Synthesis and Identification of Furfural from Cocoa Pod Husk

(CPH) with Pretreatment Process before Hydrolysis Process

Lisa Aulia Lubis, Amir Husnin, Maulida

Department of Chemical Engineering, Universitas Sumatera Utara, Jl. Almamater Kampus USU, Medan, North Sumatera,

Indonesia

Keywords: Biorefinery, Cocoa Pod Husk, Furfural, Pretreatment, Process Optimization

Abstract : Furfural is an organic compound that can be produced from agricultural waste such as oats, corn cobs, rice

husks, bagasse, and sawdust. Cocoa pod husk is a renewable raw material for furfural manufacturing.

Furfural synthesis from cocoa pod husk is an attempt to create value-added of cocoa pod husk. Furfural

synthesis was based on the hydrolysis of pentosan into xylose which was then dehydrated to furfural. Cocoa

pod husk waste contains pectin and lignin which can interfere hydolysis process. It make use pretreatment

process to reduce pectin and lignin. Percentages pectin, lignin and pentosan before pretreatment

were 9.2 ± 0.5,

14.7% and 38.9% and after pretreatment to be 1.7 ± 0.01, 4.13% and 37.5%. In this study

used hydrolysis temperature variations (110, 120, 130 and 140)

C and hydrolysis time (10, 20, 30, 40 and

50) minutes. The optimum conditions obtained at temperature and time of hydrolysis of 130

C and 30

minutes, weight furfural obtained was 6.728 g/7,50g pentosan or 6,728g/20g of cocoa pod husk and yield

furfural obtained was 82.2%. This shows that cocoa pod husk has a high potential to be converted into

furfural and can be used as a renewable raw material in furfural manufacturing. Furfural identified by color

test using aniline acetate 1:1, Gas Cromatographic Mass Spectrometry (GCMS) and infra-

spectrophotometer (FTIR).

1 INTRODUCTION

In the last decade there has been climate change and

depletion of fossil fuels which were the main

reasons humans use renewable raw materials such as

lignocellulose residues to produce fuel. In recent

years many researchers have devoted themselves to

the exploration and development of efficient

production for furfural.Many studies using

renewable raw materials for furfural production are

one of them biomass agricultural wastes (Liu, 2018).

Raw material from biomass has several

advantages, They are biomass as renewable source,

hemicellulose in biomass is high, furfural production

can be produced more than 98%, besides it was easy

to obtain, low cost and it was not pollute

environment (Machad, 2016).

Cocoa is one of the plants that produce biomass

of agricultural waste. Cocoa (Theobroma cacao L) is

the nameof fruit fromcocoa tree. Cocoa fruit consists

of seeds and shell or test. The biggest waste

component in cocoa is cocoa pod husk (CPH). The

cocoa pod husk are 70% -75% of the total cocoa

fruit (Daud, 2014). The high production made from

cocoa beans increases the world's cocoa pod husk

waste in almost 700,000 tons in year (Okiyama,

2017).

The reason of this study using cocoa pod husk as

a raw material for produce furfural is renewable,

high amount of hemicellulose, increase demand for

chemicals produce from agricultural waste, and the

growing awareness of the environment. It has

potential as a raw material for produce furfural. The

composition of CPH can be show in Table 1.

Table 1: Chemical Composition of Cocoa Pod Husk

(CPH)

Komponen

* Percentage

(%)

**(%) *** (%)

Cellulose 28.78 35.40 44.69

Hemicellulose 8.70 37.00 11.15

Lignin 42.90 14.70 34.82

Ash 1.87 12.30 7.40

Sumber : *(Syam, 2000)

**(Daud, 2014)

***(Nazir, 2016)

160

Lubis, L., Husin, A. and Maulida, .

Synthesis and Identiﬁcation of Furfural from Cocoa Pod Husk (CPH) with Pretreatment Process before Hydrolysis Process.

DOI: 10.5220/0008863801600164

In Proceedings of the 1st International Conference on Chemical Science and Technology Innovation (ICOCSTI 2019), pages 160-164

ISBN: 978-989-758-415-2

There were three step to produce furfural. First

step waspetreatment, second step was hydrolysis

process from pentoseto xylose and last step was

dehydrated xylose to furfural. The stoichiometric

equation for reaction is as below (Branca, 2012):

→ C

+ 3H

O (1)

Biomass as raw materials in the process of

produce chemicals was often carried out

pretreatment process to reduce the presence of

compounds such as lignin, pectin and other

compounds it can disturb hydrolysis process,

pretreatment was done first. In study conducted by

(Mao, 2012) using raw material corn cobs the

pretreatment process was not carried out, so the

maximum yield was produced only 67.89% due to

the presence of other compounds that inhibited the

hydrolysis process, while the study was conducted

(Liu, 2018) using a pretreatment process produces a

maximum yield of 73%. It shown the pretreatment

process can increase yield furfural.

In this study used a renewable raw materials. It

was cocoa pod husk with pretreatment process for

removal of pectin and lignin. Cocoa pod husk was a

renewable raw material, therefor researchers also do

variation of temperature and reaction time in the

hydrolysis process, to find out the optimum

conditions and the highest furfural yield that can be

produced by cocoa pod husk.

2 MATERIALS AND METHODS

2.1 Raw Material

The raw material for cocoa pod husk was obtained

from cocoa fruit trees in Naga Timbul Village,

Indonesia.

The cocoa pod husk from farm was collected,

washed, dried at 110

C until the water content is ±

10%, after dried CPH was cut into sizes up to 1cm

(Nazir, 2016).

2.2 Process Pretreatment

2.2.1 Pectin Extraction

Extraction of pectin done for elimination of pectin in

cocoa pod husk. It used a citric acid. 100g of sample

were added 1:25 citric acid solvent, extraction time

of 3 hours, pH 2.5 at 95

C (Nazir, 2016).

2.2.2 Reduction of Lignin

Samples from the pectin extraction process added

4% NaOH solution with a solid-liquid ratio of 1:25

was autoclaved at 121

C for 100 minutes, filtered

and washed until netral pH, dried at 105

C for 6

hours (Nazir, 2016).

2.3 Furfural Production

As 20g of sample was added H

3M (Stein,

2011) with a ratio of 1:15 (Kaur, 2011), added NaCl

20g reacted to batch reactor with variationsreaction

temperature (110, 120, 130 and 140)

C (Peleteir,

2016) and reaction time (10, 20, 30, 40 and 50)

minutes. Hydrolysis and dehydration results of vapor

phase-shaped samples contained in furfural

compounds. The reactions that occur can be show in

Figure 1 (Branca, 2012).

Figure 1: Hydrolysis reaction of Pentosan to Xylose and

Dehydration to Furfural (Branca, 2012)

2.4 Analysis

Analysis of the composition of cellulosa,

hemicellulose and lignin with chesson methode and

pentosan in cocoa pod husk before and after

pretreatment was carried out by gravimetri (Griffin,

1972). Furfural analysis obtained by color test of

aniline acetate 1:1, GC-2010 Serial No.

020504702444 Shimidzu Corp) and FTIR Boil

SHIMIDZU at laboratorium. Department Chemical

Engineering. Lhoksumawe State Polytechnic.

3 RESULTS AND DISCUSSION

3.1 Raw Material Composition

The composition of lignin, cellulose, hemicellulose,

pentose and pectin, before and after pretreatment

show in Table 2: In these results it show that the

composition of lignin was reduced to 10.57% after

the pretreatment process. Pentosan also reduction of

1.4%. This is because a little pentosan bond also

reacts.

Synthesis and Identiﬁcation of Furfural from Cocoa Pod Husk (CPH) with Pretreatment Process before Hydrolysis Process

161

Table 2: Results of Analysis Composition Cocoa Pod

Husk

Component

Before

Pretreatmen

After

Pretreatmen

Lignin 14.81% 4.13%

Hemicellulose 42.10% 40.30%

- Pentosan 38.91% 37.50%

Cellulose 40.00% 37.31%

Pectin 9.2 ± 0.5 1.7 ± 0.01

Result of composition CPH in this study was

different with other researcher. It was show in Tabel

1. This is due to differences in nutrients in the soil in

each region.

3.2 Effect of Time and Temperature to

Yield of Furfural.

In the process of produced furfural reaction time and

temperature greatly affect furfural yield. The effect

of the reaction time and temperature on furfural

yield show in Figure 2.

(1)

Figure 2: Effect of Time and Temperature to Yield of

Furfural.

The results of this study indicate the highest

yield value at 130

C with a time of 30 minutes of

82.20%. From these data it show at the reaction time

of 10 to 30 minutes the resulting furfural yield

increases, while at the reaction time of 40-50

minutes the resulting furfural yield decreases. This

was because the longer reaction was carried out, the

more side products are formed and can degrade

furfural (Peleteiro, 2016). The by-products formed

are 2-Furancarboxaldehyde, 5-methyl, the side

product data obtained from the results of analysis

with Gas Cromatographic Mass Spectrometry

(GCMS) conducted by researchers. Furfural yield

also increased from 110

C - 130

C and decreased at

140

C. Further demonstrating that thereaction

selectivity can be conveniently tuned by adjusting

thetemperature of the reaction. Reversely, an

increase of the reaction temperature to 140

lowered the yield of furfural, mostly due to its

degradation or condensation (Liu, 2014).

3.3 Analysis of Aniline Acetate

In this study the color test of the product by using

aniline acetate (1:1) to identify the presence or

absence of furfural compounds in the products. The

results of this color test showed a positive presence

of furfural compounds in the product of hydrolysis,

color was change to be red when aniline acetate

added to product.

3.4 Analysis with FTIR and GCMS

After testing with aniline acetate which stated the

presence of furfural, furfural test was carried out

using Fourier Transform Infra Red (FTIR) and

GCMS. FTIR test can be show in Figure 3.

Figure 3: Furfural Results by Using FTIR Simidzu.

The IR spectrum (Figure: 3) shows a very strong

absorptionC = O (1600 - 1700 cm

-1

). sample

obtained a very strong wave number absorption peak

that is equal to 1647.21 cm

-1

. This absorption shows

a very significant functional group (C = O). Internal

hydrogen bonding which occurs in conjugated

unsaturated aldehydes (Ambalkar et al, 2017).

Absorption peak of 2445.74 cm

-1

approaching

the presence of C-H aldehyde (2800 - 2860cm

-1

The presence of an aromatic C = C bond is shown by

the appearance of stretching vibrations C = C

aromatic (1475 - 1600cm

-1

) in the area of about

1415.75cm

-1

nearing the presence of the cluster. The

broad peaks observed at vibrations of 3400 to 2400

-1

from the sample showed wave absorption peaks

of 3429.43 cm

-1

and 2445.74 cm

-1

, which indicated

that the aldehyde bond of the absorption complex

showed aldehyde stretching. If the sample has an

ester - O - peak, C = C peak will be observed at

ICOCSTI 2019 - International Conference on Chemical Science and Technology Innovation

162

1685 cm

-1

to 1660 cm

-1

(Ong, 2007), but the sample

does not show the same absorption. can be show in

Table 3.

Table 3: Furfural Vibration

Vibration Furfural

Standard

1. Streching aldehyde complex 3429.43

2. Stretching C-H aldehyde 2445.74

3. Stretching C=O aldehyde 1647.21

4. Stretching C=C aromatic 1415.75

5. Stretching C- aldehyde 1249.87

6. Stretching C-O-C 1041.56

Based on the furfural standard vibration value it

can be concluded that the compound produced from

the hydrolysis of cocoa pod huskwas furfural

because it shows spectra which are almost identical

to the standard furfural vibration. Based on the

furfural standard vibration value it can be concluded

that the compound produced from the hydrolysis of

cocoa fruit skin is furfural because it shows spectra

that are identificationof furfural. Further furfural can

be identified with GCMS. The results of GCMS

identification can be show in Figure 3.

Figure 3: Furfural Results using GCMS Simidzu.

The analysis use GC-2010 Serial No.

020504702444 Shimidzu Corp) strengthens that

hydrolysis compounds are furfural. The furfural

compound for the process with pretreatment was

shown at peak 3, retention time 7,629, area

119881925% area 92.65%.

4 CONCLUSIONS

The conclusion of this study is furfural can be

produced using renewable raw materials. It is cocoa

pod husk. The pretreatment process can reduce

lignin until 10.57% and pentosan until 1.4%.

Pentosan and lignin found in cocoa pod husk after

pretreatment process was 4.13% and 37.5%. The

optimum conditions obtained in the hydrolysis

process of cocoa pod husk with a pretreatment

process and dehydration process attemperature

130

C and reaction time of 30 minutes produced a

yield of 82.02% obtained from 6.725g / 7.05g

pentose.

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