NATURAL RUBBER CONVERSION TO LIMONENE BY

VACUUM PYROLYSIS IN PRESENCE OF SOLID CaO/SiO2

CATALYST

A THESIS
Submitted in Fulfillment of the Requirements for the Degree of
Magister Teknik (M.T.)
in
Chemical Engineering Program
Faculty of Engineering University of Sriwijaya

By:
HAERANI YULIYATI
ID. 03122803002

ENGINEERING FACULTY
SRIWIJAYA UNIVERSITY
AUGUST 2014
APPROVAL PAGE
 2

Title of Thesis : Natural Rubber Conversion to Limonene by Vacuum Pyrolysis in

Presence of Solid CaO/SiO2 Catalyst

Name : Haerani Yuliyati

Student ID. No. : 03122803002

Program : Master of Chemical Engineering

Academic Major : Energy/Environmental Technology and Management

Approved by:

Advisor I Advisor II

Dr. Ir. Hj. Sri Haryati, DEA Prof. Dr. Ir. H. M. Djoni Bustan, M.Eng
NIP. 195610241981032001 NIP. 195603071981031010

Head of Chemical Engineering Dean of Engineering Faculty

Master Program

Dr. Ir. Hj. Sri Haryati, DEA Prof. Dr. Ir. H. M. Taufik Toha, DEA
NIP. 195610241981032001 NIP. 195308141985031002

DATE OF GRADUATION: JULY 25th, 2014

STATEMENT PAGE
 3

Name : Haerani Yuliyati

Date of Birth : July 27th, 1987

Program : Master of Chemical Engineering

Academic Major : Energy/Environmental Technology and Management

Student ID. No. : 03122803002

Tittle of Thesis : Natural Rubber Conversion to Limonene by Vacuum Pyrolysis

in Presence of Solid CaO/SiO2 Catalyst

Hereby states that:

1. All data, information, interpretation and declaration in the discussion and conclusion
presented herein, except for the ones mentioned by the source are the result of my
observation and thought with guidance of my advisors.
2. The thesis that I wrote is original and has never been handed in for any academic
degree, neither at Sriwijaya University nor other universities.

I certify that these statements are true, and if one day an evidence of violation for these
statements is found within this work, I am willing to accept the sanction of academic degree
cancellation that I received by this thesis.

Palembang, August 2014

Haerani Yuliyati
ID. 03122803002
 4

ACKNOWLEDGEMENTS

In the name of Allah, the Most Beneficent and the Most Merciful, writer would like to
hail all praise to Allah SWT for His blessing throughout the whole compiling process of
NATURAL RUBBER CONVERSION TO LIMONENE BY VACUUM PYROLYSIS IN
PRESENCE OF SOLID CaO/SiO2 CATALYST thesis report. Writer would also like to
utter sholawat and salaam for her beloved prophet Muhammad SAW.
This page is opened with a sincere and deep gratitude from writer, expressed for Dr. Ir.
Hj. Sri Haryati, DEA and Prof. Dr. Ir. H.M. Djoni Bustan M.Eng as her advisors for their
superb supports, encouragements and guidance during the research and writing process. A
tender love and respect to writers dearest parents and siblings for their outstanding and
irreplaceable roles. Last but not least, appreciations toward other parties involved in the nearly
two years of the writers study as follows:
1. National Education Ministry which has provided the scholarship for Master
program.
2. The Head of Chemical Engineering Master Program, Dr. Ir. Hj. Sri Haryati, DEA.
3. Lecturers of Energy/Environment program and academic staff in Chemical
Engineering Graduate Program.
4. Mr. I Made Swetra at Palembang Police Forensic Laboratory who has been
extremely helpful.
5. Fellow colleagues of Double Degree Program and other individuals that contribute
ingenuously in the working process that may not be written one by one.
Final words to round off are that the writer personally wishes that this work may be
helpful for future study of the same research theme. Nevertheless, critics and suggestions for
further improvement are also very welcomed and fully considered by the writer.

Palembang, August 2014

Writer
 5

ABSTRACT

Natural rubber latex transforms to a very valuable asset when technology is able to
change it into varied industry goods. Moreover, natural rubber is known as the potential
source of many valuable compounds. Limonene in particular, is a very valuable chemical
compound that may be used in the formulation of industrial solvents, resins, adhesives, a
dispersing agent for pigments and a feedstock for the production of fragrances and flavorings.
Therefore, it is necessary to design optimum conditions to selectively produce a narrow range
of hydrocarbons by studying the effect of catalyst activity and temperature. Using 80 grams of
natural rubber as fixed variable, catalytic vacuum pyrolysis experiment was conducted. The
experiment varied natural rubber to CaO/SiO 2 catalyst weight ratio and reaction temperature.
80, 100 and 120 grams of catalyst were used in pyrolysis with varying temperature from 325,
350, 375 and 400oC. Pyrolytic oils produced were analyzed qualitatively using GC/MS. The
highest limonene content was found in pyrolytic oil that used 120 grams of CaO/SiO 2 catalyst
with pyrolysis temperature at 400oC, as much as 14.89% area.

Keywords: natural rubber, CaO catalyst, pyrolysis, limonene

 6

TABLE OF CONTENTS

ACKNOWLEDGEMENTS..................................................................................................... ii
TABLE OF CONTENTS......................................................................................................... iii
LIST OF FIGURES.................................................................................................................. iv
LIST OF TABLES ................................................................................................................... v
LIST OF APPENDIX............................................................................................................... vi
CHAPTER I INTRODUCTION....................................................................................... 1
1.1. Background........................................................................................... 1
1.2. Problem Statement................................................................................ 3
1.3. Objectives............................................................................................. 4
1.4. Benefits................................................................................................. 4
CHAPTER II LITERATURE REVIEW............................................................................. 5
2.1. Development on Natural Rubber Conversion to Limonene-Containing
Pyrolytic Oil Technologies.................................................................... 5
2.2. Basic Theory......................................................................................... 8
2.3. Description Process of Previous Researches........................................ 47
2.4. Reaction Mechanism............................................................................. 51
CHAPTER III RESEARCH CONCEPT DESIGN.............................................................. 53
3.1. Materials............................................................................................... 53
3.2. Catalyst Preparation.............................................................................. 54
3.3. Experimental Process Description........................................................ 56
CHAPTER IV RESULTS AND DISCUSSION................................................................... 59
4.1. Catalyst Characterization...................................................................... 59
4.2. Pyrolytic Oil Characterization.............................................................. 60
CHAPTER V CONCLUSION............................................................................................ 68
REFERENCES ................................................................................................................... 69
APPENDIX ...................................................................................................................... 73
 7

LIST OF FIGURES

Figure 2.1. cis-1,4-polyisoprene Chemical Structure................................................................8

Figure 2.2. Isoprene Chemical Structural................................................................................16
Figure 2.3. Limonene Chemical Structure...............................................................................20
Figure 2.4. Limonene Derivation.............................................................................................22
Figure 2.5. Structure of faujasite..............................................................................................26
Figure 2.6. T:O and T:O:T arrangements in clays....................................................................29
Figure 2.7. Simplified Diagrams Summarizing Methods of Blending, Transforming and
Mounting Catalytic Components...........................................................................33
Figure 2. 8. Schematic Diagram of Experimental Apparatus..................................................47
Figure 2. 9. Fixed Bed Reactor Schematic...............................................................................48
Figure 2.10. Schematic Diagram of the Pyrolysis Installation................................................50
Figure 3.1. Catalyst Preparation Steps.....................................................................................54
Figure 3.2. Catalytic Vacuum Pyrolysis Reaction of Natural Rubber Conversion Apparatus. 56
Figure 3.3. Catalytic Pyrolysis Reaction of Natural Rubber Conversion Apparatus...............57
Figure 4.1. SEM analysis of CaO/SiO2 catalyst.......................................................................59
Figure 4.2. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 80 gram Catalyst and 80 gram Natural Rubber..............................61
Figure 4.3. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 100 gram Catalyst and 80 gram Natural Rubber............................62
Figure 4.4. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 120 gram Catalyst and 80 gram Natural Rubber............................63
Figure 4.5. Effect of Natural Rubber to Catalyst Ratio and Temperature on Limonene Peak
Area in Pyrolytic Oil..............................................................................................64
Figure 4.6. Effect of Natural Rubber to Catalyst Ratio and Temperature on Naphthalene Peak
Area in Pyrolytic Oil..............................................................................................65
Figure 4.7. Effect of Natural Rubber to Catalyst Ratio and Temperature on Aromatic
Compounds Peak Area in Pyrolytic Oil.................................................................66
 8

LIST OF TABLES

Table 1.1. Rank of Countries in the World with Higher Rubber Plantation Production............2
Table 2.1. Natural Rubber Characteristic.................................................................................10
Table 2.2. Degradation and Solubility Temperature of Some Rubber Type.............................13
Table 2.3. Isoprene Chemical Properties..................................................................................17
Table 2.4. Limonene Chemical Properties...............................................................................21
Table 2.5. Si/Al ratios for four types of zeolite (Source : E. B. M. Daesburg, 1993)..............27
Table 3.1. Natural Rubber Composition...................................................................................53
Table 4.1. Product Distribution of Natural Rubber from Varied Pyrolysis Condition.............60

LIST OF APPENDIX

GCMS ANALYSIS OF PYROLITIC RESULTS..................................................................... 73

ANALYSIS SAMPLE COMPOSITION................................................................................. 79
EXPERIMENTAL APPARATUS............................................................................................
.....................................................................................................................................104

CHAPTER I
INTRODUCTION

1.1. Background

Natural rubber latex transforms to a very valuable asset when technology is able

to change it into varied industry goods. Unfortunately, the price of natural rubber is

dependent to buyer countries instead of the natural rubber producer countries. Several

countries then start to develop rubber plant as their plantation commodity. Indonesia for
 9

instance, whose rubber plantation area reaches over 3 million acre, is also supposedly

sees this issue as an opportunity. Unfortunately, this large plantation area hasnt received

optimum production; in the other words it doesnt give major effect to worlds natural

rubber marketing. As it can be seen from the fact that Malaysia and Thailand whose

rubber plantation area are smaller than that of Indonesias are able to compete with

Indonesias natural rubber production. Its not only production number, but also the low

quality and quantity of Indonesia natural rubber production in world market.

Indonesia has been widely known as one of the largest producers of natural rubber

plant in the world. Other than acts as Indonesias income source and society welfare or

economy growth booster of new rural area around natural rubber plantation, this

commodity gives significant contribution as the countrys income, natural rubber

plantation does not achieve decent attention, considering 84% of Indonesias natural

rubber production is exported in the form of raw rubber while domestic rubber

consumption only reach 16%. Natural rubber is one of Indonesias plantation

commodities that hold a very important role in Indonesia economy. Along with palm tree,

rubber plants are the biggest income source from plantation sector. In the last five years,

rubber plant contributes 25% to 40% of total plantation product export. Indonesia is the

largest natural rubber producer country after Thailand, where in 2012 Indonesia natural

rubber production reached 3.27 million ton and, together with Thailand, takes over 27%

and 30% worlds need of natural rubber. Worlds natural rubber consumption has

reached 10.94 milliom ton. As revealed by Rubber Research Center representative,

Sinung Hendratno, there are five natural rubber major producer countries in the world.

Table 1.1. Rank of Countries in the World with Higher Rubber Plantation Production

Country Rubber Production

 10

Thailand 3.393.800

Indonesia 2.982.000

Malaysia 996.200

India 892.700

Vietnam 811.600

1. Thailand.

Thailands natural rubber production is the largest in the world. In 2011, it has

managed to fulfil 30.80% of worlds natural rubber need.

2. Indonesia.

Indonesia is the second largest producer of natural rubber, where it contributes

27.06% to worlds natural rubber production. Yet, Indonesia productivity is still

very weak, that is only 986 kg per acre a year.

3. Malaysia.

Malaysia contributes 9.04% to worlds natural rubber production. Total plantation

area in Malaysia is 1.020.000 acre with 93.7% is public owned. This plantation

area produce 1.450 kilogram per acre per year.

4. India

In 2011, the natural rubber production of India contribute as much as 8.10% to the

worlds natural rubber production.

 11

5. Vietnam

Based on 2011 production data, Vietnams natural rubber production reaches

811.600 ton. Therefore, it contributes as many as 7.37% to worlds natural rubber

production.

Experts studies showed the tendencies that worlds natural rubber consumption

gives a good prospect. Thus, Indonesia is supposed to take this opportunity to maximize

natural rubber production. Moreover, natural rubber is known as the potential source of

many valuable compounds, such as benzene, toluene, xylene, naphthalene, limonene,

other aromatic compounds and their derivatives. These chemical products have high

value and wide industrial applications. Limonene in particular, is a very valuable

chemical compound that may be used in the formulation of industrial solvents, resins,

adhesives, a dispersing agent for pigments and a feedstock for the production of

fragrances and flavorings (Hanson, et al. 1999), not to mention its expensive market

price. Besides, limonene is biodegradable, environmentally safe with excellent solvency,

rinsability and high wetting penetration (Hanson, et al. 1999). Therefore, it is necessary

to design optimal conditions to selectively produce a narrow range of hydrocarbons, such

as dl-limonene (Zhang, et al. 2008).

1.2. Problem Statement

Natural rubber abundant production from Indonesia rubber plantation is a very

great opportunity that it is very unfortunate to be missed. Moreover, when technologies

are able to transforms natural rubber from lower value compound to higher value

compounds.
 12

There have been many researches conducted to put an added value to natural

rubber, such as natural rubber pyrolysis to limonene. Unfortunately, the result yield of

limonene from those researches can not be satisfactory for industry scale. Some

researchers used additives or catalyst to improve limonene yield and found out that

catalytic activity was limited on producing limonene. It is the obvious reason why most

researchers use high temperature reaction. Therefore, it is not preferable regarding the

cost production

1.3. Objectives

1. To study the effect of catalyst activity by varying CaO/SiO 2 to natural rubber weight

ratio on limonene content in pyrolitic oil.

2. To investigate temperature role on the formation of limonene from the catalytic

reaction of natural rubber conversion.

1.4. Benefits

This research is expected to conveniently contribute:

1. As a reference for the development of other researches in natural rubber conversion to

more valuable compounds.

2. As the base for pilot plant scale research which is to be upgraded from laboratory

scale research.
 13

CHAPTER II
LITERATURE REVIEW

2.1. Development on Natural Rubber Conversion to Limonene-Containing Pyrolytic Oil

Technologies

There have been some experiments conducted regarding valuable hydrocarbon

compounds production from natural rubber based materials over the years by many

scientists all over the world. In majority, they utilized waste or scrap tires that have been

designated as a priority waste stream by the European Commission and as such are

subject to recycling target and recommendations regarding environmentally acceptable

treatment and disposal methods. An alternative technology to dispose waste tires is

pyrolysis that is the thermal degradation of the tire in an inert atmosphere (Bajus and

Olahova 2011).

Pyrolysis is an environmentally friendly process that converts waste tires to

flammable gas, pyrolytic oil, and carbon black, all of which are potentially recyclable.

The flammable gas can provide energy for the pyrolysis process, while carbon black can

be used as a low-grade carbon black and pyrolytic oil can be used as liquid fuel after

extracting chemical materials, such as benzene, toluene, xylene, and dl-limonene. These

chemical products have high value and wide industrial applications. To enhance the value

of waste tire pyrolysis process, optimal conditions should be designated to selectively

produce a narrow range of hydrocarbons, such as dl-limonene, benzene and derivatives

(Zhang, et al. 2008).

A number of different natural and synthetic rubbers and rubber formulation are

used to produce tires (Bajus and Olahova 2011). It is well known that natural rubber

decomposes to form oligomers of isoprene, ranging from the monomer unit up to

 14

hexamers. The major compound is usually dipentene, also known as limonene, which

represents the dimmer (Hall, Zakaria and Williams 2009). Polyisoprene or natural rubber

composes approximately 50-60% of tire formulation; both represent the ideal source of

limonene. Tire elastomers other than polyisoprene are not the main source of dl-limonene

(Pakdel, Pantea and Roy 2001).

Processing of waste rubber by pyrolysis has been intensively investigated in

recent years, particularly with regard to scrap tires. The pyrolysis of natural rubber has

also been investigated, as has the pyrolysis of natural rubbers main constituent,

polyisoprene (Hall, Zakaria and Williams 2009). Significant research has been performed

in the field of chemical recycling of rubbers by pyrolysis in 2009 by Zhang et. al. who

studied the influence of temperature and two additives, i.e. natrium hydroxide (NaOH)

and natrium carbonate (Na2CO3) on the yields of the pyrolysis products, as well as the

formation mechanism and variation of dl-limonene content in the pyrolysis oil. The

experiment results indicated that NaOH additive use in vacuum pyrolysis of waste tire

could lower pyrolysis temperature and slightly increase dl-limonene content in pyrolytic

oil in experiment run at the same temperature. However, though the addition of Na 2CO3

additive gave the same trend to increase dl-limonene content, it did not promote the

pyrolysis reaction. Zhang et. al. experiment also showed that limonene content as the

main component in pyrolytic naphtha under vacuum pyrolysis conditions was greater

than that in other atmospheric pyrolyis process.

Another investigation of catalytically upgrading pyrolysis process of natural

rubber was conducted by Hall et. al. in 2009. They passed rubber gloves that were

manufactured from natural rubber over Y-zeolite catalyst before they exited reactor. The

samples were pyrolized in a fixed bed reactor at either 380 oC or 480oC. Even though the

introduction of catalyst increased the concentration of aromatics in pyrolytic oil, it caused

 15

a large decrease in the yield of limonene. It fell from 108.8 mg/g sample to 0.9 mg/gsample

when the reaction temperature is 380oC and from 120.5 mg/gsample to 2.2 mg/gsample for

pyrolysis at 480oC.

Pyrolysis is limited by heat and mass transfer between the particle and,

consequently, as particle size is decreased the apparent kinetic constant increases.

According to Bajus and Olahova, pyrolysis oil characteristics strongly depend on

pyrolysis process characteristics, process temperature and nature of the raw material

used. In 2011, they converted scrap tires with the aim to study the experimental

conditions that maximized liquid yields. Maximum liquid component obtained as much

as 9.0%wt is d, l-limonene, produced at reaction temperature of 450 oC. Yet, with the

increasing temperature to 570oC it dropped to 4.6%wt along with other aromates C 7-C10.

This behaviour of aromatic fraction is due to Diels-Alder reactions that promote the

formation of aromatic compounds from Olefins (Bajus and Olahova 2011).

In addition to pyrolysis conversion technology, there is another approach to utilize

carbonaceous waste, called co-pyrolysis. Onenc et. al. for instance, who co-pyrolized

scrap tires and oily waste from ships to liquid fuels or chemical feedstock in the presence

and absence of catalysts. Their work was aimed to see the influence of catalyst use and

reaction temperature. It is reported that there was no influence of temperature on the

product distribution over 500oC in scrap tires pyrolysis. The catalyst showed similar

activity but Red Mud catalyst left fewer residues than that compared to ReUS-Y faujisite

catalyst. Nevertheless, both catalysts had great effect on the distribution of compounds in

the pyrolysis oils of scrap tires-oily waste mixture, particularly in D-limonene amount.

In accordance to review of some researches conducted over the last three decades,

oil yields fluctuated with both temperatures and heating rates with no discernible trend

(Quek and Balasubramanian 2013). It is also stated that low pyrolysis temperature and
 16

pressure as well as short vapour residence time increased the limonene yield (Pakdel,

Pantea and Roy 2001). As when catalysts, such as HZSM-5, HY and HBeta zeolites were

occupied in reaction, gas yield and light aromatic hydrocarbon increase at the expense of

the decreasing limonene yield (Quek and Balasubramanian 2013).

The production of limonene from natural rubber has always been done in high

operating conditions affecting the operational cost. This phenomenon obviously is not

favourable for industrial scale application of limonene production. Therefore, it is

necessary to investigate the required operating conditions in the method to obtain high

yield of limonene with proportional operating cost. The role of catalyst may also take part

in the process, so that either limonene decomposition into lighter hydrocarbon

compounds or the formation of higher hydrocarbon compounds than limonene can be

prohibited. This ability can be determined by catalyst activity provided by the ratio of

natural rubber as feedstock and catalyst weight ratio used in the fixed bed reactor.

2.2. Basic Theory

2.2.1. Natural Rubber

Natural rubber, as initially produced, consists of polymers of the organic

compound isoprene, with minor impurities of other organic compounds plus water.

Forms of polyisoprene that are useful as natural rubbers are classified as elastomers.

The major compound that composed natural rubber is cis-1,4-polyisoprene, polymer

of isoprene with high molecular weight (Heinz-Hermann 2000).

Figure 2.1. cis-1,4-polyisoprene Chemical Structure

 17

Currently, rubber is harvested mainly in the form of the latex from certain

trees. The latex is a sticky, milky colloid drawn off by making incisions into the bark

and collecting the fluid in vessels in a process called tapping. The latex then is

refined into rubber ready for commercial processing. Natural rubber is used

extensively in many applications and products, either alone or in combination with

other materials. In most of its useful forms, it has large stretch ratio, high resilience,

and is extremely waterproof (Heinz-Hermann 2000).

The major commercial source of natural rubber latex is the Para rubber tree

(Hevea brasiliensis), a member of the spurge family, Euphorbiaceae. This species is

widely used because it grows well under cultivation and a properly managed tree

responds to wounding by producing more latex for several years (Heinz-Hermann

2000).

Many other plants produce forms of latex rich in isoprene polymers, though

not all produce usable forms of polymer as easily as the Para rubber tree does; some of

them require more elaborate processing to produce anything like usable rubber, and

most are more difficult to tap. Some produce other desirable materials, for example

gutta-percha (Palaquium gutta) and chicle from Manilkara species. Others that have

been commercially exploited, or at least have shown promise as sources of rubber,

include the rubber fig (Ficus elastica), Panama rubber tree (Castilla elastica), various

spurges (Euphorbia spp.), lettuce (Lactuca species), the related Scorzonera tau-

saghyz, various Taraxacum species, including common dandelion (Taraxacum

officinale) and Russian dandelion (Taraxacum kok-saghyz) and guayule (Parthenium

argentatum). The term gum rubber is sometimes applied to the tree obtained version of

natural rubber in order to distinguish it from synthetic version (Heinz-Hermann 2000).

 18

Typically natural rubber contains a few percent of other materials, such as

proteins, fatty acids, resins, and inorganic materials. Some natural rubber sources,

called gutta percha, are composed of trans-1,4-polyisoprene, a structural isomer that

has similar, but not identical, properties (Heinz-Hermann 2000). Table 2.1 shows the

characteristics of Natural Rubber.

Table 2.1. Natural Rubber Characteristic

No. Characteristic Details

1. Chemical composition Mainly cis-polyisoprene
2. SPGR 0.915
3. Elasticity Ranging from temperature 10-60oC
4. Tensile strength Low
5. Abrasion resistant Low
Insoluble in water, alcohol, acetone, dilute
acids, and alkalis
6. Solubility
Soluble in ether, carbon disulphide, carbon
tetrachloride, petrol and turpentine
7. Physical appearance Pure rubber is transparent, amorphous solid
(Forrest 2001)
Rubber exhibits unique physical and chemical properties. Rubbers stress-

strain behaviour exhibits the Mullins effect and the Payne effect, and is often modelled

as hyperelastic. Due to the presence of a double bond in each repeat unit, natural

rubber is susceptible to vulcanisation and sensitive to ozone cracking (Heinz-Hermann

2000).

On a microscopic scale, relaxed rubber is a disorganized cluster of erratically

changing wrinkled chains. In stretched rubber, the chains are almost linear. The

restoring force is due to the preponderance of wrinkled conformations over more

linear ones. Cooling below the glass transition temperature still permits local

conformational changes but a reordering is practically impossible because of the larger

energy barrier for the concerted movement of longer chains. Frozen rubbers
 19

elasticity is low and strain results from small changes of bond lengths and angles. This

caused the Challenger disaster, where flattened o-rings failed to relax to fill a widening

gap. The glass transition is fast and reversible: the force resumes on heating (Heinz-

Hermann 2000).

The parallel chains of stretched rubber are susceptible to crystallization. This

take some time because turns of twisted chains have to move out of the way of the

growing crystallites. Crystallization has occurred, for example, when, after days, an

inflated toy balloon is found withered at a relatively large remaining volume. Where it

is touched, it shrinks because the temperature of the hand is enough to melt the

crystals (Heinz-Hermann 2000).

Vulcanization of rubber creates disulfide bond between chains, which limits

the degrees of freedom and results in chains that tighten more quickly for a given

strain, thereby increasing the elastic force constant and making the rubber harder and

less extensible (Heinz-Hermann 2000).

Polyisoprene can also be created synthetically, producing what is sometimes

referred to as synthetic natural rubber, but the synthetic and natural routes are

completely different (Heinz-Hermann 2000).

Natural rubber is an elastomer and a thermoplastic. Once the rubber is

vulcanized, it will turn into a thermoset. Most rubber in everyday use is vulcanized to

a point where it shares properties of bot; i.e., if it is heated and cooled, it is degraded

but not destroyed. The final properties of a rubber item depend not just on the

polymer, but also on modifiers and fillers, such as carbon black, factice, whiting and a

host of others (Heinz-Hermann 2000).

Rubber particles are formed in the cytoplasm of specialized latex-producing

cells called laticifiers within rubber plants (Ohya and Koyama 2001). Rubber particles
 20

are surrounded by a single phospholipid membrane with hydrophobic tails pointed

inward. The membrane allows biosynthetic proteins to be sequestered at the surface of

the growing rubber particle, which allows new monomeric units to be added from

outside the biomembrane, but within the lacticifer. The rubber particle is an

enzymatically active entity tat contains three layers of material, the rubber particle, a

biomembrane, and free monomeric units. The biomembrane is held tightly to the

rubber core due to the high negative charge along the double bonds of the rubber

polymer backbone (Paterson-Jones, Gilliland and Van Staden 1990).

Free monomeric units and conjugated proteins make up the outer layer. The

rubber precursor is isopentenyl pyrophosphate (an allylic compound), which elongates

by Mg2+-dependent condensation by the action of rubber transferase. The monomer

adds to the pyrophosphate end of the growing polymer (Paterson-Jones, Gilliland and

Van Staden 1990).

The process displaces the terminal high-energy pyrophosphate. The reaction

produces a cis polymer. The initiation step is catalyzed by prenyltransferase, which

converts three monomers of isopentenyl pyrophosphate into farnesyl pyrophosphate.

The farnesyl pyrophosphate can bind to rubber transferase to elongate a new rubber

polymer (Xie, et al. 2008).

The required isopentenyl pyrophosphate is obtained from the mevalonate

pathway, which is derives from acetyl-CoA in the cytosol. In plants, isoprene

pyrophosphate can also be obtained from 1-deox-D-xyulose-5-phosphate/2-C-methyl-

D-erythritol-4-phosphate pathway within plasmids (Casey and Seabra 1996). The

relative ratio of the farnesyl pyrophosphate initiator unit and isoprenyl pyrophosphate

elongation monomer determines the rate of new particle synthesis versus elongation of

existing particles. Though rubber is known to be produced by only one enzyme,

 21

extracts of latex have shown numerous small molecular weight proteins with unknown

function. The proteins possibly serve as cofactors, as the synthetic rate decreases with

complete removal (Kang, Kang and Han 2000).

The two main solvents for rubber are turpentine and naphta (petroleum). The

former has been in use since 174 when Francois Fresnau made the discovery.

Giovanni Fabbroni is credited with the discovery of naphtha as a rubber solvent in

1779. Because rubber does not dissolve easily, the material is finely divided by

shredding prior to its immersion. An ammonia solution can be used to prevent the

coagulation of raw latex while it is being transported from its collection site (Heinz-

Hermann 2000).

Existing varied types of rubber have different degradation and solubility

temperature based on the constituent compounds of each type, which was summarized

in Table 2.2.

Table 2.2. Degradation and Solubility Temperature of Some Rubber Type

No
Rubber Type Maximum Temperature (oC)
.
1. Polyurethane 80
2. Natural rubber and polyisoprene 80
3. Butadiene and styrene-butadiene 100
4. Nitrile and polychloroprene 120
5. Butyl styrene 130
6. Silicone above 100.000
7. Chlorosulphonate polyetheylene above 100.000
8. Nitrile above 100.000
9. Fluorocarbon above 100.000
10. Polychloroisoprene above 100.000
11. Styrene-butadiene above 500.000
12. Ethylene-propylene above 500.000
(Forrest 2001)
 22

Even though the amount of natural rubber production and consumption is

under that of synthetic rubber, its role still remains irreplaceable, considering the fact

that tire production reasonably needed natural rubber. According to several studies,

natural rubber content in vehicle tire can not be less than 35%, meaning that it is

impossible to produce tire without natural rubber. As a result, nearly 70% of worlds

natural rubber production is used to manufacture tire, while the rest is utilize in other

product manufacturing. Natural rubber as raw material is an indispensable thing for

downstream industries manufacturing process, since it can not be replaced 100% by

synthetic rubber, which has many weak characteristics compared to that of natural

rubber characteristic (Balitbang 2013).

Rubber latex is extracted from rubber trees. The economic life period of rubber

trees in plantations is around 32 years-up to 7 years of immature phase and about 25

years of productive phase. The soil requirement of the plant is generally well-drained,

weathered soil consisting of laterite, lateritic types, sedimentary types, nonlateritic red,

or alluvial soils (Cecil, et al. 2013).

The climatic conditions for optimum growth of rubber trees are:

1. Rainfall of around 250 cm evenly distributed without any marked dry season and

with at least 100 rainy days per year.

2. Temperature range of about 20 to 34oC, with a monthly mean of 25 to 28oC.

3. High atmospheric humidity of around 80%.

4. Bright sunshine amounting to about 2000 hours per year at the rate of six hours per

day throughout the year.

 23

5. Absence of strong winds.

Many high-yielding clones have been developed for commercial planting.

These clones yield more than 2,000 kg of dry rubber per hectare per year, when grown

under ideal conditions (Cecil, et al. 2013).

Natural rubber excellence properties that can not be vied when compared to

synthetic rubber are (Badri 2013):

1. Perfect elasticity and resilience

2. Good plasticity making it easier to be treated

3. High wear resistance

4. Low heat build up

5. High groove cracking resistance

6. Able to be formed with low heat

7. High glutinous to many kinds of material

These excellence properties make natural rubber difficult to be compared with

synthetic rubber, causing natural rubber as the highest component contained in off

road and aeroplane tire manufacturing (Balitbang 2013).

Natural rubber can also be used either as an intermediate or raw material for

other rubber based materials production. There are some widely known natural rubber

varieties, such as (Badri 2013):

 24

a. Rubber material (plantation latex, wind sheet, thin slab, fresh lump)
b. Conventional rubber (RSS, white crepes, and pale crepe)
c. Thick latex
d. Block rubber (SIR 5, SIR 10 and SIR 20)
e. Crumb rubber
f. Tire rubber
g. Reclaimed rubber
Latex is generally processed into either latex concentrate for manufacture of

dipped goods or it can be coagulated under controlled, clean conditions using formic

acid. The coagulated latex can then be processed into the higher-grade, technically

specified block rubbers such as SVR 3L or SVR CV or used to produce Ribbed Smoke

Sheet grades (Dick 2003).

Naturally coagulated rubber (cup lump) is used in the manufacture of TSR10

and TSR20 grade rubbers. The processing of the rubber for these grades is a size

reduction and cleaning process to remove contamination and prepare the material for

the final stage of drying. The dried material is then bales and palletized for storage and

shipment in various methods of transportation (Dick 2003).

2.2.2. Isoprene
The polyisoprene part of natural rubber thermally decomposes through a -

scission mechanism to an isoprene intermediate radical. It is then transformed to

isoprene (depropagation) (Pakdel, Pantea and Roy 2001). Isoprene that is also known

as 2-methyl-1,3-butadiene, is a common organic compound with the formula

CH2=C(CH3)CH=CH2. It is a colorless volatile liquid and one of the most important

non-methane hydrocarbons in the atmosphere (Guenther, et al. 2006).

Figure 2.2. Isoprene Chemical Structural

 25

Isoprene is produced and emitted by many species of trees into the atmosphere,

which major producers are oaks, poplars, eucalyptus, and some legumes. Its emissions

from vegetation constitute ~40% of the total mass of non-methane hydrocarbon

compounds emitted to the atmosphere. The yearly production of isoprene emissions by

vegetation is around 600 million tonnes, with half of that coming

from tropical broadleaf trees and the remainder coming from shrubs (Guenther, et al.

2006).
This is about equivalent to methane emission into the atmosphere and accounts

for approximately one-third of all hydrocarbons released into the atmosphere. After

release, isoprene is converted by free radicals (like the hydroxyl (OH) radical) and to a

lesser extent by ozone into various species, such as aldehydes, hydroperoxides,

organic nitrates, and epoxides, which mix into water droplets and help create aerosols

and haze. Atmospheric reactions of isoprene involve several thousand subsequent

reactions and hundreds of intermediate species (Daily 2009).

Table 2.3. Isoprene Chemical Properties

Properties
Molecular formula C5H8
Molar mass 68.12 g/mol
Density 0.681 g/cm3
Melting point -143.95oC
Boiling point 34.067oC
*Except where noted otherwise, data are given for materials in their standard state
(at 25oC (77oF), 100 kPa)

A second major effect of isoprene on the atmosphere is that in presence of

nitric oxides (NOx) it contributes to the formation of tropospheric (lower atmosphere)

ozone, which is one of the leading air pollutants in many countries. Isoprene itself is

normally not regarded as a pollutant, as it is one of the natural products from plants.
 26

Formation of tropospheric ozone is only possible in presence of high levels of NOx,

which comes almost exclusively from industrial activities. In fact, isoprene can have

the opposite effect and quench ozone formation under low levels of NOx.Isoprene is

made through the methyl-erythritol 4-phospate pathway (MEP pathway, also called the

non-mevalonate pathway) in the chloroplasts of plants. One of the two end products of

MEP pathway, dimethylallyl diphosphate (DMADP), is catalyzed by the enzyme

isoprene synthase to form isoprene. Therefore, inhibitors such as fosmidomycin that

block the MEP pathway also blocks isoprene formation. Isoprene emission increases

dramatically with temperature and maximizes at around 40C. This has led to the

hypothesis that isoprene may protect plants against heat stress. Emission of isoprene is

also observed in some bacteria and this is thought to come from non-enzymatic

degradations from DMADP. Isoprene emission in plants is controlled both by the

availability of substrate (DMADP) and by enzyme (isoprene synthase) activity. In

particular, light, CO2 and O2 dependencies of isoprene emission are controlled by

substrate availability, whereas temperature dependency of isoprene emission is

regulated both by substrate level and enzyme activity. The emission of isoprene

appears to be a mechanism that trees use to combat abiotic stresses. It was proposed

that isoprene emission was specifically used by plants to protect against large

fluctations in leaf temperature (Sharkey, Wiberley and Donohue 2007).

Isoprene is incorporated into and helps stabilize cell membranes in response to

heat stress, conferring some tolerance to heat spikes. Isoprene also confers resistance

to reactive oxygen species (Vickers, et al. 2009). The amount of isoprene released

from isoprene-emitting vegetation depends on leaf mass, leaf area, light (particularly

photosynthetic photon flux density, or PPFD), and leaf temperature. Thus, during the

night, little isoprene is emitted from tree leaves, whereas daytime emissions are
 27

expected to be substantial during hot and sunny days, up to 25 g/(g dry-leaf-

weight)/hour in many oak species (Benjamin, et al. 1996).

Isoprene also exist in other living organism, as an example it is the most

abundant hydrocarbon measurable in the breath of humans, The estimated production

rate of isoprene in the human body is 0.15 mol/(kgh), equivalent to approximately

17 mg/day for a person weighing 70 kg. Isoprene is also common in low

concentrations in many foods (Gelmont, Stein and Mead 1981).

The isoprene skeleton can be found in naturally occurring compounds called

terpenes, but these compounds do not arise from isoprene itself. Terpenes can be

viewed as multiples of isoprene subunits, and this perspective is the cornerstone of the

"isoprene rule". The precursor to isoprene units in biological systems are dimethylallyl

diphospate (DMADP) and its isomer isopentenyl diphosphate (IDP). The plural

isoprenes is sometimes used to refer to terpenes in general. Isoprene chains are

commonly found in numerous biologically active oligomers such as Vitamin A (Heinz-

Hermann 2000).

In industrial production, isoprene was first isolated by thermal decomposition

of natural rubber (Williams 1860). It is most readily available industrially as a by-

product of the thermal cracking of naphta or oil, as a side product in the production of

ethylene. About 800,000 tonnes are produced annually. About 95% of isoprene

production is used to produce cis-1,4-polyisoprenea synthetic version of natural

rubber (Heinz-Hermann 2000).

Isoprene is a common structural motif in biological systems. The

isoprenoids (for example, the carotenes are tetraterpenes) are derived from isoprene.

Also derived from isoprene are phytol, retinol (vitamin A), tocopherol (vitamin E),

dolichols, and squalene. Heme A has an isoprenoid tail, and lanosterol, the sterol
 28

precursor in animals, is derived from squalene and hence from isoprene. The

functional isoprene units in biological systems are dimetyhlallyl diphosphate

(DMADP) and its isomer isopentenyl diphosphate (IDP), which are used in the

biosynthesis of naturally occurring isoprenoids such as carotenoids, quinones,

lanosterol derivatives (e.g. steroids) and the prenyl chains of certain compounds (e.g.

phytol chain of chlorophyll) (Heinz-Hermann 2000).

Treatment of isoprene (2-methyl-1,3-butadiene) with catalytic amounts of acid

leads to a variety of oligomeric products, one of which is limonene: Two molecules of

isoprene may also be converted into limonene by a completely different mechanism,

which takes place in the strict absence of catalysts of any kind.

2.2.3. Limonene
Diels-Alder mechanism is postulated for the formation of dl-limonene, which

will decompose above 450oC if it is not quickly removed from the reaction zone

(Pakdel, Pantea and Roy 2001).

Limonene is a colourless liquid hydrocarbon classified as a cyclic terpene. The

more common D-isomer possesses a strong smell of oranges. It is used in chemical

synthesis as a precursor to carvone and as a renewably based solvent in cleaning

products (Guenther, et al. 2006).

Figure 2.3. Limonene Chemical Structure

 29

Limonene takes its name from the lemon, as the rind of the lemon, like other

citrus fruits, contains considerable amounts of this compound, which contributes to

their odor. Limonene is a chiral molecule, and biological sources produce

one enantiomer: the principal industrial source, citrus fruit, contains D-limonene ((+)-

limonene), which is the (R)-enantiomer (CAS number 5989-27-5, EINECS

number 227-813-5). Racemic limonene is known as dipentene. D-Limonene is

obtained commercially from citrus fruits through two primary methods: centrifugal

separation or steam distillation (Simonsen 1947).

Table 2.4. Limonene Chemical Properties

Properties

IUPAC name 1-methyl-4-(1-methylethenyl)-cyclohexene

Other name 4-isopropenyl-1-methylcyclohexene

Molecular Formula C10H16

Molar Mass 136.23 g/mol

Density 0.8411 g/cm3

Melting Point -74.35oC, -101.83oF, 198.80 K

Boiling Point 176oC, 349oF, 449 K

Chiral Rotation []D 87o-102o

Hazards

R-phrases Flammable, Irritating to Skin, May Cause

Sensitisation by Skin, Very Toxic to Aquatic
Organisms, May Cause Long-term Adverse Effects
 30

in the Aquatic Environment

Keep Out of the Reach of Children, Avoid Contact

with Skin, Wear Suitable Gloves, This Material and
S-phrases Its Container Must be Disposed of as Hazardous
Waste, Avoid Release to the Environment, Refer to
Special Instructions/Safety Data Sheet

Flash Point 50oC, 122oF, 323 K

*Except where noted otherwise, data are given for materials in their standard state (at
25oC (77oF), 100 kPa)

Limonene is a relatively stable terpene and can be distilled without

decomposition, although at elevated temperatures it cracks to form isoprene (Pakdel,

Pantea and Roy 2001). It oxidizes easily in moist air to produce carveol, carvone, and

limonene oxide. With sulfur, it undergoes dehydrogenation to p-cymene. Limonene

occurs naturally as the (R)-enantiomer, but racemizes to dipentene at 300C. When

warmed with mineral acid, limonene isomerizes to the conjugated diene -terpinene

(which can also easily be converted to p-cymene). Evidence for this isomerization

includes the formation of Diels-Alder adducts between -terpinene adducts and maleic

anhydride (Karlberg, Magnusson and Ulrika 1992).

It is possible to effect reaction at one of the double bonds selectively.

Anhydrous hydrogen chloride reacts preferentially at the disubstituted alkene, whereas

epoxidation with MCPBA occurs at the trisubstituted alkene. In another synthetic

method Markovnikov addition of trifluoroacetic acid followed by hydrolysis of the

acetate gives terpineol. Limonene is formed from geranyl pyrophosphate, via

 -H+
geranyl
pyrophosphate 31

cyclization of a neryl carbocation or its equivalent as shown. The final step involves

loss of a proton from the cation to form the alkene (Mann, et al. 1994).

OPP

Figure 2.4. Limonene Derivation

The most widely practiced conversion of limonene is to carvone. The three

step reaction begins with the regioselective addition of nitrosyl chloride across the

trisubstituted double bond. This species is then converted to the oxime with base, and

the hydroxylamine is removed to give the ketone-containing carvone (Fahlbusch, et al.

2003). Limonene is common in cosmetic products. As the main odor constituent of

citrus (plant family Rutaceae), D-limonene is used in food manufacturing and some

medicines, e.g. as a flavouring to mask the bitter taste of alkaloids, and as a fragrant in

perfumery; it is also used as botanical insecticide, particularly the (R)-(+)-

enantiomer is most active as an insecticide. It is added to cleaning products such as

hand cleansers to give a lemon-orange fragrance (see orange oil) and because of its

ability to dissolve oils. In contrast, L-limonene has a piney, turpentine-like odor. In

natural and alternative medicine, D-limonene is marketed to relieve gastroesophageal

reflux disease and heartburn (Sun 2007).

Limonene is increasingly being used as a solvent for cleaning purposes, such

as the removal of oil from machine parts, as it is produced from a renewable source

(citrus oil, as a byproduct of orange juice manufacture). It is used as a paint

 32

stripper and is also useful as a fragrant alternative to turpentine. Limonene is also used

as a solvent in some model airplane glues. All-natural commercial air fresheners, with

air propellants, containing limonene are used by philatelists to remove self-adhesive

postage stamps from envelope paper (Butler 2010).

Limonene is also finding increased use as a solvent for filament-fused 3D

printing. Printers can print the plastic of choice for the model, but erect supports, and

binders from HIPS, a polystyrene plastic, that are easily solvable in Limonene. As it is

combustible, limonene has also been considered as a biofuel (Congress 2007).

In preparing tissues for histology or histopathology, D-limonene is often used

as a less toxic substitute for xylene when clearing dehydrated specimens. Clearing

agents are liquids miscible with alcohols (such as ethanol or isopropanol) and with

melted paraffin wax, in which specimens are embedded to facilitate cutting of thin

sections for microscopy. Limonene is adenosine agonist which may explain its anti-

stress and sedative properties (Wynnchuk 1994).

Limonene and its oxidation products are skin and respiratory irritants, and

limonene-1,2-oxide (formed by aerial oxidation) is a known skin sensitizer. Most

reported cases of irritation have involved long-term industrial exposure to the pure

compound, e.g. during degreasing or the preparation of paints. However, a study of

patients presenting dermatitis showed that 3% were sensitized to limonene (Cancer

1999).

Although high doses have been shown to cause renal cancer in male

rats, limonene is considered by some researchers to be a potential chemopreventive

agent with value as a dietary anti-cancer tool in humans (Tsuda, et al. 2004). There is

no evidence for carcinogenicity or genotoxicity in humans. The IARC classifies D-

limonene as a Group 3 carcinogen: not classifiable as to its carcinogenicity to humans.

 33

No information is available on the health effects of inhalation exposure to D-limonene

in humans, and no long-term inhalation studies have been conducted in laboratory

animals. D-Limonene is biodegradable, but due to its low flash point, it must be

treated as hazardous waste for disposal (Cancer 1999).

2.2.4. Catalyst and Support Material

A. Catalyst
A catalyst is defined as a material that accelerates a chemical reaction but

remains unchanged chemically in the process. For a reaction to be possible, the

process must be accompanied by a decrease of free energy. The reduction in activation

energy is achieved by the catalyst providing an alternative pathway of lower energy

for the reaction. Often products are formed in addition to those that are desired. The

selectivity of a catalyst is a measure of the catalysts ability to direct the conversion to

the desired products. The greater the stability of a catalyst, the lower the rate at which

the catalyst loses its activity or selectivity or both.

Generally, catalysts consist of two or more components: the support and one or

more active phases. The phase is principally responsible for the catalytic activity,

whilst the support provides a vehicle for the active phase. The activity of a catalyst has

been related to the number of active (acid) sites on the catalyst surface. Strong acids

come in two fundamental types, Brnsted and Lewis acids. Brnsted acidity is

provided by the very active hydrogen ion (H+), which has a high positive charge

density and seeks out negative charge, such as pi-electrons in aromatic centres.

Brnsted acids can add to an olefinic double bond to form a carbocation. Lewis acids

have high positive charge densities and can abstract a hydride ion from a saturated

hydrocarbon, forming a carbenium ion. Catalysts employed in the petrochemical

industry include amorphous silica-alumina (SiO2/Al2O3), zeolites, acid-activated clays,

and aluminium chloride (AlCl3), amongst others.

B. Support Material
 34

1. Aluminosilicates
Aluminium is about the same size as silicon and readily substitutes for the

latter in nature. However, since aluminium is a 3+ ion and silicon is 4+, an additional

cation is required for charge balance. Thus, a Si4+ in the silicate framework can be

substituted by the combination of an Al3+ with an additional (non-framework) ion.

Aluminosilicates incorporating aluminium (Al), silicon (Si) and oxygen (O) find wide

application as industrial catalysts.

2. Zeolites
Zeolites consist of atoms or ions arranged in a periodic array and are

structurally unique in having cavities or pores with molecular dimensions, as part of

their crystalline structures, which bear catalytic sites. In zeolite ZSM-5, some of the

silicon atoms in the SiO4 tetrahedral are replaced by Al atoms. The tetrahedral are

linked to form a chain-type building block, which are then connected to other chains.

Rings consisting of 10 oxygen atoms provide access to a network of intersecting pores

within the crystal. Many molecules are small enough to penetrate into this

intracrystalline pore structure, where they may be catalytically converted. The

aluminosilicate structure is ionic, incorporating Si 4+, Al3+ and O2- ions. When some of

the Si4+ ions in the SiO4 tetrahedra are replaced by Al3+ ions, an excess negative charge

is generated. To compensate for this negative charge, positive ions (cations) must be

added to the framework Si4+ and Al3+. These non-framework cations play a central role

in determining the catalytic nature of the zeolite.

Faujasites consist of 12-membered oxygen rings (0.74 nm apertures) and a

three dimensional pore structure, and are able to admit hydrocarbon molecules larger

than naphthalene. For this reason, faujasites have applications in the catalytic cracking

of petroleum molecules into smaller gasoline-range molecules. Faujasites are made of

sodalite cages twenty-four primary building blocks of SiO 4 and AlO4 tetrahedral in a

truncated octahedron arranged in a regular array. Each sodalite cage is connected to

 35

four other sodalite cages, with each connecting unit made of six bridging oxygen ions

linking the hexagonal faces of two sodalite units. The supercage in faujasites,

surrounded by 10 sodalite units, is large enough to contain a sphere of diameter 1.2

nm. Figure 2.5. displays the structure of faujasite.

Figure 2.5. Structure of faujasite

a. Adsorption in Zeolites
The void spaces in the crystalline structures of zeolites provide a high capacity

for adsorbates. Chemisorption of polar molecules is influenced strongly by the nature

of the cations and the interactions between the cations and guest molecules. Guest

molecules can change the configuration of the aluminosilicate framework slightly.

Adsorption in the pores cannot take place unless the guest molecules are small enough

to fit through the apertures, and can be hindered by the cations.

b. Aluminium Content
The ion exchange capacity of a zeolite is equal to the concentration of Al 3+

ions, therefore the structures with low Si/Al ratios are able to have higher

concentrations of catalytic sites than the zeolites with high Si/Al ratios. However, the

stability of the crystal framework increases with increasing Si/Al ratios. Table 2.5.

lists the Si/Al ratios for four different types of zeolites.

Table 2.5. Si/Al ratios for four types of zeolite

Zeolites Name Si/Al Ratio

Zeolite A LTA 1
 36

Zeolite Y FAU 2.5

Mordenite MOR 5
ZSM-5 MFI > 12

c. Acidity of Zeolites
Both Brnsted and Lewis acid sites occur in zeolites. The hydrogen form

zeolite contains protons (H+) that are mobile within the structure. OH groups located

near AlO4- tetrahedra are thought to be strong Brnsted acids, but are said to have a

wide distribution of proton donor strengths (Cejka, Zones and Corma 2010). Zeolites

with low densities of proton donor groups, such as HZSM-5 and ultra-stable HY, have

been found to have high proton donor strengths, with the highest strengths associated

with AlO4- tetrahedra having the smallest number of Al neighbours. When a hydrogen

form zeolite is heated to high temperatures, water is driven off and coordinatively

unsaturated Al3+ ions are formed. These are strong Lewis acids, with one Lewis acid

site formed from two Bronstedt acid sites.

d. Selectivity of Zeolites
Zeolite catalysts often have a high selectivity for the following class of

reaction:

olefins + cycloparaffins paraffins + aromatics

which is accounted for by hydrogen (hydride and proton) transfers. This makes

zeolites important catalysts in the cracking of heavier petroleum fractions into smaller

paraffins and olefins that boil in the gasoline range. Chatterjee et al. (1999) studied the

interaction energy between organic molecules (reactant and product) and the zeolite

host lattice to locate the reason for the selectivity order. It was found that the positive

charges in the molecules have ionic interactions with the basic oxygen of the zeolite

framework, allowing adsorption inside the zeolite void volume. The void dimensions

of the zeolite were said to control product yield, whilst the electronic interactions

played a vital role in the mechanism of the organic reaction.

 37

(Woo, Lee and Lee 1996) investigated the catalytic skeletal isomerisation of n-

butenes to iso-butene over a natural clinoptilolite zeolite. It was found that proton

exchange was essential for the zeolite to have isomerisation activity. The exchange

created strong acid sites, with a zeolite of Si/Al ratio of 20 exhibiting greater activity

than a zeolite with Si/Al ratio of 10. Buchanan studied the effects of adding ZSM-5 to

fluid catalytic cracking (FCC) units. The zeolite was found to catalyse C 5+ olefin

isomerisation, with ZSM-5 prepared with higher silica/alumina ratio exhibiting higher

gasoline selectivity.

3. Clays
Clay minerals are found in soils, sediments and rocks and are classified as

phyllosilicates (hydrous aluminosilicates). Generally, they are said to be composed of

particles less than 2 m in size. The vast majority of clays are aluminosilicates or

magnesiosilicates, and consist of repeating layers of silicate [SiO 4]4- sheets

(tetrahedral) and metal oxide sheets (octahedral) bonded together via shared oxygen

atoms and combined in T:O (1:1) or T:O:T (2:1) arrangements, as shown in Figure

2.6. below.

Figure 2.6. T:O and T:O:T arrangements in clays

 38

The 1:1 arrangement of alternating tetrahedral and octahedral sheets uses

hydrogen bonds between the OH on one layer and a bridging O on the next

layer as the main bonding force between layers. Smectities (e.g. montmorillonite) are

composed of the 2:1 arrangement of repeating units of

tetrahedral:octahedral:tetrahedral layers. If the layers are neutral and are simply held

together by van der Waals forces (e.g. talc), then the layers can easily slip over one

another.

C. The Heating of Catalysts

In a zeolite, the aluminosilicate framework and the separate water molecules

are held together by strong bonds, but the bond between the water molecules and the

framework is relatively weak. Consequently, on heating to temperatures of

approximately 100C, water molecules are lost from the zeolite, without affecting the

framework structure.
Liengme and Hall (1966) stated that maximum activity for the zeolite was

achieved when all residual hydroxyl groups associated with catalytically active sites

were removed. Uytterhoeven, Christner and Hall (1965) found that during this

process, both Brnsted and Lewis sites were present on the silica-alumina surface,

with Brnsted sites making up only a small portion of the surface hydroxyl groups. On

heating a clay, desorption of H2O on exterior surfaces and dehydration of interlayer

H2O occurs at low temperatures (< 100C) (Guggenheim and Koster van Groos 2001).

This endothermic effect is accompanied by a loss of mass as the absorbed water is

removed. The second endothermic effect involves the removal of the hydroxyl groups

from the lattice of the mineral in the form of water vapour. For montmorillonite, this is

said to occur from 670C to 710C. On heating, kaolinite was found to show an
 39

endothermic effect at 560C and two exothermic effects with maxima at 960C and

1,250C, with a total weight loss of 14% (Korneva and Yusupov 1976).
Heating a clay is known to increase the Brnsted and Lewis acidity. However,

care must be taken when dehydrating the clay as heating can cause layer collapse

through layer crosslinking, along with elimination of water (ceramification).

Depending on the degree of order, hydrogen bonding and layer spacing, ceramification

of a clay occurs between 300C and 700C.

D. Catalyst Preparation
Catalytic materials exist in various forms and their preparation involves

different protocols with a multitude of possible preparation schemes, many times

larger than the number of known catalysts. Moreover, preparation of any catalyst

involves a sequence of several complex processes, many of them not completely

understood. As a result, subtle changes in the preparative details may result in

dramatic alteration in the properties of the final catalyst (Schwarz 1995).

The goal of a catalyst manufacturer is to produce and reproduce a commercial

product which can be used as a stable, active, and selective catalyst. To achieve this

goal, the best preparative solution is sought which results in sufficiently high surface

area, good porosity, and suitable mechanical strength. The first of these, surface area,

is an essential requirement in that reactants should be accessible to a maximum

number of active sites. The properties of a good catalyst for industrial use may be

divided, at least for the purpose of easy classification, into two categories (Schwarz

1995):
1. Properties which determine directly catalytic activity and selectivity, here such

factors as bulk and surface chemical composition, local microstructure, and phase

composition are important

 40

2. Properties which ensure their successful implementation in the catalytic process,

here thermal and mechanical stability, porosity, shape, and dimension of catalyst

particles enter.

The requirements which are fundamental for catalyst performance generally

require a compromise in order to produce a material which meets the contradictory

demands imposed by industrial processes. An acceptable solution is typically

ascertained by a trial-and-error route. Catalytic materials become catalysts when they

are used in industrial processes. A way this can be realized occurs when the variety of

methods used to prepare catalytic materials are viewed in relation to their successful

implementation in commercial applications (Schwarz 1995).

Figure 2.7. is a simplified diagram which summarizes the traditional methods

used for the preparation of heterogeneous catalysts. The vertical ordering takes into

account the fact that the final catalyst is a solid phase with new properties which have

to be acquired and stabilized during the preparation process while the horizontal

delineation depicts the various methods for blending and mounting to produce the

catalytic material. A noticeable discontinuity does develop here, however, because

some preparative procedures can fit into both cases. In Figure 2.7. two preparation

routes define the extremes of traditional procedures used in catalyst preparation:

precipitation (with the variant of coprecipitation) and impregnation (with such variants

as ion exchange, deposition, and grafting). In the precipitation route, a new solid phase

is obtained by the "blending of proper reagents (precipitating agents) from a liquid

medium; the resulting precipitate is transformed in subsequent preparation stages into

the active catalyst. During these transformations, both the mechanical properties of the

catalyst and those intrinsically related to the catalysts' performance have to be

considered simultaneously. In contrast, in the impregnation route, a solid phase

 41

preformed in a separate process is used as a support, and the catalytically active

material is "mounted" and stabilized on it. In this way, at least a part of the mechanical

properties of the final catalyst'are controlled by the preexisting support, and the

preparation process is basically focused on the introduction of the catalytic

compound(s) (Schwarz 1995).

BLENDING TRANSFORMING
MOUNTING
ACTIVE PRECURSOR

LIQUID LIQUID LIQUID of SOLID SOLID

IN VAPORS
SOLUTION
SOLID SOLID
SOLID PHASE

Metals Deposition
Chemical Reaction
Precipitation Co-Precipitation Firing Kneading
Thin Films Colloidal
Adsorption
Grafting
Complexion Gelatin Heating Evaporating
Bulk Amorphous
Ion exchange
Crystallization
SOLVENT REMOVAL (optional) REACTIONS ON THE SURFACE
INCIPIENT SOLID FORMATION
and SOLID STATE REACTIONS OF PREFORMED SUPPORT

MECHANICAL PROCEDURES
(optional)

ACTIVATION BY THERMOCHEMICAL
PREFORMED SUPPORT
PROCEDURES

FINAL CATALYST

Figure 2.7. Simplified Diagrams Summarizing Methods of Blending, Transforming and

Mounting Catalytic Components

Between these two extremes there lies methods which are best characterized as

solid transformation. Here physical and chemical processes are used to reconstruct a
 42

solid into a form that meets the demands imposed by the processes in which they will

be used (Schwarz 1995).

There are only two main routes for the preparation of almost all catalysts.

These can be divided into the two categories: methods in which the catalytically active

phase is generated as a new solid phase by either precipitation or a decomposition

reaction, and methods in which the active phase is introduced and fixed onto a

preexisting solid by a process which is intrinsically dependent on the surface of the

support (Schwarz 1995).

The simplest kinds of catalysts, from a structural point of view, are single

phase catalysts, such as bulk metals and alloys, bulk oxides, sulfides, carbides,

borides, and nitrides. These materials are, more or less, uniform solids at the molecular

level that exhibit catalytic properties on their external surface. Therefore, these

materials are preferably used in a physical form which allows for a maximum

development of contact of the surface of the material with its environment. To this

end, preparation methods are selected which avoid excessive heat treatments which

would result in the system acquiring a more stable lower surface energy state at the

expense of its active surface (Schwarz 1995).

Bulk oxide catalysts, either single metal or multimetal, used in industrial

processes are usually in the form of powders, pellets, or tablets, with either amorphous

or polycrystalline structure. The most common method used for preparation of bulk

oxide catalysts is the (co)precipitation of a precursor phase, followed by thermal

transformation that leads to the oxidic phase. The ceramic method involving grinding

and firing mixtures of oxides is not very convenient for preparation of oxide catalyst

because of the high temperatures needed. Thus, the trend in the development of

preparation methods has witnessed efforts to eliminate the high-temperature

treatments of the coprecipitated materials (such as calcination of mixtures of

 43

hydroxides and decomposition to oxides) which affect the solid state reactions that

produce the intimately mixed oxide phase that acts as a catalyst. Several alternative

preparation routes that enable a better mixing of the components have been proposed

(Schwarz 1995).
A method of continuous homogeneous precipitation was developed, wherein

the precipitating agent (hydroxyl ions in the classical coprecipitation method) is

slowly and continuously generated in the synthesis medium by a controlled hydrolysis

process (such as hydrolysis of urea). The advantage of slow precipitation is a more

efficient mixing of the components in the precipitated product. The solgel method,

although related to the coprecipitation method, provides better control of the texture of

the resulting catalyst and ensures an increased uniformity of the product. The method

consists in formation of a colloidal dispersion of the metal constituents, usually by

hydrolysis of metal alkoxides. The colloidal solution is then subjected to gelation by

either changing the pH, the temperature, or the electrolyte. The resulting gel is then

heat treated to remove the solvent. Decomposition of coordination compounds,

including polynuclear compounds, is another preparative route that starts from a

precursor where the metallic elements are intimately mixed at the molecular or at the

atomic level. Among the metal complexes that can be decomposed at relatively low

temperatures are oxalates, formates, citrates, and carbonyls (Schwarz 1995).

Bulk sulfide catalysts and mixed sulfide catalysts are prepared most commonly

by either direct sulfidation (i.e., reaction with hydrogen sulfide) of oxides, halides, or

other metal salts. The direct method may require the use of high temperatures. A

second variant is the decomposition of a sulfur-containing precursor, such as a thiosalt,

which is obtained by low-temperature precipitation. A type of low-temperature

coprecipitation is homogeneous sulfide precipitation, wherein the mixing of the metal

salts is made before any addition of the precipitant. Recently, a new genre of single
 44

phase catalysts has emerged in which the entire solid rather than just the external

surface is involved in catalysis. The new materials are crystalline solids which contain

active sites uniformly distributed throughout their bulk at the intracrystalline level.

This family of uniform heterogeneous catalysts, generally referred to as molecular

sieves, includes microporous zeolites, aluminium phosphates, with metal- and silicon-

substituted analogs, layered compounds such as clays and their pillared variants,

layered oxides with perovskite structures, and heteropolyacids with a liquid-like

behaviour (Schwarz 1995).

The possibilities for preparation of materials in this class are vast since they

exploit the virtually unlimited number of ways to link together atomic units in a

crystalline or polymeric structure. Their methods of preparation consist of a

combination of chemical (precipitation, leaching) and physical (supercritical

crystallization) procedures. The common features of all the preparation methods

summarized above for bulk catalytic materials is the use of traditional methods and

techniques from preparative chemistry, such as precipitation, hydrolysis, and thermal

decomposition. The chemistry involved during these preparation steps does not differ

much from that taught in classical handbooks of analytical or inorganic chemistry.

These processes involve mixing of solutions, blending of solids, precipitation,

filtration, drying, calcination, granulation, tableting, and extrusion. In other words, the

chemistry involved is three dimensional with the meaning that it is isotropic with

respect to the container in which it is done (Schwarz 1995).

The method of precipitation is the best known and most widely used procedure

for synthesis of both monometallic and multimetallic oxides. Precipitation results in a

new solid phase (precipitate), that is formed discontinuously (i.e., with phase

separation) from a homogeneous liquid solution. A variety of procedures, such as

addition of bases or acids, addition of complex-forming agents, and changes of

 45

temperature and solvents, might be used to form a precipitate. The term

coprecipitation is usually reserved for preparation of multicomponent precipitates,

which often are the precursors of binary or multimetallic oxidic catalysts. The same

term is sometimes improperly used for precipitation processes which are conducted in

the presence of suspended solids (Schwarz 1995).

Depending on the particular application, the newly formed solid phase may be

further subjected to various treatments, such as aging and hydrothermal

transformation, washing, filtration, drying, grinding, tableting, impregnation, mixing,

and calcination. During all these preparative steps, physicochemical transformations

occur which can profoundly affect the structure and composition of the catalyst

surface and even its bulk composition. If the adage the catalyst remembers how it

was prepared, even after being subjected to various heat treatments at elevated

temperatures is valid, then any cause-and effect correlations that can eventually be

made between the precipitation procedures and the final characteristics of the catalyst

becomes significant (Schwarz 1995).

a. Precipitation

The formation of the precipitate from a homogeneous liquid phase may occur as a

result of physical transformations (change of temperature or of solvent, solvent

evaporation) but most often is determined by chemical processes (addition of bases or

acids, use of complex forming agents). In almost all cases, the formation of a new solid

phase in a liquid medium is resulted from two elementary processes which occur

simultaneously or sequentially (Schwarz 1995):

(1) nucleation, i.e., formation of the smallest elementary particles of the new phase

which are stable under the precipitation conditions

(2) growth or agglomeration of the particles
 46

It is stressed in the importance of supersaturation, among other factors such as pH,

temperature, nature of reagents, presence of impurities, and method of precipitation in

determining the morphology, the texture and the structure of the precipitates. For example,

under conditions of high supersaturation, the rate of nucleation of solid particles is much

higher than the rate of crystal growth and leads to the formation of numerous but very

small particles. Under the condition when the critical nucleation size is very small, only a

metastable and poorly organized phase can develop; this may further change to a more

stable phase during the hydrothermal treatment of the precipitates. Obtaining high

supersaturation conditions is a difficult task in practice because of the natural evolution of

the system toward a decrease of supersaturation by nucleation of solid particles and

consumption of reagents. High levels of supersaturation can only be obtained for a short

time and within limited volumes of solution. The problem of obtaining a homogeneous

precipitate with respect to the size and structure of the particles reduces to that of

achieving a uniformly high level of supersaturation throughout the liquid before the

nucleation starts, which may be quite difficult because of mass and heat transport

imitations. The chemical and physical properties of the precipitates kept in contact with

their mother liquor may change, often substantially, due to secondary processes taking

place in the suspension. One of these processes, known as Ostwald ripening, leads to an

increase in the particle size of a precipitate. Because the solubility increases with

decreasing particle size, small particles begin to dissolve and large crystals continue to

grow (Schwarz 1995).

Another process which takes place during aging of precipitates is agglomeration of

colliding particles as a result of either Brownian motion or imposed mechanical forces.

The most common catalysts derived from precipitation are aluminas. In order to

emphasize the significance of the variables described above on the physicochemical

 47

properties of the finished material, we will devote some effort to outline the procedures

used to formulate aluminas. Because of its industrial importance, the preparation of

aluminas of controlled porosity and surface area continues to be the focus of a large

number of investigations (Schwarz 1995).

Studies on the preparation of alumina in the absence of additives showed that the

pore size distribution and the surface area are determined mainly by conditions of

precipitation and aging. Development of these properties is due to the interconversion of

amorphous hydroxide, pseudoboehmite, and bayerite formed during precipitation.

Washing and drying were found to have little influence on texture for samples precipitated

from ammonia and aluminum nitrate but contributed to the enlargement of pores when

NaOH was used in precipitation. More control is possible by the use of additives.

Alcohols added before precipitation of aluminum hydroxides only had an effect on the

pore size when their adsorption on the precipitate was strong enough to replace the

solvent barrier at the surface of precipitates. With these additives, the solubility of

precipitates is decreased, leading to decreased Ostwald ripening and thus encouraging

aggregation by particle bridging. Alcohol washing after precipitation produces higher

surface areas and higher mesoporosity due to lower surface tension and less pore collapse

during calcination (Schwarz 1995).

The thermal and physical characterization of the conversion of pseudoboehmite to

-Al2O3 were reviewed: and the relationship with the manufacturing route of the

pseudoboehmite powder was shown. In general, physical properties like particle size and

shape, crystallinity, and porosity have a distinct influence on the thermal behavior of

pseudoboehmite powders. Better characterization of thermal and physical properties has

allowed one to improve catalyst manufacturing at the industrial level. Unit operations
 48

such as mix-mulling, extrusion, drying, and calcination are clearly affected by powder

characteristics (Schwarz 1995).

The calcination step may induce further changes in the texture of the finished

supports. Under conventional operation conditions, -Al2O3 is stable, but at temperatures

between 1250 and 1350 K a phase transformation through metastable - and -Al2O3

leads to formation of -Al2O3. The process is accelerated by steamll and results in a

drastic drop in surface area which is caused by sintering of primary particles. The

versatility of alumina to be produced with a broad range of surface areas and pore size

distributions is in part due to the phase transformations during calcination. A systematic

study of aluminum oxides obtained by heat treating of -Al 2O3 showed that a

monodisperse structure is preserved below 1375 K, with a slight increase in the average

pore radius. Formation of the -Al2O3 phase is related to the generation of a new system

of wider pores that again becomes monodispersed when the -phase is completely formed.

A relationship between porosity and mechanical strength was proposed for alumina

catalyst (Schwarz 1995).

A number of studies report methods to increase the thermal stability of -Al 2O3

particles by introducing various additives. The subject was recently reviewed in relation to

preparation of stable materials for high temperature combustion. For example, it was

reported that several ions (In3+, Ga3+, and Mg2+) have an accelerating influence while

others (Zr4+,Ca2+, Th4+, La3+) have an inhibiting action during the transformation of

aluminas to the -phase. The effect of thermal stabilizing modifiers is due to surface

nucleation of stable compounds, which by interaction with the underlying alumina, results

in the formation of an aluminate surface layer which prevents transformation of to

alumina but may also modify the Lewis acidity of alumina. According to other results,

addition of alkaline earth metals (Ca, Sr, Ba) increased the ability to preserve a high
 49

surface area (5 m2 g-l) after calcination at 1700 K. Since small BaO.6Al2O3 crystallites

prepared through a coprecipitation route had a similar sintering resistance, it was

concluded that formation of barium hexaaluminate is a promising option for stabilizing

combustion catalyst supports (Schwarz 1995).

An alternate method to achieve the thermal stabilization of alumina without

foreign additives was also reported. Since the transition of metastable phases to -Al2O3

occurs predominantly at the contact between primary particles, the key for suppressing the

rate of sintering without additives is preparing active aluminas in a morphological state in

which the area of contact between primary particles is minimized. Alumina prepared by

fume pyrolysis of sols consists of fibrillar boehmite, approximately 100 nm in length and

10 nm in diameter. After calcination at 1473 K for 30 h, the material maintained a surface

area of 50 m2 g-l and still consisted of fibrils. This was ascribed to the suppression of the

phase transformation to -Al2O3. In the case of Mg(OH)2 as the starting reagent, washing

with alcohol of the hydroxide precipitate leads to a drastic decrease in surface area of the

calcined MgO. The effect was ascribed to formation of surface alkoxides and induction of

particle-particle bridges through surface condensation reactions. This process favors the

development of order in the precipitate. The bridges formed during washing were

maintained through the calcination step. Also, the morphology of Mg(OH)2 precipitates

was found to be dependent on whether the pH during precipitation and aging was above or

below the isoelectric point (pH = 12). This demonstrates the influence of the electric

charge of primary particles on their tendency toward aggregation (Schwarz 1995).

b. Coprecipitation

In the synthesis of multicomponent systems, the problems are even more complex.

Coprecipitation rarely allows one to obtain good macroscopic homogeneity. In a system

with two or more metallic compounds, the composition of the precipitate depends on the
 50

differences in solubility between the components and the chemistry occurring during

precipitation. Generally, under the conditions of either a slow precipitation rate or poor

mixing within the reaction medium, coprecipitation is selective and the coprecipitate is

heterogeneous in composition. Subsequent to formation of the coprecipitate, hydrothermal

treatments which transform amorphous precipitates to crystalline materials with improved

thermal stability and surface acidity may be carried This procedure is widely applied to

prepare molecular sieves. Depending on the composition of the precipitate formed, two

chemical routes should be distinguished in the coprecipitation procedures. The simplest

case is that of sequential precipitation of separate chemical compounds. This occurs

whenever there is a large difference in the solubility products of the compounds involved.

The so-called coprecipitates of hydroxides, hydroxo carbonates, oxalates, and formats

containing two or more different metals are generally non-homogeneous in composition

and only very seldom generate a homogeneous mixed oxide by solid phase reactions at

high calcination temperature. Doping or substitution of ions in these precipitates is

difficult because of the different reactivities involved. The second possibility is the

formation by coprecipitation of a well-defined chemical compound which might serve as a

chemical precursor from which the final catalyst is obtained. The intermediate compound

must be easily decomposed under mild calcination. This route is preferred whenever a

better intimate mixing of the catalyst components is desired. The metal ratio in the

precursor compound is, however, restricted to a quite rigid stoichiometry. Crystalline

stoichiometric precipitates formed by several metal oxyanions (vanadates, chromates,

tungstates, and molybdates) and a second metal cation may be further used to obtain an

intimate interdispersion of the two metals. As an example, the activity of Cu/Cr catalysts

depends on the amount of copper chromate, CuCrO4, formed during their preparation, and

this is the precursor of the most active sites of the final catalyst (Schwarz 1995).
 51

Other intermediates extensively studied as catalyst precursors comprise the class

of mixed-metal hydrated hydroxo carbonates with a layered structure. Thus, during

preparation of active copper catalysts used for synthesis of hydrocarbons or methanol by

hydrogenation of CO the copper phase must be obtained highly interdispersed with at least

one other oxide component. This structure stabilizes the very small CuO particles and

favors further interaction of copper with the host oxide. A high degree of homogeneity at

the atomic level for this class of catalysts may be achieved by decomposition of single

phase precursors, such as either the hydroxo carbonates with the aurichalcite structure,

(Cu,Zn)5(C02)2-(OH)6, from which binary Cu,Zn catalysts are prepared or with the

lamellar hydrotalcite-type crystalline for preparation of highly active ternary catalysts, Cu

Zn/(Al,Cr,Ga,Sc) (Schwarz 1995).

The details of precipitation of these single phase precursors involve a careful

control of pH and the rate of precipitation; the morphology of the precursor may influence

the degree of interdispersion of the final multiphase catalyst. In these systems, because all

elements are homogeneously distributed in the hydrotalcite phase, no surface segregation

is observed and pseudomorphic thermal decomposition leads to a spinel-type oxide. The

limits between which the ratio of metals in the catalyst may be varied depends on the

stoichiometry and structure of the single phase precursor: for the Cu/Zn binary

aurichalcite, it may be changed between quite large limits (0.02 to 0.301, while the

structure of the ternary hydrotalcite allows the Cd Zn/Me ratio to be varied within much

narrower limits; a typical value for single phase precursors of copper-based catalysts is

30/45/25. The hydrotalcite like coprecipitated precursors were recently used as

intermediates for the preparation of other nonstoichiometric spinel-type catalysts, with the

general formula M1+yCr2-2y/3O4 (M = Zn, Cu, Co); they are employed as catalysts for

specific hydrogenation reactions (Schwarz 1995).

 52

With a proper selection of metals and complexing agents, precipitation of mixed-

metal polynuclear coordination compounds is possible. The use of coordination

compounds as raw materials is a nonconventional procedure to prepare mixed oxides by a

mild thermal decomposition. Recent literature in inorganic chemistry often makes

reference to synthesis and characterization of several types of binuclear coordination

compounds with molecularly organized structures that contain metals of interest for

preparation of catalysts. For example, mixed metal complexes in the general series

{NBu4[MCr-(ox)3]}x (where NBu4+ = tetrabutylammonium ion, ox2- = oxalate ion, and M

= Mn2+, Fe2+, Co2+, Ni2+, form a three dimensional structure comprised of alternate arrays

of Cr(III) and M(II) metals. Also in the series of -oxo-trinuclear mixed metal carboxylate

complexes. [M2IIIMIIO(ac)6L3]. nL, where MIII = Fe, Co, Cr, M II = Fe, Co, Ni, Zn, Mn, Mg,

and L= py, H2O, the molecular structure is composed of trinuclear, oxo-centered M 2IIIMIIO

units (Schwarz 1995).

It is known that thermal decomposition of polynuclear coordination compounds of

the latter type yields mixed oxides with spinel structure. This suggests the use of other

coordination compounds such as those mentioned above as potential precursors for the

binary mixed oxides in the system CuO-ZnO-Cr 2O3. For the moment, preparation of

ternary mixed-metal compounds remains a more difficult task. Polynuclear mixed metal

complexes deserve more attention as precursors for the preparation of catalysts. This

methodology has the advantage that the component metal ions are intimately bound in the

molecular structure of the polynuclear compound and a homogeneous mixed-oxide phase

or a composite oxide is more easily formed after either a mild decomposition or a

hydrothermal treatment at moderate temperatures (Schwarz 1995).

Finally, a new approach to the precipitation method is the use of organic solvents

as precipitation media. The colloid chemistry is not easily extrapolated from the aqueous
 53

phase to organic systems. In addition, organic solvents pose practical problems to catalyst

manufacturing, but these difficulties can be offset by the special properties of catalysts

precipitated from organic so1vents (Schwarz 1995).

It is conceivable that the catalyst obtained in organic media has more accessible

active sites than the catalyst obtained from the aqueous route. The difference in the texture

corresponds to a high-performance catalyst which has found commercial recognition. In

this example, the precursor acts as an improved matrix for the crystalline growth of the

oxide active phase during the topotactic transformation. The properties that the solid will

develop as a final catalyst are strongly affected by all structural and morphological

changes which occur during the topotactic transformation (Schwarz 1995).

E. Catalyst Deactivation
Physical changes in a catalyst can lead to decay in performance. The five main

causes of deactivation are poisoning of the active sites, fouling by coke deposits,

thermal degradation, mechanical damage and corrosion/leaching by the reaction

mixture. Poisoning occurs by adsorption of impurities in the feed, whilst fouling

involves the covering of a surface with a deposit such as coke. If an impurity is not too

strongly adsorbed on the catalyst and no reconstruction of the active site has occurred,

regeneration of the catalyst may be possible. Many catalytic processes form

carbonaceous deposits or coke on the catalysts and this is the most common type of

poisoning caused by reactants or products. Coke is produced by unwanted

polymerisation and dehydrogenation (condensation) of organic molecules present in

the feed or formed as a product. The reactions leave a layer of highly hydrogen

deficient carbonaceous material on the catalyst surface, making the active sites

inaccessible.
Holdeman and Botty (1959) carried out electron microscopy studies to

characterise the carbon deposits of silica-alumina catalysts. The results indicated that
 54

the coke deposited was a finely divided, highly dispersed phase present within the

ultimate pore structure of the catalyst. Holmes et al., (1997) carried out sorption

studies on a sample of ZSM-5 to locate coke within the zeolitic pores and to

differentiate between poisoning and blockage of the active sites. The coke formation

was found to involve two major steps. The initial cracking reaction generated alkenes,

which then underwent secondary reactions (cyclisation, dehydrogenation) to form

substituted benzenes and naphthalenes. These smaller aromatics then underwent

further cyclisation and dehydrogenation to form larger insoluble aromatic compounds.

The coke was found to be located on both the external surface and within the zeolite

pores.
Hopkins et al., (1996) investigated the acidity and cracking activity during

coke deactivation of ultrastable Y zeolite. Compared to a fresh USY zeolite, coke

deactivated H-USY did not show significant changes in the acid strength distribution,

number of acid sites, fraction of Brnsted and Lewis acid sites or pore size

distribution. However, rapid loss in activity was observed and was said to be due to

deposition of coke on active sites near the external crystal surface. Active sites in the

inner portion of the zeolite particles were said to have remained unaffected by the

coke.

2.3. Description Process of Previous Researches

2.3.1. Vacuum Pyrolysis of Waste Tires with Basic Additives

Xinghua Zhang et. al. conducted an experiment of pyrolyzing Chinese car tires

rubber with NaOH and Na2CO3 additives in a vacuum condition. The experiment was

run at different temperature in order to selectively obtained valuable chemicals such as

dl-limonene.
 55

Figure 2. 8. Schematic Diagram of Experimental Apparatus

(1) Pyrolysis Reactor (4) Liquid Collector (7) Vacuum Relay

(2) Electrical Furnace (5) Secondary Condenser (8) Electromagnetic Valve
(3) Primary Condenser (6) Safe-buffer (9) Vacuum Pump

Tire granules were sieved to a size range of 20-60 mesh and manually mixed

with the powder anhydrous Na2CO3 and NaOH. The pyrolysis was performed in a

stainless steel pyrolysis reactor equipped with several stainless steel plates to

strengthen heat transfer. In the entire process the pyrolysis pressure was maintained at

3.5-4.0 kPa with temperature range from 450-600oC.

With the increasing pyrolysis temperature, the yield of oil increased and the

residue decreased correspondingly. NaOH presence in the process resulted in the

highest value of oil yield at the same temperature reaction, 49.7 wt% at 480oC.

2.3.2. Pyrolysis of Latex Gloves in the Presence of Y-Zeolite

In 2009, William J. Hall et. al. pyrolyzed two different brands of commercial

rubber gloves in a fixed bed reactor (FBR). They occupied Y-zeolite catalyst in the

process that was in the form of pellet and was activated at 550 oC for 2 hours. Y zeolite

catalyst used in this study was composed of SiO2/Al2O3 ratio of 80.

Figure 2. 9. Fixed Bed Reactor Schematic

 56

Two rubber gloves were mixed together and pyrolized in a fixed bed reactor.

The pyrolysis temperature was either 380oC or 480oC. In the absence of catalyst, the

pyrolyis oil consisted of dimmers, trimers, tetramers, pentamers, and hexamers, with

limonene (dimer) being the most abundant compound.

The Y-zeolite catalysed the formation of aromatic compounds such as toluene,

xylene, ethyltoluenes, and naphthalenes, including naphthalene itself. It is also

eliminated limonene and the polyisoprene oligomers that were present in the non-

catalytic oil.
2.3.3. Thermal Conversion of Scrap Tyres
Bajus and Olahova investigate the pyrolysis of both car and truck tires in a

vacuum condition to find out the experimental conditions that can maximized liquid

yields. Initially, scrap tyres were decomposed thermally in a batch reactor in an inert

atmosphere for around 100 minutes. The final temperature of thermal degradation is

450oC with heating rate 16.5oC/min to 350oC, 8 minutes temperature stabilization;

heating rate 9oC/min up to 44oC, heating rate of 7.5oC/min up to 480oC.

The gas samples were taken at temperature 400oC, 450oC, and one hour after

reaching the temperature 450oC in the first experiment and on reaching the

temperature 570oC in the second experiment. The results show that the production of

aromates C7-C10 decreased with the increasing temperature. This behaviour of

aromatic fraction is due to Diels-Alder reactions that promote the formation of

aromatic compounds from olefins. Isoprene and Benzene with temperature and the

yield of aromatic C7-C10 fraction decreases, which is due to thermal cracking and

secondary reactions at high temperatures. Meanwhile, Limonene is very unstable at

high temperatures and operating under these conditions its yield undergoes a reduction

to 4.6 wt. % at 570oC from 9.0 wt % at 450oC.

2.3.4. Copyrolysis of Scrap Tires with Oily Wastes
In addition to pyrolysis conversion technology, there is another approach to

utilize carbonaceous waste, called co-pyrolysis. Onenc et. al. for instance, who co-
 57

pyrolized scrap tires and oily waste from ships to liquid fuels or chemical feedstock in

the presence and absence of catalysts. Their work was aimed to see the influence of

catalyst use and reaction temperature. It is reported that there was no influence of

temperature on the product distribution over 500oC in scrap tires pyrolysis. The

catalyst showed similar activity but Red Mud catalyst left fewer residue than that

compared to ReUS-Y faujisite catalyst. Nevertheless, both catalyst had great effect on

the distribution of compounds in the pyrolysis oils of scrap tires-oily waste mixture,

particularly in D-limonene amount.

Figure 2.10. Schematic Diagram of the Pyrolysis Installation

2.3.5. Liquefaction of Waste Tires by Pyrolysis for Oil and Chemicals A Review
In accordance to review of some researches conducted over the last three

decades, oil yields fluctuated with both temperatures and heating rates with no

discernible trend (Quek and Balasubramanian 2013). It is also stated that low

pyrolysis temperature and pressure as well as short vapour residence time increased

the limonene yield (Pakdel, Pantea and Roy 2001). As when catalysts, such as HZSM-

5, HY and HBeta zeolites were occupied in reaction, gas yield and light aromatic

hydrocarbon increase at the expense of the decreasing limonene yield (Quek and

Balasubramanian 2013).

2.4. Reaction Mechanism

 58

Natural rubber conversion to limonene goes under a chain reaction, as illustrated

below:

A B

A+B C

A+C D

Therefore, to get to limonene compound, natural rubber has to take several

stages. The mechanism of natural rubber monomer dimerization to limonene is as stated

as:

Due to the given heat from thermal degradation process, polymer of isoprene

breaks forming radical ion.

Empty s orbital ion H+ later forms temporary bonds with two end C atom. This

phenomenon is known as Markownikoffs rule.

With the presence of two positively charged H atom, the reactive radical forms a

reactive 2-methyl-1-butene compound.

 59

Atom C in radical ion attacks positively charged atom C in reactive 2-methyl-1-

butene, to form limonene.

By releasing one H+ atom, electron from CH3 bond with C+H2 resulting in 1-

methyl-4-(1-methylethenyl)-cyclohexene compound, also known as limonene.

CHAPTER III
RESEARCH CONCEPT DESIGN

Limonene production from natural rubber is carried on two steps processes, which are

catalyst preparation and catalytic reaction.

 60

3.1. Materials

3.1.1. Natural Rubber

Bulk natural rubber is supplied by PT. Sri Trang Lingga Indonesia of

Palembang branch. Table 3.1 provides its composition analysis that is based on

Indonesia National Standard (SNI).

Table 3.1. Natural Rubber Composition

Parameter Analysis Result

1. Dirt (%) 0.074
2. Ash (%) 0.450
3. Volatile Matter 0.200
4. N2 0.320
5. Po 36
6. PRI 72
(SNI 06-1903-2000)
The pyrolysis reaction performed for limonene production uses fixed natural

rubber mass of 80 gram for each run.

3.1.2. Catalyst

There is barely any literature review available for using catalyst in the

formation of limonene from rubber based material. Commercial catalysts used in those

researches apt to produce oil with lower limonene content. In order to have a catalyst

that may help to increase limonene content in the reaction, it is decided to leave

commercial catalyst use and turn to self-produce it.

The catalyst used for natural rubber conversion is initially prepared through

precipitation method from CaO (calcium oxide) compound as main catalyst and SiO 2

(silica dioxide) as support catalyst. Powdered CaO supplied by PT Maju Agung

Lestari has 90% purity, while SiO 2 supplied by PT. Sinergi Bersama Sukses has 99%

purity. Due to SiO2 insolubility with various solvent other than hot base solution,

Natrium hydroxide (NaOH) is used to dissolve it. Meanwhile, Hydrochloric acid

 61

(HCl) is used to dissolve CaO and activate the catalyst. The CaO/SiO 2 catalyst is then

used in reactor with varied bed volume of 80, 100, 120 gram.

3.2. Catalyst Preparation

Precipitation method is used to prepare catalyst from CaO as main catalyst source

and SiO2 as support catalyst that is to be used in catalytic pyrolysis reaction of natural

rubber conversion. Figure 3.1 depicts the preparation stages to derive activated CaO/SiO 2

catalyst.
S
A
W
C
A D Dissolved in hot NaOH at 100oC
itg
a s
a
c r t
O
ih CaO
i
y
At 100oC for 1 hour
li v
rn Dissolved
t g
in HCl at room
c
a i temperature
At 30-35oC for 24 hours
rg
a n
ien d
id g
n
C
n
F i l
a t At 110oC for 12 hours
g
tta e r
i l
in
y n s
At 500oC for 4 hours

g
g
t
Figure 3.1. Catalyst Preparation Steps

The catalyst preparation step is initiated by having 98 gram silica dioxide (SiO 2)

dissolved in 860 mL base solution of natrium hydroxide (NaOH) at 100 oC. Then, liquid

silicate is mixed and stirred with 72 gram calcium oxide (CaO) which is dissolved in 51

mL hydrochloric acid (HCl) at room temperature prior to mixing. The mixing of both
 62

main catalyst calcium oxide (CaO) dissolved in hydrocholoric acid (HCl) and silica

dioxide (SiO2) support catalyst is intended to generate catalyst complex with

hydrocholoric acid (HCl) as the activator. The precursor catalyst complex is stirred at

temperature 100oC for 1 hour. It is then left for 24 hours at room temperature for aging.

The resulting precipitate from aging stage is washed with deionized water then

simultaneously filtered. After filtering, it was then dried at 110 oC for 12 hours. The

drying is intended to remove the physisorbed water and not the chemisorbed water

(Carlsson, et al. 2012). Finally, the CaO/SiO 2 catalyst is calcined at 500oC for 4 hours to

have an activated catalyst. Calcination is also aimed to increase the catalyst support

strength which goes along with the increasing calcination temperature (Carlsson, et al.

2012).
After the activated catalyst is prepared, it is then used to evaluate its performance

in the production of limonene from natural rubber. In a vacuum pyrolysis process, the

catalyst is placed in the fix bed reactor to be in contact with reactant. In addition, the

CaO/SiO2 catalyst characterization is performed by using SEM (Scanning Electron

Microscopy) method.

3.3. Experimental Process Description

 63

Figure 3.2. Catalytic Vacuum Pyrolysis Reaction of Natural Rubber Conversion

Apparatus
 64

Figure 3.3. Catalytic Pyrolysis Reaction of Natural Rubber Conversion Apparatus

Degradation of polyisoprene along with the formation of pyrolytic oil goes under

a catalytic reaction as described in Figure 3.2. As feed material, 80 gram of natural

rubber is fed to the raw material tank (2) to be heated at varied temperature from 325,

350, 375 and 400oC. Prior to heating, vacuum pump (1) is used to evacuate air from raw

material tank (2) to make sure that no air or oxygen exists during the heating process.

Meanwhile, pressure indicator control is occupied to monitor gas pressure resulted from

natural rubber cracking in the raw material tank. The resulting gas is channeled through

gas valve to gas storage tank (3) in order to maintain low pressure condition. There is

also a pressure indicator control installed at gas storage tank (3) to record the pressure of

gas reactant.

Gas reactant from gas storage tank (3) will then flowed to the fixed bed reactor

(4) with existing CaO/SiO 2 catalyst inside. Catalyst mass used in pyrolysis reaction is

varied 80, 100, and 120 gram. Both gas reactant and powdered catalyst are contacted in

fixed bed reactor (4) at temperature that is set to be the same as temperature at raw

material tank (2). Gas product out from reactor (4) is temporarily expanded in flash tank

(5) before entering condenser (6). Pressure at fixed bed reactor (4) as well as pressure at

flash tank (5) is also monitored.

The gas product that flows out from flash tank (5) and enters condenser (6) is

cooled down by the cooling water provided from water tank (7). A centrifugal pump (8) is

used to circulate water from water tank (7) into and out from condenser (6) to cool gas

product inside condenser tube. Thus, liquid sample as the result of condensed gas product

was collected. This sample is then to be analyzed further by Gas Chromatography/Mass

 65

Spectrometry (GC/MS) to observe quantitatively the oil content in it, limonene in

particular.

CHAPTER IV
RESULTS AND DISCUSSION

4.1. Catalyst Characterization

CaO/SiO2 catalyst that is used in this work was analyzed through SEM (Scanning

Electron Microscopy) method.

Figure 4.1. SEM analysis of CaO/SiO2 catalyst

 66

SEM analysis of CaO/SiO2 catalyst with 22500 times magnifying as depicted in

Figure 4.1. showed its irregular shape and pore size. From four spots that were measured,

the catalyst pore size was ranged between 98-647 nm.

The catalyst used in this experiment is vulnerable to coking, since it is used in

reaction with polymer reactant. Polyisoprene as the main component of natural rubber

forms other compounds beside limonene from its monomers. Too many chemical

compounds formed may cause the desired product is blocked from entering catalyst

active sites resulting in an ineffective catalyst activity.

4.2. Pyrolytic Oil Characterization

Natural rubber conversion to limonene through vacuum pyrolysis produced both

solid residue and pyrolytic oil. The detailed product distribution is as listed in Table 4.1.

Table 4.1. Product Distribution of Natural Rubber from Varied Pyrolysis Condition

Reaction Solid
Catalyst Mass Pressure Pyrolytic Oil
No. Temperature Residue
(gr) (bar) (ml)
(oC) (gr)
1. 325 5.2
3.0 1.03
2. 350 5.8
2.2 1.79
80
3. 375 8.0
3.2 3.01
4. 400 9.4
2.7 8.42
5. 325 7.6
2.2 2.48
6. 350 15.0
2.8 3.97
100
7. 375 15.5
1.0 4.19
8. 400 17.0
1.9 1.79
120
9. 325 9.5
2.2 9.06
10. 350 6.8
1.8 1.35
 67

11. 375 12.0

2.2 5.53
12. 400 11.0
2.0 3.26

Overall assessment shows that temperature plays an important role in the

increasing of pyrolytic oil. In majority, pyrolytic oil produced increases along with the

increasing temperature. Although, some result doesnt show that tendency due to other

factors that may cause improper measurement. This is possible due to the leakage of

reactant gas during the running process. Other pattern is to see the influence of pressure

to the achieved pyrolytic oil. It can be seen that, for reaction run at the same temperature

condition yet lower pressure, the resulting yield reached higher value than the one that

run at higher reaction pressure.

Furthermore, GC/MS analysis showed that the content of oil produced from the

catalytic pyrolysis of natural rubber can be simplified for classification as follow:

1. Limonene, as the main purpose of the experimental project is to produce high content

of limonene in oil yield.

2. Naphthalene along with its isomer and derivatives, as the prominent compounds

found in the pyrolytic oil.

3. Other aromatic compounds, since the rest compounds formed in pyrolitic oil are

classified as aromatic.
 68

90
80
70
60
50
Percent Area (% ) 40
Limonene Naphthalene Other Aromatic Compounds
30
20
10
0
300 325 350 375 400 425
Temperature (oC)

Figure 4.2. shows the effect of pyrolytic temperature to the content of limonene,

naphthalene and other aromatic compounds for 80 gram CaO/SiO 2 catalyst and 80 gram

natural rubber used.

Figure 4.2. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 80 gram Catalyst and 80 gram Natural Rubber
 69

70

60

50

40
Percent Area (% )
30
Limonene Naphthalene Other Aromatic Compounds
20

10

0
300 325 350 375 400 425
Temperature (oC)

The figure shows that limonene line gives insignificant increase at 375 oC and 400oC,

though the amount initially decreased at 350oC. The highest value that it reached was

5.29% area for catalytic pyrolysis at 400oC. Meanwhile, the figure shows as if

naphthalene and other aromatics other than limonene and naphthalene are influencing

each other.

Figure 4.3. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 100 gram Catalyst and 80 gram Natural Rubber
 70

Nearly the same as the result shown in Figure 4.2., Figure 4.3 also shows that

initially limonene percent area drop at 350 oC. It topped at 400oC for as much as 12.96%

area. The interesting one is that, unlike Figure 4.2., Figure 4.3 shows that the changing

of limonene is parallel to that of other aromatics compounds, and conversely to that of

naphthalene. It seems that by having bigger catalyst ratio to natural rubber, both

limonene and naphthalene content in pyrolytic oil is affected, conversely. In pyrolysis

reaction using 100 gram catalyst and 80 gram natural rubber, limonene percent area

content to the total compound found in the pyrolytic oil increases at 400 oC significantly

in comparison with the one that used 80 gram catalyst and 80 gram natural rubber.

60

50

40

30
Percent Area (% )
Limonene Naphthalene Other Aromatic Compounds
20

10

0
300 325 350 375 400 425
Temperature (oC)
 71

Figure 4.4. Effect of Temperature on Pyrolytic Oil Percent Area for Catalytic Pyrolysis
Reaction with 120 gram Catalyst and 80 gram Natural Rubber

Figure 4.4. rounds off the conclusion that limonene percent area is always

dropped at 350oC from that of the amount at 325oC and continue to increase and reach

the largest value at 400oC. Limonene percent area content for the pyrolysis reaction using

catalyst CaO/SiO2 peaks at 14.89% for reaction using 120 gram catalyst and 80 gram

natural rubber at 400oC.

In contrast with limonene amount that increases along with the catalyst mass

used, naphthalene content seems to decrease. Meanwhile, other aromatics compounds

content seems to give different pattern. It tends to be independent from both limonene

and naphthalene content in the pyrolitic oil, either judging from temperature factor or

catalyst mass used in the experiment.

Figure 4.5. to Figure 4.7. shows the effect of temperature and natural rubber to

catalyst ratio on each groups peak area. Limonene, naphthalene and other aromatics

compounds percent area change is shown in Figure 4.5, Figure 4.6 and Figure 4.7,

respectively. The ratio of natural rubber to catalyst ratio used in the experiment is

growing smaller. Initially, the ratio is 1:1 for natural rubber and catalyst used. For the

second variation, the amount of catalyst used is increased while natural rubber is fixed.

This variation change the ratio of natural rubber to catalyst be 4:5. Meanwhile, the last

variation is to have the smallest of all three variations. Catalyst mass is added to have

natural rubber to catalyst weight ratio used in the experiment is 2:3.

 72

20
18
16
14
12
10
Percent Area (% )
8
1:1 4:5 2:3
6
4
2
0
300 325 350 375 400 425
Temperature (oC)

Figure 4.5. Effect of Natural Rubber to Catalyst Ratio and Temperature on Limonene Peak
Area in Pyrolytic Oil

As it can be seen from Figure 4.5, limonene content reached its peak at 400oC for

reaction that occupied smaller natural rubber to catalyst ratio. For each ratio, limonene

content is found to drop at 350oC before it slowly rises at 375oC. Although the conclusion

may not be fully agreed due to the significant different pattern showed by the result

achieved from samples that run using 4:5 natural rubber to catalyst ratio.
 73

Leakage may be the factor that gives the unsatisfying result drawn off by samples

of catalytic pyrolysis using 4:5 ratio of natural rubber to catalyst. Despite that, it is

concluded that temperature does influences the formation of limonene from natural

rubber main component monomers, isoprene.

60

50

40

30
Percent Area (% )
1:1 4:5 2:3
20

10

0
300 325 350 375 400 425
Temperature (oC)

In contrast to limonene content that increases along with the decreasing ratio of natural

rubber to catalyst, naphthalene content tend to drop at the maximum temperature

attempted in this experiment.

 74

Figure 4.6. Effect of Natural Rubber to Catalyst Ratio and Temperature on Naphthalene
Peak Area in Pyrolytic Oil

Figure 4.6 clearly showed that naphthalene content gives no rising for

experiment that uses smallest natural rubber to catalyst ratio. Even though, it increases

along with temperature at other natural rubber to catalyst ratio variations, naphthalene

content drops at the highest temperature attempt for every ratio varied.

It reached its peak at 375oC for samples that uses 1:1 ratio or 80 gram of natural

rubber with 80 gram of catalyst. This maximum content of naphthalene reached 8.42% of

total compound found in that sample read at minute 8.77 by GC/MS.

As for aromatic compound other than naphthalene and limonene, Figure 4.7

depicts its percent area of total compound contained in the pyrolitic oil obtained. It is

obvious that more aromatic compound is to be found from the samples that occupied

higher temperature. This is due to the tendency of polymer to crack and form other

compounds with lower carbon content when subjects to high temperature condition.

100
80
60
40
Percent Area (% )
20
1:1 4:5 2:3
0
325375425
300350400
Temperature (oC)
 75

Figure 4.7. Effect of Natural Rubber to Catalyst Ratio and Temperature on Other Aromatic
Compounds Peak Area in Pyrolytic Oil

As it can be concluded from Figure 4.7, other aromatics compounds content

increase for each natural rubber to catalyst ratio variation at 400 oC. The first two

variations cause aromatics content to decrease up to trial with 375oC of reaction

temperature. However, a different result is given by samples that use 2:3 natural rubber to

catalyst ratio. It steadily increases along with the increasing temperature.

Natural rubber is very unstable after heated, it may then form many compounds

which composed of shorter carbon chain. This fact explains the graphic trends which

decreases and increases at certain temperature. Limonene was found to start composed at

300oC and mainly found at 370oC-450oC (Pakdel, Pantea and Roy 2001). It is consented

to the result that shows at temperature 350oC as in Figure 4.2 through 4.4, limonene

content decreases as other compound such as naphthalene increases. It means, that at that

operating condition, though the formation of limonene has started, other aromatic

compounds are also formed, and the previous limonene formed at 325 oC is degraded to

lower aromatic compound due to its unstable characteristic (Pakdel, Pantea and Roy

2001).

The trend that is shown at Figure 4.5 to Figure 4.7 is the decreasing content of

naphthalene and the increasing content of limonene and other aromatic compounds along

with the decreasing ratio of natural rubber to catalyst weight. The catalyst used in this

process is intended to utilize a metal compound which provides higher free Gibbs energy

in the formation of limonene. Based on the reaction mechanism of limonene formation

from natural rubber, the process needs metal compound that is able to donate more
 76

electrons. Thus, the active site of CaO/SiO2 catalyst used provides more metal compound

to aid the dimerization of isoprene which increases along with the increasing catalyst

weight used than natural rubber weight as the source of isoprene.

CHAPTER V
CONCLUSION

Natural rubber conversion to limonene by vacuum pyrolysis using CaO/SiO 2 catalyst

experiment is intended to find the optimum condition in order to obtain high limonene content

with lower cost production. There are some factors to be considered to achieve that goal;

among them are the use of catalyst and optimum operating condition.

From the experiment conducted, it can be concluded that:

1. The variation of natural rubber to catalyst weight ratios influence the amount of

limonene produced, as it is increased along with lower ratio implemented. For the

same operating condition, samples that used lower ratio produce higher limonene

content. As in 400oC, limonene content increases from 5.32% to 12.96% to

14.89% for the use of ratio 1, 0.8 and 0.6, respectively.

2. Increasing operating temperature generally increases the chance of limonene

formation for the same natural rubber to catalyst ratio occupied. Limonene content

increases from 10.96% to 14.89% for 0.6 natural rubber to catalyst ratio at 325 oC

to 400oC.
 77

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APPENDIX
GCMS ANALYSIS OF PYROLITIC RESULTS
81
82
83
84
85
 86

APPENDIX II

ANALYSIS SAMPLE COMPOSITION

SAMPLE 1 : 80 g, 3250C

No Retention Time Tentative Assigment Percent Area (%)

1 2.09 Hexane 0.08
2 3.74 Toluene 0.16
Cyclohexane, 1,3,5 - trimethyl-, alpha.,
3 4.75 3.alpha.,5.beta. 0.06
4 4.84 Ethylbenzene 0.19
5 4.93 p- xylene 2.32
6 4.93 o-xylene 2.32
7 5.19 benzene, 1,3 - dimethyl - 0.61
8 5.19 p- xylene 0.61
9 5.41 2,4,6 - Octatriene, 2,6 - dimethyl- 0.12
10 5.41 Cyclopentane, 2- methyl - 1- methylene -3-(1- 0.12
methylenyl)-
11 5.7 1,3,6 - heptatriene , 2,5,6 - triemethyl 0.19
12 5.85 D- Limone 0.62
13 5.85 Cyclohexene, 4 - ethenyl -1,4 - dimethyl- 0.62
14 5.96 Benzene , 1,3,5 - triemethyl- 0.97
 87

15 6.08 Benzene, 1- ethyl - 3 - methyl - 0.34

16 6.21 Benzene, 1,3,5 - triemethyl - 3.04
17 6.26 Benzene, 1-ethenyl - 3 - methyl - 0.5
18 6.26 Benzene, cyclopropyl - 0.5
19 6.26 Benzene, 2- propenyl 0.5
20 6.47 Cyclohexene, 1- mrthyl - 4 - (1-methyletyl)-, 0.48
21 6.47 Benzene, 2- ethyl - 1, 3 - dimethyl- 0.48
22 6.49 Benzene, 1,2 - diethyl - 2.08
23 6.54 Limonene 4.17
24 6.71 Indene 0.49
25 6.79 Benzene, 2-ethyl - 1,4 - dimethyl - 1.38
26 6.79 Benzene, 1 - ethyl - 3, 5 - dimethyl 1.38
27 6.79 Benzene, 1- ethyl- 2, 4 - dimethyl - 1.38
28 7.04 Benzene, 1 - methyl - 2 - (1 - methylethyl)- 0.53
29 7.04 Benzene, 2 - ethyl - 1, 4 - diethyl - 0.53
30 7.04 Benzene, 1 - ethyl -2, 3 - dimethyl - 0.54
31 7.07 Benzene, 1 - methyl - 4 - (1 - methylethenyl) - 0.87
32 7.07 o Isopropenyltoluene 0.87
33 7.07 Benzene, (2 - methyl - 1 - propenyl) - 0.87
34 7.11 Benzene, 1- thenyl - 3, 5 - dimethyl - 0.53
35 7.11 benzene, 4 - ethenyl -1 , 2 - dimethyl - 0.53
36 7.11 Bicyclo (4.2.0) 0cta -1, 3, 5 triene, 2, 4 - 0.53
dimethyl -
37 7.34 Benzene, 1,2,4,5 - tetramethyl - 1.37
38 7.34 Benzene, 1,2,3,5 - tetramethyl - 1.37
39 7.34 Benzene, 1,2,3,5 - tetramethyl - 1.37
40 7.41 Benzene, (1 - methyl - 1 - propenyl ) - (E) - 0.47
41 7.41 Benzene, 4 - ethenyl -1, 2 - dimethyl - 0.47
42 7.41 Benzene , 2 - ethenyl - 1,3 - dimethyl - 0.47
43 7.61 1,4 - Dihydronapthalene 1.47
44 7.61 Benzene , 1 - methyl - 1, 2 - propadienyl - 1.47
45 7.66 2 Methylindene 1.49
46 7.66 Benzene, 1- butynyl - 1.49
47 7.66 1H Indene, 1 - methyl - 1.49
48 7.8 Benzene, 2 - ethenyl - 1, 3, 5 - triemethyl 0.38
49 7.84 1H - Indene, 1,1 - dimethyl - 0.34
50 7.88 1H - Indene, 1,3 - dimethyl - 0.41
51 7.93 Napthalene 6.08
52 7.93 Azulene 6.08
53 8.14 1 - o Tolylprop - 2 - en - 1 - one 0.51
54 8.43 1H -Indene , 1,3 - dimethyl - 0.59
55 8.43 ( 1 - Methylenebut -2 - enyl ) benzene 0.59
56 8.43 (1 - Methylbuta - 1, 3, - dienyl) benzene 0.59
57 8.89 Napthalene, 1 - methyl - 2.06
58 8.89 Napthalene, 2 - methyl - 2.06
59 9.28 1,2,3 - Trimethylindene 0.64
60 9.28 1H - Indene , 1,1,3, - trimethyl - 0.64
 88

61 9.33 Biphenyl 1.47

62 9.33 Napthalene, 2 - ethenyl - 1.47
63 9.52 Napthalene, 1, 6 - dimethyl - 1.44
64 9.52 Napthalene, 1,5 - dimethyl - 1.44
65 9.52 Napthalene, 1, 7 - dimethyl - 1.44
66 9.62 Napthalene, 2,7 - dimethyl - 1.17
67 9.62 Napthalene, 1,6 - dimethyl - 1.17
68 9.65 Napthalene, 2,7 - dimethyl - 1.09
69 9.65 Napthalene, 2,6 - dimethyl - 1.09
70 9.65 Napthalene, 1,6 - dimethyl - 1.09
71 9.76 Napthalene, 2,6 - dimethyl - 0.33
72 9.76 Napthalene, 1,3 - dimethyl - 0.33
73 9.78 Napthalene, 2,6 - dimethyl - 0.48
74 9.85 1H - Benzocycloheptene, 2,4a,5,6,7,8 - 0.74
hexahydro -3,5,5,9 -tetramethyl-, (R)-
75 10.02 1,1 ' - Biphenyl, 3 - methyl - 0.65
76 10.02 1,1' - Biphenyl, 4 - methyl - 0.65
77 10.16 Napthalene, 1,4,5 - trimethyl - 0.28
78 10.16 Napthalene, 1- (1- methylethyl)- 0.28
79 10.43 Napthalene, 1,6,7 - trimethyl - 0.24
80 10.43 Napthalene, 1,4,6 - trimethyl - 0.24
81 10.43 Napthalene, 2,3,6 - trimethyl - 0.24
82 10.46 Napthalene, 1,6,7 - trimethyl - 0.17
83 10.46 Napthalene, 1,4,6 - trimethyl - 0.17
84 10.46 Napthalene, 2,3,6 - trimethyl - 0.17
85 10.54 Napthalene, 1,6,7 - trimethyl - 0.19
86 10.54 Azulene, 4,6,8 - trimethyl - 0.19
87 10.7 Fluorene 0.3
88 11.48 3H - Benz (e) indene, 2 - methyl - 0.21
89 11.87 Anthracene 1.1
90 11.87 Penantrhere 1.1
91 11.93 Anthracene 0.39
92 11.93 Penantrhere 0.39
93 11.93 2 - Cyclopropen - 1 - one, 2,3 - diphenyl - 0.39
94 12.03 Phenanthrene, 9,10- dihydro - 1 - methyl - 0.21
95 12.23 Dibenzo (a,e) cyclooctane 0.36
96 12.23 Anthracene, 9 - ethenyl - 0.36
97 12.23 Napthalene , 1- phenyl - 0.36
98 12.47 Anthracene, 1 - methyl - 0.28
99 12.47 Anthracene, 2 - methyl - 0.28
100 12.47 Penantrhene, 2- methyl - 0.28
101 12.51 Penantrhene, 2- methyl - 0.63
102 12.51 Anthracene, 1 - methyl - 0.63
103 12.55 Anthracene, 1 - methyl - 0.31
104 12.64 Penantrhene, 2- methyl - 0.35
105 12.64 Penantrhene, 1- methyl - 0.35
106 12.64 Penantrhene, 4- methyl - 0.35
 89

107 12.83 Napthalene, 2 - Phenyl - 0.41

108 13.2 9,10 - Dimethylanthracene 0.14
109 13.2 Penanthrene, 2,5 - Dimethyl - 0.14
110 13.2 di-p-Tolylacetylene 0.14
111 13.35 Fluoranthene 0.25
112 13.35 Pyrene 0.25
113 13.62 Pyrene 0.32
114 13.64 Pyrene 0.22
115 13.64 Fluorenthene 0.22
116 14.42 Pyrene, 1- methyl - 0.13
117 15.73 1,2 - Benzenedicarboylic acid, mono ( 2 - 0.98
ethylhexyl) ester
1,2 - Benzenedicarboylic acid, diissooctyl
118 15.73 ester 0.98
119 15.73 Di - n - octyl phthalate 0.98

SAMPLE 2 : 80 g, 3500C

Retention Percent Area

No Tentative Assigment
Time (%)
1 3.74 Toluena 0.10
2 4.92 p-Xylene 0.82
3 4.92 o-Xylene 0.82
4 5.19 Benzene, 1,3-dimethyl 0.18
5 5.19 o-Xylene 0.18
6 5.19 p-Xylene 0.18
7 5.84 Limonene 0.29
8 5.84 D-Limonene 0.29
9 5.89 Benzene, 1-ethyl -2-methyl 0.62
10 5.89 Benzene, 1-ethyl -3-methyl 0.62
11 5.96 Benzene, 1,2,3-trimethyl 0.25
12 5.96 Benzene, 1,3,5-trimethyl 0.25
13 6.08 Benzene, 1,3,5-trimethyl 0.07
14 6.21 Benzene, 1,2,3-trimethyl 0.83
15 6.21 Benzene, 1,2,4-trimethyl 0.83
16 6.21 Benzene, 1,3,5-trimethyl 0.83
17 6.26 Benzene, 2-propenyl 0.11
18 6.26 Benzene, 1-propenyl 0.11
19 6.49 Benzene, 1,2-diethyl 0.58
20 6.49 Benzene, 1,4-diethyl 0.58
21 6.53 Limonene 1.74
22 6.71 Benzene, 1-propynyl 0.13
23 6.79 Benzene, 1-ethyl-3,5-dimethyl 0.35
 90

24 6.79 Benzene, 4-ethyl-1,2-dimethyl 0.35

25 6.79 Benzene. 2-ethyl-1,4-dimethyl 0.35
26 6.79 Benzene, 4-ethyl-1,2-dimethyl 0.35
27 7.03 Benzene, 1-ethyl-3,5-dimethyl 0.12
28 7.03 Benzene, 1-methyl-2-(1-methylethenyl) 0.12
29 7.03 Benzene, 2-ethyl-1,4-dimethyl 0.12
30 7.07 Benzene, 1-methyl-4-(1-methylethenyl) 0.22
31 7.07 Benzene, (2-methyl-1,propenyl) 0.22
32 7.23 Benzene, 1-methyl-2-(1-methylethenyl) 0.11
33 7.23 Benzene, 1,2,4,5-tetramethyl 0.11
34 7.30 Benzene, 1,2,3,4-tetramethyl 0.19
35 7.34 Benzene, 1,2,4,5-tetramethyl 0.45
36 7.38 Benzene, 2-ethenyl-1,4-dimethyl 0.13
37 7.41 Benzene, 2-ethenyl-1,4-dimethyl 0.13
38 7.41 Benzene, 2-ethenyl-1,3-dimethyl 0.13
39 7.61 Benzene, 1-methyl-4-(1-methylethenyl) 0.52
40 7.66 Benzene, 1-butynyl 0.51
41 7.66 Benzene, (1-methyl-2-clclopropen-1-yl) 0.51
42 7.80 Benzene (3-methyl-3-butenyl) 0.15
43 7.80 Benzene, 2-ethenyl-1,3,5-trimethyl 0.15
44 7.93 Naphthalene 5.33
45 7.98 Naphthalene 0.34
46 8.14 Naphthalene, 1,2,3,4-tetrahydro-5-methyl 0.23
47 8.20 Benzene, (3-methyl-2-butenyl) 0.17
48 8.20 Naphthalene, 1,2,3,4-tetrahydro-5-methyl 0.17
49 8.89 Naphthalene, 2-methyl 1.82
50 8.89 Naphthalene, 1-methyl 1.82
51 9.33 Naphthalene, 2-ethenyl 0.45
52 9.44 Naphthalene, 2,3-dimethyl 0.72
53 9.44 Naphthalene, 2,7-dimethyl 0.72
54 9.44 Naphthalene, 1-ethyl 0.72
55 9.52 Naphthalene, 2,7-dimethyl 1.86
56 9.52 Naphthalene, 2,6-dimethyl 1.86
57 9.52 Naphthalene, 1,4-dimethyl 1.86
58 9.62 Naphthalene, 1,6-dimethyl 1.39
59 9.62 Naphthalene, 1,4-dimethyl 1.39
60 9.65 Naphthalene, 2,6-dimethyl 1.50
61 9.65 Naphthalene, 2,7-dimethyl 1.50
62 9.69 Naphthalene, 2-ethenyl 0.49
63 9.76 Naphthalene, 1,3-dimethyl 0.56
64 9.76 Naphthalene, 1,4-dimethyl 0.56
65 9.76 Naphthalene, 2,7-dimethyl 0.56
66 9.78 Naphthalene, 2,6-dimethyl 0.66
67 9.78 Naphthalene, 1,3-dimethyl 0.66
68 10.08 Naphthalene, 2-(1-methylethenyl) 1.26
69 10.08 Naphthalene, 1-(2-propenyl) 1.26
70 10.16 Naphthalene, 1,4,6 - trimethyl 0.48
 91

71 10.16 Naphthalene, 2,3,6- trimethyl 0.48

72 10.16 Naphthalene, 1,6,7 - trimethyl 0.48
73 10.29 Benzene, [1-(2,4-cyclopentadien-1-ylidine) ethyl 0.50
74 10.29 Naphthalene, 1,4,6 - trimethyl 0.50
75 10.28 Naphthalene, 1,6,7 - trimethyl 0.50
76 10.44 Naphthalene, 1,6,7 - trimethyl 0.43
77 10.44 Naphthalene, 2,3,6- trimethyl 0.43
78 10.46 Naphthalene, 1,6,7 - trimethyl 0.35
79 11.93 Anthracene 1.52
80 12.23 Naphthalene, 1-phenyl 0.93
81 12.47 Anthracene, 2-methyl 0.69
82 12.47 Anthracene, 1-methyl 0.69
83 12.55 Anthracene, 2-methyl 0.61
84 12.55 Anthracene, 1-methyl 0.61
85 12.64 Anthracene, 2-methyl 0.68
86 12.83 Naphthalene, 2-phenyl 1.59
87 13.33 Pyrene 1.54
88 13.61 Pyrene 1.96
89 13.93 Pyrene, 1-methyl 0.19
90 14.17 Pyrene, 2-methyl 0.19
91 14.22 Pyrene, 1-methyl 0.25
92 14.22 Pyrene, 2-methyl 0.25
93 14.36 Pyrene, 4-methyl 0.12
94 14.36 Pyrene, 2-methyl 0.12
95 14.36 Pyrene, 1-methyl 0.12
96 14.41 Pyrene, 1-methyl 0.29
97 16.53 Benz [a] anthtracene, 1-methyl 0.22
98 16.53 Benz [a] anthtracene, 7-methyl 0.22
99 18.58 Benzo [e] pyrene 0.44
10
0 19.76 Benzo [e] pyrene 0.34
 92

SAMPLE 3 : 80 g, 3750C

Retention Percent Area

No Time Tentative Assigment (%)
1 4.84 Ethylbenzene 0.10
2 4.92 o-Xylene 1.92
3 5.85 1-ethenyl-1,4-dimethyl-Cyclohexene 0.39
4 5.89 1-ethyl-2-methyl-Benzene 1.71
5 5.96 1,3,5-trimethyl-Benzene 0.90
6 6.08 1-ethyl-3-methyl-Benzene 0.18
7 6.21 1,2,3-trimethyl-Benzene 2.72
8 6.25 1-ethenyl-3-methyl-Benzene 0.42
9 6.53 D-Limonene 2.59
10 6.71 Indene 0.80
11 6.79 1-ethyl-3,5-dimethyl-Benzene 1.18
12 6.97 1-ethyl-2,4-dimethyl-Benzene 0.39
13 7.03 2-ethyl-1,4-dimethyl-Benzene 0.40
14 7.07 o-Isopropenyltoluene 0.60
15 7.12 Bicyclo[4.2.0]octa-1,3,5-triene,4-dimethyl 0.31
16 7.23 4-ethyl-1,2-dimethyl-Benzene 0.21
17 7.30 1,2,4,5-tetramethyl-Benzene 0.29
18 7.34 1,2,3,5-tetramethyl-Benzene 1.17
19 7.38 1-methyl-4-(2-propenyl)-benzene 0.22
20 7.66 1-methyl-1H-indene 1.37
21 7.80 2-ethenyl-1,3,5-trimethyl-Benzene 0.14
22 8.43 1,3-dimethyl-1H-indene 0.42
23 8.51 2,3-dimethyl-1H-indene 0.65
24 8.77 1-methyl-Naphthalene 8.42
 93

25 8.89 1-methyl-Naphthalene 4.39

26 9.29 1,2,3-trimethyilidene 0.52
27 9.33 Biphenyl 1.42
28 9.44 1-ethyl-Naphthalene 0.61
29 9.52 2,7-dimethyl-Naphthalene 3.52
30 9.63 1,3-dimethyl-Naphthalene 2.59
31 9.65 2,7-dimethyl-Naphthalene 2.38
32 9.76 2,6-dimethyl-Naphthalene 0.82
33 9.78 2,7-dimethyl-Naphthalene 0.65
34 10.02 3-methyl-1,1'-biphenyl 0.98
35 10.16 2,3,6-trimethyl-Naphthalene 0.46
36 10.30 1,6,7-trimethyl-Naphthalene 0.83
37 10.33 1,6,7-trimethyl-Naphthalene 1.11
38 10.44 2,3,6-trimethyl-Naphthalene 0.46
39 10.46 1,4,6-trimethyl-Naphthalene 0.54
40 10.54 2,3,6-trimethyl-Naphthalene 0.33
41 10.64 3,3-Dimethylbiphenyl 0.11
42 10.70 Fluorene 0.87
43 10.73 3,4-Dimethyl-1,1-biphenyl 0.36
44 10.90 4,4-Dimethylbiphenyl 0.31
45 11.38 1-methyl-9H-Fluorene 1.07
46 11.48 2-methyl-9H-Fluorene 0.42
47 11.87 Anthracene 2.31
48 11.93 Anthracene 0.80
49 12.00 2,3-dimethyl-9H-Fluorene 0.35
50 12.03 9,10-dihydro-1-methyl-phenantrene 0.30
51 12.23 1-phenyl-Naphthalene 0.44
52 12.46 2-methyl-Anthracene 0.53
53 12.51 2-methyl-phenanthrene 0.92
54 12.55 1-methyl-Anthracene 0.47
55 12.64 1-methyl- phenanthrene 0.50
56 12.83 2-phenyl-Naphthalene 0.62
57 13.01 9,10-dimethylanthracene 0.14
58 13.06 3,6-dimethyl- phenanthrene 0.17
59 13.09 di-p-tolylacetylene 0.11
60 13.16 9,10-dimethylanthracene 0.34
61 13.34 Flouranthene 1.00
62 13.61 Pyrene 0.59
63 13.93 1-methyl-pyrene 0.18
64 14.08 11H-benzo[b]fluorene 0.32
65 14.17 1-methyl-pyrene 0.16
66 14.22 1-methyl-pyrene 0.22
67 14.36 4-methyl-pyrene 0.11
68 14.41 1-methyl-pyrene 0.22
69 14.74 1,3-dimethyl-pyrene 0.10
70 15.54 Triphenylene 0.34
71 15.63 Triphenylene 0.87
 94

72 16.53 1-methyl-chrysene 0.28

73 16.63 1-methyl-benz[a] anthracene 0.22

SAMPLE 4 : 80 g, 4000C

Retention Percent Area

No Time Tentative Assigment (%)
1 4.92 p-Xylene 0.95
2 5.18 1,3-dimethyl-Benzene 0.29
3 5.84 D-Limonene 0.62
4 5.89 1-ethyl-2-methyl-Benzene 1.66
5 5.96 1,2,3-trimethyl-Benzene 0.79
6 6.07 1-ethyl-3-methyl-Benzene 0.23
7 6.21 1,2,3-trimethyl-Benzene 2.64
8 6.26 1-ethenyl-3-methyl-Benzene 0.46
9 6.54 Limonene 5.32
10 6.71 Indene 0.88
11 6.79 1-ethyl-3,5-dimethyl-Benzene 1.29
12 6.98 1-ethyl-2,4-dimethyl-Benzene 0.57
13 7.03 1-methyl-4-(1-methylethyl)-Benzene 0.52
14 7.07 1-methyl-4-(1-methylethenyl)-Benzene 0.91
15 7.34 1,2,3,5-tetramethyl-Benzene 1.43
16 7.51 1-methyl-4-(2-propenyl)-benzene 1.17
17 7.61 1-butynyl-benzene 1.67
18 7.66 1-methylindene 1.62
19 7.80 2-ethenyl-1,3,5-trimethyl-Benzene 0.30
20 8.77 1-methyl-Naphthalene 7.85
21 8.89 1-methyl-Naphthalene 4.00
22 9.28 1,2,3-trimethyilidene 0.71
23 9.33 Biphenyl 1.51
24 9.52 2,7-dimethyl-Naphthalene 3.07
 95

25 9.63 1,3-dimethyl-Naphthalene 2.19

26 9.65 2,7-dimethyl-Naphthalene 2.12
27 9.76 1,3-dimethyl-Naphthalene 0.76
28 9.79 2,7-dimethyl-Naphthalene 0.51
29 10.02 3-methyl-1,1'-biphenyl 1.06
30 10.16 1,4,6-trimethyl-Naphthalene 0.40
31 10.29 1,4,6-trimethyl-Naphthalene 0.73
32 10.33 1,6,7-trimethyl-Naphthalene 0.95
33 10.43 1,6,7-trimethyl-Naphthalene 0.37
34 10.46 2,3,6-trimethyl-Naphthalene 0.44
35 10.54 2,3,6-trimethyl-Naphthalene 0.26
36 10.70 Fluorene 0.78
37 11.38 2-methyl-9H-Fluorene 0.79
38 11.42 1-methyl-9H-Fluorene 0.38
39 11.87 Anthracene 2.10
40 11.93 Phenantrene 0.67
41 12.00 2,3-dimethyl-9H-Fluorene 0.14
42 12.23 1-phenyl-Naphthalene 0.33
43 12.47 2-methyl-phenanthrene 0.59
44 12.50 2-methyl- Anthracene 0.91
45 12.55 1-methyl-Anthracene 0.47
46 12.64 1-methyl- phenanthrene 0.50
47 12.83 2-phenyl-Naphthalene 0.63
48 13.01 9,10-dimethylanthracene 0.15
49 13.07 3,6-dimethyl- phenanthrene 0.19
50 13.16 9,10-dimethylanthracene 0.36
51 13.34 Flouranthene 0.65
52 13.61 Pyrene 0.99
53 14.07 2-methyl- Flouranthene 0.36
54 14.22 1-methyl-pyrene 0.25
55 15.54 Triphenylene 0.41
56 15.62 Triphenylene 1.01
57 15.73 1,2-Benzenedicarboxylicacid,mono ester 1.14
58 16.53 7-methyl-benz[a] anthracene 0.28
 96

SAMPLE 5 : 100 g, 3250C

No Retention Time Tentative Assigment Percent Area (%)

1 5.85 Limonene 1.75
2 5.85 D-Limonene 1.75
3 6.55 Limonene 11.97
4 4.92 o-Xylene 2.14
5 4.92 p-Xylene 2.14
6 5.19 o-Xylene 0.62
7 5.19 Benzene,1,3-dimethyl- 0.62
8 5.19 p-Xylene 0.62
9 5.89 Benzene,1-ethyl-3-methyl- 3.23
10 5.89 Benzene,1-ethyl-2-methyl- 3.23
11 5.96 Benzene,1,2,3-trimethyl- 1.45
12 5.96 Benzene,1,2,5-trimethyl- 1.45
13 6.08 Benzene,1-ethyl-2-methyl- 0.47
14 6.08 Benzene,1,2,4-trimethyl 0.47
15 6.08 Benzene,1,2,3-trimethyl- 0.47
16 6.21 Benzene,1,2,3-trimethyl- 4.42
17 6.21 Benzene,1,2,4-trimethyl 4.42
18 6.21 Benzene,1,3,5-trimethyl 4.42
19 6.26 Benzene,1-ethenyl-4methyl 0.95
20 6.26 Benzene,1-propenyl 0.95
21 6.26 Benzene,cyclopropyl 0.95
22 6.50 Benzene, 1,2-diethyl 4.07
23 6.50 Benzene,1-ethyl-2,3-dimethyl- 4.07
24 6.50 Benzene,4-ethyl-1,2-dimethyl- 4.07
25 6.72 Benzene,1-ethynyl-4-methyl- 1.40
 97

26 6.72 Benzene,1-propynyl 1.40

27 6.79 Benzene,4-ethyl-1,2-dimethyl- 1.94
28 6.79 Benzene,1-ethyl-3,5-dimethyl- 1.94
29 6.79 Benzene,1-ethyl-2,4-dimethyl- 1.94
30 6.98 Benzene,1-ethyl-2,4-dimethyl- 1.51
31 6.98 Benzene,1-methyl-3-(1-methylethyl)- 1.51
32 6.98 Benzene,1-methyl-2-(1-methylethyl)- 1.51
33 7.00 Benzene,1-methyl-4-(1-methylethenyl)- 0.44
34 7.00 Benzene,4-ethenyl-1,2-dimethyl- 0.44
35 7.04 Benzene,4-ethyl-1,2-dimethyl- 0.80
36 7.04 Benzene,2-ethyl-1,4-dimethyl- 0.80
37 7.04 Benzene,1-methyl-2-(1-methylethyl)- 0.80
38 7.07 Benzene,1-methyl-4-(1-methylethenyl)- 1.81
39 7.07 Benzene,(2-methyl-1-propenyl)- 1.81
40 7.23 Benzene,1-methyl-4-(1-methylpropyl)- 0.62
41 7.23 Benzene,2-ethyl-1,4-dimethyl- 0.62
42 7.23 Benzene,1,2,4,5-tetramethyl- 0.62
43 7.30 Benzene,1,2,4,5-tetramethyl- 0.62
44 7.34 Benzene,1,2,4,5-tetramethyl- 1.74
45 7.34 Benzene,1,2,3,5-tetramethyl- 1.74
46 7.52 Benzene,1-methyl-2-(2-propenyl)- 1.07
47 7.61 Benzene,1-methyl-1,2-propadienyl- 1.63
48 7.61 Benzene,1-butynyl 1.63
49 7.66 Benzene,1-methyl-4-(1-propynyl)- 1.25
50 7.66 Benzene,1-butynyl 1.25
51 7.93 Naphthalene 11.18
52 7.98 Naphthalene 0.74
53 8.76 Naphthalene,1-methyl- 5.26
54 8.76 Naphthalene,2-methyl- 5.26
55 9.33 Naphthalene,2-ethenyl- 1.25
56 9.45 Naphthalene,1-ethyl- 0.27
57 9.45 Naphthalene,2-ethyl- 0.27
58 9.45 Naphthalene,1,3-dimethyl- 0.27
59 9.52 Naphthalene,2,6-dimethyl- 1.43
60 9.52 Naphthalene,2,7-dimethyl- 1.43
61 9.62 Naphthalene,1,6-dimethyl- 0.92
62 9.62 Naphthalene,1,5-dimethyl- 0.92
63 9.65 Naphthalene,2,7-dimethyl- 0.99
64 9.65 Naphthalene,2,6-dimethyl- 0.99
65 10.29 Naphthalene,2,3,6-trimethyl- 0.39
66 10.29 Naphthalene,1,6,7-trimethyl- 0.39
67 10.33 Naphthalene,1,6,7-trimethyl- 0.56
68 10.33 Naphthalene,2,3,6-trimethyl- 0.56
69 11.87 Anthracene 2.56
70 11.93 Anthracene 0.77
71 12.23 Naphthalene,1-phenyl- 0.37
72 12.47 Anthracene 0.56
 98

73 12.51 Anthracene,2-methyl- 0.88

74 12.55 Anthracene,1-methyl- 0.38
75 12.55 Anthracene,2-methyl- 0.38
76 12.61 Anthracene,1-methyl- 0.45
77 12.61 Anthracene,2-methyl- 0.45
78 12.64 Anthracene,2-methyl- 0.38
79 12.83 Naphthalene,2-phenyl- 0.69
80 13.35 Pyrene 1.00
81 13.62 Pyrene 1.45

SAMPLE 6 : 100 g, 3500C

No Retention Time Tentative Assigment Percent Area (%)

1 3.74 Toluene 0.63
2 4.84 Ethylbenzene 0.23
3 4.93 p-Xylene 3.87
4 4.93 o-Xylene 3.87
5 5.19 o-Xylene 1.08
6 5.19 p-Xylene 1.08
7 5.19 Benzene,1,3-dimethyl- 1.08
8 5.51 Benzene,1-ethyl-2-methyl- 0.28
9 5.51 Benzene,(1-methylethyl)- 0.28
10 5.51 Benzene,1-ethyl-3-methyl- 0.28
11 5.85 D-Limonene 1.31
12 5.85 Limonene 1.31
13 5.89 Benzene,1-ethyl-2-methyl- 2.70
14 5.89 Benzene,1-ethyl-3-methyl- 2.70
15 5.96 Benzene,1,3,5-trimethyl- 1.32
16 5.96 Benzene,1,2,3-trimethyl- 1.32
17 5.96 Benzene,1,3,5-trimethyl- 1.32
18 6.08 Benzene,1,3,5-trimethyl- 0.41
19 6.08 Benzene,1,2,4-trimethyl- 0.41
20 6.21 Benzene,1,2,3-trimethyl- 3.72
21 6.21 Benzene,1,2,4-trimethyl- 3.72
22 6.21 Benzene,1,3,5-trimethyl- 3.72
23 6.26 Benzene, 2-propenyl- 0.76
24 6.26 Benzene,1-ethenyl-4-methyl- 0.76
25 6.37 Benzenemethanol,4-ethyl- 0.59
26 6.49 Benzene,1,4-diethyl- 2.69
27 6.49 Benzene,1,2,-diethyl- 2.69
 99

28 6.54 Limonene 8.26

29 6.62 Benzene,cyclopropyl- 0.62
30 6.62 Benzene, 1-propenyl- 0.62
31 6.71 Benzene,1-propenyl- 1.04
32 6.76 Benzene,1-methyl-4-propyl- 0.32
33 6.79 Benzene,4-ethyl-1,2-dimethyl- 1.45
34 6.79 Benzene,1-ethyl-4-dimethyl- 1.45
35 6.79 Benzene,1-ethyl-3,5-dimethyl- 1.45
36 6.96 Benzene,2-ethyl-1,4-dimethyl- 0.53
37 6.96 Benzene,1-methyl-2-(1-methylethyl)- 0.53
38 6.96 Benzene,1-ethyl-3,5-dimethyl- 0.53
39 6.98 Benzene,1-methyl-2-(1-methylethyl)- 0.65
40 6.98 Benzene,1-ethyl-2,4-dimethyl- 0.65
41 6.98 Benzene,1-methyl-3-(1-methylethyl)- 0.65
42 7.03 Benzene,4-ethyl-1,2-dimethyl- 0.64
43 7.03 Benzene,1-ethyl-2,3-dimethyl- 0.64
44 7.03 Benzene,2-ethyl-1,4-dimethyl- 0.64
45 7.07 Benzene,1-methyl-4-(1-methylethenyl)- 1.13
46 7.07 Benzene,(2-methyl-1-propenyl)- 1.13
47 7.23 Benzene,1-methyl-4-(1-methylpropyl)- 0.55
48 7.23 Benzene,1-methyl-2-(1-methylethyl)- 0.55
49 7.23 Benzene,2-ethyl-1,4-dimethyl- 0.55
50 7.30 Benzene,1,2,4,5-tetramethyl-1,3,8-p- 0.55
51 7.34 Benzene,1,2,4,5-tetramethyl- 1.45
52 7.34 Benzene,1,2,3,5-tetramethyl- 1.45
53 7.52 Benzene,(1-methyl-1-propenyl)-,E 1.10
54 7.52 Benzene,(1-methyl-1-propenyl)-,Z 1.10
55 7.61 Benzene,1-butynyl- 1.59
56 7.66 Benzene,1-butynyl- 1.36
57 7.66 Benzene,1-methyl-4-(1-propynyl)-2- 1.36
58 7.93 Naphthalene 8.65
59 8.76 Naphthalene,2-methyl 7.41
60 8.76 Naphthalene,1-methyl 7.41
61 8.89 Naphthalene,1-methyl 3.66
62 8.89 Naphthalene,2-methyl 3.66
63 9.33 Naphthalene,2-ethenyl 1.62
64 9.44 Naphthalene,2,3-dimethyl- 0.70
65 9.44 1-NaphthalenepropionicacidNaphtalene 0.70
66 9.52 Naphthalene,2,7-dimethyl- 2.76
67 9.52 Naphthalene,1,5-dimethyl- 2.76
68 9.52 Naphthalene,1,7-dimethyl- 2.76
69 9.62 Naphthalene,1,5-dimethyl- 1.85
70 9.62 Naphthalene,1,3-dimethyl- 1.85
71 9.62 Naphthalene,1,4-dimethyl- 1.85
72 9.65 Naphthalene,2,6-dimethyl- 1.90
73 9.65 Naphthalene,2,7-dimethyl- 1.90
74 9.65 Naphthalene,1,5-dimethyl- 1.90
 100

75 9.76 Naphthalene,1,3-dimethyl- 0.66

76 9.76 Naphthalene,1,4-dimethyl- 0.66
77 9.76 Naphthalene,2,3-dimethyl- 0.66
78 10.09 Naphthalene,2-(1-methylethenyl)- 0.89
79 10.30 Naphthalene,1,6,7-trimethyl- 0.63
80 10.30 Naphthalene,2,3,6-trimethyl- 0.63
81 10.33 Naphthalene,1,6,7-trimethyl- 0.78
82 10.33 Naphthalene,1,4,6-trimethyl- 0.78
83 10.33 Naphthalene,2,3,6-trimethyl- 0.78
84 10.44 Naphthalene,1,4,6-trimethyl- 0.31
85 10.44 Naphthalene,1,6,7-trimethyl- 0.31
86 10.57 Naphthalene,1,6,7-trimethyl- 0.34
87 10.57 Naphthalene,2,3,6-trimethyl- 0.34
88 10.57 Naphthalene,1,4,5-trimethyl- 0.34
89 11.87 Anthracene 2.02
90 11.93 Anthracene 0.85
91 12.23 Anthracene,9-ethenyl- 0.29
92 12.23 Naphthalene,1-phenyl- 0.29
93 12.47 Anthracene,2-methyl- 0.54
94 12.51 Anthracene,2-methyl- 0.84
95 12.55 Anthracene,2-methyl- 0.44
96 12.61 Anthracene,2-methyl- 0.53
97 12.64 Anthracene,1-methyl- 0.57
98 12.84 Naphthalene,2-phenyl 0.44
99 13.20 Anthracene,1,4-dimethyl- 0.46
100 13.35 Pyrene 0.51
101 13.62 Pyrene 0.62
102 15.73 1,2-Benzenedicarboxylicacid,mono ester 0.83
 101

SAMPLE 7 : 100 g, 3750C

Retention
No Time Tentative Assigment Percent Area (%)
1 3.74 Toluene 0.16
2 4.92 o-Xylene 1.72
3 5.18 1,3-dimethyl-Benzene 0.58
4 5.84 Limonene 0.54
5 5.89 1-ethyl-2-methyl-Benzene 1.87
6 5.96 1,2,3-trimethyl-Benzene 0.73
7 6.07 1,3,5-trimethyl-Benzene 0.25
8 6.21 1,2,3-trimethyl-Benzene 2.47
9 6.54 Limonene 3.90
10 6.71 Indene 0.92
11 6.79 1-ethyl-3,5-dimethyl-Benzene 1.18
12 6.98 1-ethyl-2,4-dimethyl-Benzene 0.93
13 7.00 1-methyl-4-(1-methylethenyl)-Benzene 0.24
14 7.03 1-ethyl-2,3-dimethyl-Benzene 0.61
15 7.07 (2-methyl-1-propenyl)-benzene 0.98
16 7.34 1,2,4,5-tetramethyl-Benzene 1.21
17 7.41 (1-methyl-1-propenyl)-benzene 0.38
18 7.61 1-butynyl-benzene 2.16
19 7.66 2-methylindene 1.61
20 7.80 2-ethenyl-1,3,5-trimethyl-Benzene 0.26
21 7.90 1,2,3,4-tetrahydro-1-methyl-naphthalene 0.62
22 7.92 Naphthalene 3.60
23 8.43 1,3-dimethyl-1H-indene 1.22
24 8.46 1,3-dimethyl-1H-indene 2.14
25 8.51 2,3-dimethyl-1H-indene 1.37
26 8.76 2-methyl-Naphthalene 5.28
27 8.89 1-methyl-Naphthalene 3.07
28 9.20 1,2,3-trimethyilidene 0.60
 102

29 9.52 2,7-dimethyl-Naphthalene 3.61

30 9.63 1,3-dimethyl-Naphthalene 2.33
31 9.65 2,7-dimethyl-Naphthalene 2.55
32 9.77 1,3-dimethyl-Naphthalene 0.96
33 9.99 1,2-dihydro-3,5,8-trimethyl-Naphthalene 0.33
34 10.02 3-methyl-1,1'-biphenyl 0.87
35 10.16 2,3,6-trimethyl-Naphthalene 0.82
36 10.30 2,3,6-trimethyl-Naphthalene 0.97
37 10.34 1,6,7-trimethyl-Naphthalene 1.81
38 10.44 2,3,6-trimethyl-Naphthalene 0.67
39 10.46 2,3,6-trimethyl-Naphthalene 0.63
40 10.54 2,3,6-trimethyl-Naphthalene 0.61
41 10.57 2,3,6-trimethyl-Naphthalene 0.66
42 11.38 1-methyl-9H-Fluorene 0.62
43 11.42 2-methyl-9H-Fluorene 0.36
44 11.48 2-methyl-9H-Fluorene 0.29
45 11.87 Anthracene 1.66
46 11.93 Anthracene 0.69
47 12.00 1-methyl-2-(2-phenylethenyl)-benzene 0.28
48 12.03 9,10-dihydro-1-methyl-phenantrene 0.18
49 12.23 1,4-dihydro-1,4-ethenoanthracene 0.12
50 12.47 2-methyl-phenanthrene 0.45
51 12.50 2-methyl-Anthracene 0.66
52 12.55 1-methyl-Anthracene 0.36
53 12.64 1-methyl-Anthracene 0.43
54 12.83 2-phenyl-Naphthalene 0.31
55 13.07 9,10-dimethylanthracene 0.13
56 13.16 9,10-dimethylanthracene 0.26
57 13.61 pyrene 0.59
58 15.73 mono (2-ethylhexyl) ester 1,2- 0.29
benzenedicarboxylic acid
 103

SAMPLE 8 : 100 g, 4000C

Retention
No Time Tentative Assigment Percent Area (%)
1 3.73 Toluene 1.84
2 4.93 p-Xylene 6.82
3 5.19 p-Xylene 1.91
4 5.41 1,2,6,6-tetramethyl-1,3-cyclohexadiene 0.51
5 5.85 Limonene 2.54
6 5.89 1-ethyl-3-methyl-Benzene 4.51
7 5.96 1,2,3-trimethyl-Benzene 1.32
1-methyl-4-(1-methylethyl)-,(R)-
8 6.46 cyclohexene 1.05
9 6.54 Limonene 12.96
10 6.58 5-ethylidene-1-methyl-cycloheptene 0.59
11 6.71 Indene 1.43
12 6.79 4-ethyl-1,2-dimethyl-Benzene 1.84
13 6.96 1-methyl-2-(1-methylethyl)-benzene 0.40
14 6.98 1-methyl-2-(1-methylethyl)-benzene 0.92
15 7.07 o-isopropenyltoluene 1.64
16 7.34 1,2,4,5-tetramethyl-Benzene 1.58
17 7.42 1-methyl-2-(2-propenyl)-benzene 0.40
18 7.61 1-butynyl-benzene 2.25
19 7.66 2-methylidene 1.56
20 7.89 2,3-dihydro-1,6-dimethyl-1H-Indene 0.49
21 7.92 Naphthalene 5.52
22 8.42 1,3-dimethyl-1H-indene 0.73
23 8.47 1,3-dimethyl-1H-indene 1.38
24 8.51 2,3-dimethyl-1H-indene 0.84
25 8.75 2-methyl-Naphthalene 5.68
26 8.88 1-methyl-Naphthalene 2.77
27 9.28 1,2,3-trimethyilidene 0.53
28 9.33 biphenyl 0.67
29 9.52 2,6-dimethyl-Naphthalene 1.91
 104

30 9.62 1,3-dimethyl-Naphthalene 1.24

31 9.64 2,7-dimethyl-Naphthalene 1.32
32 10.02 3-methyl-1,1'-biphenyl 0.30
33 10.29 1,6,7-trimethyl-Naphthalene 0.34
34 10.33 1,6,7-trimethyl-Naphthalene 0.61
35 11.38 2-methyl-9H-Fluorene 0.32
36 11.87 Anthracene 1.50
37 11.93 phenanthrene 0.49
38 12.47 1-methyl-phenanthrene 0.51
39 12.51 2-methyl-phenanthrene 0.69
40 13.62 Pyrene 0.82

SAMPLE 9 : 120 g, 3250C

No Retention Time Tentative Assigment Percent Area (%)

1 5.84 D-Limonene 0.85
2 5.89 1-ethyl-3-methyl-Benzene 2.25
3 5.96 1,3,5-trimethyl-Benzene 1.28
4 6.21 1,3,5-trimethyl-Benzene 4.39
5 6.46 1-methyl-4-(1-methylethyl)-,(R)-cyclohexene 0.54
6 6.53 Limonene 10.96
7 6.71 Indene 1.03
8 6.79 2-ethyl-1,4-dimethyl-Benzene 2.05
9 6.97 1-ethyl-2,4-dimethyl-Benzene 1.20
10 7.07 1-methyl-4-(1-methylethenyl)-Benzene 1.45
11 7.34 1,2,4,5-tetramethyl-Benzene 2.31
12 7.61 1-butynyl-benzene 2.86
13 7.66 1-methyl-1H-indene 2.61
14 7.92 Azulene 7.01
15 7.98 Naphthalene 1.02
16 8.42 1,3-dimethyl-1H-indene 0.76
17 8.47 1,1-dimethyl-1H-indene 1.83
18 8.75 1-methyl-Naphthalene 1.47
19 8.88 1-methyl-Naphthalene 6.59
20 9.28 1,2,3-trimethyilidene 0.76
21 9.34 biphenyl 0.93
22 9.52 2,6-dimethyl-Naphthalene 5.05
23 9.62 1,3-dimethyl-Naphthalene 3.47
24 9.65 2,7-dimethyl-Naphthalene 4.60
25 9.76 1,3-dimethyl-Naphthalene 1.47
26 10.30 1,6,7-trimethyl-Naphthalene 0.79
27 10.33 1,6,7-trimethyl-Naphthalene 1.87
28 10.44 2,3,6-trimethyl-Naphthalene 0.64
29 10.71 Fluorene 0.68
 105

30 11.89 Anthracene 0.35

SAMPLE 10 : 120 g, 3500C

No Retention Time Tentative Assigment Percent Area (%)

1 4.92 p-Xylene 1.53
2 5.19 o-Xylene 0.45
3 5.85 D-Limonene 1.16
4 5.89 1-ethyl-2-methyl-Benzene 2.04
5 5.96 1,3,5-trimethyl-Benzene 0.87
6 6.10 2,6-dimethyl-2,4,6-octatriene 1.00
7 6.21 1,3,5-trimethyl-Benzene 2,92
8 6.25 1-ethenyl-4-methyl-Benzene 0.50
9 6.46 1-methyl-4-(1-methylethyl)-,(R)-cyclohexene 0.67
10 6.54 Limonene 9.54
11 6.71 Indene 0.98
12 6.79 1-ethyl-2,4-dimethyl-Benzene 1.57
13 6.98 2-ethyl-1,3-dimethyl-Benzene 1.06
14 7.00 1-methyl-4-(1-methylethenyl)-benzene 0.26
15 7.07 (2-methyl-1-propenyl)-benzene 1.13
16 7.34 1,2,4,5-tetramethyl-Benzene 1.62
17 7.51 1-methyl-2-(2-propenyl)-benzene 1.06
18 7.66 2-methylidene 1.57
19 7.80 2-ethenyl-1,3,5-trimethyl-Benzene 0.26
20 7.92 Naphthalene 8.21
21 8.42 4,7-dimethyl-1H-indene 0.94
22 8.47 1,3-dimethyl-1H-indene 1.80
23 8.51 4,7-dimethyl-1H-indene 1.22
24 8.54 2,3-dimethyl-1H-indene 0.64
25 8.76 1-methyl-Naphthalene 7.92
26 8.89 1-methyl-Naphthalene 4.15
27 9.28 1,2,3-trimethyilidene 1.03
28 9.33 biphenyl 1.38
29 9.52 2,7-dimethyl-Naphthalene 3.59
30 9.62 1,5-dimethyl-Naphthalene 2.43
 106

31 9.65 2,7-dimethyl-Naphthalene 2.60

32 9.76 1,3-dimethyl-Naphthalene 0.91
33 9.78 1,4-dimethyl-Naphthalene 0.57
34 10.02 3-methyl-1,1'-biphenyl 0.67
35 10.16 1,4,6-trimethyl-Naphthalene 0.46
36 10.29 1,6,7-trimethyl-Naphthalene 0.56
37 10.33 1,6,7-trimethyl-Naphthalene 1.14
38 10.43 1,4,6-trimethyl-Naphthalene 0.41
39 10.45 2,3,6-trimethyl-Naphthalene 0.42
40 10.54 2,3,6-trimethyl-Naphthalene 0.24
41 10.70 Fluorene 0.74
42 11.37 2-methyl-9H-Fluorene 0.59
43 11.41 1-methyl-9H-Fluorene 0.25
44 11.87 Anthracene 1.75
45 11.93 Anthracene 0.50
46 12.47 2-methyl-Anthracene 0.67
47 12.50 2-methyl-Anthracene 0.94
48 12.55 1-methyl-Anthracene 0.52
49 12.61 1-methyl-phenanthrene 0.94
50 12.63 1-methyl-Anthracene 0.63
51 12.83 2-phenyl-Naphthalene 0.46
52 13.16 2,5-dimethyl-phenanthrene 0.31
53 13.35 Flouranthene 0.50
54 13.61 Pyrene 0.97
 107

SAMPLE 11 : 120 g, 3750C

Retention Percent Area

No Time Tentative Assigment (%)
1 3.74 Toluene 0.73
2 4.83 Ethylbenzene 0.45
3 4.93 p-Xylene 5.62
4 5.19 p-Xylene 1.48
5 5.41 1,2,6,6-tetramethyl-1,3-cyclohexadiene 0.33
6 5.85 D-Limonene 1.97
7 5.89 1-ethyl-3-methyl-Benzene 4.53
8 5.96 2-ethyl-1,4-dimethyl-Benzene 2.05
9 6.22 1,2,3-trimethyl-Benzene 5.45
10 6.25 Cyclopropyl-benzene 0.92
11 6.55 Limonene 11.59
12 6.71 Indene 1.26
13 6.79 1-ethyl-2,4-dimethyl-Benzene 2.03
14 6.98 1-ethyl-2,4-dimethyl-Benzene 1.11
15 7.00 1-methyl-4-(1-methylethenyl)-Benzene 0.27
16 7.03 1-ethyl-2,4-dimethyl-Benzene 0.75
17 7.07 o-Isopropenyltoluene 1.06
18 7.30 1,2,4,5-tetramethyl-Benzene 0.28
19 7.34 1,2,3,5-tetramethyl-Benzene 1.51
20 7.51 1-methyl-2-(2-propenyl)-benzene 0.54
21 7.61 1-butynyl-benzene 1.92
22 7.66 1-butynyl-benzene 1.47
23 8.42 1,3-dimethyl-1H-indene 0.52
24 8.47 1,3-dimethyl-1H-indene 1.14
25 8.51 4,7-dimethyl-1H-indene 0.99
26 8.76 1-methyl-Naphthalene 6.57
27 8.89 1-methyl-Naphthalene 3.52
28 9.28 1,2,3-trimethyilidene 0.44
29 9.33 biphenyl 0.69
30 9.52 2,7-dimethyl-Naphthalene 2.80
 108

31 9.62 2,7-dimethyl-Naphthalene 1.96

32 9.65 2,6-dimethyl-Naphthalene 1.95
33 9.76 1,3-dimethyl-Naphthalene 0.49
34 9.78 1,4-dimethyl-Naphthalene 0.31
35 10.02 3-methyl-1,1'-biphenyl 0.52
36 10.15 2,3,6-trimethyl-Naphthalene 0.43
37 10.29 1,6,7-trimethyl-Naphthalene 0.54
38 10.33 1,4,6-trimethyl-Naphthalene 1.14
39 10.43 1,6,7-trimethyl-Naphthalene 0.42
40 10.45 2,3,6-trimethyl-Naphthalene 0.29
41 10.70 Fluorene 0.38
42 11.37 1-methyl-9H-Fluorene 0.49
43 11.42 1-methyl-9H-Fluorene 0.23
44 11.87 Anthracene 1.20
45 11.93 9-methylene-9H-Fluorene 0.34
46 12.47 2-methyl-phenanthrene 0.53
47 12.50 2-methyl-phenanthrene 0.73
48 12.55 1-methyl-Anthracene 0.40
49 12.63 1-methyl-phenanthrene 0.50
50 12.83 2-phenyl-Naphthalene 0.32
51 13.16 9,10-dimethylanthracene 0.41
52 13.61 pyrene 0.39
53 15.73 mono (2-ethylhexyl) ester 1,2- 0.85
benzenedicarboxylic acid
 109

SAMPLE 12 : 120 g, 4000C

Retention Percent Area

No Time Tentative Assigment (%)
1 3.73 Toluene 0.85
2 4.83 Ethylbenzene 0.35
3 4.92 o-Xylene 4.24
4 5.19 1,3-dimethyl-Benzene 1.16
5 5.41 1,2,6,6-tetramethyl-1,3-cyclohexadiene 0.33
6 5.85 D-Limonene 2.32
7 5.89 1-ethyl-2-methyl-Benzene 3.81
8 5.96 1,3,5-trimethyl-Benzene 1.29
9 6.10 3,4-dimethyl-2,4,6-octatriene 2.04
10 6.21 1,2,3-trimethyl-Benzene 5.07
11 6.25 1-ethenyl-3-methyl-Benzene 0.99
1-methyl-4-(1-methylethyl)-,(R)-
12 6.47 cyclohexene 1.04
13 6.54 Limonene 14.89
14 6.58 5-ethylidene-1-methyl-cycloheptene 0.57
15 6.62 5-ethylidene-1-methyl-cycloheptene 1.01
16 6.71 Indene 1.63
17 6.79 1-ethyl-3,5-dimethyl-Benzene 2.35
18 6.98 1-methyl-2-(1-methylethyl)-benzene 1.91
19 7.03 2-ethyl-1,4-dimethyl-Benzene 0.88
20 7.07 1-methyl-4-(1-methylethenyl)-Benzene 1.52
21 7.30 1,2,4,5-tetramethyl-Benzene 0.71
22 7.34 1,2,3,5-tetramethyl-Benzene 1.89
23 7.61 1-butynyl-benzene 2.42
24 7.66 2-methylidene 1.76
25 7.80 2-ethenyl-1,3,5-trimethyl-Benzene 0.23
26 7.92 Naphthalene 5.17
27 8.42 1,3-dimethyl-1H-indene 0.59
28 8.46 1,3-dimethyl-1H-indene 1.18
29 8.51 4,7-dimethyl-1H-indene 1.05
 110

30 8.76 2-methyl-Naphthalene 5.33

31 8.89 1-methyl-Naphthalene 2.67
32 9.28 1,2,3-trimethyilidene 0.38
33 9.33 biphenyl 0.51
34 9.52 2,7-dimethyl-Naphthalene 2.48
35 9.62 2,7-dimethyl-Naphthalene 1.76
36 9.65 2,7-dimethyl-Naphthalene 1.85
37 9.76 1,3-dimethyl-Naphthalene 0.58
38 9.87 2,3-dimethyl-Naphthalene 0.68
39 10.02 3-methyl-1,1'-biphenyl 0.37
40 10.16 2,3,6-trimethyl-Naphthalene 0.58
41 10.30 1,6,7-trimethyl-Naphthalene 0.40
42 10.33 1,4,6-trimethyl-Naphthalene 0.82
43 10.43 1,4,5-trimethyl-Naphthalene 0.29
44 10.46 1,4,6-trimethyl-Naphthalene 0.31
45 10.70 Fluorene 0.48
46 11.37 2-methyl-9H-Fluorene 0.24
47 11.87 Anthracene 0.56
48 12.47 2-methyl-Anthracene 0.29
49 12.51 2-methyl-Anthracene 0.39
50 12.61 1-methyl-phenanthrene 0.11
51 13.62 Pyrene 0.18
 111

APPENDIX III

EXPERIMENTAL APPARATUS

1. Raw Material

Natural Rubber CaO, Silica

CaO dissolved in HCl Silica dissolved in NaOH Aging

 112

Drying CaO/SiO2 Catalyst

2. Product

Pyrolitic oil
113