HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION

Hydrothermal Carbonization of Musa acuminata x balbisiana ABB (Saba) Peels for

Organic Dye Adsorption

A Research Paper

Presented to

CNHS-Science Department

Rosga, Ma. Krizandra J

Timbulan, Jahnelle

Velasco, Rafaela Andrea dR.

G10-Ladislao Diwa

August 2017
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 2

TABLE OF CONTENTS

Page

Title Page 1

Table of contents 2

List of Figures 3

Abstract 4

Chapter

1. INTRODUCTION

Background of the Study 5

Statement of the Problem 7

Significance of the Study 8

Scope and Limitations of the Study 8

2. RESEARCH METHODOLOGY

Preparation of Materials 10

Production of Hydrochar 10

Adsorption Experiment 13

3. RESULTS and DISCUSSION

4. SUMMARY, CONCLUSION AND RECOMMENDATION

5. REFERENCES

6. ACKNOWLEDGEMENT
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 3

LIST OF FIGURES

Figure Page

1. Fresh and sun dried saba peels 10

2. Production of Hydrochar 10

3. Centrifugation of Hydrochar Solution 11

4. Saba hydrochar 11

5. Adsorption Experiment

6. Summary of Procedures
HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 4

ABSTRACT
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 5

INTRODUCTION

Background of the Study

Cavite City is a hook-shaped peninsula that juts into Manila Bay and ends in two tips-

Cavite Point and Sangley Point. It is bounded by Bacoor Bay to the southeast and

Cañacao bay that formed between Sangley Point and Cavite Point. It is a source of

income to local fishermen. However, the quality of water around these bays is slowly

declining because of the organic and inorganic pollutants that filled up the bodies of

water. Some of these organic pollutants came from the local market and are caused by the

inappropriate disposal of market wastes and some are waste materials from different

households. Different methods are used in order to reduce these pollutants, and one of

the effective ways is through the process of adsorption.

Charcoal is a black porous form of carbon produced by heating wood, bone or other

organic materials in little or no air. It is widely used as fuel, for drawing and in water

filters because of its high adsorbing property. There are different kinds of charcoal that

could also be used for adsorption. A well-known kind is the activated charcoal.

According to Encyclopedia Britannica, Activated charcoal is charcoal that has been

treated with oxygen to open up millions of tiny pores between the carbon atoms It is

widely used to adsorb odorous or coloured substances from gases or liquids. Activation

can be carried by physical activation, wherein the precursor is first carbonized in an inert

atmosphere then activated using oxidizing agents such as steam or CO2 (Rashidi and

Yusup, 2015); whereas during chemical activation, carbonization and activation occur in

a single step by carrying out thermal decomposition of the raw material

 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 6

impregnated with chemical agent, such as zinc chloride (ZnCl2) (Tay et al., 2001),

potassium hydroxide (KOH) (Mao et al., 2015) or phosphoric acid (H3PO4) (Belgacem

et al., 20) as cited by Puccini (2017). Another kind would be bio char. It is a solid mass of

carbon made from biomass that is heated in the absence of oxygen. Another is hydro

char, the solid product of hydrothermal carbonization. It has higher hydrogen – carbon

ratios than bio char. In this process, solid biomass matters are subjected to high

temperature and pressure in the presence of water and then converted into charcoal.

According to Elaigwu, as cited by Kambo (2015), hydro chars usually have very low

surface area and porosity compared to the bio chars; however, due to the presence of

oxygen-rich functional groups on its surface, the adsorption capacity of hydro char has

been reported to be considerably higher than that observed for the bio char.

According to Dr. Tobias Wittman ( n.d ), hydrothermal carbonization of organic

matter is a thermo-chemical process for the conversion of solid organic matter at elevated

temperature and pressure accompanied by water. The coal fraction can easily be

separated and varies significantly in its chemical and physical properties from the starting

material. Through the hydrothermal carbonization reaction, water, carbon dioxide and

other compounds are sliced form the organic matter. Otherwise, the macromolecular

structure of the original biomass will be largely to completely destroy. The product of

HTC is called “hydro char” that is a solid enriched in carbon and with chemical

characteristics comparable to those of fossil coals. After the HTC process, hydrochar is

wet in state and in the form of slurry. In certain ways, hydrochar is superior to biochar for

its reduced alkali and alkaline earth, and heavy metal content, and a higher heating value
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 7

at the same operating process temperature. Carbohydrate – based materials such as fruit

peelings are can be used to produce hydrochar.

Banana is a tropical fruit that grows abundantly in the Philippines. Different varieties

of bananas are widely sold in the local market, and one of them is the saba. It is a triploid

(ABB) hybrid of the seeded banana Musa balbisiana and Musa acuminata. According to

Anhwange (2009), banana peel contains different substances such as protein, crude lipid,

carbohydrates, and crude fiber at varying percentage composition. The result of this study

showed that it contained high amount of carbohydrate, 59.00 %. Because of the high

carbohydrate content of banana peel, the researcher will use banana peel in making

hydrochar for organic dye adsorption.

Statement of the Problem

This study primarily aims to determine the capacity of the hydrochar from saba

(Musa acuminata x balbisiana ABB) fruit peel in adsorbing organic dyes. This study

intends to:

1. create hydrochar from saba (Musa acuminata x balbisiana ABB) fruit peel

using domestic pressure cooker

2. determine the concentration of the three (3) organic dyes: methylene blue,

and methyl orange after using saba (Musa acuminata x balbisiana AAB)

fruit peelings hydrochar.

3. determine the size of the created hydrochar using Scanning electron

Microscope
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 8

Significance of the Study

The study will create a hydrochar from Saba (Musa accuminata x balbisiana ABB) fruit

peelings that could be significant for the whole community, especially for the

environment. It may also benefit the following:

Household. The created hydrochar can be used to remove stains or dyes in their clothes.

Community. Since the researchers are going to collect banana wastes or banana peels, it

can help clean the environment especially in the local markets where wastes are almost

everywhere. Banana peels are considered as waste but beyond this, banana peels has

other uses and function in removing organic dyes such as methylene blue, and methyl

orange

Future Researchers. This study may serve as the basis of future studies in relation with

the hydrochar. It can also be a reference for other uses of Saba ( Musa accuminata x

balbisiana ABB) and other plant materials.

Scope and Limitation

The primary focus of the study is to determine the adsorptive capacity of the created

hydrochar from saba (Musa acuminate x balbisiana ABB) fruit peel. Only organic dyes

such as methylene blue, and methyl orange will be tested. Other organic dyes are beyond

the scope of the study. The organic dye solutions will be subjected to ultraviolet and

visible spectroscopy ( uv vis ) before and after the treatment of banana peel hydrochar in

order to determine the adsorptive capacity of the created hydrochar. The morphology and

characterization of the hydrochar will be determined through FTIR (Fourier transform

infrared spectroscopy) and SEM (Scanning electron Microscope). The organic dye
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 9

solutions will be prepared by the researchers. Instrumentations such as uv – vis

spectroscopy will be done at DLSU-MNL Chemistry Department, SEM at Katrin Field

Incorporated while FTIR will be conducted at DOST. The study was performed at Cavite

National High School (CNHS) from June to August 2017

 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 10

METHODOLOGY

Preparation of Materials

The researchers gathered all the materials needed to perform and create the product:

150g of Saba banana (Musa acuminata x balbisiana ABB) Peel, distilled water (1000

milliliters), organic dyes: methylene blue and methyl orange, beakers, volumetric flask,

Erlenmeyer flask, and centrifuge. All the materials acquired are within Cavite City

including the banana peels which were collected from Cavite City Public Market and the

tray, beakers, centrifuge and organic dyeswere provided by the school laboratory.

Production of Hydrochar

The researchers adopted the method of Kalderis et. al. (2014) in creating the banana

(Musa acuminata x balbisiana ABB) saba peel hydrochar. Saba banana peels were

collected from the public market in Cavite City. The collected banana peels were washed

thoroughly using distilled water to remove the dirt and impurities. The washed sabapeels

were cut into small pieces and sundried for 24 hours. 150g of dried saba peels were

grinded and mixed at one Liter distilled water. The mixture was subjected at a

temperature of 115 – 120 C and a pressure of 10 - 12 psi using a domestic pressure

cooker for a residence time of 13 hours with an interval of 10 minutes. Distilled water

was added to the mixture to maintain a constant volume of one Liter. The mixture was

centrifuged in order to separate the dark precipitate from the liquid mixture. After

centrifugation, it was recovered by filtration then air dried for 36 hours.

 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 11

Upon the completion of the hydrothermal treatment, the mixture was centrifuged to

separate the dark precipitate from the mixture. The liquid mixture was transferred to

another container leaving the dark precipitate at the bottom. The dark precipitate was

washed with distilled water and then poured into a mesh cloth to recover the solid

precipitate which is the hydrochar product.

(a) (b)

Figure 1: (a) freshly collected saba peels; (b) sun dried saba peels

(a) (b)

Figure 2: Production of saba peel hydrochar: (a) Saba banana peels with distilled water

before the hydrothermal carbonization process; (b) Hydrochar solution after 13 hours of

hydrothermal carbonization process

 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 12

(a) (b)

(c)

Figure 3: Centrifugation process: (a) transferring of saba peel hydrochar solution to the

test tubes of the centrifuge; (b) saba peel hydrochar solution for centrifugation (c)

centrifugation at 3300 ppm for 30 mins

(a) (b)

Figure 4:Saba peel hydrochar in two forms: (a) Saba peel hydrochar in wet or slurry

state / form; (b) black porous state of saba peel hydrochar after air drying
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 13

Adsorption Experiment

Prepare the organic dye solutions, methyl orange and methylene blue with 1000 ppm.

1L of 1000 ppm solution was added to a 100 mL volumetric flask separately. Distilled

water was added to the volumetric flask up to the mark. The banana peel hydrochar was

mixed in a 50 mL Erlenmeyer flask containing the 10ppm dye solution. Leave the

treatment in room temperature for 24 hours. The same procedure was done to methylene

blue. After each sorption experiment, the mixture was transferred to a vial and the

concentration of the two organic dyes will be determined with a uv – vis spectroscopy at

211 nm and a standard curve. Sorption amount will be calculated according to the

difference of methylene blue and methyl orange.

(a) (b)
Figure 5: Organic Dyes: (a) Methylene blue dye; (b) Methyl orange dye

(a) (b) (c) (d)

Figure 6: Organic dye solutions: (a) and (b) MB and MO solution without hydrochar,
respectively; (c) and (d) MB and MO solution with hydrochar
HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 14
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 15

RESULTS AND DISCUSSION

Hydrochar from Musa acuminata x balbisiana (ABB) (Saba) peels.

The hydrochar was obtained by hydrothermal carbonization of Musa acuminata x

balbisiana (ABB) (Saba) peels for 13 hours and then air dried for 36 hrs. Following is the

hydrochar created. (Figure __)

Figure

The Figure above shows the hydrochar produced from Musa acuminatA x

balbisiana ABB (Saba) peels. The hydrochar is in its dark brown color with no scent

Adsorption of Methylene blue and Methyl Orange using the hydrochar

After the production of hydrochar, 0.5 g of the sample was mixed to 50mL of

10ppm methylene blue solution. The same procedure was done to methylene orange.

Figure 6 above shows the two organic dye solutions prior to the treatment of the saba peel

and during the treatment. And lastly, Figure shows the two organic dye solutions after the

treatment.

Metyhlene blue and the methyl orange solution both has a strong, saturated blue and

orange color respectively before the treatment, as shown in Figure 6 After the 24-hour
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 16

treatment of the banana peel hydrochar, the color of Methylene blue dye solution became

pale and loses its strong color as shown in Figure.

(a) (b)
Figure : Organic dyes after saba peel hydrochar treatment: (a) Methylene blue after
treatment; (b) Methyl orange after treatment.
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 17

SUMMARY, CONCLUSION, AND RECOMMENDATION

The general purpose of the study is to create a hydrochar out of Musa acuminate x

balbisiana ABB (Saba) peels using a domestic pressure cooker for organic dye

adsorption. The saba peels were subjected to a high temperature and high pressure using

a domestic pressure cooker in order to create a hydrochar solution. After the HTC

process, the created saba peel hydrochar was centrifuged to separate the dark precipitate

from the mixture. The dark precipitate was then washed with distilled water and poured

into a mesh cloth and air dried for 36 hours. The saba peel hydrochar was mixed with 50

mL 10 ppm methyl orange dye solution for 24 hours. Same procedure was done to

methylene blue. After the 24 – hour treatment , both solution loses its strong color and

became pale.

As a summary, the result of the study suggests that it is possible to create

hydrochar from Musa acuminata x balbisiana ABB (Saba) peels and the use of domestic

pressure cooker as an alternative method for HTC process. The results showed that the

created saba peel hydrochar is an effective medium for organic dye adsorption.

This study recommends further studies which include the following:

 Use the created saba peel hydrochar for adsorption of natural dyes to determine its

effectivity as an adsorbing medium;

 Use other carbohydrate-based material in creating hydrochar for dye adsorption;

 Use of different method for HTC process; and

 Determine the hydrochar yield

 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 18

REFERENCES

Anhwange, B., Ugye, J. T., Nyiatagher, T.D. (2009) Chemical Composition of Musa

sepientum (banana) peels. Retrieved June 18, 2017 from

https://www.researchgate.net/publication/233760453_Chemical_Composition_of_Mus

a_sepientum_Banana_Peels

Arellano, O. et al. (2016) Hydrothermal Carbonization of Corncob and Characterization

of the Obtained Hydrochar. Retrieved July 18, 2017 from

https://www.researchgate.net/publication/304345631_Hydrothermal_Carbonization_H

TC_of_Corncob_and_Characterization_of_the_Obtained_Hydrochar

Kalderis, D. et al. (June 2014). Characterization of hydrochars produced by hydrothermal

carbonization of rice husk. Retrieved June 18, 2017 from

http://www.solid-earth.net/5/477/2014/se-5-477-2014.pdf

Kambo, H. S., and Dutta A. (2015) A comparative review of biochar and hydrochar in

terms of production, physico-chemical properties and applications. Retrieved June

18, 2017 from

http://www.sciencedirect.com/science/article/pii/S136403211500060X

Laber, C.H. et al. (2016) Domestic Pressure Cooker as Inexpensive Hydrothermal Vessel:

Demonstrated Utility for Eco-friendly Synthesis of Non-toxic Carbon Dots.

Retrieved July 18, 2017 from

https://www.researchgate.net/publication/299424764_Domestic_Pressure_Cooker_a

s_Inexpensive_Hydrothermal_Vessel_Demonstrated_Utility_for_Eco-

friendly_Synthesis_of_Non-toxic_Carbon_Dots
 HTC OF SABA PEELS FOR ORGANIC DYE ADSORPTION 19

N.A (2017) What is Biochar? Retrieved June 18, 2017 from http://www.biochar-

international.org/biochar

Puccini, M. et al. (2017) Activated Carbon from Hydrochar Produced by Hydrothermal

Carbonization of Wastes. Retrieved from July 10, 2017.

http://www.aidic.it/icheap13/program/200puccini.pdf

Titirici Group (n.d) Hydrothermal Carbonization. Retrieved June 18,2017 from

https://titiricigroup.org/research/hydrothermal-carbonization/

Wittman, T. (n.d). Hydrothermal Carbonization. Retrieved June 18, 2017 from

http://www.htc-labs.org/en/hydrothermal-carbonisation/

http://www.springer.com/978-3-319-33890-3
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Acknowledgement

We would like to express our gratitude to the people who supported and helped us in

order to make this research paper possible.

First and foremost, this research paper won’t be possible without the help of our

Almighty God. We truly thank Him for giving us the wisdom to complete this study.

To our ever supportive family, we thank them for supporting us financially, and

showed their love and care from the beginning until the end.

We would also like to acknowledge our research teacher, Mrs. Cherry Leen Marquez

for assisting and guiding us. We also thank her for giving us her full trust.

Also, we would like to send our deepest gratitude to Mr. Aldrin Bonto, for imparting

us his knowledge, for sharing his expertise and encouraging us to pursue this project.

We are also grateful to our friends and classmates who assisted and contributed to

finish this study.

We will always appreciate all your help and support. Again, thank you very much.