Professional Documents
Culture Documents
1
Declaration
I, Monis Janjua confirm, that this work submitted for assessment is my own and is
expressed in my words. Any uses made within it of the works of other authors in any
form (e.g. ideas, equations, figures, drawings, text, tables, other forms of data, programs)
are properly acknowledged and referenced at the point of their use. A list of the
references employed is included.
Monis Janjua
MEng Chemical Engineering Group 2
2
Executive Summary
The overall process in this whole plant is to produce 10 tons of pure imidazole for use in many
industries especially the pharmaceutical. In this process there is a liquid-liquid extraction process
to purify the imidazole which requires n-butanol as the solvent for the extraction. In this report the
butanol plant was designed specifically. The butanol was required to be as pure as possible so it
would extract the waste and not contaminate it more.
The process in which glucose from molasses is converted into butanol is known as fermentation,
specifically anaerobic fermentation as oxygen is not required in the system. The fermentation is
carried out by a strain of Clostridium Acetobutyllium PCSIR-10 in a bioreactor vessel. The main
aim of Volume 4 project is to design and optimize this bioreactor, which in turn will give an
economically viable and highly yielded product.
The design of the bioreactors were optimized in order to make the design economical, firstly the
growth of the bacteria were modelled using Monod Kinetics where the change in butanol
concentration was modelled. Then a sensitivity analysis of changing the batch time on different
parameters was carried out to find the optimum batch time. Once the optimum batch time was
found the overall volume of the reactors were found, where another sensitivity analysis was done
on the aspect ratio to find the optimum vessel dimensions. Other designs for the fermenter were
the cooling system, mass transfer, impeller sizing and baffle sizing.
The CAPEX of the bioreactor vessels were correlated to be £870,000 for two including the
agitators. The utilities came to £77,500 per year. An alternative design was fully designed showing
the sizing and costing of a chemical reactor instead of a bio reactor, this design proved that the
fermentation technique was more advantageous. A pump design was also carried out to increase
pressure which required 0.01978 kW of hydraulic power with a 47% efficiency, it was proven by
calculating the NPSH that the pump will avoid cavitation.
3
Conclusion & Recommendations
This report analysed the design procedure to manufacture a bioreactor to produce butanol using
glucose as a substrate whilst providing the Clostridium Acetobutyllium bacterium to be fermented.
The procedure begun with modelling the process using Monod Kinetics to determine the most
optimum batch time for the process whilst considering many factors such as concentration of
products, concentration of substrates, productivity and the cost of the process. It was decided
from the data calculated that the batch time was 25 hours with a 10 hour downtime.
The bioreactor vessel design was done, the design was also optimised to ensure the most cost
effective and productive vessel was designed. The bioreactor was designed to produce three
days of required butanol per batch, this was so the process after the bioreactor could operate
continuously. It was shown that an aspect ratio of 3 was the most economical design with literature
backing this. 2 vessels were chosen to operate in series instead of one large vessel, this was
done to reduce costs and improve the productivity of the process with regards to mixing and mass
transfer. The capital cost of both the fermenters came to £870,000.
An alternative design was covered in this report, this was to show that the bioreactor was a
superior, more economic and more efficient design than the chemical synthesis route. The
alternative design had promise but failed in the economics, safety and operating conditions when
compared with the fermenter.
A centrifugal pump was also designed in this report to increase the pressure before it reached a
separation stage. From the design of the pump it was evident that CP23.15 doesn’t undergo
cavitation.
Finally, the plants safety was also considered by carrying out a HAZOP study which helped us in
implementing control systems to be used in worst case scenarios.
Some recommendations could be to find better downstream processing techniques after the
fermentation or to find a fermentation technique which produces less by products in order to have
economical savings in downstream processing. Another recommendation would be to find a way
to lower the batch time by changing some other parameters not considered in this report.
By considering all of the aspects required in this design report, it is clear that this process has
promise and could be implemented in industry.
4
1 Table of Contents
Declaration ............................................................................................................................................2
Executive Summary ...............................................................................................................................3
Conclusion & Recommendations ...........................................................................................................4
List of Figures .........................................................................................................................................8
List of Graphs .........................................................................................................................................9
List of Tables ........................................................................................................................................ 10
List of Symbols ..................................................................................................................................... 11
1 Introduction................................................................................................................................ 13
2 Biology of the ABE Fermentation ................................................................................................ 14
2.1 Bacteria Selection .......................................................................................................... 14
2.2 Substrate ........................................................................................................................ 15
2.3 Nutrients ......................................................................................................................... 15
2.4 Temperature & pH Control ............................................................................................. 15
3 Reaction Chemistry ..................................................................................................................... 16
3.1 Acidogenic Phase ........................................................................................................... 16
3.2 Solventogenic Phase ...................................................................................................... 16
3.3 Fermentation Stoichiometric Reactions ......................................................................... 16
4 Batch Vs. Continuous .................................................................................................................. 17
4.1 Batch .............................................................................................................................. 17
4.2 Continuous ..................................................................................................................... 17
5 Process Flow Diagram ................................................................................................................. 18
5.1 Detailed PFD .................................................................................................................. 19
6 Mass Balance Diagram ................................................................................................................ 20
7 Stream Energy Balance Diagram ................................................................................................. 21
8 Process Description .................................................................................................................... 22
8.1 Stream S19.10-S21.20 ................................................................................................... 22
8.2 Bioreactor BR20.20/BR21.20 ......................................................................................... 22
8.3 Stream S20.45-S22.20 ................................................................................................... 22
8.4 Storage Tank T22.20 ...................................................................................................... 22
8.5 Centrifuge CEN22.20/ Pump CP23.10 ........................................................................... 22
9 Unit Design BR20.20/21.20 ......................................................................................................... 23
9.1 Modelling Of Fermentation ............................................................................................. 23
9.1.1 Modelling Conclusion ................................................................................................. 27
9.2 Bio-Reactor Sizing .......................................................................................................... 28
9.2.1 Reactor Volume ......................................................................................................... 28
9.2.2 Sizing of Reactor Including Optimization ................................................................... 28
9.2.3 Aspect Ratio Effect on Agitation Power ..................................................................... 30
9.2.4 Aspect Ratio Effect on Structural Thickness of Bioreactor ........................................ 31
9.2.5 Final Aspect Ratio Conclusion ................................................................................... 33
9.3 Impeller Sizing ................................................................................................................ 33
9.4 Baffle Sizing.................................................................................................................... 34
9.5 Vessel Bottoms .............................................................................................................. 34
9.6 Mass Transfer ................................................................................................................ 35
9.7 Heat Transfer.................................................................................................................. 36
9.7.1 Reactions of the Process ........................................................................................... 36
9.7.2 Vessel Agitation ......................................................................................................... 36
9.7.3 Overall Energy Removal Requirement ...................................................................... 36
9.7.4 Jacket Design............................................................................................................. 38
9.8 Costing Evaluation ......................................................................................................... 39
5
9.8.1 Operating Cost ........................................................................................................... 39
9.8.2 Utility Cost .................................................................................................................. 39
10 Alternative Reactor Design ......................................................................................................... 40
10.1 Reactor Type .................................................................................................................. 40
10.2 Reaction Chemistry ........................................................................................................ 40
10.3 Catalyst Selection/Properties ......................................................................................... 41
10.4 Reaction Kinetics ............................................................................................................ 41
10.4.1 Rate Constant ........................................................................................................ 41
10.4.2 Derive Rate Equation............................................................................................. 42
10.4.3 Calculation of Initial Concentration of Reactant .................................................... 42
10.4.4 Calculation of Catalyst Rate Constant Kcat ............................................................ 43
10.5 Reactor Sizing ................................................................................................................ 44
10.5.1 Calculation of Effective Diffusivity .......................................................................... 44
10.5.2 Calculation of Thiele Modulus & Internal Effectiveness Factor ............................. 45
10.5.3 Volume of Reactor ................................................................................................. 45
10.5.4 Mass of Catalyst Required .................................................................................... 46
10.5.5 Residence Time ..................................................................................................... 46
10.5.6 Reactor Vessel Height & Diameter ........................................................................ 46
10.5.7 Vessel Wall Thickness ........................................................................................... 47
10.5.8 Vessel Head & Closure ......................................................................................... 47
10.5.9 Internal Catalyst Arrangement ............................................................................... 48
10.6 Pressure Drop across Reactor ....................................................................................... 48
10.7 Heat Balance .................................................................................................................. 49
10.7.1 Heat of reaction ..................................................................................................... 49
10.7.2 Enthalpy of Reactant/Product Streams ................................................................. 49
10.7.3 Heat Balance ......................................................................................................... 49
10.8 Alternative Design Mass & Energy Balance ................................................................... 50
10.9 Costing Evaluation of Alternative Reactor ...................................................................... 51
10.9.1 Equipment Cost ..................................................................................................... 51
10.9.2 Operating Cost ....................................................................................................... 51
10.10 Conclusion of Alternative Design ............................................................................... 52
11 Pump CP23.10 Design ................................................................................................................. 53
11.1 Pipeline Design (Suction/Discharge) .............................................................................. 53
11.1.1 Static/Discharge Head ........................................................................................... 54
11.1.2 Pipe Diameter ........................................................................................................ 54
11.1.3 Velocity of Flow ...................................................................................................... 54
11.1.4 Absolute Roughness.............................................................................................. 54
11.1.5 Miscellaneous Losses............................................................................................ 55
11.1.6 Total Length of Pipe............................................................................................... 55
11.1.7 Friction Factor ........................................................................................................ 55
11.1.8 Frictional Pressure Loss ........................................................................................ 55
11.2 Pump Power Requirement ............................................................................................. 56
11.3 Pump Suction Side ......................................................................................................... 57
11.3.1 Line Loss Pressure ................................................................................................ 57
11.3.2 Entrance Loss Pressure ........................................................................................ 57
11.3.3 Static Pressure ...................................................................................................... 57
11.3.4 Suction Pressure ................................................................................................... 57
11.3.5 NPSH ..................................................................................................................... 57
11.4 Pump Discharge Side ..................................................................................................... 58
11.4.1 Dynamic Pressure Loss ......................................................................................... 58
11.4.2 Static Pressure ...................................................................................................... 58
11.4.3 Discharge Pressure ............................................................................................... 58
11.4.4 Pump Head ............................................................................................................ 58
11.5 Pump Costing ................................................................................................................. 59
11.5.1 Equipment Cost ..................................................................................................... 59
11.5.2 Operating Cost ....................................................................................................... 59
11.6 Conclusion of Pump CP23.10 ........................................................................................ 59
12 Overall Utilities & Overall Costing ............................................................................................... 60
6
13 AutoCAD Reactor Drawings ........................................................................................................ 61
13.1 Impeller Dimensions ....................................................................................................... 62
14 Materials of Construction ........................................................................................................... 63
15 Downtime Period........................................................................................................................ 64
15.1 Cleaning ......................................................................................................................... 64
15.2 Maintenance ................................................................................................................... 64
16 Bioreactor Specification Sheet .................................................................................................... 65
17 Safety & Control Systems ........................................................................................................... 66
17.1 P&ID Diagrams ............................................................................................................... 66
17.2 Discussion of Controls .................................................................................................... 69
17.2.1 Storage Tank ST18.50 .......................................................................................... 69
17.2.2 Bioreactors BR20.20/BR21.20 .............................................................................. 69
17.2.3 Storage Tank ST22.20 .......................................................................................... 69
17.2.4 Centrifuge CEN23.10............................................................................................. 69
17.2.5 Centrifugal Pump CP23.15 .................................................................................... 69
17.3 HAZOP Analysis on Bioreactor ...................................................................................... 70
17.4 Plant Safety & Hygiene .................................................................................................. 71
18 Sustainability .............................................................................................................................. 72
18.1 Social Sustainability ....................................................................................................... 72
18.2 Economic Sustainability ................................................................................................. 72
18.3 Environmental Sustainability .......................................................................................... 72
19 Start-up & Shutdown .................................................................................................................. 73
19.1 Start-up ........................................................................................................................... 73
19.2 Shutdown........................................................................................................................ 73
20 Bibliography ............................................................................................................................... 74
21 Appendices ................................................................................................................................. 77
21.1 Appendix 1 – Metabolism of Biomass ............................................................................ 77
21.2 Appendix 2 – Mass Balance Table per Batch ................................................................ 78
21.3 Appendix 3 – Stream Energy Balance Table per Batch ................................................. 79
21.4 Appendix 4 – Fermenter Calculations ............................................................................ 80
21.4.1 - Monod Spreadsheet Calculation ......................................................................... 80
21.5 – Sample Calculations .................................................................................................... 81
21.5.1 – Mass Balance/Energy Balance Calculations ...................................................... 82
21.5.2 – Surface Area to Volume Ratio for Use in Determining Aspect Ratio & Number of
Reactors 82
21.5.3 – Power of Agitation............................................................................................... 82
21.5.4 – Thickness of Vessel Calculation ......................................................................... 83
21.5.5 – Mixing Time Calculation for Mass Transfer ........................................................ 84
21.5.6 4.1.7- Vessel Bottoms Calculations ....................................................................... 84
21.5.7 4.1.8 – Heat Transfer Calculations ........................................................................ 85
21.6 Appendix 5 – Alternative Design HYSYS ....................................................................... 86
21.6.1 Appendix 5.2 – HYSYS Cost of Alternative Design ............................................... 86
21.7 Appendix 6 – Alternative Design Mass Balance ............................................................ 87
21.8 Appendix 7 – Alternative Design Stream Energy Balance ............................................. 88
21.9 Appendix 8 – GAPS Guideline for Pipe Length.............................................................. 89
21.10 Appendix 9 – Risk Matrix Key for HAZOP ................................................................. 89
21.11 Appendix 10 – Specification Sheets .......................................................................... 90
21.11.1 Pump CP23.15 Specification Sheet ...................................................................... 90
7
List of Figures
Figure 5.1- Process flow diagram of overall process, the boxed section is the section, which is
designed in this report. ................................................................................................................ 18
Figure 5.2- Detailed PFD of section design for this report. ......................................................... 19
Figure 6.1- Mass balance diagram of this design section. .......................................................... 20
Figure 7.1 - Energy balance of streams for this design section. ................................................. 21
Figure 10.1- Guerbet reaction mechanism.................................................................................. 40
Figure 10.2- Effectiveness vs Thiele modulus graph. ................................................................. 45
Figure 10.3 - Illustration of a tori spherical head. ........................................................................ 47
Figure 10.4 - Mass/Energy Balance of packed bed catalytic reactor. ......................................... 50
Figure 13.1 - Bioreactor AutoCAD design. .................................................................................. 61
Figure 13.2 - Impeller dimensions. .............................................................................................. 62
Figure 17.1 - P&ID for storage tank containing feed for bioreactor 1/3....................................... 66
Figure 17.2 - P&ID for fermenter 2/3. .......................................................................................... 67
Figure 17.3- P&ID for after the fermentation 3/3. ........................................................................ 68
Figure 21.1 - Metabolism of biomass to butanol. ........................................................................ 77
Figure 21.2 - Monod spreadsheet snapshot. .............................................................................. 80
Figure 21.3 - HYSYS of alternative catalytic assumed to be PFR. ............................................. 86
Figure 21.4 - HYSYS cost of alternative reactor. ........................................................................ 86
Figure 21.5 - GAPs guideline for pipeline sizing. ........................................................................ 89
Figure 21.6 - Key for risk matrix. ................................................................................................. 89
8
List of Graphs
Graph 9.1 : Concentration of bacteria cells as a function of time ............................................... 24
Graph 9.2- Concentration of bacterial cells as a function of time with product poisoning. ......... 25
Graph 9.3- Concentration of butanol as a function of time with product poisoning .................... 25
Graph 9.4- Productivity of the system as a function of batch time .............................................. 26
Graph 9.5- Glucose concentration as a function of time. ............................................................ 26
Graph 9.6- Graph of surface area to volume ratio for different number of reactors. ................... 29
Graph 9.7- Surface area as a function of aspect ratio of reactors for given volume ................... 30
Graph 9.8- Agitator power input against the aspect ratio of the reactor. .................................... 31
Graph 9.9- Wall thickness against aspect ratio. .......................................................................... 32
Graph 9.10- Volume of material required for each reactor as a function of aspect ratio. ........... 32
Graph 9.11- The required heat removal as a function of fermentation time. .............................. 37
Graph 9.12 - Amount of cooling water required against time. ..................................................... 38
9
List of Tables
Table 0.1 - Summary of main design. ......................................................................................... 3
Table 0.1 - Nomenclature table. .................................................................................................. 11
Table 1.1- Advantages and disadvantages of the ABE fermentation technique. ........................ 13
Table 2.1- Different clostridia descriptions. ................................................................................. 14
Table 3.1- Reactions and conversions of ABE fermentation using Clostridium Acetobutyllium
PCSIR-10. ................................................................................................................................... 16
Table 4.1 - Benefits & risks of batch. .......................................................................................... 17
Table 4.2- Benefits & risks of continuous. ................................................................................... 17
Table 9.1- Dimensions of each bioreactor. ................................................................................. 33
Table 9.2- Dimensions of impeller ............................................................................................... 33
Table 9.3- Dimensions of baffles. ................................................................................................ 34
Table 9.4- Ellipsoidal tops & bottoms dimensions....................................................................... 34
Table 9.5- The mixing values of the impeller/ Rushton turbine. .................................................. 35
Table 9.6- Value of maximum and required duty. ....................................................................... 37
Table 9.7- Properties of the cooling jacket. ................................................................................. 38
Table 9.8- Properties of the cooling water for within the cooling jacket. ..................................... 38
Table 9.9- Equipment cost for main design. ................................................................................ 39
Table 9.10- Electricity operating cost for main design bioreactor. .............................................. 39
Table 9.11 - Cost of utility for main design equipment per year. ................................................. 39
Table 10.1- Properties of the catalyst. ........................................................................................ 41
Table 10.2- Rate constant for guerbet reaction. .......................................................................... 41
Table 10.3- Antoine constants for ethanol. ................................................................................. 42
Table 10.4- Data obtained/calculated for reactor sizing. ............................................................. 44
Table 10.5 - Heat of formations of reactants and products. ........................................................ 49
Table 10.6 - Enthalpy of feed and product stream for reactor. ................................................... 49
Table 10.7 - Cost of alternative design equipment...................................................................... 51
Table 10.8- Operating cost of electricity per year for main design. ............................................. 51
Table 10.9 - Discussion of alternative design compared with main bioreactor design. .............. 52
Table 11.1 - Parameters known for pump design. ...................................................................... 53
Table 11.2- Suction/Discharge length as recommended by GAPs. ............................................ 53
Table 11.3 - Heads of pipes. ....................................................................................................... 54
Table 11.4- Pipeline parameters. ................................................................................................ 54
Table 11.5 - Total length of pipeline ............................................................................................ 55
Table 11.6 - Pressure losses on the line of pipe. ........................................................................ 58
Table 11.7- Equipment pressure summation with static pressure. ............................................. 58
Table 11.8 - Cost of pump ........................................................................................................... 59
Table 11.9- Operating cost of electricity per year for pump. ....................................................... 59
Table 11.10 - Data for manufacture of pump as calculated in this section. ................................ 59
Table 12.1- Summary of utility details for this section of the process. ........................................ 60
Table 12.2 - Cost of all the equipment within this design section. .............................................. 60
Table 12.3 - Operating costs of section per year. ....................................................................... 60
Table 14.1 - Composition of type 304 stainless steel. [42] ..................................................... 63
Table 14.2- Physical properties of Type 304 stainless steel. [42] ............................................... 63
Table 16.1 - Fermenter specification sheet. ...................................................................................... 65
Table 17.1- HAZOP analysis on main design fermenter based on P&ID. .................................. 70
Table 17.2 - Potential safety issues and solutions in and around the plant. ............................... 71
Table 19.1 - Timeline of startup of plant. ..................................................................................... 73
Table 21.1 - Mass balance table. ................................................................................................ 78
Table 21.2 - Stream energy balance table. ................................................................................. 79
Table 21.3 - Explanation of nomenclature for thickness. ............................................................ 83
Table 21.4 - Enthalpy of formations for main reaction. ............................................................... 85
Table 21.5- Alternative design mass balance table. ................................................................... 87
Table 21.6 - Alternative design stream energy balance table. .................................................... 88
Table 21.7 - Pump specification sheet. ............................................................................................. 90
10
List of Symbols
Table 0.1 - Nomenclature table.
11
Ρcat Density of catalyst kg/m3
k Rate constant mol/hrm3
ra Rate of reaction mol/hr
Psat Vapor pressure Pa
n Mole mol
CA0 Initial concentration of A kmol/m3
nA0 Initial moles of A mol
Kcat Rate constant of catalyst m gas/m3cat.s
3
ө Thiele modulus -
𝝉 Batch time hr
ր Effectiveness -
Vcat Volume of catalyst m3
Pi Internal vessel pressure mPa
𝝈 Design stress N/mm2
PUMP
∈ Absolute roughness -
m Flowrate of fluid kg/s
Q Volumetric flowrate m3/s
f Friction factor -
A Area of pipeline m2
L Total length of pipeline m
W Work done by fluid J/kg
n Efficiency -
di Pipeline diameter m
u Velocity of fluid m/s
Pf Pump suction pressure loss Pa
PV Vapor pressure of pump at suction Pa
P Pressure above the liquid in the feed vessel Pa
z1 Height at suction side m
z2 Height at discharge side m
H Height of liquid above suction of pump m
COSTING
Ce Equipment purchase cost $
S Size parameter Diff units
n Exponent of equipment -
a,b Constants of cost -
12
1 Introduction
Butanol is an alcohol with four carbons (C4H9OH). There are many structural isomers, four to be
exact, however in this section the main focus is the production of n- butanol. N-butanol is a
naturally occurring isomer which has many uses in industry including:
Recently, butanol has been in talks as a potential biofuel especially in internal combustion
engines. Butanol could replace ethanol as the main biofuel as it is more advantageous due to it
being a little bit non polar as it has long hydrocarbon chain this means if fuel is contaminated with
water the butanol is less likely to separate from petrol or diesel than ethanol thus butanol is less
hygroscopic than ethanol. There are two main ways to produce butanol:
This design is based on using the ABE fermentation technique to produce renewable bio butanol
but the alternative design of this report is the chemical production of petro butanol from ethanol
so both ways have been taken into consideration in this process design.
ABE fermentation has been used in industry for more than 100 years, the process was initially
discovered by C.Weizmann a Russian chemist at Manchester University where he isolated a
bacteria strain of Clostridium Acetobutyllium which resulted in the first production plant in 1912.
ABE fermentation was only used during the war to form acetone used for the manufacture of
weapons, butanol and ethanol were considered as waste products. After world war one the
process was abandoned due to the reduced demand of acetone [1].
However since the rise in fuel prices of finite resources, butanol has become of increased interest
as a potential biofuel alternative for companies such as BP, Virgin Atlantic. It is said by the year
2022 the market size of butanol specifically bio butanol will reach to 18 billion USD [2]. Despite
the perks of using renewable and sustainable method to produce butanol using ABE fermentation
there are also some potential disadvantages.
Advantages Disadvantages
Safer than bio ethanol. The ABE fermentation has low butanol yields
about 30-40 times less than bio ethanol.
Renewable. High product recovery costs.
Less corrosive than other fuels. Low productivity due to product inhibition.
This process design is to produce ABE which will go on to further separation stages and hence
to be used as a solvent in the LLE of imidazole. The design is based on the work of [3].
13
2 Biology of the ABE Fermentation
The reaction is biological so selection of bacteria, nutrients, conditions needed to be chosen, the
biology of the process and selection of these are discussed in this section.
Anaerobic.
Rod shaped.
Heterogeneous.
Spore forming.
There are four groups of solvent producing clostridia; Table 2.1 below shows the relevant
information about these four groups of Clostridia.
To conclude this section, the chosen bacteria for this process was the Clostridium Acetobutyllium
PCSIR-10, this is because there is an abundance of research in these bacteria, the focus is to
produce butanol and this bacterium produces the most butanol. PCSIR-10 also has a high
butanol yield of 34%.
14
2.2 Substrate
Glucose from molasses was chosen as the substrate for the ABE fermentation process it has a
high sugar content and its properties include:
Dark colored.
Treacly.
By product of a sugar refinery.
[4]
2.3 Nutrients
Nutrients are required in order to ensure the metabolic activities in the cell for example in ATP
production for energy transfer and the activation of the substrate. Corn steep water and Iron
sulfate were the chosen nutrients as it is believed to be more economically viable and achieves
results similar to the optimum nutrient media for this process [6].
15
3 Reaction Chemistry
There are two main growth phases during the fermentation of Clostridium Acetobutyllium these
are the acidogenic phase and the solventogenic phase.
Butyric acid.
Acetic acid.
Carbon dioxide.
Hydrogen.
Ethanol.
Cell death threat is posed as the formation of acid results in a decrease in the pH, however this
is avoided due to the metabolic shift at the end of this exponential phase which indicates the end
of the acidogenic phase and start of the solventogenic phase.
Table 3.1- Reactions and conversions of ABE fermentation using Clostridium Acetobutyllium PCSIR-10.
As illustrated in
Table 3.1 the highest conversion is reaction 3 which is considered the main reaction in the design
of the bioreactor and is the butanol producing reaction so is an extra advantage. Appendix 1 –
Metabolism of Biomass shows the full metabolism of biomass using clostridium.
16
4 Batch Vs. Continuous
In the design of the fermenter there were two options in how the fermentation would occur these
were batch and continuous. This section discusses the advantages and disadvantages of both.
In the end batch was chosen due to the less chance of contamination as the butanol is already
poisoning and cannot risk having another risk of contamination.
4.1 Batch
In batch fermentation, the fermenter is filled with the feed and the fermentation occurs under
optimum pH, the products stay in the fermenter until the fermentation time is over. After the
fermentation, the product is extracted and the tank is cleaned in the downtime period and
sterilized before the next fermentation thus the process is done in separate batches. Batch is a
closed system, the advantages and disadvantages of batch are shown below in Error! Reference s
ource not found..
Advantages Disadvantages
High application in the industrial production. Less control over the growth of bacteria and
products.
Can produce secondary microbes. Conditions inside fermenter not constant.
More suitable to large-scale fermentation. Bacteria has lag and stationary phases,
which increase fermentation time.
Easy to set up and run. Lower yield of products.
Less investment needed. Larger sizes than continuous.
Less chance of contamination.
Less labor required.
Easier and quicker methods of control.
[8]
4.2 Continuous
In continuous, the feed is fed continuously and the process the growth of bacteria is continuous
due to the nutrients being added continuously thus the process never stops in between and occurs
for long periods.
Advantages Disadvantages
Process is not stopped for collecting product, Limited application in industry.
it is continuously taken out.
More control of the growth of bacteria. Less common for large scale fermentation.
Higher yield in less time. Difficult to set up.
Optimum growth is maintained. More chance of contamination.
Less size. More labor demand.
[8]
17
5 Process Flow Diagram
Figure 5.1- Process flow diagram of overall process, the boxed section is the section, which is designed in this report.
18
5.1 Detailed PFD
19
6 Mass Balance Diagram
Actual mass balance table can be found in Appendix 2 – Mass Balance Table per Batch.
Water 57471 kg
Acetone 12 kg
Ethanol 19 kg
ABE Butanol 633kg
Fermenter Acetic Acid 25 kg
Butyric Acid 25 kg
Glucose 8211 kg 33oC
Water 57471 kg
Clostridium Acetobutyllium 1288 kg
1 atm 33oC
Nutrients 0.884 kg pH 5 1 atm
33oC
Centrifuge 1 atm
Glucose 0 kg
Water 57471 kg
Clostridium Acetobutyllium 1288 kg
Clostridium Acetobutyllium 1288 kg
Nutrients 0.884 kg
Nutrients 0.844 kg
Acetone 12 kg
Ethanol 19 kg
Butanol 633kg
Acetic Acid 25 kg
Butyric Acid 25 kg
20
7 Stream Energy Balance Diagram
Actual energy balance table and more information can be found in Appendix 3 – Stream Energy Balance Table per Batch.
1 kJ/s
ABE
Fermenter
33oC
Centrifuge 1 atm
21
8 Process Description
This section of the imidazole production process is focused on the fermentation of glucose from
molasses to form butanol. This section will refer to streams from the process flow diagram in
Figure 5.1.
The feed consisting of glucose as the substrate, water, Clostridium Acetobutyllium PCSIR-10 as
the bacteria and the nutrients enters in S19.10 at a temperature of 330C and a pressure of one
atmosphere. The stream is then split into two where half the feed goes to S20.10 and the other
half to S21.10, the split feed then enters its respective bioreactor so S20.10 flows through
GV20.10 a globe valve and enters bioreactor BR20.20 through stream S20.20. Stream S21.10
flows through GV21.10 and enters bioreactor BR21.20 through stream S21.20.
The fermentation begins here where the clostridium acetobutyllium cells are converted into
acetone, ethanol, butanol, acetic acid, butyric acid, carbon dioxide and hydrogen through five
reactions the chemistry and biology of the fermentation process are discussed in, Biology of the
ABE Fermentation and Reaction Chemistry sections of the report. The fermentation time takes
25 hours and 10 hours is given after the fermentation for maintenance, cleaning etc. thus a total
of 35 hours batch time. The fermentation products leave the bioreactor after 25 hours through
streams S20.40 and S21.40. The carbon dioxide and hydrogen produced from this process are
vented off at the top of the reactor through streams S20.30 & S21.30.
The bottoms products of the fermentation are travelling through S20.45 & S20.50 until both
streams meet to become one and flow through S22.10 then through S22.20 reaching the storage
tank.
The product of the fermentation is stored in this tank; the tank releases the product continuously
through stream S23.10 making the rest of the process continuous. The products are stored at
atmospheric pressure and a temperature of 33oC. The products will not be stored for long periods
due to the toxicity of butanol.
The products are then continuously fed from the storage tank to the centrifuge where 100% of
the biomass is removed (Clostridium Acetobutyllium, Nutrients). The rest of the products
(acetone, butanol, ethanol, acetic acid & butyric acid) leave the bottom of the centrifuge and are
pumped to the next separation section. The Pump CP23.10 increases the pressure of the liquid
from 1atm to 1.1 atm.
22
9 Unit Design BR20.20/21.20
The process of fermentation needs to be modelled in order to show what is happening in the
reactor and to show the growth of microorganisms whilst proving that the batch time chosen is
right for the reactor. The butanol fermentation is modelled using the Monod kinetics of
microorganism of growth. The equation for Monod is shown below as Equation B.1 [9].
𝑑𝑥 𝜇𝑚 𝑆𝑥
= (B.1)
𝑑𝑡 𝐾𝑠 +𝑆
When Equation B.1 is combined with the unknown mass balance calculated on the glucose
(substrate) in the reactor, thus the unknown mass of the substrate could be written in the form of
the initial glucose concentration 𝑆0 , whilst the cells mass (𝑥0 & 𝑥) and yield coefficient (𝑌𝑥𝑠 ) are
incorporated into the new Equation B.2.
𝑥− 𝑥0
𝑆 = 𝑆0 − (B.2)
𝑌𝑥𝑠
Now substituting Equation B.2 into B.1 and integrating the full equation gives the final equation of
kinetics as illustrated in Equation B.3.
𝑌𝑥𝑠 × 𝐾𝑠 𝑥 𝑌𝑥𝑠 × 𝐾𝑠 𝑥0 𝑥
{ } ln [ ]−{ } ln [ ] + ln [ ]
(𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 (𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 − 𝑥 (𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 𝑌𝑥𝑠 × 𝑆0 𝑥0
=𝑡 (B.3)
𝜇𝑚
Once this equation is solved, the concentration of the clostridium acetobutyllium cells at various
times can be found as the cells grow throughout the culture. Equation B.3 can be easily solved
when using a Microsoft excel spreadsheet to give the profile of the bacteria cells at various times
in the bioreactor. The Monod constant value (𝐾𝑠 ) was obtained experimentally from [10]. The
maximum specific growth (𝜇𝑚 ) was obtained by the amount of growth of the bacteria in the system
from the mass balance and combined with the batch time from various articles to obtain a final
growth rate for this process Appendix 4 – Fermenter Calculations.
The Equations B.1, B.2 & B.3 were put into an excel sheet in order to model the growth of the
clostridium acetobutyllium cells within the fermenter. The sample calculations, method and values
for the process of modelling the growth are described in – Sample Calculations.
23
The first step of the modelling is to model the growth of the bacteria cells, as they are a basis for
the modelling of the overall bioreactor. Thus, in Graph 9.1 the growth of the cells as a function of
time is illustrated.
95
Clostridium Acetobutyllium Cell
90
85
Concentration (g.L-1)
80
75
70
65
60
55
50
0 0.5 1 1.5 2 2.5
Time (hr)
Graph 9.1 : Concentration of bacteria cells as a function of time
Graph 9.1 shows the ideal growth rate of the bacterial cells under the conditions given; there is a
relatively linear relationship, due to a high concentration at the beginning. There is a low growth
rate however; it is high enough to give a high yield of butanol. However, high yield of butanol
produced can affect the growth of the yeast as it also acts as an inhibitor when its concentration
gets to a certain point. This poisoning due to butanol is modelled by the decline in specific growth
rate as a function of the concentration of butanol & maximum specific growth rate which is
compared to the maximum tolerable concentration of the bacterial cells. Equation B.4 describes
this behavior [11].
𝑃
𝜇 = 𝜇𝑚 (1 − ) (B.4)
𝑃𝑚
Equation B.4 was then programmed into the spreadsheet showing the effect of the yeast
concentration with time when butanol is inhibiting the growth. Equation B.4 replaces the constant
𝜇𝑚 in Equation B.3. Graph 9.2 shows the effect of inhibition on growth of bacterial cells.
24
95
90
Clostridium Acetobutyllium Cell 85
Concentration (g.L-1)
80
75
70
65
60
55
50
45
0 5 10 15 20 25 30 35 40 45
Time (hr)
Graph 9.2- Concentration of bacterial cells as a function of time with product poisoning.
The presence of butanol has an effect on the bacteria and limits its growth in the system as shown
in Graph 9.2 at which it levels off once the maximum concentration of butanol the bacteria can
live at has been reached. From the data in the graph and using, the yield coefficients calculated
from the mass balance a graph can be shown to show the concentration of butanol in the reactor
against time instead of the concentration of bacteria cells. This is done using Equation B.5.
𝑃 = 𝑌𝑝𝑥 × 𝑑 (B.5)
25
Concentration Of Butanol (gL-1)
20
15
10
0
0 10 20 30 40 50
Time (hr)
25
Graph 9.3 shows the effect of butanol concentration again reactor time. It is used to decide the
required batch time of the reactor. However, further analysis is required to be sure that the chosen
batch time is suitable for operation. The first method to do this is by analyzing the productivity of
the system, which is also used to give the minimum volume required of the reactor for the process.
The productivity against batch time is shown in Graph 9.4.
0.7
0.6
Productivity (g.L-1hr-1)
0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50
Time (hr)
Graph 9.4- Productivity of the system as a function of batch time
As seen in Graph 9.4, the highest productivity occurs at about 6 hours including the downtime.
However, this batch time would not be feasible for the plant as at 6 hours a lot of glucose will
remain in the reactor unused, as shown in Error! Reference source not found.. This means low y
ields are achieved hence a much higher glucose feed being required.
55
Glucose Concentration In Reactor
50
45
40
35
(gL-1)
30
25
20
15
10
0 10 20 30 40 50
Time (hr)
Graph 9.5- Glucose concentration as a function of time.
26
Because of this higher feed of glucose being required at a low batch time even though it is at its
highest productivity the capital cost would increase by a vast amount. Error! Reference source n
ot found. shows at a batch time of 6 hours 40% of the glucose remains in the reactor, which is
very uneconomical and low yields of butanol, will be achieved.
To conclude, the modelling of the fermenter shows the best fermentation for the reactor would be
25 hours with a downtime of 10 hours for maintenance etc. thus overall 35 hours, which gives
sufficient time for the maximum conversion of glucose to butanol whilst giving the most
economical type of operation.
Graph 9.2 shows at 25 hours the bacterial cells have grown by 98% this is sufficient to provide
the reaction and ensure a high yield whilst also lowering cost and saving time as maximum cell
concentration is at 45 hours.
Graph 9.3 shows the butanol concentration is at 95% of its maximum at 25 hours this means a
high yield of butanol is produced whilst at a lower fermentation time.
Graph 9.4 shows the productivity of the system is at 75% of the maximum, which is a high
productivity compared with other times. Error! Reference source not found. shows almost all o
f the glucose has been used up at 25 hours meaning a high yielding reaction will occur at a
reduced cost thus optimizing the reactor to its fullest.
Overall, a compromise is made to have a high yielding reaction at a low cost whilst the bacteria
cells are at a maximum concentration and the fermentation time is relatively low. The productivity
will not be at its maximum but is still high. This results in an optimized and efficient bioreactor for
the fermentation of glucose from molasses to butanol.
27
9.2 Bio-Reactor Sizing
The reactor vessel was assumed to be cylindrical for the initial sizing procedure, then later on in
the section accurate dimensions were calculated from mechanical calculations of the ellipsoidal
top and bottoms plates. Detailed calculation for all sections in sizing are in – Sample Calculations.
The specification sheet for BR20.20/21.20 is provided in Error! Reference source not found..
The minimum required reaction volume was calculated from using the modelling section for each
batch time interval from this the minimum volume was calculated using the formula as given by
Equation B.6 [12]:
𝑚 × 𝑇𝐵
𝑉𝑟 =
𝜌 (B.6)
Equation B.6 was used to calculate the minimum required reactor volume for each point in time
from the modelling sheet, obviously the lowest volume was the highest productivity reactor but
for reasons given in the modelling section 35 hours was the chosen batch time the corresponding
reactor volume with this was 53m3.
When designing a fermenter, extra volume needs to be added at the top, which allows for the
foam build up and gas production during the fermentation reaction as carbon dioxide can cause
foaming and hydrogen is produced during the reaction. The accepted level of headspace as
dictated by [9] is around 10-20%, thus if 10% is chosen then the new reaction design volume
would be 60m3.
From this volume, various configurations of the reactor can be chosen for example the dimensions
and number of reactors in the process, which are discussed in this section. Following optimization
of the vessel in the following sections the amount of product produced is feasible within the mass
balance. There is also extra space for an increase in feed throughput by about 5% if needed.
Knowing the volume of the reactor means an investigation into the dimensions and arrangement
of the reactors can be done. The number of reactors needs to be considered and the effect the
number of reactors has on the system properties e.g. surface area and aspect ratio (diameter to
height ratio).
28
4.0
3.0
2.5
2.0
1.5
1.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0
Number of Reactors
Graph 9.6- Graph of surface area to volume ratio for different number of reactors.
𝑫
V = 60m3, =𝟑
𝑯
Firstly, the effect of varying the number of reactors to the surface area to volume ratio of the
reactors whilst keeping the aspect ratio constant. By varying the number of reactors, the volume
of each reactor is changing.
Graph 9.6 shows that as number of reactors increase the surface area to volume ratio also
increases. Advantages of this are:
Volume of each reactor is less, thus less duty required to be removed from the reactor
for overall process.
Higher surface area means higher area for heat transfer this means flowrate of cooling
water required for the cooling jacket will decrease making the process more economical.
However, a high number of reactors can also bring its disadvantages these include:
More number of reactors means more material needed for construction thus increasing
capital cost.
More control and measurement devices needed meaning more operators required
increasing OPEX and CAPEX.
This means a large number of small reactors will not be beneficial for the plant.
Fewer large reactors can decrease the capital cost of the process however, the larger size could
bring difficulties in the performance of the mixing higher volume means less better mixing
performance and higher agitator power being required for the larger volume of feed to be mixed.
Mixing performance is decreased because in the corners (dead spots) of the reactor can occur
where mixing is very minimal and so fermentation process is affected as concentrations across
the reactor will not be consistent.
Literature states 2-4 reactors for a fermentation in this set up would be sufficient up to 1000m 3
each [13], depending on requirements of feed and product quality. Four reactors would be too
high due to the volume of this process being low.
29
Consequently using this data and following from literature two reactors of 30m3 each were chosen
to carry out the bio reaction process.
Once the number of fermentation vessels are decided then each reactor, volume is also decided
then the next step is to decide the aspect ratio of the height to diameter. The first step to decide
this to show the effect aspect ratio has on the surface area of each reactor.
70
65
Surface Area (m2)
60
55
50
45
1.0 2.0 3.0 4.0 5.0 6.0
Aspect Ratio
Graph 9.7- Surface area as a function of aspect ratio of reactors for given volume
𝑽= 30m3, Reactor number = 2
In order to choose the correct aspect ratio they were measured against different parameters like
the agitation power & structural thickness of the vessel.
For homogeneity within the fermentation vessel, it must be agitated this will ensure even
distribution of the feed and products throughout the vessel. Literature shows that a typical impeller
tip velocity would be about 2m/s [14]. Knowing the impeller tip velocity means the number of
revolutions per minute can be calculated using Equation B.7 & B.8 [15].
𝑉𝑡𝑖𝑝
𝑁=
𝜋 × 𝐷𝐴 (B.7)
𝐷𝑇
𝐷𝐴 =
3 (B.8)
Equation B.9 is used to calculate the power input into the system once the number of revolutions
has been calculated [16].
𝑁𝑝 × 𝑁 3 × 𝐷𝐴5 × 𝜌𝐵
𝑃𝑖𝑛𝑙𝑒𝑡 =
𝑔𝑐 (B.9)
30
Equation B.9 means a graph to show the effect of changing fermenter diameter on power input
of the agitator system.
3.00
2.50
Power Input (kW)
2.00
1.50
1.00
0.50
0.00
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Aspect Ratio
Graph 9.8- Agitator power input against the aspect ratio of the reactor.
Graph 9.8 shows that the power requirement decreases vastly when aspect ratio is increased
thus less agitation power required the reason for this is:
If the aspect ratio of the fermenter increases, the height of the vessel will increase alongside this,
leading to an increase of the thickness of the vessel due to higher hydrostatic pressure acting on
the reactor the thickness increase is to ensure the vessel can safely contain its contents. Firstly,
the static pressure needs to be calculated for a static liquid using the pressure head Equation
B.10.
𝑃𝑠 = 𝜌𝐵 × 𝑔 × ℎ (B.10)
By summation of the static pressure and fermenter pressure (1atm), the total pressure is
calculated. Using Equation B.11 the required thickness of the vessel can be calculated taking into
account the welding strength, pressure and radius of the reactor [17].
𝑃𝑡𝑜𝑡𝑎𝑙 𝑟𝑖 𝐹𝑠
𝑡𝑉𝑒𝑠𝑠𝑒𝑙 = (B.11)
𝑆𝐸𝑗 − 0.6𝑃𝑡𝑜𝑡𝑎𝑙
31
Equation B.11 was used to calculate the thickness of the vessel at different aspect ratios, which
is shown below in Graph 9.9.
11.00
10.00
Wall Thickness (mm)
9.00
8.00
7.00
6.00
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Aspect Ratio
The optimum thickness seems to be at an aspect ratio of three, which will results in the least cost,
however more evidence is needed to prove this aspect ratio is sufficient. If aspect ratio increases,
the volume also changes. A comparison of the overall thickness of the material required against
aspect ratio needs to be done to see how much material is required.
0.70
Volume Of Material (m3)
0.60
0.50
0.40
0.30
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Aspect Ratio
Graph 9.10- Volume of material required for each reactor as a function of aspect ratio.
𝑽= 30m3, Reactor number = 2
32
Graph 9.10 shows after an aspect ratio of 2.5-3 the volume of material required increases almost
linearly illustrating that the effect of changing aspect ratio has more of an effect on the volume of
material than the structural thickness of the vessel.
Referencing to the sensitivity studies done in the previous sections a higher aspect ratio will give
the most efficient mixing power as seen in Graph 9.8; however, it can decrease the performance
of the mixing system within the agitator. A higher aspect ratio can cause an increase in capital
costs, as more volume of material is required.
Overall, taking into consideration literature and the sensitivity studies above, the best aspect ratio
for this process for each fermentation vessel would be 3. A compromise was made and this value
is what most industrial companies use as their aspect ratios for biological reactions [9]. With the
aspect ratio known, the dimensions of each fermentation vessel can be finalized as shown below
in Table 9.1.
A standard set of design equations were used to design the impeller as were given in [9], the
sizing of impeller is based on the sizing of the fermentation vessel.
𝐷𝐴 1
= (B.12)
𝐷𝑡 3
𝑊 1
= (B.13)
𝐷𝐴 5
𝐸 1
=
𝐷𝑡 3 (B.14)
𝐿 1
=
𝐷𝐴 4 (B.15)
33
9.4 Baffle Sizing
The design of the baffle like the impeller is also linked to the dimensions of the fermentation
vessel. The way a baffle is arranged within a reactor is:
4 rectangular baffles are equally spaced around the inner perimeter of the fermenter
and it has a diameter that is a 12th of the reactor diameter.
There is also a little spacing of the baffle from the reactor wall; this is to ensure no dead
spots created by the ends of the reactor [9].
Three baffles are known to provide good mixing.
The equations below are used to find the geometries of the baffles, in order to provide stability to
the baffle the thickness will be about 0.5 of the width of the baffles.
1
𝐷𝑏 = × 𝐷𝑡 (B.16)
12
1
𝑂𝑏 = × 𝐷𝑡 (B.17)
72
There were two options either have a flat vessel bottom or a dished bottom. The flat bottoms
cause dead spots in the corner of the vessel due to a rapid change in direction, this can lead to
accumulation of bacterial cells and they will not mix with the rest of the vessel, thus a dished
bottom will ensure smoother flow hence better mixing. An ellipsoidal bottom of height to width
ratio 1:2 as used in industry and literature [12]. The same dimensions will be used for the top of
the reactor.
The dimensions of the bottoms and tops are shown in detail the mechanical drawing section of
the report where the ratios were used and the volume of the shape was calculated by using
Equation B.18 [17]. Appendix 4.1.7- Vessel Bottoms Calculations shows detailed calculation.
𝜋 × 𝐷𝑡3 (B.18)
𝑉=
24
34
9.6 Mass Transfer
Due to the reaction being anaerobic, no oxygen is in the system thus the oxygen mass transfer
rate does not affect this process. However, there are other issues which could affect the process
due to mass transfer. The main one is the impeller speed and mixing time.
It is important to ensure homogenous mixing within the system and to guarantee a high mass
transfer rate. In this fermenter a Rushton turbine is used this is because:
[9].
1.54𝑉
𝑡𝑚 =
𝐷𝑖3 × 𝑁𝑖 (B.19)
Equation B.19 only works at a high Reynolds number (turbulent flow), Table 9.5 below shows the
mixing time of the system in order to reach homogeneity.
It can be inferred from Table 9.5 the mixing time is a reasonable time for effective mixing of the
fluid by the impeller to sweep the entire reactor. The Reynolds number shows the flow is turbulent
which means mixing will not be poor. These values suggest even distribution hence macromixing.
High mass transfer occurs when there is a good degree of dispersion, as dispersion facilitates
rapid transfer. The value of mixing time fits with what literature says. [9] States “stirred vessels
with working volumes between 1 & 100m 3 have mixing times between about 30 & 120s”.
35
9.7 Heat Transfer
The ideal temperature within the bioreactor is 37oC in order to ensure optimum production of
butanol, thus this temperature needs to be maintained within the reactor for the duration of the
batch. There are three main sources of heating which can heat the fluid throughout the process,
these need to be taken into consideration so the cooling water requirement can be decided thus
maintaining the temperature of the vessel. Sample calculations in this section are illustrated in
4.1.8 – Heat Transfer Calculations.
There are five reactions occurring during the fermentation of glucose using Clostridium
Acetobutyllium, however four of these reactions have a low conversion and are considered
negligible towards energy production/requirements. The main reaction, which has the highest
conversion hence the most heat removal, is the butanol production as shown in Equation B.20.
The heat of reaction for this reaction is calculated using the standard enthalpy of formations
method shown in 4.1.8 – Heat Transfer Calculations.
As can be seen the reaction is exothermic meaning heat needs to be removed from the system
during the fermentation process.
Explained in the reactor sizing section the reactor requires agitation to ensure homogenous
mixing within the reactor. A constant rate of agitation is assumed thus a power input was
calculated to keep the agitator motor running. Due to the Rushton turbine being used, the type of
mixing is rotational this energy is assumed to be converted into heat energy (all of it), this ensures
the worst case is designed. Accordingly, as stated in the agitator power section the input power
is 1.2kW, which is all, converted into heat energy so 1.2kW of heat is produced from the agitation
process.
From the above sections the required heat removal from the system can be calculated however
due to the product poisoning from butanol inhibiting the bacterial cell growth the rate of energy
production throughout the process is not constant. Using the Monod spreadsheet the power can
be calculated at each fermentation time interval, once this has been calculated and assuming
constant agitation power the required heat removal at different times is found and shown in Graph
9.11.
36
100.00
90.00
The cooling jacket must be able to deal with the maximum duty of the system which occurs at the
start at time t=0 which equates to 90kW.
Now knowing the maximum demand of the fermentation vessel the cooling jacket may be
designed and calculation can be done to see if a standard jacket covering the outer part of the
vessel is adequate to remove the 90kW duty. The maximum duty that can be removed from the
system is calculated from Equation B.21 [18].
𝑄 = 𝑈𝐴∆𝑇𝐿𝑀 (B.21)
The overall heat transfer coefficient was found from literature for a standard sized vessel [9]. The
cooling jacket area was assumed to be from the liquid level area. The maximum duty was then
calculated and shown in Table 9.6.
37
9.7.4 Jacket Design
Table 9.6 infers that a standard cooling jacket design is tolerable to control and maintain the
temperature within the reactor vessel. [19] States that the cooling jackets should have a spacing
between the vessel and jacket of about 50-300mm depending on size of vessel. Due to the vessel
being relatively small, the spacing can be about 70mm. The properties of the cooling jacket are
shown below in Table 9.7.
The amount of cooling water required to remove all of the energy from the system can be
calculated using Equation B.23.
𝑄̇
𝑚̇ = (B.23)
𝐶𝑝 (𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛)
The water properties were calculated using Equation B.22, these are shown in
Table 9.8- Properties of the cooling water for within the cooling jacket.
It is important to take into consideration that as the fermenter is running; during the batch time
the rate of energy production changes at different time intervals, hence the required cooling water
rate also changes. Graph 9.12 below illustrates what happens to the required cooling water over
fermentation time.
0.0005
Flow Of Water (m3/s)
0.0004
0.0003
0.0002
0.0001
0
0 10 20 30 40 50
Time (hr)
38
9.8 Costing Evaluation
Cost correlations were used to estimate the equipment costs, the correlations were provided from
[19] in Table 6.6. Equation B.24 was used to calculate the cost in the year 2007.
𝐶𝑒 = 𝑎 + 𝑏𝑆 𝑛 (B.24)
Ce is the cost in the year 2007, S is the size parameter as specified in table 6 for each piece of
equipment, a, b and n are constants. Sample calculation for bio-reactor,
610.1
𝐶𝑜𝑠𝑡 𝐼𝑛 𝑌𝑒𝑎𝑟 2019 = 470000 + [20]509.7 [18]= $560000
Water comes to £0.26/ton [18], mass of cooling water per year was calculated by converting the
volumetric flow in to kg/hr and then multiply by 7700 hours which is hours of operation per year.
Table 9.11 - Cost of utility for main design equipment per year.
Amount of cooling water (kg) Amount of cooling water (ton) Cost Per Year (£)
55440000 55440 14500
39
10 Alternative Reactor Design
An alternative to the biofuel method to produce butanol is the chemical synthesis of butanol from
ethanol using the Guerbet Reaction mechanism. The ABE fermentation is the industrialized way
to synthesize butanol however, this alternative is taken into consideration. The design is based
on a patent [22]. Several assumptions were made in this process design.
The reactor type chosen for this process is a catalytic packed bed reactor the advantages of this
are:
Achievement of a high conversion per mass of catalyst compared with other catalytic
reactors.
Easy to construct.
Low capital costs and maintenance costs when compared with fixed bed reactor and
fluidized bed reactor.
This type of reactor is more effective at high temperatures.
Disadvantages of using a packed bed is that the control of temperature may be difficult as
undesirable thermal gradients may occur.
[23]
The reaction is called the Guerbet reaction where ethanol is introduced to pressurized hydrogen
and butanol and water is produced. The net reaction for this process is shown in Equation B.24:
𝐻2
2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 (𝐶𝐻2 )3 𝑂𝐻 + 𝐻2 𝑂 (B.24)
The overall reaction is more complex and has more side products forming which form part of the
mass balance and are taken into consideration within this design. Figure 10.1 shows the full
mechanism [22].
40
10.3 Catalyst Selection/Properties
The patent suggests the most efficient catalyst to be used within this process is ruthenium (III)
acetylacetonate (Ru(acac)3). Spherical pellets of this Ru(acac)3 are used so spherical packing
within the packed bed reactor are also used. With this catalyst, the reaction has a butanol
selectivity of approximately 90% and a yield of 20%. The major side products include:
2-Ethylbutanol
2-Ethylhexanol
N-hexanol
N-octanol
[22].
The conditions of the reaction occur at 180 oC and 5Mpa. Before sizing the reactor the kinetics
need to be found for modelling the reaction the sections below do this.
The first step is to determine the rate constant (k) at the conditions of the reaction. [27] Suggests
𝑚𝑜𝑙
the rate constant for this reaction at a temperature of 1800C is1.8 × 10−5 .
ℎ𝑟𝑚3
Due to literature showing the rate constant at the conditions that the reactor will be at it means
the Arrhenius equation does not need to be used to extrapolate data to find a different rate
constant.
41
10.4.2 Derive Rate Equation
From Equation B.24 it can be seen the reaction is of second order thus the rate equation can be
described as:
Thus Overall,
2
−𝑟𝑎 = ƞ𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝐴0 (1 − 𝑥𝐴 )2 (B.26)
The value of reactor rate constant 𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 can be found using the rate constant of the reaction
K1.
Firstly, the vapor pressure of ethanol needs to be calculated at 180oC, this was done using the
Antoine equation. The Antoine constants were found from [28].
Component A B C
Ethanol 4.92531 1432.526 -61.819
𝐵
𝑃 𝑠𝑎𝑡 = 10𝐴−𝑇+𝐶 (B.27)
1432.526
𝑃 𝑠𝑎𝑡 = 104.92531−453−61.819 = 18.3 𝑏𝑎𝑟 = 𝟏. 𝟖𝟑 × 𝟏𝟎𝟔 𝑷𝒂
To calculate the molar density and hence mass density of ethanol for the reactant the ideal gas
equation is used.
𝑛 𝑃
=
𝑉 𝑅𝑇 (B.28)
42
Now the volumetric flow of the reactant was calculated using the density calculated in Equation
B.29 and the mass flow of reactant from the mass balance.
𝑚
𝑉𝐸𝑡ℎ𝑎𝑛𝑜𝑙 = (B.29)
𝜌
77.7/3600 𝑚3
𝑉𝐸𝑡ℎ𝑎𝑛𝑜𝑙 = = 0.00096
22.4 𝑠
77.7
𝑚𝑜𝑙
The molar flow of ethanol entering the reactor is 3600 = 0.00047 . Thus the initial concentration
46 𝑠
of the reactant ethanol can be calculated using equation B.30.
𝑛𝐴0
𝐶𝐴0 =
𝑉𝑒𝑡ℎ𝑎𝑛𝑜𝑙 (B.30)
To find the catalyst rate constant using K1 it was just a matter of unit conversions as shown in the
range of calculations below.
𝑚𝑜𝑙 1 𝑚3 1 𝑚3
𝑘1 = 1.8 × 10−5 × × = 𝑚3 𝑔𝑎𝑠/𝑘𝑔ℎ𝑟
ℎ𝑟𝑚3 𝜌𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑘𝑔 𝐶𝐴0 𝑚𝑜𝑙 (B.31)
𝑚𝑜𝑙 1 𝑚3 1 𝑚3
= 1.8 × 10−5 × × = 1.64 × 10−6 𝑚3 𝑔𝑎𝑠/𝑘𝑔ℎ𝑟
ℎ𝑟𝑚3 22.4 𝑘𝑔 0.49 𝑚𝑜𝑙
43
10.5 Reactor Sizing
With most of the data now obtained, it is possible to size the reactor a reminder of the data
obtained is shown in
Table 10.4.
R 0.00015 m
∈ 0.391 -
Deff 𝐷𝐴𝐵 × ∅ × 𝜎 m2/s
𝜏
𝝆𝒄𝒂𝒕 1350 kg/m3
The effective diffusivity is required in order to calculate the Thiele modulus, which will be used to
calculate the required size of the packed bed reactor. Mass transfer can limit the catalytic reaction
thus the diffusivity coefficients are required in order to take into account the mass transfer
limitations.
𝐷𝑉 × ∅ × 𝜎
𝐷𝑒𝑓𝑓 =
𝜏 (B.33)
1 1 0.5
1.013 × 10−7 × 𝑇 1.75 × ( + )
𝑀𝐴 𝑀𝐵 (B.34)
𝐷𝑉 =
𝑃(∑ 𝑉𝑖𝑎 )1/3 + (∑ 𝑉𝑖𝑏 )1/3 )
The special diffusion volume coefficients (Vi) are obtained from [29].
1 1
1.013 × 10−7 × 4531.75 × ( + )0.5 𝑚2
𝐷𝑉 = 46 2 = 1.93 × 10−5
1/3
30𝑏𝑎𝑟(∑ 50.36) + (∑ 7.07) )1/3 𝑠
The constriction factor (𝜎) & tortuosity (𝜏) are standard values obtained from literature [30]. So
using Equation B.10:
44
10.5.2 Calculation of Thiele Modulus & Internal Effectiveness Factor
𝑅 𝐾𝑐𝑎𝑡
∅= ×√ (B.35)
3 𝐷𝑒𝑓𝑓
0.003 9.01
∅= ×√ = 𝟎. 𝟏𝟏
3 2.01 × 10−6
From Figure 10.2 And the Thiele modulus above the internal effectiveness factor (ƞ) is shown to
be 1.
The reactor designed will be based on a plug flow reactor due to it being able to achieve a high
conversion in a small volume. The calculation of the volume is shown below. An assumption of
99% conversion is assumed from the patent [22].
𝑥𝐴𝐹 0.99
𝜏 𝑑𝑥𝑎 𝑑𝑥𝑎
= ∫ =∫ 2
𝐶𝐴0 0 −𝑟𝑎 0 ƞ𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝐴0 (1 − 𝑥𝐴 )2 (B.36)
0.99
1
𝜏ƞ𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝐴0 = ∫ 𝑑
0 (1 − 𝑥𝐴 )2 𝑥𝑎
Integrating,
1 0.99 1 1
𝜏ƞ𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝐴0 = [ ]0 = ([ − ]) = 99
1 − 𝑥𝐴 1 − 0.99 1 − 0
99 99 𝑉𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝜏= = = 37000 =
ƞ𝐾𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐶𝐴0 1 × 5.54 × 0.00049 𝑉′
45
10.5.4 Mass of Catalyst Required
The volume of catalyst within the reactor and the weight required can be obtained using the
reactor volume; this is done using Equation B.37 & B.38 [31].
𝑉𝑟𝑒𝑎𝑐𝑡𝑜𝑟 (B.39)
𝜏=
𝑉′
35.01
= = 𝟑𝟕𝟎𝟎𝟎 𝒔𝒆𝒄𝒐𝒏𝒅𝒔 = 10 hrs.
0.00096
For the packed bed reactor a cylindrical reactor is chosen with a diameter of 2m being sensible
chosen for this type of size of reactor.
𝑉𝑐𝑦𝑙𝑖𝑛𝑑𝑒𝑟 = 𝜋 × 𝑟 2 × ℎ (B.40)
35.01
ℎ= = 𝟏𝟏. 𝟏𝒎
𝜋 × 12
𝑑 = 𝟐𝑚
46
10.5.7 Vessel Wall Thickness
In order for the vessel to withstand the high pressure and temperature, the vessel wall thickness
needs to be calculated to ensure it is a thickness for which there is safe operation. Using Equation
B.41 [32].
𝑃𝑖 𝐷𝑖
𝑡= (B.41)
2𝜎 − 𝑃𝑖
The internal vessel pressure Pi is in milliPascals as is the diameter, the design stress (𝜎) is given
as 108 N/mm2 in [32].
3 × 2000
𝑡= = 28.2𝑚𝑚
(2 × 108) − 3
To allow for corrosion an extra 4mm is added so the overall thickness of the vessel is 32.2mm.
Domed heads and bottoms are used commonly industry for each end of the cylindrical vessel. A
tori spherical head will be designed as it has high strength and relatively low cost. [29].
𝑃𝑖 × 𝑅𝑐 × 𝐶𝑠
𝑡= (B.42)
2𝜎 + 𝑃𝑖 (𝐶𝑠 − 0.2)
1 𝑅𝑐 1 1.81
𝐶𝑠 = (3 + √ ) = × (3 + √ ) = 1.319
4 𝑅𝑘 4 0.35
3 × 2000 × 1.319
𝑡= = 𝟑𝟔𝒎𝒎
(2 × 108) + 3(1.319 − 0.2)
𝑆𝐹 = 2 × 𝑡 = 2 ∗ 36 = 72𝑚𝑚 = 𝟎. 𝟎𝟕𝟐𝒎
Height h of dished portion
ℎ = 0.25 × 𝐷𝑖 = 0.25 × 2 = 𝟎. 𝟓𝒎
47
10.5.9 Internal Catalyst Arrangement
The diameter of the packed bed catalyst is equal to the diameter of the reactor vessel; the height
of the packed bed can be calculated using Equation B.43 and the volume of the catalyst.
𝑉𝑐𝑎𝑡
ℎ= (B.43)
𝜋 × 𝑟2
21.32
ℎ= = 𝟔. 𝟕𝟗𝒎
𝜋 × 12
The Ergun equation is used to calculate the pressure drop across the reactor.
𝑉𝑠 = 0.008𝑚/𝑠
𝜇 = 0.000103 𝑃𝑎. 𝑠
∆𝑃 = 0.0000423 + 5472𝑃𝑎
48
10.7 Heat Balance
The Guerbet reaction is an exothermic process thus energy will be released within the vessel. It
is required to see how much heat is released thus how much power is required for the cooling
jacket in order to maintain temperature.
Using the standard enthalpies of formation the standard heat of reaction can be calculated whilst
taking into account the stoichiometric coefficient.
The enthalpy of reaction is the enthalpy of formation for the products minus the enthalpy of
formation of the reactants each component is multiplied by its stoichiometric coefficient.
𝒌𝑱
∆𝐻𝑟 = (−327.01 − 285.82) − (2 × −234.7) = −𝟏𝟒𝟑. 𝟒𝟑
𝒎𝒐𝒍
𝑚𝑜𝑙 𝑀𝐽 𝒌𝑱
𝑄𝑅 = ∆𝐻𝑟 × 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑏𝑢𝑡𝑎𝑛𝑜𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = −(−143.43) × 8.1 = 1161.8 = 𝟑𝟐𝟑
ℎ𝑟 ℎ𝑟 𝒔
𝐻𝑖 = ∑ 𝑛𝑖 𝐶𝑝 𝑑𝑇 (B.45)
The sum of the enthalpy product and inlet stream is shown in the stream energy balance section
of this report. Equation B.23 was used to calculate the enthalpy for each component.
323 kJ/s of heat is released in the reactor. A cooling method will be required.
49
10.8 Alternative Design Mass & Energy Balance
Packed Bed
Catalytic Reactor
Ethanol 60.8 kg/hr
Water 3.4 kg/hr
180oC Butanol 12.5 kg/hr
Ethanol 77.7 kg/hr
Hydrogen 0.5 kg/hr
3Mpa 2Ethyl-Butanol 0.2 kg/hr
2Ethyl-Hexanol 0.3 kg/hr
N-Hexanol 0.2 kg/hr
Enthalpy In = 405 kJ/s N-Octanol 0.3 kg/hr
Hydrogen 0.5 kg/hr
Actual Mass/Energy balance full table can be found in Appendix 6 – Alternative Design Mass Balance/Appendix 7 – Alternative Design Stream Energy
Balance.
50
10.9 Costing Evaluation of Alternative Reactor
The method of costing was done using the same method as the Costing Evaluation section of the
report as stated in [18].
The assumption in this calculation was that the vessel was a pressure vessel thus S was
measured as shell mass calculated using:
𝑆 = 𝜋𝐷𝐶 𝐿𝐶 𝑡𝑤 𝜌 (B.46)
All the parameters in Equation B.46 have been calculated, ρ is the density of the metal which was
found to be 7860 kg/m 3 [37].
Table 10.8- Operating cost of electricity per year for main design.
The batch time is 11 hours, there is 1 week downtime so 357 days operation which once multiplied
by batch time which is 11 hours gives 5355 hours per year operation.
51
10.10 Conclusion of Alternative Design
As can be seen from the design, it is clear that the alternative design catalytic packed bed reactor
has potential due to its smaller volume and faster batch time. However, the bio-chemical route is
still preferred as it is more sustainable, renewable and overall it is a reduced cost in operating.
Table 10.9 shows the problems with the alternative design and why the bioreactor is more
advantageous.
Table 10.9 - Discussion of alternative design compared with main bioreactor design.
Parameter Discussion
52
11 Pump CP23.10 Design
This section shows the design of the centrifugal pump on stream 23.10 which is designed to
increase the pressure from 101.325kPa to 111.458kPa. Some assumptions made in this process
design were that the fluid properties are those of water due to the fluid being composed of 99-
wt% water. Also due to the fluids being generally incompressible, it was assumed that the
temperature stays constant throughout. To account for the worst-case scenario the capacity of
design will be 20% above the normal working rate. The specification sheet can be found in Pump
CP23.15 Specification Sheet.
Minimum Temperature 27 oC
Maximum Temperature 38 oC
To start with, the suction side (S23.15) and discharge side (S23.20) need to be designed in order
to see the work done etc. The length of the pipes on the suction and head side were found from
the GAPs guidelines which provides recommended pipe lengths dependent on the equipment’s
on either side of the plant [38]. The illustration is provided in Appendix 8 – GAPS Guideline for
Pipe Length.
53
11.1.1 Static/Discharge Head
The static head will be the height of the reactor and the discharge head will be the same with an
extra elevation of 1m.
The pipe diameter was calculated by using the formula for economic pipe diameter where the line
size of the pipe needs to be specified.
Schedule 40 pipes are the standard at low pressures; from the diameter, it is clear a 2-inch pipe
size is best.
[39]
𝜋 × 𝑑2 𝜋 × 0.042 (B.48)
𝐶𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎 = = = 0.0013𝑚2
4 4
𝑄 0.00046 𝑚
𝑢= = = 0.354 (B.49)
𝐴 0.0013 𝑠
From table 5.2 in [18] the absolute roughness for a steel pipe is 0.046 mm.
54
11.1.5 Miscellaneous Losses
The pipe length is not accurate as there is a valve on the discharge side of the pump this needs
to be taken into account. The velocity heads method in [18] was used to account for this.
𝑢2 0.3542 (B.50)
= = 0.0064𝑚 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑
2𝑔 2 × 9.81
Thus head loss,
TOTAL 6.1024 m
The friction factor needs to be calculated in order to account for pressure losses due to friction.
𝒇 = 𝟎. 𝟎𝟎𝟐𝟕𝟓
55
11.2 Pump Power Requirement
Now the pipeline parameters are found the pump can be designed, the section below finds the
different parameters for the pump.
In order to see if a pump is even required, the power needs to be calculated if it is negative then
a pump is required if not then a pump is not required.
∆𝑃 ∆𝑃𝑓
𝑊 = 𝑔∆𝑧 + − (B.54)
𝜌 𝜌
∆𝑃 ∆𝑃𝑓
𝐻𝑒𝑎𝑑 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = −∆𝑧 − + (B.55)
𝜌𝑔 𝜌𝑔
Ƞ = 0.47
𝑊×𝑚
𝑃𝑜𝑤𝑒𝑟 = (B.56)
Ƞ
20.21 × 0.46
𝑃𝑜𝑤𝑒𝑟 = = 𝟏𝟗. 𝟕𝟖 𝑾
0.47
56
11.3 Pump Suction Side
The suction side of the pump is designed in this section, in the sample, calculations the normal
parameters were used to calculate each section in the specification sheet the maximum
parameters were also considered. The overall aim is to calculate the net positive suction head
(NPSH) and make sure it is less than the NPSH available this is to prevent cavitation. Vapour
pressure of water is known to be 5.63kPa [40].
𝜌𝑢 2 (B.58)
𝐸𝑛𝑡𝑟𝑎𝑛𝑐𝑒 𝐿𝑜𝑠𝑠 =
2
1000 × 0.3542
𝐸𝑛𝑡𝑟𝑎𝑛𝑐𝑒 𝐿𝑜𝑠𝑠 = ÷ 1000 = 𝟎. 𝟎𝟔𝟑 𝒌𝑷𝒂
2
11.3.5 NPSH
𝑃 𝑃𝑓 𝑃𝑣
𝑁𝑃𝑆𝐻 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 = +𝐻− − (B.60)
𝜌𝑔 𝜌𝑔 𝜌𝑔
𝑆𝑃−𝑃𝑣 168200−5630
𝑁𝑃𝑆𝐻 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = = = 𝟏𝟔. 𝟓𝟕𝒎
𝜌𝑔 1000×9.81
57
11.4 Pump Discharge Side
In the discharge side, the length is different, the line loss pressure will different, and however the
valves and equipment pressures need to be taken into consideration. The flows, velocity, and
friction are all the same as the suction side.
The specification sheet will show all the data calculated for the pump.
58
11.5 Pump Costing
The method of costing was done using the same method as the Costing Evaluation section of the
report as stated in [18].
59
12 Overall Utilities & Overall Costing
In this section of the design the only utility required is the one for the fermenters BR20.20 and
BR21.20. The utility for this was discussed in the Cooling Water Requirement section and was
costed in Utility Cost section of the report. A summary is detailed in Table 12.1.
Table 12.1- Summary of utility details for this section of the process.
Utility Type Load on Utility Cost Per Year £ Utility Flow Inlet Temp Outlet
(kW) (m3/s) (oC) Temp (oC)
Cooling Water 138 77,500 0.002 15 30
The costing for each of the equipment designed was calculated in its own section so the pump
and bioreactors costing and utility/power costs were calculated in the costing section for each
design. However, in this section of the design as shown in Figure 5.1 there is also a storage tank
and centrifuge (ST10, CEN23.10).
Table 12.2 - Cost of all the equipment within this design section.
For the equipment not designed the parameters required for costing were estimated with a simple
sizing procedure. The power of the centrifuge was found from [41] and costed using the same
procedure as Utility Cost section of bioreactor design.
TOTAL 105,000
60
13 AutoCAD Reactor Drawings
61
13.1 Impeller Dimensions
62
14 Materials of Construction
The bioreactors must remain in sterile conditions inside; there are certain considerations, which
need to be taken in order to choose a good material first they need to offer adequate structural
support for the vessel and then, withstand sterilization process without decaying.
Normally, when lab scale fermentations, glass is normally used as it has many advantages:
Due to the process being on an industrial scale, glass is not viable due to safety reasons, stainless
steel is more advantageous in industry due to:
Strength is more.
Ability to be shaped.
Ease of maintenance and fixture if any problems.
Contains chromium, which prevents corrosion.
Less chance of rusting and forming weak spots compared with other steels.
Type 304 stainless steel is the “most versatile and widely used stainless steel” [42], thus is the
chosen material of construction for the bioreactors due its high composition of chromium
henceforth less corrosion. The composition of Type 304 stainless steel is given in Table 14.1.
Element % Present
Chromium (Cr) 17.50-19.50
Nickel (Ni) 8.00-10.50
Manganese (Mn) 0.0-2.00
Silicon (Si) 0.0-1.00
Carbon (C) 0.0-0.07
Phosphorous (P) 0.0-0.05
Sulphur (S) 0.0-0.03
Nitrogen (N) 0.0-0.11
Iron (Fe) Balance
With the conditions of the fermenter as specified in the design, it is clear from Table 14.2 that it is
mild conditions for the stainless steel.
Property Value
Tensile Strength (MPa) 500-700
Hardness (HB) 215
Proof Stress (MPa) 190
63
15 Downtime Period
There is a downtown period of 10 hours between each batch, within this downtime period several
processes occur to make sure the tank is ready for the next fermentation batch. In the downtime
it is of paramount importance to make sure everything is done properly to ensure the next batch
can proceed without any problems. This section will discuss what occurs during the downtime
period.
15.1 Cleaning
The bioreactor has designated cleaning spray machines at the top of the bioreactor which will
spray caustic once the products have left the bioreactor this will sterilize the tank, the time taken
to spray will be ten minutes per bioreactor. For the next 6 hours the cleaning people will be able
to enter the bio reactor and clean it with aseptic spray.
It is also important that the valves on the feed of the bioreactor are also cleaned properly to
prevent contamination, as valves can leak fluid which can cause feed to become poisoned. Thus
it is vital the part where valves can leak is cleaned and sealed to prevent further leaks in the next
batch.
15.2 Maintenance
The rest of the 4 hours left are used for maintenance checks this includes:
Check the mechanical parts of the bioreactor are fitted properly e.g. no screws loose.
64
16 Bioreactor Specification Sheet
Table 16.1 - Fermenter specification sheet.
Bioreactor BR20.20/21.20
Identification
Item BR20.20/21.20
No. required 2
Temperature (oC) 33
Pressure (atm) 1
Design Data
Fermentation Time hr 25
Volume Litre 30000
Diameter m 2
Height m 6
Thickness m 0.093
Growth rate hr-1 0.29
Working Volume Litre 27000
Head/Bottom - 2:1
Height of Head/Bottom m 0.5
Material Stainless Steel Type 304
Jacket, Heat Exchanger, Agitator, Support, Lugs, Stress relieve & baffles included.
65
17 Safety & Control Systems
Figure 17.1 - P&ID for storage tank containing feed for bioreactor 1/3.
66
Figure 17.2 - P&ID for fermenter 2/3.
67
Figure 17.3- P&ID for after the fermentation 3/3.
68
17.2 Discussion of Controls
The type of valve used for control is a globe valve. The globe valve has many advantages
including, good shutoff capability, excellent throttling capability, easy to operate and finally if
needed the disc can be removed and valve can be used as a check valve [43]. Control instruments
are vital to ensure safe operation and make sure equipment are operating economically well. This
section discusses the control for each piece of equipment and what it signifies.
This storage tank is where the main feed is put into, the tank contains level alarms in order to
prevent over spilling which can result in loss of production. There is also ratio controls for each of
the feed streams before it to ensure the right ratio of feeds are going in which gives the highest
productivity. To ensure there isn’t any over pressurization there is also a pressure control.
The bioreactors have many sensors and controls as it is vital there is no issue as any change in
condition could result in bacteria denaturing. The coolant water flow stream has a temperature
sensor to ensure the bioreactor doesn’t get too hot or too cold. The buffer stream contains a pH
sensor to ensure the fluid is not too alkali or too acidic. There is a flow stream in the antifoam
which will change the flow depending on amount of foam present within the reactor. There is a
pressure control on the gas stream to ensure the pressure within the reactor does not get too
high as reaction is exothermic so explosion could occur. The bacteria composition is controlled
to ensure there is not too much bacteria in the system or if contamination occurs then bacteria
flow needs to stop as it will be wasted and the cost to replace bacteria is very expensive.
The products from fermenter are fed to this storage tank where it is then continuously sent through
the whole process in downstream processing. There is flow control to ensure this continuous
supply. Also the product needs to be stored at certain pressure so there is pressure control to
control the flow into the tank if pressure changes.
Quantity control to ensure the 100% of biomass is removed and none is left in centrifuge.
There is flow control on discharge side to prevent cavitation by altering pump speed. Check valve
also to make sure no back flow as it can damage pump.
69
17.3 HAZOP Analysis on Bioreactor
Section PARAMETER GUIDE WORD CAUSES CONSEQUENCES SAFEGUARDS/ACTIONS RISK BEFORE RISK POST
SAFE GUARD CONTROL
A CV 3 blocked on line S3 Reactor heats up, thus increase in bioreactor temperature due to TT101 alarm should go off which will alert the operator to
(Temperature) reaction being exothermic, therefore bacteria will denature resulting in take action and close the valve to prevent further flow. 15 2
no or very low conversion into butanol. Production is hindered.
B Blockage of CV-20.20/21.20 on line S- Bio reaction does not occur, thus production is lost. Operator will see nothing is happening in the batch process
20.20/21.20 (Main Feed Line) when he opens the valve, also level alarm will go off 6 1
notifying him level is too low.
C No/Less Blockage of CV1 on line S1 (Antifoaming) Same as Section F 6 1
D Blockage of CV-18.15 on line S-18.15 Loss of production. Quantity alarm should go off showing composition of the
(Bacteria Feed Stream) bacteria is too less which will notify operator to unblock the 6 1
valve.
E CV 3 fully open on line S3 Increase in amount of cooling water results in bioreactor cooling down TT 101 high alarm should go off alerting someone to close
(Temperature) too much, revenue lost due to unwanted increased use of utility. the valve if it doesn’t automatically close. 6 1
Flow Production of butanol will be lost.
F Fully open of CV-18.10 on line S-18.10 Reactor will overfill causing spillages of important bacteria and nutrients Quantity alarm should go off showing composition of the 6 1
(Bacteria Feed Stream) which can cause contamination and hence loss of production. bacteria is too much which will notify operator to close the
valve.
G More Fully open of CV-20.20/21.20 on line S- Overfilling of the bioreactor. Revenue loss due to waste of glucose and Level alarm should go of indicating operator to close the 10 2
20.20/21.20 (Main Feed Line) nutrients. Loss of production as feed is lost and spilled. feed stream valve.
H Fully open of CV1 on line S1 Overfilling of the bioreactor. Loss of revenue due to waste of antifoam. QI-101 high alarm should go off notifying the operator to fix
(Antifoaming) Too much antifoam can cause issues in the production of the gases and the valve. 10 2
hence the butanol.
J More CV 3 blocked on line S3 Same as Section A 15 2
(Temperature)
K Temperature Less CV 3 fully open on line S3 Same as Section E 6 1
(Temperature)
L Pressure More Same as Section A Pressure control valve on off gas stream to relieve pressure. 6 1
Failure of AI101/102 Impurities is the biggest issue in the bio reaction as it can cause 2 indicators means there is double detection should one
M Impurities More contamination of products even causing the product not being formed indicator fail as contamination is most important factor to 5 2
and depending on the type of contamination it has different safety measure in this process.
hazards.
N Blockage of CV-20.20/21.20 on line S- Overfilling of the bioreactor. QI101 high alarm should go off notifying the operator to
Level More 20.20/21.20 (Main Feed Line) close the valve. 10 2
Risk key for before and after safeguard can be found in Appendix 9 – Risk Matrix Key for HAZOP.
70
17.4 Plant Safety & Hygiene
Table 17.2 - Potential safety issues and solutions in and around the plant.
71
18 Sustainability
Sustainability consists of three main aspects, these are social, economic and environmental. It is
important the people of the plant adhere to ensure the plant is as sustainable as possible by
recognising the financial, social and environmental risks correctly.
The plant will be located in fife, near the North Sea thus there are people living in residential areas
nearby. It is paramount to have their support in operating a plant there. As mentioned in the group
report the ten pillars of sustainability will be followed ensuring the people will be happy particularly
with wages and job prospects for them. It is planned that the people of fife will be considered first
for work depending on their qualifications. The people of Fife will be educated on what the plant
is about emphasising that the product is a pharmaceutical which is intended to help many ill
people this will help us get their support more. Fair wages, fair working hours are all agendas
which will be followed [44].
Economically, the process is sustainable as it is renewable so not wasting infinite resources. Also
there are many by products which are formed and will be sold on. Acetone and ethanol are
produced which can be sold on to relevant companies as they have many uses in industry. Money
is also saved by the fact that a chemical reactor wasn’t used as it would have had higher operating
costs. Transport of the feed and product will not be as expensive as they are readily available in
this country. The materials of construction are stainless steel hence equipment have a long
lifespan.
The ABE fermentation is environmentally friendly as no major dangerous gases or products are
formed in the process. Greenhouse gases are produced (Carbon dioxide), which contributes to
pollution and hence global warming. The carbon dioxide produced here will be transported to a
carbon capture facility hence it will not be released into the environment thus not contributing to
pollution. There will be wastewater treatment within the plant thus the wastewater produced in
this process will be cleaned and used again elsewhere in the plant.
72
19 Start-up & Shutdown
The start-up and shutdown of a plant is extremely important and if not done properly can result in
dangerous outcomes. It should be completed by experienced engineers or even external
companies that are experts in start-up/shutdown of plants.
19.1 Start-up
Before the process is started, the pipelines and units need to be physically inspected to ensure
there are not any cracks in the lines, loos flanges or screws and open valves. The following steps
need to be done:
Table 19.1 - Timeline of startup of plant.
[45]
19.2 Shutdown
Units are required to be cleaned regularly after batches and maintenance checks also. Whilst one
reactor is operating the other reactor can be shut by closing the valve in the feed line before it. It
is also important to check all the product has left the reactor at the exit stream, after this the valve
in the exit streams of each unit can be closed. Time must be given to cool the reactors and other
equipment’s down.
At the end of the unit’s life, the materials of the units can be separated then recycled or sold to
other companies in need of it.
73
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ANTOINE. [Accessed 20 02 2019].
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Pensylvannia, Pensylvannia, 2014.
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6.htm. [Accessed 26 12 2018].
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[47] D. W. Green and M. Z.Southard, Perrys Chemical Engineeris Handbook, 9th ed., New
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76
21 Appendices
21.1 Appendix 1 – Metabolism of Biomass
[5]
77
21.2 Appendix 2 – Mass Balance Table per Batch
Table 21.1 - Mass balance table.
Components Molar Mass Density S20.20+S21.20 S20.30+S21.30 S22.10 S23.20 Centrifuge Bottom
kg/kmol kg/m3 kg kg kg kg kg
H2 2 0.08988 - 374.7563 - - -
78
21.3 Appendix 3 – Stream Energy Balance Table per Batch
Table 21.2 - Stream energy balance table.
kj/kgK
Bacteria 0.00 - - - - -
Nutrients 0.00 - - - - -
Ethylhexanol 2.44 - - - - -
H2 14.40 - 43172 - - -
Temp 33 33 33 33 33
79
21.4 Appendix 4 – Fermenter Calculations
The modelling of the growth of clostridium acetobutyllium bacteria and production of butanol in
the system was done using Microsoft excel as recommended by Professor Gerrard Markx. A
screen shot of the spreadsheet is shown below.
The conditions at the start were from the mass balance, the Monod constant 𝐾𝑠 was found from
literature. The value of maximum specific growth rate 𝜇𝑚𝑎𝑥 was also found from literature and
changed when product poisoning was involved from the mass balance data. The growth rates
could have been more accurate by using experimental data however, this was not readily
available so mathematical modelling of growth rate was used. Finally, the yield coefficients
𝑌𝑥𝑠 (substrate to cells) and 𝑌𝑝𝑥 (bacteria to product) were obtained from the mass balance.
80
21.5 – Sample Calculations
A concentration sample of bacteria cells of 50.2 gL-1 will be used in this sample calculation. To
work out the time required with butanol poisoning (without is the same method but 𝜇 is kept
constant), Equation B.5 is used to calculate the concentration of butanol at the growth of
50.2gL-1:
𝑃 = 𝑌𝑝𝑥 × 𝑑𝑥
𝑌𝑝𝑥 is the yield of product to bacteria cells so is calculated from the mass balance by mass of
butanol divided by mass of bacteria. Equation B.4 is used to calculate the inhibited growth rate:
𝑃
𝜇 = 𝜇𝑚 (1 − )
𝑃𝑚
0.098
𝜇 = 0.29 × (1 − ) = 𝟎. 𝟐𝟗 𝒉𝒓−𝟏
20.6
𝑌𝑥𝑠 × 𝐾𝑠 𝑥 𝑌𝑥𝑠 × 𝐾𝑠 𝑥0 𝑥
{ } ln [ ]−{ } ln [ ] + ln [ ]
(𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 (𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 − 𝑥 (𝑌𝑥𝑠 × 𝑆0 ) + 𝑥0 𝑌𝑥𝑠 × 𝑆0 𝑥0
=𝑡
𝜇𝑚
The productivity was calculated the concentration of butanol was divided by the overall time
including down time:
0.098
𝑃= = 0.005 𝑔𝐿−1 ℎ𝑟 −1
0.015 + 10
81
21.5.1 – Mass Balance/Energy Balance Calculations
For the mass balance, the products were known due to the ratios being given in literature. The
conversions for each of the 5 reactions were also found from literature. From this, the amount of
glucose required was found then amount of water and bacteria required was found from using
ratios given in a journal article. The product ratio of ABE was 6:3:1 as industrially known. The
energy balance was calculated using the mass balance and the specific heat capacities.
21.5.2 – Surface Area to Volume Ratio for Use in Determining Aspect Ratio & Number of
Reactors
We know the overall required reactor volume is 60m3. If two reactors are chosen then each
reactor is 30m3 and using the aspect ratio of three thus:
𝜋 × 𝑑2
𝑉𝑟 = ×ℎ
4
ℎ = 3𝑑
Combine
3 4 × 𝑉𝑟
𝑑= √
3𝜋
d = 2m
h = 3 × 2 = 6m
𝑆𝐴 59
∴ = = 2.02 𝑚−1
𝑉 30
The same procedure was used to calculate the surface to volume ratio for aspect ratio graph for
number of reactors except number of reactors were fixed and aspect ratio changed.
2.3
𝐷𝐴 = = 0.77m
3
2
𝑁= = 0.83 𝑠 −1
𝜋 × 0.77
82
To calculate power requirement:
Again, for aspect ratio of three, the height is 7m and diameter is 2m, however this is height and
diameter of vessel the height of the liquid is different as 10% was factored in for the gas and
foaming thus height of liquid is:
Height = 6.2m
181325 × 1.2 × 9
𝑡𝑣𝑒𝑠𝑠𝑒𝑙 = = 0.0093𝑚 = 9.3𝑚𝑚
(20000000 × 1) − (0.6 × 181325)
Volume of material:
Data from:
83
21.5.5 – Mixing Time Calculation for Mass Transfer
Before mixing time could be calculated the Reynolds number needed to be found the velocity
from literature is 2m/s and viscosity was assumed viscosity of water at temperature of thirty
degrees, which is 0.0008 Pa.s [46]:
1268.5 × 2 × 0.77
𝑅𝑒 = = 𝟐. 𝟒𝟒 × 𝟏𝟎𝟔
0.0008
Since Reynolds number is above 30000, flow is turbulent, thus Equation B.19 can be used to
determine mixing time.
Using equation B.19, the volume of reactor from the reactor sizing section and the diameter of
the impeller from the impeller section:
1.54 × 29
𝑡𝑚 = = 𝟏𝟏𝟗 𝒔𝒆𝒄𝒐𝒏𝒅𝒔
0.773 × 0.83
In the previous design the vessel was assumed to be just cylindrical, however we have an
ellipsoidal head and bottom plate with a radius to height ratio of 2:1. The dimensions of the
ellipsoidal head and bottom were calculated using the data calculated in the vessel design when
it was assumed to be a cylinder.
2
𝐻𝑒𝑖𝑔ℎ𝑡 = × 0.5 = 0.5𝑚
2
𝜋 × 23
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝑙𝑙𝑖𝑝𝑠𝑜𝑖𝑑𝑎𝑙 𝐻𝑒𝑎𝑑 𝑜𝑟 𝐵𝑜𝑡𝑡𝑜𝑚 = = 1.05𝑚3
24
84
21.5.7 4.1.8 – Heat Transfer Calculations
Enthalpy of formations:
Heat of reaction is equal to the heat of formation of the products minus the reactants while
considering stoichiometry:
𝑘𝐽
∆𝐻𝑅 = ((−286) + (−394 × 2) + (−328)) − (−1275) = −125.9
𝑚𝑜𝑙
Within the Monod spreadsheet the production rate was calculated and converted into kmol/hr by
dividing concentration of butanol by time, to convert this into kmol per hour the production rate
was multiplied by the mass from mass balance then divided by the molecular weight so for point
t = 0.007hr the production rate was 2.59 kmol/hr.
The power required for heat removal was calculated by summation of the various energies so
agitation power and heat required producing butanol so for 0.007 hr.
𝑘𝐽 𝑘𝐽
𝑄 = 0.2 × 53 × 13.1 = 4.98 × 105 = 138
ℎ𝑟 𝑆
The required duty of 90kW is less than the maximum duty of 138kW thus cooling is possible.
85
21.6 Appendix 5 – Alternative Design HYSYS
The alternative design was modelled in Aspen HYSYS, however many values had to be
assumed in HYSYS and a plug flow reactor was used which assumes 100% conversion, some
HYSYS information for the Guerbet reaction are shown below.
HYSYS also assumed no by products were formed and all of ethanol had been used up.
The text file below gives the full HYSYS Report for the alternative design:
86
21.7 Appendix 6 – Alternative Design Mass Balance
kg kg kg/hr kg/hr
87
21.8 Appendix 7 – Alternative Design Stream Energy Balance
88
21.9 Appendix 8 – GAPS Guideline for Pipe Length
[49]
89
21.11 Appendix 10 – Specification Sheets
Line Pressure
Drop
Suction Discharge
90
Vapour 5.63 5.63 kPa
Pressure
NPSH available 16.63 m Discharge 415.33 514. kPa
Pressure 13
NPSH required 16.58 m Suction Pressure 168.26 167. kPa
93
Differential 247.07 346. kPa
Pressure 20
Pump Data
Sketch
91