CHAPTER 1 INTRODUCTION

1.1 Background of the Study

The energy needs of the developed world are currently over-dependent on the utilization

of finite mineral resources. While renewable-power technologies, such as wind and photovoltaics,

may have major roles in the future for the production of electricity, provision must still be made

for the supply of industrial chemicals and motor fuels that are currently produced predominately

from oil. In fact, of the approximately 170 chemical compounds produced annually in the US in

volumes exceeding 4.5x106 kg, 98% are derived from oil and natural gas. The vast majority of

modern synthetic products are also derived from oil. Emerging bio-refinery technologies offer a

sustainable alternative through the utilization of carbohydrates, the most abundant organic

chemicals on the surface of the earth. In recent years, increasing the supply of bio-based products

has gained importance as a step towards improving environmental issues by reducing the use of

fossil fuel. The sugar industry has large amounts of biomass products suitable for conversion into

fuels and chemicals in a biorefinery context where the objective, similar to petroleum refineries,

is to supplement the manufacture of large amounts of low value products with higher value

products for greater financial viability.1

Lignocellulosic materials are the most abundant renewable resources. Over the last decade,

there has been a growing interest in the potential of lignocellulosic biomass as an alternative for

pertroleum resources; this is how because of its abundance as a feed stock and its carbon neutrality.

Due to the development in chemical technology and biotechnology, it is possible to convert

lignocellulosic materials into such platform chemical as ethanol, succinic acids, fumaric, furfural,

and many others at commercial scale in the near future.2

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 Furfural is clear, colorless, motile liquid with a characteristic almond-benzaldehyde

odor.7 Furfural is a natural precursor to furan based chemicals and has the potential to become a

major renewable platform chemical for the production of biochemical and biofuels. Recently,

furfural, the sleeping beauty of bio-renewable chemical has gained a renewed attention. Furfural

is consumed by the chemical industry as an intermediate product in synthesizing chemical products

such as nylons, lubricants and solvents, adhesives, medicines and plastics. It is produced mainly

by acid hydrolysis of cellulose or hemicellulose materials using acid solutions (usually mineral

acids) to break down the polysaccharides into sugars.8 Furfural is derived from the hemicellulose

fraction of lignocellulosic biomass.The importance of furfural and its derivatives has increased

due to its very wide applications and this has made it imperative for the search for cheap, renewable

and always available feedstock for the production of furfural.9 Biomass feedstocks for Furfural

production includes corncobs, rice hulls, bagasse, cottonseed hulls, wheat straw, peanut shells and

many others.

In the year 2000, steady price starts to increase due to shortage of corncobs in China,

growth of Chinese domestic demand, and Indian market increasing. Furfural has been projected to

grow at a substantial rate from the actual 300 kton/year due to demand of green and bio-based

products. One Mton/year is easily achievable in 2020.10 Current furfural processes are based on

cooking of biomass in acid conditions with continuous stripping (Furfural recovered as 6%

solution in water). Energy intensive production is from 15 to 50 ton of high pressure steam per ton

of Furfural are used. Total yields are around 60% of the theoretical yield.11

Cacao is a well-adapted agro-forestry plantation crop grown in hot, rainy climates. Its

cultivation is concerned between 0 and 20 degrees north and south of the Equator sometimes called

the the Cacao Belt. Although it is mainly known as principal ingredient of chocolate, there are

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actually other products derived from cacao beans: cocoa liquor, cocoa butter, cocoa cake and cocoa

powder.3 For each metric ton of cacao beans harvested, nearly 10 metric tons of wastes (pods, pulp,

etc.) are created. In the past, the waste was often kept in the plantation and used as organic fertilizer

or mulch. Such waste can also be used as mosquito breeding grounds and can be responsible for

the spread of diseases to humans as well.4 Based on the study of Adeyi, Oladayo (2010), Cocoa

Pods have approximately 35.36% hemicellulose content making it as a potential source of Furfural.

This study using discarded by-product of cacao (Cacao pod husk and the part holding the

seeds) as a potential source of furfural would open a new way to solve issues regarding

economical and supply stability of furfural. Waste products are used in order to address the

problems regarding waste disposal and health hazards. Furthermore, furfural percent yield per kg

of biomass, economical cost for production and environmental effects are also to be evaluated.

1.2 Statement of the Problem

The main problem of the study is to determine the optimum parameters to obtain the highest

percent yield of furfural from Cacao residues.

Specifically, it attempts to answer the following questions:

1. What is the highest yield of Furfural obtained from the acid hydrolysis of Cacao

Biomass?

2. What are the effects of the following parameters on the percent yield of furfural?

a. Concentration of acid catalysts used

b. Amount of salt

c. Residence time

3. In terms of the following parameters, at what optimum conditions will have the

highest percent yield of furfural?

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 a. Concentration of acid catalyst used

b. Amount of salt

c. Residence Time

1.3 Objective of the Study

The main objective of this study is to find an alternative source of furfural through the

utilization of organic biomass such as Cacao residues.

Specifically this study aims to:

1. To obtain the highest Furfural yield from the acid hydrolysis of Cacao Biomass.

2. Determine the effects of the following parameters on the yield of Furfural.

a. Concentration of the acid catalysts used

b. Concentration of Salt used

c. Residence Time

3. Identify the optimum conditions that will yield the highest percentage of Furfural in

terms of the following variables.

a. Concentration of the acid catalyst used

b. Concentration of Salt Used

c. Residence Time

1.4 Scope and Limitations

The main focus of this study is to determine the optimum parameters e.g., concentrations of

acid catalysts used, pH, and contact time during hydrolysis in obtaining the highest yield of furfural

from Cacao biomass. Other parameters such as effect of temperature, and condition of the biomass

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(ripe or unripe) were not included in the study. Response Surface Methodology was used for the

optimization of operating conditions of the experiments.

The study will be true for the production of furfural from Cacao biomass only. The gathered

results may vary from different sources of furfural and different catalysts used during hydrolysis.

The findings will only be true for the acid catalyzed hydrolysis of Avocado and Cacao residues for

furfural production only. Other methods for furfural extraction such as biomass pyrolysis will not

be used. The study will not also cover energy requirement analysis and minimization.

1.5 Significance of the Study

This study could be an alternative source of furfural and potentially will produce higher

percent yield of furfural compared to the already established sources nowadays. Also, the use of

biomass from Cacao residues as raw materials could be more economical and efficient because of

its availability in our country. This study will also be a solution to the scarcity of raw materials for

furfural production.

This study is also significant to the Government especially the Department of Energy (DOE)

because this study will help develop and promote the use of furfural that can be used as an

alternative precursor for biodiesel production. The Bicol University especially the Chemical

Engineering Department will also benefit because this study will serve as a reference and

assistance to the professors to teach the students about the use of local biomass such as Cacao

residues as source of furfural that is very important in energy industry. Lastly, this research study

will be much of help to the future researchers as their reference to their related literature and studies

and provide information to those who will conduct studies related to the present research.

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 CHAPTER 2 REVIEW OF RELATED LITERATURE AND STUDIES

2.1 Related Literature

2.1.1 Furfural and its Derivatives

Furfural is a heterocyclic aldehyde of the compound furan with the CHO group

in the 2-position. It has the chemical formula C4H3OCHO. Synonyms to furfural include

2-Furaldehyde (IUPAC Name), 2-furanaldehyde, 2-furancarboxaldehyde, formylfuran, 2-

furfural, 2-Furfuraldehyde, Furaldehyde, furan-2-carbaldehyde and Furfuraldehyde.

Figure 2-1 Chemical Structure of Furfural

Furfural is a colorless motile liquid with an almond-like odor that quickly darkens

when exposed to air. This compound is denser than water and considered to be water

soluble. It may be toxic by ingestion, inhalation or skin absorption.1 Other physical and

chemical data of furfural are are shown in table 2-1. Excellent furfural physical properties

make it a great selective extractant that can be used in aromatics removal from lubricant

oils improving relationship between viscosity and temperature, aromatics removal from

diesel to improve ignition properties, cross-linking in polymers and use as fungicide.2

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 Table 2-1 Physical and Chemical Data for Furfural 3

In addition to attractive thermosetting properties, physical strength, and corrosion

resistance furfural is a natural precursor to a range of furan-based chemicals and solvents.

Figure 2-2 outlines some of these potential chemical products from furfural which have

high value applications. Furfural and its derivatives have been widely applied as resins,

transportation fuels, insecticides, drugs, fungicides, nematicides, lubricants, gasoline

additives, bio-plastics, flavor enhancers and also for wood modification and book

preservation.

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 Figure 2-2 Conversion of furfural into several high value added chemicals 3

2.1.2 Lignocellulosic Biomass

Lignocellulosic biomass including agricultural and forestry residues is

uniquely suited for large-scale production of renewable fuels and chemicals with the

potential for minimal environmental impact when properly managed.4 Biomass residues

constitute a potential source for production of chemicals such as ethanol, reducing sugars

and furfural using enzyme or acid-catalyzed hydrolysis. Figure 2-3 outlines a diverse range

of potential co-products that could be made from lignocellulosic biomass in addition to

furfural.

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 Figure 2-3 Conversion of sugars, lignin, and protein in lignocellulosic biomass for the
integrated production of fuels, chemicals, materials,heat,power, food, and feed.4
The cell walls in plant materials are made up primarily of four polymeric structures

that are identified by their solubility: pectins that are soluble in water and dilute alkali,

hemicelluloses which can be solubilized with concentrated alkali, cellulose and lignin that

are insoluble in alkali.5 Pectins are composed of long chains of galacturonic acid, arabinose,

and galactose, while hemicelluloses are made up of pentosans or polymers of xylose,

arabinose, rhamnose, and other sugars. Pentosan is one of the important fibre component

of non-starch polysaccharides called hemi-cellulose.6 On the other hand, cellulose is made

up of long chains of glucose units.

All pentosans containing fibrous material could in theory be used as raw material

for furfural production; however, industrial production of furfural requires a minimum

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 content of 18-20%. of pentosans.7 Only about one third of the pentosans from raw biomass

can be converted into furfural by means of existing production processes. Pentosans are

five carbon polysaccharides contained in the hemicellulose fraction of lignocellulosic

biomass and are primarily composed of complex heteromorphous structures of

predominantly xylan (C5) and lesser amounts of arabinan (C5), glucan (C6), mannan (C6),

galactan (C6), acetic acid, and uronic acids. Table 2-2 outlines the approximate pentosan

content of several plants and agricultural residues potentially suitable for furfural

production.

Table 2-2 Pentosan content of plants and agricultural residues 4

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 2.1.3 Furfural Applications and Products Insight

Major application segments for furfural solvent include petroleum refining,

agricultural formulations, paints & coatings, and pharmaceuticals. Globally, petroleum

refining occupied the largest market share among all applications. It is particularly used in

lubricating oils and butadiene extraction in petroleum refineries and accounted for over

57% of the overall volume in 2014. Increasing demand for bio-based solvents in numerous

drug formulations, medicinal intermediates and even for cleaning medical devices &

equipment is likely to boost product demand in this sector. Pharmaceuticals are very likely

to emerge as another fast growing segment with CAGR of 17.2%. Other niche segments

are increasingly utilizing furfural solvents owing to its low toxicity, high compatibility &

heat resistance, and biodegradability. The growth of major end-use industries in emerging

economies such as China, India & Brazil, coupled with increasing sustainability concerns

is likely to drive product demand in numerous applications.[3]

Figure 2-4 U.S. furfural solvent market revenue by application, 2012-2022, (USD Million)

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 2.1.4 Global Furfural Market Industry Insights

Global furfural solvent market size was USD 59.9 million in 2014. The industry is

characterized by rising preference for biodegradable solvents in petroleum refining &

butadiene extraction applications. Technological advancements have paved the way for

innovative solvents produced from renewable agricultural by-products such as furfural,

which in turn has generated higher demand for non-toxic, low VOC (volatile organic

compound) content products in several end-use industries. The introduction of furfural

solvents into agricultural formulations has revolutionized pesticides, fungicides, herbicides

and other synthetic chemical compounds, replacing environmentally detrimental products

and boosting consumer safety and health as well. These solvents have also found their way

into other applications including paints & coatings, pharmaceuticals, textiles, resins and

metals owing to their high compatibility, versatile nature, non-toxic &biodegradable

nature. Furfural by itself is used as a solvent, along with several of its derivatives such as

tetrahydrofuran (THF), methyltetrahydrofuran (MeTHF), tetrahydrofurfuryl alcohol

(THFA) and furfuryl alcohol as well. China is likely to remain the dominant producer and

consumer in solvent applications, owing to tremendous capacity and expanding end-use

industries. However, developed regions such as Europe and North America are also likely

to generate high demand on account of regulatory pressure encouraging the application of

bio-based and renewable chemicals in several industries. Demand for furfural in Asia

Pacific region is expected to grow highest in the forecast years.[1]

2.1.5 Global Furfural Market Dynamics

Globally, demand for furfural is anticipated to grow significantly owing to

increasing demand for green chemical. Other factors driving the demand for furfural

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 includes environmental awareness to renewable alternatives in order to replace fossil

resources and increasing production in developing countries. Raw materials such as agro

products and wastes are widely available in developing countries such as India, China,

Indonesia and Malaysia with a low production cost. This is in turn expected to lead towards

efficient raw material procurement from these countries leading to increasing availability

of furfural across the globe. Demand for furfural in pharmaceutical industry is expected to

witness significant increase in the near future. However, inefficient technological

advancement and lack of production process framework, restrain the furfural market

globally. Furfural being renewable in nature is anticipated to witness increased adoption

among various end use industries. Also, development of efficient and new technologies is

a key factor leading to create furfural product possibilities in chemical industry.[2]

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 2.1.6 Cacao

Cacao (Theobroma Cacao) is an important agricultural and economic crop grown

exclusively in tropical areas in three principal producing regions namely Africa, Latin

America and the Caribbean, Asia and Oceania. Synonyms to Cacao include Coco, Cocoa,

Chocolate, Cacahuatl, Tlapalcacauatl, Cacauaxochitle (T. augustifolium). The cacao fruit

or pod is berry-like, ovoid fruit (12 to 30 cm long and 8 to 12 cm wide) with an average

weight of 400 600 g. A cacao fruit usually contains 30 to 40 seeds or beans imbedded in

a white pulp that is sweet when the pods are ripe and fresh. The seeds have a reddish brown

external color and a dark brown interior owing to their rich polyphenolic content. 9 The

aromatic and mucilaginous pulp in which the seeds are contained are composed of spongy

parenchymatous cells that contain a sap rich in carbohydrates. The cacao seeds and pulp

together amount to about one - third to one - half the total weight of the fruit (125 200g).

Figure 2-5 Theobroma Cacao10

The Cacao pod husks are cellulosic materials comprised of lignin, hemicellulose,

and cellulose. Hemicellulose as the source of Furfural makes Cacao biomass as a

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 potential raw material for Furfural production. From the table below, the Cacao pod husk

approximately contains 37% hemicelluloses.

Table 2-3 Chemical Composition of Cassava Peels and Cocoa Pod Husks32

2.1.7 Local Cocoa Industry

The Philippine cocoa industry is presently making a comeback. With production

volumes progressing since 2006, the government undertook policy measures to secure the

industrys progress through R.A. 7900 or the High Value Crop Development Program Act

which lists the intensification of cocoa production as one of its priorities. In addition, local

farmers have increased their interests in the cultivation of cocoa due to the growing demand

from local and international markets. Based on data gathered by the Department of Industry

(DTI) and the Bureau of Customs, the volume of cacao products exported by the country

has increased impressively from 151 metric tons to 1113 metric tons in 2009. In 2008, the

United States and China were the biggest export destinations of Philippine cocoa. By 2009,

the export market also expanded to Europe.40

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 Table 2-4 Cocoa Products Export, In Kilos
Particulars 2007 2008 2009 2010
Quantity Quantity Quantity Quantity
Cocoa Bean, 75000 103000 296235 180659
Whole/Broken,
Raw/Roast
Cocoa Paste 174000 0 0 0
(Liquor)
Cocoa Paste 0 0 118608 40000
(Cocoa Cake)
Cocoa Butter 687209 702,294 542000 720350
Cocoa Powder 226,633 62,935 286255 636320
Cocoa 898,388 547268 516255 589978
Confectionary
Source: Bureau of Agricultural Statistics, 2011 data

For each metric ton of cacao beans harvested, nearly 10 metric tons of wastes (pods,

pulp, etc.) are created. In the past, the waste was often kept in the plantation and used as

organic fertilizer or mulch. This practice, however, favors the propagation of witches

broom and black pod rot unless the materials are properly composted to eliminate diseases.

Such waste can also be used as mosquito breeding grounds and can be responsible for the

spread of disease to humans as well. 41

2.1.8 Furfural Formation via Hydrolysis and Dehydration Reactions

A method of producing furfurals is to hydrolyze the biomass into the constituent

sugars and then dehydrate.11 Both of these reactions are acid catalyzed. Among all the pre-

treatments (dilute) acid hydrolysis is found to be most effective and inexpensive so far.12

In the first step, the pentose chains are hydrolyzed at high temperatures to

monomeric pentoses in aqueous media. The introduction of a water molecule causes the

glycosidic bond to break (hydrolysis) and form xylose or arabinose. This reaction proceeds

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 rapidly and at high yield. The acid catalyzed hydrolysis of polysaccharides comprises the

following steps, (1) protonation of an oxygen link leading to a trivalent oxygen, (2)

heterolytic cleavage of a CO bond to form a carbocation and a hydroxyl group, (3)

reaction of a water molecule with the carbocation, and (4) release of a proton from the

resulting H2O+ with consequent regeneration of the catalyst and yield of a hydroxyl

group.13 The process is repeated until the polysaccharide is fully converted into the

corresponding sugars.

In the second step, pentoses are converted into furfural by the elimination of water.

Three water molecules are released from the respective sugars to form furfural

(dehydration). The transformation of the pentose (C5) sugars is performed through the

sequence of two 1,2-eliminations, followed by 1,4-elimination of water molecules. In the

final step, ring formation occurs facilitated by the tendency of sp2 carbon atoms to form

planar structures. 13 Figure 2-4 shows the reaction pathway for conversion of pentose sugars

to furfural. Considerable losses of furfural occur during the dehydration step. Furfural

generated by cyclization of xylose can be destroyed by the decomposition and

recondensation side reactions leading to reduction in yield.7

Figure 2-6 Reaction pathway for conversion of pentose sugars to furfural 14

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 2.1.9 Processing Technologies

Furfural is a liquid aldehyde with its typical CHO structure. It is produced from the

dehydration of pentoses, typically produced after an initial hydrolysation stage, with acid

catalysts (e.g. sulphuric or phosphoric acid) used to intensify the extraction process.

Furfural has derivatives, including FFA (and its derivative furfuralamine), furoic acid,

furanacrylic acid, furylidene ketones, furan, and tetrahydrofuran (Lichtenthaler 2002).22

Both batch and continuous processing methods are used, but batch processing is

mostly used nowadays. Previous manufacturers of the plant for the continuous process

include Defibrator and Rosenlew (Sweden and Finland), Societa Italiana Furfurola (Italy),

and Escher Wyss (Germany), but these manufacturers now have either stopped production

or scaled back. Batch plants are available from China and possibly in South Africa. The

option to engage in further processing of the lignocellulose residue or use it as an energy

source for the initial furfural process is available in both methods. In each of the methods

there is different emphasis on the yield and recovery of co-products, raw material inputs

and their prices, plant size and capital investment and product quality.15

2.1.9.1 Quaker Oats Process

One of the earliest patents on furfural was that of Isenhour taken out in 1932

and assigned to The Quaker Oats Company (US Patent Office). This process

involves a two-step process, in which the plant raw materials containing pentosans

is mixed with dilute sulphuric acid, with hydrolysing of pentosans to pentoses

(C5H10O5) taking place in the first step (Gravitis, Vedernikov et al. 2000).23

Byproducts are typically used for energy. The pentoses are then cyclohydrated to

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 furfural in the second step, with recovery by steam distillation from a mixture of

acid and undigested biomass.

The foremost problem of this technology is that the first step is 50 times

faster than the second step, leaving the dehydration reaction process as the limiting

factor. Steam costs are very high. There are other problems, including producing

valuable co-products such as bioethanol, and yield recovery limits of 55 per cent

(often less than 35 per cent in practice) due to secondary reactions. Nevertheless,

the subsidiary of Westpro Company in California, is using a variation of the Quaker

Oats technology to produce furfural in China.15

Figure 2-7 Quaker Oats Furfural production process (Zeitsch, 2000)24

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 2.1.9.1.1 Quaker Oats Batch Process

The initial production process was developed by Quaker Oats at their Cedar

Rapids plant. Though Quaker no longer produces furfural, their process where the

feedstock is mixed with sulphuric acid and then reacted in a rotating spherical

digestor (up to 6 m in diameter) at 150 degrees Celsius while being sparged with

superheated steam (Zeitsch, 2000).25 As furfural is formed it is stripped off by the

steam passing through the bed. After 5 hours the process is stopped and the residue

is emptied from the digestors. It consists of the cellulose and lignin fractions and in

many cases is used as fuel. The steam and furfural vapors extracted from the

digestors are condensed and then separated using decanting and distillation. 16

2.1.8.1.2 Quaker Oats Continuous Process

The much later developed continuous process of Escher Wyss or Rosenlew

utilizes the Quaker Oats principle of moistening the raw material particles with

dilute sulphuric acid but utilizes tall-shaft reactors in which the raw material is

introduced from above through a gate in the reactor. The raw material descends in

counterflow from the steam which is introduced from below in a fluid-bed system

and the vapour is discharged. The reactor operates at a temperature of up to 184

degrees Celsius and at a pressure up to 11 atm. The residence time in the reactor is

about half hour.16

2.1.9.2 Hauxia Furfural Technology (Westpro)

In modern furfural plants, large digesters (about 1.5 x 8 m) are used to contain

agricultural residues for conversion. Typically, sulfuric acid is used as the catalyst, and

steam is employed for digester heating and furfural stripping. Due to the corrosiveness of

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 sulfuric acid and the resulting residues, expensive metals are needed for containment, and

the process is not environmentally attractive. Heavy furfural losses are also sustained in

industrial production methods from by-product formation and inefficient recovery due to a

high steam-to-furfural ratio. For Huaxia/Westpro plats currently operating in China, 25-35

tons of steam is consumed per ton of furfural at about a 50% yield of theoretical pentosan

content. Remarkably, these plants are estimated to make $ 1-2 million in profits each year

with the sale of higher value by-products contributing to a significant portion of their

revenues. Thus, integrated production recovers value from a relatively inefficient process.4

2.1.9.3 Mandalika and Runge Batch Process

Mandalika and Runge applied the concept in a batch reactive distillation approach,

in which a continuously heated batch reactor was fitted with a throttle valve that released

the vapour contents over the course of the reaction, allowing the solution to boil under

depressurization and furfural to escape from the reactor as it was produced, resulting in

upwards of 80% yield from wood chips. 4

2.1.9.4 Vedernikovs Process

At the Latvian State Institute of Wood Chemistry, a new process to enhance furfural

production yields and minimize cellulose loss has been put forward as an alternative to the

conventional dilute acid process (Gravitis, Vedernikov et al. 2001).26 The process applies

small aliquots of strong acid catalysts and use of salts to ensure differential catalysis of

hydrolysis and dehydration reactions. The process has been patented from about 10 years

ago, covering differnet production aspects (Vedernikovs 1996; Vedernikovs 1998;

Vedernikovs 1998).27,28,29

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 A process schematic is depicted in Figure 2-8. This development in the hydrolysis

process has solved two notorious problems: the furfural yield has increased from 55%to

75% of the theoretical value and the degree of cellulose degredation has been reduced

fivefold. On the basis of fundamental studies, a new technology including two-step

selective catalysis of wood and other pentosan-containing raw materials has been devised.

This paper considers alternative routes of chemical processing of the cellulose residues into

valuable monomers such as levoglucosan and ethanol as well as integration with other

biomass treatment methods such as steam explosion.12

Figure 2-8 Furfural production process invented by Vedernikovs 26

2.1.9.5 Suprayield Semi-Batch Process

Suprayield was developed from patented technology owned by Karl Zeitsch, a

pioneer in a furfural technology, and it has been taken up by a South African group.

SupraYield claims higher yields (50-70 percent furfural) and lower operating costs. This

technology does not appear to be in commercial use, although Queensland sugar producers

are evaluating a form of it.15

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 Figure 2-9 Acid hydrolysis reactor with Suprayield technology (Zeitsh 2000)24(left), picture of

the plant at Proserpine sugar mill (Prosugar 2009).30

2.1.9.6 Rosenlew Process

The Rosenlew process is similar to the Chinese process in that vertical digestors

are used however they are operated in a continuous fashion. The only Rosenlew plant

operating at the present uses sifted bagasse as the feedstock. The coarse fraction is admitted

to the top of the digestors via a lock hopper and residue is discharged from the bottom

through valves. Steam at 10 bars is fed into the bottom and flows upwards through the

bagasse. Unlike other processes, sulphuric acid is not added to assist furfural production;

instead, organic acids formed by side reactions concentrate within zones of the digestors

and promote furfural production. Steam and furfural leave from the top of the digestors

(Zeitsch, 2000).25

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 2.1.8.7 Biofine Process

The Biofine process is a high temperature, dilute acid-catalysed rapid hydrolysis of

lignocellulosic biomass. The process cost-effectively refines biomass into four principal

products that can be separated and purified for sale: levulinic acid, a versatile platform

chemical; formic acid and furfural, which are commodity chemicals; and a carbonaceous

bio-char consisting of over 60% carbon that can be burned or gasified to produce steam

and electric power.

The process is carried out in a novel, continuous two-stage thermocatalytic reactor

system that enhances the yield of the major product, levulinic acid, to over 70% of

theoretical, making the process commercially viable. Unlike biological processes that can

take several days, the main biomass conversion process is very fast, being complete in

under twenty minutes. Because of its non-biological, thermocatalytic nature, the process is

flexible enough to utilise a wide range of lignocelluloses such as forest residues, waste

paper, paper sludge or straw and other carbohydrate materials such as starch and sugars.

The process consists of five main continuous processing steps to convert raw

lignocellulose to levulinic acid. The raw feedstock is chipped and fed to a pre-treatment to

remove hemicellulose. The high-cellulose residue is then slurried with dilute acid and

pumped into the first-stage plug flow reactor, where the temperature is raised to 210

degrees Celcius. The residence time in the first reactor is 15 seconds.

The first-stage reactor breaks down the cellulose into a mixture of sugars and

hydroxymethylfurfural. This mixture then flashes into a second stage, completely mixed

reactor where the sugars are converted to levulinic and formic acids in a residence time of

fifteen minutes at below 200 degrees C. The insoluble char byproduct produced in the

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 reaction is separated and levulinic acid is then extracted and purified from the clarified

hydrolysate. Formic acid is extracted from the flash vapours and the pentose fraction of the

pre-extracted hemicellulose is converted to furfural by acid-catalysed dehydration.21 A

schematic diagram is shown in Figure 2-10 below.

Figure 2-10 The Biofine process 31

2.1.8.8 MTC Process

A new process is developed at TU Delft for furfural, first aimed at a production

capacity of approximately 10 kton/year, which is near 3% of the current market production

capacity. Figure 10 shows a block scheme in which the main unit operations are shown.

The reaction part is the biomass pretreatment and the hydrolysis reactor producing a

gaseous raw furfural stream and a solid residue. The purification part (extraction with base

added to aqueous phase and toluene is applied as organic phase; furthermore subsequent

distillation section) is where furfural is produced on-spec. Finally, filtration to obtain the

cellulose-lignin solid fraction.12 The schematic diagram of MTC process is shown in Figure

2-11 below.

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 Figure 2-11 MTC Schematic Diagram 21
2.2 Response Surface Methodology

As an important subject in the statistical design of experiments, the Response Surface

Methodology (RSM) is a collection of mathematical and statistical techniques useful for the

modeling and analysis of problems in which a response of interest is influenced by several

variables and the objective is to optimize this response (Montgomery 2005). By careful design of

experiments, the objective is to optimize a response (output variable) which is influenced by

several independent variables (input variables). An experiment is a series of tests, called

runs, in which changes are made in the input variables in order to identify the reasons for

changes in the output response. 33

Originally, RSM was developed to model experimental responses (Box and Draper,

1987), and then migrated into the modelling of numerical experiments. The difference is in the

type of error generated by the response. In physical experiments, inaccuracy can be due, for

example, to measurement errors while, in computer experiments, numerical noise is a result of

incomplete convergence of iterative processes, round-off errors or the discrete representation of

26 | P a g e
continuous physical phenomena (Giunta et al., 1996; van Campen et al., 1990, Toropov et al.,

1996). In RSM, the errors are assumed to be random.

If the response can be defined by a linear function of independent variables, then the

approximating function is a first-order model. The design of response surface models starts with

the estimation of parameters, pure error, and lack of fit. Equation 2.1 represents the general

equation for first-order model (Bradley, 2007).

= 0 + 1 1 + 2 2 + . (, )

If there is a curvature in the response surface, then a higher degree polynomial should be

used. The approximating function with two variables is called a second-order model expressed in

Equation 2.2 (Bradley, 2007)

2 2
= 0 + 1 1 + 2 2 + 11 11 + 22 22 + 12 1 2 + . (, )

An important aspect of RSM is the Design of Experiments (Box and Draper, 1987),

usually abbreviated as DoE. These strategies were originally developed for the model fitting of

physical experiments, but can also be applied to numerical experiments. The objective of DoE is

the selection of the points where the response should be evaluated. In a traditional DoE,

screening experiments are performed in the early stages of the process, when it is likely that

many of the design variables initially considered have little or no effect on the response. The

purpose is to identify the design variables that have large effects for further investigation.33

The application of RSM to design optimization is aimed at reducing the cost of expensive

analysis methods (e.g. finite element method or CFD analysis) and their associated numerical

noise. The problem can be approximated with smooth functions that improve the convergence of

the optimization process because they reduce the effects of noise and they allow for the use of

27 | P a g e
derivative-based algorithms. Venter et al. (1996) have discussed the advantages of using RSM

for design optimization applications.33 The field of response surface methodology consists of the

experimental strategy for exploring the space of the process or independent variables, empirical

statistical modeling to develop an appropriate approximating relationship between the yield and

the process variables, and optimization methods for finding the values of the process variables

that produce desirable values of the response.34

Some stages in the application of RSM as an optimization technique are as follow: (1) the

selection of independent variables of major effects on the system through screening studies and

the delimitation of the experimental region, according to the objective of the study and the

experience of the researcher; (2) the choice of the experimental design and carrying out the

experiments according to the selected experimental matrix; (3) the mathematical-statistical

treatment of the obtained experimental data through the fit of a polynomial function; (4) the

evaluation of models fitness;(5) the verification of the necessity and possibility of performing a

displacement in direction to the optimal region; and (6) obtaining the optimum values for each

studied variable.33

The RSM is important in designing, formulating, developing, and analyzing new

scientific studying and products. It is also efficient in the improvement of existing studies and

products. The most common applications of RSM are in Industrial, Biological and Clinical

Science, Social Science, Food Science, and Physical and Engineering Sciences. 35

2.2.1 Box-Behnken Design

One of the second-order response surface designs is called Box-Behnken Design.

It is an independent quadratic design in that it does not contain an embedded factorial or

28 | P a g e
 fractional factorial design.36 In this design the treatment combinations are at the

midpoints of edges of the process space and at the centre. The use of the BoxBehnken

design is popular in industrial research because it is an economical design and requires

only three levels for each factor where the settings are -1, 0, 1.37 Some BoxBehnken

designs are rotatable, but, in general, this design is not always rotatable. The designs have

a limited capability for orthogonal blocking compared to the central composite designs.

Box-Behnken Design is very useful in the same setting as the central composite

designs. The primary advantage is in addressing the issue of where the experimental

boundaries should be, and in particular to avoid treatment combinations that are extreme.

By extreme, we are thinking of the corner points and the star points, which are extreme

points in terms of region in which we are doing our experiment.38 The Box-Behnken

design avoids all the corner points, and the star points.39

2.3 Related Studies

This section presents articles and studies that have bearing to the present study.

The study of D. Wankasi, T. J. Tarawou, and E. P. Berezi entitled Furfural Production

from the Peels of Ripe English Mango (Mangnifera Indica) Fruits by Acid Catalyzed Hydrolysis

revealed that peels of ripe Mangnifera Indica fruits produce good yield of furfural. The furfural

was produced through acid hydrolysis in the presence of Hydrochloric Acid. The distillates were

tested for furfural using UV/Visible spectrophotometric scanning and IR spectroscopic scanning.

Examination of the resulting spectra as shown in Figure 2-10 revealed broad absorption band in

the region between 350-500nm for the mangnifera indica fruit peel distillate indicating the

29 | P a g e
presence of conjugated unsaturated bonds. This result confirms the presence of furfural as the

broad band may be due to the conjugation in the furfural. Several tests for determination of

physiochemical properties were also done such as density, boiling point, and pH. The UV/Visible

Scans, IR Scans and other tests confirmed the presence of furfural.17

Figure 2-12 UV/Visible scan of mangnifera indica fruit peel distillate17

In the study of Jian Du, Hongling Gao, Jing Guan, Guang Yu, Yuedong Zhang, Haisong

Wang and Xindong Mu titled Furfural Formation from Corn Cobs in a One-Pot Method Catalyzed

by ZSM-5, a one-pot method of furfural production was designed. The production process

involved hydrolysis reaction in the presence of recoverable solid-acid ZSM-5. Catalyst recycling

study showed that ZSM-5 could be repeatedly reused with high catalytic activity.18 Varying

different parameters such as reaction temperature, amount of ZSM-5, residence time and type of

organic solvent used influenced the yield of furfural. The study showed that production of furfural

from corn cobs catalyzed by ZSM-5 is a suitable process.

30 | P a g e
 Another study by V.U.Ambalkar and Mohd I. Talib titled Synthesis of Furfural from

Lignocellulosic Biomass as Agricultural Residues: A Review investigated the potential of rice

husks as source of furfural. The study was carried out in a batch reactor system and the conversion

process involved acid hydrolysis. The hydrolysis process was done in the presence of hydrochloric

acid, sulfuric acid, lactose and mild oxidizing agents such as H2O2 and bromine water. The use of

lactose increased the yield of furfural and the said phenomenon is still under investigation. The

effect of acid type and acid concentration was investigated in the study and part of the result

showed that sulfuric acid gives more yield of furfural. The Fourier Transfer Infrared Spectrometer

(FTIR) was used in the identification of furfural. This study revealed a good yield of the furfural

from rice husk which have been confirmed by the various tests including infrared

spectrophotometric scans.19

In the study of Magdalena Modelska et al. entitled Waste Biomass as a Raw Material for

Furfural Production, transformations of various types of waste biomass into furfural by acidic

hydrolysis were presented. Among the studied groups of biomass were wastes from agro-food

industry, brewing, sugar, mill industry as well as greenery and municipal bio-waste. Furfural in

the form of water solution was obtained by the addition of concentrated H2SO4.20 The obtained

amount of furfural ranged from 0.12 to 4.20% (w/w), based on the dry weight of the sample

subjected to hydrolysis. The yields of furfural estimated for all types of biomass used are presented

in Figure 2-13. The composition of the obtained products was monitored in a quantitative manner

by using HPLC-UV-Vis and GC-FID techniques. This study revealed that depending on the used

biomass, furfural was obtained with different degree of contamination. The condensates resulting

from the H2SO4 catalyzed hydrolysis were tested by GC-MS for the presence of other compounds.

The results of the analysis are shown in Table 2-5.

31 | P a g e
 Figure 2-13 The yields of furfural obtained from various type of waste biomass expressed as a
percentage by mass, based on the dry weight of the raw material 20

32 | P a g e
Table 2-5 The qualitative composition of condensates obtained by GC-MS analysis20

Another similar study by Hayelom Gebre et al. titled Synthesis of Furfural from Bagasse

stated that the yields of furfural depend on the temperature and on the amount of salt used during

the production process. The main raw material for the furfural production was bagasse and some

chemicals were used such as sulfuric acid, sodium chloride and water. Bagasse is a good source of

pentosan and containing about 25 to 27%.16 Sulfuric acid was used as catalyst for the hydrolysis

and dehydration reactions. To dissolve the pentose contained in the biomass material, water was

used. The salt NaCl was used for enhancing furfural selectivity and rate of formation. From the

33 | P a g e
experiment, it was observed that increasing the temperature leads to an increase in furfural yield.

The salt had a positive effect on enhancing the rate of formation of furfural. From the result, the

increasing acidity of the obtained product indicated high yields of furfural.

2.4 Theoretical Framework

The theoretical framework presented below aids the application of scientific analysis to

come up with synthesis and characterization study of furfural (C5H4O2) production using cacao

(Theobroma cacao) Residues via acid-catalytic hydrolysis.

Environmental
Engineering

Organic Acid-Catalytic
Chemistry Characterization and Hydrolysis
Optimization of
Furfural(C5H4O2)
from Cacao
(Theobroma cacao)
Residues Via Acid-
Catalytic Hydrolysis

Optimization Green
Process (RSM) Chemistry

Figure 2 14 Theoretical Paradigm.

34 | P a g e
2.5 Conceptual Framework

The conceptual framework helps in the completion of the study by presenting the outline of
the study and serving as the guide of the researchers.

Narrowing and selection of research topic

Gathering of data and related studies to support the study
Determining the variable parameters to be studied
Input Determining the availability of materials and raw materials to be
used

Collection of Cacao biomass from local source

Experimental design and procedure of furfural synthesis and
extraction
Analysis and optimization of data obtained from variable
Throughout parameters studied
Final experimental runs

Determination of the highest percentage yield of furfural from

Cacao residues
Optimization and analysis of data obtained using response
surface methodology
Output Stating of conclusion and recommendation for future studies

Figure 2 15 Conceptual Paradigm.

2.6 Definition of Terms

Acid Hydrolysis a process in which a protic acid is used to catalyze the cleavage of a chemical
bond through nucleophilic substitution reaction, with the addition water (H2O).

Aldehyde an organic compound containing a functional group with the structure CHO, in
which a carbon atom shares a double bond with an oxygen atom, a single bond with
a hydrogen atom, and a single bond with another atom or group of atoms.

35 | P a g e
Aromatic having a closed ring of alternate single and double bonds with delocalized electrons.

Biomass an organic matter derived from living, or recently living organisms especially plant
matter, that can be converted to fuel and is therefore regarded as a potential energy source.

Dehydration Reaction a chemical reaction between two compounds where one of

the products is water.

Glycosidic Bond a covalent bond that joins a carbohydrate to another functional

group or molecule, which is formed by the removal of a molecule of water.

Hemicellulose any of a group of gummy polysaccharides that hydrolyze to monosaccharides

more readily than cellulose.

Hydrolysis a chemical process of decomposition involving the splitting of a bond by the

addition of water.

Lignocellulosic biomass refers to plant dry matter composed of an aromatic polymer called
lignin and carbohydrate polymers that includes cellulose and hemicellulose.

Lipids hydrophobic biological compounds that are insoluble in water, but soluble in nonpolar
solvents.

Mulch shredded vegetable or mineral matter used to cover the top layer of soil for protection
or insulation.

Pectins white, amorphous, colloidal carbohydrates of high molecular weight that bind adjacent
cell walls in plant tissues and yield a gel which is the basis of fruit jellies .

Pentosan any polysaccharide composed of pentoses.

Pentoses a monosaccharide containing five carbon atoms.

Polysaccharides a polymer formed by the condensation of more than two monosaccharides

linked by glycosidic bonds.

Xylan yellow gummy pentosan occurring in plant cells and woody tissues that yields xylose
on hydrolysis.

Xylose a monosaccharide belonging to the group of pentoses.

36 | P a g e
 CHAPTER 3 MATERIALS AND METHODS

3.1 Methodology Flowchart

Synthesis
Preparation of
of Furfural Optimization
Raw Biomass
via Acid
and Reagents
Hydrolysis

Batch Reactor Furfural Yield

Set-up Determination
Construction

Figure 3 1

3.2 Materials and Equipment

3.2.1 Cacao Residues

Cacao pods are to be gathered from households and local markets that will serve as

the raw biomass to be used in the experiment. The waste biomass are chopped to reduce

the sizes and then dried in an oven to a constant weight at 100C for 4 to 5 hours. The dried

product is subjected to grinding. The crushed biomass is then sieved using a 1mm screen.

3.2.2 Hydrochloric Acid

Hydrochloric acid is to be used as the catalyst for the hydrolysis and dehydration

reactions. For this study, dilute HCl solutions are to be prepared: 1 M, 2 M, and 3 M. In

the preparation of 1M HCl solution, 41.39 mL of 37% HCl is measured using a 100-mL

graduated cylinder. The measured sample is poured in a 500mL-volumetric flask and then

diluted to mark. 82.78 mL of 37% HCl was measured for the preparation of 2M HCl

solution and 124.18 mL of 37% HCl for the preparation of 3M HCl solution.

37 | P a g e
 3.2.3 Sodium Chloride

Sodium chloride is to be used to enhance the furfural selectivity and rate of

formation.

3.2.4 Spectrophotometer

A single beam scanning spectrophotometer was used to scan the distillates. The

equipment was set to scan from 200-700nm at a scan speed of 5mm per minute.

3.3 Experimental Procedure

The production of furfural is to be done using a batch reactor system. The set-up is

divided into five main parts: 250mL-capacity three-neck round bottom flask as batch

reactor, a condenser, a mechanical stirrer, receiving flask and a device to measure

temperature.

About 300g of dried raw biomass and a certain amount of sodium chloride (NaCl)

are to be mixed together in a clean beaker. Then the mixture is placed in the 250-mL three-

neck round bottomed ask. About 50mL of diluted HCl solution is to be added into the

ask. The heating media to be used for the distillation process is an electric heater. The

temperature is to be set at 170C. The distillate composed of water-furfural mixture is set

to flow into a receiving flask.

The yield of Furfural is determined by the UV/Visible spectrophotometric scanning

of distillates.

38 | P a g e
3.4 Experimental Design

3.4.1 Pre-experimental Design

The pre-experimental design is performed with a total 9 of runs. For each set-up,

300 grams of sample containing cacao residues are used. The amount of diluted acid to be

used is 50 mL for each run.

Table 3-1 Pre-experimental Design

Concentration No. of Trials
Experimental of Hydrochloric Residence Time Concentration of
Run Acid (mole/L) (min) NaCl (mole/L)
1 1 30 0.1 3
2 1 60 1 3
3 1 120 0.1 3
4 2 30 0.5 3
5 2 60 0.5 3
6 2 120 1 3
7 4 30 1 3
8 4 60 0.1 3
9 4 120 0.5 3

3.4.2 Experimental Design and Operation

The design is performed with a total of 17 experimental runs generated by Design

Expert 7.0.0 using Box-Behnken Design. There are three ranging parameters and three

trials for each run.

Table 3-2 Experimental Design

Concentration No. of Trials
Experimental of Hydrochloric Contact Time Concentration of
Run Acid (mole/L) (min) NaCl (mole/L)
1 3
2 3
3 3
4 3

39 | P a g e
 5 3
6 3
7 3
8 3
9 3
10 3
11 3
12 3
13 3
14 3
15 3
16 3
17 3

3.4.3 Optimization of Parameters

The optimal conditions are to be determined by the Design Expert based on the

parameters constraints.

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