioxidant activity

Total flavonoid, DPPH, and FRAP levels were significantly higher, but phenol and ABTS were
significantly lower. Table 6 shows the decrease in antioxidant activity of powder samples after storage at
room temperature. The total phenol content of sample S1, S2 and S3 was found to decrease after one to
three months of storage. On the other hand after two months DPPH and FRAP value of all samples
decrease. The decrease in total phenolic could be attributed to oxidation, phenolic compound degradation,
and phenolic compound polymerization with proteins

3.3 Effect of storage on sugar content

The samples' sugar levels increased while they were kept at room temperature (Table 6). According to the
data, total sugars significantly increase from S1 (18.83-34.23 mg/100g), S2 (41.5-75.64 mg/100g), and S3
(44.27-81.26 mg/100 g) over the span of 5 months of storage. Three months of storage at room
temperature resulted in a noticeably worsening sugar decline. Total sugars of apple candies significantly
increased over the duration of storage at room and chilled temperatures, according to Sharma, Dhaliwal,
and Kalia’s research [66].

Page | 1018
3.4 Effect of storage on Beta-carotene content

During the storage of drinks powder at room temperature, beta-carotene levels drop S1 (34-20 mg/100 g),
S2 (12-6 mg/100 g) and S3 (18-7 mg/100 g). During the first month of storage, there was a non-
significant drop, followed by a significant decline. The amount of carotene in pumpkin puree reduced
considerably after three months of storage, possibly due to auto-oxidative degradation and non-enzymatic
browning during preparation and storage at high temperature.

Page | 1019
Table 3: Storage studies of physicochemical characteristics and antioxidant activity of pumpkin
powder and its products

Analysis Sample 0 month 1 month 2 month 3 month

Phenol S1 522.70 ±20.9 374.41±130b 296.44±5.93c 275.96±10.47c


a
(μg/g)
S2 194.00±45.3 204.33±7.50b 227.98±43.38 134.10±18.08d
c a
S3 362.00±26.4 410.85±15.48 405.89±9.31a 347.28±54.95b
b a
Flavonoid S1 471.30±57.4 795.31±585d 1109.93±10.1 1081.86±14.18b
2e 7a
(μg/g)
S2 428.00±23.0 414.03±3.5b 408.18±8.82c 402.33±8.82c
1a
S3 722.80±21.3 712.27±16a 708.76±7.01b 695.90±34.43b
3a
DPPH(μmol S1 1069.20±26. 1136±6.56a 443.90±39.21 430.08±58.61c
e/g) 10b c
S2 476.00±98.1 392.1±22.64b 362.04±87.58 234.40±33.11d
1a c
S3 740.45±173. 115.57±66.72 268.04±32.04 231.66±40.41d
42a f b
ABTS S1 2.56±0.25a 2.65±0.00a 2.43±0.01a 2.29±0.00a

(μmole/g)
S2 2.85±0.07a 2.62±0.03a 2.38±0.09a 2.21±0.00a

S3 3.12±0.45a 2.78±0.14a 2.66±0.08a 2.42±0.01a

FRAP S1 20369.28±14 28176.63±29. 25398.53±38. 24932.00±11.00b


.79c 05a 49b
(μmole/g)
S2 8754.32±16. 8276.3±20.85 9209.76±35.2 8849.95±12.66b
85b b 9a
S3 14865.44±38 17509.86±88. 14854.33±32. 11410.76±19.69c
.58b 18a 04b
Total S1 18.83±2.37d 22.49±0.17c 28.86±3.15b 35.58±2.7a
sugar(mg/100g)
S2 41.5±4.8d 41.42±5.30d 51.89±2.18c 70.02±0.03b

S3 44.27±3.66d 44.14±3.49d 51.89±1.59c 75.85±1.16b

Page | 1020
Here, each value is expressed as mean ± SD of each sample. (S1) pumpkin powder, (S2) 20% pumpkin and (S3) 30% pumpkin
powder-based drinks powder. Values having the different superscript letter in a row are significant (p ≤ 0.05).

3.5 Sensory analysis of pumpkin drinks powder

The mean sensory scores for the organoleptic features of pumpkin pulp powder drinks. In diverse
versions of pumpkin powder-incorporated drinks powder, the mean sensory ratings were not substantially
different for all of the sensory features assessed. When compared to other versions, sample S1 earned the
greatest rankings for color (8.66), sample S2 earned higher score for taste (7.9) and overall acceptance
(8.3) than compare to sample S3. It was discovered that increasing the amount of pumpkin pulp powder
increased the taste, texture, and general acceptance but not more than 30%. This could be because the 20-
30% pumpkin pulp powder-incorporated drinks have a brilliant aroma taste and a more appealing flavor
than the control. As a result, the panelists chose 20 % incorporated pumpkin pulp powder drinks as the
best accepted product.

4. SUMMARY AND CONCLUSION

Large amounts of pumpkin pulp are wasted after seed collection so it needs to be utilized through proper
processing. This study demonstrated that, dehydrated pumpkin pulp powder is a rich source of
carotenoids and phytochemicals such as phenol, flavonoid and has antioxidant activity. In our
investigation, we discovered that it is feasible to make or use drinks powder using pumpkin powder.
Pumpkin drinks powder exhibited enough nutrient content and high consumer acceptability compared to
pumpkin powder. This research will be helpful for people to know the phytochemicals and nutrients
present in pumpkin pulp. So the outcome of this research will suggest that pumpkin pulp along with its
nutritional potential regarded as an excellent food source to meet the daily dietary.

References

1. Bangladesh Bueau of Statistics (BBS) 2014.

2. Pereira, M.A., Ramos, H.A., Krolow, R.C.A., Santos, R. and Gularte, A. M. Physicochemical
characterization, carotenoid content and protein digestibility of pumpkin access flours for food
application. Food Sci. Technol. 2020, Campinas, 40(Suppl. 2): 691-698.

3. Malkanthi, H. H. A. and Umadevi, S. H. (2018). Effect of dried pumpkin pulp and seed powder
on physical, chemical and sensory properties of biscuits. Int J Sci Res. 2018, 7, 32-4.

4. Nakazibwe, I., Wangalwa. R., Olet, E.A. and Kagoro, G.R. Local knowledge of pumpkin
production, performance and utilization systems for value addition avenues from selected agro-
ecological zones of Uganda. African Journal of Agricultural Research. 2019, 14(32), 1509-1519.

5. Mehditabar, H., Razavi, S. M. A., & Javidi, F. Influence of pumpkin puree and guar gum on the
bioactive, rheological, thermal and sensory properties of ice cream. International Journal of Dairy
Technology. 2019, 73 (2), 447-458.
6. Yildiz, E. and Ozcan, T. Functional and textural properties of vegetable-fibre enriched
yoghurt.
International Journal of Dairy Technology. 2019, 72(2), 199-207.

7. Jabeen, A., Hassan, S., Masoodi, L., Ajaz, N. and Rafiq, A. Physico-chemical composition and
functional properties of blended flour obtained from lentil, pumpkin and barley for development
of extrudates. Journal of Food Processing & Technology. 2018, 9(1), 1-9.

Page | 1021
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 113

Assessment of Heavy Metal Pollution in Discharge


Wastewater from Sylhet Gas Fields

Md. Numan Hossain*, M. Farhad Howladar*

Dept. of Petroleum and Mining Engineering,

Shahjalal University of Science & Technology,Sylhet-3114, Bangladesh.

*Corresponding author: Md. Numan Hossain, M. Farhad Howlada]

Abstract: SGFL is a major natural gas producer in Bangladesh. To meet the nation's
Keywords:
growing energy needs, SGFL produces 95 MMSCF of natural gas and 610 barrels of
condensate per day at its 149 MSCFD capacity. Discharge water is the main byproduct
● Wastewater; of oil and gas production. After processing oil and gas, this waste stream is released.
● Heavy Metals; Studies found that produced water poses a greater threat to the environment and living
things than crude oil. This study will measure heavy metal concentrations in SGFL
● Environmental
wells' produced water, assess trace element hazard ratings in the waste stream,
Pollution; determine heavy metal pollution, and compare discharge and produced water risk
levels. Nineteen samples were collected from producing wells, discharge locations,
● Toxicity Index;
and drinking water supplies in the gas field region. After laboratory analysis, statistical
● Carcinogenic and analysis determines discharge stream contamination. To map trace metal
contamination, the Heavy Metal Index (HMI), Environmental Toxicity Index (ETI),
Non-carcinogenic
Ecological Hazard Score (EHS), Carcinogenic Risk, and Non- Carcinogenic Risk were
Risk; assessed. The produced water contained higher levels of heavy metals than the
● Oil & Gas Industry. discharge and drinking water. The water was moderately polluted for Cr and Co,
severely polluted for Mn, Ni, Zn, and Cd, and barely polluted for As and Pb, according
to a number of trace element indices and ratings. The majority of cancer risk factors
and non-cancer risk factors are below acceptable levels. This study found that
discharge and drinking water pose minimal risk, whereas produced water poses
moderate to high risk. Heavy metal concentrations vary with well age, season, and
reservoir structure, so monitoring is necessary. Otherwise, metal toxicity could harm the
environment, ecology, and public health.

1. Introduction
Heavy metals in water are highly concern topics in the present era (Kumar et al.,2019) due to their
toxicity, persistence, contamination behavior, and non-degradability (Jordan et al., 2014). Trace metals
concentration in aquatic environments increasing exponentially in the last few decades due to rapid
industrial development, mining exploration, accidental release, agricultural activities (Howlader et
al.,2021), geological weathering, atmospheric precipitation, domestic or municipal effluent, and so on
(Kumar et al.,2019; Salomons & Förstner, 2012). However, petroleum-produced water (PW) is the
primary waste stream generated in the oil and gas industry

Page | 1022
(Santos et al., 2014). Petroleum PW generally refers to the surface water generated as a byproduct during
hydrocarbon production (Clark & Veil, 2009). It is a mixture of organic and inorganic compounds
(Ahmadun et al., 2009), containing some chemical properties of formations and hydrocarbons (Clark &
Veil, 2009). This may include water from the reservoir, water injected into the formation, and any
chemical additives used during production (Autofi & Lampert, 2020). Studies found that the disposal of
PW may contaminate surface and groundwater, the surrounding environment, and ecosystems (Hedar &
Budiyono, 2018; Neff et al., 2011). Oil and gas operationscan affect species, populations, assemblages, or
ecosystems by altering ecological parameters, including biodiversity, anaerobic digestion, productivity,
and so on (Cordes et al., 2016). Organic compounds (Akob et al., 2015), metalloids (Lutz et al., 2013),
toxic metals (Schifter et al., 2015), radionuclides (Rowan et al., 2011; Brown, 2014), and salt stress
(Haluszczak et al., 2013; Gazali,2017).
Bangladesh's energy industry is highly dependent on the oil and gas industry. The 22 producing gas
fields out of 28 in Bangladesh produce around 113 million standard cubic feet per day (MMSCFD)
(Petrobangla, 2022). Sylhet gas fields limited (SGFL) is one of the major gas- producing companies of
Bangladesh. Currently, SGFL is producing approximately 90 MMSCFD of gas is produced daily
(Petrobangla, 2022), along with a significant amount of water. In recent years, the water production rate
has increased dramatically. The water gas ratio of SGFL well varies from 7 bbl/MMSFD to 55
bbl/MMSCFD, which is discharged to the surrounding gas fields after processing. Because wastewater
discharge from gas fields has a variety of environmental impacts, it is a matter of concern. This study
assessed the environmental and ecological impact, toxicity, and health risk of heavy metals in
discharged and produced water of SGFL's well, and in the groundwater of SGFL's region. This study will
be helpful for the higher authority and policy makers for understanding the overall scenario of metals
risks in wastewater discharged from gasfields.
2. Materials and methods
2.1 Sample collection, preparation, and Analysis Procedures
A total of 19 water samples were collected from four fields named Haripur gas field (HGF), Kailashtila
gas field (KGF), Beanibazar gas field (BGF), and Rashidpur gas field (RGF) of Sylhet gas fields limited,
where nine samples were well-produced water (PW), five are discharged water (DW)samples, and five
are drinking water (GW) samples around the gas field region. The sampling locations are displayed in
figure 1. The sampling was conducted following the standard procedure of the EPA (2016) in the middle
of August 2021. High-density 1 L plastic bottles were used for the collection of water samples. Prior to
sampling, bottles were cleaned with distilled water and dried properly. After the completion of sampling,
water bottles were closed tightly and appropriately marked with unique identification numbers. After
that, samples were sent to the laboratory immediately for analysis. In addition, water samples were kept
in the refrigerator in the laboratory and were acidified with 2 mL of concentrated HNO3 before metal
analysis (Wang et al., 2017; Ahsan et al., 2019). The heavy metals were analyzed using an atomic
absorption spectrometer (AAS). The trace elements Pb, Cd, Cr, and Ni presence in the water samples
were measured by Zeeman-AAS (Model: GTA 120-AA240Z, Varian, Australia), where the as contents
were measured by electric hydride vapor generation technique of AAS (Model: SpectrAA 220 equipped
with ETC-60 & VGA-77, Varian, Australia). Moreover, the rest of the elements were measured by
flame-AAS (Model: AA240 FS, Varian, Australia). The relative standard deviation during analysis was
maintained at less than 5%. The accuracy and precision of the measurements using AAS analytical
techniques were further ensured by performing blank samples after each of

Page | 1023
the ten samples and performing three replicate measurements in the analysis of each sample(Ahsan et
al.,2019).

Figure-1. Study area.

2.2 Data analysis, toxicity indices and risk assessments


The data were analyzed using IMB SPSS 20 software, a spatial distribution map was developed by
ArcGIS 10.3, and further analyses were performed using Microsoft excel 2016. The Metal index (HMI)
is a quick tool of assessing the effects of metals on human health (Ojekunle et al, 2016). It can evaluate
the quality of drinking water as well as river and canal water (Withanachchi,
2018).
∑𝑛
The formula used to calculate metal index: 𝐻𝑀𝐼 𝐻𝑐
𝑖=
= 1
∑𝑛𝑖 𝐴𝑐
=
1

Where, Hc= heavy metal concentrations and Ac= allowable concentrations. The Ac value (in ppb) used in
this study was: used for calculation are Zn (5000), Cd (5), Pb (10), Cu (50), Ni (20), Co (4), Fe (300),
Mn (100), As (10) and Cr (50) (Shil & Singh,2019; WHO, 2017). Based on HMI
water can be classified as: Class-1 (very pure water) when HMI<0.3; Class-2 (Pure water) when
0.3<HMI<1.0; Class-3 (slightly affected water) when 1.0<HMI<2.0; Class-4 (Moderately affected
water) when 2.0<HMI<4.0; Class-5 (Strongly affected water) when 4.0<HMI<6.0 and Class-6(Seriously
affected water) when HMI>6.0 (Ojekunle et al., 2016).

Page | 1024
The “Environmental Toxicity Index (ETI)” in this study was evaluated for identifying temporal and
spatial indication of environmental pollution (Goher et al, 2014), as well as the general contamination
level in water (Withanachchi, 2018). The equation used for that purpose was
𝑁
𝐸𝑇𝐼 = √𝐶𝑐(1) ∗ 𝐶𝑐(2) ∗ ∗ 𝐶𝑐(𝑛) where, Cc= Hc/Ac. ETI indicated pollution when
its value is greater than one (Withanachchi, 2018).

Another index, Ecological Hazard Score (EHS) was evaluated using the following equation:
𝐸𝐻𝑆 = 𝑖 𝐸 where, ERI= TRF* Cc. Here, TRF= Toxic response factor of heavy metal
∑𝑚 = 𝑅
1
𝐼
(Cd=30,As=10,Co, Cu, Ni, Pb=5, Cr=2, Zn, Mn=1) and Cc= contamination level of trace metals
(Proshad et al,2020). Based on EHS, hazard can be classified low at EHS <150, medium at 150
≤ EHS <300, high when 300 ≤ EHS <600, and extreme when PER ≥ 600 (Akarsu et al, 2022; Chen et
al, 2019)
The processes that must be followed to assess the non-carcinogenic risk involve, first and foremost,
determining the average daily dose of exposure. The following stage is to calculate the hazard factors,
and the final step is to calculate the hazard score by combining all of the danger factors together. The
average daily dose of exposure can be obtained by following equation (Huang et al,2021):
Mc ∗ Ri ∗ Ef ∗ Ed
𝐴𝐷𝑖 =
Bw ∗ At
Mc ∗ Sa ∗ Kp ∗ Ri ∗ Ef ∗ Ed ∗ Et ∗ Cf
𝐴𝐷𝑑 =
Bw ∗ At
ADi and ADd =average daily dose of exposure by ingestion and dermal absorption respectively
(mg/kg/day), Mc=Heavy metal concentrations (ug/L), Ri=Rate of ingestion (L/day), Ef=Exposure
frequency (day/year), Ed= Exposure duration (year), Bw=Body weight (kg), At= Average time of intake
(days), Et= Exposure time (h/day), Sa= Exposed skin area (cm2), Kp= Coefficient of permeability
(dermal) of metal in water (cm/h), Cf= Conversion factor
(L/cm3)=0.001.
"Non-carcinogenic Hazard Index" can be calculated as HI = HFi+ HFd . The findings suggest that HI
values less than one are safe, however HI values larger than one indicate a non-carcinogenic risk (Wagh
et al., 2018).
The purpose of determining the carcinogenic risks (CR) of heavy metals was to assess the
likelihood of developing cancer after exposure to cancer-causing agents (Kumar et al., 2019).
Carcinogenic risk can be calculated by multiplying the dose of exposure by the cancer slope
factor developed by the USEPA (2009)(Huang et al., 2021). According to USEPA, the
acceptable range of carcinogenic risk index is approximately1×10-4 to 1×10-6 (Habib et al, 2020;
Howladar et al., 2021). The potential for cancerous growth can be calculated using the
following formulas (Kumar et al., 2019; Kamunda et al., 2018). Carcinogenic risk from
ingestion, 𝐶𝑅𝐼 = 𝐴𝐷𝑖 × 𝐶𝑆𝐹.Carcinogenic risk from dermal absorption, 𝐶𝑅𝐷 = 𝐴𝐷𝑑 × 𝐶𝑆𝐹.
And, the total carcinogenic risk index, 𝐶𝑅𝐼 = 𝐶𝑅𝐼 +
𝐶𝑅𝐷.
3. Result and Discussions
3.1 Heavy metal pollution scenario from HMI:

The outcome of the heavy metal index is presented in table 1. The HMI indicated that the produced
water samples (PW) are slightly affected to seriously affected due to heavy metals in the water. The
discharge water samples are very pure and pure in quality. In addition, drinking water samples (GW) are
also very pure.

Page | 1025
Table-1. Water quality according to HMI.
Sample ID HMI Water Category Comments
PW01 0.271743 Class1 Very Pure Water
PW02 0.468355 Class 2 Pure Water
PW03 4.9002 Class 6 Seriously Affected
PW04 0.202604 Class1 Very Pure Water
PW05 1.631519 Class 3 Slightly Affected
PW06 2.652656 Class 4 Moderately Affected
PW07 0.066657 Class1 Very Pure Water
PW08 3.043294 Class 6 Seriously Affected
PW09 0.313884 Class 2 Pure Water
DW01 0.141467 Class1 Very Pure Water
DW02 0.192496 Class1 Very Pure Water
DW03 0.236046 Class1 Very Pure Water
DW04 0.384359 Class 2 Pure Water
DW05 0.058996 Class1 Very Pure Water
GW01 0.69495 Class 2 Pure Water
GW02 0.069061 Class1 Very Pure Water
GW03 0.076864 Class1 Very Pure Water
GW04 0.065075 Class1 Very Pure Water
GW05 0.045387 Class1 Very Pure Water

3.2 Environmental toxicity status according to ETI:


The environmental toxicity index measures a water sample's toxicity (Islam et al., 2015), which is
displayed in figure 2 for this study. The results of ETI provide comparatively better results, representing
low to medium risk. The ETI of PW 06 and PW 08 represents a high risk (greater than 1) (Khosnam et
al.,2017).

Page | 1026
5
4.5
4
3.5
3
2.5
E
T
I 2
1.5
1
0.5
0
PW01

DW01
DW02
DW03
DW04
DW05
GW01
GW02
GW03
GW04
PW02
PW03
PW04
PW05
PW06
PW07
PW08
PW09

05
W
G
SAMPLING STATION

Figure 2. Environmental toxicity index of water samples.


3.3 Possible ecotoxicological hazards:
The ecological hazard score (EHS) is typically employed to assess the potential toxicity of heavy metals
in an ecosystem (Liu et al., 2021). Table 2 depicts the results of EHS and the ecological risk of
individual metals. Higher concentrations of EHS were found in PW08, while moderate concentrations
were found in PW01. EHS levels in samples of discharge water and drinking waterrange from low to very
low. The individual metals with the highest ERI are Co, Ni, Cd, and Mn, followed by Cu, Pb, As, Cr,
and Zn. As produced water is an instruction of formation liquid into the well from the top or bottom of
the petroleum zone (Hedar & Budiyano, 2018) and its geological and temporal and seasonal properties
vary (Ahmudun et al., 2009), the ERI values of the same well may vary over time.
Table 2. Ecological hazard scores of studied water samples.

Sample Ecological risk of individual metals


EHS Remark
ID
s
As Cd Co Cr Cu Mn Ni Pb Zn
PW01 0. 17.7 162.5 0. 1.00 0.26 70.53 1.12 0. 254.05 Mediu
65 0 0 23 07 m
PW02 0. 1.20 49.75 0. 1.50 1.02 7.92 0.69 0. 63.28 low
83 28 09
PW03 0. 3.10 11.69 0. 3.00 2.94 6.79 2.80 0. 30.88 low
33 19 04
PW04 0. 12.8 6.09 0. 1.30 1.91 110.03 1.16 0. 134.15 low
65 0 21 01
PW05 0. 2.20 6.04 0. 1.70 0.84 1.09 3.08 0. 15.75 low
60 20 01
PW06 2. 9.50 65.63 0. 6.40 3.92 9.83 3.03 0. 101.80 low
95 42 13
PW07 0. 1.30 1.88 0. 2.20 1.50 5.63 0.71 0. 13.88 low
48 18 01
PW08 5. 41.1 293.7 0. 22.5 56.8 127.65 27.1 0. 575.70 High
13 0 5 64 0 5 92
PW09 2. 10.7 14.25 0. 0.90 0.47 6.27 0.79 0. 36.62 low
98 0 25 02
DW0 0. 17.0 9.43 0. 0.90 0.21 74.20 1.74 0. 104.37 low
1 58 0 26 05

Page | 1027
DW02 0.75 2.30 17.13 0.22 1.60 0.92 4.20 0.13 0.00 27.24 low

DW03 0.90 3.80 3.60 0.18 1.20 1.30 1.67 0.71 0.02 13.37 low

DW04 0.53 3.20 6.56 0.21 1.20 3.24 7.23 0.41 0.02 22.59 low

DW05 0.43 18.00 17.25 0.20 2.00 0.53 16.57 0.99 0.00 55.97 low

GW01 2.00 2.10 8.14 0.19 1.30 5.92 2.39 0.07 0.06 22.16 low

GW02 8.58 10.10 20.00 0.16 0.80 0.14 3.57 0.54 0.01 43.90 low

GW03 10.8 4.20 2.28 0.22 1.50 0.10 0.41 1.03 0.03 20.56 low

GW04 0.43 2.50 3.11 0.20 2.80 0.17 2.53 0.62 0.04 12.40 low

GW05 0.65 10.10 7.41 0.22 0.70 0.15 0.64 0.34 0.01 20.22 low

3.4 Carcinogenic and Noncarcinogenic risk:


The presence of heavy metals in water endangers the health of the general population, including children
and adults. Ingestion and dermal absorption of water result in the spread of health risks. Understanding
the harmful effects on humans requires an evaluation of the noncarcinogenic risks associated with trace
elements in water (Dung et al., 2013). Figure 3 shows the noncarcinogenic hazard index (HI). Due to the
elevated concentrations of Ni, Cd, Co, and Mn, the noncarcinogenic risk for PW08 has been high. The
hazard score for samples of drinking water and groundwater is within acceptable limits (Howlader et
al.,2021).
Hazard
Index

Figure 3. Non carcinogenic risk index of gas fields wastewater.


The possible heavy metals of carcinogenic risk are As, Cd, Cr, Ni, Pb which was evaluated for this
study (Figure 4). Ni and Cr in water samples were especially accountable for causing health risk. For
most of the cases Ni found as higher than other metals which contributed most of the cancer risk.

Page | 1028
100%

80%

Chil
60%

dre 40%

20%

0%

100%
80%
mal

60%
Fe

40%
20%
0%
1
0
0
%
M
al

8
e

0
%
6
0
%
A C C N P
4
0 s d r i b
%
Figure 4.20 Carcinogenic risk of water samples.
%
The Incremental Lifetime Cancer Risk (ILCR) of heavy metals in the Sylhet gas fields region is
illustrated0 in Table 3. An ILCR smaller than 1×10-6 can be considered insignificant, but a value of ILCR
%
greater than 1×10-4 is significant enough to cause health risks (Howladar et al., 2021; Mohammadi et
al., 2019). The mean value of As, Cd, Cr, Ni, and Pb for adults is about 8.83E-05, 1.54E-04, 8.50E-05,
4.57E-03, and 1.17E-06, respectively. For children, the ILCR means are about 1.91E-04, 3.34E-04,
1.85E-04, 9.85E-03, and 2.53E-06 in the case of As, Cd, Cr, Ni, and Pb, respectively. However, the
ILCR levels of Cd and Ni demonstrate possible health risks for females, children, and males. The As
and Pb are less dangerous among them in the study region.
Table 3. Incremental lifetime Cancer risk of individual metals.
ILCR Value As Cd Cr Ni Pb
maximum 9.74E-04 1.51E-03 4.86E-04 5.21E-02 2.78E-05
Childre

Minimum 2.98E-05 4.40E-05 1.23E-04 1.67E-04 6.64E-08


Average 1.91E-04 3.34E-04 1.85E-04 9.85E-03 2.53E-06
n

maximum 4.59E-04 7.11E-04 2.28E-04 2.46E-02 1.31E-05


Minimum 1.40E-05 2.07E-05 5.77E-05 7.90E-05 3.13E-08
Female

Page | 1029
Average 9.01E-05 1.57E-04 8.67E-05 4.66E-03 1.19E-06
maximum 4.50E-04 6.97E-04 2.24E-04 2.41E-02 1.28E-05

Mal
Minimum 1.38E-05 2.03E-05 5.65E-05 7.75E-05 3.07E-08

e Average 8.83E-05 1.54E-04 8.50E-05 4.57E-03 1.17E-06

4. Conclusion
The research was carried out in the Sylhet gas fields region to ascertain the dangers of heavy metals and
their toxicity in the gas fields area. According to the findings, the levels of trace elements in the
produced water ranged from moderate to low, and the levels of heavy metals found in the discharged
water and the drinking water in the area around the gas fields were low. Among all metals, Fe is rated as
extremely high, Ni and Cd as moderate, and the rest as low. The metal index demonstrated that the
produced water posed a moderate to high risk, but the discharge and drinking water samples posed a low
or very low risk. According to environmental and ecotoxicological scores, some produced water posed a
moderate to significant risk, while others displayed a low risk. The noncarcinogenic risk was found to be
minimal, whereas the carcinogenic risk was found to be significant in the presence of Cd and Ni for
males, females, and children. The trace element arsenic (As) has also been linked to significant
carcinogenic risk in children. Pb exposure has been linked to a low lifetime cancer risk.
Acknowledgment
The authors thank Sylhet gas fields limited for granting permission to conduct research on their sites.
Additionally, the authors are grateful to the department of petroleum industry and the BCSIR for
providing the opportunity to conduct laboratory analysis.
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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 129

Diversity and enhancement of mixed-culture


polyhydroxyalkanoate producing organism

Nanda Kishor Roy*, Tashfiqul Islam, Md. Jakaria Hossain, Aishi Acharjee andMd.
Salatul Islam Mozumder

Department of Chemical Engineering & Polymer Science,


Shahjalal University of Scienceand Technology, Sylhet-3114, Bangladesh.

*Corresponding author [nanda.roy@gmail.com]

Keywords:
Abstract: Processes for Polyhydroxyalkanoates (PHAs) production involving mixed
culture was a two-step process which includes enhancement of PHAs accumulation
• PHA
organisms followed by PHA accumulation. Advantages of using mixed microbial
• Pseudomonas culture are the possibility to exploit waste as a substrates and comparatively lower
production cost. The mixed culture used in this study was collected from a local
• Alcaligenes wastewater treatment plant and the molecular analysis through 16S rRNA had shown
• Acetate that Pseudomonas and Halomonas species were predominant in this mixed culture
• Glucose system and these species had a high potentiality to produce PHAs. The sludge also
contains a number of non-PHAs producing organism. The PHAs producing bacteria
was enriched using the feast-famine cycles. The optimal PHAs producing condition
was 30oC temperature and pH 7. In this study glucose and acetate was used as carbon
sources to evaluate the potentiality of this mixed organism to produce PHAs.
Ammonium sulphate ((NH4)2SO4) was used as the nutrient. After the enrichment of
PHAs producing organism through the feast- famine cycle, there was no need to
undergo further feast-famine process even while this organism was used as the seed
culture for other PHAs production operation. The analysis of enriched organism
shown that Pseudomonas was predominant while glucose was used as a substrate
whereas using acetate as the substrate Alcaligenes was the dominant organism.
However, both substrate as well as the organism showed a high potentiality on PHA
production.

1. Introduction

Biodegradable polymers are in high demand around the world as a potential solution to the
environmental problem of plastic pollution. Biodegradable polymers are also used in biomedical and
other specialized applications. Polyhydroxyalkanoates (PHAs) are a family of biodegradable polymers
with a broad range of applications (Philip, 2007). PHAs can be produced in open, mixedmicrobial cultures
as part of biological treatment of municipal and industrial wastes and residuals (Serafim, 2008). Since
PHAs can be produced biologically from renewable feedstocks, have attracted considerable industry
attention (Anderson, 1990) as biodegradable and biocompatible thermoplastics. At present, PHAs are
mostly produced using pure cultures, often employing genetically modified organisms. The processes
are typically operated under sterile production conditions involving the use of pure carbon sources.
All these specific conditions add

Page | 1033
considerably to the costs of the final product (Steinbuchel, 1998). The use of inexpensive mixed culture
biomass, such as activated sludge, to produce biodegradable plastics from renewable waste streams has
been proposed as an alternative. This reduces costs for raw materials and processing (Satoh H. I., 1998)
and adds environmental value (Chuang, 1998).
PHA production with wastewater treatment implies selectively growing/enriching PHA-storing bacteria
in activated sludge based on engineered environments exerting dynamic conditions with respect to
substrate feeding (i.e., alternating conditions of carbon availability and unavailability) (Dionisi, 2004) or
electron acceptor availability (aerobic-anaerobic cycle)(AN/AE) (Satoh H. I., 103–109) (Bengtsson,
2008b). Substrate aerobic dynamic feeding (ADF) or feast–famine has been the commonly applied
enrichment approach (Dias, 2006). The efficiency of PHA production from wastewater depends upon the
selection and enrichment of a MMC with high PHA storage capacity (Johnson, 2009). The aerobic
dynamic feeding (ADF) mode of operation for the enrichment reactor has been successfully used for this
purpose. Under alternating feast-famine conditions, the MMC is subjected to ecological pressure that
selects PHA-accumulating bacteria over other non-accumulating bacteria. PHA-accumulating bacteria
store the majority of the carbon source as PHA in the feast phase and continuously grow throughout the
cycle, utilizing the stored PHA in the famine phase. This process can be economically competitive with
PHA production from pure cultures and it has the advantages of being simpler and requiring less
investment and operating costs.

In this study, feast-famine cycle was applied using two different substrates – glucose and acetate
- and ammonium sulphate((NH4)2SO4) as the sole nutrient source to enhance PHA producing bacteria
from the mixed microbial culture. Pseudomonas and Halomonas species were the dominant species
found in this mixed microbial culture system and the change of microbial composition was followed
through the feast-famine cycle.

2. Experimental
2.1 Source of Bacteria
Bacteria used were collected as sludge from the final settling tank of a Sequential Batch Reactor (SBR)
in wastewater treatment unit of Shahjalal Fertilizer Company Limited, (SFCL) located in Fenchugonj,
Sylhet, Bangladesh.
2.2 Materials
UV-Vis Spectrophotometer: UV-1800 (SHIMADZU, Japan), Centrifuge machine: Z 287A (HERMLE
Labortechnik Gmb, Germany), Analytical Balance: AS 120.R1 PLUS (Radwag, Poland), A&D
Company, Limited (Japan), Chemicals: SMART-LAB(Indonesia), Sisco Research Laboratories (SRL)
Pvt. Ltd.(India), Qualikems Lifesciences Private Limited(India).,Digester: DRB200, Digital Reactor
Block (Hach Company, USA), Hot plate Magnetic Stirrer Digital Model: HSD180 (Mtops, South
Korea), pH meter: HI- 8224 (HANNA Instruments, Romania),Glassware (Pyrex), Aquarium pump: RS
248A(local provider)

Page | 1034
2.3 Experimental procedure
The (Blaszczyk., 1993) model was used as growth medium for the enrichment process. In the PHA
accumulated bacteria enrichment reactor the temperature was maintained to 30℃. To ensure the
homogeneous mixture throughout, the circular reactor was aided with a magnetic stirrer with 500 rpm.
For aeration, an aquarium pump (RS 248A) was used. For the enrichment of the mixed culture, feast-
famine cycle was applied using (NH4)2SO4 as the sole nutrient and Acetate and Glucose as the substrate
in separate batches. At the end of the enrichment, aerator and magnetic stirrer were turned off and the
reactor was put into rest for two hours for the settlement of the sludge. The enriched PHA accumulated
bacteria sludge was then extracted by centrifuging the settled sludge taken from the reactor and was
stored for use.
2.4 Calculation
Active biomass was calculated based on nitrogen consumption and biomass yield over nitrogenis 12 g
biomass/g-Nitrogen.
Active Biomass = (A-B) *12/1000 (g/L) where A=
Total amount of supplied N in mg/L
B= Amount of nitrogen presence in any moment in mg/LTotal
Biomass = DCW+ Optical Density(400nm)
PHA Calculation: Amount of PHA was calculated by the weight difference between Total
Biomass and Active Biomass:
PHA Accumulation = Total Biomass - Active biomass (g/L)
Theoretical PHA content was measured using this formula:
PHA Content (g-PHA/g-Total Biomass) = (PHA Accumulation/Total Biomass) *100

2.5 Analytical methods


Ammonium-N determination standard method
The measurement of ammonium-nitrogen (NH4-N) in wastewater was determined by Nessler method. In
this method gradually yellow to brown color was produced by Nessler ammonium reaction which was
strongly absorbed over a wide range of wavelength. The absorbance was ammonium-Nessler was
determined at 390 nm wavelength. Growth media aided distilled water was used in diluting the sample
for measurement and the value of slope from calibration curve was used for further procedure.
Glucose determination standard method
The measurement of glucose presence in bioprocess in determined by phenol sulfuric acid method. In
this method gradually, blackish brown color was produced by reaction which was strongly absorbed
over a wide range of wavelength. The absorbance was determined at 710 nm wavelength. Growth media
aided distilled water was used in diluting the sample for measurement and the value of slope from
calibration curve was used for further procedure.

Chemical Oxygen Demand (COD) Determination


The spectrophotometric method of measurement of COD in the batch was determined by using K2Cr2O7
and a catalyst, Ag2SO4, dissolved in concentrated HgSO4 is also used. These two are mixed into 1:3 ratio
and the mixture were used as a reagent for COD. Digester is used for the digestion of the mixture and it
was kept in it for 4 hours. In this method gradually increasing dark yellow color was produced. The
absorbance was determined at 600 nm wavelength. Growth media aided distilled water was used in
diluting the stock solution for calibration and the value of slope from calibration curve was used for

Page | 1035
determination of concentration of sample. This method was used to measure the amount of acetate in the
batch.

3. Result and Discussions


The feast famine cycle was applied for glucose and acetate as substrate and ammonium sulphate was the
solo nutrient source.
3.1 Feast-Famine Cycle (Acetate)
A total of 814mg/L of NH4-N and a total of 50g/L (72g) acetate was consumed in this process. Active
biomass formed was 9.77g/L and total biomass was found to be 23.52g/L at the end of the process.
Total PHA accumulation was 13.75g/L. Theoretical PHA content was 58.46%. Theexperiment was
conducted for 213.5hrs.

3 0
0 .
3
2 0
5 .
2
2 0
5
0 .
2
1 0
PHA,COD,Total

NH4-N
(g/L)
5 .
Biomass(g/L)

1
1 0
5
0 .
1
5 0
.
0
0 0
5
0 50 100 150 200 250
Time(h)

PHA( COD( Total NH4-N


g/L) g/L) Biomass(g/L) (g/L)
Fig. 1 Feast famine data using acetate as substrate

3.2 Feast-Famine cycle (Glucose)


In this experiment 1056.1 mg/L of NH4-N and 55.79 g/L glucose were consumed. Total active bacteria
formed was 19.6 g/L and PHA accumulation was 6.93 g/L that indicated the 35% PHAcontent. The
experiment was run for 200 hrs, means the productivity was 0.035 g/L/h.

Page | 1036
2 0
5 .
3
2 0
0 .
2
5
1
PHA,Glucose,Total
5

N(g/L)
0

NH4-
0
.
Biomass(g/L)

1 .
1
0 0
2
5
.
5 1
0
.
0
0 0
5
0 50 100 150 200 250
Time(h)

PHA Glucose( Total Nh4-


(g/L) g/L) Biomass(g/L) N(g/L)
Fig. 2 Feast famine data using gluvose as substrate

3.3 Bacteria Analysis


3.4 Composition of initial mixed microbial culture
Halomonas and Pseudomonas are the bacteria which are predominant in the initial mixed microbial
culture, as shown in figure 3, collected from Shahjalal Fertilizer Company Limited, (SFCL) situated
in Fenchugonj, Sylhet, Bangladesh.

Fig. 3 Composition of mixed microbial culture

Page | 1037
3.5 Composition of bacteria after feast-famine cycle (Acetate)

Fig. 4 Composition of bacteria using acetate as substrate

After the mixed microbial culture was subjected to feast famine processes using acetate as substrate and
(NH4)2SO4 as nutrient, we have seen that Georgenia(25.90%) and Alcaligenes(22.74%) are the dominant
bacteria, as shown in fig. 4, which were cultured by feast famine process using Acetate as substrate and
thus have high potential for PHA production.
3.5 Composition of bacteria after feast-famine cycle (Glucose)

Fig. 5 Composition of bacteria using glucose as substrate

Page | 1038
After the mixed microbial culture was subjected to feast famine processes using glucose as substrate and
(NH4)2SO4 as nutrient, we have seen that Pseudomonas (70.65%) is the dominant bacteria, as shown in
fig. 5, which were cultured by feast famine process using glucose as substrate and thus has high
potential for PHA production.
4. Conclusion
Bacteria analysis results of feast famine cycle using acetate as substrate showed Georgenia (25.90%)
and Alcaligenes (22.74%) as the predominant PHA producing bacteria enriched from the initial mixed
microbial culture whereas for glucose as substrate, Pseudomonas (70.65%) was found out to be the
dominant bacteria. We can conclude from this that, different substrates lead to enrichment and selection
of different bacteria which have high potential for PHA production.
Additionally, the batch with acetate as substrate showed higher theoretical PHA content than the batch
with glucose as substrate. Therefore, acetate and the dominant bacteria Georgenia and Alcaligenes have
higher productivity for PHA than glucose and the bacteria Pseudomonas.

Acknowledgment
We are grateful to Bangladesh Bureau of Educational Information & Statistics (BANBEIS) forfinancing
this project. (Project/User ID: SD20211542).

References
1. Anderson, A. D. (1990). E.A. Microbiol. Rev. 54, 450–472.
2. Bengtsson, S. W. (2008b). Production of polyhydroxyalkanoates by activated sludge treating apaper
mill wastewater. Bioresour. Technol. 99, 509–516.
3. Blaszczyk., M. (1993). Effect of Medium Composition on the Denitrification of Nitrate by
Paracoccusdenitrificans. Applied and Environmental Microbiology, 59(11), 3951-3953.
4. Chuang, S. O. (1998). Water Sci. Technol. 37, 593–597.
5. Dias, J. M. (2006). Recent advances in polyhydroxyalkanoate production by mixed aerobic
cultures: from substrate to the final product. Macromol. Biosci. 6, 885–906.
6. Dionisi, D. M. (2004). Biodegradable polymers from organic acids by using activated sludge
enriched by aerobic periodic feeding. Biotechnol. Bioeng. 85 (6), 569–579.
7. Johnson, K. J. (2009). Enrichment of a mixed bacterial culture with a high
polyhydroxyalkanoate storage capacity. Biomacromolecules 10, 670–676.
8. Philip, S. K. (2007). Polyhydroxyalkanoates: biodegradable polymers with a range ofapplications. J.
Chem. Technol. Biotechnol. 82, 233-247.
9. Satoh, H. I. (103–109). Activated sludge as a possible source of biodegradable plastic. WaterSci.
Technol. 38 (2), 1998.
10. Satoh, H. I. (1998). Water Sci. Technol. 38,, 103–109.
11. Serafim, L. S. (2008). Strategies for PHA production by mixed cultures and renewable waste
materials. Applied Microbiology and Biotechnology volume 81, 615–628.
12. Steinbuchel, A. B. (1998). Trends Biotechnol. 16, 419–427.

Page | 1039
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 150

Co-Digestion of Two-Phase Livestock and Municipal Solid Wastes:


Influence of Solids Content on Biofuel Production Performance

Nadira Sultana Urme*, Muhammad Rashed Al Mamun

Department of Farm Power and Machinery, Faculty of Agricultural Engineering and Technology,
SylhetAgricultural University, Sylhet-3100, Bangladesh
Email: nadiraurme54@gmail.com*, rashed.fpm@sau.ac.bd

Corresponding Author: [Nadira Sultana Urme]

Keywor ds: Abstract: Utilization of non-renewable energy sources, which are difficult to
recycle and need a long process to produce the fuel, can result in energy crisis
• Biofuel;
issues. Biofuel production technique is one of the energy technologies that
• Renewable and Non-
comply with these parameters. The purpose of the study is to investigate biofuel
Renewable Energy;
production rate through anaerobic co-digestion of different biodegradable wastes
• Co-Digestion
and to compare the biofuel production yield of different feedstock materials. A
Process;
3000L batch-type digester, under mesophilic environment was used for this
• Fossil Fuel;
experiment with a 1:1 mixing ratio of materials and water, and having hydraulic
• Rumen Digesta.
retention period of 30 days. The amount of produced biofuel was assessed by
water displacement process. In this study, cow (RWC) and goat (RWG) rumen
waste, poultry droppings (PD), spent tea waste (STW), kitchen waste (KW) and
fish waste (FW) was used in two phases with different mixing ratios. In first
phase, three mix samples were prepared in the ratio of RWC:PD:STW (1:1:1),
RWG:PD:STW (1:1:1) and RWC:RWG:PD:STW (1:1:1:1). Maximum
production was obtained 228 L/day at 14th day from RWC, PD and STW with
an average of 71.32 L/day. In second phase, three mix samples was prepared in
the ratio of RWC:PD:STW:KW (1:1:1:1), RWG:PD:STW:KW
(1:1:1:1) and RWC:RWG:PD:STW:KW (1:1:1:1:1). The highest
production of 200.67 L/day was obtained from RWG:PD:STW:KW at 5th day
with an average of 75.31 L/day. In this experiment, highest production was
obtained from RWC, PD and STW (1:1:1). So these substrates are recommended
for obtaining maximum biofuel production. Use of non-renewable energy causes
green- house gas emissions, acid rain, depletion of ozone layer, and global
warming etc. Reducing the environmental pollution, overcoming the energy crisis
and decreasing the increase of global temperature can be possible by using
renewable energy.

1. Introduction
In the 21st century, energy instability and environmental pollutions are two of humanity’s major concern.
In order to lessen the reliance on fossil fuels, alternate energy sources must be explored by mitigating CO2
emissions and global warming. The key to improving the standard of living in underdeveloped countries
is to produce low-cost energy and to use bioenergy effectively (Garnier, 2014; Jacqueline et al., 2015,
Changhua et al., 1999).

Page | 1040
The rapid depletion of carbon-containing fossil resources causes the bound carbon to be released as CO2,
which causes global warming and climate change. Furthermore, once fossil fuels are depleted, there will
be a long-term shortage of energy carriers and excessive use of non-renewable energy might lead to energy
crisis issues (Wahyuni et al., 2011). One of the energy technologies that meet these parameters is
renewable energy. It is a viable alternative to traditional fossil-fuel-based energy, and it is generally less
destructive to the environment. Biomass, whose carbon neutral status is up for question, can be used to
make biofuels as a renewable gaseous fuel made from the anaerobic digestion of a wide range of livestock,
agricultural, municipal, and industrial feedstock (Al Mamun and Torii, 2015 and Lijo et al., 2017).
The anaerobic digestion generates bioenergy, mainly consists of CH4, CO2 and traces of other
contaminated gases (NNFCC, 2011). This bioenergy can be used directly, or refined to natural gas-
quality bio-methane, in combined heat and power gas engines (clarke-energy.com).

Anaerobic co-digestion is an appropriate and efficient method for the management of organic wastes,
and it is expected to play a significant part of renewable energy production in the future time (Surendra et
al., 2014; Appels et al., 2011; Buffiere et al., 2008; Ju et al., 2005).
The overall process of biofuel generation can be characterized by a chemical reaction in which anaerobic
microbes biochemically degrade organic materials such as glucose to produce carbon dioxide (CO2) and
methane (CH4).
C6H12O6 → 3CO2 + 3CH4 .....................................................................(1)
Hydrolysis
When water is broken down into H+ cations and OH- anions, a chemical event called hydrolysis occurs
which is the first step in anaerobic digestion. Some hydrolysis products, such as hydrogen and acetate, can
be used by methanogens later in the anaerobic digestion process.
The reactions 2 occurs during hydrolysis process,
Biomass + H2O → monomers+ H2 .................................................................... (2)
Acidogenesis
Acidogenic bacteria further break down of the biomass products by using the acidogenesis process. At the
time of producing H2S, H2, CO2, ammonia, shorter volatile fatty acids, alcohols, carbonic acids, and other
byproducts, these fermentative microbes create an acidic environmental condition in digestion tank.
Acetogenesis
Acetogenesis is the process through which acetogens convert carbon and energy into acetate and a
derivative of acetic acid. Most of the chemicals produced during acidogenesis are catabolized by these
bacteria into CO2, H2 and acetic acid.
Methanogenesis
Methanogenesis is the ultimate stage of anaerobic digestion, in which methanogens produce methane
from acetogenesis's final products and also some of the intermediate products of hydrolysis and
acidogenesis. Methane and CO2 are the two primary products of anaerobic digestion.
Animal waste makes up the majority of rumen digesta, could be a good source of renewable energy. After
preparing tea, tea waste is disposed of as slurry in open area increases anthropogenic emissions, soil and
water pollution, and unpleasant surroundings, among other things (Cooper et al., 2011). Converting this
waste into usable energy or a cost-effective product could help to alleviate the problem of disposal and
anthropogenic activity. Because of high nitrogen concentration, poultry droppings make a good and
abundant input material for anaerobic co-digestion also.
This research focused at how to reduce waste from slaughterhouses, poultry farms, and kitchens, as well
as the possibilities of producing biofuel from livestock, fish, and municipal solid waste to reduce
pollution.

Page | 1041
Objectives:
On the basis of above proposition, the study was undertaken -
• To investigate biofuel production rate through anaerobic co-digestion based on different
biodegradable wastes.
• To compare the biofuel production yield of different feedstock materials.
2. Experimental:
2.1 Sample preparation
In phase 1, rumen waste of cow (RWC) and goat (RWG), poultry droppings (PD) and spent tea waste
(STW) were weighted properly and three samples were made for fermentation process with a mixing ratio
of RWC:PD:STW in 1:1:1 (405 kg of each), RWG:PD:STW in 1:1:1 (405 kg of each) and
RWC:RWG:PD:STW in 1:1:1:1 (303 kg of each). In phase 2, three samples were made for fermentation
in the ratio of RWC:PD:STW:KW in 1:1:1:1 (303 kg of each), RWG:PD:STW:KW in 1:1:1:1 (303 kg
of each) and RWC:RWG:PD:STW:KW in 1:1:1:1:1 (243 kg of each). Each sample
was diluted with 1215 liters of water and mixed properly to get homogenous condition.
2.2 Materials
For conducting the experiment, cow and goat rumen waste was collected from slaughterhouse in
Shibganj. Poultry droppings and kitchen waste were collected from the Baluchor bazaar, and spent tea
waste was collected from tea stall in Tilagar.
2.3 Experimental procedure
For each observation, 3000 L digester, water cum gas chamber, and water collection were used. A
12.7 mm GI pipe connected the digester to the water cum gas chamber to pipe the generated gas from the
digester to the water chamber. Gas creates pressure in the water chamber, forcing the same volume of
water to flow through another 10 mm hose line to the water collector. The top of the water chamber was
attached to one end of the digester, while the other end was connected to the water collector. To control
the flow of produced gas, a gas control valve was added to GI pipe. A thermometer, glass tube, gas
pressure gauge, gas flow control valve, graduated plastic bucket, beaker, and hosepipe were also utilized in
the experiment. During the research period, biofuel production was monitored for 30 days using water
displacement method.

Page | 1042
2.4 Sample size

A fixed-dome biogas plant of 3000L in


volume with a fixed, non-movable gasholder
GI was employed in this experiment. The plant
Pip Hose Pipe
e
was constructed underground to protect it
Water from physical damage and saving space. A
Collector 12.7 mm GI pipe was utilized to connect the
digester to the water cum gas chamber and 10
mm hose pipe was used to collect biofuel in
the form of biogas in the upper part of the
digester. The slurry was moved into the
compensating tank when gas productionbegan.

Dige Water
ster chamber

Figure 1: Schematic diagram of experimental set up


4. Result and Discussions
4.1 Comparative Biofuel Production Profile
The comparative production of
250 biofuel in phase 1 is shown in
figure 2. The biofuel production
200
began with the quick
Production of Biofuel

150
decomposition of undigested
RWC, RWG, STW, and PD
100 feedstock. For RWC, STW, and
PD, production began on the 2nd
50 operating day as shown by red line
(L)

in graph. The highest biofuel


0 output of 228 L/day at 14th day and
0 5 1 15 2 2 3 average output was 71.32 L. The
0 0 5 0 biofuel production from RWG,
Time (Days)
RWC, STW & PD RWG, STW
STW and PD is shown by green
& PD line in fig. 2. The maximum
RWC, RWG, STW & PD biofuel production was measured
Figure 2: The comparative biofuel production profile in 36.1 L/day at 2nd day of digestion.
phase 1.

Page | 1043
After the 2nd day of digestion, breakdown of undigested feedstock was started by fermentative
bacteria present in the bio-digester and production was decreasing. It started to increase from 4th day and
highest production was obtained 33 L/day at 14th day. The average gas production was 15.55 L/day. The
production of biofuel from RWC, RWG, STW and PD is shown by purple line in fig. 2. The maximum
production was 2.7 L/day at 17th day and average production was 0.85 L/day.
According to this study, the production of biofuel from RWC, STW, and PD was higher than the
production of biofuel from RWG, STW, and PD.

Biofuel production from co-


250 digestion of RWC, RWG, STW, PD
and KW is shown in fig. 3. In this
Production of Biofuel

200
phase, kitchen waste was added
150 with other undigested feedstock for
observing the difference in biofuel
(L)

100 production rate from phase 1. For


50 RWC, STW, PD and KW, biofuel
production started from the 2nd
0 operating day as shown by red line
0 5 1 1 2 2 3 in fig. 3. The maximum production
0 5 0 5 0 was 145 L/day on 17th day and
Time (Days) average production was 34.67
RWC, STW,PD & RWG, STW, PD & L/day. The biofuel production from
KW
RWC, RWG, STW, PD & KW
KW RWG, STW, PD and KW is shown
by green line in fig. 3.
Figure 3: The comparative biofuel production profile in
phase 2.
The production of biofuel was started from the beginning day and production rate was 191.67 L/day due
to production of trace amount of O2, N2, CO2, H2 and CO. The greatest biofuel output was 200.67 L/day
on the 5th day and average biofuel output was 75.31 L/day. The purple line in fig. 4 shows the production
of biofuel from RWC, RWG, STW, PD and KW. The maximum production of biofuel was 102 L/day at 2nd
day and average production was 14.63 L/day. This experiment shows that the production of biofuel from
RWG, STW, PD and KW was more than the production from RWC, STW, PD and KW, and production
from RWC, RWG, STW, PD and KW.

4.2 Comparison Profile of Biofuel Generation


In phase 1, figure 4 depicts the
difference in biofuel output after
1600 every 10 days. This graph shows
Production of Biofuel

1400 that production was minimal after


1200 10 days in all digesters except the
1000 one that was loaded with RWC,
(L)

800 STW, and PD. The chart also


600
demonstrates that biofuel
400
production from RWC, STW, and
200
0
PD grew in the 2nd 10 days due to
(1-10 ) (11-20) (21-30)
the digestion of undigested
feedstock such grass, straw, grain,
Time (Days) and so on, and then declined in the
RWC, STW & PD RWG, STW & PD RWC, RWG, STW & PD last 10 days due to the high
decomposition rate.
Figure 4: Variation of biofuel production in every 10 days (Phase
1).
Biofuel production was high in 2nd and 3rd 10 days than 1st 10 days for RWC, STW and PD. Production
of biofuel from RWG, STW and PD was low in 1st and 3rd 10 days and high in 2nd 10 days. The figure
shows that production of biofuel RWC, RWG, STW and PD was firstly low in 1 st 10 days and gradually
increasing in 2nd 10 days because of co-digestion of all substrates.
Page | 1044
1800 In the second phase, fig. 5 depicts the
1600 variation in biofuel production after
Production of Biofuel1400 every 10 days. In 1st 10 days, highest
1200 biofuel production was obtained from
1000 RWG, STW, PD and KW due highest
800 decomposition rate of these substrates.
600 In 2nd 10 days, production was started to
400 decrease in digester filled with RWG,
200 STW, PD and KW and the digester
(L)

0 filled with RWC, RWG, STW, PD and


(1-10) (11-20) (21-30) KW due to high digestion rate in first 10
Time (Days) days. But production was increasing in
RWC, STW, PD & KW RWG, STW, PD & KW digester that was filled with RWC,
RWC, RWG, STW, PD & KW
STW, PD and KW.
Figure 5: Variation of biofuel production in every 10 days (Phase 2).
In last 10 operating days, biofuel production was lower in every digester. Among the three digesters filled
with substrates, highest production was found in RWC, STW, PD and KW. The highest biofuel
production was found 1744.34 L/day from RWG, STW, PD and KW in 1st 10 days, 921.9 L/day from
RWC, STW, PD and KW in 2nd 10 days and 122.7 L/day from RWC, STW, PD and KW in last 10 days.
4.3 Cumulative Biofuel Production Profile
Figure 6 represent the cumulative
biofuel production from (RWC, STW
2500
Cumulative Production of

and PD), (RWG, STW and PD) and


2000 (RWC, RWG, STW and PD). The
figure shows that cumulative
Biofuel (L)

1500
production was 2139.4 L/day for
1000 RWC, STW and PD, 466.5 4 L/day
500 from RWG, STW and PD, and 27.9
L/day for RWC, RWG, STW and PD.
0 Biofuel production was high in RWC,
0 5 10 15 20 2 3 STW and PD and low in RWC,
5 0 RWG, STW and PD. For this reason,
Time (Days)
the line for RWC, STW and PD is
RWC, STW & PD RWG, STW & PD
RWC, RWG, STW & PD upward while RWC, RWG, STW and
PD line is at the bottom area in the
Figure 6: Cumulative Biofuel Production Rate (Phase cumulative graph shown in fig. 6.
1).
2500 Figure 7 shows the cumulative
Cumulative Production of

2000
biofuel production from (RWC,
STW, PD and KW), (RWG, STW,
Biofuel (L)

1500 PD and KW) and (RWC, RWG,


STW, PD and KW).The figure shows
1000
that cumulative production of
500 1173.23 L/day from RWC, STW, PD
and KW, 2261.33 L/day from RWG,
0 STW, PD and KW, and 438.93 L/day
0 5 10 15 20 25 30 from RWC, RWG, STW, PD and
Time (Days) KW. Figure 7 shows that highest
RWC, STW, PD & KW
RWG, STW, PD & KW cumulative production was obtained
RWC, RWG, STW, PD & from RWG, STW, PD and KW
KW
indicated by an upward curve. The
biofuel production in digester filled
Figure 7: Cumulative Biofuel Production Rate (Phase with RWC, RWG, STW, PD and KW
2). was increased gradually. Page | 1045
And after maximum decomposition it gradually became zero. So a stable curve is found for RWC,
RWG, STW, PD and KW in fig. 7.
5. Conclusion
Biofuel production technology has the potential to alleviate a number of issues related to ecological
imbalance, reducing critical fuel demand, improving hygiene and health, and thus improving the overall
quality of life in rural and semi-urban areas in both developed and developing countries. In this study,
anaerobic co-digestion technology was applied in two different stages. In phase 1, highest biofuel
production of 228 L/day was obtained from RWC, PD and STW. In phase 2, highest biofuel production of
200.67 L/day was obtained from RWG, PD, STW and KW. The goal of this research is to produce biofuel
from various feedstocks that could be used to generate renewable energy and reduce environmental
pollution.
Acknowledgement
This research was supported by the Ministry of Science and Technology, and Sylhet Agricultural
University. The authors would like to thank Afroja Kabir Lucky for her cooperation during sample
collection and preparation.

References
1. Al Mamun M.R., Torii S., Enhancement of production and upgradation of biogas using different
techniques–A review, International Journal of Earth Sciences and Engineering. 2015, 8(2); 877-92.
"Anaerobic Digestion". NNFCC Renewable Fuels and Energy Factsheet. National Non-Food Crops
Centre. Retrieved 22 November 2011.
2. Appels L., Lauwers J., Degreve J. et al., Anaerobic digestion in global bio-energy production:potential
and research challenges, Renewable and Sustain Energy Reviews. 2011, 15(9); 4295–4301. Buffiere
P., Mirquez L.D., Steyer J.P. et al., Anaerobic digestion of solid wastes needs research to face an
increasing industrial success, International Journal of Chemical Reactor Engineering. 2008, 6(1).
3. Cooper J.M., Butler G., Leifert C., Life cycle analysis of greenhouse gas emissions from organic and
conventional food production systems, with and without bio-energy options, NJAS-Wageningen
Journal of Life Sciences. 2011, 58(3-4); 185-192.
4. Garnier G., Grand challenges in chemical engineering, Frontiers in chemistry. 2014, 2; 17.
5. "Jenbacher Gas Engines". clarke-energy.com.
6. Ju X., Zhang F., Bao X. et al., Utilization and management of organic wastes in Chinese agriculture:
Past, present and perspectives, Science in China Series C: Life Sciences. 2005, 48(2); 965-979.
7. Lijo L., Gonzalez-Garcia S., Bacenetti J. et al., The environmental effect of substituting energy crops
for food waste as feedstock for biogas production, Energy. 2017, 137; 1130-1143.
8. Surendra K.C., Takara D., Hashimoto A.G. et al., Biogas as a sustainable energy source for
developing countries: Opportunities and challenges, Renewable and Sustainable Energy Reviews.
2014, 31; 846-859 Wahyuni, S., Biogas energi terbarukan ramah lingkungan dan
berkelanjutan. Kongres Ilmu Pengetahuan Nasional (KIPNAS), 2011

Page | 1046
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 154

Experimental Study of Rock Size Effects on Tensile StrengthUsing


the Brazilian Test

Mohammad Islam Miah*, Tirtho Bormon, Rahat Iqbal and MohammedAdnan Noor
Abir

Department of Petroleum and Mining Engineering,


ChittagongUniversity of Engineering and Technology, Chattogram 4349, Bangladesh
Email: islam.m@cuet.ac.bd, tirtho127@gmail.com, rahatiqbal54@gmail.com, adnan@cuet.ac.bd
*Corresponding author:[ Mohammad Islam Miah]

Keywords: Abstract: The rock strength parameters including tensile strength are crucialvariables to
investigate wellbore failure modes as well as rock stability of petroleum, mining and
● Sedimentary rocks;
geotechnical engineering exploration and design projects, respectively. The main focus
● Rock strengths; of the study is to investigate the effect of rock specimen sizes to obtain the tensile
strength of sedimentary rocks. To accomplish the research objective, the sedimentary
● Wellbore stability;
rock samples are collected from the Sahasradhara Jhorna which is located in the
● Geomechanics; Sitakunda Eco Park and Botanical Garden of Chittagong Hill Tracts area. The Brazilian
disc (indirect) test method is applied to measure the tensile strength of sandstone and
siltstone rock samples using rock mechanics testing machine by following standard
procedures. Additionally, numerous rock (disc) samples are prepared using rock sample
preparation units of different sizes (such as 25mm, 38mm, 50mm, and 55mm diameter)
with a diameter/thickness ratio of 2. According to the experimental results, it is found
that the magnitude of tensile strength significantly varied with rock sample sizes and
averaged 1.47-6.72 MPa for sedimentary rocks of the Sahasradhara Jhorna area.
Meanwhile, the tensile strength of the rocks is increasing with the ratio of disc thickness
and diameter. The petroleum and mining engineers can apply the studied systematic
procedures to estimate rock mechanical properties and also investigate rock
failure patterns as well as wellbore stability analysis during drilling operations and mine
design with the same specimens of sedimentary formations.

1. Introduction
Tensile strength is crucial and often the most critical factor in mining engineering, because rocks are
frequently weaker in tension than in compression or shear. Furthermore, tensile failure has a significant
impact on numerous mining engineering tasks, including rock drilling, cutting, and blasting, wellbore or
tunnel hydraulic fracturing, rock slope exploitation, and subterranean structure excavation (Jiang et al.,
2021). The essential properties of rock masses are also described by tensile strength, whereas the
maximum tensile stress that a rock material can withstand is

Page | 1047
typically defined as its tensile strength (Demirdag et al., 2019). As a result, correct calculation of tensile
strength is important for structural analysis and sustaining design in many rock-related engineering
disciplines.
There are two methods of direct and indirect tensile test are commonly used for determination of tensile
strength of rocks. The most common two indirect tensile test are the Brazilian test and the three-point
bending test (Jiang et al. 2021). The direct tensile test is the most reliable method for determining tensile
strength since its mechanical mechanism is unaffected by other influences after the test is fully
conducted. Because direct tensile testing is difficult, indirect tensile testing, often known as the Brazilian
test, is a popular alternative. The mechanical characteristics of intact rocks have been shown to be
significantly affected by changes in size or scale (Zhai et al., 2020). This is significant because the
process of intact rock characterization frequently begins in the laboratory and is subsequently extended
to the fieldwork context. It is difficult to test a complete rock at the size of a field scale in a laboratory
because to the restrictions imposed by the environment. Using a suitable size effect model, which is first
evaluated against laboratory testing and then used to calculate the mechanical characteristics of rock
mass in the area of field scale, may overcome this problem. There are now three primary size effect
models such as Weibull (1939), Hoek and Brown (1980), and Carpinteri (1995) available for
extrapolating laboratory results to the outdoor context (Darlington et al., 2011; Masoumi et al., 2011, Li
and Wong, 2013).
The main focus of the current study is to investigate the effect of rock specimen sizes to measure the
tensile strength of sedimentary rocks in the area of Sitakunda hilly, Chattogram.

2. Literature Review
2.1 Previous Study
The influence of size on the tensile strength of Brazilian rocks has received very little attention, with the
majority of prior research focusing on concrete. Previous research on the influence of sample size on
tensile strength has yielded mixed results. Some studies suggest that tensile strength falls as sample
diameter increases, whereas others show no scaling impact on a tensile strength increase. Furthermore,
the majority of these researches focused on a narrow range of sample diameters, and there is no unified
and commonly recognized tensile scale effect model. Only a few researches on the influence of
specimen size on tensile strength of intact rock have been conducted in comparison to studies on the
effect of specimen size on compressive strength. Nishimatsu et al. (1969) and Lundborg (1967)
presented results, in which the tensile strength displays a clear downward trend with specimen size.
Furthermore, Masoumi et al. (2018) and Thuro et al. (2001) found that tensile strength decreases within a
given range of diameter, 19–118 mm and 50–80 mm, correspondingly. On the other hand, the tensile
strength data for the 145- mm-diameter samples analyzed by Masoumi et al. (2018) and the 30-mm-
diameter samples studied by Thuro et al. (2001), do not follow this pattern and are considerably
different from the results for practically all other sample (specimen) sizes (Kong, 2021). Additionally,
Masoumi et al. (2018) hypothesized that when the size of a specimen in a Brazilian disc test exceeds a
certain range, the failure pattern of the specimen may change. Recently, Jiang et al. (2022) investigated
the effects of heterogeneity on both macro and micro scale-based strength on the differences between
tensile tests of brittle rocks. It is concluded that the rock heterogeneity has pointedly effect on the dip
angle of rock cracks and also minor affect on the dip direction of the cracks.

Page | 1048
2.2 Relevant Theory for Tensile Strength Measurement
Tensile strength denotes to an object's breakdown capability when a pressure able to break numerous
strands of the element which is applied at a constant rate of extension/load. In laboratory, it is often
measured using two methods: (i) direct test and (ii) indirect test (Brazilian disk test). The Brazilian disk
test offers an indirect indication of tensile strength. The test can be accomplished on a core disk cut from
a core plug with a thickness (length) of roughly 0.5 the diameter of the plug (McPhee et al., 2015).
The Brazilian test is a straightforward indirect method which can be used not only for obtaining the
tensile strength of brittle materials but also concrete disc, sedimentary rocks, and rock-like materials
(Demirdag, 2019). A thin circular disc is diametrically crushed to failure in this indirect test. The most
four common loading configurations are depicted in Figure 1.

Figure 1: Typical Brazilian tensile test loading configurations


The indirect tensile strength is usually estimated using the assumption that failure occurs at the location
of maximal tensile stress with the disc's center. Based on the Brazilian test, the recommended formula
for estimating the splitting rock tensile strength σt (MPa) is (ISRM, 1977;Hatheway, 2009)
𝜎𝑡 =
2𝑃
= 0.636 ∗ (1)
𝜋 𝑃
𝐷
𝑡 𝐷∗𝑡

Where P is the load at failure (N), D is the test specimen's diameter (mm), and t is the test specimen's
thickness measured at the center (mm).
The Brazilian test is achieved on disk specimens that have been sliced and smoothened, whereas the
surface defects are smaller than 0.25 mm. Both surfaces must be parallel to within 0.25 degrees.
Samples must be representative of the rock material being studied. Visual inspection of the minerals and
grains can be used to make the selection, but faults like as fractures and voids should be avoided. A
sample's thickness must be between 0.2 and 0.75 times its diameter (less than 54 mm), with the ideal
rock thickness being around half of the diameter. At least three measurements are required to determine
the diameter and thickness to the closest 0.25 mm. The cylindrical specimen is put in a specifically
constructed cell that is made up of two steel components that are assembled so that they make contact
with the sample on two opposing ends.

3. Experimental Methodology
3.1 Sample Collection
In order to, performing Brazilian Test in the laboratory and to fulfill the objectives, authorscollected
the sedimentary rock samples. For this purpose, the samples were collected from

Page | 1049
“Sahassradhara Jhorna”, which is located in the “Sitakunda Eco Park and Botanical Garden” in
Chittagong. As the experiment is subjected with the different sample sizes enough, rock samples were
collected from the mentioned place. A list of rock samples was collected from different coordinates of
“Sahassradhara Jhorna”. From these samples, disc of different diameters was prepared for Brazilian
testing in the laboratory. The latitudes and longitudes of sample location were recorded by hand GPS.
3.2 Sample Preparation
Disc samples are made from the collected rock specimen in the laboratory. For this purpose, first authors
have plugged a core from collected rock specimen. As our goal is to investigate the size effect of rock
sample in determining tensile strength, the plug cutter of different diameter is used. The discs were
prepared core of 25 mm, 38 mm, 50 mm and 55 mm diameter with diamond coring bit in the rock
mechanics laboratory. Then these cores were cut to prepare disk of different thickness. The experiments
are maintained with thickness to diameter ratio of nearly about 0.5. After cutting the discs with proper
thickness to diameter ratio they have been dried in the oven before performing Brazilian Test. The disc
samples with different diameter are present in figures 2 and 3 also shows the discs with measured
thickness to maintain the ratio 0.5 (t/d ratio). There are total four group of discs specimen have been
prepared from the four different parent rock sample. Each group of specimens are containing with four
different diameter of discs which are 54 mm, 50 mm, 38 mm and the 25 mm, respectively.
Figure 2: Disc with different diameter Figure 3: Disc with different thickness

3.3 Brazilian Test


The disc samples are tested in a universal testing machine with uniaxial load. Flat platens were used to
set the disc in the machine. The disc samples were kept on the platens diametrically and the uniaxial line
load have been applied to determine the maximum load under which the rock can withstand. Figure 4
shows the discs specimen of different diameter are kept under the loading platens. All the discs have kept
diametrically to ensure the tensile failure of the discs. To reach preloading, slowly carried the loading
platens together until the top platen barely and gently contacts the specimen with little as well as no load
on it. After preloading, a continuously increasing compressive load have been applied maintaining 0.05
Mpa/s of loading rate. The maximum load sustained by the specimen has been recorded. Then using the
equation 1 the tensilestrength of each specimen is calculated.

Page | 1050
Figure 4: Disc samples under loading platen

4. Data Analysis and Results


The maximum load is obtained from the Brazilian test with different specimens and the calculated tensile
strength of each specimen which are presented in this section.
4.1 Load Calculation and Results
From the collected parent rock samples, four different diameter of disc specimen have been adopted in
the study. So, in each group of specimens there are discs of four different diameter such as 54 mm, 50
mm, 38 mm and 25 mm. From a list of collected samples, only reliable four samples have been selected
to prepare the discs of desired diameter. After conducting the Brazilian test, the tensile strength of each
disc of each group has been measured. From the experimental analysis, the summarized results (t/d ratio
=0.5) are given in tables 1 to 4.
Table 1: Test results of disc specimens of group 1

Sample Diameter Max load, P Tensile Strength


ID (mm) (KN) (MPa)
S1D1 54 3.5 1.473
S1D2 50 3.5 1.782
S1D3 38 3.3 2.9
S1D4 25 3.3 6.72
Average 3.4 3.14

Table 2: Test results of disc specimens of group 2

Sample Diameter Max load, P Tensile Strength


ID (mm) (KN) (MPa)
S2D1 54 3.62 1.58

Page | 1051
S2D2 50 3.43 1.74
S2D3 38 3.00 2.65
S2D4 25 2.80 5.94
Average 3.21 2.97

Table 3: Test results of disc specimens of group 3


Sample Diameter Max load, P Tensile Strength
ID (mm) (KN) (MPa)
S3D1 54 3.74 1.63
S3D2 50 3.46 1.76
S3D3 38 3.22 2.83
S3D4 25 2.76 5.85
Average 3.29 3.02

Table 4: Test results of disc specimen of group 4


Sample Diameter Max load, P Tensile Strength
ID (mm) (KN) (MPa)
S4D1 54 4.90 2.13
S4D2 50 4.56 2.32
S4D3 38 3.50 3.08
S4D4 25 3.20 6.79
Average 4.40 3.58
It is observed that the group 2 rock specimens produce the minimum tensile strength of average value of
2.97 MPa, whereas the group 4 rock specimens produce the maximum tensile strength of average value
of 3.58 MPa. As the rock sample of group four is stronger than the other groupof rock samples.

4.2 Size Effect on Tensile Strength


From the calculation of tensile strength of each group of discs, it is observed that the tensile strength
varies with the diameter. The tensile strength variation with the diameter of each group has been plotted
and also discussed in the below.
The graphical representation of calculated tensile strength with the various diameter of the discs of group
1 is shown figure 5. From the graph, it is observed that tensile strength of discs of group 1 sedimentary
rock is increasing with the decrease in specimen diameter. This shows a descending type relation for
tensile strength with the increase in diameter. From many previous studies, the researchers have got the
same descending type test results for weak sedimentary rocks. As per graph, we can see that the disc
sample diameter with 25 mm withstands against maximum tensile stress. It is because in the larger size
specimen there is the possibility of remain micro crakes more than the smaller specimen. As a result,
cracks initially occur at the larger specimen than thesmaller one. From the table 1, the maximum load for
the disc specimens are ranging from 3.3 to

Page | 1052
3.5 whereas it varies more when the tensile strength is calculated. The tensile strength of disc 25 mm is
6.72 MPa which is maximum whereas the tensile strength of disc 54 mm is 1.473 MPa which is
minimum. Similarly, the relationship between disc diameter and it’s tensile strengths is shown in Figures
6, 7 and 8 with different group of rock sample.

8 7
7 6
6 5
Tensile Strength

Tensile Strength
5 4
4
3
3
2 2
(Mpa)

(Mpa)
1 1
0 0
2 3 40 5 6 2 3 40 5 6
0 0 Diameter (mm) 0 0 0 0 0 0
Diameter
(mm)
Figure 5: Tensile strength variation with various Figure 6: Tensile strength variation with various
diameter (group 1) diameter (group 2)

7 8
6 7
5 6
Tensile Strength

5
4
Tensile strength

4
3
3
(Mpa)

2 2
(Mpa)

1 1
0 0
2 3 40 5 6 2 3 40 5 6
0 0 Diameter (mm) 0 0 0 0 Diameter (mm) 0 0

Figure 7: Tensile strength variation with various Figure 8: Tensile strength variation with various
diameter (group 3) diameter (group 4)

As per experimental results and graphical representation, it is found that the relationship trends between
tensile strength and disc diameters for all cases in the studied samples. As per Table 4 and Figure 8 for
group-4, the maximum load for the disc specimens are ranging from 3.20 to 4.90 whereas measured
tensile strength (average) is 3.58. The tensile strength of 25 mm disc (S4D4) is 6.79 MPa which is
maximum whereas the tensile strength of 54 mm disc (S4D1) is 2.13 MPa which is minimum. All four
group of discs shows the same, like tensile strength increases with the decrease in disc diameter. So, it is
noted that tensile strength depends on the specimen diameter. Furthermore, there is an effect of
specimen size in determination of tensile strength. It is because diameter is the key parameter which is
directly related to the volume of the specimen.

Page | 1053
5. Recommendations
This study was conducted with a little number of samples, it is recommended to study the size effect of
sedimentary rock with a large number of samples with different size (more than 4 groups and diameter
size). The laboratory test result should have to be compared with known size effect models to determine
the applicability of existing models. It is also important in order to extrapolate laboratory data in field
context. Additionally, after completing the test, the fractured degree and positioning can be investigating
to demonstrate the fracture pattern of each disc of thestudied samples.

Acknowledgment
We greatly appreciate to the University Grants Commission (UGC) of Bangladesh and Department of
Petroleum and Mining Engineering (PME), Chittagong University of Engineering and Technology
(CUET) for their financial assistance and research support during the study period.

References
1. Darlington, W. J., Ranjith, P. G., & Choi, S. K. (2011). The effect of specimen size on strength and
other properties in laboratory testing of rock and rock-like cementitious brittle materials. Rock
mechanics and rock engineering, 44(5), 513-529.
2. Demirdag, S., Tufekci, K., Sengun, N., Efe, T., & Altindag, R. (2019). Determination of the direct
tensile strength of granite rock by using a new dumbbell shape and its relationship with Brazilian
tensile strength. In IOP Conference Series: Earth and Environmental Science (Vol. 221, No. 1, p.
012094). IOP Publishing.
3. Durmeková, T., Bednarik, M., Dikejová, P., & Adamcová, R. (2021). Influence of Specimen Size
and Shape on the Uniaxial Compressive Strength Values of Rocks.
4. Hatheway, A. W. (2009). The complete ISRM suggested methods for rock characterization, testing
and monitoring; 1974–2006.
5. ISRM, (1977). Suggested methods for determining the strength of rock materials in triaxial
compression. Int. J. Rock Mech. Min. Sci. Geomech..15, 47-51.
6. Jiang, R., Duan, K., & Zhang, Q. (2022). Effect of Heterogeneity in Micro-Structure and Micro-
Strength on the Discrepancies Between Direct and Indirect Tensile Tests on Brittle Rock. Rock
Mechanics and Rock Engineering, 55(2), 981-1000.
7. Kong, X., Liu, Q., & Lu, H. (2021). Effects of rock specimen size on mechanical properties in
laboratory testing. Journal of Geotechnical and Geoenvironmental Engineering, 147(5), 04021013.
8. Li, D., & Wong, L. N. Y. (2013). The Brazilian disc test for rock mechanics applications: review
and new insights. Rock mechanics and rock engineering, 46(2), 269-287.
9. Masoumi, H., Roshan, H., Hedayat, A., & Hagan, P. C. (2018). Scale-size dependency of intact
rock under point-load and indirect tensile Brazilian testing. International Journal of Geomechanics,
18(3), 04018006.

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Science (Vol. 64, pp. 671-779). Elsevier.
11. Nishimatsu, Y., Yamaguchi, U., Motosugi, K., & Morita, M. (1969). The size effect andexperimental
error of the strength of rocks. J Soc Mater Sci Jpn, 18, 1019-1025.
12. Perras, M. A., & Diederichs, M. S. (2014). A review of the tensile strength of rock: concepts and
testing. Geotechnical and geological engineering, 32(2), 525-546.
13. Thuro, K., Plinninger, R. J., Zäh, S., & Schütz, S. (2001, June). Scale effects in rock strength
properties. Part 1: Unconfined compressive test and Brazilian test. In ISRM regional symposium,
EUROCK (pp. 169-174).
14. Zhai, H., Masoumi, H., Zoorabadi, M., & Canbulat, I. (2020). Size-dependent behaviour of weakintact
rocks. Rock Mechanics and Rock Engineering, 53(8), 3563-3587.
15. Zhang, Y., & Yu, D. (2019). Comparative study on the test method for tensile elastic modulus ofrock
materials. Advances in Civil Engineering, 2019.

Page | 1055
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 168

Effect of drying on physicochemical and antioxidant propertiesof


pomegranate peel

Md. Anarul Haque*, Animesh Sarkar, Mahabub Alam and Fiaz Bin Osman

Department of Food Engineering and Tea Technology,

Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh

Email: anarul09@student.sust.edu, animesh-fet@sust.edu, mahabub-fet@sust.edu,


fiaz38@student.sust.edu

* Corresponding author: [Md. Anarul Haque]

Abstract
Pomegranate peel is commonly disposed of as waste in household and food industries, creating a
post processing handling issue. It may be used in a variety of ways, but they all rely greatly on how
well they are dried before being used in other procedures. Determining the ideal drying conditions
for pomegranate peel is crucial. The purpose of this study was to compare the effects of four
different drying methods on the physicochemical characteristics of pomegranate peels. These four
methods of drying were sun drying, oven drying at 50 °C, microwave drying at 900 W, and freeze
drying. From these four different drying techniques the prepared dried pomegranate peel power were
subjected to analyze total phenolic content (TPC), total flavonoid content (TFC), total tannin content,
and vitamin C content using colorimetric methods while the antioxidant activities were measured by
radical scavenging activity (RSA) and ferric reducing antioxidant power (FRAP). The outcomes
showed that the freeze-drying technique had higher levels of physical, functional, chemical, and
antioxidant properties than the oven, solar, and microwave drying methods. Freeze dried peels
showed DPPH of 77.86%, total phenolic content of 186.24 mg GAE/g DM, Vitamin C of 77.5 mg
AA/100g DM, ferric reducing antioxidant power of 31.1 mg AAE/g DM which were significantly
higher than the others. Besides that, oven dried peel powder contained DPPH of 72.64%, total
phenolic content of 174.29 mg GAE/g DM, ferricreducing antioxidant power of 24.98 mg AAE/g
DM, and ash content of 4.30% which were significantly greater than those of solar and
microwave dried peel powder. Pomegranate peel might be used as an effective food ingredient
and/or as a potential by products in food industries.

Keywords: Pomegranate peel; Oven drying; Freeze drying; Microwave drying; Antioxidant
properties

Page | 1056
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 169

Thermo-sonication processing of beetroot juice: effect on


physicochemical properties, antioxidant activity, and analysis
on enzyme and microbial inactivation

Fiaz Bin Osman*, Animesh Sarkar, Mahabub Alam and Md. Anarul Haque

Department of Food Engineering and Tea Technology,

Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh

Email: fiaz38@student.sust.edu, animesh-fet@sust.edu, mahabub-fet@sust.edu,


anarul09@student.sust.edu

* Corresponding author: [Fiaz Bin Osman]

Abstract
Beetroot juice can be consumed alongside other processed items. Such items must be treated to
extend their shelf life and preserve their sensory qualities because of the rapid breakdown brought on
by microbial growth and enzyme activity. Therefore, in order to make beet juice widely accessible,
it is crucial to develop an effective preservation method. Modern technologies are available to
guarantee the quality and safety of processed foods. Thermosonication was taken intoconsideration as
a viable preservation method in our study since it can increase the inactivation rates of enzymes, kill
microorganisms, and improve the availability of bioactive substances. In this study, the impact of
thermosonication on physiological traits, antioxidant activities, microbes,and enzyme inhibition were
assessed. Samples were initially treated at 45, 50, and 55 ℃ and sonicated for 5, 10 and 15 minutes.
The results demonstrated that the combination of moderate heat treatment and sonication is
effective in generating more bioactive chemicals and ensuring maximal inactivation of enzymes and
microorganisms. It offers a rapid, reliable, and efficient technique to keep beetroot juices' quality
while also increasing their shelf life.

Keywords: Beetroot juice; Thermosonication; Physicochemical properties; Antioxidant properties;


Microbial and enzyme inhibition.

Page | 1057
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 186

Effect of in-situ methane (CH4) production on nitrogen (N2)


removal in a granular sludge reactor

Rahatun Akter*, Md. Mashiur Rahman Tusar, and Dr. Md. Salatul Islam Mozumder

Dept. of Chemical Engineering and Polymer Science,


Shahjalal University of Science andTechnology, Sylhet-3114,
Email: rahatun-cep@sust.edu, mashiur248@gmail.com, salatul- cep@sust.edu
* Corresponding author: [Rahatun Akter]

Abstract: This study deals with the influence of greenhouse gases, methanogenesis,
Keywords:
and denitrification through anaerobic methane oxidation on heterotrophic growth on
autotrophic nitrogen removal from wastewater. The activated sludge model-2 (ASM2)
● Greenhouse gases; for nitrification and denitrification in a granular sludge reactor was extended including
● Nitritation- nitrifier denitrification process, methanogenesis process that causes the coexistence of
denitrifying anaerobic methane-oxidizing (DAMO) bacteria, along with the autotrophic
denitrification;
and heterotrophic growth and decay in the granules from a partial nitrification-
● Aquasim Software; denitrification process. The constructed mathematical model was implemented in
AQUASIM Software; and MATLAB was used to evaluate the influence of dissolved
● Granular sludge
oxygen concentration, dissolved organic materials, and hydraulic retention time (HRT).
reactor; Compared to the conventional nitrification and denitrification in a single chamber
granular sludge reactor, while methanogenesis and denitrifying anaerobic methane
● Hydraulic
oxidation by bacteria was taken into account, at low oxygen concentration and high
Retention Time; influent organic carbon condition shows the production of nitrogen gas was mostly by
● Denitrifying anaerobic methane oxidizing bacteria. And, at high oxygen concentration and low
influent organic carbon condition, the nitrogen gas was produced by anoxic
Anaerobic Methane-
heterotrophs. Thus, a moderate amount of influent organic carbon and oxygen
oxidizing(DAMO)
concentration should be maintained. Increasing HRT increased the nitrogen removal
Bacteria. performance as well as 𝑁2 gas production by anaerobic methane oxidizing bacteria. But
higher hydraulic retention time increased the diffusion of oxygen and the efficiency of
nitrogen removal by anoxic heterotrophs decreases. So, a suitable hydraulic retention
time need to uphold.
Overall, a moderate HRT and an optimal influent organic carbon would be required for
efficient nitrogen removal.

1. Introduction
Due to the enormous water demand for the increasing population worldwide, massive wastewater is produced and
discharged. These wastewaters contain nitrogen pollutants either ammonium (𝑁𝐻+) form or 4 organic nitrogen
compounds which are ultimately converted to ammonium through hydrolysis. However, dissolved ammonium, a
highly detrimental element for aquatic life (Effler et al. 1990), is needed to remove from wastewater. Following
processes are mainly used to remove nitrogen from wastewater.

Page | 1058
1.1 Conventional nitrification-denitrification over nitrate
Biologically nitrification and denitrification are two individual processes that are carried out by distinct groups of
bacteria. Nitrification is a two-step aerobic microbial process in which two groups of chemolithoautotrophic
bacteria oxidize ammonia to nitrate.− Aerobic ammonia-oxidizing bacteria, (𝑋𝐴𝑂𝐵),
convert ammonium to nitrite ((𝑁𝑂 ) (𝐸𝑞. 𝑖_𝑎, 𝐸𝑞. 𝑖), which is then further oxidized to nitrate, (𝑁𝑂−),
2 3
(𝐸𝑞. 𝑖_𝑏) by nitrite oxidizing bacteria (𝑋𝑁𝑂𝐵) (Bock and Wagner 2001)(Koops and Pommerening-Röser2001).
Nitrification:

𝑁𝐻+ + 1.5 𝑂2 → 𝑁𝑂− + 𝐻2O + 2𝐻+ ....................... (𝑖_𝑎)


4 2
𝑁𝑂− + 0.5 𝑂2 → 𝑁𝑂− … … … … … … . (𝑖_𝑏)
2 3
Overall: 𝑁𝐻+ + 2 𝑂2 → 𝑁𝑂− + 𝐻2O + 𝐻+ ....................... (𝑖)
4 3
Denitrification: 𝑁𝑂3− + 𝐶 + 2𝐻+ → 𝐶𝑂2 + 0.5 𝑁2 + 𝐻2O ........................ (𝑖𝑖)
In the case of heterotrophic denitrification, nitrate is transformed to nitrogen gas (𝐸𝑞. 𝑖𝑖) by using four step
reduction processes. In 𝐸𝑞. 𝑖𝑖, C denotes the carbon source; for autotrophic denitrification it is carbon
dioxide (𝐶𝑂2) and for heterotrophic it is organic carbon., In this step, nitrogen gas (𝑁2) is generated by
converting nitrate (𝑁𝑂3−) over nitrite (𝑁𝑂−2 ), nitric oxide (𝑁𝑂) and nitrous oxide (𝑁2O). Each reduction
step is catalyzed by different enzymes (Baumann et al. 1997). This conventional biological nitrification and
denitrification process is considered as more favorable than the chemical nitrogen removal by magnesium-
ammonium-phosphate (MAP) precipitation or by air stripping (Siegrist 1996) for the removal of ammoniumnitrogen
from the wastewater (De Clippeleir et al. 2013)(Gilbert et al. 2015) (Strous et al. 1998)(Lotti et al.2014). However,
eventual emission of intermediate denitrification intermediate products, NO or 𝑁2O, to the atmosphere is highly
undesirable because 𝑁2O is a powerful greenhouse gas which is 298 times strongerthan carbon dioxide over a 100-
year time frame (IPCC, 2013).
Ammonium in a concentrated stream is oxidized to nitrite only (𝐸𝑞. 𝑖_𝑎) by controlling the aeration, saving up to
25% aeration cost. The denitrification of nitrite to nitrogen gas is based on external carbon source (𝐸𝑞. 𝑖𝑖𝑖).
2𝑁𝑂 + 0.5 𝐶 + 𝐻 → 𝐶𝑂2 + 𝑁2 + 𝐻2O ........................ (𝑖𝑖𝑖)
− +

Nitrification-denitrification over nitrite needs less external carbon source, saving 40% cost for external
carbon. Moreover, the process emits less carbon dioxide (𝐶𝑂2) and produces less sludge compared to
conventional nitrification-denitrification over nitrate.
1.2 Anaerobic ammonium oxidation (Anammox)
As it was believed until early 1990s, the oxidation of ammonium could only proceed under aerobic conditions.
The concept of the anaerobic ammonium oxidation process (Mulder et al. 1995) dramatically changed the
biological nitrogen removal process. In this process, nitrite and ammonium are directly converted into Nitrogen
gas. The overall reaction is follows:

𝑁𝐻+ + 1.32 𝑁𝑂− + 0.13 𝐻+ → 1.02 𝑁2 + 0.26 𝑁𝑂− + 2.03 𝐻2O (𝑖𝑣)
4 2 3
(Strous et al. 1998) found NO as an intermediate product of the anammox process. As the process is anoxic,
anammox bacteria do not need oxygen which results in decreased aeration costs. Furthermore, anammox bacteria
use 𝐶𝑂2 as a carbon source and hence they do not require the addition of organic compounds. They grow relatively
slowly, leading to a low sludge production.
1.3 Partial nitritation combined with anaerobic ammonium oxidation
To remove nitrogen / ammonium from wastewater more efficiently, the anammox process can be combined with
nitritation process in which ammonium is converted to nitrite (𝐸𝑞. 𝑖_𝑎) by using AOB (Mulder et al. 1995). In the
next step, the resulting nitrite and unconverted ammonium are converted to nitrogen gas in the anammox process
(𝐸𝑞. 𝑖𝑣). The overall process stoichiometry becomes (𝐸𝑞. 𝑖_𝑎 + 𝐸𝑞. 𝑖𝑣).
𝑁𝐻+ + 0.75 𝑂2 + 𝐻𝐶𝑂− → 0.5 𝑁2 + 𝐶𝑂− + 2.5 𝐻2O ....................... (𝑣)
4 3 2

Page | 1059
This combined process requires 63% less oxygen with no additional organic carbon source. Besides, these
processes can take place in a single reactor in which AOB and anammox coexist in a biofilm or form compact
granules. Batch experiments and microbial analysis showed that nitrite is at the outer biofilm layer under aerobic
conditions. The remaining ammonium and nitrite diffuse into the deeper part of the biofilm where anoxic
conditions are maintained and nitrite acts as an electron acceptor, reacting with the remaining ammonium to form
nitrogen gas (Koch et al. 2000). The success of partial nitritation-anammox process depends first of all on the
continuous suppression of nitrite oxidizers and, secondly on the produced nitrite to ammonium ratio ( 𝐸𝑞. 𝑖𝑣)
(Dapena-Mora et al. 2007) (Jung et al. 2007) (Strous et al. 1998).
1.4 Relation between influent organic carbon and biological nitrogen removal
Both autotrophic and heterotrophic bacteria are utilized in the case of conventional nitrogen removal nitrification-
denitrification process. In this case, nitrification is autotrophic while denitrification is heterotrophic and requires
external organic carbon. In case of completely autotrophic nitrogen removal through partial nitritation-anammox,
no organic carbon source is required. In this process, even if the influent does not contain organic carbon,
heterotrophic growth is possible by generating organic material from biomass decay (Lackner, Terada, and Smets
2008) and/or on excretion of the living cells (Rittmann et al. 1999).
The influent COD/N ratio is a very important factor for the biological nitrogen removal processes which affects
both nitrifying and denitrifying bacterial population growth in the system. In a granular sludge reactor the
performance of both AOB and NOB significantly increased with a decreasing influent COD/N ratio from 20 to 3.3
(Yang, Tay, and Liu 2004). Besides that the amount of oxygen used by nitrifying bacteria increased with
decreasing COD/N ratio level whereas the specific heterotrophic oxygen utilization rate tended to decrease (Yang,
Tay, and Liu 2004). Therefore, higher COD/N ratio is favorable for heterotrophic population. Moreover, use of
high organic carbon enhances the heterotrophic bacteria growth which in turn competed with ammonium oxidizing
bacteria for oxygen.

Figure 1.1. Full reaction scheme of this study.


This study aims to develop a mathematical model to describe the in-situ methane production and nitrogen removal
efficiency in a granular sludge reactor. The developed model with well identified parameter values was used to
predict distribution of biomass fraction inside granules. Mode simulations were also run to evaluate the impact of
varying hydraulic retention times (HRTs), dissolved oxygen concentration, different substrate condition, and
different granule size. The developed model is expected to gain an enhanced understanding to pave the way for its
implementation in practice.

Page | 1060
2. Materials and Methods
2.1 Model development
The activated sludge model 2 (ASM-2) was based on the autotrophic and heterotrophic growth and decay in the
granules from a nitrification-denitrification process (Henze et al. 2015). This study extends the ASM- 2 for
nitrification and denitrification process by including nitrifier denitrification (ND) process and methanogenesis
process that causes the coexistence of denitrifying anaerobic methane-oxidizing (DAMO)bacteria.
2.2 Process stoichiometry and kinetics
To assess the effect of methane, eight different types of bacteria such as, ammonium oxidizing bacteria (𝑋𝐴𝑂𝐵),
nitrite oxidizing bacteria (𝑋𝑁𝑂𝐵), aerobic heterotrophic bacteria (𝑋𝐻_𝐴) methanogenesis bacteria (𝑋𝐶𝐻4), anoxic
heterotrophs on consuming substrate (𝑆𝑆), and 𝑁𝑂− (𝑋𝐻_𝑁𝑂3), anoxic 3 heterotrophs on 𝑆𝑆 and 𝑁𝑂− (𝑋𝐻_𝑁𝑂2),
denitrification
2 anaerobic methane oxidizing (DAMO) bacteria (𝑋𝐷𝑏) and denitrification anaerobic methane
oxidizing (DAMO) archaea (𝑋𝐷𝑎) were considered in this extended model.
Nitrification is a two-step process: the growth of 𝑋𝐴𝑂𝐵, ammonium was oxidized to nitrite, followed by the
oxidation of nitrite to nitrate by 𝑋𝑁𝑂𝐵. Methanogenesis process was conducted under anaerobic condition
consuming substrate 𝑆𝑆 and produces 𝐶𝐻4 gas by the growth of methanogens (𝑋𝐶𝐻4). Denitrification process is
occurred by the growth of two different types of bacteria. Denitrification through anaerobic methane oxidizing
(DAMO) archaea (𝑋𝐷𝑎), is generated by the consumption of 𝐶𝐻4, produce nitrite (𝑁𝑂−) using nitrate (𝑁𝑂 −
2 ) as the
electron acceptor 3and denitrification through anaerobic methane oxidizing (DAMO) bacteria (𝑋𝐷𝑏) originated
from 𝐶𝐻4, produce nitrogen gas (𝑁2_𝐶𝐻4) using nitrite (𝑁𝑂−) under anoxic condition. Besides, 2 heterotrophic
bacteria can be grown under both aerobic and anoxic conditions. Organic carbon is the mere source of
heterotrophic growth which can be initially present in reactor influentor originated from biomass decay.

Figure 2.1. Schematic representation of the model.


The existence of dissolved oxygen (DO) yields aerobic heterotrophs (𝑋𝐻_𝐴) on 𝑆𝑆. The deficiency of DO causes
nitrite (𝑁𝑂−) or nitrate
2
(𝑁𝑂−) as an3electron acceptor. Therefore, two different anoxic heterotrophs:
(i) anoxic heterotrophs on 𝑆𝑆 and 𝑁𝑂− (𝑋𝐻_𝑁𝑂3) and (ii) anoxic heterotrophs on 𝑆𝑆 and 𝑁𝑂− (𝑋𝐻_𝑁𝑂2)
3 2
were produced. 𝑋𝐻_𝑁𝑂3 produced nitrite (𝑁𝑂−) using nitrate (𝑁𝑂−) as the electron acceptor and 𝑋𝐻_𝑁𝑂2
2 3
produced nitrogen gas (𝑁2) using nitrite (𝑁𝑂2−) under anoxic condition.
The death-regeneration concept has been used to model biomass decay, which comprises a transition of live cells to
substrate as well as a fraction of inert material produced by microbe decay and/or hydrolysis (Van Loosdrecht and
Henze 1999). First-order kinetics govern all decay processes, which convert biomass to inert and organic
particles. Hydrolysis of particulate organics produces soluble organic substrate, which is consumed by
heterotrophic bacteria. In the decay and hydrolysis stages, decay is the rate-limiting step.

Page | 1061
Furthermore, under the death-regeneration notion, hydrolysis is associated with degradation. As a result,
hydrolysis was not taken into account in this model, and soluble organic substrate was originated directly from
biomass decomposition (Mozumder et al. 2014).
The stoichiometric matrix format was outlined in supplementary section Table_S 1 and Table_S 2 (supplementary
material) which gives the process rate expressions. The values for kinetic and stoichiometric parameters were
based on literature (Pocquet et al. 2016)(Strous et al. 1998)(Van Loosdrecht and Henze 1999)(Mozumder et al.
2014)(Join et al. 2017). Eighteen processes are included in this model. The growth and decay of 𝑋𝐴𝑂𝐵 and 𝑋𝑁𝑂𝐵
were considered in autotrophic process. The heterotrophic process
comprises growth and decay of 𝑋𝐻_𝐴, 𝑋𝐻_𝑁𝑂2 and 𝑋𝐻_𝑁𝑂3. The nitrifier denitrification (ND) process was
based on (Pocquet et al. 2016), where the effect of DO on the kinetics of the ND pathway was introduced by
Haldane kinetics. Conforming the hypothesis, the deficiency of DO stimulates 𝑁2O production by ND pathway
and presence of higher amount of DO inhibits it (Guo and Vanrolleghem 2014). Methanogenesis and
denitrification through anaerobic methane oxidation processes include growth and decay of 𝑋𝐶𝐻4, 𝑋𝐷𝑎and 𝑋𝐷𝑏.
2.3 Reactor configuration, simulation parameters and initial conditions
A one-dimensional biofilm model, based on just radial gradients, was created to represent the interplay of
autotrophic, heterotrophic, methanogenesis, and DAMO in a granular sludge reactor. Aquasim software was used
to implement the model (Reichert, von Schulthess, and Wild 1995). A set volume of 400 𝑚3 was used in the
reactor. Spherical biomass particles (granules) with initial radius 0.10 mm were grown to a predetermined steady
state granule radius, (particulate radius, 𝑟𝑝 between 0.75 mm and 2.75 mm). The oxygen level in the bulk liquid
was kept at a constant level (between 0.1 and 4.00 g O2/𝑚3).
Assuming that, biomass granules were typically thick, with very small pores, and no significant suspendedparticles
motion. In addition, the biofilm porosity was assumed to be constant (𝜀𝑤 =0.75), with the initial proportions of
particle components determining its value.
The reactor with a flow rate of 2500 𝑚3𝑑−1 was modelled for an influent containing mostly ammonium. The
influent ammonium content was 100 g 𝑁𝑚−3 throughout the operation, assuming no nitrite or nitrate was present
initially. The hydraulic retention time was varied from 2 hours to 24 hours. The oxygen concentrations ranged
from 0.1 to 3.0 g 𝑂2/𝑚3 for the most part. The concentration of quickly degradable organic substrate was changed
from 100 to 800 g COD/𝑚3 to observe the behavior of the reactor performance. The processes were run at 30 ˚C,
and simulations were performed for several years of operation to ensure steady state conditions.

3. Result and Discussions


3.1 Effect of oxygen concentration on substrate and biomass fraction on nitrogen removal
To evaluate the effect of oxygen concentration on substrate and biomass fraction in this model, a series of
simulations were performed for an influent containing 100 𝑁𝐻4+_𝑁/𝑚3 ammonium-nitrogen and 300
𝑔𝐶𝑂𝐷/𝑚3 influent organic carbon. The steady-state model behavior was outlined in Figure 3.1 and Figure
3.2 with a fixed hydraulic retention time 6h and varying bulk oxygen concentration from 0.1 to 1.0 𝑔𝑂2/𝑚3. Figure
3.1 showed the steady-state concentration of different nitrogen forms and 𝑁2 production through nitrification-
denitrification, heterotrophic denitrification and methanogenesis process.

Page | 1062
2 0.1 AOB
NH4
5 NOB
0 X_H
0.08 X_H_NO2
NO2
200 NO3 X_H_NO3
S_S 0.06 X_CH4
N2_CH4
Concentration

150 N2_N2O
N2_NO2 0.04

Biomass
Fraction
N2_total
[𝑔𝑁/𝑚3]

100 CH4
0.02

50 0
0.1 0.2 0.3 0.45 0.55 0.65 0.85
0
Oxygen Concentration [𝑔O2/𝑚3]
0 0.2 0.3 0.45 0.55 0.65 1
. 0.85
1 Oxygen Concentration
[𝑔O2/𝑚3]
Figure 3. 1. Effect of 𝑶𝟐 concentration on substrate. Figure 3. 2. Effect of 𝑶𝟐 concentration on biomass
(Process conditions: S_in = 300 𝒈𝑪𝑶𝑫/𝒎𝟑; 𝑵𝑯𝟒_𝒊𝒏 = fraction. (Process conditions: S_in = 300 𝒈𝑪𝑶𝑫/𝒎𝟑;
100 𝑵𝑯𝟒+_𝑵/𝒎𝟑; HRT = 6h). 𝑵𝑯𝟒_𝒊𝒏 = 100 𝑵𝑯𝟒+_𝑵/𝒎𝟑; HRT = 6h).

From figure 3.1, the maximum nitrogen removal (98%) as 𝑁2 gas was observed at oxygen concentration
0.55 𝑔 𝑂2/𝑚3. Increasing oxygen concentration gave advantages firstly to AOB and then to NOB, enhanced the
nitrate and nitrite accumulation for 0.6 – 0.9 𝑔𝑂2/𝑚3 and above 0.8 𝑔 𝑂2/𝑚3, ammonium was almost fully
converted to nitrate. AOB fraction in the granules was not changed with further increasing
of oxygen concentration. The 𝑁2 production was directly correlated to the anoxic heterotrophic organism on 𝑁𝑂−
2 ). Insignificant amount of anoxic heterotrophic organism on 𝑁𝑂 (𝑋𝐻_𝑁𝑂3
(𝑋𝐻_𝑁𝑂2 −
3 ) indicated that
the major nitrogen removal steps were ammonium oxidation to nitrite by AOB and then nitrite to 𝑁2 gas by
𝑋𝐻_𝑁𝑂2 .
Considering methanogenesis, denitrifying anaerobic methane oxidation (DAMO) by archaea and bacteria
in the granular sludge reactor, maximum removal of 𝑁2 due to 𝐶𝐻4 production (92-97%) was achieved by
maintaining oxygen concentration 0.2 – 0.6 𝑔𝑂2/𝑚3 (Figure 3. 2). The difference between the nitrogen removal
and conversion to N2 gas was due to the consumption of nitrogen for microbial body cells. At a low oxygen
concentration (< 0.45 𝑔𝑂2/𝑚3) methanogenesis was more active to produce methane from organic carbon source
and the 𝑁2 gas production was mainly followed denitrifying anaerobic methane oxidation (DAMO) by bacteria
(𝑋𝐷𝑏); methane was oxidized by 𝑁𝑂− to produce 𝑁2 gas (𝑁2_𝐶𝐻4). 2
Above 0.85 𝑔𝑂2/𝑚3 oxygen concentration, sufficient nitrite was produced to enhanced the growth of
𝑋𝐻_𝑁𝑂2 that also enhanced the nitrogen removal. The maximum concentration 𝑋𝐻_𝑁𝑂2 was observed at 0.65
𝑔𝑂2/𝑚3 (Figure 3. 2) and was the cause for the maximum nitrogen removal from 2 𝑁𝑂 (88%) at that oxygen

concentration. Increasing oxygen concentration higher than 0.55 𝑔𝑂2/𝑚3 reduced the amount of 𝐶𝐻4 production.
A lower amount of oxygen concentration promotes 𝐶𝐻4 production hence, 𝑁2 production from methane.
Comparatively higher oxygen concentration enhances 𝑁2 production from nitrate. After all, a moderate amount
(0.55 𝑔𝑂2/𝑚3) shows the maximum nitrogen removal (98%) by combining 𝑁2_𝐶𝐻4 and
𝑁2_𝑁𝑂2.
3.2 Effect of influent organic carbon on substrate and biomass fraction in this model
In previous simulation study a fixed influent organic carbon (300 𝑔𝐶𝑂𝐷/𝑚3) was used, so to find out the effect of
(soluble, readily biodegradable) influent organic substrate (𝑆𝑖𝑛) on substrate and biomass fraction in nitrogen
removal, a number of model simulation were conducted with varying influent organic carbon from 100 to 700
𝑔𝐶𝑂𝐷/𝑚3 with a fixed 100 𝑔𝑁/𝑚3 influent ammonium concentration and 6h hydraulic
retention time. The simulation outcome maintaining a fixed bulk oxygen concentration (0.55 𝑔𝑂2/𝑚3),

Page | 1063
optimum value based on Figure 3.1 and varying influent organic carbon are shown in Figure 3.3 and Figure3.4.

180 NH4
160 NO2 0.09
NO3
140 S_S 0.08
0.07 AOB
120 N2_CH4 NOB
N2_N2O 0.06
100 X_H
Concentration

N2_NO2
0.05
80 N2_total X_H_NO2

Biomass
Fraction
CH4 0.04 X_H_N
[𝑔𝑁/𝑚3]

60
0.03 X_CH4
40
0.02
20
0.01
0
0
100 200 300 400 600 700 100 200 300 400 600 700
Substrate Concentration [𝑔COD/𝑚3] Substrate Concentration
[𝑔COD/𝑚3]
Figure 3.3. Effect of influent organic carbon on Figure 3.4. Effect of influent organic carbon on
substrate biomass fraction
The simulation performance shows the removal of nitrogen was increased with increasing influent organic carbon
from 100 to 300 𝑔𝐶𝑂𝐷/𝑚3 and then decreased (Figure 3.3). The production of 𝐶𝐻4 was significantly increased
while increasing the influent organic concentration while, both nitrate and nitrite production got impeded. The
production of 𝑁2 from 𝐶𝐻4 was decreased initially and then increased. Whereas both 𝑁2 production from 𝑁𝑂− and
total 𝑁2 production were increased 2through a certain influent concentration (200 and 300 𝑔𝐶𝑂𝐷/𝑚3
respectively) and then decreased gradually. The aerobic
heterotrophic organism (𝑋𝐻) was increased sufficiently after 200 𝑔𝐶𝑂𝐷/𝑚3. Increasing influent organic carbon
gave advantages to anoxic 𝑋𝐻_𝑁𝑂2 and limited the growth of AOB and NOB that increased 𝑁2
production from 𝑁𝑂−. The maximum 𝑁2 production from 𝑁𝑂−, 51.97 𝑔𝑁/𝑚3 was achieved at 200
2 2
𝑔𝐶𝑂𝐷/𝑚3 influent organic carbon concentration. Higher than 200 𝑔𝐶𝑂𝐷/𝑚3 influent organic carbon enhanced
the growth of aerobic heterotrophs that consumed a higher amount of oxygen and made an oxygen limitation to
AOB.
The decreasing of AOB decreased the ammonium conversion to nitrite, resulted ammonium accumulation. Lower
conversion to nitrite limited the growth of 𝑋𝐻_𝑁𝑂2 that ultimately reduced the nitrogen production as well as
nitrogen removal by anoxic heterotroph 𝑋𝐻_𝑁𝑂2 at high influent organic carbon concentration. But, above 200
𝑔𝐶𝑂𝐷/𝑚3 influent organic carbon enhanced the production of 𝑁2 by DAMO process up to 400 𝑔𝐶𝑂𝐷/𝑚3 and
then decreased. Conjoining this two, the maximum 𝑁2 production was found at 300
𝑔𝐶𝑂𝐷/𝑚3.
3.3 Effect of hydraulic retention time (HRT) on nitrogen removal
The influence of hydraulic retention time on overall steady-state process performance in terms of nitrogen
removal, at a fixed oxygen (0.55 𝑔𝑂2/𝑚3), influent organic carbon (300 𝑔𝐶𝑂𝐷/𝑚3) concentration was evaluated.
In this model, the maximum nitrogen gas 97.86 𝑔𝑁/𝑚3 was produced at the HRT 6 h with accumulation of
1.0383 𝑔/𝑚3 𝑁𝐻+ and 4 1.5102 𝑔/𝑚 𝑁𝑂 (Figure
3 −
2 3.5). The highest nitrogen removal at 6h HRT was
due to a balance activity among production of AOB, 𝑋𝐻_𝑁𝑂2 and 𝐶𝐻4 (Figure 3.6). Above this, the maximum
nitrogen production in this combined process, 45.89 𝑔𝑁/𝑚3 (46.89% of total produced 𝑁2) came from anaerobic
methane oxidation and 51.97 𝑔𝑁/𝑚3 (53.1% of total 𝑁2) came from heterotrophic denitrification by 𝑋𝐻_𝑁𝑂2.
Deviation from this HRT, the 𝑁2 gas as well as nitrogen removal was decreased.

Page | 1064
AOB
0.1 NOB
X_H
0. X_H_NO2
08 X_H_NO3
1 X_CH4
2 0.
0 06
NH4
100 NO2
NO3
0.
80 04
Concentration

S_S

Biomass
Fraction
N2_CH4
60 N2_N2O 0.
[𝑔𝑁/𝑚3]

N2_NO2 02
40 N2_t
otal 0
20
2.67 4 6 8 12 24 2.67 4 6 8 12 24
0 Hydraulic Retention Time Hydraulic Retention Time (HRT)
(HRT)
Figure 3.5. Effect of Hydraulic Retention Time on Figure 3.6. Effect of Hydraulic Retention Time on
substrate concentration. biomass fraction.

At low HRT, 𝑁𝐻4+ accumulation was observed due to lack of sufficient time to grow AOB; steady-stateAOB
concentration was lower and complete ammonium oxidation was not performed. The highest AOB
concentration was observed at 8h HRT that leads the highest 𝑁𝑂−accumulation (9.244 𝑔𝑁𝑂−/𝑚3). The
2 2
aerobic heterotroph (𝑋𝐻) was found maximum at the lowest HRT as well as the 𝐶𝐻4 production. The maximal
𝑋𝐻_𝑁𝑂2 was found at 8h HRT. Combinedly, the maximum total 𝑁2 production was found at HRT 6h. Increasing
HRT increased the interaction between the bulk oxygen and microbial community that ultimately control the
overall process. The microbial community had got more time to react and more time to diffuse oxygen resulted
complete oxidation of ammonium− to nitrite and then nitrite to nitrate. Hence,
increasing HRT, increased 𝑁𝑂 accumulation. At 24 h HRT shows a total of 101.1 𝑔𝑁𝑂−/
3 3
𝑚3 accumulation.

4. Conclusion
To save aquatic life from the threat of an ammonia-based wastewater, nitrogen removal in the form of N2 is an
indispensable part. At low oxygen concentration and high influent organic carbon condition, the nitrogen gas was
mainly produced by anaerobic methane oxidizing bacteria. In addition, at high oxygen concentration and low
influent organic carbon condition, the nitrogen gas was produced by anoxic heterotrophs. Thus, a moderate
amount of influent organic carbon and oxygen concentration should be maintained.
Increasing HRT increased the nitrogen removal performance as well as 𝑁2 gas production by anaerobic methane
oxidizing bacteria. But higher hydraulic retention time increased the diffusion of oxygen and the efficiency of
nitrogen removal by anoxic heterotrophs decreases. So, a suitable hydraulic retention time need to uphold. The
presence of 𝐶𝐻4, another greenhouse gas, may not cause health problem in drinking water, but it might be the
primary contributor to the formation of ground-level ozone formation. So, the least amount of 𝐶𝐻4 is tolerable.
Nitrate and Nitrite presence in water decrease the pH and can harm the environment. Therefore, the finest portion
of these components need to be maintained. Also, to decrease the amount of ammonia concentration towards null
as well to produce maximum amount of 𝑁2 is essential. The performed simulation shows an existence of 𝑁2𝑂, a
potent greenhouse gas which is 300 times more powerful than 𝐶𝑂2 (Process condition: [𝑁𝐻+] = 100 𝑔/𝑚3;
Influent organic carbon = 300 𝑔𝐶𝑂𝐷/𝑚3; HRT 4 = 24 h and Bulk oxygen concentration = 0.50 𝑔𝑂2/𝑚 ). Hence, this
3

process condition must be avoidedwhile performing this operation.


After all, considering all the afore-mentioned circumstances, the most efficient process condition derived from
this study is to keep initial concentration of 𝑁𝐻+ = 1004 𝑔/𝑚 ; influent organic carbon = 300
3

𝑔𝐶𝑂𝐷/𝑚 ; bulk oxygen concentration = 0.55 𝑔𝑂2/𝑚 and, hydraulic retention time = 6 h.
3 3

Page | 1065
Acknowledgment
This work was supported by the SUST Research Center. (Reference no: Project ID- AS/2021/1/11)

References
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Ammonium Oxidizing Bacteria Supported by the NO/N2O Variation.” Water Research 88: 948–59.
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Depleting Substance Emitted in the 21st Century.” science 326(5949): 123–25.
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Page | 1066
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 192

An approach to Pipeline Flow Capacity Enhancement of Titas


Gas Transmission Network (Dhaka Metropolitan Area)

Anindita Barua*, Md. Zayed Bin Sultan

Chittagong University of Engineering and Technology


Email address: anindita.oishi97@gmail.com, zayed@cuet.ac.bd
*Corresponding author [Anindita Barua]

Abstract: The pipeline network and related facilities created for gas supply to
Keywords:
consumers are referred to as the transmission and distribution scheme of natural
gas. Because of the extended lifespan of the pipeline and factors affecting
● Titas Gas transmission, the throughput can occasionally decrease significantly. However,
Transmission keeping the pipeline's throughput constant is preferred. The placement of one or
more lines in parallel-either entirely or partially, or the replacement of a segment
Network(Dhaka of the line with one with a bigger diameter, are both frequent, economically
Metropolitan Area); sustainable solutions to the problem. The Titas Gas Transmission and
Distribution Company Limited (TGTDCL) is the natural gas distributor in
● Flow Capacity Bangladesh, with an 80% market share. The TGTDCL is already facing a shortfall
Enhancement; of at least 300mmcfd gas against a demand of around 2,200mmcfd. In the Dhaka
metropolitan area alone, the demand is nearly 1,700mmcfd. This issue is most
● PIPESIM 2017.2; probably originated from pipeline corrosion and pipeline lifespan. This paper
● Series Pipeline; aims to examine the Titas Gas transmission network (Dhaka Metropolitan Area),
its current capacity, and capacity usage, as well as to enhance performance by
● Parallel Pipeline; implementing required changes. In this paper, the Weymouth equation and the
● Looped Pipeline. Modified Panhandle equation are used to alter the pipeline network of Titas gas
transmission network (Dhaka Metropolitan Area).The simulation software
PIPESIM 2017.2 will serve as the primary platform here. The existing pipeline
network would be compared to a simulated efficient one, and the improvements
necessary at various locations throughout the network would be identified through
simulation. Consequently, the most suitable approach is recommended for
enhancing the flow capacity of Titas gas transmission network (Dhaka
Metropolitan Area)

1. Introduction
At the beginning of the natural gas transmission sector, the equations utilized for design purposes were
basic and adequate because the pressure was low. However, as capacity demands rise, pressure likewise
rises as demand rises in the modern world. Equations were also created to meet brand-new requirements.
The Weymouth equation, Panhandle equation, and Modified Panhandle equation are typically employed
for this pipeline design purpose. The pipeline flow equation most frequently and extensively used is the
Weymouth equation. This equation is preferable when the pipeline diameter is equal to or less than 15
inches. Panhandle A equation and Modified Panhandle (Panhandle B) equation are applied to
transmission lines of larger magnitude. Of the two, the Modified Panhandle (Panhandle B) equation is
the most frequently used and applied for pipeline natural gas distribution and transmission [A].In the

Page | 1067
design of a complex transmission network, most often, only a part of the line is paralleled. This
phenomenon is termed a looped pipeline system.
Titas Gas Transmission and Distribution Company was established on 20 November 1964. On 28 April
1968, commercial activities started with the supply of gas to Siddhirganj Thermal Power Station through
the Titas-Demra gas pipeline. TGTDCL served 2.8 million domestic customers, 12,000 commercial
customers, and 5,300 industrial customers [B] With 2,865,907 consumers, including 45 power plants,
three fertilizer factories, 1,680 captive power producers, and 5,279 industrial units, the TGTDCL
supplies gas under seven categories to the Dhaka and Mymensingh divisions. Titas' household consumer
number is 2,846,419 currently, with the number of commercial and CNG users standing at 12,075 and
394, respectively. The TGTDCL is already facing a shortfall of at least 300mmcfd gas against a demand
of around 2,200mmcfd. In the Dhakametropolitan area alone, the demand is nearly 1,700mmcfd [C]
In this paper, the pipeline flow capacity enhancement of Titas Gas Transmission Distribution Company
Limited (TGTDCL) are analyzed sensibly. For developing the TGTDCL network, the Weymouth,
Panhandle, and Modified Panhandle equations are employed. Pipeline systems in series, parallel, and
loop configurations are employed for computation. The Weymouth equation is applied when a pipeline's
diameter is less than or equal to 15 inches. However, the Panhandle B equation is utilized when the
pipeline diameter is greater than the value.
2. Experimental
2.1 TGTDCL Transmission Network (Dhaka Metropolitan Area)

Figure 1: Titas Gas Franchise Area (Part 1)

Page | 1068
2.2 Materials
Mainly three techniques are approached here to increase the flow capacity. These techniques include
incorporating gas-flow in series pipelines, gas-flow in parallel pipelines, and gas-flow in looped
pipelines. When a pipeline is joined to one or more pipelines in continuation, these are called pipes in
series. If a pipe branches out into two or more parallel pipes and then rejoins at a junction downstream,
it is known as a parallel pipeline system. In designing a challenging and complex transmission system,
only a part of the line must be parallel rather than the whole length of a line. This phenomenon is known
as looping. Looping of pipeline reduces pipeline pressure loss and increases flow efficiency. Flow
capacity increment is less in the series system and high in the parallel system. As a parallel pipeline
system costs much, it is not economically feasible.

For series flow using Weymouth Equation, the percentage change in flow rate can be approximated by
[1]
1 1
(𝐿𝐴𝑒𝑞 )0.5 −(𝐿)0
.
Δ𝑞ℎ = [ 1 5 ] ×100 (1)
( )0.5
𝐿

where 𝐿′ = 𝐿 (𝐷𝐴)16/3
𝐴 𝐵 𝐷𝐵

Where ′ Δ𝑞ℎ is the percent change in gas flow rate, 𝐿𝐴𝑒𝑞 is the total equivalent length (𝐿𝐴𝑒𝑞 =
𝐿𝐴 + 𝐿 ) of series line and 𝐿′ is the equivalent length of DA inch line.
𝐴 𝐴
Using Modified Panhandle Equation, the percentage change in flow rate can be approximated by[1]
1 1
(𝐿𝐴𝑒𝑞 )0.510 − 𝐿 0.510
Δ𝑞ℎ = [ 1 ( ] × 100 (2)
( )0.510
𝐿 )
𝐷
where 𝐿𝐴′ = 𝐿𝐵 ( 𝐴)4.96
𝐷𝐵

For parallel flow using Weymouth Equation [1],


8/3
Δ𝑞ℎ = 100 ( 𝐷𝐵 ) , when the lengths of parallel pipes are equal (3)
𝐷𝐴
Δ𝑞 = 100 [(𝐷𝐵)8/3 (𝐿𝐴)1/2 ] , when the lengths of parallel pipes are not equal (4)
ℎ 𝐷𝐴 𝐿𝐵

𝑃3 𝐿

𝑃1 𝐷𝐵 𝐷𝐴 𝑃2 𝐷𝐴
𝑃1 𝑃2
𝐿
𝐷𝐵
Figure 2: Pipes in Series [1] Figure 3: Pipes in Parallel [1]

Page | 1069
𝑃1 𝐴 𝑃3
𝐶 𝑃2
𝐷𝐴 𝐷
𝐵
𝐷𝐵 𝐿𝐵

Figure 4: Looped Pipelines [1]


Using Modified Panhandle Equation [1],
Δ𝑞ℎ = 100 ( 𝐷𝐵 )2.530 , when the lengths of parallel pipes are equal (5)
𝐷𝐴
𝐷𝐵 2.530 (𝐿𝐴)0.510 ] , when the lengths of parallel pipes are not equal
Δ𝑞 = 100 [( ) (6)
ℎ 𝐷𝐴 𝐿𝐵

For Looping segment using Weymouth Equation [1],


Δ𝑞ℎ = 100 [(𝐿𝑜 )0.5 – 1] (7)
𝐿𝘍
Here 𝐿𝑜 is the original length of pipeline, 𝐿′ (𝐿′ = 𝐿𝐴′ + 𝐿𝑐) is the equivalent length of pipelineafter
looping, 𝐿′ 𝐴𝐵
is equivalent length of the looped
𝐵 segments A and B and 𝐷𝐴𝐵 ′ is the
corresponding equivalent diameter of A and B. To obtain the total flow rate, the looped andunlooped
sections are solved as series flow systems.
𝐿′ = [ 1 1
𝐷
]2, when the lengths of the parallel line are equal
𝐴𝐵 ( )1/2 { 1 +( 𝐵)8/3}
𝐿𝐴 𝐷𝐶
𝐿′ = [ 1 ]2, when the lengths of the parallel line are not equal
𝐴𝐵 (
1
)1/2
𝐷 1
+( 𝐵)8/3 ( )1/2
𝐿𝐴 𝐷𝐶 𝐿𝐵

Using Modified Panhandle Equation, Δ𝑞ℎ = 100 [(𝐿𝑜 )0.510 – 1] (8)


𝐿𝘍
𝐿′ = [ 1 ]2, when lengths of parallel lines are equal
𝐴𝐵 (
1 𝐷
)0.510 { 1 +( 𝐵)2.530}
𝐿𝐴 𝐷𝐶

𝐿′ = [ 1 ]2, when lengths of parallel lines are not equal.


𝐴𝐵 1 𝐷 1
( )0.510 +( 𝐵)2.530 ( )0.510
𝐿𝐴 𝐷𝐶 𝐿𝐵

Series, parallel and looped flow system are shown in Figure. 2, Figure. 3 and Figure. 4.

2.3 Experimental procedure


The workflow diagram and the PIPESIM 2017.2 simulation flow chart for this study is displayedin the
following figure

Page | 1070
Field data collection from Titas Gas Transmission
and Distribution Company Limited (TGTDCL)

Reviewing the existing problems in the gas


transmission network

Determining necessary modifications across the


pipeline

Simulating the modified network using PIPESIM


Software

Identifying better performance and contrasting


with the previous one

Figure 5: Experimental Procedure


2.4 Questionnaire formulation and administration
Table 1: Data on Titas Gas Transmission Network's length and corresponding diameters (DhakaMetropolitan
Area)
Sl. Distance Length Diameter (inch)
(mile)
No.
1. Ghorashal CGS-Joydevpur CGS 15.22 14

2. Joydevpur CGS-Ashulia 13.05 16


3. Joydevpur-Tongi DRS 7.77 12

4. Aminbazar CGS-Mirpur DRS 7.59 16

5. Aminbazar CGS-Hazaribagh DRS 9.94 16

6. Tongi DRS-Uttara 3.60 12

7. Tongi DRS-Joarshara 4.35 12

8. Narsingdi-Demra CGS 20.14 14

9. Demra CGS-Nandipara 4.16 12

10. Nandipara-Tejgaon 3.42 12

11. Tejgaon-Agargaon DRS 4.72 16


12. Tejgaon TBS/DRS-Gulshan 1.34 12

13. Demra CGS-Dhania TBS/DRS 3.55 16

14. Dhania TBS/DRS-City central 4.08 16


DRS
15. Demra CGS-Postogola 3.98 10

3.Calculation
3.1 Theoretical Approach
These calculations involve changing either the diameter or a piece of the length. Again, in some
instances, both diameter and length are altered to increase the pipeline's flow capacity. When
pipeline diameter is smaller than 16 inches, Weymouth equation is used. When pipeline diameteris larger
than 16 inch, Modified Panhandle Equation is used.

Page | 1071
3.1.1 Flow Capacity Enhancement for Transmission Lines Using Series Scheme
Equation (1) is used for the flow capacity increment for the distance from Ghorashal CGS to Joydevpur
CGS, from Joydevpur to Tongi DRS, from Tongi DRS to Uttara, from Tongi DRS to Joarshara, from
Narsingdi to Demra CGS, from Demra CGS to Nandipara, from Nandipara to Tejgaon, from Tejgaon
TBS/DRS to Gulshan and from Demra CGS to Postogola. Moreover, Equation (2) is used for the flow
capacity increment for the distance from Joydevpur CGS to Ashulia, from Aminbazar CGS to Mirpur
DRS, from Aminbazar CGS to Hazaribagh DRS, from Tejgaon to Agargaon DRS, from Demra CGS to
Dhania TBS/DRS, from Dhania TBS/DRS to City central DRS. The approximate results are shown in
Table 2.
Table 2: Flow capacity increment using the series scheme

Distances Existing Existing Length of Diameter of Length of Equivalent Total Flow Capacity
pipeline pipeline Changed Changed unchanged Length of Equivalent Increment,Δ𝑞ℎ
Length, L Diameter, Portion, Portion, Portion, Pipeline at Length, 𝐿𝐴𝑒𝑞 (%)
(mile) 𝐷𝐴 𝐿𝐵 𝐷𝐵 (inch) 𝐿𝐴 existing (mile)
(inch) (mile) (mile) Diameter,
𝐿𝐴′ (mile)
GhorashalCGS 7.0 16 8.22 3.43 11.65 14.3
to 15.22 14 7.22 18 8.0 1.89 9.89 24.05
JoydevpurCGS 6.22 20 9.0 0.93 9.93 23.80
JoydevpurCGS 3.55 18 9.5 1.98 11.48 6.76
13.05 2.55 18 10.5 1.42 11.92 4.73
to Ashulia 16
2.05 20 11.0 0.68 11.68 5.82
Joydevpur toTongi 3.77 14 4.0 1.66 5.66 17.17
DRS 7.77 12 2.77 16 5.0 0.59 5.59 17.89
1.77 18 6.0 0.20 6.20 11.95
Aminbazar CGS 3.0 18 4.59 1.67 6.26 10.32
to Mirpur DRS 7.59 16 2.8 18 4.80 1.23 7.59 12.56
2.59 20 5.0 0.86 5.86 14.10
AminbazarCGS 3.0 16 6.94 3.0 9.94 12.45
to 9.94 16 4.0 18 5.94 2.23 8.17 10.52
Hazaribagh DRS 4.94 18 5.0 2.78 7.78 13.31

Tongi DRSto 1.5 14 2.1 0.66 2.76 14.21


Uttara 3.60 12 1.6 16 2.0 0.35 2.35 23.77
0.6 18 3.0 0.07 3.07 8.29
Tongi DRSto 1.85 14 2.5 0.81 3.31 14.64
Joarshara 4.35 12 1.35 14 3.0 0.59 3.59 10.08
0.35 16 4.0 0.08 4.08 3.26
Narsingdi to 8.0 16 12.14 7.85 19.99 27.76
Demra CGS 20.14 14 10.0 18 10.14 5.24 15.38 57.45
8.14 20 12.0 1.21 13.21 23.47
Demra CGS to 2.0 14 2.16 0.88 3.04 16.98
Nandipara 4.16 12 1.66 14 2.5 0.73 3.23 13.49
1.16 16 3.0 0.25 3.25 13.14
Nandipara to 1.42 14 2.0 0.62 2.62 14.25
Tejgaon 3.42 12 0.92 16 2.5 0.19 2.69 12.76
0.42 16 3.0 0.09 3.09 5.20
Tejgaon to 1.22 16 3.5 1.20 4.72 2.12
Agargaon DRS 4.72 16 0.72 18 4.0 0.40 4.40 3.65
0.22 18 4.5 0.12 4.62 1.09
Tejgaon TBS/DRS 0.50 14 0.84 0.22 1.06 12.44
to 1.34 12 0.34 14 1.0 0.15 1.15 7.95
Gulshan 0.22 16 1.12 0.05 1.17 7.02
Demra CGSto 1.55 18 2.0 0.86 2.86 11.65
Dhania TBS/DRS 3.55 16 1.05 18 2.5 0.59 3.09 7.33
0.55 18 3.0 0.31 3.31 3.63
Dhania TBS/DRS 2.0 18 2.08 1.12 3.2 13.19
toCity central 4.08 16 1.58 18 2.5 0.88 3.38 10.08
DRS 1.08 18 3.0 0.60 3.60 6.59

Demra CGSto 1.98 12 2.0 0.75 2.75 20.30


Postogola 3.98 10 1.68 14 2.3 0.28 2.58 24.20
1.48 16 2.5 0.12 2.62 23.25

Page | 1072
3.1.2 Flow Capacity Enhancement for Transmission Lines Using Looped Scheme
Equation (7) is used for the flow capacity increment for the distance from Ghorashal CGS to Joydevpur
CGS, from Joydevpur to Tongi DRS, from Tongi DRS to Uttara, from Tongi DRS to Joarshara, from
Narsingdi to Demra CGS, from Demra CGS to Nandipara, from Nandipara to Tejgaon, from Tejgaon
TBS/DRS to Gulshan and from Demra CGS to Postogola. Moreover, Equation (8) is used for the flow
capacity increment for the distance from Joydevpur CGS to Ashulia, from Aminbazar CGS to Mirpur
DRS , from Aminbazar CGS to Hazaribagh DRS, from Tejgaon to Agargaon DRS, from Demra CGS to
Dhania TBS/DRS, from Dhania TBS/DRS to City central DRS. The approximate results are shown in
Table 3.
Table 3: Flow capacity increment using the looped scheme
Existing Existing Diameter Length of Length of Equivalent Total Flow
pipeline pipeline of looped Looped Portion Unchanged Length of Equivalent Capacity
Distanc Length, Diameter, pipeline, (mile) looped Length after Increment,
Portion, LC
es
𝐿𝑜(mil 𝐷𝐶(inch) 𝐷𝐵 parallel looping,
e) (inch) pipelines, 𝐿′ 𝐴𝐵 𝐿′(mile)
(mile) (mile) Δ𝑞ℎ (%)
LA L
B

Ghorashal 16 7.0 7.0 8.22 1.19 9.41 27.18


CGS to 18 6.0 6.0 9.22 0.69 9.91 23.93
15.2 14
Joydevpur 20 5.0 5.0 10.22 0.39 10.61 19.77
2
CGS
Joydevpur 16 3.55 3.55 9.5 0.91 10.41 12.22
13.0 18 2.55 2.55 8.5 0.47 8.97 21.07
CGS to 16
5 20 2.05 2.05 11.0 0.27 11.27 7.77
Ashulia
Joydevpurto 14 3.77 3.77 4.0 0.60 4.60 29.97
TongiDRS 7.77 12 16 2.77 2.77 5.0 0.28 5.28 21.31
18 1.77 1.77 6.0 0.11 6.11 12.78
Aminbazar 16 3.0 3.0 4.59 0.77 5.36 19.41
CGS to 18 3.59 3.59 4.0 0.69 4.69 27.83
7.59 16
Mirpur 20 2.59 2.59 5.0 0.35 5.35 19.53
DRS
Aminbaza 16 3.0 3.0 6.94 0.77 7.71 13.83
rCGS to 9.94 16 18 4.0 4.0 5.94 0.75 6.69 22.38
Hazaribag 18 4.94 4.94 5.0 0.93 5.93 30.14
h DRS
Tongi DRS 14 1.5 1.5 2.1 0.24 2.34 24.03
to 3.60 12 16 1.6 1.6 2.0 0.16 2.16 29.10
Uttara 18 0.6 0.6 3.0 0.04 3.04 8.82
Tongi 12 1.85 1.85 2.5 0.46 2.96 21.23
DRS to 4.35 12 14 1.35 1.35 3.0 0.21 3.21 16.41
Joarshara 16 0.35 0.35 4.0 0.04 4.04 3.77
Narsingdi 16 8.0 8.0 12.14 2.72 12.86 16.42
to Demra 20.1 14 18 10.0 10.0 10.14 2.29 12.43 27.29
CGS 4 20 8.14 8.14 12.0 0.63 12.63 26.28
Demra CGS 12 2.0 2.0 2.16 0.5 2.66 25.06
to 4.16 12 14 1.66 1.6 2.5 0.26 2.76 22.77
Nandipara 6
16 1.16 1.16 3.0 0.12 3.12 15.47

Nandiparato 12 1.42 1.42 2.0 0.36 2.36 20.38


Tejgaon 3.42 12 14 0.92 0.92 2.5 0.15 2.65 13.60
16 0.42 0.42 3.0 0.04 3.04 6.07
Tejgaon to 16 1.22 1.22 3.5 0.31 3.81 11.54
Agargaon 4.72 16 16 0.72 0.72 4.0 0.18 4.18 6.39
DRS 18 0.22 0.22 4.5 0.04 4.54 2.0

Demra 16 1.55 1.55 2.0 0.39 2.39 22.36


CGS to 3.55 16 16 1.05 1.05 2.5 0.26 2.76 13.70
Dhania 18 0.55 0.55 3.0 0.09 3.09 7.33
TBS/D
RS
Dhania 16 2.0 2.0 2.08 0.51 2.59 26.08
TBS/DRS 4.08 16 16 1.58 1.58 2.5 0.40 2.90 19.02
to City 18 1.08 1.08 3.0 0.20 3.20 13.19
central
DRS
Demra CGS 12 1.98 1.98 2.0 0.29 2.29 31.83
to 3.98 10 14 1.68 1.68 2.3 0.14 2.44 27.72
Postogola 16 1.48 1.48 2.5 0.07 2.57 24.44

Page | 1073
3.1.3 Flow Capacity Enhancement for Transmission Lines Using Parallel Scheme
Equation (3) is used for the flow capacity increment for the distance from Ghorashal CGS to Joydevpur
CGS, from Narsingdi to Demra CGS. Equation (4) is used for the flow capacity increment for the
distance from Joydevpur to Tongi DRS, from Tongi DRS to Uttara, from Tongi DRS to Joarshara, from
Narsingdi to Demra CGS, from Demra CGS to Nandipara, from Tejgaon TBS/DRS to Gulshan, from
Demra CGS to Postogola. Equation (5) is used for the flow capacity increment for the distance from
Joydevpur CGS to Ashulia. Equation (6) is used for the flow capacity increment for the distance from
Aminbazar CGS to Mirpur DRS , from Aminbazar CGS to Hazaribagh DRS, from Tejgaon to Agargaon
DRS, from Demra CGS to Dhania TBS/DRS, from Dhania TBS/DRS to City central DRS. The
approximate results are shown in Table 4.
Table 4: Flow capacity increment using the parallel scheme
Distances Existing Existing Length of Diameter of Length of existing Flow Capacity
pipeline pipeline additional Portion, additional Portion, Increment, Δ𝑞ℎ
Length, Diameter, 𝐿𝐵 Portion, 𝐷𝐵 𝐿𝐴 (%)
L (mile) 𝐷𝐴 (mile) (inch) (mile)
(inch)
Ghorashal CGS to 15.22 16 15.22 142.77
Joydevpur CGS 15.22 14 15.22 18 15.22 195.46
15.22 20 15.22 258.86
Joydevpur CGS to 13.05 16 13.05 100
13.05 13.05 18 13.05 134.71
Ashulia 16
13.05 20 13.05 175.87
Joydevpur to Tongi 4.0 14 7.77 210.24
DRS 7.77 12 5.0 16 7.77 188.04
6.0 18 777 171.65
Aminbazar CGS to 3.0 16 7.59 160.54
Mirpur DRS 7.59 16 4.0 18 7.59 186.76
5.0 20 7.59 217.59
Aminbazar CGS to 3.0 16 9.94 184.22
Hazaribagh DRS 9.94 16 4.0 18 9.94 214.31
5.0 18 9.94 191.25
Tongi DRS to 1.5 14 3.60 233.68
Uttara 3.60 12 2.0 16 3.60 288.94
3.0 18 3.60 322.97
Tongi DRS to 2.5 12 4.35 131.9
Joarshara 4.35 12 3.0 14 4.35 181.64
4.0 16 4.35 224.58
Narsingdi to Demra 20.14 16 20.14 142.77
CGS 20.14 14 20.14 18 20.14 195.46
20.14 20 20.14 258.87
Demra CGS to 2.0 12 4.16 144.23
Nandipara 4.16 12 2.5 14 4.16 194.58
3.0 16 4.16 253.60
Nandipara to 2.0 12 3.42 130.77
Tejgaon 3.42 12 2.5 14 3.42 176.42
3.0 16 3.42 229.94
Tejgaon to 3.5 16 4.72 116.48
Agargaon DRS 4.72 16 4.0 16 4.72 108.81
4.5 18 4.72 138.03
Tejgaon TBS/DRS 0.5 12 1.34 163.71
to Gulshan 1.34 12 1.0 14 1.34 174.61
1.2 16 1.34 189.55
Demra CGS to 2.0 16 3.55 133.99
Dhania TBS/DRS 3.55 16 2.5 16 3.55 119.58
3.0 18 3.55 146.79
Dhania TBS/DRS to 2.0 16 4.08 143.85
City central DRS 4.08 16 2.5 16 4.08 128.38
3.0 18 4.08 157.59
Demra CGS to 2.0 12 3.98 229.39
Postogola 3.98 10 2.3 14 3.98 322.67
2.5 16 3.98 441.86

3.2 Simulative Approach


A schematic transmission network map of the Dhaka Metropolitan Area is created by the Pipesim 2017.2
software utilizing the existing data in Table: 5.1: Data on Titas Gas Transmission

Page | 1074
Network's length and corresponding diameters (Dhaka Metropolitan Area), as shown below. The
following table illustrates the simulation's final output for this map. Roughness of the pipe is assumed
0.0006. Moody correlation has been set for calculation.

Figure 6: Existing schematic map and the simulated outcome of transmission network (DhakaMetropolitan
Area)
Either the diameter or a section of the length is altered for these simulations in order to generate a
modified transmission network map in the Dhaka Metropolitan Area. Again, in some instances, both
diameter and length are altered to increase the pipeline's flow capacity. Following figure shows the
modified schematic map of transmission network (Dhaka Metropolitan Area) The table illustrates the
simulation's final output for this map. Roughness of the pipe is assumed 0.0006. Moody correlation has
been set for calculation.

Figure 7: Modified schematic map and the simulated outcome of transmission network (Dhaka
Metropolitan Area
4. Result and Discussion
From the study of flow capacity enhancement through pipeline, the discussion of the results areas
follows:

Page | 1075
• Despite a significant increase in flow capacity, parallel arrangement is quite costly to construct.
It is only considered for sources that branch off into numerous more connections because it can
significantly improve the flow capacity for those additional connections.
• Apart from parallel connections, looped connections are favoured over series connections.
Because looping increases flow rate more effectively than a sequential seriessetup.
• Since both parallel and looped connections are more expensive than series connections when the
distance is short, they are less feasible to consider. Series connections are takeninto consideration
for short distances.

VI S UAL R E P R E S E N T ATI ON OF
S I M UL ATI ON R E S UL TS COM P ARI S ON

Before Modification q After Modification q


1 (mmcf/d) (mmcf/d)
0
0
8
0
6
0
4
0
2
0
0
Table 5: Recommendations
Name Recommendations
Ghorashal CGS- to connect the present line in parallel with a 15.22-mile-long, 20-inch-diameter line, which could enhance
Joydevpur CGS capacity by 256.86 %
Joydevpur CGS- to connect a 2.55-mile pipeline with a 18-inch diameter in parallel to the 13.05-mile existing system's 2.55-
Ashulia mile length,which will increase 14.94% flow capacity.
Joydevpur-Tongi to connect the present line in parallel with a 4-mile-long, 14-inch-diameter line , which could enhance capacity
DRS by 210.24 %
Aminbazar CGS- to connect a 3.59-mile pipeline with a 18-inch diameter in parallel to the 7.59 existing system's 3.59-mile
Mirpur DRS length , which will increase 27.83 %. flow capacity
Aminbazar CGS- to connect a 4.94-mile pipeline with a 18-inch diameter in parallel to the 9.94 existing system's 4.94-mile
Hazaribagh DRS length, which will increase 30.14 %. flow capacity
to connect a 1.6-mile pipeline with a 16-inch diameter in parallel to the 3.60 existing system's 1.6-mile length, which will
Tongi DRS-Uttara
increase 29.10 %. flow capacity
to connect a 1.85-mile pipeline with a 12-inch diameter in parallel to the 4.35 existing system's 1.85-mile
Tongi DRS-Joarshara length,which will increase 21.23 %. flow capacity
Narsingdi-Demra to connect the present line in parallel with a 20.14-mile-long, 20-inch-diameter line, which could enhance
CGS capacity by 258.87 %.
Demra CGS- to connect the present line in series with a 2-mile-long, 14-inch-diameter line, which could enhance capacity by
Nandipara 16.98 %.
to connect the present line in series with a 1.42-mile-long, 14-inch-diameter line, which could enhance capacity
Nandipara-Tejgaon by 14.25 %.
Tejgaon-Agargaon to connect the present line in parallel with a 4.5-mile-long, 18-inch-diameter line, which could enhance capacity
DRS by 138.03 %.
Tejgaon TBS/DRS- to connect the present line in parallel with a 1.34-mile-long, 16-inch-diameter line, which could enhance capacity by 189.55 %
Gulshan
Demra CGS-Dhania to connect the present line in parallel with a 3.0-mile-long, 18-inch-diameter line, which could enhance capacity
TBS/DRS by 146.79 %.
Dhania TBS/DRS- to connect the present line in series with a 2.0-mile-long, 18-inch-diameter line, which could enhance capacity
City central DRS by 13.19 %.
Demra CGS- to connect a 1.98-mile pipeline with a 12-inch diameter in parallel to the 3.98 existing system's 1.98-mile length, which will
Postogola increase 31.83 % flow capacity

Page | 1076
4.1 Units
In this paper, the length of the pipelines is calculated in (mile) and the diameter of the pipelines are
estimated in (inch)
5. Conclusion
The main goal of pipeline design is to safely and cost-effectively convey fluid to its destination with a
reasonable amount of pressure loss. The environment will be saved if there is a sufficient supply of
natural gas at the consumer level. Considering that natural gas is a clean energy source, it emits 50% less
CO2 than other fossil fuels. Scales or other debris left in the pipeline, however, can occasionally obstruct
the passage of fluid. This paper's primary objective was to shed some insight into how to modify pipes
to increase gas flow rates. It would have been highly expensive to increase sources or add more
compressor stations, thus, alternative pipeline configurations have been simulated to address the issue.
The existing pipes will need to be updated soon due to the rising daily demand for gas. The best-suited
system must be selected after thorough economic feasibility assessments.
Acknowledgment
I must express my gratitude to Bangladesh Oil, Gas, and Mineral Corporation (Petrobangla) for
allowing me to collect data from Titas Gas Transmission and Distribution Co. Ltd (TGTDCL).
Additionally, I would like to express my gratitude and highest regard to Engr. Md Shafiqul Islam,
Deputy General Manager, Civil Engineering Department of TGTDCL, and Md. Zayed Bin Sultan,
Assistant Professor, Department of Petroleum and Mining Engineering, Chittagong University of
Engineering and Technology for their assistance, collaboration, and guidance.

References
[A] Chi U. Ikoku, Natural Gas Production Engineering, KRIEGER PUBLISHING COMPANY,
KRIEGER DRIVE, MALABAR, FLORIDA 32950, Original Edition, 1984, pp 249-306.
[B] Titas Gas Transmission and Distribution Company Limited, Available in:
http://www.titasgas.org.bd/ (accessed 12 July 2022)

[C] Dhaka Tribune, ‘Titas’ consumers bracing for gas outage, low pressure amid high Eid demand’, in
https://archive.dhakatribune.com/ Published at 05:25 pm July 30th, 2020 (accessed 06 July 2022)

Page | 1077
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 196

Nitrogen removal and nitrous oxide emission from granularsludge


bioreactor
Rahatun Akter*, Rasheda Begum Mim, Md. Mashiur Rahman Tusar, and Dr.
Md. Salatul Islam Mozumder

Dept. of Chemical Engineering and Polymer Science,


Shahjalal University of Science andTechnology, Sylhet-3114,
Email: rahatun-cep@sust.edu, rashedabmim@gmail.com, mashiur248@gmail.com, salatul-
cep@sust.edu
*Corresponding author [Rahatun Akter]

Abstract: This investigation deals with the treatment of ammonium-rich wastewater by


Keywords: employing Activated Granular Sludge (ASM) reactor and evaluates the effect of bulk
oxygen concentration and organic carbon concentration on nitrogen and greenhouse gas
● N-removal; (N2O) removal through the activities of autotrophic and heterotrophic organisms. A
● Nitrifier- mathematical model was applied to investigate the factors that influence nitrogen removal
by varying nitrogen compounds from wastewater. The constructed mathematical model
nitrification; was implemented in Aquasim Software, while MATLAB was used to calculate the values
● Nitrifier- of dissolved oxygen concentration along with organic materials. This theoretical work
demonstrates a good prediction of the evolution of N2 and N2O emissions for varying
denitrification;
levels of bulk oxygen and influent organic carbon. Without influent organic material, N2
● Heterotrophic- gas removal totally dependent on the anammox (anaerobic ammonium oxidation) process
denitrification; by anammox bacteria (XAN ), and the maximum N-removal was achieved at around
75%. Two pathways are involved in N2O emission; Nitrifier- Nitrification (NN)
● Aquasim Software; and Nitrifier-Denitrification (ND). An insufficient amount of organic carbon hindered the
N2O formation via Heterotrophic- Denitrification (HD) due to the limited growth of
anoxic organisms on NO− 2
(XH,NO2). In contrast, simulation performed with influent organic carbon concentration
enhanced the N2 gas removal up to 80%. In this case, increasing influent organic carbon
gave an advantage to anoxic XH,NO2 growth, which contributed to N2 emission along with
XAN. The accumulation rate of N2O was influenced by anoxic heterotroph (XH,NO2) via
heterotrophic-denitrification (HD) pathway along with Nitrifier-nitrification (NN) and
Nitrifier- denitrification (ND) pathways. The optimal condition of N2 gas removal with a
low amount of N2O emission was found at 0.34 g O2/m3 bulk oxygen level
using 60 g COD/m3 influent organic carbon.

1 Introduction

Environmental issues, regarding the chemical and biological contaminations of water, have become a key concern
for society, public authorities, and the industry. Most domestic and industrial activities produce wastewater
containing undesirable hazardous contaminants. Discharge of wastewater containing nitrogen- based compounds
has become one of the severe problems for the environment (Molinuevo et al., 2009). N-compound rich wastewater
could be a significant source of nitrous oxide (N2O), which is a highly potential greenhouse gas (GHG), with a
global warming potential around 300 times that of carbon dioxide gas (CO2)(Montzka et al. 2011). Besides, N2O is
chemically stable and may persist in the atmosphere for over 120
Page | 1078
years (Kampschreur et al. 2009). The conventional nitrogen removal process is the combination of
nitrification/denitrification reactions.
At first, ammonium oxidizing bacteria (AOB) oxidize a part of ammonium to nitrite to remove ammonium from
wastewater. Then, the remaining ammonium, together with the initially formed nitrite, is converted into nitrogen
gas under anaerobic conditions by anammox bacteria with a small amount of nitrate, which is produced
simultaneously by nitrite-oxidizing bacteria (NOB). Besides, N2O is produced as an intermediateduring the process
which is imposed to nitrification and heterotrophic denitrification. Three routes are involved for N2O production
(shown in Figure 1. 1) : nitrifier nitrification (hydroxylamine oxidation), nitrifier denitrification and heterotrophic
denitrification, respectively (Wunderlin et al., 2012).

Figure 1.1 Schematic representation of 𝑁2𝑂 Formation pathways


Hydroxylamine oxidation refers to the production of N2O from intermediates of biological hydroxylamine
oxidation (Poughon et al., 2001), might be related to a highly imbalanced metabolic activity of AOB (Chandran et
al., 2011; Law et al., 2012), or chemical deposition of NH2OH as well as to chemical oxidation

with NO− which act as an electron acceptor. Nitrifier denitrification is attributed to reduction of NO− by
2 2
AOB in combination with NH+, as electron donors, for example, at O2-limiting conditions or elevated NO−
4 2
concentrations (Colliver & Stephenson, 2000). During heterotrophic denitrification, when N2O is produced as an
obligatory intermediate and assumed to be due to an imbalanced activity of N-reducing enzymes, for instance, due
to O2 inhibition, NO− an accumulation
2 (Schulthess et al., 1995), or limited availability of biodegradable organic
compounds (Itokawa et al., 2001).
The pathways of nitrous oxide production by the action of AOB falls into two categories, represented by single-
pathway models and two-pathway models (Kampschreur et al., 2007; Harris et al., 2015). Besides, two distinct
concepts have been proposed for the Modeling of N2O production by heterotrophic denitrifiers. These concepts are
outlined by the Activated Sludge Model for Nitrogen (ASMN) (Hiatt & Grady, 2008) and the Activated Sludge
Model with Indirect Coupling of Electrons (ASM-ICE) (Pan et al., 2013), respectively. Activated Sludge Model
for Nitrogen (ASMN) includes the carbon oxidation and nitrogen reduction processes which are directly coupled.
This model describes all four steps as a separate and independent oxidation-reduction reaction and applies to the
reaction-specific kinetics.
The amount of nitrogen removed and the proportion of nitrous oxide, which is either accumulated or emitted to the
environment, from the wastewater treatment during nitrification and denitrification is possible to predict from the
developed mathematical models. The ability to predict N2O production by modeling provides an opportunity to include
N2O production as an significant consideration in the design, operation, and optimization of biological nitrogen removal
processes (Ni et al., 2013). Furthermore, mathematical modeling should be a more appropriate for estimating site-specific
nitrous oxide emission than the oversimplified model with fixed nitrous oxide emission factors (Spérandio et al., 2016).
In addition, mathematical models provide hypotheses related to the mechanisms for nitrous oxide production and thus
serves as a tool to support the development of mitigation strategies (Ni et al., 2013b). In this study activated sludge model
(ASM) was used to predict nitrogen removal and corresponding N2O accumulation(Mozumder et al., 2014). This study
aimed to investigate the nitrification-denitrification performance on N2 removal and N2O emission.

Page | 1079
2 Materials and Methods

2.1 Model Description

In this study, a mathematical model was constructed to describe the Nitrification-Denitrification process to N2
removal considering N2O formation pathways. Mainly three microbial pathways are involved in N2O formation:
Nitrifier Nitrification (NN), Nitrifier Denitrification (ND) and Heterotrophic Denitrification (HD). The
assumptions for the description of NN and ND pathways are based on previous single-pathwaymodels (Pocquet et
al., 2016). This model described the metabolism of ammonium oxidizing bacteria (XAOB), nitrite-oxidizing bacteria
(XNOB), Anammox bacteria (XAN), and different types of heterotrophs. A schematic description of the N2O
Formation pathways is outlined in Figure 2. 2.
Following five AOB reactions were involved in this model (Pocquet et al., 2016): (1) NH4+ oxidation to NH2OH,
(2) NH2OH oxidation to nitric oxide (NO), (3) NO oxidation to NO− (4) NO2 reduction to N2O along with the NH2OH
oxidation to NO− (N2O production 2 via the NH2OH oxidation pathway), (5) NO reduction

2
combined with NH2OH oxidation to produce N2O (N2O production by the nitrifier denitrification pathway,
combination of reactions 5a and 5b). The rest four reactions given below were related to the heterotrophic
denitrification pathway.
Ammonia-oxidizing
1 bacteria
1. NH+ + ⁄ O → NH OH + H+
4 2 2 2
2. NH2OH + ⁄4 O2 + NH4+ → NO + 3⁄2 H2O + XAOB
3
3. NO + 1⁄4 O2 + 1⁄2 H2O → NO−2 + H+
4. NH2OH + 4 NO → NO− + 2N O + H O + H+
2 2 2
Nitrifier-denitrification pathway
5a. NH2OH + 3NO−2 + 3H+ → 4NO + 3H 𝑂 3 3
2 and 5b. NH OH
2 + 2NO → ⁄2 N O
2 + ⁄2 H 2O
By using (5a + 2×5b)/3, = > 5. NH2OH + NO− + H+ → N O + 2H O
2 2 2
Heterotrophic-denitrification pathway
1. NO− + 2e− + 2H+ → NO− + H O
3 2 2
2. NO− + e− + 2H+ → NO + H O
2 2
3. NO + e− + H+ → 1⁄2 N2O + 1⁄2 H2O
4. 1⁄2 N2O + e− + H+ → 1⁄2 N2 + 1⁄2 H2O
This study also deals with an alternative process called anammox (anaerobic ammonium oxidation) for
nitrogen removal from wastewater. Anammox is an autotrophic process by which bacteria convert nitriteand
ammonia to N2 gas (equation 1; Jetten et al., (2005)), it is strictly anaerobic and is performed by
anammox bacteria. NH+ + NO− → N + 2H O − − − − − −(equation 1)
4 2 2 2
Biomass decay has been modeled according to the death-regeneration concept. This concept includes a transition
of living cells to substrate together with a fraction of inert material by the decay of microorganisms (Gujer et al.,
1999). All decay processes follow first-order kinetics and convert biomass to inert and particulate organics.
Eighteen processes were included in this model. Monod-type expressions were incorporated to describe the action
of autotrophs and heterotrophs. The growth and decay of XAOB were based on Pocquet et al., (2016). Aerobic and
anoxic growth and decay were based on Hiatt and Grady, (2008). The metabolism of XNOB and anammox were
taken from Mozumder et al., (2014).

2.2 Reactor configuration, simulation strategy and initial condition

In this study, a one-dimensional biofilm model for each microorganism was implemented in Aquasim to describe
the interaction among autotrophic and heterotrophic bacteria in a granular sludge reactor. This model only
considers the radial diffusion of soluble components and microbial competition for space inside biomass granules.
The total reactor volume was taken 400 m3. The reactor contained 300 m3 of perfectly mixed bulk liquid and 100
m3 of particulate materials, comprising both active biomass as well as inert material generated during growth and
decay. The reactor cross-section area of 36.6 m2 was chosen to calculate the interphase transport coefficients
(KLa) between the gas and liquid phases. Spherical biomass particles were grown from an initial radius of 0.10
mm to a predefined steady-state granule radius, rp (0.75mm < rp< 2.75 mm). The number of granules was
calculated from the assumed total volume of sludge and steady-state radius. The reactor was operated with the
following cycle: aerated period (nitrification), and anoxic period (denitrification). The duration of aerobic and
Page | 1080
anoxic periods was adapted during the study in order to achieve full nitrification and denitrification. The aerobic
period was initiated by feeding with ammonium-rich synthetic wastewater, with a flow rate of 2500 m3d−1. The
ammonium concentration through the process was 100 gN.m−3. It was assumed that the influent was totally free
from nitrite and nitrate. Ammonium oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) initiate the
formation of nitrite and nitrate, respectively. After a while, denitrification contributed to nitrite and nitrate
formation. The initial concentrations of soluble compounds in the bulk liquid had been assumed equal to influent
concentrations. To evaluate the effects of oxygen concentration on reactor performance, the influent was
assumed not to contain any readily degradable or particulate organic substrate. To analyze the effect of organic
substrate concentration on nitrogen removal, the concentration of organic substrate was varied from 20 to 100
gCOD.m-3. The hydraulic retention time was maintained 3.84 h. These tests were performed in aerobic conditions
with varying air flow rates maintained from 0.1 – 1.0 gO2/m3. The reactor behavior had been observed at a
temperature of 30°C. Simulations had been performed for several years of operation to attain steady state
condition.

3 Result and Discussions


3.1 Effect of Oxygen concentration on Nitrogen and greenhouse gas removal:
To evaluate the effect of Oxygen concentration on Nitrogen removal as nitrogen (N2) and Nitrous oxide (N2O), a
series of simulations were conducted for an influent containing 100 g NH4-N/m3 ammonium- nitrogen. The
influent was considered not to contain any organic carbon. The steady-state model behavior is outlined in Figure
3.1. 1 and Figure 3.1. 2 with a fixed hydraulic retention time 3.84 h and varying bulk oxygen concentration from
0.2 to 1.0 g O2/m3.

Figure 3.1. 1 Effect of Oxygen concentration on nitrogen Figure 3.1. 2 Effect of Oxygen concentration on biomass
and nitrous oxide removal (process conditions: 𝑆𝑖𝑛 = 0 fraction (process conditions: 𝑆𝑖𝑛 = 0 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 =
gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h ) 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)

Figure 3.1.2 shows the steady-state concentration of different nitrogen forms and N2 production through
nitrification-denitrification. The maximum nitrogen removal (75%) as N2 gas was observed at an2 oxygen
concentration 0.25 g O2/m3. Below this oxygen level, growth of XAN was limited due to low NO−
conversion. And after this oxygen concentration rapid production of NO− from NO− again reduced XAN
3 2
growth along with increased XNOB production. Below this point XAOB growth is limited because of the higher
oxidation rate of NH2OH to NO and NO to NO−, respectively.
2 Therefore, at an oxygen concentration
0.2 gO2/m , N2O formation through nitrifier nitrification (NN) and nitrifier denitrification (ND) was observed
3

high around 6.4 gN/m3. At an oxygen concentration 0.6 gO2/m3, the N2O production was found
around 4.3 gN/m3 with zero N2 gas removal. Due to the insignificant amount of organic substrate, theaccumulation of
2 aerobic
3 heterotroph and anoxic heterotrophic organisms+on NO− and NO− were negligible.
Therefore, the N2 production directly relied on the NH oxidation with NO− reduction by XAN, while the
4 2
major N2O production steps were correlated to the NO reduction to N2O through NN pathway and
NO2−reduction to N2O through ND pathway.

Page | 1081
3.2 Evaluation of organic material on nitrogen removal process:
In the previous simulation study, the effect of varying oxygen concentration on nitrogen removal was evaluated by
assuming an influent containing no readily degradable organic substrate. Hence finding out the combined effect of
influent organic carbon and bulk oxygen concentration, several model simulationswere conducted with varying
influent organic carbon concentration from 20 to 100 gCOD/m3 and bulk oxygen concentration from 0.1 to 1.0
gO2/m3 with a fixed influent ammonium concentration 100 gNH4- N/m3 and HRT 3.84h. The simulation outcomes
are summarized in the following figures (3.2.1, 3.2.2).

Figure 3.2. 1 Effect of oxygen concentration on (A) Nitrogen compounds removal and (B) Biomass fraction (process
conditions: 𝑆𝑖𝑛 = 20 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)

Figure 3.2. 2 Effect of oxygen concentration on (C) Nitrogen compounds removal and (D) Biomass fraction (process
conditions: 𝑆𝑖𝑛 = 40 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)
The above figures display that the nitrogen removal as N2 gas was increased with increasing influent organic
carbon. Using 20 gCOD/m3 influent organic carbon, at 0.25 gO2/m3 oxygen concentration level, the maximum
nitrogen removal was 81.6% as nitrogen gas along with 0.18% N2O, 14% NH2OH, 0.32%
NO−, 0.83% NO− and trace amount of NO formation. Further increase in oxygen concentration limited the
3 2
N2 gas removal. By using 40 and 60 gCOD/m3 influent organic carbon, the maximum N2 removal was
achieved at 0.27 and 0.34 gO2/m3 bulk oxygen concentration respectively. Above these optimum oxygen
concentrations, the production rate of N2 gas was reduced and maximum nitrogen converted to NO−, NH2OH
along with the trace amount of N2O, NO and NO− formation. Simulation conducted with 80 gCOD/m3 organic
material was not capable to remove more than 66.7% nitrogen as N2 gas. But further increasing influent organic
carbon to 100 gCOD/m3 again enhanced N2 gas removal to 82% at 0.53 gO2/m3 bulk oxygen concentration.

Page | 1082
3

Figure 3.2. 3 Effect of oxygen concentration on (E) Nitrogen compounds removal and (F) Biomass fraction
(processconditions: 𝑆𝑖𝑛 = 60 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)

Figure 3.2. 4 Effect of oxygen concentration on (G) Nitrogen compounds removal and (H) Biomass fraction
(processconditions: 𝑆𝑖𝑛 = 80 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)

Figure 3.2. 5 Effect of oxygen concentration on (I) Nitrogen compounds removal and (J) Biomass fraction (process
conditions: 𝑆𝑖𝑛 = 100 gCOD/𝑚3; 𝑁𝐻4𝑖𝑛 = 100 g𝑁𝐻4-N/𝑚3; HRT = 3.84h)
Figures (G) and (I) represents a slow decline of N2 gas removal with increasing oxygen concentration; however,
the other figures (figures (A), (C), and (E)) displayed sharp decline curves of N2 gas removal with increasing
oxygen concentration. In the previous simulation, without considering influent organic carbon, nitrogen gas
production mostly depended on XAN growth. But using influent organic carbon, nitrogen gas production relied on
both of XAN and anoxic heterotrophic organism on NO− (XH,NO2). The use of organic substrate gave an advantage to
the growth of both aerobic and anoxic heterotrophs. Therefore, in this simulation, heterotrophic denitrification
(HD) also took participation along with nitrifier nitrification (NN) and nitrifier denitrification (ND) in N2O
formation. But the accumulation of N2O concentration was negligible due to its balanced production and
consumption rate. From the above discussion, it was outlinedthat efficient nitrogen removal (83.2%) was found at
0.34 gO2/m3 bulk oxygen concentration for 60 gCOD/m3 influent organic carbon.

Page | 1083
4. Conclusion
Simulations conducted without organic carbon do not show a sufficient effect on heterotrophic microbial
activities. The limitation of organic carbon sources enhances the N2O production rate. The maximum N2O
concentration was observed at around 4.3 g N/m3 without using organic carbon. Organic substrate feeding has a
noticeable effect on nitrifying and denitrifying organisms and the enhanced possibility of higher N2 production
capacity but is limited to the N2O accumulation rate. The maximum N2 productivity with the addition of organic
substrate was achieved at about 83 g N/m3 with very few N2O accumulation. This theoretical study needs to
compare in a lab-based experiment to check whether the model is valid for practical purposes.
Acknowledgment
This work was supported by the SUST Research Center. (Reference no: Project ID- AS/2021/1/11)

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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 198

Effect of Physico-Chemical Treatment and Drying


Temperature on Drying Kinetics and Quality Characteristics
of Green Mango Pulp

Hossain*,M.S., Rayhan, S.M.J., Boni, S.F.T., and Rahamn, M.N.

Department of Chemical & Food Process Engineering,

Rajshahi University of Engineering &Technology (RUET), Rajshahi-6204, Bangladesh

Email: rayhan1611ruet@gmail.com, fahimtahmid111@gmail.com,


sajjad.hossain@cfpe.ruet.ac.bd, nurur@cfpe.ruet.ac.bd
*Corresponding author [Md. Sajjad Hossain]

Keywords: Abstract: Mango is a seasonal nutritious fruit and a huge amount of green mango
spoils every year as a result of unfavorable environmental factors. The effect of
● Mango powder; pretreatment (1% citric acid solution, hot water blanching & steam blanching) and
● Blanching; different temperatures (60℃, 65℃, and 70℃) by hot air drying on drying kinetics of
mango pulp and sensory properties of green mango powder were evaluated. It has been
● Drying rate; found that the drying rate was increased with increasing temperature, and drying time
● Moisture was decreased with increasing temperature. The data recorded during drying was
plotted on the exponential model. The maximum drying rate was observed for hot
diffusivity water blanching, 0.941 per hour in 70℃, and minimum for 1% citric acid treated
coefficient; sample, 0.434 per hour in 60℃. The moisture diffusivity coefficient (De) was
calculated and the diffusivity coefficient (De) improved with the rising of temperature.
● Flavor Highest diffusivity coefficient (De) was noticed for 70℃, hot water blanched sample
9.93×〖10^(-5)] (cm2/min), and60℃, 1% citric acid pre-treatment sample’s
diffusivity coefficient (De) was found minimum, 4.58×〖10^(-5)] (cm2/min). A
significant effect of pre-treatments (Citric acid solution and blanching) on mango
powder was clearly visualized. It was noticed that the mango powder which was
treated by citric acid was lighter than any other samples in terms of color. Furthermore,
the flavor of all samples contains a good mango flavor even after conducting the
physico-chemical treatments.

1. Introduction
Mango is an edible stone fruit, which is produced by the tropical tree Mangifera indica. The region
between northwestern Myanmar, Bangladesh, and northeastern India is believed to be place from where
mango is originated. Moreover, Bangladesh is the seventh largest mango producer in the world.
According to Bonneau, mango is a climacteric fruit with a very short shelf life and rapid ripeness
after harvest causing the deterioration of texture, flavor and taste. Consequently, mangoes are mainly
consumed either fresh or processed into different food items such as juice, puree, jam and dried fruit
with low water activity and long shelf life [20-21].

Page | 1086
The fruit pulp is high in prebiotic dietary fiber, vitamin-C, polyphenols and carotenoids. It is an
excellent source of β-carotene (provitamin A carotenoid), vitamin C, and polyphenolic compounds with
traces of vitamin E, K, and B. As these bioactive compounds are good antioxidants, daily intake of these
in diet has been related to the prevention of degenerative processes such as cardiovascular diseases and
cancer [22].
As a seasonal fruit, mango is manufactured into varied forms like frozen and canned slices, nectar,
toffee, puree, jam, squash, powder, and wine [15]. Energy, dietary fiber, carbohydrates, proteins, fats,
and phenolic compounds are provided by Mango pulp, which are vital to normal human growth,
development, and health [19]. Drying is the most convenient method to extend the shelf life of food
component. Mass transfer and heat happens simultaneously during drying, because of this reason,
appropriate method selection relies on several factors such as raw materials type and its properties, final
physical form of products which is predicted and mainly operating cost [1]. Generally, before drying,
pre-treatments are applied to diminish the adverse changes which might occur at the time of drying as
well as subsequent storage. In spite of having the fact that the integrity of food remains constant, due to
pre-treatments, various properties of dehydrated foods such as organoleptic, nutritional, texture as well
as functional properties [2]. Pretreatment such as blanching inactivate the enzymes, which are
responsible for the deterioration of products’ quality [12]. Moreover, citric acid treatment enhances the
sensoryproperties and shelf life of mango pulp.

2. Experimental
2.1 Mango Collection
Fresh mangoes mango (BARI Mango-9) were collected from Charghat, Rajshahi.
2.2 Mango pulp preparation
Collected mangoes were cleaned properly using running tap water to ensure that no dirt is present. After
that, peel was removed using a peel remover and pulps were sliced into 2.5 mm thickness using a slicer.
2.3 Blanching Pretreatments
A thermostatic water bath (Model HJ-A4) was used for steam blanching. Steam blanching was carried
out using steam at (90±2℃). In contrast, Hot water blanching was carried out for 1min at (90±2℃), using
a boiling pan and gas stove [16]. After blanching, both types of blanched samples were dipped into cold
water (4℃) immediately for reducing the temperature.
2.4 Citric Acid Solution Pretreatment
Sliced mango pulps are dipped into 1% citric acid solution and kept there for 30 minutes.
2.5 Convective Drying
Initial moisture content of green mango pulp was assessed [3]. In order to dry the pre-treatedand
control samples, cabinet dryer (model DHG-9075A) was used. Different trays were used to arrange
different samples (Control, Hot water blanched, Steam blanched, citric acid treated) in a single layer and
dried in three different temperatures 60℃, 65℃ and 70℃ upto seven hours [8].

2.6 Exponential modelling


In order to analysis the characteristics of drying of untreated and pre-treated samples, the drying data
were evaluated by using exponential model. The moisture ratio (MR) values were plotted against drying
time (t) on a semi-log coordinate and drying rate constants were determined as slope from the straight
line of the plots. Fick’s second law of diffusion was used to calculate Diffusivity coefficient.

Page | 1087
2.7 Sensory Evaluation
Dried mango samples were grounded into powder using an electric blender and screened by passing
through a 150µm opening. Color and flavor of mango powder were evaluated based on 9-scale hedonic
scale [13]. Ten trained panelists of CFPE department participated in the evaluation process.
2.8 Statistical Analysis
All sensory data were expressed as (mean value ± SD). The mean values were compared and tested
using Fischer’s least significant difference (LSD) at 5% level of significance using statistical software
[17].

3. Result and Discussions


3.1 Effect of Physico-chemical pretreatments and temperature on drying rate of
mango pulp
The drying characteristics of green mango pulp dried at different temperature are showed in fig. 1(a).
Pretreatments and drying temperature had a significant influence on drying time and drying rate
constants. The maximum drying rate was recorded for hot water blanched sample, dried at 70℃,
0.941/hr and minimum value was found for 1% citric acid solution treated sample, 0.434/hr in 60℃. At
60℃ drying temperature, hot water blanched sample exhibited the highest drying rate, 0.553/hr. By
analyzing fig. 1(a) and the developed equations, the drying of hot water blanched mango pulp required
the least amount of time than other samples. Altogether, maximum drying efficiency was at 70℃ with
hot water pretreatment. Shrivastava showed that drying rate of hot water blanched oyster mushroom was
higher comparing to steam blanched and unblanched sample [16]. Minimum drying time was found at
maximum temperature for hot water blanched sample. The equations developed using Fick’s second law
of diffusion during drying of mango pulp by applying different temperature and pretreatment are given
below:

MR = 0.5537𝑒−0.434X (Citric acid treated at 60℃) ; MR = 0.7074e−0.617X (Steam blanched at 65℃)


MR = 0.6354𝑒−0.515X (Control at 60℃) ; MR = 0.6196e−0.888X (Hot water blanched at 65℃)
MR = 0.477𝑒−0.544X (Steam blanched at 60℃); MR = 0.5299e−0.551X (Citric acid treated at 70℃)
MR = 𝑒−0.553X (Hot water blanched at 60℃); MR = 0.5825e−0.573X (Control at 70℃)
MR = 0.427𝑒−0.474X (Citric acid treated at 65℃); MR = 0.4962e−0.577X (Steam blanched at 70℃)
MR = 0.4875e−0.569X (Control at 65℃); MR = 0.613e−0.941X (Hot water blanched at 70℃)

Page | 1088
1
. 1
0 .
0 0
0 0
0 0
. 0
1 .
0 1
0 0
0
0 0
. .
0 0
1 1
0 0
0 0
. 0 2 4 6 8 1 .
0 0 2 4 6 8
0 0
0 0 MR (Control)
1 MR (Control) MR(Citric) MR(SB) MR(Citric) MR(SB)
MR(HWB) 1 MR(HWB)

1
.
0
0
0
0
.
1
0
0
0
.
0
1
0
0
. 0 2 4 6 8
0
0 MR (Control) MR(Citric) MR(SB)
1 MR(HWB)

fig. 2. Effect of pretreatments on convective drying characteristics of Mango pulp at (a)60℃,


(b) 65℃, and (c) 70℃ temperatures.

3.2 Effect of Physico-chemical pretreatments and temperature on diffusivity


Minimum value of diffusivity coefficient was found for citric acid treated sample at 60℃, 4.58*10−5
(cm2/min), while highest value was found for hot water blanched sample at 70℃ and the value was
9.93*10−5 (cm2/min)(Table 1). In an individual temperature, the citric acid treated sample exhibited
lower diffusivity than the blanched samples. With the increment of temperature, the diffusivity
coefficient increased.
Table 1 Drying constant rate and diffusion coefficient of green mango pulp at different temperature and
parameters

Sample Diffusivity
Drying Rate
Temp coefficient,(De*𝟏𝟎−𝟓)
Constant, m (𝐡𝐫−𝟏)
(𝐜𝐦𝟐/min)
Citric acid 0.434 4.58
60℃
Control 0.515 5.38
Steam 0.544 5.74

Page | 1089
Hot water 0.553 5.83
Citric acid 0.474 5.00
Control 0.569 6.00
65℃
Steam 0.617 6.51
Hot water 0.888 9.37
Citric acid 0.551 5.81
Control 0.573 6.04
70℃
Steam 0.577 6.08
Hot water 0.941 9.93
By contrast, the diffusivity coefficient decreased with decreasing temperature. Doymaz reported that
drying pretreatment increased water diffusivity of leek slices during drying [6].

3.3 Organoleptic Characteristics


MPP organoleptic score is illustrated in fig. 3. In terms color and flavor, Citric acid treated sample was
the highest rated in both cases, in all the three different temperatures. By contrast, control samples were
less attracted in terms of color and flavor. The mean value of color and flavor for citric acid treated
samples at 60℃ were (7.9±0.2) and (8.2±0.2) respectively, which was higher than other samples. Like
flavor, control samples exhibited the least attractive color than other samples as well. It was also
observed that the value reduced as the drying temperature increased for almost all of the samples.

fig.3 Sensory evaluation of Green mango pulp powder samples (a) flavor, (b)colour

4. Conclusion
The research was done to analyze the effect of pretreatments and different drying temperatures on
drying behavior and quality characteristics of green mango pulp and mango powder respectively. It was
clear that pretreatments improved the quality of mango pulp as well as it improved the organleptic
characteristics of samples as well. Moreover, the best results of drying rate were found for blanched
samples, the quality was also improved as blanching inactivates enzymes. The moisture diffusivity
coefficient was higher for blanched samples than unblanched samples. Furthermore, the highest value
was found for hot water blanched samples. As the temperature increased, the drying rate became faster.

References
1. L.A. Adepoju, Z.D. Osunde, Effect of Pretreatments and Drying Methods on Some Qualities of Dried
Mango (Mangifera indica) fruit, Agricultural Engineering International:

Page | 1090
2. AOAC, Official methods of analysis, (17𝑡ℎed.).MD: Association of Official Analytical Chemists,
Gaithersburg, 2000.
3. BBS (Bangladesh Bureau of Statistics), Yearbook of Agricultural Statistics. Statistics and Informatics
Division, Ministry of Planning, Government of the People's Republic ofBangladesh, pp. 360, 2017.
4. S. Dennis, Improving Solar Food Dryers, Home Power Magazine, (69), pp. 24-34, 1999.
5. I. Doymaz, Influence of blanching andslice thickness on drying characteristics of leek slices. Chemical
Engineering and Processing: Process intensification, 47(1), pp. 41-47, 2008.
6. FAO. Food and Agricultural Commodities Production, Available at:
http://faostat.fao.org/site/339/default.aspx. Accessed 27 November, 2011.
7. S.K. Giri, and S. Prasad, Drying kinetics and rehydration characteristics of microwave- vacuum and
convective hot-air dried mushrooms. Journal of food engineering, 78(2), pp. 512-521, 2007.
8. A. Isik, M. Ozdemir, and I. Doymaz, Effect of hot air drying on quality charecteristics and
physicochemical properties of bee pollen. Food science and technology, 39, pp. 224-231, 2018.
9. M.N. Kobayakawa, V. Silveris-Junior, and J. Telis-Romero, Drying of mango slices using heat
pump dryer. In Proceedings of the 14th International drying sympozium (pp. 22-25), 2004.
10. R. Oliver-Simances, M.C. Diaz-Maroto, M.S. Pérez-Coello, and M.E. Alañón, Viability of pre-
treatment drying methods on mango peel by-products top reserve flavouring active compounds for its
revalorisation. Journal of Food Engineering, pp.279, 109953, 2020.
11. K.S. Raja, F.S. Taip, M.M.Z. Azmi, & M.R. Shishir, Effect of pre-treatment and different drying
methods on the physicochemical properties of Carica papaya L. leaf powder. Journal of the Saudi
Society of Agricultural Sciences, 18(2),
pp. 150-156, 2019.
12. S. Ranganna, Handbook of Analysis and Quality Control for Fruits and Vegetable
Products Tata McGraw Hill Publishing Co. Ltd., New Delhi, 2005.
13. P. Russo, G. Adiletta, M. Di Matteo, V. Farina, O. Corona, L.Cinquanta, Drying Kinetics and
Physico-chemical Quality of Mango Slices , Chemical Engineering Transactions, 75, pp.109-114
DOI:10.3303/CET1975019, 2019.
14. S. Varakumar, Y.S.Kumar, and O.V.S. Reddy, Carotenoid composition of mango (Mangifera
indica L.) wine and its antioxidant activity. Journal of Food Biochemistry,35(5), pp.1538-1547, 2011.
15. B. Srivastava, K.P. Singh, and W. Zímik, Effects of blanching methods on dryingkinetics or oyster
mushroom. International Journal of Food Engineering, 5(4), 2009
16. StatGraphics, Advanced Regressions.Using Logistic Regression. In User Manual (Chapter 7).
StatGraphics Plus for Windows, Version 5.1. Professional edition. Rockville, MD. USA: Manugistic,
Inc., 1999.
17. T. Malik, R. Gehlot, Rekha and R. Sindhu, International Journal of Current Microbiology and Applied
Sciences ISSN: 2319-7706 Special Issue-11 pp. 684-687, 2020.
18. R. N. Tharanathan, H.M. Yashoda, and T.N Prabha, Mango (Mangifera indica L.), “The king of
fruits”—An overview. Food Reviews International, 22(2), pp. 95-123, 2006.
19. B. Önal, G. Adiletta, A. Crescitelli, M. Di Matteo, and P. Russo, Optimization of hot air drying
temperature combined with pre-treatment to improve physico-chemical and nutritional quality of
„Annurca‟apple. Food and Bioproducts Processing, 115, pp. 87-99,2019.
20. A. Fratianni, G. Adiletta, M. Di Matteo, G. Panfili, S. Niro, C. Gentile, and O. Corona, Evolution of
carotenoid content, antioxidant activity and volatiles compounds in dried mango fruits (Mangifera indica
L.). Foods, 9(10), 1424, 2020.
21. R.H. Liu, Protective role of phytochemicals in whole foods: implications for chronic disease
prevention. Applied Biotechnology Food Science and Policy, 1, pp. 39-46, 2003.

Page | 1091
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 200

Radiation-Induced Grafting of Acrylonitrile onto Non-woven


Polypropylene Fabric and Its Amidoximation for the Removal of
Methyl Orange

Sardar*, M. N., Rahman, N., Sultana, S., Dafader, N.C.


Nuclear and Radiation Chemistry Division, INST, Atomic Energy Research Establishment,

Bangladesh Atomic Energy Commission, Ganakbari, Savar, Dhaka-1349, Bangladesh

Email:*nabilchemist.ru@gmail.com, naziabaec@gmail.com, shahnazju32@gmail.com, nirmaldafader@gmail.com

Corresponding Author:[ Sardar]

Keywords: Abstract: The present study gives emphasis on the removal of methyl orange (MO) from
water using a waste plastic material as adsorbent. The pre-irradiation method was applied
• Pre- irradiation for the grafting of 60% acrylonitrile (AN) and H 2SO4 (2% of AN) as additive on the waste
polypropylene (PP) fabric at 80 o C for 6 hours. At 30 kGy radiation dose, the graft yield
• Grafting was 150%. The treatment of grafted PP with hydroxyl amine hydrochloride (NH2OH.HCl)
produces AN-g-PP adsorbent. The amidoximated adsorbent, AN-g-PP and the pristine PP
• Adsorption fabric were characterized by FTIR, SEM, and TGA. The study also investigated the effect
of different parameters on adsorption capacity such as contact time, MO concentration and
pH. Langmuir and Freundlich adsorption isotherms were applied to explain the
• Isotherm
equilibrium adsorption data. The maximum adsorption capacity was 15.80 mg/g after 24
hours at pH 3.23 and concentration 50 ppm. To elucidate the kinetic data, different kinetic
• Desorption models were utilized and the data were better fitted to the pseudo first-order model with a
good consensus between the experimental and the theoretical adsorption capacity.
Moreover, desorption of adsorbed MO from the surface of the adsorbent gave satisfactory
result. Thus, the amidoximated AN-g-PP fabric could be used as an adsorbent for the
removal of MO from the aquatic environment.

1. Introduction
Nowadays, environmental pollution caused by plastic waste and industrial dyestuffs has become great concerns
across the world as they are very poisonous to human, animals and plants. Methyl orange (MO) is a carcinogenic,
inhibits the photosynthesis in underwater plant [1, 2]. Plastic materials such as shopping bags, Filter paper, N-95
masks surgical masks, etc. are made with non-woven polypropylene (PP) fabric [3]. Unplanned discarding of
these plastic waste causes dangerous plastic pollution. Therefore, it is very crucial to pursue a new way of proper
utilization of this plastic waste and also essential to remove the toxic MO from the industrial wastewater before
discharging into the environment.
Among various adsorbents, the use of graft polymer as adsorbent becomes very convenient as graft
polymerization allows the addition of multiple functional groups [4]. Furthermore, radiation- induced grafting
allows extensive perforation into the polymer pattern resulting in the rapid and uniform production of free
radicals [5].
In this study, AN grafted waste PP adsorbent was prepared using pre-radiation method and its amidoximation to
remove the MO from its aqueous solution. The adsorption data were fitted to Langmuir and Freundlich isotherm
models and kinetic data were explained using several kinetic models. Finally, desorption and reuse of the
amidoximed AN grafted PP was also investigated.

Page | 1092
2. Experimental
2.1 Sample preparation
The PP bags were obtained from local landfill (Savar, Dhaka) and cut into small parts beforewashing
with acetone and dried in oven.
2.2 Materials
AN was procured from BDH, England. Acetone, sodium carbonate, sulfuric acid were purchased from
Merck, Jermany. Hydroxyl amine hydrochloride (Sigma Aldrich, USA) was used for amidoximation of
PP fabrics. MO was supplied by the Fluka, Switzerland.
Instruments and apparatus
The gamma radiation was from the Co-60 source (BRIT, India) having activity and dose rate
68.63 kCi and 13.7 kGy/h respectively. The surface morphology was determined by scanning electron
microscope (SEM) of model JEOL 6400 at acceleration voltage 20 kV. Dynamic mechanical analyzer
(DMA) from Triton Techonology TTDMA, UK was employed analyzing the mechanical property of the
adsorbent. FTIR spectrometer (model: 8400S, Shimadzu, Japan) at wavelength range 700-4000 cm−1 has
been implemented to investigate the functional groups. The MO concentration was determined by UV-
Visible spectrophotometer (model: AA-6800, Shimadzu, Japan).
Formation of AN grafted fabric
The gamma irradiated (30 kGy) waste PP fabric was preserved in a freeze at dry-ice condition until use.
The monomer solution prepared by mixing 60% AN and H2SO4 (2 % of AN) in methanol was
deoxygenated by passing Ar gas and then poured into a glass bottle occupying the irradiated PP fabrics.
The grafting reaction was employed at 80oC for 6 hours. The percentage ofgrafting was calculated by the
equation
Grafting %= 𝑾𝟐−𝑾𝟏 × 𝟏𝟎𝟎 (1)
𝑾𝟏

Where, W1 and W2 are the dry weight of the PP fabrics and grafted PP fabrics respectively.
Amidoximation of nitrile group
NH2OH.HCl (80 g) was dissolved in 1L distilled H2O and the solution was neutralized by Na2CO3. The
amidoximation reaction was carried out at 80oC for 4 hours. The conversion (Cn) of of nitrile group to
amidoxime one was calculated using the equation-
𝑴
𝑪 = 𝑾𝟑−𝑾𝟐 × 𝑨𝑵 × 𝟏𝟎𝟎 (2)
𝒏 𝑾𝟐 𝑴𝑯𝑨

Where W3 and W2 are the weight of the amioximated and AN grafted fabrics respectively. MHAdenotes
the molecular mass of NH2OH.HCl and MAN represents the molecular mass of the AN.
Adsorption of methyl orange
The batch experiment was employed by soaking amioximated AN-g-PP in MO solutions. The
adsorption capacity was estimated by the equation-
𝒄𝑶−𝒄𝟏
𝒒=𝒗( ) (3)
𝒎
Where q is the adsorption capacity in mg/g, v is the volume in a liter, c o and c1 are the concentrations
before and after immersing of the adsorbent in MO solutions respectively and m is the mass of the
adsorbent.

Page | 1093
Desorption study
Desorption study of MO from the adsorbent surface was carried out using 2M NaOH for 5 hours.
𝐌𝐎 𝐝𝐞𝐬𝐨𝐫𝐛𝐞𝐝 𝐢𝐧 𝐦𝐠
𝑫𝒆𝒔𝒐𝒓𝒑𝒕𝒊𝒐𝒏 % = × 𝟏𝟎𝟎 (4)
𝐌𝐎 𝐚𝐝𝐬𝐨𝐫𝐛𝐞𝐝 𝐢𝐧 𝐦𝐠

Results and discussion


Grafting of AN onto the PP fabrics and Conversion of nitrile group into amidoxime
The percentage of grafting was 150% and the percentage of conversion of nitrile group into amidoxime
became 75 %. The mechanism of grafting of AN and the amidoximation of the graftedPP fabric could be-
Fig. 1: Possible grafting of AN on to the non- woven PP
fabric and amidoximation of AN-g-PP

Thermo-gravimetric analysis (TGA)

The thermal stability was investigated by TGA and represented by


Fig.
2. As observed, the original PP fabric remains thermally stable up
to 227o C and gives 6.58% residue over 600o C. The degradation of
AN-g-PP starts after 230o C and produces 28.64% residue over 600o
C. On the other hand, after amidoximation, the AN-g-PP left 2.78%
residue over 600o C. Thus, the modification of AN-g-PP decreases it Fig. 2: TGA thermogram
thermal stabilityalthough it was remained stable up to 230o C.
FTIR analysis
The FTIR spectra of PP fabric (Fig. 3) shows symmetric stretching vibrations of the methylene (−CH2−)
and methyl (−CH3) groups at 2914 and 2953 cm−1 respectively and their asymmetric stretching are
appeared at 2872 and 2835 cm−1; the bending vibrations are observed at 1374 and 1452 cm−1. The strong
peak at 2243 cm−1 assigning to nitrile group (−CN) indicates a successful grafting of AN. In the
spectrum of amidoxime AN-g-PP, peaks at 912, 1267 and 1647 cm−1 attributing to N−O, bending
vibration of the amine group N−H and −C=N− group respectively [6].

Fig. 3: FTIR spectra of original PP, AN-g-PP and amidoximatedAN-g-


PP

Page | 1094
Meanwhile, a sharp increase of the −C=N− peak at 1647 cm−1 suggesting the successful conversion of
nitrile group into amidoximed group [7].
SEM analysis
To investigate the surface structure Scanning electron microscopy (SEM) was employed and
corresponding results are shown by the Fig. 4. A significant change is observed in the SEM photos of
original PP, AN grafted PP and amidoximated adsorbent that the average diameter of the AN grafted
chain is increased remarkably in comparison to that of pristine PP polymer.
Fig. 4: SEM photos of (a) PPfabric,
(b) AN-g-PP (c) Amidoxime AN-g-PP

This extension of chain diameter after reaction of PP fabric with AN is a clear physical evidence of
grafting nitrile group to the polypropylene polymer chain.
Batch experiments
Effect of initial dye concentration and adsorption isotherms
The adsorption capacity of amidoxime PP fabrics at pH 1.88 increases gradually as the concentration of
MO increases Fig. 5a. This is due to the fact that at low dye concentration, ratio of dye molecules to
adsorption sites is low, thus a large number of active sites available for dye adsorption.

Table 1. Adsorption isotherm parameters

Langmuir Value Freundlich Value


parameters parameters
qo (mg/g) 79.37 Kf (mg/g) 1.12
Fig. 5 (a) Change of adsorbent capacity with concentration RL 0.007 n (L/mg) 1.35
of the MO (b) Langmuir and (c) Freundlich
R2 0.837 R2 0.988
isotherm

The equilibrium adsorption data were fitted to linear form of the Langmuir and Freundlich isotherms
[8]. It was observed that the value of correlation coefficient, R2 for Langmuir isotherm (Fig. 5b) was
found to be 0.8373 which is very small compared to Freundlich isotherm (>0.98). Again, in Freundlich
isotherm (Fig. 5c) n greater than one demonstrates a favorable adsorption
[9] and it was 1.35 (Table 1) for MO adsorption indicating favorable sorption process. So MO
adsorption describes a better fitting to Freundlich isotherm.
Effect of contact time and adsorption kinetics
Fig. 6a shows that initially the adsorption rate was first due to the large number of adsorption sites on
the adsorbent surface. The removal rate became slower and finally reached a plateau after 24 hours giving
the maximum q of 15.8 mg/g. It was observed that the magnitude of R2 was almost similar (˃ 0.99) for
PFO (Fig. 6b) and IPD (Fig. 6d) models and higher than Langmuir isotherm (Fig. 6c). In case of IPD
model the line produced from the plotting qt against t did notpass through the origin. Thus, the IPD was
not the rate limiting step.

Page | 1095
Table 2: kinetic parameters for the adsorptionstudy of MO

PFO Val PSO Val


paramet ue parameters ue
ers
k1 0.1 k2 0.0
19 10
qe 15. qe 17.
41 27
R2 0.9 R2 0.91
95 67

Fig. 6 (a) Change of adsorption capacity with time (b) PFO (c) PSO, (d) IPD model and (e) EM
The experimental kinetic data were fitted to linear form of pseudo-first order (PFO), pseudo- second
order (PSO), intra-particle diffusion (IPD) and Elovich kinetic models (EM) [10].
On the other hand, the experimental (15.80 mg/g) theoretical (15.41 mg/g, Table 2) qe values from PFO
kinetic model were in good agreement with each other. So, it can be concluded that PFO kinetic model
follow the kinetic of MO adsorption onto the amidoxime AN-g-PP.
Effect of pH

The Fig. 7 demonstrates the maximum adsorption was found to be 39.41 at pH


1.88 and 50 ppm concentration due to the fact that the surface of the adsorbent
possesses amino groups (− NH2) which undergo protonation and become
positive charge species forming −NH3+ at low pH values. The protonated group
strongly attracks the negatively charged MO molecule and thus, qe increases.
Conversely, the adsorbent
surface was negatively charged forming NH2...OH− species due to Fig. 7: Effect of pH on
the de-protonation at high pH values that effectively repel the the q of the adsorbent.
negative charge MO dye molecule in the solution resulting in the
decrease of theadsorption capacity.

Desorption study
The percentage of desorption was found to be 75%.
Conclusion
In this study, a waste plastic material (Non-woven PP) was successfully converted into a graft polymer
(AN-g-PP) using radiation-induced grafting method by treating with 60% AN and then modify the graft
polymer into an amidoxime adsorbent. The adsorbent was applied for the removal of MO from aqueous
solution. The equilibrium adsorption data follow the Freundlich adsorption isotherm while the kinetic
data were well matched to the pseudo first-order kinetic model.The pH of the solution also greatly
affects the removal of MO. A better outcome also obtained from the desorption investigation. Thus, it is
clear that amidoximated AN grafted adsorbent produced from the waste PP fabric is a good candidate for
the MO adsorption owing to high removal capacity, very low cost, easy availabi lity and better
application of a plastic waste of our daily life.

Page | 1096
Acknowledgement
The authors would like to acknowledge the IAEA for technical support to conduct the study. Wealso
grateful to the Gamma Source Division of Institute of Food and Radiation Biology, AtomicEnergy
Research Establishment, Savar, Dhaka.
References

1. Parshettia, G.K., Telkeb, A.A., Kalyanib D.C., et al., Decolorization and detoxification of
sulfonated azo dye methyl orangeby Kocuria rosea MTCC 1532, Journal of Hazardous Materials.
2010, 176 (1-3); 503–509.

2. Jalil, A. A., Triwahyono, S., Adam S. H.,, et al., Adsorption of methyl orange from aqueous
solution onto calcined Lapindo volcanic mud, Journal of Hazardous Materials. 2010, 181 (1-3);
755–762.

3. https://www.textiletoday.com.bd/types-non-woven-fabrics-manufacturing-processes- applications/
(accessed 08 September 2022)

4. ABDEL-BARY, E. M., SARHAN, A. A., et. al., Effect of Graft Copolymerization of 2-


Hydroxyethyl Methacrylate on the Properties of Polyester Fibers and Fabric, Journal of Applied
Polymer Science. 1988, 35 (2); 439-448.

5. NASEF, M. M., Gamma Radiation-Induced Graft Copolymerization of Styrene onto Poly


(ethyleneTerephthalate) Films, Journal of Applied Polymer Science. 2000, 77 (5),1003–1012.

6. Long, H., Zhao, Z., Chai, Y., Binding Mechanism of the Amidoxime FunctionalGroup on
Chelating Resins toward Gallium(III) in Bayer Liquor, Industrial & Engineering Chemistry
Research. 2015, 54 (33), 8025−8030.

7. Ávila, M., Burks, T., Akhtar, F., et. al., Surface functionalized nanofibers for the removal of
chromium (VI) from aqueous solutions, Chemical Engineering Journal.2014, 245; 201-209.

8. Dada, A.O., Olalekan, A. P., Olatunya, A.M., Langmuir, Freundlich, Temkin and Dubinin-
Radushkevich isotherms studies of equilibrium sorption of Zn2+ontophosphoric acid modified
rice husk, IOSR Journal of Applied Chemistry.2012, 3 (1); 38-45.

9. Ayawei, N., Ebelegi, A. N., Wankasi, D., Modelling and Interpretation of Adsorption Isotherms.
Journal of Chemistry. 2017, 2017; 1-11.

10 Largittea, L., Pasquier, R., A review of the kinetics adsorption models and their application to the
. adsorption of lead by an activated carbon, Chemical Engineering Research and Design. 2016, 109;
495-504.

Page | 1097
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 229

The Future of Large-Scale Microalgal Biofuel Production


Md. Mirazul Islam*, Faiaj Mahmud, Salma Akhter

Department of Chemical Engineering and Polymer Science,

Shahjalal University ofScience and Technology, Sylhet-3114, Bangladesh.

Email: mirazulislam.cep@gmail.com, faiajmahmud0097@gmail.com, salmacep@gmail.com

*Corresponding author [Md. Mirazul Islam]

Abstract: A number of factors, including the continued depletion of petroleum


Keywords:
reserves, economic expansion as well as the prevention of climate change, are propelling
the development of platforms for renewable energy that are both commercially viable
● Microalgae; and eco-friendly. Microalgae have made a comeback as a popular raw material for
● Biofuel; making biofuels and other valuable products. In this experiment had great expectations
for microalgal biofuels for years, but the percentage of biofuels generated from algae now
● Large-scale
pales in relation to the amount of traditional oil. No comprehensive study of the influence
production; of these parameters on algal productive employment has been undertaken. Only biofuels
have been generated so far. The purpose of this study is to examine the advantages,
● Transport;
disadvantages, opportunities, and threats. To assess algal biofuel's production possibilities
● Reliability; for biofuels, as well as the risks associated with its market. The findings of the study
reveal that algal biomass production efficiency can be improved. It is possible to make
algal biofuels production more resource by combining it with the other process, such as
sewage treatment, which is widespread, although it is often not the case in practice. The
future of the production of algal biodiesel is significantly impacted by state laws and
policies. Electric automobiles pose a serious threat to the production of biodiesel because
of the rising strict environmental regulations. A significant difficulty challenges the
production of biofuels. When all the pertinent factors are considered, it is not anticipated
that algal feedstock will play a significant role in the fuel market.

1. Introduction

It is unsustainable to use fossil fuels for energy and is directly connected to pollution of the environment
and the depletion of natural resources (such as water and land). Motor fuel is used in a variety of types of
vehicles, energy plants, and farming, accounting for a significant share oftotal fossil fuel use. For its part, as
the number of transportation facilities grows considerably, as does the quantity of fuel used by those
facilities, the globe confronts the task of finding alternative fuels, since fossil-fuel sources are depleting.
Industry (25.8%), homes (26.1%), and transportation (25.8%) were the three most significant end-use sectors
for energy in the EU-28 in 2018. (30.5%).According to the EU, the automotive department accounts for 24.9
percent of greenhouse gas discharge, 36.48 percent of NOx emissions, and 10.67 percent of PM2.5
emissions. As a result, reducing emissions from transportation is one of the strategic priorities. The
progressive replacement of fossil fuels by renewable energy sources will be required to attain this goal.
Biofuels have the potential to make significant contributions in this regard. Biofuel production. may also

Page | 1098
serve to boost employment in rural regions, which will aid in the development of such communities. This is
where biodiesel comes in as a viable energy option. Worldwide, palm oil accounts for 31% of total biodiesel
production, followed by soybeans (27%), oilseed rape (20%), and used cooking oil (10%). A total of 44
percent of biodiesel is generated in the European Union, with the remainder coming from palm oil (29%),
used cooking oil (15%), and soy oil (5%). In theremainder of the composition, you'll find sunflower, coconut,
peanuts, hemp (including jatropha), maize, and algae. To reduce our reliance on fossil fuels, algae biodiesel
may be used as a substitute. A notable benefit of algae cultivation over traditional biofuel crops is that it
produces much greater yields. The oil reduced to dry biomass of certain algae species (Schizochytrium sp.,
Nitzschia sp., and Botyococcus braunii) contains more than 50% of the oil, which may be recovered and
converted to fuel (Oladapo Martins Adeniyi, 2018), (A.AlaswadaM.DassistibT.PrescottaA.G.Olabia, 2015).
A variety of fuels, including bioethanol, biodiesel, methane, airplane fuel (kerosene), biobutanol, biogas, and
green diesel, may be created from algae. A variety of environments, including freshwater or saltwater
(TiyapornLuangpipatYusufChisti, 2017), but also harsh ones, allow microalgae to flourish. Thus, they may
be found in a wide range of environments, including dormant and liquid aquatic ecosystems
(A.AlaswadaM.DassistibT.PrescottaA.G.Olabia, 2015) among others. The generation of lipids by
microalgae, as opposed to macroalgae, is the foundation of biodiesel production. Macroalgae, on the other
hand, have a tendency to generate sugars and other carbs rather than lipids and are thus not suitable for
biodiesel production. They were not commercially feasible feedstock for biodiesel production since their oil
percentage was lower than 5 percent of their dull weigh (A.AlaswadaM.DassistibT.PrescottaA.G.Olabia,
2015), and as a result, they will not be discussed further in this study. (Shin1, 2018) Algae are capable of
converting carbohydrates into oil and biomass, from which they may be used to produce a variety of products
including as biofuels as well as chemicals, medicines, meals, and cosmetics. Because the production of
biodiesel from algae is technically feasible and environmentally friendly, it has the potential to replace oil-
derived fuel in a methodical and sustainable way (Marwa G. Saad 1, 2019). The manufacture of large-scale
biodiesel from algae has not yet been shown to be economically feasible, despite the fact that several papers
have said that it has a future (Kirrolia, Bishnoi, & Singh, 2013), (Musa, et al., 2019). Only those microalgae
can be utilized in the manufacture of biodiesel because they have a high concentration of oil, produce a
large amount of biomass, and are resistant to a variety of environmental impacts (Remmers, et al., 2018).
These characteristics have not yet been discovered in any known microalgae species. These quantities are
for single backpacks, lakes, or photobioreactors, and a production plant needs many to create enough algal
biomass.
2. Outdoor cultures on a large scale
Light, temperature, and nutrients are the most important factors influencing the growth and productivity of
all algal cultures. The fact that virtually all production of algal biomass on a mass production takes place
outside in the sunlight is another factor to take into account. This exposesthe algae to daily different variants
in illumination and also differences in illumination for fewer hours that are resulted by clouds (Richmond,
2013), (Torzillo G. &., 2013). We will simply covera few of the most significant considerations here.

2.1 Temperature
Probably the first thing to look for when choosing a strain is how well it can handle temperature changes
and what temperature is best for it (Borowitzka, 2013c ). In large raceway ponds, it is difficult to control
the temperature, and it is expensive to control the temperature in closed photobioreactors. As a
consequence of this, it is of particular interest to choose a stress that is capable of developing far below the
temperature circumstances that are typical in the bioreactor that is situated at the site in question of the
manufacturing unit that is under consideration. Furthermore, if the strain has to endure severe heat induced
by equipment or power outages, as well as extreme heat days, the maximum fatal temperatures were
crucial. Heating rate has a big factor in how algae work and grow. When cultivated at of there ambient
temperature, algae are better able to deal with ecologic or such challenges.

Page | 1099
Changes in light and rain, as well as changes in temperature from one year to the next, all play a role in the
range of temperatures that an outdoor-living culture experiences through a well-populated area.
Temperature has significant effects on the overall efficiency of a plant or animal process that are often
omitted or undervalued. These effects go beyond the direct effects of temperature on performance and
growth. The first one is caused by the difference between how fast the light gets brighter in the morning and
how fast the climate warms up. But even though the light might get brighter very quickly in the early hours,
reaching over 80% of its highest within 2–3 hours of sunrise, the temperature in the culture will rise quite
steadily and reach its peak around noon or later. Because of this, the environment has to deal with less than
ambient temperature in the early hours. Because of this, the culture hasthermal photo-inhibitory destruction,
which was found to cause a possible loss of production of many over 24.9% (Vonshak A. T., 2001),
(Vonshak A. L., 2014). An experiment in which the temperature of one of two parallel heated ponds was
raised by 3-5°C just before sunrise and examined to the temperature of a counterpart untreated pond
successfully established the detrimental effect of post-morning pond temperature just before sunrise sunrise
(Moheimani, 2007)The rise in temperature during the early morning hours resulted in a biomass production
increase of 11–21% as a consequence. Identifying strategies to reduce the harm caused by inadequate
temperatures on a wide scale is difficult. Potential solutions include the installation of a solar-powered
heating system or the deployment of shading devices to minimize the amount of light that reaches the
process before the sunrise; Measures weren’t cost-effective on industrial scale. There is a correlation
between the temperature at night and the nighttime respiratory that takes place, which is an extra influence
of temperature. This often-over looked phenomena have received insufficient attention, mostly due to the
fact that only a small number of large-scale institutions evaluate biomass content in their ponds at least
twice a day (Torzillo G. S., 1991). The requirement to repair damage to the photosystems caused by high
“EUROPEAN JOURNAL OF PHYCOLOGY 411” irradiances experienced during previous day may need
vigorous dark respiration in many places where nighttime temperatures do not fall below 25°C (Raven,
2016).
2.2 Light
A variety of light/dark regimes are used to cultivate algal cultures in raceway ponds that are grown outdoors.
The first of these events takes place when the stirring device, which is often a paddle wheel, causes a
turbulence of the culture. The pace at which this event takes place is what controls how often light regime
cycles take place in the culture. The second occurs when the stirring apparatus (a paddle wheel) induces a
turbulence flow of the culture, and the rate at which this occurs determines how often light regime cycles
take place in the culture (Laws, 1988). Because of this, the microalgal cells in open ponds go through cycles
in which they are fully exposed to solar radiation while they are present at the top culture surface and in
which they are completely obscured by darkness when they reach the bottom of the culture, which is typically
between 15 and 20 centimeters in depth. Variations in the solar irradiance that occur during the day, from
dawn till sunset, are what cause the second regime, which is far slower than the first. When it comes to the
way in which algal cells that have been grown outside respond to light, these two different light regimes
each impose a unique physiological state on the organism. This state progresses from one that is extremely
light-limited to one that is saturated with light and perhaps cause oxidative stress. (Figure 1). Fig. 1.
Volume of algal culture required to produce 1 t of product per year assuming a cell densityof 0.5 g dry wt l–1,
a doubling time of 2 days and 365 days of production. Product cell contents used in the calculation
(Grobbelaar, 1991). In addition, there is a seasonal variation in light availability that has been less well
documented owing to a paucity of long-term outdoor trials in the past. The yearly productivity of a large-
scale manufacturing plant, on the other hand, may be significantly affected by seasonal changes. An
important concern when choosing the site of an industrial plant is whether or not the location will be
economically viable in the long run. At any given illumination, the photosynthetic output of microalgal
cultures will vary depending on the biomass density of the cultures. This is because the cells of the algae will
shade themselves from the light. This is because the real irradiance received by the cells is less when the
biomass density is high. Therefore, in suitably rich culture, there is an optimal cell density (OCD) at which
production is at its peak, and this is a measure of the current irradiance the microalgae get on a particular day

Page | 1100
2.3 Carbon and oxygen
Another important function of mixing and water volume is the removal of oxygen throughout the day to
prevent photo-oxidation, and the supply of oxygen even in night to avoid the creation of an oxygen-depleted
environment that might develop denitrification. As a result, oxygen loss in open ponds is restricted.
Moreover, because of algal photosynthesis, the air pressure in the pond may reach very high levels during
the daytime. In a similar manner, in tubular photobioreactors, photosynthetically generated oxygen will

accumulate while the concentration of inorganic carbon decreases as the tube is extended. As a consequence
of the high O2 concentration, ribulose bis- phosphate carboxylase/oxygenase is inhibited in its ability to fix
carbon in the photosynthetic process, resulting in a significant decrease in productivity. Considering that the
relative oxidase and carboxylase functions of RuBisCo are determined by their respective oxygen and
carbon dioxide concentrations, adding carbon dioxide to ponds might boost productivity by lowering both
inorganic carbon(C) deficiency and oxygen inhibition. CO2 injection may help big ponds, but the process is
not very effective because CO2 is slowly absorbed. This has the benefit of keeping the pH of the culture
close to the optimal range for the specific algal strain being used. Another option is to add inorganic carbon,
such as HCO3-, however it slowly raises the ionic concentration (Na+ or K+, based on that sodium
hydroxide or potassium hydroxide is used), which slows down growth of algae. Arthrospira requires a mix
of HCO3- and CO2 additions to keep a high alkalinity that helps it grow and provides a source of
denitrification for the photosynthetic process. This is done by starting with a large amount of Sodium
bicarbonate and then adding Carbon dioxide as needed, while keeping an eye on pH change to control the
process.

2.4 Nutrient source and supply


Once the goal of making cultivation systems bigger is reached, supplements will be a big cost. It's important
to think about where nutrients come from and how much they have. Normal nutrients used in bacterial
cultures are usually too expensive to be used in industrial microalgae biomass production. However apart
from additional expense, there are a few other things to thinkabout when it comes to nutrient content: 1) how
they affect the ability of the medium to regenerate; 2) the characterization and possible contaminants related
to legal prerequisites when the product is aimed at the feed and food markets; and 3) if the goal is to get
"licenses," some of the relatively cheap and easy-to-manage sources of phosphorus and nitrogen cannot be
used (Barminski, 2016). When it comes to algal cultivation, maintaining adequate nutrient concentrations is
regarded to be a simple process. However, it may serve as an illustrative example of the challenges that may
develop when transitioning between large to small running condition. The challenges of delivery method
and nutrient solubility, which are not addressed inthis article, compound the apparent concerns of monitoring
the amount of nutrition and the timing of surveillance. Only when accelerating is there more obstacles to
overcome. Other considerations include the availability and cost of nutrients in the local area, as well as
transportation and communication expenses.

Page | 1101
Nitrate is one possibility; however, the biochemical conversion of NO3 to NH3 requires the effort (ATP)
until it can be utilized as in creation of protein, hence impairing performance. The use of ammonia as a
nitrogen source is preferred in most cases, however excessive NH3 concentrations may be hazardous to
microalgal growth process Additionally, it may influence the synthesis of secondarymetabolites such as beta-
carotene. In addition, the rapid uptake of ammonia that happens in packed cultures can lead to high acidity
of the substrate, which can lead to the death or decomposition of the algae, especially when growth rates are
high.
3. Recycling of the culture medium
In order to maximize economic and environmental benefits from large-scale algae production, it is necessary to
recycle the medium after harvesting. Recycling the medium lowers the cost of water as well as the expenditure of
nutrients, since nutrients are still available in huge levels in the medium after harvesting. Recycling the medium
also saves money by decreasing the costs and potential environmental damage associated with dumping the
extremely huge amounts of water required for microalgal cell cultivation (Borowitzka M. &., 2013b). When
contemplating and testing harvesting techniques, the capacity to reuse the material must be taken into account
as a major factor. There are several issues that can arise from the recycling of media, including
(1) selective enrichment of culture-contaminating organisms or undesirable cell morphologies;
(2) build-up of specific ions that can negatively enhance the development of the algae; (3) build-up of auto-
inhibitors. However, the medium to be recycled may require some pre-treatment or conditioning before
it can be returned to the culture ponds. The majority of large-scale commercial algae growers have
found success in medium-scale recycling practices.

4. Contaminants and disease


There is always a possibility of contamination in massive cultivation, regardless of if the system in question
is a "open" one, such as pollutant removal, or a "closed" one, such as tubular photobioreactors. This is
because there is no way to completely eliminate the possibility of contamination. This holds true for all
different types of algae and predatory protozoa, in addition to fungus and bacteria. Although rapidly
increasing species with selectively environmental standards, such as D. salina (high salinity), Arthrospira
(high alkalinity), or Chlorella (high nutrients), can reduce the risk of contamination, the majority of algal
species of interest are not extremophiles. It is important to make note of the fact that, with the exception of
heterotrophic cultures, all vast algal cultures will not be axenic and will instead be coupled with a bacterial
flora. This is something that must be taken into consideration (microbiome). When the algae are threatened,
and the system is not appropriately mixed, the bacteria in the system are not merely acause for concern; they
have the potential to become a substantial factor in the failure of the culture. And on the other hand,
predatory protozoans and invertebrates (such as rotifers and crustaceans) may be controlled in the majority
of instances; however, the managerial method(s) that are applied likely to be quite species- and local
cultural. When it comes to fungal diseases, particularly pathogenic caused by parasitic fungus, they present
a more difficult treatment issue in both open loop and closed conditions. When it comes to the infectivity of
the parasite, it appears that it is influenced by a number of different characteristics, some of which include
irradiance, temperature, the nutritional state of the algal cells, and the population density of the algal cultures'
populations. Because it has been documented that various varieties with same organism can have varying
degrees of sensitivity to the same environmental conditions, it is possible that this feature could be exploited
to reduce the risk of infection by selecting strains with greater care. After many years of research and testing,
we came to the conclusion that algal cultures that are not growing in conditions that are ideal for their
development are more likely to become infected or consumed by other organisms. As a consequence of this,
the most essential factor in mitigating the risks andeffects posed by these pollutants is ensuring that optimum
values are preserved within a habitat that is in a state of perpetual flux in which they operate (Flynn,
2017).This highlights, once more,the need of selecting breeds for whom temperature significant correlate to
the temperatures that are present as during development of the productive forces.

Page | 1102
5. On-line and daily monitoring
In point of fact, huge algal biomass theory is a type of factory agriculture, with the primary objective being
the upkeep of an economically sustainable monoculture that produces a high volume of product. In order to
accomplish this goal, it is necessary to develop culture management methods and to have an in-depth
understanding of the physiological aspects of the seaweed that is being cultivated. A key duty is monitoring
system that provides early notification of any flaws and enables early corrective action to be done before the
culture fully fails is another thing that is in high demand. This monitoring system needs to be sturdy and
dependable. Additionally, it must be capable of being installed in a significant number of ponds or
bioreactors within a production plant while maintaining a reasonable price point. It is essential for the
operator to have strong visual observation skills in addition to extensive prior expertise. For instance, if the
color of the culture changes, this could be an indication that it is contaminated or that it is lacking in one or
more of the nutrients. In addition, if faiths start to "stick" to the walls of the waterbody or photobioreactor,
then there is an overabundance of bubbling, this signals that either the heritage is now under strain, and that
an implosion of the culture is likely to occur soon after. Visual observation, on the other hand, is only able
to detect major changes in the surrounding environment, making it an ineffective method of early warning
in the majority of situations. pH and oxygen content are the parameters that are examined in actively
growing cultures the most frequently, aside from temperature and light, and they are also the parameters
that are the easiest to measure. Other parameters include temperature and light. In cultures that are actively
growing,the pH and oxygen concentration will alter throughout the course of the day in a manner that canbe
predicted. Any deviation from the daily routine that is typically followed will be evidence that there is a
problem with the culture that is being observed there. If the cells are grown in culture using an ionic strength
approach for the administration of Carbon dioxide, then the rates of carbondioxide production can be used as
a metric to track how much the cultures have expanded over time. The use of a computer is all that is
required to carry out this kind of monitoring. Another technology that has sparked a significant amount of
interest in the realm of laboratory research and that is attracting an increasing amount of focus in the
agricultural sector is variable fluorescence parameters (Masojidek, 2011). Using a straightforward test such
as the Fv/Fm ratio, that indicates its maximum or prospective photochemical performance of the
photosynthetic apparatus (PSII), might well function as an important signal for the development of a strain
process as in civilization, which can result in a significant reduction in yield. This decline in efficiency may
be caused by a number of factors, including but not limited to: It is necessary to do additional study using
this metric online in different outdoor cultures in order to obtain a deeper knowledge of the findings and a
more nuanced interpretation of them. The bulk of the locations make use of an estimate of a select few
variables to monitor growth and productivity. These variables include turbidity, chlorophyll content, and
dry weight, among others. Each of them has a unique set of advantages and disadvantages, both in terms of
the amount of effort required and the amount of money spent. Without initially inventing an accurate
monitoring and interpolation method that is reliable, it will be extremely difficult, if not impossible, to have
a profitable magnitude and shared prosperity of a substantial algae business. The process of bringing
microalgae cells up to industrial numbers as well as keeping them cultivated is not an easy one, and it
involves the employment of personnel that is both highly knowledgeable and experienced, in addition to the
use of scientific principles that are sound. Large-scale commercial microalgae biomass culture has several
operational requirements, including: (1) effective and dependable manufacturing of inoculation with in
strictest sense of the word; (2) surveilling processes of the faiths to detect any potential issues that might
impact the solidity of the way of life in time for curative charges to be brought; and (3) progress of
maintenance and support protocols to manage the cultures under changing environmental conditions. Large-
scale commercial microalgae biomass culture has several operational requirements, including: (1) the
efficient and dependable production of All of these issues and procedures will need to be adapted to the
specific site and species in question, while also bearing in mind the fact that the enterprise as a whole need
to be profitable.

Page | 1103
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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 317

Visible Light Activated BiVO4/SrTiO3 Nanocomposites as


Photocatalyst for the Degradation of Organic Dye

Uddin*, M. T., Mukhlish, M.Z.B., Saha, A., and Nehrin, K

Department of Chemical Engineering and Polymer Science,

Shahjalal University of Scienceand Technology, Sylhet-3114, Bangladesh

Email: mtuddin-cep@sust.edu; zobayer_ceps@yahoo.com; arjansaha.cep@gmail.com;


kashfia.nehrin6055@gmail.com
*Corresponding author [Md. Tamez Uddin]

Abstract: Over the years, pollution of water caused by dyes and pathogens is a global
Keywords:
concern, but this environmental problem is disproportionately higher in low-income
countries, where water treatment facilities are typically inadequate. As a result,
● Photocatalyst; developing a viable approach for removing dyes and pathogens from aquatic systems is
vital for human and environmental health. In recent decades, heterogeneous
● Visible light; photocatalysis has been studied extensively for the removal of a variety of pollutants from
BiVO4/SrTiO3; aqueous solutions and generally, they were investigated under UV light irradiation. So,

here an approach has been taken for the development of photocatalyst system which are
● Recombination; activated under the irradiation of visible light as this light source has the potential of
utilizing freely available solar energy for environmental remediation. Moreover, to
● Dye degradation; overcome the charge recombination limitations, a heterostructure photocatalyst under
visible light was developed. In this context, heterostructure BiVO4/SrTiO3 photocatalyst
● Wastewater. was synthesized by solid-state method. The synthesized photocatalyst was subsequently
characterized by X-ray diffraction (XRD), FTIR, N2 adsorption-desorption isotherm, X-
ray photoelectron spectroscopy (XPS), UV–visible Diffuse Reflectance Spectroscopy
(DRS), and transmission electron microscopy (TEM). Photocatalytic activity of the
prepared photocatalyst was investigated by degrading methylene blue dye. Result
demonstrated the higher activity of heterostructure BiVO4/SrTiO3 (1:0.25 molar ratio)
for the degradation of methylene blue compared to bare BiVO4, SrTiO3 and reference
P25. The result achieved in this study may open the door for enhanced photocatalytic
activity in heterojunction composites used in wastewater treatment.

1. Introduction
Significant amounts of synthetic dyes are used in a variety of different chemical industries, including
textile, food, paper, printing, leather, cosmetics, and other industries for the purpose ofcoloring their finished
goods (Garg et al., 2004; Hagan and Poulin, 2021). It is projected that more than 10,000 different dyes and
pigments are used in industry, with over 7x 105 tons of synthetic dyes manufactured annually (Ogugbue and
Sawidis, 2011). About two-thirds of the dyes are usedin textile industry, around 10-15% of which is emerged
as effluent (Garg et al., 2004). The dyeing process in the textile industry consumes a significant amount of
water. The production of 1 kg fabrics requires about 0.08-0.15 m3 of water. After processing 12-20 tons of
textiles per day, an estimated 1,000-3,000 m3 of water is released as effluent.

Page | 1106
Additionally, the demand for textiles and the subsequent increases in manufacturing as well as the use of
synthetic dyes, have all led to dye wastewater becoming one of the most important causes of Coloring
effluents constitute a major hazard to the environment because they contain a complex mixture of
chemicals, auxiliaries, and dyestuffs that belong to several chemical classes and have varied chemical
constitutions (Carney Almroth et al., 2021). It is difficult to handle dye-contaminated wastewater due to the
fact that they are chemically highly stable. It also raises BODand causes a lack of dissolved oxygen, which is
essential for marine life to survive. Furthermore, most dyes used as coloring materials are harmful to certain
microorganisms and aquatic life, even at very low concentrations, and may cause inhibition of their catalytic
abilities (Berradi et al., 2019). Since many dyes are immune to aerobic digestion, they are difficult to
degrade. Dyes can also irritate the skin and cause allergic dermatitis. It has been discovered that some of
them are carcinogenic and mutagenic (Ferraz et al., 2011). Dye pollution is not only a major public health
issue, but it also has the potential to cause serious environmental issues due to its persistence. Therefore, the
removal of such dye from process effluent becomes environmentally important.
The removal of dyes from wastewater can be accomplished using a variety of techniques such asadsorption,
photo-degradation, coagulation, flocculation, chemical oxidation, electro-chemical oxidation, and biological
processes (Collivignarelli et al., 2019; Noor et al., 2022; Shu et al., 2015; Uddin et al., 2016). These existing
technologies are often inefficient to reduce pollutant concentrations to anticipated level in a cost-effective
and efficient manner. Each one has its own set of advantages and disadvantages. Therefore, there has been a
constant search for more efficient, innovative, and less costly technologies for the treatment of industrial
effluents. Over the past decades, heterogeneous photocatalysis on semiconducting oxide
photocatalyst such as titanium dioxide (TiO2), tin oxide (SnO2), or zinc oxide (ZnO), has received a
lot of interest due to its efficiency in degrading organic contaminants in water and air (Ibhadon and
Fitzpatrick, 2013; Uddin et al., 2013, 2012). However, due to the quick recombination of the
photogenerated electron-hole pairs, this approach has some constraints in degrading water and air
pollutants. Furthermore, most commonly used photocatalyst, such as ZnO and TiO2, have high
band gap energy which limits the absorption of visible light directly (VL). As a result, such
techniques are not effective when used on a broad scale because UV light makes up just about 4-
5% of the overall solar spectrum. Recently, cadmium sulphide (CdS), bismuth vanadate (BiVO4)
and bismuth oxy-iodide (BiOI) have emerged as promising photocatalyst for the degradation of
organics under visible light irradiation. Among them, bismuth vanadate (BiVO4), a n- type
semiconductor, has attracted significant interest due to its outstanding features, such as low band
gap (~2.4 eV), good dispersibility, non-toxicity, resistance to corrosion and outstanding
photocatalytic result in organic pollutant degradation under visible-light illumination (Hu et al.,
2017). However, due to the rapid recombination of photo- generated electron-hole pairs, its broad
application is severely limited [24]. In this context, the great challenge of practical application of
BiVO4 for the degradation of organics is to reduce the recombination of photogenerated charge
carriers. Combining semiconductors with different band gap values is an effective way to improve
photocatalytic activity when exposed to visible light (Uddin et al., 2012). It was established that
BiVO4 could be coupled with various semiconductors, such as TiO2 (Zhang et al., 2013), g-C3N4
(Tian et al., 2014), BiOI (Xiang et al., 2016), and AgI (Chenet al., 2016). Synthesizing new materials
based on BiVO4 is still required in order to fulfill the requirements for further enhancing
photocatalytic efficiency. SrTiO3, a typical perovskite (ABO3) oxide, is applied in many fields
because of its stable physical and chemical properties, such as optical materials and ceramic
materials (Fan et al., 2015).

Page | 1107
However, the main disadvantage of poor light utilization ability in the visible light region was
denounced by researchers due to its broad band gap (Eg = ~3.2 eV) (Reunchan et al., 2013), which
restricts the light absorption at UV light range only possessing 4% of the solar light. It is expected
to promote carrier separation and enhance photocatalytic activity by fabricating BiVO4-SrTiO3
heterojunction. The conduction band (CB) and the valence band (VB) offsets existing at the
interface of BiVO4/SrTiO3 heterojunction spatially transfer photogenerated electron holes in
opposite directions, and thus reducing the charge recombination and consequently, increasing the
degradation efficiency. Based on our best experience, no efforts have been made to evolve
BiVO4/SrTiO3 photocatalysts to improve their photocatalytic efficiency.
In this study, BiVO4/SrTiO3 nanocomposite (NC) has been synthesized by precipitation and sol-gel
methods. The as-synthesized nanoparticles are then characterized by different technique such as by
X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV–visible Diffuse
Reflectance Spectroscopy (DRS). The photocatalytic activity of the prepared photocatalyst was then
investigated by degrading MB dye under visible lightirradiation.

2. Experimental
2.1 Synthesis of BiVO4/SrTiO3 NC
The BiVO4/SrTiO3 heterostructure photocatalysts were prepared by the solid-state sintering
method. Firstly, BiVO4 nanoparticles was prepared by precipitation method using bismuth nitrate
and ammonium metavanadate as precursor. Secondly, the SrTiO3 nanoparticles were synthesized
by hydrothermal method using Sr (OH)2. 8H2O and TiO2 as precursors. In a typical method for the
preparation of BiVO4/SrTiO3 NCs, 0.7 g BiVO4 and 0.0991 g SrTiO3 were thoroughly mixed and
ground in a mortar for 40 min through the agate mortar and pestle. The ground powder was then
calcined at 500°C for 2 h in a furnace. The heat treatment enhanced the chemical binding among
the particles and strengthened the mechanical properties of the BiVO4/SrTiO3 NC. The obtained NC
was then labeled 20 mol% BiVO4/SrTiO3 and stored for further use. The BiVO4/SrTiO3 NCs
containing other mol% SrTiO3 were prepared by following the same procedure.

2.2 Characterizations of nanoparticles

The crystallinity of the prepared NPs was investigated using X-ray diffractometer ((SMARTLAB, RIGAKU,
Japan). The 2θ data were obtained using a continuous scan mode in the 2θ range of 10 to 80°.The mean size
of crystallite was calculated using Scherrer’s formula. X-ray photoelectronspectroscopy (XPS) spectra of
the as-prepared NPs were recorded using a K-Alpha KA1066 spectrometer (Thermo Scientific) to
elucidate their elemental and chemical state. Monochromatic X-ray (Kα: 1486.61 eV) from an Al
anode was used for excitation. The charge effect was evaluated using the main component of the C
1s peak, associated with adventitious hydrocarbons with a binding energy of 284.8 eV as reference
for calibration.

Page | 1108
The base pressure in the sample during the measurements was less than 3x10-8 mbar. The band gap
energy of the prepared NPs was determined by measuring UV-vis diffuse reflectance spectra (UV-vis DRS)
of the NPs at ambient condition. The UV-vis DRS was recorded by scanning the samples in wavelength
ranging from 200 to 800 nm with a UV-vis-NIR spectrometer (LAMDA 750, PerkinElmer, Inc, USA) using
sintered PTFE as standard reference.

2.3 Photocatalytic experiment


The photocatalytic activities of the as-prepared photocatalysts were investigated by degrading MB dye
irradiated with a UV-Visible lamp (LUMATEC SUPERLITE 400),). The photodegradation tests were
conducted by placing lamp over a 250 mL glass beaker. The reaction cell was maintained at 25 °C by
circulating water. In a typical experimental procedure, 0.1 g of the photocatalyst was disperse in 100 mL of
MB (10 ppm) solution at pH 7. All the tests were carried out in the air at room temperature. Before adding
photocatalyst, 5 ml of MB solution was collected in order to measure initial concentration. The suspensions
were stirred in the dark condition for 10 minutes prior to light irradiation to achieve the adsorption
equilibrium. The solution was then irradiated with Visible light under continuous stirring. 5 ml dispersion
aliquot was collected as a sample after a predetermined time interval and separated the photocatalyst after
centrifugation (5500 rpm, 10min). The concentration of MB blue in the supernatant was then calculated by
measuring absorbance at 664 nm using a UV-VIS spectrophotometer (LAMDA 750, Perkin Elmer, Inc,
USA).

3. Result and Discussions


3.1 Characterization of nanoparticles
Fig. 1 shows the XRD patterns of the as-prepared BiVO4 nanocrystals and BiVO4/SrTiO3 heterogeneous
nanostructures. The main peaks shown in Fig. 1(a) could be indexed as (1 1 0), (1 2 1), (0 4 0), (2 0 0), (0 0
2), (2 1 1), (1 5 0), (1 3 2), (2 4 0) and (0 4 2) planes of monoclinic
BiVO4 (JCPDS card No. 14-0688). The main diffraction peak of SrTiO3 (Fig.1 (e)) at 2θ = 32.0, 40.0, 46.5,
57.5 and 68.0 ⁰ could be indexed of (110), (111), (200), (211) and (220) planes of cubic perovskite SrTiO3,
respectively (JCPDS No. 86-0176). The XRD pattern of BiVO4 and SrTiO3 in BiVO4/SrTiO3
nanocomposites were well agreed with the diffraction line of pure BiVO4 and SrTiO3. However, the peak
intensity of SrTiO3 is less than that of BiVO4.

Page | 1109
1
1
( 0
(

1 )

12
)0
0
(

2
1
1
1(

()

)
c

Intensity(a
BiVO
4
SrTi (

.u)
b

1
2
1
(

(2
(132)
(040

(200

(211

(150
(

40)
(

0
)4
2
)(

)
1

)
a

10 20 30 40 50 60 70
2 (o)

Fig. 1 XRD spectra of (a) BiVO4 (b) 20 mol% BiVO4/SrTiO3 (c) SrTiO3.

To investigate the chemical composition and the chemical state of the elementals of BiVO4/SrTiO3 nano-
composites, XPS study was conducted. The survey spectra of 20 mol% BiVO4/SrTiO3 in Fig. 2 show only
the emissions of Bi, V, Ti, Sr and O with a very weak emissionline of C. The C signal can be attributed to the
adventitious carbon-based contaminant which commonly exists for XPS.
1600000
B
1400000 i
O
1200000

1000000
C
P
S

800000 T V 2p3
i Ti 2p
600000
C
400000 S
r
200000

0
600 500 400 300 200 100
Binding energy (eV)

Fig. 2 XPS survey spectra of 20 mol% BiVO4/SrTiO3 .

Page | 1110
The high-resolution spectra of Bi, Sr, Ti, V and O species are shown in Fig. 3. The emission lines of Bi 4f
appearing in Fig. 3 (a) were symmetric and centered at 158.80 and 164.10 eV, which were attributed to Bi
4f7/2 and Bi 4f5/2, respectively, confirming that the Bi species exist as Bi3+. The peak (Fig. 3(b)) centered at
516.40 eV was attributed to the V 2p3/2 and the other one at
523.70 eV to V 2p1/2, indicating a normal oxidation state of V5+ in the BiVO4/SrTiO3 photocatalyst. Fig. 3(c)
displays high-resolution spectra of Sr 3d indicating the element's chemical state to be Sr2+, with symmetric
peaks at 132.70 and 134.45 eV, which were assigned to Sr 3d5/2 and Sr 3d3/2, respectively. The Ti 2p
spectrum shows peaks located at 458.8 eV assigned to Ti 2p3/2 core level. This binding energies was fully
consistent with the formal oxidation state Ti4+ and with the presence of SrTiO3 crystallites. Thus, it could be
confirmed that Bi, V, Sr, Ti and O elements exist mainly in the as-prepared samples. As a result of the XPS
results, it is clear that aBiVO4 and SrTiO3 heterostructure has been successfully constructed.

110000
Bi
250000
( Bi
4f
100000 (
200000 a 4f
90000
b
150000
80000
C
P
S

C
P
S
100000
70000

50000 60000

50000
0
168 166 164 162 160 158 156 526 524 522 520 518 516 514 512 510
Binding energy (eV) Binding energy (eV)

40000
85000

35000
( 80000
(
30000
c 75000 d Ti
2p
70000

25000 65000
C
P
S
C
P
S

60000
20000
55000

15000 50000

45000
10000
40000
475 470 465 460 455 450
142 140 138 136 134 132 130 128 126
Binding energy (eV) Binding energy (eV)

Fig. 3 XPS high-resolution spectra of 20 mol% BiVO4/SrTiO3 sample: (a) Bi 4f region, (b) V2p region,
(c) Sr 3d region, (d) Ti 2p region

The optical property like band gap of a semiconductor plays an important role in determining its activity as
photocatalyst for the degradation of organic dyes. The UV-Vis DRS was employed to inspect the optical
property of the synthesized NCs as displayed in Fig. 4. The Fig.4 demonstrates the absorption edges of pure
SrTiO3 at around 380 nm. Compared to that of SrTiO3 sample, the

Page | 1111
absorption edges of BiVO4/SrTiO3 nanocomposites were observed to be red-shifted towards higher
wavelength indicating the absorption of light more efficiently by the heterostructure BiVO4/SrTiO3. The
calculated energy band gap (Eg) for SrTiO3 was found to be 3.11 eV. The analysis reveals lower Eg
of BiVO4/SrTiO3 NCs compared to the pure SrTiO3. The Eg for pure BiVO4 and 20 mol%
BiVO4/SrTiO3 were found to be 2.34, and 2.30 eV,respectively.

16

14

12
(
10 c
R

8
F
(

(
6 b

2
(
0 a
200 250 300 350 400 450 500 550 600 650 700 750 800 850
wavelength,nm

Fig. 4 UV-visible diffuse reflectance spectra of synthesized nanoparticles (a) SrTiO3 (red line); (b)
BiVO4 (black line) and (c) 20 mol% BiVO4/SrTiO3 (blue line).

3.2 Photocatalytic studies


The photocatalytic performance of the as-synthesized nanoparticles was evaluated by degrading MB dye
under UV light irradiation. For sake of comparison, the photocatalytic degradation of MB is monitored on
the prepared photocatalysts and commercial P25 as references. In addition, the photocatalytic degradation
of MB under only UV light irradiation and without using photocatalyst is also investigated as blank
experiment in order to justify the degradation performance of BiVO4/SrTiO3 NCs. The adsorption of MB
onto BiVO4/SrTiO3 NCs without light irradiation is also investigated as blank experiment. The
photocatalytic degradation kinetics of different photocatalysts is presented in Fig. 5 in form of C/C0 vs. t
plot, where C is the concentration of MB at any time, t, and CO is its initial concentration. From Fig. 5, it is
observed that the 20 mol% BiVO4/SrTiO3 showed higher degradation efficiency compared to T SrTiO3,
BiVO4 and commercial P-25. After 20 min of photocatalytic reaction, the degradation efficiency of SrTiO3,
BiVO4, 20 mol% BiVO4/SrTiO3 and P-25 for the degradation of MB were about 9%,

Page | 1112
49%, 64% and 36%, respectively. In summary, mesoporous BiVO4/SrTiO3 nanocomposite containing 20
mol% SrTiO3 had the fastest MB decomposition rate, confirming the approach presented in this study. It is
well known that photocatalytic degradation of organics follows pseudo-first order kinetic rate law: ln(C/C0)
= -kt, where k is the reaction rate constant. If ln(C/C0) is plotted against t, a straight line will be obtained
whose slope is equal to reaction rate constant,
k. The experimental values of ln(C/C0) were plotted against time, t (Fig. not shown here) in orderto evidence
the higher degradation efficiency of BiVO4/SrTiO3 NCs. The BiVO4/SrTiO3 NCs exhibited higher
degradation efficiency with degradation rate constant 0.0144 min-1, which was about 1.44 and 2.87 times
higher than those obtained with the pure BiVO4 and commercial P25, respectively.

1.0

0.8

0.6
C/
C
0

0.4
BiVO4
SrTiO3
0.2

0.0
0 20 40 60 80 100 120
Time (min)
Fig. 5 Photocatalytic degradation kinetics of MB with different photocatalysts under UV light irradiation.
(Initial dye solution concentration =10 mg/L; Volume = 100 mL, pH = 7; catalyst dose
= 1 g/L).

The enhanced degradation efficiency of heterostructure BiVO4/SrTiO3 NCs can be rationalized by band
alignment at the interface between SrTiO3 and BiVO4 nanoparticles. The BiVO4 photocatalyst is excited by
the photon which has sufficient energy to generate the photo-induced electron-hole pairs. The estimated
values of ECB and EVB for BiVO4 were found to be 0.38and 2.7 eV, respectively. On the other hand,
ECB and EVB for SrTiO3 were calculated to be –0.655 and 2.455 eV, respectively. The VB edge
potential of BiVO4 is more positive than that of SrTiO3, and the CB of BiVO4 is more positive than that of
SrTiO3. The local electric field at the BiVO4/SrTiO3 interface pushes the photogenerated holes of the VB of
BiVO4 diffuse to the VB of SrTiO3. The photogenerated electrons can be effectively collected by BiVO4 and
holes by SrTiO3, leading to the effective separation of photogenerated electrons and holes. Thus, the
electron-hole recombination process was prohibited and the BiVO4/SrTiO3 composites exhibit enhanced
performance as compared to BiVO4 and SrTiO3 alone.

Page | 1113
4. Conclusion
Heterostructure BiVO4 /SrTiO3 NCs are successfully synthesized via hydrothermal method followed by a
simple solid-state reaction method at 500°C and used as heterogeneous photocatalysts for the
decomposition of methylene blue (MB) dye from aqueous solution under Visible light irradiation. UV-
vis/DRS analysis revealed that the BiVO4/SrTiO3 composite has excellent optical properties within the
visible region. The BiVO4/SrTiO3 NCs containing 20 mol% SrTiO3 exhibited the highest MB degradation
efficiency compared to pure BiVO4, SrTiO3 and reference TiO2 (P25). The band offsets at the interface of
BiVO4 and SrTiO3 NPs reduce the photogenerated charge recombination resulting in enhanced degradation
efficiency of BiVO4/SrTiO3 NCs. The basic media is favorable for the degradation of MB BiVO4/SrTiO3
NCs. The result achieved in this study may open the door for enhanced photocatalytic activity in
heterojunction composites used in wastewater treatment.

Acknowledgements
We gratefully acknowledge the financial support of the work by Shahjalal University of Science and
Technology (SUST) Research Centre (Grant No.: AS/2021/1/05).

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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 333

Energy Utilization Opportunity From Liquefied Natural Gas


Regasification Terminal Using The Flue CO2 Gas from The Coal
Based Powerplant In Bangladesh

Department of Chemical & Food Process Engineering


Rajshahi University of Engineering & Technology, Bangladesh

Abstract
In this paper, LNG (liquefied natural gas) energy utilization during regasification process was proposed
which exchanges heat with the exhaust CO2 gas discharged from coal based thermal power plant in
Matarbari, Cox's Bazar, Bangladesh. A twin-stage Organic Rankine cycle with R14and R-290 as working
fluid are also included in this system. As a heat sink , LNG and as a heat source exhaust CO2 is used in
the power generation subsystem. The results show that, the amount of, LNG cold energy received at
Matarbari LNG terminal can theoretically exchange heat with the exhaust CO2 gas from the Matarbari
Coal based power plant. In addition, when the 1000 MMSFCD LNG fed at 111.15 K exchanges heat with
flue gas flowing at 75°C with a flow rate of 8.94 × 106 m3/ℎ𝑜𝑢𝑟 .The energy efficiency of that system
was calculated 80 % in that system.

Keywords: Liquefied natural gas, Cold energy utilization, Exhaust CO2, Energy efficiency

1. Introduction
1.1 Definition

Liquefied natural gas (LNG) is natural gas (predominantly methane, CH4) which for ease of storage
or transport has been converted to liquid form. It is cooled to -162 ° C, turning it into a liquid from a
gas that is 1/600th of its original volume [1]. This reduction makes it possible to ship safely and
easily on specially built LNG vessels. LNG is heated after arrival at its destination to return it to its
gaseous state and supplied via local pipelines to natural gas customers. It is odorless, non-toxic,
colorless and non-corrosive. A higher volume reduction than compressed natural gas isaccomplished
by LNG (CNG). Cryogenic marine vessels (LNG carriers) or correctly built cryogenic road tankers

Page | 1116
are used to transport them. It is not stored under high pressure environments and is not explosive.
While a large amount of energy is contained in LNG, it cannot be released quickly enough to cause
an explosion-related over-pressure in an open space.

1.2 Properties of LNG

LNG is no different than natural gas, LNG has a greater heating benefit of 24MJ/L.LNG’s lower
heating value is 21MJ/L. LNG’s energy density is 2.4 times greater than CNG’s energy density [2].

o Boiling Point -162°C (-259°F). o

Density between 430 kg/m3 and 470 kg/m3.

o Ignition flame temperature of 1,027°C (1,880 °F)

o Heat of combustion is 50.2 MJ/kg.

Essential properties of LNG are as follows:

Chemical composition

Natural gas is a fossil fuel formed millions of years ago by organic material deposited and buried in
the ground. Crude oil and natural gas are fossil fuel types known as "hydrocarbons" because they
contain chemical fuels and combinations of hydrogen and carbon atom. The chemical makeup of
natural gas is a function of the source of gas and the kind of processing. It is a mixture of methane,
ethane, propane and butane with small quantities of heavier hydrocarbons and some

Page | 1117
impurities, including nitrogen, water, carbon dioxide and complex Sulphur compounds. And the
sulphide of hydrogen that may occur in the feed gas but is extracted before liquefaction. Table-1.1
displays the various compositions found in LNG.

Table 1.1: Typical Chemical Composition of LNG [3]


Chemical Chemical Low High
Formula
Methane CH4 87% 99%
Ethane C2H6 <1% 10%
Propane C3H8 1% 5%
Butane C4H10 0.005 1%
%
Nitrogen N2 0.1% 1%

Density and Specific gravity

Density is a mass measurement per volume unit. LNG isn't a fully pure material. LNG's density
varies slightly depending on its composition. LNG has a density of about 430 kg/m3 to 470 kg/m3
and (3.5 to 4 pounds/US gal). LNG is less than half the price of natural gas. Because of the density
of water, LNG can float if spilled on water. LNG vapors have a relative density of approximately
1.8 at boiling point temperature and atmospheric pressure, which means that LNG vapors are
heavier than air when initially emitted and can remain close to the ground. LNG vapors are very
cold. In low places, they are negatively buoyant and more likely to collect before the vapor. A
release of LNG that occurs in an enclosed space or low spot would, therefore, appear to replace the
air (and oxygen) and make the environment a breathing hazard. The rate of LNG vapor ascent is
determined by the amount of LNG released and the weather conditions. Conditions and the location
of the LNG release Input of heat to LNG in a (3,18,763.6 MMSCF) is a number that can be used to
represent a number of items. From the beginning of the operation until June 30, 2020, RLNG was
supplied to the national grid by Terminal Co. (Pvt.) Ltd [4] . A short distance from the SLNG
Terminal is any form will boost dispersion and vaporization. Depending on the soil quality
vaporizes five times faster on water than on
land. In fact, using a water hose to warm the LNG vapors is another method for reducing the
flammability risk. The liquid raises the vaporization rate more rapidly and makes the vapors
buoyant faster, at ground level, rising away from ignition sources

Page | 1118
Flammability

The property that makes natural gas attractive as an energy source is flammability, and yet
flammability can be a safety hazard for the same reason. Because of the lack of oxygen in LNG, it
is not flammable. 'Flammable Range' means the range of a gas or vapor concentration that can burn
if an ignition source is added. The "Lower Flammable Limit" (LFL) and the "Higher Flammable
Limit" (UFL) are the two thresholds (UFL). Methane's flammability limits are 5 per cent LFL and
15 per cent UFL by air volume. The methane/air mixture is not flammable outside of this range.
The tank or vessel in a closed storage tank or ship
The methane percentage is essentially 100 percent (mostly liquid and some vapors).In a
wellventilated environment, any small leakage of LNG vapor from a tank is likely to mix rapidly
and quickly dissipate to less than 5 percent methane in the air. Due to the speedy mixing, only a
small area near the leak will have the concentration required to allow the leak to
Fuel engineered to fire. To detect any leaks or combustible gas mixtures, all LNG terminals use a
range of equipment on and around the storage tanks and piping in the facility. The flammability
limits of hydrocarbon fuels are shown in Table 1.2. appearing in LNG.

Table 1.2: Flammability limits of hydrocarbon fuels [5]


Fuel LFL (%) UFL (%)
Methane 5.0 15.0

Butane 1.86 7.6


Kerosene 0.7 5.0
Propane 2.1 10.1

Hydrogen 4.0 75.0

Boiling Point

One of the most important characteristics is the boiling point, since it determines when gas becomes
liquid. At atmospheric pressure, the boiling point of a liquid is defined as the temperature at which
it boils or rapidly transforms from a liquid to a vapour. The temperature at which water boils. At
atmospheric pressure, the temperature of pure water is 100°C (212°F).
LNG's boiling point varies depending on its basic composition, but it is usually -162°C (-259°F).

Page | 1119
LNG starts to “boil” as it comes into contact with warmer air, water, or the climate [6] . Since the
ambient temperature is higher than the LNG's boiling point remark. The liquefaction process cools
natural gas to turn it into a liquid that decreases the gas volume by approximately 600 times the
volume occupied by the gas.

1.3 MOTIVATION

Natural gas is Bangladesh's main source of primary energy. Locally generated gas now controls
more than 75% of factories and power plants. The nation is currently experiencing a gas shortage.
Domestic primary fuel supply is becoming so limited that it is requiring drastic steps such as
shutting down fertilizer plants, limiting gas supplies for household and transportation purposes, and
idle power plants. It's important to keep the gap between gas demand and supply in the country as
minimal as possible. A new energy source is needed. Energy that is stable and long-term. For
Bangladesh's growing economy, a reliable source of energy is needed. Energy that is stable and
long-term. For Bangladesh's growing economy, a reliable source of energy is needed. Imports of
liquid natural gas (LNG) may be one of the fuel sources for increasing energy demand in order to
deal with the current energy crisis. Imported LNG is regasified in regasification terminal. During
regasification a Massive amount of energy (around 830 kJ/kg of LNG) is wasted in the LNG
regasification terminals [7]. This heat can be utilized and minimized the wastage of cold energy
during regasification in Bangladesh.
On the other side for generating power to cope up with the growing energy demand Bangladesh
governmet is setting up numerous coal-based power plant as generating power from this source is
cheaper. But huge amount of CO2 is present in the flue gas of the coal-based power plants which
cause adverse effect on the environment. The CO2 can be captured by using cryogenic separation
and the cryogenic energy can be utilized from LNG.

1.4 Objectives
• To utilize the waste heat during regasification of LNG
• To minimize the flue CO2 emission from the coal based powerplant in the environment.
• To asses the efficiency of the heat utilization system.

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2.1 History of Literature Review
Natural gas has been known in the Middle East since ancient times, particularly as a result of seeping
gas that caught fire (“burning springs” or “eternal flames”), and it was even the subject of religious
worship in Persia, Greece, and India. Despite the fact that the first natural gas well was drilled two
centuries before our age in China, the resource was not put to practical use until the year 900.Natural
gas was discovered in the United Kingdom in 1659, but it was not intended for use. Until 1790, it
was used for commercial purposes. In the United States, William Hart drilled the first well in 1821,
and the town of Fredonia obtained gas for lighting five years later. New York was the home of one of
the first gas distribution firms. The “Fredonia Gas Light Company” is one of the companies in the
“Fredonia Gas Light Company” category [8]. Until 1890, natural gas was mostly used as a light
source and was distributed and consumed locally. However, gaskets changed significantly in that
year, and gas pipes could reach further with less people. A setback despite this, gas pipelines did not
exceed 150 kilometers in length until the early twentieth century. The British chemist and physicist
Michael Faraday made the first attempt at liquefying different gases, including methane, in the mid-
nineteenth century [9]. Karl Von Linde, a Munich-based German engineer, aided developments in
gas technology, on a broad scale, liquefaction. He invented a heat exchanger, and his name is
synonymous with fundamental studies on lowtemperature techniques for liquefying air and
industrially extracting nitrogen, oxygen, and noble gases. In 1870, he invented the first absorption
machine and the first cooling system. In 1873, he used methyl ether as a cooling fluid for this unit. In
1876, ammonia was discovered. In 1895, he used compression and expansion with intermediate
cooling to liquefy air, yielding nearly pure liquid oxygen and gaseous nitrogen [10]. Godfrey Lowell
Cabot of the United States of America was the first to apply for a patent in 1914. On a barge,
liquefied natural gas is transported. Godfrey L. Cabot, Inc. later became the Cabot Corporation,
whose subsidiary Cabot LNG constructed the Everett regasification terminal in Boston, the first LNG
import terminal in the United States, in 1971. In 1941, the first industrial liquefaction plant for peak
use was installed in the United States. LNG was first transported by sea in 1959 onboard the Methane
Pioneer, a World War II container ship that had been converted to carry LNG in prismatic aluminum
tanks. The first methane discovery was made by the Methane Pioneer, seven LNG-laden voyages
from Lake Charles, Louisiana to canvey Island, United Kingdom of Great Britain. The British Gas
Council signed the first LNG supply deal with Algeria in 1964, for just over 1 million tons per year.
For over 15 years, Arzew had become the first liquefaction plant in the Mediterranean (Algeria) to
supply the UK.

Page | 1121
Libyan facility at the Marsa El Brega had become the Mediterranean's second liquefaction factory,
with its production is exclusively dedicated to Spain. In the Pacific basin, the Kenai plant (Alaska,
USA) began production in 1969 and currently exports 1.3 million tons per year to Japan [11]. A few
years later, in 1972, the first Asian LNG factory, located in Lumut, Brunei, began exporting not only
to Asia but also to the rest of the world, not only to Japan, but also to South Korea. The rise in oil
prices encouraged Japan to follow a policy of replacing oil with coal, which prompted the
development of regasification terminals in the United States between 1971 and 1981. Indonesia
succeeded Brunei in the Pacific in 1977. As an LNG manufacturer, it began exporting to Japan, later
spreading to South Korea, the year was 1986. Malaysia joined the party of LNG exporters in
1983[12]. The Middle East began diversifying its exports in 1977, when the Das Island plant in Abu
Dhabi began exporting LNG (UAE).

Most current inventions and evolution

Not only has the number of liquefaction and regasification plants increased in the last decade, but so
has LNG production and transportation capacity. The nominal capacity of liquefaction trains has
risen from an average of 3-4 to an average of 8-10 mtpa to a height of 7-8 mtpa. Qatar has been the
driving force behind this achievement, with expansions with "mega-trains" at the Qatar gas and Ras
gas plants between 2005 and 2010 resulting in a substantial increase in production volume. On the
other hand, moving all of this LNG is a huge undertaking from 100 ships in 1998, the global fleet of
LNG ships has expanded at an exponential pace. By March 2010, the number had risen to close to
340, having risen from 200 in 2006 to 300 in 2009. The total size was around 120,000 m3 at the end
of the 1990s, but it's now around 80,000 m3. Approximately 153,000 m3 to 130,000 m3 [13] is the
most common size. Australia has reached a new age is posing a significant challenge to Qatar's status
as the world's largest LNG exporter in the future the designers. If the majority of the more than 20
LNG projects in the pipeline are completed, Australian LNG will account for more than half of the
Pacific basin's output. The majority of the feed gas for these projects will come from unconventional
sources, specifically coal, methane in the bed Unconventional gas has also had a major effect on the
Atlantic in the basin. The growth of shale gas in North America has oversupplied the market, which,
coupled with the global recession, has resulted in a decrease in US and Canadian gas prices,
rendering LNG imports unattractive. Furthermore, it has ignited a new rush to develop LNG plants,
this time for exports only (liquefaction). The first proposals call for liquefaction terminals to be
converted from regasification terminals. Kitimat LNG (British Columbia, Canada) and Sabine LNG
(British Columbia, Canada) plants were grown projects in Louisiana's Pass. These two pioneering
projects

Page | 1122
in both countries were immediately followed by a slew of others. Kitimat's LNG has already been
given an export license by the National Energy Board (NEB) in Canada, and the Department of
Energy in the United States. The Department of Energy (DOE) has only granted Sabine Pass an
export permit. At this time, there is a heated debate in the US about the potential effect of LNG
exports on domestic gas prices, rendering the final number of approved export projects uncertain. On
the demand side, the Fukushima tragedy has raised the LNG needs of the world's first LNG importer,
leading to the 12th International Atomic Energy Agency's decision to shut down all nuclear power
plants, Government of Japan. Japan now needs about 10 million tons of LNG per year on average,
holding prices high in both short and long-term contracts and confirming the Pacific Basin as the
world's primary LNG destination. Another major advancement in recent years has been the
development of floating LNG devices, either for liquefaction or regasification. The term excellerate
came to mind. The company was the first to build LNG tankers with a regasification device on board.
The most important accomplishment of this breakthrough, however, has been that it has created a fast
lane for new importers. As a result, the LNG industry has become one of the most international in the
world, sector that is competitive and continues to expand.

LNG Importers

Japan and Korea are the world's largest LNG importers, accounting for 48 percent of all LNG
delivered in 2011. Owing to increased demand for Japan as a result of the Fukushima disaster, which
saw the nuclear power plant melt down, this number was significantly higher than 2010 volumes. The
country's nuclear power fleet is being phased out in favor of gas-fired power. The advent of smaller
LNG importers is a second significant and growing aspect of global LNG imports.

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Figure2.1: 2019 LNG imports and market share by Market (in MT) [14]

LNG Exporters

By the end of 2011, 18 countries had started exporting LNG from their gas reserves. Furthermore,
Belgium, Brazil, Mexico, Spain, and the United States were re-exporting LNG that had previously
been imported from another source. Qatar is the world's largest LNG exporter by far. In 2011, the
nation supplied the market with 75.5 MT of LNG, accounting for nearly a third (31%) of global
production. In 2011, Malaysia overtook Indonesia as the world's second-largest LNG exporter.
These nations, along with Australia, around 27% of the world's LNG supply came from three
Pacific Basin exporters. Qatar's projected name plate capacity of 77 MTPA was achieved in 2011,
ensuring Qatar's supremacy as the world's largest LNG exporter. Despite plans to eventually exceed
Qatar's liquefaction potential, Australia remained the world's fourth largest LNG producer in 2011.
Table 2.1 depicts the LNG exporting countries until the year 2011.

Page | 1124
Figure2.2: 2019 LNG Exports and market share by Market (in MT) [15]

The LNG production process

LNG output, export, import, and distribution have followed a process sequence similar to that shown
in Figure 2.3 below since 1964. The following is a short rundown of the different steps in this chain.

Figure 2.3: LNG Production Process

Page | 1125
Extraction

The first step in the process is to remove natural gas from the surface of the earth. When domestic gas
supplies are insufficient to satisfy intra-country demand, LNG is imported. After a team of research
geologists and geophysicists has discovered a possible natural gas field, a team of specialists drills
down to where the natural gas is believed to occur. The next step is to extract natural gas (and/or oil)
from the ground and process it after a well has been drilled and the existence of commercially viable
quantities of gas has been confirmed. The natural gas extracted from the ground is now referred to as
"fed" gas. The gas associated with oil went unused and was discarded in a landfill until there was a
commercial demand for LNG, flare-up It can now be used as LNG. It is important to stress that raw
natural gas must be refined before being used in homes or factories. While natural gas is associated
with a number of other substances and gases (e.g., ethane, propane, butane, pentanes, hydrogen), the
natural gas used by customers is almost exclusively methane. (H2S, CO2, helium, and nitrogen), as
well as oil and water prior to liquefaction, which must be extracted during processing.

Liquefaction

Natural gas is transformed from a gaseous to a liquid state before being transported by tanker. To put
it simply, the liquefaction process takes raw feed gas, eliminates impurities and other elements, cools
the gas until it liquefies, and then transports it. Finally, the liquid is transferred into storage tanks.
The LNG is then loaded onto tankers for transportation to market. The three basic steps of the
liquefaction process are as follows:

Impurities are extracted and natural gas liquids are recovered (NGLs)

The gas must be refrigerated before it liquefies.

Transportation of LNG to storage and then to the tanker.

1. Impurities are extracted and NGLs are restored.

Page | 1126
Raw feed gas is the gas supply that comes from the production sector. Methane is commonly
combined with other hydrocarbons like ethane, propane, butane, and pentane, as well as other
substances like water, Sulphur, mercury, and other elements. Uncleanliness a pipeline transfers the
raw feed gas to a manufacturing plant. Here the gas is processed to remove impurities as well as
valuable NGLs (Fig-2.3). The first step is pretreatment which includes the removal of acid gas such
as carbon dioxide and Sulphur as well as mercury and other substances. All of these must be
removed, either because their freezing points are far above the final LNG product's temperature, or
because they are impurities that must be removed in order to satisfy pipeline specifications at the
point of distribution. Next water is removed. After the above steps, the NGLs such as ethane,
propane, butane, and pentanes (also known as heavy hydrocarbons) are removed and collected. In
many cases the gas is processed upstream of the liquefaction unit using traditional gas processing
technology. In certain situations, the recovery of NGLs is an essential part of the liquefaction process.
The collected NGLs are useful items in and of themselves, and they can be used as refrigerants in the
liquefaction phase or re-injected into LNG to change the Btu content and flammability characteristics
of the stream at a later time. Pentanes and other heavy hydrocarbons are generally exported as a
gasoline product. Butane and propane are often also exported as separate products or used as
refrigerants. Ethane is often re-injected into the LNG stream and may also be used as a refrigerant.

Figure 2.4: Integrated NGLS and LNG process [16]

Page | 1127
1 . Liquefaction of Methane

Using LNG liquefaction technology, the methane, as well as any re-injected materials, is then cooled
to –2600 F. The methane mixture liquefies into the liquid state in this step. While different
liquefaction facilities use slightly different procedures, the basic cooling and liquefaction concepts
which are modular units. A train is a full processing unit on its own, but multiple trains are often built
side by side. Currently, train sizes vary from less than or equivalent to 1 to 5 mtpa [17].

3. Storage and pumping the LNG into tankers

The LNG is pumped into a cryogenic storage tank after it has been liquefied. These tanks are
typically double-walled, with a reinforced concrete outer wall lined with carbon steel and a nickel
steel inner wall. Insulation is mounted between the two walls to keep ambient air from warming the
LNG. These tanks retain LNG until a tanker is available to carry it to market. LNG is loaded onto an
empty tanker by cryogenic pump by insulated pipes connected to the tanker by rigid loading arms
after it docks at the berth. The pipes are removed after the tanker is loaded, and the loading arms are
swung away from the ship, and the tanker is ready to sail.

LNG transportation

Transporting liquefied natural gas to the end user is the third stage in the LNG process chain. The key
modes of transport are by sea and truck, with rail being used in a few areas (Japan).

By Sea

If LNG must be transported over a long distance, it is typically done so by sea in specially built LNG
carriers. In 1959, the MV Methane Pioneer made its maiden voyage from Lake Charles,

are the same. Heat exchange is the most important technology. The natural gas stream is allowed to
flow over cooling coils while a cold liquid refrigerant is passed through them, cooling the gas stream.
As the temperature drops to about -2600 F (-162 0C), the gas becomes liquid, and the pressures that
are maintained in this liquefaction phase are 40 bars and 65 bars, respectively. The APCI MCR
Process, the Phillips Optimized Cascade Process, and the Linde/Shell Fluid Cascade Process are three
separate liquefaction processes. The method chosen is a design decision that is affected by a variety
of factors, including the feed gas composition, refrigerant availability, whether NGLs are extracted
upstream, the size of the plant, operational flexibility requirements, and the cost/availability of
compressor fuel. Liquefaction plants are normally installed in trains,

Page | 1128
Louisiana, to Canvey Island, United Kingdom [18]. The MV Methane Progress and MV Princess
made their first commercial voyages in 1964 from Algeria to the Isle of Canvey. The safety systems
on LNG carriers, as well as the training of the 21 crew members who run the vessels, have evolved
over time. They've changed and are now more durable. LNG is now being transported on double-
hulled ships that are designed to hold the cargo at or above atmospheric pressure at a cryogenic
temperature of -162°C (-259°F). LNG carriers (Fig. 2.5) are vessels that carry LNG. Traditional ship
construction combined with specialized materials and advanced systems for the transportation of
cryogenic cargoes. The containment tanks have layers of insulation that separate the LNG cargo from
the hull by maintaining a minimum distance from the sides and bottom of the hull in compliance with
the International Gas Codes (IGC) and applying layers of insulation to the hull, safety in the event of
a crash or grounding. Furthermore, the amount of LNG that boils off or evaporates during the
voyages is limited by this insulation device. Boil-off gas is used to replace fuel on many LNG ships
during the journey. The design and operation of LNG carriers at sea ports are subject to strict
international regulations.The International Maritime Organization (IMO) is the United Nations body
in charge of implementing and updating international shipping safety and protection treaties. The
International Code for the Construction and Equipment of Ships Carrying Liquefied Gases in Bulk
(IMO Gas Code) and the International Code for the Construction and Equipment of Ships Carrying
Liquefied Gases in Bulk (IMO Gas Code) are two of the 40 conventions and protocols accepted by
the IMO. The International Maritime Dangerous Goods Code (IMDG) regulates the shipment of
dangerous goods by sea. Approximately 362 LNG ships (with a capacity of more than 18000m3)
were in service at the end of 2012, with the majority of them capable of carrying 120,000 to 150,000
m3 (31 to 37 million gallons) of LNG each. The cargo capacity of LNG carrier ships has increased to
264,000 m3 thanks to new vessel construction (71 million gallons). LNG ships cost between $225
and $250 million for a 135,000 m3 carrier and about $300 million for larger ships [19].

By truck

Tank trucks are the most cost-effective mode of LNG transportation in areas where a liquefaction
plant is located near regasification facilities around the world. Liquefied natural gas can be
transported using specialized, double-skinned tank trucks to a regasification facility in a timely and
efficient manner. Since 1968, trucking has been used to transport LNG in many parts of the world.
LNG trucking is now a well-established industry (Fig- 2.6). Use 6 to 20-ton tanker trucks that meet
industry requirements requisites. Several countries use tank trucks to carry LNG on a daily basis. 284
LNG tank trucks transported nearly 1,900,000 ton of LNG in 2009; 65,000

Page | 1129
individual truck loads traveled more than 18,000,000 kilometers in Europe, delivering approximately
1,200,000 tonnes of LNG to the Americas; Over 21,000 individual truck loads travel over 3,000,000
kilometers carrying nearly 370,000 tonnes of LNG; in the Far East, 56,000 truckloads travel over
8,000,000 kilometers carrying more than 370,000 tonnes of Longmore than 350,000 metric tons of
LNG [2010]

Terminals for receiving and regasification of LNG

An LNG receiving and regasification terminal is a facility at which liquefied natural gas is regasified
after shipment by sea from the area of production. The unit has four main functions:

Receiving LNG tankers and unloading their cargo

Storing LNG in cryogenic tanks able to withstand temperatures below -160°C

Regasifying LNG to meet demand

Name Location Regasification capacity

Moheshkhali Moheshkhali 500 million standard cubic


LNG Island feet of gas per day
terminal (MMscf/d)

Summit LNG Cox’s Bazar 500 million standard cubic


terminal feet of gas per day
(MMscf/d)

Matarbari Matarbari, 1000 million standard


LNG Cox's Bazar cubic feet of gas per day
terminal (MMscf/d)

Feeding gas into the national transmission network.

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LNG Terminals in Bangladesh

Table 2.1 – LNG terminals in Bangladesh [21]

Land Based LNG Terminal at Matarbari on BOOT basis

The government has agreed to develop a 1000 MMS Land Based LNG Terminal on a BOOT basis in
Matarbari, Cox's Bazar. In accordance with this decision, Expressions of Interest (EOI) for the
selection of a terminal developer were requested on January 29, 2019. As a result, a total of 12
companies have submitted proposals before the deadline. The proposal review is currently underway.
By reviewing the proposals, a shortlist of terminal developers will be generated very soon. The
selection of a consultant from Petrobangla for "Techno-Economic Feasibility Research, Engineering
Services, and Tender Management Services for Construction of a Land Based LNG Terminal at
Matarbari, Cox's Bazar" is nearing completion for all types of work ranging from the Feasibility
Study to the RFP planning of the Terminal Developer of the Land Based LNG Terminal at Matarbari.
The RFP paper will be prepared by a consulting firm. To be able to choose the Terminal Creator. The
shortlisted firms will be given RFP papers, and their proposals will be approved. Following the
review of the proposals, a Terminal Developer will be chosen. The process of appointing a consultant
to perform a feasibility study for the construction of a landbased LNG terminal in Matarbari is
currently underway. The acquisition of 111.72 acres of land for the Land Based LNG Terminal is in
the works.

There is also an obligation to purchase 4.409 acres of land in Bijoy Ekattor Mouza, Maheshkhali
Economic Zone-3, Cox's Bazar for a portion of the sub- sea pipeline and platform (tie-in point) of the
MLNG and SLNG FSRU Terminals. Bangladesh Economic Zone Authority has given its approval in
this regard (BEZA) . BEZA should be paid US Dollar 2,34,184.20 in Bangladeshi currency as a lease
fee for 4.409 acres of land.

Page | 1131
The Land Lease Agreement is currently being signed. Import of LNG from Qatar Gas: Under the
Sale and Purchase Agreement (SPA) signed with Qatar Gas on September 25, 2017, Qatar Gas is
expected to import

1.8 million tons of LNG as Base Annual Contract Quantity (BACQ). An Annual Delivery Program
(ADP-2020) has been finalized to import LNG for the year 2020, with the aim of taking 29 BACQ
cargoes and 11 additional cargoes, for a total of 40 cargoes as per the contract. This software is based
on a ninety-day schedule (NDS) and is updated monthly. From April 24, 2018, to June 30, 2020, a
total of 9.75 million cubic meters (4.29 million tons) of LNG was imported from Qatar via 70
cargoes. 1.3.2 Import of LNG from OQ Trading Ltd. (0Q1): Under the terms of a Sale and Purchase
Agreement (SPA) signed with Oman Trading Intonational Ltd., the company will import LNG from
OQ Trading Ltd. (Current alias: 007) As of 00 06 May 2018, OQT is expected to import

1.0 million tons of LNG as part of the Base Annual Contract Quantity (BACQ). An Annual Delivery
Program (ADP-2020) has been finalized in order to import LNG for the year 2020, with the intention
of taking 16 BACQ cargoes and 08 additional cargoes, for a total of 24 cargoes as per the contract.
This program follows a ninety-day schedule (NDS), which is updated monthly. From 31 January
2019 to 30 June 2020, a total volume of 5.43 million cubic meters (2.39 million tons) of LNG was
imported from Oman via 37 cargoes. 1.3.3 LNG Imports on the Spot Market.

To build opportunities for importing LNG from the international market at a fair price, the
government agreed to import LNG from the spot market.

The commercial supply of RLNG from EEBL's MLNG Terminal to the national gas grid began on
August 19, 2018. In fiscal year 2019-20, a total of 2,912.69 Million Cubic Meters (1,02,860.67
MMSCF) of RLNG was supplied to the national grid from the MLNG terminal, and a total of
5,915.23 Million Cubic Meters (2,08,894.3 MMSCF) of RLNG was supplied to the national grid
from the start of the operation until 30 June 2020. The Managing Director of RPGCL paid a visit to
Dry Dock Limited, which is used for LNG activities [22].

Commercial supply of RLNG from Summit LNG's SLNG terminal, on the other side, totaled
2,832.19 million cubic meters (1,00,016.96 MMSCF) In fiscal year 2019-20, 3,111.17 million RLNG
units were delivered to the national grid. From the start of the operation until June 30, 2020,
1,09,869.3 MMSCF of RLNG was transmitted to the national grid. 1.4.2 In fiscal year 2019-20, a
total of 5,744.88 Million Cubic Meters (2,02,877.63 MMSCF) of RLNG was supplied to the national
gas grid from the above-mentioned Terminals, and a total of 9,026.4 Million Cubic Meters of RLNG
was supplied to the national gas grid from the above-mentioned Terminals. (3,18,763.6 MMSCF) is a

Page | 1132
number that can be used to represent a number of items. From the beginning of the operation until
June 30, 2020, RLNG was supplied to the national grid by Terminal Co. (Pvt.) Ltd. A short distance
from the SLNG Terminal [23].

Coal based thermal power plant

Basically, coal based thermal power plant is a source of flue gas which gives heat to LNG and
produce NG. Flue gas mainly CO2 is used here. The Matarbari coal-fired power plant is being
constructed in Moheshkhali, Bangladesh's Cox's Bazar district. On a 1,500-acre site, the Matarbari
thermal power plant will be installed. It will be made up of two thermal units, each with a 600MW
installed capacity, based on ultra-supercritical coal-fired technology. A steam-based pulverized coal-
fired boiler unit, a 600MW steam turbine, and a 750MVA steam generator will be contained in each
of the two units. The plant will have a 275-meter-high flue gas stack and an electrostatic precipitator
that will hold particulate emissions below 100 micrograms per cubic meter. The power plant would
need 3.73 million tonnes of coal per year, which will be imported via the Matarbari Port from
Indonesia, Australia, and South Africa.

Table2.2: The proposed coal-fired thermal power plant's basic details (estimated) [24]
Component Design Condition
Plant type
Gross power output 1,200 MW (2 x 600 MW)
Primary fuel (type) Sub-bituminous Coal having GCV of
42005200 kcal/kg and low
Sulfur content (1.0 wt.% or less)
Coal flow (at 100% ECR) 12,800 ton/day
Annual coal requirement 3.73 mil. ton/year (considering 80% load
factor)
Temperature of flue gas at stack 75OC

Flue Gas Flow 2 x 4.47 x 106 m3 /hr


Maximum emission of Sox Less than 820 mg/Nm3

Maximum emission of NOx 50 mg/Nm3 (from each unit)

Page | 1133
Systems for using LNG as a source of cold energy are currently in use

LNG cold energy utilization systems are those that need a low-temperature operating environment
and can be incorporated into the LNG regasification process without needing major adjustments to
the systems. LNG is primarily used as a heat sink in these systems. In certain situations, LNG is used
as both a heat sink and a source of energy, the stream of knowledge. The heat transfer efficiency
between LNG and the working fluid of these systems defines their energy efficiency. The device for
using LNG cold energy varies in general because the required energy type varies from country to
country in various applications. Power generation, air separation, conventional desalination,
cryogenic carbon dioxide capture, and natural gas are all examples of modern LNG cold energy
utilization systems. Recovery of liquids (NGL). The progress of these projects is discussed in this
section. The structures will be extensively analyzed, as well as the problems debated and examined.

Over the last few decades, energy demand has risen by 2.4 percent per year due to global economic
development and population growth. Because of its transportability and high combustion efficiency,
natural gas, one of the cleanest fossil fuels energizing modern society, has become the fastest
growing primary energy source, performance, and a low contribution to the emission of greenhouse
gases. Natural gas was an excellent choice for bridging the gap between traditional energy supplies
and the future of renewable energy because of these attractive characteristics. Two mature natural gas
transportation technologies are liquefied natural gas (LNG) and pipelines. If the distance between the
production site and the market is less than 2000 kilometers, the pipeline is the chosen mode of natural
gas transportation. Pipeline transportation, on the other hand, is not technically or economically
feasible for long-distance transportation across oceans. As a result, LNG is the best alternative for
transporting natural gas over long distances (greater than 2000 km), as well as cross-ocean and
offshore natural gas output. LNG is made by cooling natural gas to 162 degrees Celsius at
atmospheric pressure. The energy density of LNG is slightly higher than that of natural gas, as one
cubic meter of LNG contains approximately 625 cubic meters of natural gas. Gas processing,
liquefaction, transportation, storage, and regasification are all part of the conventional LNG supply
chain. LNG ships (tankers) carry LNG from the output area to the import region. The LNG is
processed in LNG regasification terminals and then regasified to provide natural gas to the gas
distribution network, power plants, and industrial users until the LNG tankers arrive at the import
terminal. LNG vaporizers release the cold energy of LNG, which is about 830 kJ/kg, into the
seawater during the regasification stage [25]. If used efficiently, a large amount of useful cold energy

Page | 1134
will greatly increase the energy efficiency of the LNG supply chain and reduce greenhouse gas
emissions. The huge amount of cold LNG energy available around the world can be used to boost
energy efficiency, minimize greenhouse gas emissions, and add value to the regasification process.
Typical LNG cold energy systems include power generation, air separation, desalination, and food
processing, among others.

Cycles of cryogenic power generation

Cryogenic power generation is one of the most common ways to use LNG cold energy, as LNG can
be used to substitute cooling water as a heat sink in the process. The simplest LNG-fueled cryogenic
power generation cycles. The direct expansion cycle and the organic Rankine cycle are examples of
cold energy. The direct expansion cycle is unusual in that it only uses LNG's mechanical exergy
(pressure exergy). LNG is pumped to a built pressure that is higher than the pipeline delivery
pressure in the direct expansion cycle, and then regasified into natural gas in the LNG vaporizer.
After that, the high-pressure natural gas in the turbine lowers its pressure to that of the pipeline
delivery pressure to produce power. The cold energy, on the other hand, is still squandered
throughout this cycle. As a result, to increase overall power generation performance, the direct
expansion cycle is often combined with other cycles. Furthermore, the Kalina cycle is regarded as a
possible cycle for recovering LNG cold energy.

Organic Rankine Cycle

The Organic Rankine Cycle (ORC) recovers LNG cold energy in the condenser by using a working
fluid with a low boiling point. To produce power in ORC, the working fluid goes through
compression, evaporation, expansion, and condensation in that order. The organic Rankine cycle with
propane as the working fluid was stated to have a power output of 1450 kW. The studies on organic
Rankine cycles to use LNG cold energy primarily focused on working fluid selection and cycle
configuration in order to optimize cold energy utilization. They investigated the optimization of three
different organic Rankine cycle configurations to use LNG cold exergy and low grade heat, namely
single-stage ORC (SORC), parallel two-stage ORC (P2SORC), and parallel threestage ORC
(P2SORC) [26]. The high net power performance of ORC for recovering LNG cold energy is due to
the pump's low energy consumption. However, because of the system's extremely nonlinear
characteristic, choosing the mixed working fluid to fit the evaporation curve of LNG is difficult.

Page | 1135
Air separation

The cryogenic air separation process cools the air to cryogenic temperatures (below 195 degrees
Celsius at atmospheric pressure) and then separates it into oxygen, nitrogen, and other gases in a
distillation column. The refrigeration cycle uses a large amount of electricity because it runs at such a
low temperature. As a result, using LNG cold energy in the air separation process will minimize
energy consumption while also Regasifying LNG into natural gas [27].

Cryogenic carbon dioxide capture

The method of liquefying CO2 from flue gas is known as cryogenic carbon dioxide capture. The
typical cryogenic carbon dioxide capture system relies on an external refrigeration cycle to cool and
liquefy CO2, which consumes a lot of energy. If the power plant uses natural gas or LNG as a fuel,
combining the LNG regasification process with the cryogenic carbon dioxide capture process will
save a lot of energy while also lowering the carbon footprint.

LNG cools the flue gas produced by the boiler to a temperature below CO2's dew point temperature
in the condenser, resulting in liquid CO2. The natural gas is then regasified and used as a fuel in the
boiler. A novel LNG cold energy system that included both power generation and carbon dioxide
capture. Based on 1 ton of LNG, the results showed that 119.42 kW of electric power and 0.75 ton of
liquid CO2 could be generated. A revolutionary power plant that uses LNG cold energy to absorb
CO2 from flue gas [28].

Page | 1136
Figure 2.5: A cryogenic carbon dioxide capture process using LNG cold energy [29]

Over the last few decades, energy demand has risen by 2.4 percent per year due to global economic
development and population growth. Because of its transportability and high combustion efficiency,
natural gas, one of the cleanest fossil fuels energizing modern society, has become the fastest
growing primary energy source, performance, and a low contribution to the emission of greenhouse
gases. Natural gas was an excellent choice for bridging the gap between traditional energy supplies
and the future of renewable energy because of these attractive characteristics. Two mature natural gas
transportation technologies are liquefied natural gas (LNG) and pipelines. If the distance between the
production site and the market is less than 2000 kilometers, the pipeline is the chosen mode of natural
gas transportation. Pipeline transportation, on the other hand, is not technically or economically
feasible for long-distance transportation across oceans. As a result, LNG is the best alternative for
transporting natural gas over long distances (greater than 2000 km), as well as cross-ocean and
offshore natural gas output. LNG is made by cooling natural gas to 162 degrees Celsius at
atmospheric pressure. The energy density of LNG is slightly higher than that of natural gas, as one
cubic meter of LNG contains approximately 625 cubic meters of natural gas [30]. Gas processing,
liquefaction, transportation, storage, and regasification are all part of the conventional LNG supply
chain. LNG ships (tankers) carry LNG from the output area to the import region. The LNG is
processed in LNG regasification terminals and then regasified to provide natural gas to the gas
distribution network, power plants, and industrial users until the LNG tankers arrive at the import
terminal. LNG vaporizers release the cold energy of LNG, which is about 830 kJ/kg, into the
seawater during the regasification stage. If used efficiently, a large amount of useful cold energy will
greatly increase the energy efficiency of the LNG supply chain and reduce greenhouse gas emissions.

Page | 1137
The huge amount of cold LNG energy available around the world can

be used to boost energy efficiency, minimize greenhouse gas emissions, and add value to the
regasification process. Typical LNG cold energy systems include power generation, air separation,
desalination, and food processing, among others.

METHODOLOGY

Natural gas is a nontoxic, high-energy-density, low-cost energy source. LNG is contained at a


cryogenic temperature of only about -162 degrees Celsius. During the LNG regasification process,
more than 800 kJ/kg cryogenic exergy can be released. ORC is a Rankine cycle that uses a low
boiling point fluid as the working fluid instead of water. The heat sink (or cold source) of ORC is
LNG, which is used to cool the working fluid to a low temperature [31].

Cox's Bazar the coastal city of Bangladesh is transforming into a city of joy for the people of South
and Southeast Asia, thanks to its rich natural resources. Its excellent geographical location, which
includes the world's longest flat sandy sea beach, huge prospects for untapped maritime resources,
excellent prospects for the construction of fuel import infrastructures and power generation plants,
and export manufacturing industrial zones, offers unique opportunities for this green and blue city to
grow into a major economic hub..Bangladesh's government has undertaken a number of
megaprojects, many of which have already started or are in the planning stages. The ongoing and
expected power and energy hub is transforming Cox's Bazar, a popular tourist destination, into a
power and energy hub. LNG terminal and Coal Fired Power Plants are the main features of this
power & energy hub.

LNG is imported and regasified in LNG regasification terminal and later fed to the national grid. On
the other side coal is imported and burned to generate power in the coal based thermal power plant.
LNG is stored at a cryogenic temperature of around -162 degrees Celsius. During the LNG
regasification process, more than 800 kJ/kg cryogenic exergy can be utilized.

Coal based thermal power plants emit a large amount of carbon dioxide at a high temperature. This
CO2 emission has an adverse effect on the environment. This Hot CO2 can be used as a heating
source during the regasification of LNG. This will Improve thermal efficiency and minimize CO2
emissions.

Page | 1138
Site selection

For heat utilization we selected cold stream from LNG feed from Matarbari LNG regasification
terminal and hot stream CO2 from the flue gas from the Matarbari thermal power plant. These two
plants location is very close to each other. So, it will be technically and economically easy to bring
the flue CO2 to LNG regasification terminal and utilize the waste heat energy. The exact location of
these facilities is Location: Matarbari, Cox's Bazar District, Chittagong, Bangladesh and the
Coordinates: For Matarbari LNG terminal is 21.7271477°N, 91.8797371ºE and Matarbari coal based
thermal powerplant is 21.7018395°N, 91.8834003ºE.

Figure 3.1: Selected site of Matarbari LNG Terminal and Matarbari coal power plant [32]

Page | 1139
Process Description

The fundamental configuration for using LNG cold energy for power generation and CO2 capture
is shown in figure 3.1 and 3.2. This system uses LNG cold energy recovery to liquefy CO2. The
system uses flue gas from the Matarbari coal based thermal power plant as a heat source for a
parallel twin-stage Rankine cycle that uses LNG from the Matarbari LNG regasification terminal
as a heat sink to produce power. A CO2 capture sub-system, a twin-stage organic Rankine system.
CO2 compressor, two heat exchangers, and a liquid vapor separator make up the CO2 capture
cycle power generation sub-system, and an LNG regasification sub-system make up the overall
sub-system. To overcome pressure drops within heat exchangers, the flue gas is first compressed
by the compressor. The flue gas is then cooled in two different heat exchangers. Finally, CO2 is
liquefied and removed from air in the liquid vapor separator by releasing heat to the Rankine
cycle. The only source of heat energy for the power generation sub-system is waste heat from the
flue gas. The phases are called C1 through C6. Air and liquefied CO2 are denoted by the letters C5
and C6, respectively.

Liquid CO2 Flue CO2 gas


from Matarbari
Thermal plant
Heat Exchange by two stage
organic Rankine cycle with R-14 &
R-290 working fluid

LNG feed from Natural Gas Fed


Matarbari LNG to the pipeline
terminal LNG storage

Figure 3.2: The Block diagram of the heat utilization process

CO2 compressor, two heat exchangers, and a liquid vapor separator make up the CO2 capture. A
parallel twin-stage organic Rankine cycle is chosen for the power generation sub-system to utilize the
use of LNG cold energy while simplifying the overall system. Though the organic Rankine cycle is a
popular option for generating power in the LNG regasification process, it requires a working fluid
with the right physical properties. R-14 (Tetrafluoromethane) and R-290 (Propane) are chosen as

Page | 1140
working fluids for Rankine cycle I and II, respectively. A pump, a vapor generator, a turbine, and a
condenser are all part of a Rankine cycle. The pump compresses the working fluid, which then
reaches the vapor generator. The working fluid in the vapor generator is vaporized by collecting heat
from the flue gas. The high-temperature working fluid then passes through a turbine, where it
expands to generate mechanical energy, which is used to power an electric generator. After exiting
the turbine, the exhaust working fluid is condensed in a condenser by LNG. RC11 to RC14 and RC21
to RC24 are the two Rankine cycles, respectively.

LNG tank, LNG booster pump, heat exchangers, and NG turbine comprise the LNG regasification
sub-system. LNG from the LNG tank is pumped under regasification pressure at a low temperature of
162 degrees Celsius. After that, LNG passes through the condensers of two Rankine cycles,
absorbing heat from R-14 and R290, respectively. As a result of absorbing heat from the working
fluids and releasing cold energy to condense the working fluids, LNG is vaporized to natural gas.
Finally, natural gas is fed into an NG turbine, which produces energy while lowering the pressure in
the city gas pipeline. L1 to L5 reflect the method.

Page | 1141
Page | 1142
Project Overview

The desired LNG plant of Matarbari is a land-based LNG regasification terminal. The annual
regasification capacity is 7.5 million tones. That means the daily regasification capacity is
around 1000 Million standard cubic feet. The major amount of LNG is imported from Quarter
& OMAN. Table 3.1 Composition of LNG from Ras Laffan [33]

Component Chemical Percentage


Name Formula
Methane CH4 90.28%
Ethane C2H6 6.33%
Propane C3H8 2.49%
Butane C4H10 0.49%
Pentane C5H12 0.02%
Nitrogen N2 0.41%

The flue CO2 comes from the coal-fired thermal power plant with two 600 MW total capacity
of 1200 MW. The Power Plant IS designed in such a way that it will not pollute the
atmosphere. Additional units may be installed in the future. The planned ultra-supercritical
(USC) bituminous pulverized coal plant will be installed on a longer - term basis with a
capacity of 2 x 600 MW (gross power output). The project's capacity is also 2 x 600 MW at
400 KV [34]. Bituminous coal with a Gross Calorific Value (GCV) of 4700 Kcal/kg will be
the plant's primary fuel. The plant's capacity factor (CF) is 80 percent, with major train
components spared.

Table 3.2 Basic plant information of the proposed coal based thermal power plant (estimated) [35]
Component Design Condition

Page | 1143
Plant type ultra-supercritical coal based thermal power
plant
Gross power output 1,200 MW (2 x 600 MW)
Primary fuel (type) Sub-bituminous Coal having GCV of
42005200 kcal/kg and low
Sulfur content (1.0 wt.% or less)
Coal flow 12,800 ton/day
Annual coal requirement 3.73 mil. ton/year (considering 80% load
factor)
Temperature of flue gas at stack 75°C

Flue Gas Flow 8.94x 10^6 m3 /hr


Maximum emission of Sox Less than 820 mg/m3

Maximum emission of NOx 50 mg/m3 (from each unit)

3.1 Mathematical modeling


Aspen hysys version 10 is used to calculate the physical and thermodynamic properties. Aspen
hysys, a division of aspen ONE Engineering, offers state-of-the-art physical property methods,
models, algorithms, and data to allow chemical engineers to quickly perform engineering
calculations using rigorous and validated thermo-physical property models and data. It allows
users to collect and spread clear physical property data and information throughout the
enterprise. Aspen Properties is linked to the world's largest archive of pure components and
binary parameter databank.
The P-R (Peng-Robinson) equation is more suitable for measuring the physical properties of
mixtures and pure substances than other state equations.

Page | 1144
Figure 3.4: Component list selection in Aspen Hysys

Page | 1145
Figure 3.5: Peng-Robinson Fluid package selection in Aspen Hysys

As a consequence, the P-R equation is used to measure the thermodynamic and thermophysical
characteristics of LNG, CO2, R-290, and R-14.
To make the system modeling simpler, the following assumptions are made.

The pressure drop in the LNG regasification sub-system is calculated to be 3%. As a result, the
pressure drops through the power generation sub-vapor system's generators and condensers are also
measured at 3%.
There is no consideration for heat transfer between the environment and the system.
The isentropic efficiency of turbine, pump and compressor is equal to 75%
The flue gas composition from the Matarbari thermal powerplant is denoted below Table
Flue gas composition [36]

Page | 1146
Flue Gas Percentage
CO2 15.8 %
H2O 6.3%
N2 77 %
Others 0.90%

CO2 capture sub-system

The flue gas is cooled down in the CO2 capture system by R-14 and R-290, respectively. In the Vapor-
generator 1, the heat released to R-14 is determined by
Qflue gas, VG1 = mflue gas (hc4-hc3) (1)

In the Vapor-generator 2, the heat released to R-290 is

Qflue gas VG2 = mflue gas (hC3- hC2) (2)


A compressor compresses the flue gas to overcome pressure rises in the heat exchangers. The power
consumption of the compressor is

Wcompressor, flue gas = mflue gas (hc2-hc1) (3) Organic Rankine cycle
power generation sub-system

Rankine cycle I

The Rankine cycle is a well-known thermodynamic power generation cycle. Two heat exchangers, a
pump, and a turbine make up the system. As heat is allowed to flow from a heat source to a heat sink,
the Rankine cycle produces mechanical power.

In the Vapor generator 1, the heat absorbed by R-14 from the flue gas is determined as follows: QR-
14, VG1 =m R-14 (hRC11-h RC14) =Qflue gas, VG1 (4)

Page | 1147
In the Condenser 1, the heat discharged from R-14 to LNG is

QR- CD1 14, = mR-14(hRC13 -hRC12) (5)

The pump power consumption in the Rankine cycle I is

Wpump RC1 = mR-14(hRC14 - hRC13) (6)


The R-14 turbine generates mechanical power which is

Wturbine, RC1 =mR-14(hRC12 - hRC11) (7)


As a consequence, the Rankine cycle I's net power output can be determined by Wnet, RCI =
Wturbine, RCI - Wpump, RCI (8)
Rankine cycle II
Rankine cycle II has a mathematical model that is similar to Rankine cycle I and is shown below. In
the Vapor generator 2, the heat absorbed by R-290 from the flue gas is measured as follows:
QR-290, VG2 = m R-290(hRC21- hRC24) = Q flue gas, VG2 (9)
In the Condenser 1, the heat discharged from R-290 to LNG is

QR-290, CD2 = mR-290(hRC23- hRC22) (10)


In the Rankine cycle II, the pump power consumption is

Wpump, RC2 = mR-290(hRC24-hRC23) (11)


The R-290 turbine produces mechanical energy which is

Wturbine, RC2 = mR-290(hRC22 - hRC21) (12)


As a consequence, the Rankine cycle II's net power output can be determined by

Wnet, RCII = Wturbine, RCII- Wpump, RCII (13) LNG regasification sub-
system
The LNG is pumped up and vaporized in two heat exchangers, absorbing heat from the Rankine cycle
I and II. The heat absorbed by LNG in Condenser 1 from R-14 is measured as follows:

QLNG, CD1 = mLNG (hL3- hL2) = QR-14, CD1 (14)


The heat absorbed by LNG in Condenser 2 from R-290 is

Page | 1148
QLNG, CD2 = mLNG (hL4 -hL3) = QR-290, CD2 (15)
The power usage of the booster pump is

Wpump, LNG = mLNG (hL2 - hL1) (16)


Finally, a turbine vaporizes LNG completely and expands it to a low pressure for use in a city gas
pipeline.

The NG turbine generates mechanical power that is

Wturbine, NG = mLNG (hL5- hL4) (17)

As a result, the LNG regasification sub-net system's power output can be calculated as follows:Wnet,

LNG = Wturbine, NG -Wpump, LNG (18)

The overall system's exergy analysis

For analyzing the system's performance, some thermodynamic parameters such as net power output,
exergy efficiency, and specific quantity of CO2 recovery are calculated.

The overall system's net power output is calculated by

Wnet, overall = Wnet, RCI + Wnet, RCI +Wnet, LNG – Wcompressor, CO2 (19)
There is a lot of interest in using an exergy analysis in thermodynamic analyses of thermal systems
because the deterioration of energy quality cannot be reflected by the energy method based on the first
thermodynamic law. The maximum theoretical work obtainable from a system in disequilibrium with
the reference environment is defined as exergy. Physical and chemical exergy are two types of exergy.
Because the system proposed in this paper contains no chemical reactions, the exergy investigated in the
system is primarily physical exergy.
The exergy of a substance at a given state point can be defined as
E = m (h -h0) -T(S-S0) (20)

where h0 and s0 are also the reference state's enthalpy and entropy, respectively. The exergy losses of
both heat exchangers and power machines can be calculated once the exergy at state points has been
established. In the Vapor-generator 1, the exergy loss is
IVG1 = EC3 + ERC14 - EC4 - ERC11 (21)
The exergy loss in the Vapor-generator 2 is

Page | 1149
IVG2 = EC2 + ERC24 - EC3 - ERC21 (22)
The exergy loss in the Condenser 1 is
ICD1 = ERC12 + EL2 -ERC13 - EL3 (23)
Similarly, the exergy loss in the Condenser 1 is
ICD2 = ERC22 + EL3 - ERC23 -EL4 (24)
The exergy loss in the LNG booster pump is
Ipump, LNG = EL1 + Wpump, LNG - EL2 (25)
The exergy loss in the pump of Rankine cycle I is
Ipump, RCI = ER13 + Wpump, RCI - ER14 (26)

The exergy loss in the pump of Rankine cycle II is


Ipump, RCII = ERC23 + Wpump, RCII -ERC24 (27)

The exergy loss in the turbine of Rankine cycle I is


Iturbine, RCI =ERC11- Wturbine, RCI - ERC12 (28)The exergy loss in the turbine
of Rankine cycle II is
Iturbine, RCII = ERC21- Wturbine, RCII - ERC22 (29)The exergy loss in the CO2
compressor is
Icompressor, CO2 = EC1 + Wcompressor, CO2 -EC2 (30)The exergy loss in the NG
turbine is
Iturbine, NG = EL4 -Wturbine, NG -EL5 (31)

When each device's exergy loss is determined, the exergy efficiency can be assessed as well.The exergy

efficiency of a system is
Ƞ= Egain/Epay

The exergy efficiency of the overall system is

𝑊𝑛𝑒𝑡,𝑂𝑣𝑒𝑟𝑎𝑙𝑙+𝐸𝐶𝑂2
Ƞoverall= (33)
𝐸𝑓𝑙𝑢𝑒 𝑔𝑎𝑠+𝐸𝐿𝑁𝐺

Page | 1150
where,
Eflue gas = m flue gas [(hC1 - hC0) - T0(sC1- sC0)] (34)

ELNG = mLNG [(hL1- hL0)- T0(SL1- SL0)] (35)

ECO2= mC6[(hC6 - hC0) - T0(sC6- sC0)] (36)


The amount of Carbon dioxide captured divided by the amount of LNG consumed in the overall system
is the precise quantity of CO2 recovery. It can be described as follows:

𝑚𝑐6 α =
(37) 𝑚𝐿𝑁𝐺

36

Page | 1151
Table 3.4: The Primary modeling Condition of the whole system[37]
Overall system Data
Ambient temperature (K) 298.15
Ambient pressure (MPa) 0.101
Heat exchanger pressure drop (MPa) 0.003
Pump adiabatic efficiency 75%
Compressor adiabatic efficiency 75%
Turbine adiabatic efficiency 75%
LNG regasification subsystem
Mass flow rate of LNG (kg/hr) 888704
LNG booster pump inlet temperature (K) 111.15

LNG booster pump inlet pressure (MPa) .10


LNG booster pump outlet pressure (MPa) .60
NG turbine inlet pressure (MPa)0.594

NG turbine outlet pressure (MPa) 0.15


L3 temperature (K) 168.15
CO2 capture subsystem
CO2 compressor inlet temperature (K) 348
CO2 compressor inlet pressure (MPa) 0.10
CO2 compressor outlet pressure (MPa) 0.15
C3 temperature (K) 255.15
C4 temperature (K) 163.15
ORC power generation subsystem
RCI pump inlet temperature (K) 113.15
RCI pump inlet pressure (MPa) 0.185
RCI pump outlet pressure (MPa) 0.40
RCI turbine inlet pressure (MPa) 0.397
RCI turbine outlet pressure (MPa) 0.188
RCII pump inlet temperature (K) 173.15
RII pump inlet pressure (MPa) 0.13
RCII pump outlet pressure (MPa) 0.90
RCII turbine inlet pressure (MPa) 0.897
RCII turbine outlet pressure (MPa) 0.133

37

Page | 1152
RESULTS AND DISCUSSION

38

Page | 1153
Heat flow in CD1

Heat flow in CD 2

Figure 4.2: The Temperature Difference and Heat Flow in heat exchangers

Page | 1154
From the temperature difference vs heat flow graph, it appeared that the cold LNG input is
exchanging heat with working fluid R-14 & R-290 which gained heat from the hot CO2 coming from
the coal powerplant. The inlet LNG is heated from -162°C to -105°C and the working fluid R-14 is
cooled from 100°C to -160 °C. Similarly, in CD2 the -105°C cold LNG stream is heated by the
working fluid R-200. By exchanging heat among the working fluid, the flue co2 and LNG the energy
can be utilized from liquefied natural gas regasification terminal using the flue CO2 gas from the coal
based powerplant in Bangladesh. A great amount of energy can be saved during this process and
moreover CO2 emission from the coal based powerplant can be reduced by implementing this
process.

Page | 1155
Table 4.1: The result of the whole system denoting the Energy input, output, loss and energyefficiency
Term Value (KW)
Energy Input

LNG (L1) 1278064


CO2(C1) 8046547
CO2 Compressor 173362
LNG Booster Pump 359
RCI Pump 71
RCII Pump 147
Total Energy Input 9498550
Energy Output

LNG (L5) 1059583


CO2 (C6) 5516632
NG Turbine 10271
RCI Turbine 359982
RCII Turbine 686243
Total Energy Output 7632711
Energy Loss 1865839
Air (C5) 363095
Devices of the system 1502744
Energy Efficiency 80 %

Page | 1156
CONCLUSIONS

Energy utilization opportunity from liquefied natural gas regasification terminal using the flue CO2
gas from the Coal based powerplant in Bangladesh was investigated in this study. To cope with the
growing energy, demand the LNG import amount is increasing. On the other side power plants are
also increasing with the growing energy demand. For cheap source Coal based Power plants are
increasing also. The CO2 emission from those power plants is also increasing that makes an adverse
effect on the environment. In addition, a large amount of wastage of heat can be utilized when the
flue CO2 is used during the regasification of LNG. The 80 % energy efficiency also indicates the
implementation of this energy utilization process is highly recommended in Bangladesh.

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31. Gomez MR, Garcia RF, Gomez JR, Carril JC. Thermodynamic analysis of a Brayton cycle
and Rankine cycle arranged in series exploiting the cold exergy of LNG (liquefied natural
gas). Energy 2014; 66:927e37

32. Google maps, https://www.google.com/maps/@23.4612401,91.1833054,15z

33. Composition of natural gas. July 14, 2018, from www.Naturalgas.org

34. Energybangla.2019, 02 September. Govt to add 1,185mmcfd gas to national grid by 2019.
35. Environmental Impact Assessment of Construction of Matarbari 600X2 MW Coal Fired
Power Plant and Associated Facilities

36. Environmental Impact Assessment of Construction of Matarbari 600X2 MW Coal Fired


Power Plant and Associated Facilities
37. Zhao L, Dong H, Tang J, Cai J. Cold energy utilization of liquefied natural gas for
capturing carbon dioxide in the flue gas from the magnesite processing industry. Energy
2016; 105:45e56.

Appendix-A

Conversion
Factor1 Bar =
14.73 Psi
1CM= 35.3147 CFT
1 MMCFD = 1000MCFD
1 liter = 1000 Cubic Centimeter
Barrel of Oil (BOE)= 42 US Gallon=1Barrel/bbl.=158.987 Liters of crude
oil=5.8×1061bbl of oil = roughly 1000ft3 of Natural gas=106 BTU

1Kg = 2.204lb
1Day = 24Hours
1Year = 365
Days
1 ton of LNG = 2,1930 m3 of

Page | 1159
Appendix- B
Material, composition and energy of different streams and equipment

Page | 1160
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 336

Mohammad Nurur Rahman , Md. Abid Hasan Badhon Dipto Das, Sk. Fahim Tahmid Boni

Department of Chemical & Food Process Engineering

Rajshahi University of Engineering & Technology

Email: nurur@cfpe.ruet.ac.bd, fahimtahmid111@gmail.com , abidhasanbadhon74@gmail.com,


1511030@student.ruet.ac.bd

ABSTRACT

Energy efficiency has become a growing concern in the modern times for both economic and environmental reasons.
Researchers are hard at work all over the world in trying to figure out new design and materials for more energy efficient
systems. The novel material aerogel shows very promising characteristics in being used as a material for increasing the efficiency
and insulation of a system. This study aims to investigate the change in aerogel characteristics by manipulating different external
processing factors for it to be used in a specific purpose. Based on the review of literature showing changes of different
characteristics with certain processing parameter, a graphical model has been made to understand this variations a little bit
better. Analysis of the model demonstrates the properties we can manipulate to better suit our needs for a certain purpose. On the
basis of the model, it is recommended that the user consider the external properties of the place where aerogel is being used and
its processing parameters to optimize the material is best suited for his needs.

Keywords:
Insulation, Mechanical properties, Thermal properties, Modelling, Aerogel, Thermal co-efficie

Page | 1161
INTRODUCTION

Energy conservation is a big issue for the human’s sustainable development and improving the quality of
people’s life and environment. A lot of natural resources and different kinds of energy are consumed during the
process of the construction and during using of buildings, which takes up a considerable part of total energy
consumption of the world.

Building insulations means using some materials as thermal insulation for reducing the heat transfer in the
construction or retrofit of building. Since maintaining a comfortable temperature in buildings uses a large
proportion of global energy, thermal insulation will help to reduce unwantedheat loss and can decrease the energy
demands of heating and cooling system.

The effectiveness of insulation is commonly evaluated by the key property of a thermal insulation
material―thermal conductivity k (W∙ (mK) −1), which refers to a material’s ability to conduct heat. Another two
corresponded parameters should also be introduced: thermal resistance R-value (m2K/W) and thermal
transmittance (or overall heat transfer coefficient) U-value (W/ (m2K)), where thermal resistance is a measure of
a temperature difference by which an object or material resist a heat flow per time unit and thermal transmittance
refers to the rate of heat transfer through one square meter of a structure divided by the temperature difference
across the structure. As good insulation materials, it is needed to achieve as low thermal conductivity as possible,
which enables,accordingly, a high thermal resistance as well as a low thermal transmittance.

Moreover, common insulation materials are characterized by light weight, small apparent density, loose and
porous, which can barrier the thermal conductivity by the internal non-flow air. Among these, the inorganic
insulation materials have non-flammability, a wide temperature range, good resistance to chemical corrosion
while the organic materials have high intensity, low water absorption as well as good impermeability.

Aerogel, also called solid smoke, is a synthetic porous material with a lot of remarkable properties. Studies for
silica aerogel originate from early 1931 by an American scientist Steven. S. Kistler who invented the first
aerogel material by hydrolysis of sodium silicate and supercritical drying.

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Then after the seventies of last century, research on aerogels developed rapidly, and American Science
magazine ever set aerogels as one of the top ten popular sciences.
Silica aerogel is the most common and the most extensively used type of aerogel, which is a kind of gel material
using gas as dispersion medium. This nano-porous material is generated through the polymerization between
polymer molecules or colloidal particles. It has a three-dimensional network structure formed by a series of
molecules and additionally, both the solid phase and pore structure of silica aerogel are based on nanoscale.
Normally, the temperature range for silica aerogel is -190℃~1200℃. Because of the nano-porous structure,
silica aerogel material has extremely low thermal conductivity values, about 13- 16mW/(m∙K), at 10 ℃ and at
atmospheric pressure (Weina.Zhang, 2006), lower than thermal conductivity of static air (20mW/(m∙K) and
silica aerogel molecules will not decompose at high temperatures and no harmful gases release. Even at 800℃,
its thermal conductivity is only 43 mW/ (m∙K) (Weina.Zhang, 2006). Composited with varieties of heat –
resistant fiber materials, silica aerogels can also be made into different insulation materials, diffusely used in
industry, construction, plumbing, automotive, aerospace and other fields.
Energy consumption in the European Union is projected to decline by 20% in 2020 and by 50% in 2050 relative
to energy use in 1990. (European Commission, 2008). A significant part of the energy consumption is linked to
the heating of buildings and the processing of domestic hot water. To ensure the optimum efficiency of a system
proper insulation a must have criteria. For insulation conventional insulating materials are the ones which have
low thermal conductivity. Aerogel is such a material which has been discovered quite recently that shows
promising insulating & capacitance capabilities. A study was done on the thermal conductivity of silica aerogel
and its composite insulation materials (Wei, 2011) which shows the promising characteristics of aerogel as an
efficient insulating material.

1.1 Motivation of the Research

Though showing promising characteristics as an efficient insulating material aerogel has a lot of drawbacks.
Pressing softly on an aerogel typically does not leave even a minor mark but pressing more firmly will leave a
permanent depression. Pressing extremely firmly will cause a catastrophic breakdown in the sparse structure,
causing it to shatter like glass. The thermal conductivity of

Page | 1163
aerogel also changes with respect to temperature and pressure. All of these factors must be carefully considered
when thinking of aerogel as an insulating material.
Objectives

The objectives of this study are given below:

Developing a model that describes the changes of thermal conductivity of insulating material depending on the
concentration of aerogel in that material.
Finding out the mechanical strength profile with respect to the aerogel percentage in the insulating material.
Modelling of efficient aerogel incorporated insulating material.

LITERATURE REVIEW

2.1 Heat Transfer in Insulating Materials


The role of insulation materials is to reduce heat transfer through the construction. The heat transport can
typically be divided into three parts: strong conduction, gas phase conduction and porous radiation, as shown in
the Equation (2.1)
λtotal =λgas +λsolid +λrad [(W/(m·K)] (2.1)

Where λtotal =λgas +λsolid +λrad [(W/(m·K)] are the total conductivity, the conductivity for gas conduction,
the conductivity for solid conduction and the conductivity for radiation . Very frequently, strong conduction is
the largest of these variables. Therefore, with limited amounts of rigid structure, insulation materials are
extremely porous.
The importance of radiation will increase in a medium with a minimal volume of solids, as seen in Figure 2.1.
For a certain substance, this provides an optimum point from the insulation standpoint, where the total of the
radiation inputs is summarized and there is a minimum of strong conduction. This sum will contribute to the
conduction of the gas that it can be called constant for typical insulation materials. This gives a total thermal
conductivity down to around 30 mW/(m·K) minimum, which can be Compared with 25 mW/(m·K) air
conductivity. Also, Figure 1 shows the efficient correlation of conductivity and density.
Mineral wool, polystyrene expanded or extruded, loose-fill cellulose fiber or foam glass are common products in
this group. Their heat conductivity as seen in Table 1.

Page | 1164
Table 1.Thermal conductivity of a number of common porous insulation Materials (Peterson, 2007).

Thermal conductivity, λ
Insulation material
[mW/(m·K)]

Foam glass 39-45


Mineral wool 33-40
Expanded/extruded polystyrene 30-40
Loose-fill cellulose fibre 39-42

Page | 1165
Figure-1. Thermal conductivity in porous materials divided in conduction
throughthe solid, conduction through gas phase and radiation through pores
(Simmler et al., 2005).

2.1.1 Solid conduction

The solid conduction for different materials also varies somewhat. For solid conduction, this makes the solid
material and its physical characteristics significant. A suitable solid material should be picked to minimize solid
conduction. As seen in figure 2.1, if the density is reduced, the strong conduction will be reduced. Diminished.
The solid's actual conductivity will not change, but the field of the solid will change. In a cross section of the
material, the solid will decrease and therefore lower the solid per square meter of porous material conduction. A
decreased density, as described earlier, would increase the heat flow due to radiation that will offset the solid
conduction gain.

Radiation

Electromagnetic radiation, which is produced from all surfaces, induces heat transfer by radiation. The
discrepancy between the radiation from the warm surface and the radiation from the cool

Page | 1166
surface is the net radiation. The transmitting rate of heat by radiation depends on a surfacetemperature
that can be defined by the Equation (2.2).

3
λr = 16𝑛2𝜎𝑇
(W/(m·K)) (2.2)
3𝐾

Where n [-] is the refraction index, σ [J/(K4·m2·s)] the Stefan-Boltzmann constant,


T [K] the mean temperature and K [1/m] the extinction coefficient. The heat transfer by radiation increases
exponentially as the temperature rises, which can be mitigated by adding an opacifier to the material.
Examples of opacifiers include TiO2 (titanium dioxide) scatters radiation, while carbon soot absorbs it.
Ionizing radiation (Fricke et al, 1991). The conductivity would be reduced by the additives, but at the around
the same time, the material's transparency reduces.

2.1.2 Gas Conduction

Gas conduction is determined by the form of gas and the gas's ability to transfer heat. To obtain a lower value,
the gas could be substituted for one with a lower conductivity or the gas could be stopped from transmitting
heat.

A typical approach where gas is transferred between the glazing panes is in windows where argon or krypton is
used. Another case is polyurethane foam, where low-conductivity reaction gases are stuck in a closed pore
structure. By reducing the pore size of the substance, the gas conductivity may be minimized. The collisions
between gas molecules and solids are elastic, which, relative to the collisions between gas molecules, transmit
small quantities of energy. Smaller pores increase the risk of colliding with pore walls rather than other gas
molecules. The gas conductivity, λg is regulated by Equation (2.3), which is based on the Knudsen number, Kn
[-], which is determinedby Equation (2.4). (Baetens et al, 2011).

λg 0
λg = (W/(m·K)) (2.3)
1+2𝛽𝐾𝑛

𝐾𝑛 = 𝑙𝑚𝑒𝑎𝑛 (−) (2.4)

where δ [m] is the characteristic system size, which can be interpreted as the distance between twoparallel
walls, lmean [m] is the mean free path, λg0 [W/(m·K)] is the conductivity of the gas when

Page | 1167
moving freely and β [-] is a constant for the effectiveness of the energy transfer between the gas molecules and the
solid pore walls with a value commonly between 1.5 and 2 (Baetens et al, 2011).

The ratio between pore size and the mean free path of the gas within the pores has a significant effect on gas
conductivity. The mean free path, the lmean, is the average distance a molecule moves before another molecule
collides. Equation can be used to measure the radius (2.5).

𝑘𝐵𝑇
𝑙𝑚𝑒𝑎𝑛 = (𝑚) (2.5)
√ 𝑔
2
Where T [K] is𝜎 the temperature, Pg [Pa] is the pressure, σ [m] is the molecular cross-sectional areaand kB [1.38·10-
𝑃
23 J/K] is the Boltzmann constant.
The molecular cross-sectional area is about 0.4 nm2 for nitrogen and oxygen, the primary components of air
(Engel and Reid, 2006). At average temperature and pressure (20°C and 100 kPa), the mean free path is
approximately 70 nm. The effect on the conductivity is shown in Figure2.

Figure-2. Calculated gas conductivity for air as a function of characteristicsystem size based on Equations (2.3),
Equation (2.4) and
Equation (2.5). The input temperature is 20°C and the pressure is 100kPa. The characteristic system size can be
related to the pore size of amaterial.

Page | 1168
It can be difficult to decide the signature device scale, but it is related to pore size. However, the conductivity
becomes closer to the natural conductivity of the gas as the pores get bigger. For pores greater than 10000 nm or
0.01 mm, it seems that the Knudsen effect is marginal.

The effect of reduced pressure on thermal conductivity is highly affected by pore size. Pressure is seen in the
denominator in Equation (2.5) for the estimation of the mean free path. With a lower strain, the mean free path is
longer, resulting in a greater Knudsen effect. It can be seen from Equations (2.3) and (2.4) that increasing the
mean free path raises the Knudsen sum, decreasing the gas conductivity.

2.2 AEROGEL- THE INSULATING MATERIAL OF FUTURE


An aerogel is a dried-out liquid process from a previous gel. The rigid structure of the gel must be maintained
during the drying period to be an aerogel, as opposed to a xerogel (Iler, 1979). In the early 1930s, Kistler (1931a)
first researched the notion of aerogels. Kistler's theory was that during drying, the shrinkage was produced by
capillary forces. Kistler heated his gel samples to the criticaltemperature of the solvent while the pressure was kept
above the liquid's vapor pressure to verifythe theory.

Silica aerogels, which are made from a silicon-based gel, are the most widely used for construction applications.
These are translucent aerogels with a high porosity and pores with a diameter of 20-40 nm on average (Soleimani
Dorcheh et al.,2008). The thermal conductivity will become lower than for still air (25 mW/(mK)) due to the
Knudsen effect (explained in Section 2.3). The aerogel can be manufactured in a variety of ways, including
monolithic blocks, granulates of differing fineness, and carpets lined with a fiber content. Aerogel composites
come in a range of shapes andsizes.

Aerogels are three-dimensional (3D) network structures made up of nanoparticles linked together. Kistler
developed the first aerogel in 1931. The bulk of the space in aerogels is filled up by air, with just a slight amount
of solid phase left, as seen in Fig.3. Aerogel pores are usually 2–50 nm in size, which is the same pore size range
as mesopores.

Page | 1169
Aerogels include a high porosity ([80 percent], moderate density (0.003–0.35 g cm-3), high real surface area
(100–3,000 m2 g-1), and a significant number of percolating mesopores, among otherstructural attributes.

Figure-3. Illustrative structure of an aerogel

These unique structural features foster a wide range of applications for aerogels. Aerogels, for example, are a
promising candidate for thermal insulators in energy-saving applications due to their high porosity. Aerogels can
be used as electrode materials in supercapacitors and lithium ionbatteries because of their high specific surface area
and mesoporous composition. Sol–gel methods have historically been used to build these mesoporous structures, in
which nanoparticles are cross- linked to form 3D networks. To clear the trapped solvent without inducing undue
structural shrinkage or even collapse of the fragile 3D network structure, wet gels obtained via the sol–gel process
typically require supercritical fluid drying.

2.2.1 Properties of Aerogel

Monolithic silica aerogel is a brittle material. Parmenter and Milstein (1998) measured the compressive strength
was about 1 MPa, while the tensile and shear strengths were slightly lower. Silica aerogels usually have a density
of about 100 kg/m3 (Soleimani Dorcheh et al., 2008), but Tillotson et al. (1992) were able to make measurements
with a density of just 3 kg/m3, which is only 2.5 times the density of air, which is 1.2 kg/m3. It has very small
pores with a diameter of 20-40 nm, considering the fact that it has a very small volume of solid content. The strong
thermalefficiency of the aerogel is due to the combination of small pores and a small fraction of solid.

Page | 1170
There are two separate places from which to maximize the efficiency of aerogel's thermal properties. Aerogels
can be partly translucent, allowing them to be used as a light inlet with a low thermal conductivity as opposed to
glass. Around the same time, this would result in a moderately high radiation conductivity. The aim may also be
to enhance the thermal properties of the material in order to mitigate radiation through it.

Kistler found that one of the amazing properties of aerogels is their exceptionally low thermal conductivities.
About 1980, the revival of aerogel technology coincided with a growing concern for energy conservation and the
impact of chlorofluorocarbons (CFCs) on the climate. Because of their low thermal conductivities and
environmentally sustainable processing practices, silica aerogels became a promising alternative to conventional
thermal insulation materials.

Synthesis of Aerogel

Producing the gel is the first step in creating an aerogel. A sol-gel procedure is used to create the gel, in which the
solid elements are dispersed in a solvent such as water or alcohol. The solvent disperses as liquid in the gel pores,
inducing gelation and the forming of the gel.

Sections of the solid structure will crumble during regular drying of a gel due to the strain produced as the
moisture in the pores evaporates. The gel shrinks dramatically as a result of this, and the solid's density increases
as a result. The gel should be dried at the liquid's critical state, above its critical temperature and pressure, to
avoid shrinkage.

The substance becomes a supercritical fluid as it hits the critical point. There will be no stress generated by the
phase transition and there will be no distinction in the liquid and gas phases. The fluid can be separated without
altering the solid's composition, resulting in an extremely porous, low-density composite known as an aerogel
(Kistler, 1931b).

A phase diagram, such as the one seen in Figure 4, can be used to represent the operation. The temperature and
pressure associated with the various phases of the pore liquid are represented in the diagram. The liquid begins at
room temperature (point 1) and steadily rises in temperature and pressure until it enters the supercritical state
(point 2). For the conditions dividing the liquid phase from the gas phase, the combination of pressure and
temperature is often held above the line (e.g. following the dashed arrow). The fluid will remain a liquid until it
enters the critical state, at which

Page | 1171
point it can be substituted for another fluid, most usually air, without causing any pressures on the gel structure.

Figure-4. Example of a phase diagram.

The temperature and pressure can be returned to ambient after the fluid exchange without disturbing the gel
structure. A dry gel with the initial gel form preserved as seen on the left.

374°C and 221 bar are the critical temperatures and pressures for water, respectively. To produce an aerogel from
a gel with water as the fluid, high pressure and high temperature are necessary. The liquid in the gel may be
substituted for a liquid with a lower critical temperature and/or critical pressure to minimize the energy used to
produce aerogel. Different liquids are compared in Table

3. Carbon dioxide, in fact, is intriguing since its critical temperature is 31°C, which is very similar to room
temperature. However, the critical pressure for most fluids is much greater than ambient pressure. This means that
making aerogel requires a lot of energy.

A life cycle evaluation of clear silica aerogel was performed by Dowson et al (2011). They studied the method of
laboratory-produced aerogel because they did not have numbers from real industrial- made goods. They argued
that since the aerogel would be manufactured in bigger batches, mass manufacturing would reduce the
environmental effects much further. They devised a

Page | 1172
refurbishment scenario in which single-glazed windows were covered with translucent aerogel. After 0.3 to 1.9
years, the energy savings exceeded the energy consumed in production.

Table 2.Some different fluids and their critical temperature and critical pressure (NIST, 2011).

Fluid Tcr [K] Tcr [°C] Pcr [bar]


Carbon dioxide, CO2 304 31 74
Methanol, CH3OH 513 ± 1 240 ± 1 81 ± 1
Water, H2O 647 ± 2 374 ± 2 221

Kirkbir et al. (1998) dry silica aerogel for various liquids at various pressures between ambient and critical
pressure. The theory was that above a certain pressure, the forces produced in the pores during drying are weaker
than the gel structure's intensity. They discovered that the critical strain for certain solvents could be lowered by
more than half without the aerogel breaking and with just a 2% shrinkage. Even so, a pressure of 18 bar was
required.

The gel is prepared by silylation, which is the substitution of silyl groups to the gel structure, which is used to dry
aerogels at atmospheric pressure. The silylation makes the gel strongly hydrophobic, which decreases the forces
induced by cell water evaporation. The gel shrinks at first due to internal water currents, but after enough water
has been absorbed, the residual water can form droplets within the cell layer, repelling the pore walls and
allowing the solid structure to return to its original size (Soleimani Dorcheh et al., 2008). The thermal
conductivity of aerogel samples dried at atmospheric pressure was tested by Parvathy Rao et al. (2005) and was
found to be about 100 mW/(mK), well exceeding the properties of aerogels dried at supercritical conditions.

Applications of Aerogel

Aerogel materials have a wide range of outstanding properties, which has resulted in a vast variety of
applications. Many industrial uses of aerogels, such as catalysts, thermal insulation, windows, and particle
detectors, are in the works, and new ones have been announced since the ISA4 Conference in 1994: for example,
supercapacitors, insulation for heat storage in cars, electrodes for capacitive deionization, and so on. As the
science and technical world gets more familiar with the peculiar and extraordinary physical properties of aerogels,
more uses will arise.

In the early 1980s, aerogels were recognized for their exceptional properties, especially homogeneity and
uniformity, which were essential for primary applications. When physicists and

Page | 1173
engineers became more conscious of the properties of aerogels and considered how to use them, they started to
order custom aerogels.

Because of their unusual and beneficial structural properties of high porosity, high specific surface area, and
percolating mesopores, aerogels have a wide variety of applications. Aerogels are useful in any application that
involves high functional surfaces and fast transport for participating organisms. Aerogels will almost definitely be
used in further applications in the future. Aerogels must be manufactured in appropriate processes to achieve the
required application characteristics to satisfy various product specifications.

Aerogels can be used to build energy-saving screens. Rubin et al (1982) U-values, on the other hand, are not
higher than those of modern triple-glazed windows. Caps and Fricke (1984) observed that evacuating the aerogel
raised the U-value to about 0.7 W/(m2K) for a 1 cm thick aerogel and

0.35 W/(m2K) for a 2 cm thick aerogel. They didn't give a figure for solar transmission.

Another use of transparent aerogel that has been tested is as a solar collector. The results of mounting a
transparent aerogel insulation sheet on the outside of the exterior walls were studied by Schreiber et al (1986).
The sun's rays will move through the aerogel and warm the wall behind it. The energy from solar radiation will
pass through the building if the conductivity of the wall is greater than that of the aerogel. Heat may be contained
as well with a thick interior wall.

Svendsen (1992) coated a metal solar collector in clear aerogel and attached it to water pipes. The annual energy
gain per square meter of the solar collector was 766 kWh for a 60°C device, compared to 316 kWh for a normal
solar collector without aerogel. The annual energy gain per square meter solar collector was 684 kWh with
aerogel and 183 kWh without aerogel for an 80°C device.

To minimize wall thickness, invisible aerogels may be used as insulation in the building envelope. It is now
highly costly, costing more than ten times as much as traditional insulation materials like mineral wool (Baetens
et al, 2010).

As drain insulation, reinforced aerogel carpets are used (Baetens et al, 2010). Because of the lower conductivity,
the pipes can be made narrower, which is advantageous for shipping and assembly space. Since heat losses are
radial, pipe thickness is highly significant. The insulating potential becomes more important when you get closer
to the cylinder's center, where the circumferring

Page | 1174
region is smaller. For the same design losses, halving the thermal conductivity will result in more than half the
insulation thickness.

Stahl et al. (2012) developed a façade rendering using aerogel. The conductivity of the rendering was 25
mW/(mK), which is smaller than that of traditional rendering systems. The density was 200 kilograms per cubic
meter. Although the rendering is still in the early stages of development, it may be a promising choice for exterior
insulation when renovating older structures.

Aerogels have been found to be superior in terms of energy efficiency and energy recovery as electrode structures
for supercapacitors and lithium–ion batteries. The new trend is to build composite aerogels that incorporate the
benefits of individual components to satisfy the needs of multiple applications. Aerogels made up of materials
other than metal oxides and carbon still deserve further analysis. Aerogels have a lot of scope for extending their
uses.

2.3 CONVENTIONAL HIGH PERFORMANCE THERMAL INSULATORS

Foamglass, polyurethane (PUR), polyisocyanurate (PIR), and polystyrene with additional graphite are among the
innovative thermal insulation products and components used in the construction industry. Novel nanomaterials
could be combined with existing building materials like concrete to produce potential materials.

Polyurethane (PUR) and Polyisocyanurate (PIR)

One way to minimize heat transfer into an insulation material is to fill it with a gas that has a lower conductivity
than air. To hold the gas within the material, either a closed pore system or some sealing around the insulation
core is necessary. The air has been replaced with a blowing agent that has a lower thermal conductivity than air in
polyurethane (PUR). Hydrofluorocarbons (HFC), carbon dioxide (CO2), and cyclopentane (C5H10) are examples
of these gases. The gas is trapped in the PUR's closed pore structure, which is constructed from polyisocyanates
and polyols interacting together. In the event of a burn, PUR will release the toxic substances hydrogen cyanide
(HCN) and isocyanates (Jelle, 2011). The thermal conductivity of PUR varies depending on density and moisture
content, but it is usually about 24 mW/(mK) for building applications. Polyisocyanurate (PIR) is a polyurethane
(PUR) that has been improved by adding other ingredients, reactants, and catalysts to the manufacturing process.
As a result, a material with a

Page | 1175
thermal conductivity of around 22 mW/(mK) (EcoTherm, 2010) and better fire efficiency than PUR has been
established. The PIR has an aluminum covering on both sides that can be coated with various facing materials
(Kingspan, 2010).

Roofs, plastered walls, sandwich walls, and floors will all benefit from PUR and PIR insulation, which can be
moulded as a board material. Since its properties are identical to those of EPS, it can be used in areas where EPS
has historically been used. When cutting PIR, however, some dust is released, which can be harmful to one's
wellbeing and irritating to the skin and respiratory system. The PIR ages as well, and the thermal conductivity
increases with time due to gas diffusion. Another concern is PIR shrinkage of up to 1%, which can result in air
gaps between the plates.

Graphite polystyrene

For several years, stretched polystyrene (EPS) and extruded polystyrene (XPS) have been used in the construction
industry. EPS is constructed from polystyrene that has been extended with a gas such as pentane C5H12 to form a
rigid board. Another technique for manufacturing XPS is to use a nozzle to manufacture the polystyrene, which
then releases the strain, allowing the substance to stretch. Hydrofluorocarbons (HFC), carbon dioxide (CO2), and
pentane (C5H12) are some of the gases used to extend the XPS (Jelle, 2011). EPS and XPS have a thermal
conductivity of about 36 mW/ (mK).

Graphite polystyrene is an enhanced version of EPS that uses graphite in the mix. The graphite decreases heat
transport by radiation through the pores in the EPS, resulting in a thermal conductivity of 31 mW/ (mK), which is
roughly 20% less than the conventional material. The material shrinks after processing, much like EPS, so it
should be processed for a while before being used in building (BASF, 2011).

GPS has a permeability value of 2.5 to 5.5, based on the thickness and density of the insulation. This allows water
vapor to escape the wall assembly. The graphite in GPS insulation enhances the material’s R-value as
temperatures decrease. Compared to other polystyrene-based and polyiso rigid foams, GPS retains more of its R-
value in colder temperatures. The insulation also has the

Page | 1176
same fast drying and low long-term moisture retaining properties as EPS insulation. GPS insulation is well-suited
for high-moisture conditions because of these two characteristics.

2.3.2 Materials of Tomorrow

Jelle (2011) gave a review of existing and potential thermal insulation materials and parts, as well as an outlook
on what can be built in the future. The gas filled panels are a part that is currently available but has a grim future
outlook (GFP). The GFP is created by replacing the air in a panel with an internal honeycomb structure with a
less conductive gas like argon, krypton, or xenon. Since the part does not have to survive the ambient gas pressure
on the envelope, it needs a less sophisticated core and envelope content than the VIP. The gas conductivity, on the
other hand, is even higher than in VIP, where the gas is evacuated. The use of high emissivity coatings on the
interior surfaces eliminates heat transfer by radiation. The theoretical thermal conductivity is lower than the lab
measurement of 40 mW/(mK).

For the future thermal insulation material, Jelle (2011) predicted great possibilities using custom made
nanomaterials as thermal insulation. Vacuum insulation materials (VIM), nano insulation materials (NIM), gas
insulation materials (GIM), and dynamic insulation materials (DIM) are among the latest materials suggested
(DIM). The production of these materials has only just begun, and only time can tell which material or part will
be used in future buildings. Future materials can have physical properties that are equal to or greater than VIP, but
without the drawbacks.

The VIP cannot be cut on site and is prone to mechanical forces as well as air and moisture diffusion. VIM is
similar to VIP, but instead of the protective envelope, it has a closed pore structure. Maintaining the void in the
VIM for the remainder of its service life is challenging (Jelle, 2011).

An alternative to the VIM discussed above, is the GIM which is similar to VIM but with a gas filling. GIM will
probably have a longer service life than VIM since the pore structure will not be exposed to the same pressure
difference (Jelle, 2011).

DIM should actively control the thermal conductivity of the material either by varying the internal gas pressure,
the emissivity in the material or the conduction through the solid. The DIM should work in a similar way as
electrochromic and phase change materials, i.e. adapting to the changes in the surrounding climate (Jelle, 2011).

Page | 1177
METHODOLGY

For our research we tackled the problem of showing a model of how the insulating property of the material
aerogel worked on varying different external conditions. We are hopeful that this modelling will help the better
understanding manipulation criteria that is needed for aerogel to suit a specific purpose. For this we needed data
that showed the variation of different external conditions that can be controlled and the change of the properties of
aerogel respective to the changes in those conditions.

For our problem, we primarily needed quantitative data that showed the relations of changes in the external
processing properties and the change of the properties of the material aerogel.

Due to global pandemic situation for the reason of the covid-19 condition and the time limitation on our thesis
submission we were unable to collect the primary data for tackling the problem ourselves by conducting direct
experiments. We had to rely on the data and equations that were collected by other researchers experienced in this
field of aerogel. This modelling is based on research papers and reports which have been gathered by experts all
around the globe. For the modelling Microsoft excel was used.

The data for our modelling were gathered by controlling and manipulating various external processing conditions
by doing experimental analysis by researchers. This method was considered the most suitable and feasible
considering the overall conditions.

Modeling the tensile modulus & stress at break for various percentage of aerogel

Composite preparation: Four composites of PVC/aerogel were prepared using 0, 2, 3 and 4% aerogel (all of the
percentages in this report is mass percentage w/w).For this purpose, aerogel was weighed and poured into a 250-
mL beaker; then the coating mixture with the above-mentioned composition was poured on it and mixed with a
mechanical mixer at ambient temperature and pressure with a three-blade propeller (5cm diameter), first at the
speed of 400r/min for 2h, then 900r/ min for 4h and finally 1700r/min for 6h to obtain a homogeny and smooth
plastisol without any agglomerates. Then, Theas prepared plastisol (PVC coating redients, including aerogel) was
applied on both sides of a polyester fabric with a knife coating method by means of a lab coating

Page | 1178
instrument (the thickness of each layer of coating was 0.4 mm and thickness of fabric was 0.2 mm, giving a total
thickness of 1mm for each composite). The curing temperature and time were 180 deg C and 2.5min,
respectively, for the first side and 190 deg C and 1.5 min for the other side. The neat composite was named ‘0%-
aerogel’ and the 2, 3 and 4% aerogel-containing composites were named as ‘2%-aerogel’, ‘3%-aerogel’ and‘4%-
aerogel respectively.

The tensile properties were evaluated in accordance with the standard method ISO 527. The dumbbell shaped test
bodies were cut by a laser cutter. The test bodies were tested on a MTS 20/M (MTS Systems Corporation, Eden
Prairie, MN, USA), fitted with a 10kN load cell and a special grip for films, using a crosshead speed of 5mm/min.
The gauge length, preload force and first approach speed were 0.5N, 2 mm/ min and 33mm, respectively. A
minimum of five test bodies was tested for each material. The specimens were all cut in the warp direction As the
composites contain woven fabric, to obtain high-quality test specimens for tensile strength measurement, cutting
of all specimens were done with a laser cutting machine (GCC Laser Pro Spirit GLS, GCC, Taiwan) with the
speed of 7.8 mm/ min, power of 84 mill watt (mW) and pulses per inch (PPI) of 1486 with compressed air
purging as cooler stream.

Tensile modulus: Tensile modulus is a mechanical property that measures the tensile stiffness of a material. It is
defined as the relationship between tensile stress (force per unit area) and axial strain (proportional deformation).

Stress at break: Stress at break or breaking point is defined as the maximum stress a specimen can handle while
being stretched before breaking.

Gas conductivity analysis of aerogel based on thermal energy

Gaseous conductivity in a xonotlite type calcium silicate material can be found by using the following equation:

K=1+2𝜁𝑘𝑛……………………………………………………………. (5.2.1)

Where, ζ is a constant specific to the gas in the pores, for air ζ= 2, kg0 is the temperature dependent gaseous
conductivity at atmospheric pressure. Kn is the Knudsen number defined as lm/dm. Here,

Page | 1179
dm is the characteristic system size (the mean pore size of xonotlite-type calcium-silicate in this work) and lm is
the mean free path of gas molecules in free space.

Literature showed that this equation is not in agreement with experimental data and so the following equation was
used to calculate the gaseous thermal conductivity in aerogel.

Here, S is the specific surface area of aerogel defined as surface area per unit mass, pae is the aerogel density, and
is got by measuring the weight and volume of silica aerogel sample, Φae is the porosity of the aerogel determined
as Φae = 1- ρ / ρ bulk (ρbulk =2200kg/m3 is the density of the bulk silica. P is the pressure, and T is the medium
local temperature.

The following assumptions were considered for the analysis of the model:

The shrinkage in supercritical drying process is negligible, and no chemical actions occur between xonotlite-type
calcium silicate and aerogel in compositing process.

Aerogel fills in the interspace of xonotlite-type calcium silicate with a constant filling coefficient w, and the
parallel law of thermal resistances is used to consider the filled and unfilled part of xonotlite-type calcium silicate.

The contact resistance between the solid and gas is negligible.

The variability of microstructure of the material with the temperature is negligible.

The heat is flowing along one-dimension just as considered in the other unit cell models.

By simplification, xonotlite-type calcium silicate is considered as a periodical array of hollow cubic structures
with connecting bars.

It can be shown that the density of the composite material is:

𝜌=𝜌𝑥+𝛷1𝜓𝜌𝑎𝑒……………………………………………….. (5.2.3)

Where, 𝜌𝑥 and 𝜌𝑎𝑒 are the densities of xonotlite-type calcium silicate and aerogel respectively.

Page | 1180
Gas conductivity analysis of aerogel based on pressure energy

The gas pressure dependence of the apparent thermal conductivity displays the two-step picture expected for
porous materials with two distinctive different pore sizes. The fit curve represents a behavior

𝛬(𝑝𝑔𝑎𝑠) = 𝜆0 + 𝜆1 + 𝜆2 …………………………………………….. (5.3.1)

1+𝑝1/𝑝𝑔𝑎𝑠 1+𝑝2/𝑝𝑔𝑎𝑠

Where, λ0. = 10.3*10-3 W/(m-K) is the conductivity for an evacuated fill. Λ1 =7.6*10-a W/(m.K) represents the
low pressure increase in conductivity caused by the space between the pellets and λ2

= 9.5~10-~ W/(m.K) the high pressure increase of λ caused by the pores within the pellets. P1=

0.09 mbar and p2= 1050 mbar are the pressures where λ 1/2 and λ 2/2, respectively are reached.

Overall thermal coefficient analysis of aerogel coated walls

Another use of aerogel is the use of its insulation properties in building applications. Using data from existing
researches the effect of aerogel when used as a retrofit insulation material in existing building materials can be
modelled.

Based on information obtained during the literature review the three type of materials most commonly used in the
UK for building wall structures are:

225mm solid brick masonry (internal plaster finish)

600mm solid stone (Lath & internal plaster finish)

250mm cavity brick wall (With/without insulation)

Item 3 above is a hybrid wall type which has been selected for simulation modelling as it is not only a common
existing wall construction type but can also be modelled to include insulation within the cavity space.

WALL TYPE C: this wall type has been simulated to include no cavity insulation as well as full- fill cavity
insulation. In this construction method, the exterior brick acts as a type of rain screen and the cavity acts as a
drainage layer. Once full fill or partial fill insulation is introduced the thermal performance can be greatly
improved. For this research both of these variations will be simulated to include 10 and 15mm aerogel.

Page | 1181
Material Physical Properties Data

In order to attain accurate results from each of the software simulations, the physical properties of each material
used for each simulation was consistent and without variation. Values for the following material properties were
sourced from data provided by the Fraunhofer Institute for Building Physics material catalogue in the WUFI
software. The only exception to this was the thermal conductivity data provided by the environmental chamber
tests and moisture vapor transmission tests discussed earlier in this thesis.

Material Thickness

Thermal Conductivity

Bulk Density

Specific Heat Capacity

Vapor Diffusion Resistance Factor (Mu Value)

In evaluating the thermal performance of the proposed systems, the software used was BuildDesk U 3.4. This
software program has the ability to determine the U-Value of the wall samples, as well as simulated moisture
conditions. Once the simulations were completed they were then compared and evaluated.

The following information shows the physical properties of the materials used and the U-Value calculations for
each wall sample without any form of additional insulation other than aerogel.

Page | 1182
RESULTS AND DISCUSSION

Mechanical property analysis of aerogel based thermal insulations

A novel aerogel/PVC composite on polyester fabric was created and characterized. It was discovered during the
preparation of the plastisol for aerogel-doped PVC-coated fabric composites that increasing the aerogel content in
the plastisol increases the viscosity, to the point that 5% aerogel was too viscous and difficult to combine. As a
result, up to 4% aerogel was studied in this study.

From the tensile strength test data for 0–4 wt% aerogel containing poly (vinyl chloride) (PVC)- coated fabrics
(Jabbari, 2015) and we have achieved the average tensile modulus data with respect to % of aerogel given at table
3

Table 3. The average tensile modulus data with respect to % of aerogel (Jabbari, 2015).

Composite Tensile modulus (MPa)

0% Aerogel 56.89

2% Aerogel 54.48

3% Aerogel 53.5

4% Aerogel 52.07

The data of stress at break are also found from the experiment and the average data of stress at break are given
with respect to % of aerogel used in the plastisol in table 4.

Table 4. The average stress at break data with respect to % of aerogel (Jabbari, 2015).

Composite Stress at break (MPa)

0% Aerogel 56.88

2% Aerogel 52.4

3% Aerogel 51.75

4% Aerogel 50.88

For analyzing the both parameter at once a curve was developed through Microsoft excel which is given in figure
5

Page | 1183
Mechanical Property
5 Analysis 5
8 8
5 5
7 7
5
6 5
6
5
5 5
5 5
4 5
5 4
3
5
3
5
Stress at break

5 5
1 2
5 5
0 0% 5% 1
(MPa)

1% 2% 3% 4%

Tensile Modulus
% of Aerogel

Stress at break Linear (Tensile modulus

(MPa)
(MPa) (MPa))

Figure-5. The average stress at break and tensile modulus data with respect to % of aerogel.

Here we can come to a decision that increasing amount of aerogel in plastisol decrease the tensile modulus along
with it also decrease the ability to survive the stress. From the plot we can say that the tensile modulus of the
material decreases proportionally with the percentage of Aerogel. Including other perspectives adding 2% aerogel
is more beneficial.

Gas conductivity analysis of aerogel based on thermal energy

We have developed a relation between gaseous thermal conductivity of aerogel with temperature through an
empirical equation where the composite material is xonotlite type calcium silicate. Applied temperatures and
resulting gaseous thermal conductivities are given in table 5.

Table 5. Gaseous thermal conductivity of aerogel with different temperatures.

Temperature (K) Gaseous thermal conductivity of


aerogel Kg (W/m.K)

300 0.0259

Page | 1184
400 0.0299

500 0.0334

600 0.0336

700 0.0395

800 0.0422

Page | 1185
The plot consisting of these data from table 5 indicates clearly that the thermal conductivity do increase in aerogel
with the respect to increasing local temperature in a regular manner. The plot was done with the help of Microsoft
excel and it is given below in figure 6.

Figure-6. Gaseous thermal conductivity of aerogel vs temperature curve

Gas conductivity analysis of aerogel based on pressure energy

Gaseous thermal conductivity is highly dependent on pressure. By manipulating the pressure in silica aerogel we
can see the deference in gaseous thermal conductivity. We have changed the pressure in the equation for several
time for getting the gaseous conductivity profile. The gaseous thermal conductivity found for different pressure
are given at table 6.

Table 6. Gaseous thermal conductivity of silica aerogel with respect to pressure.

Pressure (mbar) Gaseous thermal conductivity


(W/m.K)

Page | 1186
10 0.0698

100 0.708

200 1.406

400 2.8

700 4.89

1000 6.99

1500 10.48

10000 69.82

Page | 1187
The sketch we found by the implementation of the data from table 6 gives us a curve which indicates the
characteristics of the aerogels gaseous thermal conductivity with respect to pressure. We can see the relation
between them in figure 7.

Figure-7. Gaseous thermal conductivity of silica aerogel with respect to pressure.

Increased pressure causes a great loss of insulation for aerogel. High pressure causes increased diameter of the
pores of aerogel. As diameter increases the aerogel gets for comfortable for transfer of heat. As we can see that
much higher pressure can completely destroy the insulation characteristics of the aerogel which is undesirable.

So we can come to a decision from the analysis that we require the pressure as low as possible for getting the best
insulation performance from the aerogel.

Overall thermal coefficient analysis of aerogel coated walls

Coating the industrial and other walls for insulation purpose is one of the most important application of the
aerogel. Here we have studied three types of walls with different thickness of aerogel and compared them on the
basis of thermal coefficient. The three types of walls are 225mm solid Brick wall, 600mm Stone and 250mm
brick cavity.

Coating with different thickness causes different profile of thermal coefficient in these three walls. The data were
collected (Carty, 2017) are given in table 7.

Page | 1188
Table 7. Overall thermal coefficient of different solid walls with different thickness of aerogel coating

Aerogel Overall Overall Overall


thickness thermal thermal thermal
(mm) coefficient coefficient coefficient
of 225mm of 600mm of 250mm
Solid Brick Stone Brick
wall cavity

0 1.79 1.61 1.61

10 0.93 0.89 0.5

15 0.75 0.73 0.44

The values of the overall thermal coefficient are plotted together with respect to aerogel coating thickness for
getting a clear overview about the performance of the aerogel coating with the individuals.

The plot is done with the help of Microsoft excel and given at figure 8.

Figure-8. Overall thermal coefficient of different solid walls with different thickness of aerogel coating.

Page | 1189
From the curve we can see that the thermal coefficient decreases as the thickness of aerogel coating increases, but
giving a much thicker coating is not economically feasible. Giving a coating of optimum thickness is our main
goal.

As we can see that the change of thermal conductivity in 10mm and 15mm thickness is very low but 15mm
coating causes much more cost than 10mm coating. So, 10mm coating should be our priority.

On the other hand we have to tricky for choosing the composite material. As we can see that the 250mm brick
cavity shows the better result in purpose of insulation.

So here we can say that using the 250mm brick cavity with 10mm coating of aerogel is the most desirable option
here.

CONCLUSION

The study aimed to show the change in properties of aerogels by manipulating research variables. Based on the
analysis of the models it can be concluded that certain property changes have a higher impact on aerogel property.

The modelling approach was taken to help get a better understanding of the properties of aerogel. The models
match the expected theory that has been developed.

Based on the conclusions, the practitioner should consider the condition of where aerogel is being used to get the
best results.

Page | 1190
References:

i. Bock, T. (2011). Study visit at va-Q-tec production facility in Wuerzburg,


Germany,June 10,2011.
ii. Boverket. (2010). Energi i bebyggelsen - tekniska egenskaper och beräkningar -
resultat frånprojektet BETSI. Karlskrona, Sweden: Boverket.
iii. Brodt, K. H. (1995). Thermal insulation: CFC-alternatives and vacuum
insulation (Dissertation). Delft, The Netherlands: Delft University of
Technology, Faculty ofApplied Physics.
iv. Brodt, K. H. and Bart, G. C. (1994). Performance of sealed evacuated panels
as thermalinsulation. International Journal of Refrigeration, 17(4), 257-262.
v. Brunner, S., Gasser, P., Simmler, H., and Wakili, K. G. (2006). Investigation of
multilayered aluminium-coated polymer laminates by focused ion beam (FIB)
etching. Surface andCoatings Technology, 200(20-21), 5908-5914.
vi. Brunner, S., Tharian, P. J., Simmler, H., and Ghazi Wakili, K. (2008). Focused
ionbeam (FIB)etching to investigate aluminium-coated polymer laminates subjected
to heat and moisture loads. Surface and Coatings Technology, 202(24), 6054-6063.
vii. Caps, R. & Fricke, J. (1986). Infrared radiative heat transfer in highly transparent silica aerogel.

viii. Solar Energy, 36(4), pp.361–364.

ix. Fricke, J., Heinemann, U., and Ebert, H. P. (2008). Vacuum insulation panels – From
research tomarket. Vacuum, 82(7), 680-690.
x. Garnier, G., Marouani, S., Yrieix, B., Pompeo, C., Chauvois, M., Flandin, L., and
Brechet, Y. (2011). Interest and durability of multilayers: from model films to
complex films.
xi. Polymers for Advanced Technologies, 22(6), 847-856.

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xii. Ghazi Wakili, K., Bundi, R., and Binder, B. (2004). Effective thermal conductivity
of vacuuminsulation panels. Building Research and Information, 32(4), 293-299.
xiii. Jelle, B. P. (2011). Traditional, state-of-the-art and future thermal building insulation
materials and solutions - Properties, requirements and possibilities. Energy and
Buildings, 43(10),2549–2563.
xiv. Jelle, B. P., Gustavsen, A., and Baetens, R. (2009). Beyond vacuum insulation panels-
How may it be achieved? Proceedings of the 9th International Vacuum Insulation
Symposium, September 18-19, 2009, London, UK.
xv. Johansson, P. (2012a). Retrofitting of old Exterior Wall with Vacuum Insulation
Panels: Measurements of Thermal Properties, Moisture Performance and
Practical Considerations (Lic. Thesis 2012:2). Gothenburg, Sweden: Chalmers
University ofTechnology, Department of Civil and Environmental Engineering.
xvi. Johansson, P. (2012b). Vacuum Insulation Panels in Buildings: Literature Review
(Report 2012:1). Gothenburg, Sweden: Chalmers University of Technology,
Department of Civiland Environmental Engineering.
xvii. Johansson, P., Adl-Zarrabi, B., and Hagentoft, C.-E. (2012). Using Transient
Plane Source Sensor for Determination of Thermal Properties of Vacuum
Insulation Panels.
xviii. Proceedings of the 5th International Building Physics Conference, May 28-31,
2012,Kyoto, Japan.
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36(1), pp.52-64.

Page | 1192
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 337

Adsorption Behavior of Eggshell on Arsenic (V) Ion

Anan, M.A.A., Rahman, M.S., Boni, S.F.T., Badhon, M.A.H., and Rahman, M.N.*

Department of Chemical & Food Process Engineering,


Rajshahi University of Engineering &Technology (RUET), Rajshahi-6204, Bangladesh
Email: mdaanan@gmail.com, 1511004@student.ruet.ac.bd, fahimtahmid111@gmail.com,
abidhasanbadhon74@gmail.com, nurur@cfpe.ruet.ac.bd
* Corresponding Author: [Mohammad Nurur Rahman]

Abstract: Arsenic-contamination in groundwater is a big concern. So, the present study


Keywords:
has been focused on to absorb arsenic from the aqueous solution using eggshell. Arsenic
adsorption process was performed by investigating the effect of particle size of powdered
● Arsenic; eggshell keeping various parameters such as pH, initial arsenic concentrations,
● Isotherm; temperature and adsorbent dosage constant. Initial concentration of 2.5 mg/L was used.
The whole experiment was conducted using 5 different particle sizes keeping pH as 7.
● Solution; After reaching equilibrium condition, Langmuir Isotherm & Freundlich Isotherm were
● Eggshell; drawn. By calculating correlation co-efficient it was noticed
that Freundlich Isotherm model correlate significantly.
● Adsorption.

1. Introduction
Arsenic is the most hazardous element and its presence in drinking water can cause several problems. This
problem is very severe in rural areas where water treatment techniques are not affordable because they are
expensive. Arsenic exists in water as organic as well as inorganic forms with basically two different states,
i.e. As(III), As(V) (Smith, 2000). Chronic Arsenic exposure can cause Cardio Vascular disease, Cancer and
the eventual death. Many methods of Arsenic removal are available but most of these are too expensive to
be implemented in poor countries such as Bangladesh. Every particular process has its own limitations and
can be usedto a limited extend only (Saifuddin, 2011).
Arsenic cannot be destroyed but it can be transformed into different forms. It can be combined with other
elements converting into insoluble compounds. In groundwater, Insoluble forms of Arsenic are Arsenate
As(V) and Arsenate As(III) are predominately present. Arsenic is a metalloid having lack of color, odor and
taste, which make it the most successful secret weapon. The evidence for carcinogenicity of arsenic is very
strong in humans, but weak in animals, a unique and different scenario that is found for other carcinogens.
The arsenic level is generally present more in groundwater where geochemical conditions are favorable for
the dissolution of arsenic. Contamination can occur from both organic and inorganic compounds. The
inorganic compounds are more toxic than organic compounds.

Page | 1193
The toxicity of the trivalent inorganic species (arsenite) is higher than the toxicity of the pentavalent species
(arsenate). The toxicity of Arsenic can be presented as follows; Arsine>Inorganic As(III) > Organic As(III)
> Inorganic As(V) > Organic As(V) > Arsonium compounds and elemental arsenic. Toxicity of Arsenic
depends on its pH, oxidation state and redox potential. Arsenite is more mobile in ground water and 25-60
times more toxic than Arsenate. Because it is carcinogenic and non-bio degradable in nature and exists for
long timein environment (Ahmed, 2001).
The process of adsorption can be defined as the accumulation of material at the liquid/solid boundary layer.
Adsorption is basically a mass transfer process in which a component is transferred from the liquid phase to
the solid phase (surface of the solid). This accumulation is bound either through chemical or physical forces.
In adsorption process, transfer of arsenic in water depends on the specific surface area and high surface
energy of the adsorbent. The ability of the adsorbent depends on the properties of the material which is
being used for adsorption. The most commonly used adsorbent is metal oxide, activated carbon and
activated alumina (Sauvé, 2014).
Classification of adsorption is based on how the interaction between the absorbate & absorbent is. If the
interaction force is weak, the type of adsorption is called physical adsorption (physisorption). The forces of
physical adsorption are Van de Waal’s force & electrostatic force. On the other hand, if the interaction
between solute & adsorbent is strong because of chemical bond, then it is known as chemical adsorption
(Chemisorption). The heat of chemisorption is larger than the heat of physical adsorption. The reverse of
adsorption is known as desorption (Verma, 2014).
A recent report from the World Bank has estimated that 20 million inhabitants of Bangladesh may be
drinking arsenic-contaminated water (18). Groundwater in Bangladesh contains a higher concentration of
arsenic than surface water sources and the groundwater contains both forms of inorganic arsenic (AsIII and
AsV), and AsIII is the predominant species. Though both AsIII and AsV are toxic, AsIII has been reported to
be the most toxic species. Arsenic contamination has been found more commonly in the tube wells which
were installed within the depth of 15–50 m (Inauen, 2013). However, in some areas, the arsenic
contamination is found in the tube wells that were installed in greater depths. Initially, the arsenic
contamination in tube well water of Bangladesh was thought to be in Gangetic delta plain, later, the
contamination was detected in almost all the sedimentary areas of Bangladesh, except in Hilly and
Pleistocene Uplands areas (Terrace Land). So, it is very important to remove arsenic form our drinking
water (Carpenter, 2013); however, all the processes of removing arsenic from ground water are expensive as
it takes complex technology and/or long time to separate arsenic from drinking water and general people of
our country cannot afford these technologies. So, a method which can be used by all sorts of people is
undoubtedly a crying need.

2. Experimental
Eggshells were collected, washed with distilled water, air-dried & grounded into powder. White eggshells
were selected based on its availability. Grounded powder is classified using British Standard (BS) sieve
(53μm, 63μm, 75μm, 150μm, 250μm). In our research, stock solution was prepared by dissolving arsenate
(Na2HAsO4·7H2O) in distilled water with 99% of purity, and

Page | 1194
then, required concentrations of arsenic was obtained by dissolving 4.63 gm of Na2HAsO4·7H2O in distilled
water which contains 2.5mg/L of arsenic ion in the solution. 1gm of adsorbent powdered eggshell of particle
size 53μm was added into beaker (300ml of known conc. (2.5mg/L) of arsenic ion). The pH was adjusted by
pH meter using 0.1N sulfuric acid or 0.1N sodium hydroxide solution. pH of the solution was maintained as
7. The mixtures were stirred at 60 revolutions per minutes (rpm) for 5 minutes and for getting equilibrium
concentration, it was allowed to stand for 15 hours. The mixture was filtered through a filter paper to
remove suspended solids and finally arsenic ion concentration in the filtrate was determined. Amount of
solute uptake by powdered eggshell was calculated by the following
formula, q = (C0–C𝑒 ).V/W. This process was again repeated 4 times for 4 different particle sizes. In the
similar way amount of uptake was calculated by the formula indicated above. For 5 different particle sizes,
we got 5 different amounts of uptake corresponding to the equilibrium
conc. remaining in the solution. And finally, Langmuir isotherm & Freundlich isotherm were plotted for
finding the behavior of eggshell.

3. Theory
3.1 The Langmuir isotherm
• Adsorption cannot proceed beyond monolayer coverage,
• All surface sites are equivalent and can accommodate at most one adsorbed atom;
• And the ability of a molecule to adsorb at a given site is independent of the occupationof
neighboring sites

Can be expressed by the following equations


𝑎𝑏𝑐
𝑎=
1 + 𝑎𝐶
q = the adsorption capacity at equilibrium (mg/g)b =
constants related to adsorbent only
a = the Langmuir adsorption constant
C = experimental concentration in the solution at equilibrium (mg/l) (Mafu, 2012)
The essential characteristics of the Langmuir isotherm can be expressed by a dimensionlessconstant
called the separation factor R𝐿
1
𝑅=
1 + 𝑏𝑐
Where b is Langmuir constant (mg.g−1) and 𝐶𝑜 is initial concentration of adsorbate (mg.g−1), R𝐿 values
indicate the adsorption to be unfavorable when R𝐿> 1, linear when R𝐿 = 1, favorable when 0< R𝐿<1, and
irreversible when R𝐿 = 0.
3.2 Freundlich Isotherm
In 1909, Freundlich expressed an empirical equation for representing the isothermal variation of adsorption
of a quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This equation is known as
Freundlich Adsorption Isotherm or Freundlich Adsorption equation or

Page | 1195
simply Freundlich Isotherm. Though Freundlich Isotherm correctly established the relationship of
adsorption with pressure at lower values, it failed to predict value of adsorption at higher pressure. This
relation is called as the Freundlich adsorption isotherm.
Freundlich isotherm is applied to adsorption processes on heterogonous surfaces. This isotherm gives us an
expression which indicates the surface heterogeneity and the exponential distribution of active sites
energies.
The linear form of the Freundlich isotherm is as follows:
R = K𝐶-1
q = the adsorption capacity at equilibrium (mg/g)
C = experimental concentration in the solution at equilibrium (mg/l)\K =
Freundlich constant (l/g)
N = exponential constant for Freundlich model (mg/g) (Rahdar, 2018)
Freundlich is an empirical equation which represents heterogeneous and multilayer adsorption on the
surface of adsorbent. This model indicates an empirical relationship between q and C. It is obtained by
assuming a heterogeneous surface with non-uniform distribution of the adsorption sites on the adsorbent
surface.
The Freundlich constants can be obtained by drawing the Log q versus Log C based onexperimental data,

log q = 1log𝐶 + logK


𝑁

4. Result and Discussions (Times New Roman, 12 Bold)


4.1 Langmuir Isotherm Model
Here, Theoretical model is noticed here as dotted line where experimental data through deep line. Excel has
been used to compare whether the experimental data is fitted with the theoretical model or not. Because in
the theoretical model, some assumptions are made, which are not actually true in the real case. So how far it
is from the actual case, this has been showed in the following calculations:

➢ The equation that has been found through Excel is Y= -0.1126 X +1.9111, where theoretical
equation is 1/q = 1/b + (1/ab) (1/C𝑒 ) where, b = Langmuir Constant. From these two eqn –
b= 0.523

➢ As known from theory, R𝐿 = 1/(1 + bC0)=0.433, which is 0<0.433<1. Hence adsorption sys-tem is
favorable.

➢ From graphical comparison through Excel, 𝑅2 = 0.9088 indicates the adsorption of arseniccould
not be modeled perfectly. It’s not very close to unity.

Page | 1196
Table 2. Experimental Data (Langmuir Isotherm)

Particle Size(μm) C𝑒 (mg/L) q (mg/gm Adsorbent)


53 0.25 0.675
63 0.375 0.63
75 0.45 0.615
150 0.525 0.5925
250 0.625 0.5625

fig.2. Comparison through Excel between Theoretical Model & Experimental Data (a) LangmuirIsotherm, (b)
Freudlich Isotherm.

4.2 Freundlich Isotherm Model


Here, In the Freundlich isotherm model, assumption that has been made are based on actualphenomena of
adsorption. The calculations are done as follows:

➢ From the Excel, Y= -0.2936X + 0.7456 where from Freundlich Isotherm model log(q)=(1/N)logCe +
logK. From these two equations, K=5.56.

➢ 𝑅2 = 0.9941>0.9088 indicates that Freundlich isotherm represents a good fit of the observeddata.
Table 3. Experimental Data (Freundlich Isotherm)

Particle Size(μm) C𝑒 (mg/L) q (mg/gm Adsorbent)


53 0.25 0.675
63 0.375 0.63
75 0.45 0.615
150 0.525 0.5925
250 0.625 0.5625

4.3 Discussion
From the theoretical models & observed data, it is clear that Freundlich Isotherm fits the experimental data
better. The level of accuracy obtained from adsorption processes is greatly dependent on the successful
modelling and interpretation of adsorption isotherms. While linear regression analysis has been frequently
used in accessing the quality of fits and adsorption performance because of its wide applicability in a variety
of adsorption data, nonlinear regression analysis has also been widely used by a number of researchers in a
bid to close the gap between predicted and experimental data. Thus, behavior of the adsorption of arsenic
by

Page | 1197
eggshell can be described more accurately by Freundlich Isotherm model than Langmuir Isotherm as it is
more practical model. Arsenic ion adsorption could be better described by Freundlich Isotherm model
because only in this model the value of regression co-efficient approaches to unity. This indicates that
powdered egg-shell contains more heterogeneous types of adsorption site.
The variation in adsorption capacity also varies due to the influence of pH on the adsorption characteristics
of the powdered eggshell, which indicates that the adsorption capacity of the adsorbent is clearly pH
dependent. The removal of arsenic from solution was also dependent on the initial concentration of arsenic
and particle size since the adsorption dynamic kinetics increase with an increase in the arsenic ion
concentration. But the effect of pH, particle size and initial concentration of arsenic was kept constant in the
study to simplify and understand the effect of theoretical model and practical model clearly.

5. Conclusion
This work indicates that arsenic can be removed by waste product eggshell which are inexpensive. Here,
equilibrium time was 08 hours. When particle size was small, adsorption rate was high because of large
surface area. Then obviously equilibrium time was decreased because of high rate of adsorption. If size of
particle is possible to make smaller, equilibrium time will be low enough. And approximately all of the
arsenic inside solution will be possible to remove within a short time (maintaining a constant PH &
concentration).
When a prototype will be planned for a particular capacity, then this experiment will help the design
engineer to choose the right model for modelling the prototype. For designing this, perfect adsorption model
is must. After choosing a perfect model, how the adsorption rate can be increased which is an important
idea for further work.

References
Ahmed M. F., An overview of arsenic removal technologies in Bangladesh and India, 2001. Carpenter,
S.R., Caraco, N.F., Correll, D.L., Howarth, R.W., Sharpley, A.N., & Smith, V.H. Nonpoint pollution of
surface waters with phosphorus and nitrogen. Ecological applications,8(3), pp. 559-568, 1998.
Flanagan, S.V., Arsenic in Tube well Water in Bangladesh: Health and Economic Impacts andImplications
for Arsenic.
Inauen, J., Hossain, M. M., Johnston, R. B., and Mosler, H. J., Acceptance and use of eightarsenic-safe
drinking water options in Bangladesh, 2013.
Islam, M.S., Arsenic Contamination In Groundwater In Bangladesh: An Environmental AndSocial Disaster.
Rahdar, S., Adsorption of arsenic (V) from aqueous solution using modifed saxaul ash:Isothermand
thermodynamic study, 2018.
Smith, A., Contamiantion of Drinking-Water by arsenic.
Sauvé, S., Desrosiers, M., A review of what is an emerging contaminant, 2014 Saifuddin, M.,
Arsenic Contamination of Ground Water in Bangladesh: A Review, 2011.Verma, P., Arsenic
Removal From Water through Adsorbtion-a review, 2014.

Page | 1198
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 338

Synthesis and Characterization of Visible Light Activated Nanoparticles


for The Photocatalytic Degradation of Toxic Organic Compounds

Mondal, J., Islam, M. A., Mukhlish, M.Z.B. and Uddin*, M. T.,

Department of Chemical Engineering and Polymer Science,

Shahjalal University of Scienceand Technology, Sylhet-3114, Bangladesh

Email: joyanta199844@gmail.com; amirulislamsust1994@gmail.com; mtuddin-cep@sust.edu;


zobayer_ceps@yahoo.com

*Corresponding author [Md. Tamez Uddin]


Abstract: The toxic and hazardous pollutants discharged from different industries
Keywords: adversely affect the environment and pose significant health risks since they are highly
toxic and carcinogenic to mammals, microorganisms and anaerobic bacteria. Particularly,
● Photocatalyst; Bangladesh is facing enormous environmental threat as a consequence of rapidly growing
● CdS/WO3 chemical, tannery and textile dyeing industries. Therefore, it is very important to treat these
wastewaters before releasing in to environment in order to protect the environment and
nanocomposites; health. This traditional method for treating wastewater is ineffective since it results in the
● Visible light; production of secondary waste such as sludge, which in turn requires additional treatment.
Recently, semiconductor photocatalysts have been widely used in the field of environmental
● Degradation protection due to their particular advantages in decomposing organic contaminants into
efficiency; water, carbon dioxide, and mineral acids. However, large band gap energy of the majority
of photocatalysts is a critical limitation that prevents them from being widely used in
● Hydrothermal method practical applications under solar light. Therefore, further advancements in photocatalysis are
● Dye required for the development of visible light-activated photocatalysts. In thepresent work, an
attempt has been taken to develop heterostructure CdS/WO 3 nanocomposite (NCs) as an
efficient photocatalyst for the degradation of organic contaminants under visible light
illumination. The CdS/WO3 nanocomposite was synthesized using a two-step approach,
which included first the synthesis of WO3 by precipitation method and second the synthesis
of heterojunction CdS/WO3 by hydrothermal method. The nanocomposites CdS/WO3
were characterized using variety of techniques. The photocatalytic activity of the
photocatalysts was evaluated by the degradation of methyl orange dye under visible light
irradiation. The photocatalytic degradation efficiency of 20 wt% CdS/WO3 NCs was much
higher than that of the reference CdS and WO3. The enhanced photocatalytic activity of
CdS/WO3 NCs was due to suppression of charge recombination resulted from the vectoral
charge transfer. As a result, it can be concluded that the CdS/WO3 heterostructure
photocatalyst would be anexcellent candidate for application in wastewater treatment.
.

1. Introduction
Every residential, commercial, and industrial activity requires water as a primary resource. Nevertheless, the
wastewater that is produced as a byproduct of these activities may raise considerable environmental issues
due to the contaminants that are introduced into water systems (Zahoor et al., 2018). The contaminants
such as heavy metals, dyes, pesticides, and other

Page | 1199
contaminants decrease water quality over time, causing a variety of illnesses and harm to human health
(Jadhav et al., 2010; Kar et al., 2008; Qamruzzaman and Nasar, 2015). Particularly, dyes extensively used in
numerous industries including textiles, leather, cosmetics, paper, printing, plastic, medicines, and food to
color products are carcinogenic and mutagenic and can be injuriousto certain microbes, aquatic life and human
even at extremely low concentrations (Carneiro et al., 2010; Chequer et al., 2011; Jäger et al., 2004).
Therefore, the removal of such dyes from processeffluent becomes environmentally important.
In recent years. the development of nanotechnology and the implementation of photocatalytic technology in
environmental pollution treatment [1-3] have led to the widespread usage of semiconducting metal-oxide
nanostructures for water purification due to their excellent photocatalytic performance. Since UV radiation
accounts for just around 4-5% of the solar spectrum, such strategies are not viable when used on a large
scale. Recently, CdS has received considerable interest in the fields of photocatalytic degradation, water
splitting, and solar energy conversion due to its narrow band gap, (2,4 eV), suitable band edge position and
excellent photocatalytic activity (Anwer et al., 2019; Korala et al., 2017; Nasir et al., 2020). However, due to
the rapid recombination of photo-generated electron-hole pairs and the strong photo-corrosion effect, its
broad application is severely limited. Combining semiconductors with different band gap values is an
effective way to improve photocatalytic activity when exposed to visible light (Uddin et al., 2012). One of
the most common semiconducting materials used in electrochromic devices, sensors and photocatalysis is
Tungstentrioxide (WO3) (Abstract, n.d.; Kumar and Rao, 2015; Lam et al., 2015). The narrow band gap ofthe
WO3 photocatalyst has several advantages, including high solar absorption capacity, chemical inertness, high
thermal stability, and good photostability (Kako et al., 2015; Zhu and Chen, 2014). Additionally, the position
of valence band edge of WO3 is better suited for photo-oxidation of a wide range of organic pollutants than
the oxidation potential of H2O/O2 (Hisatomi et al., 2014; Zhang et al., 2018). It is anticipated that the coupling
of CdS with WO3 would result in a reductionin the recombination of photogenerated charge carriers. Both the
valence and conduction band edges of CdS are located higher than those of WO3, and their steps are in the
same direction (Kudo and Miseki, 2009). Chemical potential difference between CdS and WO 3 produces
band bending at the interface of heterojunction. The band bending provides a built-in field that guides
photogenerated electrons and holes in opposite directions, resulting in electrons and holes on distinct sides
of heterojunction (Uddin et al., 2017, 2013). Therefore, coupling of CdS with WO3 forms type-II
heterostructures, which is a great approach for increasing charge separation efficiency for the goal of
promoting photocatalytic degradation activity.
In this study, heterostructure CdS/WO3 nanocomposites (NCs) were made by a hydrothermal method, using
sodium tungstate dihydrate and Cadmium acetate as WO3 and CdS precursors, respectively. A variety of
techniques including XRD, UV-vis diffuse reflectance spectroscopy (UV-vis DRS) and X-ray photoelectron
spectroscopy (XPS) were used to analyze the nanocomposites. The degradation of methyl Orange (MO) dye
was used to test their photocatalytic activity under visible light irradiation.

2. Materials and Methods


2.1 Preparation of CdS/WO3 NCs

All the chemicals and reagents were obtained from Sigma Aldrich and Alfa Aesar. All reagents were utilized
in their original form without additional purification. The CdS/WO3 NCs were synthesized by hydrothermal
method. First, WO3 nanoparticle was prepared by sol-gel method using tungstate dihydrate as precursor
followed by calcination at 450 °C NC. In order to prepare heterostructure CdS/WO3 nanoparticles, a
calculated amount of prepared WO3 nanoparticles was dispersed in 50 mL deionized water. Then,
predetermined amount of (Cd (CH3COO)2·2H2O), Na2S and 300 µL of analytical grade thioglycolic acid
were added into the suspension, respectively. After magnetic stirring for 30 min, 40 mL of the suspension
was added to a 50 mL Teflon-lined stainless-steel autoclave and heated at 160 ℃ in an oven for 14 h.

Page | 1200
The autoclave was then cooled at room temperature. Afterwards, the product was centrifuged and then
washed with deionized water and ethanol. Then, the product was dried at 120℃ in an oven for 10 h. Finally,
the CdS/WO3 powder was ground with agate mortar-pestle and stored for further use. The CdS/WO3 NCs
containing different weight percentage of CdS (10, 15, 20 and 30%) were preparedfollowing the same process.

2.2 Characterizations of nanoparticles

(XRD) analyses were conducted using X-ray diffractometer (Model: SMART LAB, brand: RIGAKU, 45
kV, 200 mA) with a Cu anode (Kα radiation). The continuous scan mode was used to capture 2θ data from 10
to 80°. Scherrer's formula, D = (0.9 λ)/(β½ cosθB) was used to calculate the average crystallite size of the
materials produced, where D is the average grain size, λ is the wavelength of Cu Kα (= 1.5405Å), β1/2 is the
FWHM, and θB is the diffraction angle (full width at half maximum). Using a UV-vis-NIR spectrometer
LAMDA 750, UV-vis diffuse reflectance spectra in the 200–800 nm wavelength range were measured at
room temperature (PerkinElmer, Inc., USA). As a reference sample, pure BaSO4 powder was employed.
Thermo Scientific's K- Alpha + XPS was used to record X-ray photoelectron spectra (Thermo Fisher
Scientific, UK). Monochromatized X-ray from an Al anode used as an excitation source (Kα: 1486.6 eV).

2.3 Photocatalytic experiment

The photodegradation of methyl orange (MO) in aqueous solution under Visible Light irradiation was used to
assess the photocatalytic activity of commercial TiO2 (Degussa, P25), CdS, WO3 nanoparticles, and the as-
synthesized CdS/WO3 nanocomposites. Photocatalytic experiments were carried out in a horizontally
positioned Visible Light reactor setup over a 1000 mL Pyrex glass beaker. In each experiment, 100 mL of
MO dye solution was mixed with 0.1 g of photocatalyst to create a suspension, which was then agitated in the
dark for 10 minutes to achieve adsorption-desorption equilibrium before being exposed to light. By taking 4
ml samples of the solution at suitable irradiation intervals, the MO degradation process was evaluated. The
concentration of MO was determined by UV-vis spectrophotometer (LAMDA 750, Perkin Elmer, Inc., USA)
measurements the absorbance at 480 nm. The effect of dose and the pH of solution on the degradation
efficiencies were conducted adopting the similar procedure. The catalysts were recycled and utilized in three
separate batches with identical parameters.

3. Result and Discussions

Page | 1201
3.1 Characterization of nanoparticles

Intensity(
a.u)

20 30 40 50 60

Fig.1 XRD spectra of the synthesized nanoparticles in the 2θ region of (a) WO3, (b)10wt%
CdS/WO3, (c) 15wt% CdS/WO3, and (d) 20wt% CdS/WO3
To check the crystallinity and size of the produced NPs, XRD analysis was carried out. The principal
diffraction lines shown in Fig. 1 at 2θ = 20.46°, 22.90°, 23.70°, 24.3°, 27.20°, 28.67°,
33.22°, 34.2° could be indexed to the (011), (002), (020), (200), (120), (112), (202), (220), (122),
(222), (004), (040), (114), (024), and (420) planes, respectively, of monoclinic phase WO3 (JCPDS card No.
83-0950) (Deepa et al., 2006; Hatel and Baitoul, 2019; Qian et al., 2018). The extra diffraction peaks at 2 =
24.8 °, 26.5 °, 28.1 °, 43.7 ° and 51.8 ° respectively correspond to (100), (002), (101), (110) and (112) planes
of hexagonal CdS (PDF#41-1049).
The chemical composition and chemical state of the elements of the CdS/WO3 nanocomposites were
evaluated with XPS. The XPS spectra of the as-prepared 20wt% CdS/WO3 are shown in Fig. 2A. Fig. 2A
only shows the emissions from Cd, W, S, and O, together with a very faint emission line from C. No other
elemental peaks were found which evidenced that the CdS/WO3 NCs was composed of Cd, W, S and O. The
normal carbon-based contamination seen in XPS samples may be responsible for the C signal. Fig. 2B-D
displays the high-resolution spectra of the Cd, W, and S species, respectively. The emission lines shown in
Fig. 4B were symmetric and centered at 405.1 and 412 eV ascribing to Cd 3d5/2 and Cd 3d3/2, respectively,
which were consistent with the reported values for Cd2+ (Yang et al., 2013). The deconvoluted XPS peaks of
W 4f shown in Fig. 2C exhibited two separate peaks at 35.7 eV and 37.8 eV corresponding to W 4f7/2 and
W 4f5/2 stated, respectively which evidenced that the oxidation state of W exist in CdS/WO3 is +6 (Adhikari
et al., 2018; Qian et al., 2018). Fig. 2D shows two peaks at the binding energies of 162.5 and 161.3 eV
representing S 2p1/2 and S 2p3/2 states, respectively. This indicatesthat S mainly exists with S- in CdS/WO3.

Page | 1202
, S
yl
h
et

Fig. 1 X-ray photoelectron spectra (XPS) of as-synthesized (A) survey spectra of 20 wt% CdS/WO3 Nc;
High resolution spectra of (B) Cd 3d region, (C) W 4f region and (D) S 2p region.

The optical feature of a semiconductor, such as its band gap, plays a significant role in determining the
degree to which it can function as a photocatalyst for the degradation of organic dyes. The UV-Vis DRS was
utilized in order to carry out an analysis of the NCs' optical properties, the results of which are presented in
Figure 3. Fig. 3A shows that pure WO3 and CdS exhibited characteristic strong absorption edges at 440 nm
and 551 nm, respectively, which confirmed that the as-synthesized were active under visible light irradiation.
The absorption edges for the 10 wt% CdS/WO3, 20 wt% CdS/WO3, and 30 wt% CdS/WO3 nanocomposite
were, at 552nm, 750 nm, 490 nm, and 524 nm, respectively. In the visible region, the main valence band
structure of the catalyst can be calculated by the converted Kubelka-Munk formula: α(hv) = A(hv-Eg)1/2
where the symbols carry their usual meaning (Davis and Mott, 1970). Combining the above formulas with
the results of UV-vis DRS, as shown in Fig. 3(B), the Eg of WO3 and CdS were found to 2.85 eV and 2.44
eV, respectively. The band gap energies of CdS/WO3 NCs were determined to be 2.42, 2.49, and 2.37 eV for
10 wt% CdS/WO3, 20 wt% CdS/WO3, and 30 wt%CdS/WO3, respectively.

Page | 1203
Fig. 4 shows the (A) UV-vis diffuse reflectance spectra, (B) (F(R) hν)2 vs. hν plot (a) WO3, (b)
CdS, (c) 10wt% CdS/WO3, (d) 20wt% CdS/WO3 and 30wt% CdS/WO3.

3.2 Photocatalytic studies

To demonstrate the photocatalytic performance of CdS/WO3 nanomaterials, methyl orange (MO) was
degraded photo-catalytically under visible light irradiation as a test reaction. The time- dependent UV-vis
spectra of MO under visible light irradiation are shown in Figure 4A. According to Fig. 4A, after 50 min
irradiation of visible light, the MO at 480 nm maximum absorption peaks totally vanished in the presence of
CdS/WO3 nanomaterials. The photocatalytic degradation kinetics of the as-synthesized photocatalysts are
shown in Fig. 4B. According to Fig. 4B, neither the presence of photocatalysts nor the lack of visible light
irradiation will result in anydegradation of MO.

Fig. 5 Photocatalytic degradation kinetics of MB with different photocatalysts under UV lightirradiation. (Initial
dye solution concentration =10 mg/L; Volume = 100 mL, pH = 7; catalyst dose
= 1 g/L).

Page | 1204
The 20 wt% CdS/WO3 NC exhibited the best photodegradation performance of all the photocatalysts tested
in this work. After 20 min of photocatalytic degradation, the MO degradation efficiency defined as (1 -
C/C0) ⅹ100 for 10 wt% CdS/WO3, 15 wt% CdS/WO3, 20 wt% CdS/WO3, 30 wt% CdS/WO3, pure CdS and
WO3 was found to be 54%, 89%, 93%, 80%, and 62%, 6%, respectively. For 30 wt% CdS/WO3 NC, the
excess CdS may form a layer on the active surface of WO3 that inhibits the photocatalytic activation of WO3
with visible light and reduces its photocatalytic degradation efficiency; consequently, 30 wt% CdS/WO3 NC
demonstrates a lower degradation capacity than 15 and 20wt% CdS/WO3 samples.
Higher photocatalytic of CdS/WO3 NCs can be explained with band alignment as is shown in Fig.
5. It was found that the conduction and valence band positions of WO3 were lower than the corresponding
positions of CdS. Thus, the conduction and valence band offsets of 1,05 and 1,45 eV, respectively, were
found at the heterostructure CdS/WO3 nanocomposite interface. As depicted Fig. 5, both WO3 and CdS
generate photo-excited electrons and holes when exposed to visible light. The band structure of CdS/WO3
NC is suitable for the construction of a Z-scheme system. The electrons generated by light irradiation
transfer from the WO3 conduction band to the CdS valence band. Photogenerated electrons that are still
present in the conduction band of CdS interact with oxygen to form the superoxide radical 𝑂•−, and the
photogenerated holes of WO3 react with H2O or -OH to generate 2 𝑂𝐻•. Therefore, this heterojunction can
effectively promote the separation of photogenerated electron-hole pairs and reduce the possibility of
photoinduced charge recombination. The OH• is a strong oxidizing agent which completely mineralized
organic compounds (herein MO dye) to the final degradation products CO2 and H2O (Uddin et al., 2020,
2013).

E (eV) vs NHE O •-
2

-1.5 O
-1.0 ECB = -0.55 eV
-0.5
E
ECB = 0.50 eV 0.0
E
0.5
2.40 eV

1.0
Eg =
Eg = 2.80

1.5
E
2.0
EVB = 1.80
2.5
eV

eV EVB
3.0
OH-
3.5 CdS
EVB = 3=30 eV
4.0
WO3 OH•
MO
H2O, CO2

Fig. 5 Band alignment and the charge transfer mechanism of heterojunction CdS/WO3 NCs

Page | 1205
4. Conclusion
The Visible light activated CdS/WO3 NC photocatalysts were successfully synthesized by hydrothermal
method. Methyl orange (MO) dye was decomposed in water to test the photocatalytic activity of the
produced photocatalysts. Based on the results of the UV-vis DRS investigation, the CdS/WO3 NCs possesses
outstanding optical absorption characteristics within the visible range. In comparison to pure CdS, WO3, and
the TiO2 used as a reference, the CdS/WO3 NCs with 20 mol% CdS displayed the best MO degrading
efficiency. This higher degrading efficiency of CdS/WO3 NCs is a result of the band offsets at the interface
between CdS and WO3, which limit the photogenerated charge recombination. The findings of this study
may pave the way for enhanced photocatalytic activity of CdS/WO3 NCs in industrial wastewater treatment.

Acknowledgements
We gratefully acknowledge the financial support of the work by Shahjalal University of Science and
Technology (SUST) Research Centre (Project Code: AS/2022/1/08). Authors would also like to
acknowledge the contribution of Center of Excellence, SUST for providing instruments.

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7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 339

Extraction of Shrimp Chitosan and its Application on Shelflife


Extension of Tomato

Hossain*, M.S., Farshi, S.A., Boni, S.F.T., and Badhon, M.A.H.

Department of Chemical & Food Process Engineering,

Rajshahi University of Engineering &Technology (RUET), Rajshahi-6204, Bangladesh


*Corresponding author [Md. Sajjad Hossain]

Abstract: Shrimp processing by product was utilized to extract valuable carbohydrate


Keywords:
polymer chitosan. Chemical method of extraction consisting demineralization,
deproteinization and deacetylation was applied to extract chitosan. Study showed that
● Shrimp; 3% HCI and 4% NaOH is suitable concentration for demineralization and
deproteinization respectively at ambient temperature (28±2°C). Based on initial shrimp
● Chitosan; shell waste, the yield of purified chitosan after extraction was 16%.Tomato
(Lycopersicon esculentum) is one of the most nutritious and widely consumed fresh
● Waste material; vegetables all over the world. Several treatments such 0.25% chitosan coating, 0.25%
chitosan coating+ 1% perforated LDPE and 0.25% chitosan coating+ paper bag were
● Shelf-life. applied to extend shelf life of tomatoes. The physico-chemical parameters were studied
up to 12 days of storage period at 24±2°C and 70±5 relative humidity. The results
indicated that tomatoes treated with 0.25% chitosan coating+ 1% perforated LDPE were
better in preserving most of the physicochemical characteristics and sensory property
than control sample throughout the storage period. The study summarize that packaging
materials application integrated with chitosan coating could be
better option to increase shelf life of fresh fruits and vegetables.

1. Introduction
Shrimp is one of the important fisheries products worldwide including Bangladesh. Shrimp industries
generate large amounts of shrimp bio-waste during processing, approximately 45- 55% of the weight of raw
shrimp (Lertsutthiwong,2002). Chitosan is a modified natural carbohydrate polymer derived from chitin
which has been found in a wide range of natural sources such as shrimp, crustaceans, fungi, insects and
some algae. Chitosan is a fiber-like substance and a homopolymer of ß-(1→4)-linked N-acetyl-D-
glucosamine. Chitin is made up of a linear chain of acetylglucosamine groups while chitosan is obtained by
removing enough acetyl groups (CH3-CO) for the molecule to be soluble in most diluted acids. The only
difference between chitosan and cellulose is the amine (-NH2) group in the position C-2 of chitosan instead
of the hydroxyl (-OH) group found in cellulose (Li, 1992). In this respect, chitin and chitosan have attained
increasing commercial interest as suitable resource materials due to their excellent properties including
biocompatibility, biodegradability, adsorption, and ability toform films, and to chelate metal ions (Rout,
2001).

Page | 1209
This study aims at investigating the effect of an edible film like chitosanlysozyme (Park, 2004) on the shelf
life and marketability of fresh tomatoes stored under different conditions of storage.

2. Experimental
2.1 Raw Material
Fresh shrimp was collected from local market of Rajshahi. Shrimp head and skin was separated from shrimp
using sharp knife. The collected shrimp wastes were then washed with tap water and crushed with mortar
pastle. Crushed shrimp waste was kept in a polyethylene bags at ambient temperature (28±2℃) for 24 hours
for partial autolysis to facilitate chemical extraction of chitosan and to improve the quality of chitosan.
2.2 Physicochemical Properties Measurement
2.2.1 Moisture Content
Moisture content of the shrimp chitosan was determined by the gravimetric method. Calculated moisture
content as: [(wet weight, g - dry weight, g)/ (wet weight, g)] x 100 = % of moisture content
2.2.2 Ash Content
Ash of the sample was calculated according to the standard method (AOAC, 2005). Place 2.0g of sample into
previously ignited, cooled and tarred crucible. The samples were heated in a muffle furnace preheated to
600°C for 6 hr. The crucibles were allowed to cool in the furnace to less than 200°C and then placed into
desiccators with a vented top. Allowed them to cool and weighed the crucible and ash. Calculation: (Weight
of residue, g)/(Sample weight, g) x 100 = % Ash
2.3 Post harvest treatment application on tomato
Tomato at breaker ripening was purchased from a local market. Prepared chitosan and glycerol (87%), Low
density polyethylene (LDP) bag, paper bag were used from laboratory stock. Tomatoes were dipped into hot
water at 40°C for 30minutes for disinfection purpose. 0.25% chitosan solution was prepared using 0.6%
acetic acid, adding 25% glycerol (w/w chitosan) as plasticizer. Each of the solutions was thoroughly mixed,
filtered and the pH was adjusted to 5.6 using 1M sodium hydroxide. This resulted in a set of treatments as
listed below:
𝑇0 = Control (Uncoated), 𝑇1 = 0.25% chitosan, 𝑇2 = 0.25% chitosan + paper bag, 𝑇3 = 0.25% chitosan + 1%
perforated LDP
Tomatoes were dipped into the prepared coating emulsions for 1 min and then drained. Uncoated tomatoes
as control samples were immersed in a 0.6% glacial acetic acid solution at pH 5.6 for the same duration of
time. The treated and control tomato samples were dried in ambient conditions (26±2°C and 40-50% RH)
for 2 hours. Then, specified treatment packaging was done. Then, all the samples were kept at laboratory for
shelf life study.

Page | 1210
3. Result and Discussions

3.1 Properties of shrimp waste and purified chitosan


Results of the moisture content, ash content and yield percentage of fresh shrimp shell and chitosan samples
are presented in Table 1. Li stated commercial chitosan products contain less than 10% moisture [2]. A high
quality grade of chitosan should have less than 1% of ash content [5]. Yield has been calculated for shrimp
waste, chitin and chitosan. Waste from the freshshrimp was found to be 45%. The yield obtained here found
to be within the range, showed that waste content varies approximately from 45 to 55% of the weight of raw
shrimp (Lertsutthiwong,2002). Hossain and Iqbal (2014) reported that chitosan yield is 15.4% which is
closely relevant to our study.
Table 1 Analysis of shrimp waste and purified chitosan

Parameter Shrimp waste Chitosan


Moisture content (%) 69.5 10.12
Ash content (%) 31.27 0.31
Yield (%) 45 16

fig.2. Chitin fig.3. Chitosan

3.2 Shelf life study of tomato


3.2.1 Total Weight loss
Different treatments investigation showed a remarkable effect on total weight loss of tomato during storage
shown in fig. 4(a). At 3rd day after storage maximum weight loss (3.77%) was in untreated tomato where
minimum weight loss (0.72%) was in 0.25% chitosan coating tomato integrated with 1% perforated LD
packaging materials. Similarly untreated tomato noticed the maximum weight loss and 0.25% chitosan
coating integrated with 1% perforated low density packaging materials treated tomato showed the minimum
weight loss (0.72%, 1.45%, 3.1% and 5.7%) at 3rd, 6th , 9th day and 12th days of storage respectively.
Table 2 Effect of post-harvest treatment on weight loss (%) of tomato

Treatment Weight loss (%) at different days


03 06 09 12
𝑇0 (Control) 3.77(0.27) 𝑎 7.59(0.1) 𝑎 11(0.25)𝑎 14.54(0.19)𝑎
𝑇1 (0.25% chitosan) 3.62(0.09) 𝑎 7.11(0.01) 𝑎 10.5(0.28)𝑎 13.9(0.08)𝑎
𝑇2(0.25% chitosan+paper bag) 3.25(0.14)𝑎 6.9(0.15)𝑎 10.1(0.17)𝑎 13.54(0.31)𝑎
𝑇3 (0.25% chitosan+paper bag) 0.72(0.25)𝑎 1.45(0.1)𝑏 3.1(0.09)𝑏 5.7(0.05)𝑏
*Means with different letters in each column are significantly different (p < 0.05).

Page | 1211
3.2.2 Colour
At 9th days of storage chitosan coating combined with perforated LDP sample showed significantly lower
colour score indicating lower colour development than control sample. Among all the treatments, 0.25%
chitosan coating combined with perforated LDP delayed the colour development of tomato significantly.
Fig.4(b) Ali noticed that the delay of color development in the papaya fruit treated with higher
concentrations of chitosan could be attributed to the slow rate of respiration and reduced ethylene
production, leading to a delayed fruit ripening and senescence [11].
Table 3 Effect of post-harvest treatment on colour (score) of tomato

Treatment Color (score) at different days


03 06 09 12
𝑇0 (Control) 3.8 𝑎 5.2𝑎 5.6𝑎 6𝑎
𝑇1 (0.25% chitosan) 3.3a 𝑏 4.5𝑎 5.5𝑎 5.𝑎
𝑇2(0.25% chitosan+paper bag) 3.1a 𝑏 4.1𝑎 5.3𝑎𝑏 5.8𝑎
𝑇3 (0.25% chitosan+paper bag) 2.5 𝑏 3.5𝑎 4.5𝑏 5.3𝑎
*Means with different letters in each column are significantly different (p < 0.05).

fig.4. Effect of post-harvest treatment on (a)weight loss (%) (b)color (score) of tomato

3.2.3 Total soluble solid (TSS)


In this study the TSS of uncoated tomatoes was very different from the coated tomatoes though not
statistically significant (Table 4). There is increase in some and decrease in the rest. There was a sharp rise
in TSS in the uncoated tomatoes compared to the small changes seen at different treatments (fig.5(a)).
TSS Decrease was seen more clearly at the end of 20 days in film coated tomatoes stored at 12℃ [9].
Table 4: Effect of post-harvest treatment on total soluble solid (TSS) of tomato

Treatment TSS at different days


03 06 09 12
𝑇0 (Control) 3.52 𝑎 3.7𝑎 3.75𝑎 3.82𝑎
𝑇1 (0.25% chitosan) 3.55 𝑎 3.41 𝑎 3.1𝑎 3.05𝑎
𝑇2(0.25% chitosan+paper bag) 3.49 𝑎 3.43 𝑎 3.39𝑎 3.35𝑎
𝑇3 (0.25% chitosan+paper bag) 3.5𝑎 3.65 𝑎 3.76𝑎 3.8𝑎
* Means with different letters in each column are significantly different (p < 0.05).

3.2.4 pH
Chitosan coating and application of packaging materials reduced the pH of tomato at different days of
storage where after 12th days of storage highest pH was obtained for control sample and 0.25%
(chitosan+paper bag) treatment showed the least pH. All the treatments slowed down the tomato pH
increasing but no treatment has significant effect at lowering of tomato pH (Tab. 5). Acidity decreased with
maturation and increased with high sugar content in fruit (Raffo, 2002).

Page | 1212
fig.5. Effect of post-harvest treatment on (a)total soluble solid (TSS), (b)pH of tomatoTable 5. Effect of post-

harvest treatment on pH of tomato

Treatment pH at diff. days


03 06 09 12
𝑇0 (Control) 4.22𝑎 4.36𝑎 4.56𝑎 4.58𝑎
𝑇1 (0.25% chitosan) 4.2𝑎 4.31𝑎 4.42𝑎 4.44𝑎
𝑇2(0.25% chitosan+paper bag) 4.01𝑎 4.11𝑎 4.13𝑎 4.16𝑎
𝑇3 (0.25% chitosan+paper bag) 4.26 𝑎 4.29 𝑎 4.3𝑎 4.22𝑎
* Means with different letters in each column are significantly different (p < 0.05).

3.2.5 Disease incidence


Control sample showed highest 20% of disease incidence, after 12 days, and all other treatment showed
6.66% which is significantly different (Tab. 6). (fig.6).
Table 6. Effect of post-harvest treatment on disease incidence of tomato

Treatment Disease incidence at different days


03 06 09 12
𝑇0 (Control) 0 0 13.33𝑎 20𝑎
𝑇1(0.25% chitosan) 0 0 6.66𝑏 6.66𝑏
𝑇2(0.25% chitosan+paper bag) 0 0 6.66𝑏 6.66𝑏
𝑇3(0.25% chitosan+paper bag) 0 0 0 6.66𝑏
* Means with different letters in each column are significantly different (p < 0.05).

fig.6. Effect of post-harvest treatment on disease incidence of tomato

4. Conclusion
Freshly harvested tomato was subjected to three different treatment 𝑇1(0.25% chitosan),
𝑇2(0.25% chitosan + paper bag), 𝑇3 (0.25% chitosan + 1% perforated LDP) including a control (𝑇0) sample.
Among the postharvest treatments control tomatoes showed significantly the maximum on weight loss
(14.54%), at 12th day of storage, where 𝑇3(0.25% chitosan + 1% perforated LDP) sample showed higher
performance but minimum on this parameter (5.7% weight loss) respectively. All the treatments had no
significant effect on TSS and pH upto 12th days of storage period. 𝑇3(0.25% chitosan + 1% perforated LDP)
sample showed significantly better colour (colour score 5.6) retention than uncoated tomatoes (colour
score 4.5) upto 9thdays of storage. Chitosan coating and packaged samples had significant effect on disease
incidence showed that 20% uncoated tomatoes spoiled upto 12th days of storage where the disease incidence
rate is only 6.66% for all other samples. So, higher conc. of chitosan coating along with packaging materials
can be applied to extend tomato shelf life.

Page | 1213
References
1. AOAC official method 2005.02: total monomeric anthocyanin pigment content of fruit juices,
beverages, natural color-ants, and wines by the pH differential method. Official methods of
analysis of AOAC International, 2.
2. Hossain, M.S., Iqbal, A., Production and characterization of chitosan from shrimp waste.
J.Bangladesh Agril. Univ. 12(1): pp. 153–160, 2014.
3. Ali, A., Muhammad, M.T.M., Sijam, K., and Siddiqui, Y., Effect of chitosan coatings on the
physicochemical characterist-ics of Eksotika II papaya (Carica papayaL.) fruit during cold
storage. Food Chem. 124, pp. 620-626, 2011.
4. Lertsutthiwong, P.,How, N.C., Chandrkrachang, S., and Stevens, W.F., Effect of Chemical
Treatment on the Characteristic of Shrimp Chitosanm, Journal of Metals, Materials and
Minerals. 12(1): pp. 11-18, 2002.
5. Li, Q., Dunn, E.T., Grandmaison, E.W., and Goosen, M.F.A., Applications and properties of
chitosan, J. Bioactive and Co-mpatible Polym.7: pp. 370-397, 1992.
6. No, H.K., Meyers, S.P., Preparation and Characterization of Chitin and Chitosan-A Review,
Journal of Aquatic Food Product Technology, 4(2), pp. 27-52, 1995.
7. Park, S.I., Daeschel, M.A., and Zhao, Y., Functional properties of antimicrobial lysozymechitosan
composite films, J. Food Sci., 69(8), M215, 2004.
8. Rout, S.K., Physicochemical, Functional, and Spectroscopic analysis of crawfish chitin andchitosan
as affected by process modification Dissertation, 2001.
9. Raffo, A., Leonardi, C., Fogliano, V., Ambrosino, P., Salucci, M., Gennaro, L., Bugianesi, R.,
Giuffrida, F., and Quaglia, G., Nutritional value of cherry tomatoes (Lycopersicon esculentum cv.
Naomi F1) harvested at different ripening stages. Journal of Agricultural and Food Chemistry
50(22): 6550-6556, 2002.
10. Shahidi, F., Arachchi, J.K.V, and Jeon, Y.J., Food applications of chitin and chitosans, Trends
Food Sci. Technol., 10: pp. 37–51, 1999.
11. Tasdelen, O., and Bayindirli, L., Controlled atmosphere storage and edible coating effects on
storage life and quality of tomatoes, J. Food Proc. Pres 22, pp. 303-320, 1998.

Page | 1214
pp.
PAGE
\*
7th International Conference on Engineering Research, Innovation and Education MER
January 12-14, 2023, Sylhet, Bangladesh GEF
ORM
PAPER ID: 367 AT 2

Experimental Investigation of Drilling Mud Rheology UsingAloe Vera as an


Additive

*Pretom Ranjan Das

Chittagong University of Engineering and Technology

Email: pretom10332@gmail.com

*Corresponding author: Pretom Ranjan Das

Keywords: Abstract: Drilling fluid is one of the major components in drilling operations for
hydrocarbon explorations. A success of drilling mostly dependent on using proper type of
● Drilling Fluid; drilling fluid or mud. For this, millions of dollars are invested in purchasing and
maintaining drilling fluids all over the world. Fluid for drilling that is made of water and
● Additive; bentonite is very common in this field. Different kinds of additives are also added to this
fluid to change its density, viscosity, and other rheological properties, such as its apparent
● Viscosity; viscosity, plastic viscosity, gel strength, alkalinity, and so on. Also, lost circulation
additives are used to cut down on filtrate loss and make sure that the mud cake is the right
● Rheology; size. The goal of the experiment is to use Aloe Vera as a natural additive and figure out
how well it works as a drilling mud. At the same time, using natural additives will be good
● Filtrate loss; for the environment and cut down on the toxicity that chemical additive spread. An
experimental analysis would be performed in the Drilling Fluids Laboratory, which would
● Aloe Vera. reveal a change in rheological properties and mud filtrate loss, both of which are critical in
the petroleum industry and can be greatly reduced. Also, apparent viscosity, plastic
viscosity, sweep efficiency, hydrostatic pressure, gel strength, and filtration loss would be
observed after using Aloe Vera as a natural additive in making of the drilling fluid which
could be used to solve many drilling problems such as pipe sticking, blowout etc.

1.Introduction

Petroleum engineering, drilling mud, also known as drilling fluid, is a thick, viscous fluid combination used
in oil and gas drilling operations to cool and lubricate the drill bit as well as transport rock shavings to the
surface. Based on the base fluid, drilling fluids can be put into four main groups. These are water-based
drilling fluids (WBDF), oil-based drilling fluids (OBDF), synthetic-based drilling fluids (SBDF), and gas-
based drilling fluids (GBDF). Four major characteristics govern the behavior of drilling muds as drilling
fluids. The four properties are viscosity, yield point, gel strength, and filtering. Aside from pH, clay
concentration, and calciumcontent, there are a few other less important characteristics.

Page | 1215
Therefore, it is abundantly obvious that drilling fluid serves a variety of purposes. This fluid is almost
entirely necessary for drilling to succeed. According to statistics, the cost of drilling mud in some drilling
projects may approach $1 million. It is a significant sum. Drilling fluids with different characteristics, such
as those based on water, oil, or air, are employed. In the petroleum business, drilling fluid with a bentonite
water base is particularly popular and efficient. This fluid contains a variety of additives, such as weighing,
pH control, alkalinity control agents, etc. In order to decrease mud filtrate loss, lost circulation additives are
also used. As far as we are aware, drilling fluid has a lot of additives that are added to achieve particular
qualities.
Waste from drilling fluid is just one of the many ways that people contaminate the environment. On the other
hand, given its significance in the drilling process, drilling fluid is referred to as the "life" of the drilling
business. Drilling fluid additives are essential because of how important economic and environmental
concerns are to the drilling process. When choosing a drilling fluid, drilling engineers are influenced by
technical, environmental, and cost-effective issues. To get the rheological qualities for this investigation,
natural additives can substitute for chemical additives in drilling fluid made of bentonite water. Also, it can
state that rheological modifiers will be the natural additives. In this study, Aloe Vera was used as a natural
addition. Rheological qualities and the construction of a rheological model was examined in relation to the
generation of drilling fluids employing this additive. It may conclude from this that natural additives will
take the place of chemical additives and significantly reduce the cost of drilling fluid while also reclaiming
the environment from the destructive effects of chemical additives that endanger both humankind and the
entire eco-system.
An experimental analysis in Drilling Fluids Laboratory would be done which would find a modification in
rheological properties and mud filtrate loss which is considered very crucial in the petroleum industry that
can be reduced to a great extent. Also, apparent viscosity, plastic viscosity, sweep efficiency, hydrostatic
pressure, gel strength, and filtration loss would be observed after using Aloe Vera as a natural additive in
making of the drilling fluid which could be used to solve many drilling problems such as density increase,
pipe sticking, blowout etc.
2. Experimental
In the drilling fluid laboratory, mainly two different experiments were done to show the differences. The
first one was for the existing standard water-based drilling mud which is knownas conventional drilling mud.
Another was for the new drilling mud by using aloe vera as a natural additive. These two types of drilling
fluids will be the prime concern of this study.
2.1 Materials
The Experiment required different types of chemical and some natural ingredients. It was needed mineral
water, bentonite clay, sodium hydroxide, soda ash, starch, calcium carbonate, xanthan gum, and most
importantly aloe vera. Some types of machinery were also used to make this experiment successful. They
are: a commercial blender, a typical mud balance, marsh funnel viscometer, OFITE Model 800 viscometer,
low pressure OFITE filter, a mud retort, an OFITE Sand Content Kit and an OFITE Digital Resistivity
Meter.

Page | 1216
2.2 Sample preparation
As two different drilling fluid were made so the formulation was also different.
Formulation of conventional drilling mud: Here 350 ml of mineral water was taken and 20gm of bentonite
clay was mixed in for control viscosity. Then 1g sodium hydroxide used for pH control,0.5gm soda ash used
for maintain calcium concentration ,6g starch used for control fluid loss,5g calcium carbonate used as a
bridging agent,0.7gm xanthan gum used as a thickening agent and 70gm of barite is mixed with this
ingredient. A blender is used to combine the ingredients properly.
Formulation of new drilling mud: The main ingredient of the new drilling mud is Aloe Vera. In a number of
ways aloe vera particles may be harvested. After cutting from the plant, aloe vera leaves may be processed
as soon as possible. Fast processing reduces degradative decomposition of the aloe vera. Such as natural
enzymatic reactions will take place also encourages the growth of bacteria due to the presence of oxygen.
Cutting the aloe vera leaves was washed in water. Then it’s0/ time to separate aloe vera from leaf by first
slicing. After that, though grinding machine desired size of aloe vera particles was obtained. After that the
same amount of all the ingredients of conventional drilling mud was taken and 1gm of aloe vera is added to
this mixer as a natural additive. Then a blender is used to mix up the ingredients properly.
2.3 Experimental procedure
The main purpose of this lab analysis is to reduce the environmental degradation of water-baseddrilling mud
using natural additives. For this lab analysis specially, aloe vera is used and it is collected from aloe vera
plant. Then the proposed model of drilling mud is prepared. After that lab analysis of this proposed drilling
mud is conducted by various tests in the drilling fluids laboratory. These tests are:
2.3.1 Mud balance test
In this test, a mud balance is used to measure the weight of the mud to an accuracy of within 1/10lb/gal or 1/2
lb./ft3. Mud weight, also called mud density, is the weight of a unit of mud. It is the amount of weight in one
unit of drilling fluid. It is one of the most important parts of the drilling fluid because it controls the pressure
in the formation and helps keep the wellbore stable. It is often given in lbm/gal (ppg), kg/m3, g/cm3 (also
known as specific gravity or S.G.), or psi/1000ft of depth (hydrostatic gradient).
2.3.2 Marsh funnel viscosity test
In this test, a marsh funnel viscometer is utilized to assess the viscosity of the drilling fluid. The marsh
funnel viscometer is a straightforward instrument used for common, rapid measurements of the viscosity of
fluids. It is an effective indication of changes in the characteristics of drilling fluids. The marsh funnel
viscometer is conical in shape, with a top diameter of 6 inches (152 mm), a length of 12 inches (305 mm), and
a capacity of 1500cm3. Half of the top is covered by a 12- mesh screen designed to eliminate any foreign
particles or drill cuttings from the fluid. The liquid flows through a 2 inch (50.8 mm) by 3/16 inch (4.7 mm)
fixed aperture located at the

Page | 1217
funnel's end. In addition to the marsh funnel, this test needs a container to collect a sample of the drilling
fluid, a graduated cup to catch the drilling fluid as it runs out of the funnel, a stopwatch, and a thermometer.

2.3.3 Mud rheology test


The OFITE Model 800 viscometer is used to measure the rheological properties of a substance at different
rotational speeds. In addition, it determines the flow properties of oils and drilling fluidsin terms of shear rate
and shear stress over a range of time and temperature at atmospheric pressure. Speeds are simply adjusted
through a control knob, and shear stress readings are presented on a magnified, illuminated dial for easy
reading. These are the eight tightly regulated test speeds (in RPM): 3, 6, 30, 60, 100, 200, 300, and 600.
Additionally, faster stirring rates are given. Changes in speed can be made using a control knob without
stopping the motor.
2.3.4 Mud filtration test
The low pressure OFITE filter press is used to find out how drilling fluids filter and how they build up wall
cakes. The construction of the filter press includes a cell body for holding the mud sample, a pressure inlet,
and a base cap with a screen and filter paper.
2.3.5 Mud retort analysis
Understanding the liquid and solid content of a drilling mud is essential for managing its qualities. Typically,
this information explains poor mud system performance and indicates whether the mud must be conditioned
by adding water, treating it with a chemical thinner, or removing a specific contaminant. The test is a
distillation of a sample of mud that quantifies the amount of condensedoil and water collected from the retort.
A typical mud retort is used to separate and measure the amounts of water, oil, and solids in a drilling fluid.
2.3.6 Sand content analysis
API sand is defined as solid particles larger than 74 microns (200 mesh) [1 micron () = 10-6 m]. It is
desirable to know the sand content of drilling muds because excessive sand might result in the deposition of
a thick filter cake on the wall of the hole or settle in the hole around the tool when circulation is halted, thus
hindering the operation of drilling tools or the placement of casings. The OFITE Sand Content Kit is
designed to determine the volume percent of particles of sand-sized in the drilling fluid. The sand content set
includes a 200-mesh sieve with a 2.5" diameter, a funnel, a 500 ml wash bottle, and a 0-20% graded glass
tube.
2.3.7 Mud resistivity analysis
The OFITE Digital Resistivity Meter is utilized to measure the drilling fluid's resistivity. Resistivity is
determined by measuring the resistance to the flow of electrical current through a sample with a specified
configuration. The OFITE Digital Resistivity Meter is a portable measuring instrument created to provide a
quick and accurate assessment of the resistivity of a tiny sample in ohm-meters. The digital display shows
resistivity (in ohms), NaCl concentration (in ppm, kppm, and gr/gal), and temperature (in °C or °F).

Page | 1218
3. Theory/calculation
3.1 Mud Balance Test
The laboratory analysis of both conventional & new drilling fluid is observed. The reading of themud balance
in case of fluid specific gravity and density,

For conventional drilling mud:


Fluid specific gravity = 1.10 SP.GRDensity =
9.2 ppg
For new drilling mud:
Fluid specific gravity = 1.11 SP.GRDensity =
9.21 ppg
3.2 Marsh Funnel Viscosity Test
The calculation for this test:
For conventional drilling mud
Fluid density = 9.2 ppg = (9.2*0.12) gm/cm3 = 1.104 gm/cm3Required
time, t =80.53s
The apparent viscosity can be determined from following simple formula.
𝜇𝑎 = p (t – 25)Where,
𝜇𝑎 = apparent viscosity in centipoisesP = density
in g/cm
t = required time in seconds
So apparent viscosity, 𝜇𝑎 = p (t – 25) = 1.104(80.53-25) cp = 61.305 cpFor new
drilling mud
Fluid density = 9.21 ppg = (9.21*0.12) gm/cm3 = 1.1052 gm/cm3Required
time, t = 98.23 s
The apparent viscosity can be determined from following simple formula.

Page | 1219
Apparent viscosity, 𝜇𝑎 = p (t – 25) = 1.1052(98.23 - 25) cp
= 80.933 cp

3.3 Mud Rheology Test


For conventional drilling fluid the reporting data is given below in Table-1 and 2.
❖ Viscosity data
Table-1 Rheological parameters of conventional drilling mud

RPM Dial reading

600 123

300 106

200 102

100 93

6 86

3 78

❖ Gel strength data


Table-2 Rheological parameters of conventional drilling mud

Run Dial reading

10 seconds run 135

10 minutes run 245

Page | 1220
Calculations and results:
❖ Apparent viscosity, 𝜇𝑎 = 600 𝜃𝑁/2
= 123/2
= 61.5 cp
❖ Plastic viscosity, 𝜇p = ꆪ (600 -300)
= 123-106
= 17cp
❖ Yield point, Ty = ꆪ 300 - 𝜇p (1b/100 ft2)
= 106- 17
= 89 1b/100 ft2
❖ Thixotropy = [Gel strength@10 minutes] - [Gel strength @10 seconds]
= 245-135
= 110
For new drilling fluid the reporting data is given below in Table-3 and 4.
❖ Viscosity data
Table-3 Rheological parameters of new drilling mud

RPM Dial reading

600 162

300 135

200 112

100 93

6 72

3 61

❖ Gel strength data


Table-4 Rheological parameters of new drilling mud

Run Dial reading


10 seconds run 142

Page | 1221
10 minutes run 268

Calculations and results for new drilling fluid:


• Apparent viscosity, 𝜇𝑎 = 600𝜃𝑁/2
= 162/2
= 81 cp
• Plastic viscosity, 𝜇p = ꆪ (600 -300)
= 162-135
= 27cp

• Yield point, Ty = ꆪ 300 - 𝜇p (1b/100 ft2)


= 135-27
= 108 lb./100 ft2
• Thixotropy = [Gel strength@10 minutes] - [Gel strength @10 seconds]
= 268-142 = 126
3.4 Mud filtration test
From the laboratory analysis of conventional drilling fluid, mud cake thickness is found be 1.01mm = 0.101
cm.and the test data and calculation are given below.
Vf vs. √t graph is shown in Figure 1. Figure:1 Filtrate volume vs. t graph

2
5

2
0

1
5
ume
Vol

1
0

0
0 1 2 3 4 5 6

Page | 1222
From Vf vs. √t graph
The value of spurt loss Vsp = 0 cm3From data
table, V7.5= 9.65cm3
Standard API water loss, V30 = 2(V7.5 - Vsp) + Vsp = 2(9.65 - 0) + 0 = 19.3
Again, from the laboratory analysis of new drilling fluid, mud cake thickness is found to be 1.00mm = 0.1
cm. and the test data and calculation are given below.

Vf vs. √t graph is shown is Figure 2.

1
4

1
2

1
0

2
0 1 2 3 4 5 6

Figure:2 Filtrate volume vs. t graph

From Vf vs. √t graph


The value of spurt loss Vsp = 0.00 cm3From data
table, V7.5= 6.35cm3
Standard API water loss, V30 = 2(V7.5 - Vsp) + Vsp =2 (6.35-0)-0= 12.7
3.5 Mud retort analysis
For conventional drilling mud

Page | 1223
Sample volume = 50 mL
After performing the test, the volume of water & oil is measuredWater =
47.5 mL
Oil = 0.5 mL Calculations &
Results:
The measured volumes (mL) of oil and water are converted into volume percent based on thevolume of whole
mud in the retort cup.
A. Volume Percent (%) Oil (Vo) =100 (Oil Volume Collected, mL) / Sample Volume, mL
= 100*0.5/ 50
= 1%

B. Volume Percent (%) Water (Vw)=100 (Water Volume Collected, mL) / Sample Volume, mL
= 100* 47.5 / 50
= 95%
C. Volume Percent (%) Solid (Vs) = 100 – (Vo + Vw)
= 100- (95+1)
= 4%
For new drilling mud Sample
volume = 10 mL
After performing the test, the volume of water and oil,Water = 9.3
mL
Oil = 0.1 mL Calculations &
Results:
The measured volumes (mL) of oil and water are converted into volume percent based on thevolume of
whole mud in the retort cup.
A. Volume Percent (%) Oil (Vo) =100 (Oil Volume Collected, mL) / Sample Volume, mL
= 100*0.1/ 10
= 1%
B. Volume Percent (%) Water (Vw) =100 (Water Volume Collected, mL) / Sample Volume, mL
= 100* 9.3/ 10
= 93%

Page | 1224
C. Volume Percent (%) Solid (Vs) = 100 – (Vo + Vw)
= 100– (93+1)
= 6%
3.6 Sand content analysis For
conventional drilling mudSand
volume = 0.15%
For new drilling mud Sand volume
= 0.14%
3.7 Mud resistivity analysis
Resistivity of water = 229 ohm-meter Concentration of
sodium chloride = 11 ppmTemperature = 29.8 degree
Celsius
For conventional drilling mud Resistivity of mud
= 2.36 ohm-meter
Concentration of sodium chloride = 1947 ppm
Temperature = 29.5 degree Celsius
For new drilling mud
Resistivity of mud = 0.64 ohm-meter Concentration of
sodium chloride = 7580 ppmTemperature = 30.5 degree
Celsius
4. Result and Discussions
4.1 Mud balance test result
Table-5 Mud balance test result of the both drilling fluid

Properties Conventional drilling mud New drilling mud

Fluid specific gravity 1.10 SP.GR 1.11 SP.GR

Density 9.2 ppg 9.21 ppg

From the upper table it is observed that both the value of density and specific gravity of the conventional
drilling fluid is less than the new drilling fluid. For this reason, there will be also a rise in viscosity,
hydrostatic pressure in new drilling mud.

Page | 1225
4.2 Marsh funnel viscosity test result
Table-6 Marsh funnel viscosity test result

Conventional Drilling Mud New Drilling Mud

Required Time 80.53 sec 98.23 sec

Apparent Viscosity 61.305 cp 80.933 cp

From the above results it is observed that the value of apparent viscosity of the new drilling fluid is
higher than the conventional drilling fluid. For this reason, there will be increase in sweep efficiency in
the new drilling mud.

4.3 Mud rheology test result


Bringing all the values of mud rheology test (AV, PV, Yield point, Thixotropy) the result is shown in Figure-3
through a comparison and the comparison in a same frame will be useful to judge thesamples.

Figure: 3 Mud rheology test (AV, PV, Yield point, Thixotropy) result

There is an increase in apparent viscosity and plastic viscosity in new drilling mud, which will improve the
sweep efficiency and hydrostatic pressure of the drilling fluid. Also, there is an increase in yield point in new
drilling mud, which indicates that more force of attraction between

Page | 1226
the particles of mud colliding with one another. So, it can be said that there is an increase in gel strength
reading for new drilling mud which may boost the solids-holding capacity of drilling fluid.
4.4 Mud filtration test result
According to the results from the calculation of mud filtration test the comparison between the
conventional drilling mud and the new drilling mud is given below in Figure-4.

Figure-4 Comparison of mud filtration test result

From the above analysis, the water loss of conventional drilling mud is higher than the new drilling mud.
From the above results, it shows that there is a reduction in water loss in new drilling mud, which will improve
the fluid performance. This will solve many drilling problems, like a pipe that won't move or a blowout.
4.5 Mud retort test result
Table-7 Mud retort test result

For conventional drilling mud For new Drilling mud

Volume of water 95% 93%

Volume of oil 1% 1%

Volume of solid 4% 6%

From the above results, it is shown that there is a higher percent of solids in new drilling mud,which
indicates a decrease in the rate of penetration in drilling operations
4.6 Sand content analysis
The sand volume percentage of conventional drilling mud is 0.15 and new drilling mud is 0.14.The
graphical comparison of sand volume percentage of two samples is given below in Figure-5.

Page | 1227
Figure-5 Comparison of sand content analysis

Excessive sand may result in the deposition of a thick filter cake on the wall of the hole, settle in the hole
about the tool when circulation is stopped, thus interfering with successful operation of drilling tools or
setting of casings. From the above results, there was negligible amount or percent of sand getting in both mud
samples, which might not significantly affect the both mud sample.
4.7 Mud resistivity analysis
The resistivity of conventional drilling mud is 2.36 ohm-m and new drilling mud is 0.64 ohm-m. The NaCl
concentration of conventional drilling mud is 1.947 kppm and new drilling mud is 7.58 kppm. The graphical
comparison of two samples is given below in Figure-6.

Figure-6 Comparison of mud resistivity analysis

Page | 1228
From the above results, there is a decrease in resistivity of new drilling mud, which indicates lessresistance to
the flow of electrical current through the new drilling mud compare with conventional drilling mud. Also,
NaCl concentration is inverse of resistivity.
4.8 Discussions
As demonstrated by the aforementioned results, using natural additives in drilling fluid leads to a substantial
change in rheological characteristics and a decrease in mud filtrate. There is an increase in apparent viscosity
and plastic viscosity, which will improve the sweep efficiency and hydrostatic pressure of the drilling fluid.
Also, it is evident from the results that gel strength has improved, which may boost the solids-holding
capacity of drilling fluid. Additionally, there is a decrease in filtrate loss. This will significantly improve
fluid performance. Utilizing aloe vera as a natural additive would be a fabulous idea, as demonstrated by the
results of experiments and analyses. Rheological knowledge is absolutely vital for understanding drilling
fluid. With this information, it can figure out the equivalent circulating density, how much the system
pressure drops, and how well the holes get cleaned.
5. Conclusion
In this study, the main goal was to use natural materials (aloe vera) in existing water base drilling fluid as an
additional ingredient and compare it with the existing standard water base drilling fluid clear way. Different
chemical additives are added to simple water-based drilling fluid to change its rheological properties and
reduce the amount of mud filtrate loss. That chemical additives could be poisonous and bad for both people
and the environment. In this study, drilling fluid was made with aloe vera as a natural ingredient. This study
comes to a good conclusion through both experiments and analysis. There was a change in the rheological
properties, and the loss of mud filtrate, which is very important in the petroleum industry, can be cut by a lot.
There was a rise in both apparent viscosity (AV) and plastic viscosity (PV) when aloe vera was used as a
natural additive. This means that the drilling fluid will be easier to sweep. So it will be easier to get rid of the
cuttings than before. There will be a rise in hydrostatic pressure. Also, drill bits might get greasy more
quickly. If the gel strength goes up, the drilling fluid might be able to hold more solids. That would let more
solids float on top of the liquid. Also, it would keep the level of alkalinity in the drilling fluid at the same
level. From the results, it was also found that aloe vera, when used as an additive, reduces the loss of filtrate
at very high levels. This will solve many drilling problems, like a pipe that won't move or a blowout, for
example. So, it's clear that using aloe vera could make the drilling fluid work better, and we wouldn't have to
worry about so many expensive and dangerous additives. Using natural ingredients will help keep our
environment in good shape.
Acknowledgment
I acknowledge the support and help of my supervisor Md. Mizanur Rahman, Assistant Professor, Department
of Petroleum and Mining Engineering, Chittagong University of Engineering & Technology. I would like to
specially mention Prof. Dr. Muhammad Mostafa Kamal Bhuiya, for his constant support during the entire
process.
References
1. Amanullah Md, Jothibasu Ramasamy, Mohammed K. Al-Arfaj, Application of an indigenous eco-
friendly raw material as fluid loss additive, Journal of Petroleum Science and Engineering. 2016,
16(1); 191-197.

Page | 1229
2. Amanullah Md, Long Yu, Environment friendly fluid loss additives to protect the marine
environment from the detrimental effect of mud additives, Journal of Petroleum Science
and Engineering. 2005, 4; 199-208 .
3. Caenn R., Darlcy H. C. H., Gray G.R., 2011.Composition and Properties of Drilling andCompletion
Fluids, 6th edn. Gulf Professional Publishing, Houston.
4. Dhiman, Annudeep Singh, 2012. Rheological properties & corrosion characteristics of drilling
mud additives. MS-Thesis, Halifax: Dalhousie University.
5. Ekeigwe O. N., Anyiam C.K., Ayo M.D. and Ekebafe L.O., The Formulation Of Water
Based Drilling Fluid from Local Materials, Caspian Journal of Applied Sciences Research
(CJASR). 2013, 2 (1); 18-22.
6. M. Enamul Hossain, Mohammed Wajheeuddin, The use of grass as an environmentally friendly
additive in water-based drilling fluids, Pet. Sci.2016.
7. Wajheeuddin, M., Hossain, M.E., An experimental study on particle sizing of natural substitutes for
drilling fluid application, J. Nat. Sci. Sustain.Technol. 2014, 8(2); 259-272.

Page | 1230
7th International Conference on Engineering Research, Innovation and Education
January 12-14, 2023, Sylhet, Bangladesh

PAPER ID: 389

Efficacy of slightly acidic electrolyzed water in combination with


ultrasound and mild heat on microbial decontamination and quality of
fresh cauliflower
Sharmin Akther¹, Md. Rashedul Islam¹, Md. Jahangir Alam², Shafi Ahmed¹*

¹ Department of Agro Product Processing Technology, Jashore University of Science and


Technology, Jashore-7408, Bangladesh

²Department of Chemical Engineering, Jashore University of Science and Technology, Jashore–


7408, Bangladesh

Email: Sharmin Akther: sharminakterlima95@gmail.com, justappt151716@gmail.com,


mj.alam@just.edu.bd, shafi@just.edu.bd

* Corresponding author:[ Shafi Ahmed]

Abstract: Slightly acidic electrolyzed water (SAEW) has recently gained a lot of interest as a chlorine sanitizer
which provides higher decontamination effect with minimum available chlorine. Nevertheless, microbial
reductions via only SAEW treatment are not sufficient to assure safety. The disinfection efficacy of SAEW
can be improved by combining with other compatible techniques. SAEW with a pH of 5.5-5.6, available
chlorine content (AAC) 20-22 mg L-1, oxidation-reduction potential 900-950 mV was applied on fresh-cut
cauliflower to determine the antimicrobial activity. SAEW was also applied in combination with ultrasound
treatment (US) and moderate heat (45 °C) to enhance the bactericidal efficacy of SAEW. The impacts of
individual (SAEW) and combined treatments like (SAEW + US), (SAEW + US + mild heat 45 °C) on
microbial population, physicochemical properties, the antioxidant activity of fresh-cut cauliflower were
evaluated. The combined treatment with mild heat showed better effectiveness on microbial decontamination
than other treatments but it significantly degraded the quality of fresh cauliflower regarding antioxidant and
physicochemical properties. However, SAEW with US treatment preserved bioactive compounds and
antioxidant activity with significant reduction of microbial load. The present study suggests that SAEW with
US treatment can be a promising decontamination technique to improve postharvest quality and minimize
postharvest losses of fresh produce.

Keywords: Electrolyzed water; Ultrasound treatment; Cauliflower; Microbial reduction; Antioxidant


activity.

Page | 1231

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