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Lubricant from 1-decanol via oligomerization reaction over novel heterogeneous
catalysts by Snunkhaem Echaroj
From Dissertation (ET900)
Processed on 07-Jun-2017 06:46 ICT

ID: 822738471
Word Count: 32494
Similarity Index
12%
Similarity by Source
Internet Sources:
8%
Publications:
9%
Student Papers:
3%
sources:
< 1% match (publications)

1
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5
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6
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7
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10
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18
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39
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40
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42
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44
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61
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62
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81
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paper text:
LUBRICANT FROM 1-DECANOL VIA OLIGOMERIZATION REACTION OVER NOVEL HETEROGENEOUS
CATALYSTS BY MR. SNUNKHAEM ECHAROJ
44A DISSERTATION SUBMITTED IN PARTIAL FULFILLMENT OF THE

REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN
ENGINEERING FACULTY OF ENGINEERING THAMMASAT UNIVERSITY
ACADEMIC YEAR 2016 COPYRIGHT OF THAMMASAT UNIVERSITY
24 105 7/6/2560 7:43


CATALYSTS BY MR. SNUNKHAEM ECHAROJ A DISSERTATION
26SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR

THE DEGREE OF DOCTOR OF PHILOSOPHY IN ENGINEERING FACULTY OF
ENGINEERING THAMMASAT UNIVERSITY ACADEMIC YEAR 2016
COPYRIGHT OF THAMMASAT UNIVERSITY THAMMASAT UNIVERSITY
CHEMICAL ENGINEERING DISSERTATION BY MR. SNUNKHAEM ECHAROJ
ENTITLED

CATALYSTS Chairman Advisor Committee Committee Committee Dean
19was approved as partial fulfillment of the requirements for the degree of

Doctor of Philosophy on June
16, 2017 ______________________________________ (
58Assoc. Prof. Dr. Woranee Mungkalasiri )

______________________________________ ( Asst. Prof. Dr. Malee Santikunaporn
) ______________________________________ ( Asst. Prof. Dr. Patcharaporn
Thitiwongsawet ) ______________________________________ ( Asst. Prof. Dr.
Channarong Asavatesanupap ) ______________________________________ ( Prof. Dr. Sumeth

Chavadej ) ______________________________________ ( Assoc. Prof. Dr. Prapat Wangskarn )
THAMMASAT UNIVERSITY CHEMICAL ENGINEERING DISSERTATION BY MR. SNUNKHAEM
ECHAROJ ENTITLED LUBRICANT FROM 1-DECANOL VIA OLIGOMERIZATION REACTION OVER
NOVEL HETEROGENEOUS CATALYSTS Chairman Advisor Committee Committee Committee Dean
19was approved as partial fulfillment of the requirements for the degree of

Doctor of Philosophy on June
16, 2017 ______________________________________ (
58Assoc. Prof. Dr. Woranee Mungkalasiri

______________________________________ ) ( Asst. Prof. Dr. Malee
Santikunaporn ______________________________________ ) ( Asst. Prof. Dr.
Patcharaporn Thitiwongsawet ) ______________________________________ ( Asst.
Prof. Dr.
25 105 7/6/2560 7:43

Channarong Asavatesanupap ) ______________________________________ ( Prof. Dr. Sumeth

Chavadej ) ______________________________________ ( Assoc. Prof. Dr. Prapat Wangskarn ) (1)
Dissertation Title LUBRICANT FROM 1-DECANOL VIA OLIGOMERIZATION REACTION OVER NOVEL
HETEROGENEOUS CATALYSTS Author MR. SNUNKHAEM ECHAROJ Degree Doctor of Philosophy
Faculty/University Chemical Engineering/Thammasat University Thesis Advisor Asst. Prof. Dr. Malee
Sanitkunaporn, Ph.D Academic Years 2016 ABSTRACT The oligomerization of olefins to heavier
hydrocarbons with lubricant-like properties was investigated over different acid heterogeneous catalysts
including Beta-38, Mordenite-20, HY-30 and tungstated-zirconia. Textural characterization was performed
using N2 sorption technique and X-ray diffraction (XRD).
178Acidity of the catalysts were found using the temperature-programmed

desorption (TPD) of NH3
Among the zeolite catalysts, HY-30 zeolite gave the highest amount of lubricant due to high acidity, large
pore size and cage-like framework of catalyst. Operating parameters that have
164a significant effect on the formation of lubricant were reaction temperature and
the amount of
catalyst. Over HY-30 zeolite,
208an increase in temperature from 150 to 210 oC was found to increase
1-decene conversion from 60 to 87 wt% and amount of lubricant from 5 to 25 wt%. An increase in the
amount of HY- 30 used from 5 to 15 wt%
199resulted in an increase in conversion from 40 to
80 wt% and amount of lubricant from 1 to 18 wt%. An increase in conversion was accompanied by a
reduction in viscosity index of the lubricant products. Investigation of oligomer structure through C13-NMR
analysis revealed oligomers with low viscosity index consisting of high composition of short-chain branches.
A reduction in viscosity index from 150 to 104 resulted in a rise in the amount of short-chain-branches from
28 to 48 %. Conversion of double-bond oligomers to saturated molecule through hydrogenation reaction
over 1%Pt/Al2O3 catalyst
256was confirmed by using Fourier Transform Infrared Spectroscopy (FTIR).
43Comment [m1]: Using 14 point bold font with uppercase in each alphabet
(2) Catalyst modification can be performed to increase catalytic activity, pore size and reduce acidity of the
26 105 7/6/2560 7:43

catalysts. Three different methods were employed to modify zeolite catalysts including fluorination,
ion-exchange and incipient impregnation. Modification of Beta-38 zeolite through the fluorination process
resulted in an improvement in catalytic activity, but reduces the viscosity index of the oligomers.
Ion-exchange was successfully performed to increase the pore size of the Beta-38 zeolite, which cause the
viscosity of the oligomer product to increase from 100 to 140. A micro-kinetic analysis of the oligomerization
reaction over tungstated- zirconia catalyst was also conducted to study the mechanism of oligomerization of
1- decene. The optimal condition resulted in 1-decene conversion of 70 % and product consisting of 49 %
dimers and 23 % trimers. Dimerization and trimerization reaction required apparent activation energy of 21
and 33 kJ/mol respectively. Trimerization reaction was found to proceed through the combination of dimer
and monomer molecules. According to the modeling equation, the dimerization reaction required two active
sites at low temperature (150 oC and 175 oC) and three active sites at high temperature (200 oC and 210
oC). For trimerization reaction three active sites were required
233at low temperature and four active sites at high temperature. The
best modeling equation fitted appropriately with the experimental data. Keywords: Oligomerization,
heterogeneous acid catalyst, C13-NMR, micro-kinetic analysis, synthetic lubricant Comment [m2]: Using 12
point normal font (3) ACKNOWLEDGEMENTS
107I would like to express my gratitude to the following people and institutions
who made the production of this dissertation possible.
140First of all I would like to thank my supervisor, Assistant Professor Malee

Suntikunaporn for her dedication, interest and
expertise. Her help was crucial in making this research and journal publication successfully. Thammasat
University, in particular the department of engineering, for providing partial funding, a location, laboratory
and facility for the research to be conducted in. Petroleum Authority of Thailand Research & Technology
Institute
222for their financial and technical support. Individually, I also wish to thank
Mr. Kornthape Prasirtsiriphan, a researcher at PTT RTI, for providing important guideline and insightful
information on this research. In additional,
81I would also like to thank Mr. Rangsan Rungrueangsee for his help
on analyzing some products. Comment [m3]:
5Using 14 point bold font with uppercase in each alphabet Snunkhaem Echaroj
27 105 7/6/2560 7:43

(4) TABLE OF CONTENTS ABSTRACT Page (1) ACKNOWLEDGEMENTS (2)

LIST OF TABLES (7) LIST OF FIGURES (9) CHAPTER 1 INTRODUCTION 1 1.
1271 Background Information 1 1.2 Objective of this research 3 1.3 Overview of

dissertation 4
Comment [m4]:
93Using 12 point normal font w an uppercase in each alphabet CHAPTER 2

REVIEW OF LITERATURE 6 2.1
Overiew of the types of oligomerization reaction 2.2 Overview of the types of catalyst for oligomerization
2.2.1 Lewic acid /ionic liquid 2.2.2 Co-ordination catalyst 2.2.2.1 Ziegler-Natta catalyst (Ti metal) 2.2.2.2
Chromium-silica (Phillips catalyst) 2.2.3 Heterogenous acid catalyst 2.2.3.1 Zeolite catalyst 2.2.3.2 Metal
loaded zeolite catalyst 2.2.3.3 Doped metal oxide 2.3 Heterogenous Catalyst Characterization Techniques 6
7 9 9 9 13 15 17 20 21 22 2.4 Product Characterization Techniques 2.4.1 Theory on spectrocopy techniques
2.4.1.1 Principle of 13C-NMR 2
216.4.1.2 Fourier transform infrared spectroscopy (FTIR)
2.4.2 Calculation of Viscosity Index (ASTM D2270) 2.5 Micro-kinetic for heterogenous catalyst 2.5.1 Theory
on catalytic surface reaction 2.5.2 Internal and external diffusion 2.5.3 Previous work on kinetic modeling of
Oligomerization (5) 28 28 29 35 36 37 37 46 47 CHAPTER 3 EXPERIMENTAL PROCEDURE 55 3.1
Concept Outlined 3.2 Expiermental setup 3.2.1 Solid catalysts, apparatus and chemicals 3.2.2 Catalyst
pretreatment and modification 3.2.2.1 Ion-exchange 3.2.2.2 Incipient impregnation 3.2.3 Oligomerization
reaction 3.2.4 Catalyst regeneration 3.2.5 Hydrogenation reaction 3.3 Catalyst Chracterization 3.4 Product
chracterization 55 57 57 58 58 58 59 60 60 62 63 CHAPTER 4 OLIGOMERIZATION OF 1-DECENE AND
MIXED-DECENE OVER ZEOLITE CATALYSTS 66 4.1 Introduction 66
1434.2 Experimental setup 4.3 Results and discussion 4.3.1
Catalysts chracterization 4.3.2 Effect of temperature and amount of catalyst 4.3.3 Effect of feedstock
composition (1-decene content) 4.3.3 Effect of feedstock composition (1-decene content) 4.3.4 Catalyst
deactivation and regeneration 4.3.5 Modification of zeolite catalyst 4.4 Conclusion (6) 67 67 68 70 77 77 80
85 88 CHAPTER 5 OLIGOMERIZATION OF 1-DECENE AND MIXED-DECENE OVER MODIFIED
ALUMINA AND ZIRCONIA 90
2155.1 Introduction 5.2 Experimental setup 5.
573 Results and discussion 5 .3.1 Catalyst characterization 5 .3.2 Effect of
28 105 7/6/2560 7:43

reaction temperature 5 .3.3 Effect of
amount of catalyst 5.3.4 Product characterization 5.3.4.1 Viscosity measurement 5.3.4.2 FTIR analsysis
5.3.4.3 Structural investigation using C13-NMR technique 5.4 Conclusion 90 91 91 91 95 99 101 101 102
104 110 CHAPTER 6 MICRO-KINETIC MODELLING OLIGOMERIZATION REACTION OVER
HETEROGENEOUS REACTION 110 6.1 Introduction 6.2 Kinetic modeling formation 6.3 Kinetic modelling
results 6.4 Conclusion 110 112 117 124 CHAPTER 7 CONCLUSIONS AND FUTURE PROSPECTIVE
Reference (7) 125 127 APPENDICES APPENDIX A Gas chromatography analysis APPENDIX B Micro-
kinetic simulation APPENDIX C C13-NMR analysis APPENDIX D Estimation of acidic using NH3 TPD
APPENDIX E Zeolite catalyst 136 140 143 146 149 BIOGRAPHY 150 (8) LIST OF TABLES Tables Table 2.1
Information on different organometallic available in the market Table 2.2 Summary of the source and
reaction required for the generation of Page 13 sustainable and alternative fuel and energy. 15 Table 2.3
Different type of characterization techniques for heterogeneous catalysts 22 Table 2.4 Characteristic of
different types of spectroscopy; NMR, IR and UV-VIS17 29 Table 2.5 Chemical shift of carbon location in
different position of a long-chain molecule. 35 Table 2.6 The value for different carbon configuration 35 Table
2.7 The value of L and H for calculation of VI 37 Table 2.8 Rate equation from oligomerization over different
type of catalysts 50 Table 3.1 Chemical reagents used in this research 57 Table 3.2 Gases used in this
research 57 Table 3.3 Equipment and apparatus 57 Table 3.4 Constant and the range of viscosity for
different sizes of canon-fenske glass 65 Table 4.1 N2 sorption characterization of zeolite catalysts 68 Table
4.2 Calculation of the acidity of catalyst sample obtained from TCD area 70 Table 4.3 Summary of the
modification of Beta-38 through ion-exchange and 86 incipient impregnation. Table 5.1 Trend lines equation
for the consumption of C10 used to find the rate 98 of reaction. Table 5.2 Trend lines equation for the
generation of C20 used to find the rate of 98 reaction. Table 5.3 Trend lines equation for the generation of
C30 used to find the rate of 98 reaction.
13Comment [m5]: Numbering of tables of each chapter Comment [m6]: Using

12 point normal font
(9) Table 6.1 Rate equations derived from the assumption above for dimerization 115 over tungstated-
zirconia. Only one mechanism is assumed for the dimerization: C10=+C10= DI n=1,2 or 3 Table 6.2 Rate
equations derived from the assumption for trimerization over 115 tungstated-zirconia (Mechanism 1: C10= +
C10= + C10= Ti, Mechanism 2: DI + C10= Ti) n = 1,2,3 or 4 Table 6.3 Estimated parameters and
equilibrium constant from D1b(n=2) at 121 lower temperature (150oC K and 175oC K) and D1b(n=3) at
higher temperature (200 oC and 210 oC) for dimerization reaction Table 6.4 Estimated parameters and
equilibrium constant from T2b(n=3) at 121 lower temperature (150 oC and 175 oC) and T2b(n=4) at higher
temperature (200 oC and 210 oC) for trimerization reaction. Table A.1 List of hydrocarbon and the area
according to the gas chromatogram 137 Table A.2 Summary of the response factor of each hydrocarbons
contained in 138 the Boiling Point Calibration Sample#1 mixed with stock solution (0.5g n-tridecane in
isopropanol 50mL) Table A.3 Calculation of the oligomer product composition obtained by GC analysis 139
Table B.1 Rate of 1-decene (C10) consumption obtained by taking derivative of the trendlines equation at
reaction temperature between 150oC to 210oC. Table B.2 Rate of dimer formation (C20) obtained by taking
derivative of the trendlines equation at reaction temperature between 150oC to 210oC. 140 141 Table B.3
Rate of trimers formation (C30) obtained by taking derivative of the 142 trend lines equation at reaction
temperature between 150oC to 210oC. Table C.1 Operating condition for the production of lubricant oil to be
analyzed 143 by C13-NMR Table C.2 Integral from C13-NMR analysis of synthesized lubricant oil obtained
29 105 7/6/2560 7:43

144 (10) from oligomerization reaction (operating conditions shown in Table C.1) Table D.1 Calibration of
acidity using 4 different loops. 146 Table D.2 Calculation of the acidity of catalyst sample obtained from TCD
area 148 Table E.1 Structural characteristic of zeolite catalyst 149 (11)
221LIST OF FIGURES Figures Page Figure 1.1 Novel reaction path for the
synthesize of lubricant oil from vegetable 3 oil (Step 1 is the hydrogenation reaction, step 2 is the
dehydration reaction and step 3 is the oligomerization reaction). Figure 2.1 Different types of catalysts for
polymerization and oligomerization 8 reaction. (a) Ziegler-Natta, (b) chromium catalyst, (c) lewis acid
catalyst, (d) metallocene, (e) late-transition metal Figure 2.2 Three typical molecular structure of polymers
from polymerization; 10 isotactic a), syndiotactic b), and atactic c) Figure 2.3 Mechanism of polymerization
over Ziegler-Natta heterogeneous 12 catalyst; Ti dispersed on MgCl2 a), incorporation of Ti2+ in MgCl2
structure b), interaction between olefins molecule and Ti2+ site c), addition of hydrogen d), and formation of
active center e). Figure 2.4 Effect of chromium loading (during impregnation onto silica) on the 14 activity of
the catalyst Figure 2.5 Oxidation of chromium trioxide (Cr+3) on silica at 500oC to Cr+6 (a) 14 and reduction
of Cr+6 to Cr+2 in the presence of CO gas. Figure 2.6 Influence of textural characteristic on degree of
branching (a) and 18 catalytic activity for oligomerization reaction (b). Figure 2.7 Model of the Faujasite
zeolite catalyst (a), H-ZSM-5 catalyst (b) and 18 the pore structure of the HZSM-5 catalyst (c). Figure 2.8
13C-NMR analysis of lubricant derived from oligomerization of 19 1-decene using H-ZSM5 as a catalyst at
473 K: Oligomerization reaction over modified H-ZSM5 (a), oligomerization reaction over unmodified
H-ZSM5 (b). Figure 2.9 Characterization of modified (MMZ-H) and unmodified (H) Beta 24 zeolite from N2
sorption a), NH3-TPD b) and XRD c). Catalyst testing of modified and unmodified Beta zeolite through
oligomerization of dicyclopentadiene d). Figure 2.10 Characterization of modified gamma-alumina calcined
at 400oC a) 25 Comment [m7]:
13Using 14 point bold font with uppercase in each alphabet Comment [m8]:
Numbering of Figures of eac chapter. Comment [m9]: Using 12 point normal
font
(12) and 500oC b). Pore size distribution of gamma-alumina modified with different ratio of swelling agent to
surfactant c) Figure 2.11 Characterization of sulfated-alumina using X-ray technique a) and 26 NH3-TPD for
acidity analysis b). Figure 2.12 X-ray diffraction patterns of Beta catalyst contained different nickel 27
content a) and conversion of ethylene b) Figure 2.13 Movement of nuclei in the absence of magnetic field a),
movement 30 of nuclei under the presence of the magnetic field b) and activation of nuclei from low energy
level to high energy level by applying radiofrequency wave c). Figure 2.14 Chemical shift of carbon atom
attached to different function group 31 Figure 2.15 Symbols represent carbons in different part of the
molecular 32 structure with long chain (a), molecular structure with short branched chain (b)-(d), longchain
hydrocarbons (e) and alkene (f). Figure 2.16 Stretching and bending of molecule in FTIR 35 Figure 2.17
FTIR spectrum of different functional group 36 Figure 2.18 Different configuration of the atomic structure;
face-centered cubic 38 a), body-centered cubic b), and hexagonal c). Figure 2.19 Langmuir adsorption
isotherms 40 Figure 2.20 Catalyst of different metal incorporated catalysts demonstrating the 45 Sabatier
principle Figure 2.21 Illustration of the 6 steps involved in the reaction on heterogeneous 47 catalyst;
1.external diffusion, 2. 1st internal diffusion, 3. Adsorption, 4.Surface reaction, 5.Desorption and 6. 2nd
internal diffusion. Figure 3.1 Framework for production of fuel and lubricating oil. 56 Figure 3.2.
Oligomerization reaction of 1-decene using a rounded bottom flask 59 (a) and the Parrs stainless steel
30 105 7/6/2560 7:43

autoclave. Figure 3.3 Boiling point and cut ranges for distillation of oligomer product. 60 Figure 3.4
Preparation 1%Pt/Al2O3 through incipient impregnation using 61 chlorophlatinic acid hydrate solution.
Figure 3.5 Finished solid catalyst ready to be used for hydrogenation reaction 61 Figure 3.6 Fix-bed reactor
setup for hydrogenation of oligomers product. 62 (13) Hydrogen gas a), Mass flow controller b), check valve
c), vent gas #1 d), fixed-bed stainless steel reactor e), split-furnace f), high-pressure pump g), feedstock
solution h), Figure 3.7 Measurement of viscosity using the cannon-fenske technique with a 65 water bath (a)
and the important parts of the canon-fenske glass (b) Figure 4.1 N2 sorption isotherm a) and pore size
distribution b) of zeolite 69 catalysts. Figure 4.2 NH3-TPD results for zeolite catalysts 70 Figure 4.3
9Effect of temperature on the conversion of 1-decene over zeolite 73 catalyst a),

amount of C20 b),
amount of C30 c) and amount of C40 d) formed. Reaction conditions: Atmospheric pressure, agitation speed
=400 rpm and 10wt% catalyst Figure 4.4 Influence of reaction temperature on viscosity and viscosity index
of 74 oligomer product from oligomerization over HY-30. Reaction conditions: Atmospheric pressure,
agitation speed = 400 rpm and 10wt% catalyst Figure 4.5 Influence of reaction temperature on viscosity and
viscosity index of 74 oligomer product from oligomerization over Beta-38. Reaction conditions: Atmospheric
pressure, agitation speed = 400 rpm and 10wt% catalyst Figure 4.6
6Effect of the amount of catalyst on the oligomerization reaction
for 76 HY-30 a) and Beta-38 b). Synthesis conditions: Temperature = 200oC, Reaction time = 2 hours,
agitation speed = 300 rpm and atmospheric pressure. Figure 4.7 Influence of the amount of catalyst on
viscosity and viscosity index of 76 oligomer product from oligomerization over HY-30. Reaction conditions:
Temperature = 200oC, atmospheric pressure, and agitation speed =400 rpm. Figure 4.8 Influence of the
amount of catalyst on viscosity and viscosity index 77 of oligomer product from oligomerization over
Beta-38. Reaction conditions: Temperature = 200oC, atmospheric pressure, and agitation speed =400 rpm.
(14) Figure 4.9 GC analysis of feedstock containing 45.3 %wt. 1-decene a) and 78 96 %wt. 1-decene b).
Figure 4.10 Effect of feedstock composition on conversion a), amount of C20 b) 80 ,amount lubricant oil
(C30+C40) c) and viscosity index d). Reaction conditions: Temperature =200oC, agitation speed = 400 rpm,
atmospheric pressure, and 10wt% catalyst. Figure 4.11 Fresh and used Beta, HY and tungstated-zirconia
catalyst from 82 oligomerization reaction Figure 4.12 Percentage weight loss during TGA analysis of HY-30
and Beta-30 82 zeolite catalysts. Treatment condition: air flow rate = 100 mL/min and sample weight =
0.1gram. Figure 4.13 Regeneration stage for zeolite catalysts and catalytic testing 83 Figure 4.14 Catalytic
activity testing of fresh HY-30 catalyst compared with the 84 regenerated catalysts (cycle 1, cycle 2 and
cycle 3). Testing conditions: Temperature reaction = 200oC, agitation speed = 300 rpm and 10 %wt. catalyst.
Figure 4.15 Catalytic activity testing of fresh Beta compared with the regenerated 84 Beta catalysts (cycle 1,
cycle 2 and cycle 3). Testing conditions: Temperature reaction = 200oC, agitation speed = 300 rpm and 5
%wt. catalyst. Figure 4.16 Effect of the ammonium fluoride concentration and modification 87 agent on the
amount of HC20 produced and the viscosity of lubricant products Figure 4.17 Effect of the Ni metal on the
amount of HC20 produced and the 88 viscosity of lubricant product. Figure 5.1 Physical characterization of
tungstated-zirconia revealing adsorption 92 and
100desorption isotherm a) and pore-size distribution b).
31 105 7/6/2560 7:43

Figure 5.2 X-ray diffraction pattern profile of tungstated-zirconia a) 94 NH3 desorption profile of tungstated-
zirconia b) Figure 5.3
9Effect of temperature on the conversion of 1-decene over tungstated- 97

zirconia a), amount of C20 b),
and amount of C30 c) at different temperature between 150oC to 200oC. Reaction conditions: (15)
Atmospheric pressure, agitation speed = 400 rpm and 10 Figure 5.4 Effect of the amount of tungstated-
zirconia on the conversion of 100 1-decene a), amount of C20 b), and amount of C30 c) at different
temperature between 150oC to 200oC. Reaction conditions: Temperature = 200oC, atmospheric pressure,
agitation speed. Figure 5.5 Relationship between the VI index and the amount of HC20 (wt%.) 102 in the
product from oligomerization over zeolite and tungstated-zirconia. Figure 5.6 FTIR analysis of the oligomer
product from TZ catalyst before and 103 after hydrogenation reaction. The dashed box are zoom and
depicted
51in Figure 5. 5 a and b. Figure 5. 7 Zoomed image of
oligomer product before hydrogenation (a) and 103 after hydrogenation (b). Figure 5.8 Correlation between
location of peaks on the spectrum and structure 105 of the molecule for iso
76-1 (a) , iso -2 (b) iso -3 (c) iso -4 (d) iso -5 (e)
iso-6 (f) and iso-7 (g) Figure 5.9 C13-NMR of the commercial 95% 1-decene. 106 Figure 5.10 C13-NMR of
product obtained from dehydration reaction 106 (containing 1-decene and 1-decanol). Figure 5.11 C13-NMR
of linear hydrocarbon with 15 to 18 carbon atoms 107 Figure 5.12 C13-NMR product collected from
oligomerization over 10%wt. 107 tungstated-zirconia at 200oC and atmospheric pressure. Figure 5.13
C13-NMR product collected from oligomerization over 10%wt. 108 HY-30 at 200oC and atmospheric
pressure. Figure 5.14 C13-NMR of the product collected from oligomerization over 108 10%wt. Beta-38 at
200oC and atmospheric pressure. Figure 5.15 Relationship between the VI index of the lubricant product
and 109 short-chain branching (%). Figure 5.16 Relationship between the VI index of the lubricant product
and 109 branching ratio. Figure 6.1 Activation energy for dimerization and trimerization. 112 Figure 6.2 Level
of fitness corresponding to the estimation of the rate of 118 (16) equation for dimerization assuming
mechanism 1 (D1). D1a (group a) also assumes that the unoccupied sites available for dimerization reaction
are relatively small compared to the site that is occupied. Figure 6.3 Level of fitness corresponding to the
estimation of the rate of 120 equation for trimerization assuming mechanism 1 (T1). T1a (group a) also
assumes that the unoccupied sites available for trimerization reaction are relatively small compared to the
site that is occupied. Figure 6.4 Level of fitness corresponding to the estimation of the rate of 120 equation
for trimerization assuming mechanism 2 (T2). T2a (group a) also assumes that the unoccupied sites
available for trimerization reaction are relatively small compared to the site that is occupied. Figure 6.5
Plotting experimental data (symbol) with the calculated rate of 122 dimerization (dash line) at lower
temperature range r =k1*KAD*[M10=]2/(KAD*[M10=]+[Di]*KDi+KTi*[Ti]) Figure 6.6 Plotting experimental
data (symbol) with the calculated rate of 122 dimerization (dash line) at lower temperature range r=k1*KAD*
[M10=]2/(KAD*[M10=]+[Di]*KDi+KTi*[Ti])3 Figure 6.7 Plotting experimental data (symbol) with the calculated
rate of 123 trimerization (dash line) at lower temperature range r =k2.2*KDi*[DI]*[M0=]/(KAD*[M10=]+
32 105 7/6/2560 7:43

[Di]*KDI+KTi*[Ti])3 Figure 6.8 Plotting experimental data (symbol) with the calculated rate of 123
trimerization(dash line) at higher temperature range r =k2.2*KDI*[Di]*[M10=]/(KAD*[M10=]+[Di]*KDi+KTi*
[Ti])4 Figure A.1 Gas chromatogram of the boiling point calibration sample #1 Kit 137 (Agilent) Figure A.2
Gas chromatography analysis of standard hydrocarbon mixed with 138 the stock solution Figure A.3 Gas
chromatography analysis of the oligomer product obtained from 139 oligomerization at 200oC over 10 wt%
HY-30 Figure C.1 C13-NMR of commercial group 4 lubricant oil from PTT company 144 Figure C.2
C13-NMR of commercial group 3 lubricant oil from Yubase 145 Company (17) Figure C.3 C13-NMR of
commercial group 3 lubricant oil from Ultra Company 145 Figure D.1 Calibration curve for the NH3-TPD
analysis 147 Figure E.1 Modeled framework of FAU (HY), MOR (mordenite) and BEA 149 (Beta) zeolite
catalyst
51 CHAPTER 1 Comment [m10]: Using 14 point bold font wi an uppercase in

each alphabet INTRODUCTION 1.1
Background Information In the 20th century, most researches had focused on the development of refinery
and petroleum based products, because crude oil was still considered as inexpensive and sufficiently
available. Unfortunately due to continuous exploitation to serve our expanding population crude oil is no
longer regarded as sustainable, which triggered an undesirable rise in the price of crude oil. In response to
higher prices of crude oil, numerous researches in the 21st century have been conducted to investigate
chemical reactions that can convert sustainable natural feedstock to useful commodities that had the
potential to replace crude oil. Successful pathways included, the conversion of triglyceride in vegetable oil to
biodiesel via transesterification reaction 1-3 and to linear hydrocarbon (bio-hydrogenated diesel; BHD) via
the deoxygenation reaction series4. It is clear that most of these endeavors have been focused on the
development of the production of transportation fuel. Although biodiesel can now be produced in an industry
scale, its viscosity is still too high for most commercial vehicles. However, not a lot of researches were
conducted to develop new pathways for lubricant oil, despite the fact that lubricant oil is also necessary for
vehicle and machinery to function properly. Moreover, it is obvious that the demand for lubricant oil increases
with demand for transportation fuel. In China, an increase of 1 million owned cars had caused an increase of
about 90,000 tonnes in demand for lubricant oil 5. Since lubricant oil is also derived from
123crude oil, the shortage of crude oil
would also trigger undesirable fluctuation
123in the price of lubricants. Apart from the shortage of crude oil
as a feedstock, there is also another problem with the current production technology of lubricants. As shown
in Figure 1a, lubricant oil is derived from atmospheric and vacuum distillation of crude oil. However, before
this fraction can be used as a lubricant oil, it has to be treated first to eliminate asphalt (using a de-asphalt
unit), aromatics (using a solvent extraction unit) and wax (using a solvent dewaxing unit) 6. According to the
American Petroleum Comment [m11]: Using 12 point bold font 1 2 Institution (API), the final product that is
obtained from these treatment processes is categorized as Group III lubricant oil. The first problem is that
these treatment processes are time and energy consuming. Additionally, it is impossible to eliminate all the
undesired contaminant (sulphur, aromatic and wax). This is why there had been attempts to create a
33 105 7/6/2560 7:43

different path for the production of lubricants. In 1970, a new group of lubricant known as synthetic lubricant
oil was available in the market. This group of lubricant is characterized as group IV by the API associations
and can be produce from ethylene gas as shown in Figure 1b. One of the most successful and well known
group IV lubricant oil is called polyalphaolefin (PAO), which is derived from oligomerization of ethylene into
1-decene and then oligomerization of 1-decene into long-chain hydrocarbon7. If the majority of these
hydrocarbons molecule contained 30 carbon atoms, it will be used as lubricant oil for transportation vehicle.
However, if the majority of the hydrocarbons contained more than 30 carbon atoms, the lubricant will be
used for machinery in the factory (industrial lubricant oil). An annual increase of 7 percent in the demand for
PAO was anticipated up until year 2020 8. One problem regarding the production of synthetic lubricant oil is
that it is also expensive and difficult to produce. Presently, most PAO lubricant is either synthesized via
Ziegler-Natta catalyst or metallocene catalyst. These catalysts also required high-safety facilities to prepare
because they have to be used along with air- sensitive substances such as Et2AlCl 9. Due to the above
difficulties, it is presently very hard for Thailand to develop a pathway for lubricant production on a
commercial scale. Therefore, it is very clear to us that the way to solve these problems is to find a better,
and more importantly, a cheaper way to synthesize lubricant from 1-decene. After literature review from
various scientific journals and textbook information, we found that a promising catalyst for lubricant
production from 1-decene is the heterogeneous acid catalysts.
177The aim of this research is to investigate the production of
lubricant oil through oligomerization of 1-decene over heterogeneous acid catalyst. This process, shown in
Figure 2, can be made sustainable by using 1-decene that is obtained from 1- decanol via the dehydration
reaction 10 and that the 1-decanol is derived from vegetable oils. 3 Figure 1.1 Novel reaction path for the
synthesize of lubricant oil from vegetable oil (Step 1 is the hydrogenation reaction, step 2 is the dehydration
reaction and step 3 is the oligomerization reaction).
1651.2 Objective of this research The main aim of this research is to
investigate different aspects of the oligomerization reaction over heterogenous catalyst for the production of
long-chain hydrocarbons for transportation fuel and lubricating oil. In addition to monitoring and comparing
catalytic activities of different type of heterogneous catalyst, this research also plan to study the
169relationship between the catalytic activity and the chracteristic of the

catalyst. In
other words, this research is designed to find out about how catalysts chracteristic
27such as surface area, pore volume and pore siae, have an effect on the
oligomerization reaction. This research investigated two different types of heterogenous catalysts; plain
zeolite catalyst and modified support catalysts. The feedstocks used for these experiments are the
commercial 95% 1-decene, synthesized olefins 1 containing 40% 1-decene (60% internal olefins) and
34 105 7/6/2560 7:43

synthesized olefins 2 containing 98% 1-decene (2% internal olefins). This research also performed kinetic
modelling of the oligomerization reaction by formulating rate equations and applying them to non-linear
regression with the experimental data. 4 1. Investigate catalytic activity of the mix-decene oligomerization
over plain and modified zeolite catalysts for production of transportation fuel and lubricant oil. 2. Investigate
catalytic activity of the mix-decene oligomerization over modified alumina and zirconia catalysts for
production of transportation fuel and lubricant oil. 3.
159Study the effect of the characteristic of the catalyst on catalytic activity and
characteristic of
the oligomer products. 4. Study the possibility of catalyst regeneration of used zeolite and tungstate
catalysts. 5. Perform micro-kinetic modeling to obtain kinetic constants and understand the mechanism of
the oligomerization reaction over heterogeneous catalyst. 1.3 Overview of dissertation This dissertation is
divided into 6 chapters. The first chapter offered background information on the topic, the inspiration that led
to this research and the objective of the research. The second chapter explained different type of
oligomerization reation and the different kind of catalyst availible for oligomerization reaction. Additionally,
this chapter will give an overview of different type of characteriszation technique for the solid catalyst and the
oligomer products. Lastly, this chapter highlighted the significant of micro-kinetic modelling in theory and how
researchers around the world use them
3as a tool to understand the mechanism of
chemical reaction and production simulation. The third chapter described the experimental setup for
oligomerization over different kind of catalysts and the chemical used for each experiments. This chapter
also explained the different types of catalyst and product characterization that will be performed through out
the research. The fourth chapter will reveal the result of oligomerization reaction of plain and modified
zeolite. In addition to the catalytic activity testing, this chapter 5 also contained information on the analysis of
the characteristic of solid catalyst and structural information regarding the product. The fifth chapter is similar
to the fourth chapter. However, instead of plain and modified zeolite, this chapter investigates the
oligomerization reaction over modified alumina and zirconia. The sixth chapter used experimental data
obtained from oligomerization of 1-decene over tungstate-zirconia (from the fifth chapter) to formulate the
rate equations with accurate kinetic constants, coefficients and mechanisms using the Langmuir-
Hinshelwood-Hougen-Watson. 6 CHAPTER 2 REVIEW OF LITERATURE 2.1 Overiew of the types of
oligomerization reaction Oligomerization reaction is the combination of 2 to 50 molecules of olefin to form
larger molecular weight oligomers. This is similar to polymerization reaction, but in the case of
polymerization more than 50 molecules of olefins are involved. Polymerization is usually referred to the
conversion of gas, such as ethylene and propylene, to solid-state plastic molecules 11-14. Oligomerization
reaction is usually referred to for the synthesis of transportation hydrocarbons in the range of gasoline and
diesel fuel. Additionally, oligomerization also included transformation of small olefins to lubricant oil
containing hydrocarbon with 30 to 50 carbons. There are four main types of oligomerization reaction; Free
Radical, Ziegler-catalyzed, FriedelCrafts catalyzed and carbenium ion arrangement on heterogeneous acid
catalyst. Free Radical oligomerization can also be referred to as thermal oligomerization where the free
radical process is started by active peroxide. Since this process required high activation energy and give low
quality products, there has not been much research regarding this topic. Additionally, it was found that for
free radical process the degree of oligomerization is very difficult to control. This resulted in product
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containing a wide range of molecular weight oligomers. However, it was revealed that addition of di-tertiary-
alkylperoxide or benzoyl peroxide helped decrease the energy required for the oligomerization to take
place15,16. Most of the researches that are devoted to Ziegler-catalyst aimed to study oligomerization
reaction over the modified first-generation catalyst. One of the significant parameters that have strong
influence on yield and product properties is the aluminium/titanium ratio. This ratio is dictated by the amount
of titanium metal in the catalyst and the amount of organometallic solution used to activate the titanium
centers. Liquid product is obtained from gas
85if the Al/Ti ratio is
0.8:1. However,
85if the Al/Ti ratio is
1:1 then waxy products will be obtained. More details regarding the mechanism of oligomerization reaction
based on Ziegler- catalyst is described in the next section. Currently, a novel type of catalyst known as
metallocene, similar to Ziegler-natta, has been developed. However, metallocene is a single site 6 7 type of
catalyst where oligomerization can occur to obtain narrower molecular weight distribution oligomers13,17.
The third type of oligomerization reaction is usually employed in a FriedelCrafts alkylation process, which is
where aromatic substitution took place under
251the presence of a strong lewis acid. In the case of oligomerization reaction
this process is usually referred as the cationic oligomerization. The chain growth step of this reaction
involved the transfer of charge from the cationic initiator to the monomers. These monomers become active
and then combine with another monomer in the bulk solution. Lewis acids can be use either in gaseous form
or liquid formed. For instance, lewis acid that is in gaseous form is BF3 and in liquid form AlCl3 is used.
However in both cases, a proton activator is required to start the cationic oligomerization. The proton
activators used are usually either water or alcohol molecules. The fourth type of oligomerization reaction is
conducted over heterogeneous acid catalyst. The mechanism for oligomerization over
225this type of catalyst is usually referred to as
formation through carbenium ion rearrangement. This reaction relied on formation of carbenium ion with a
brnsted acid site located on catalyst surface. Carbenium ion is formed when electrons are transferred
through the bond with brnsted acid site. Since it is reactive, the carbenium ion will try bond with other
molecules, which in this case is another olefins molecule. After combination of the two olefins, the resulted
molecule is still reactive, so the carbenium ions shift to a more stable condition resulting in a protonated
cycloproyl. The carbenium ion continued to shift to the terminal carbon. Since 1-decene with ten carbon
atoms is used in the product, after the first combination of molecule is the C20 hydrocarbon which is in the
range of diesel fuel. However the oligomerization may not stop here. If the active C20 hydrocarbon is
combined with another olefin then the resulting oligomers will contain C30 which is in the range of lubricating
oil. 2.2 Overview of the types of catalyst for oligomerization Oligomerization reaction is the conversion of
36 105 7/6/2560 7:43

olefins molecule to larger compound with higher viscosity under the presence of a catalyst. It is similar to
polymerization reaction, except polymerization involves larger number of molecules, while oligomerization
involve at most 50 molecules. Through oligomerization reaction, light alpha-olefins from cracking unit can 8
be turned into diesel, while heavy alpha-olefins, such as 1-decene, can be combined to produce lubricant oil
7. Intensive studies in this field confirmed that the mechanism for the oligomerization reaction, the amount of
product obtained and the molecular structure of the oligomer are all
168dependent on the type of catalyst used. To the best of our knowledge,

catalysts used
for oligomerization reaction are divided into three main groups, which include coordination catalysts,
heterogeneous acid catalysts and Lewis acid catalysts. Examples of coordination catalyst, such as Ziegler-
natta, chromium (Phillips catalyst), and metallocene, are shown in Figure 2.1 (a,b,e). In a nutshell,
coordination catalysts are catalysts that use metal atoms such as titanium
265(Ziegler-natta) and chromium (metallocene and Phillips catalyst)
as active centers, which is where the reaction takes place. In contrast, both heterogeneous acid catalyst
(Figure 2.1c) and lewis acid catalyst uses acid as their active centers. 9 Figure 2.1 Different types of
catalysts for polymerization and oligomerization reaction. (a) Ziegler-Natta, (b) chromium catalyst, (c) lewis
acid catalyst, (d) metallocene, (e) late-transition metal. 2.2.1 Lewis acid /ionic liquid The oldest method for
oligomerization of heavy olefins to lubricant oil had been performed under the
235presence of lewis acid catalyst, such as BF3
in gas phase 18 and AlCl3 in liquid phase 19. These Lewis acids can be activated by adding a proton donor,
such as water or alcohol into the solution. Although successful synthesis of long-chain hydrocarbon with 30
carbon atoms or larger had been accomplished, oligomerization reaction over BF3 gas and AlCl3 gave
lubricant oil with low viscosity index and they are known to be hazardous chemicals. According to OSHAs
standard, the highest concentration of BF3 allow in the atmosphere of the work place is 1 ppm 20.
Furthermore, AlCl3 tends to produce HCl gas when it is exposed to oxygen. Kumar
175et al. reported the effect of AlCl3 and the type of alcohol used on
the catalytic activities 21. In their experiment, an increase in AlCl3 was shown to increase the viscosity of the
product obtained. Moreover, an increase in the molecular size of alcohol used as a proton promoter was
found to decrease the viscosity of the product obtained. 2.2.2 Co-ordination catalyst 2.2.2.1 Ziegler-Natta
catalyst (Ti metal) There are generally three kinds of coordination catalysts; Ziegler-Natta, chromium-silica
catalyst and metallocene. Ziegler-Natta catalyst was invented by two Nobel- prize winning scientists. In 1954
Karl Ziegler discovered a titanium-based aqueous catalyst that could polymerize ethylene gas into plastic,
which is usually
37 105 7/6/2560 7:43

105referred to as the first generation polymerization catalyst. The first generation
catalyst is composed of TiCl3 and an air-sensitive organometallic AlEt2Cl solution. However, this first
generation catalyst can only be used for polymerization of ethylene molecule because ethylene contains
only two carbon atoms which are symmetric. Due to our need to polymerized higher olefins such as
1-pyopylene, the first generation catalyst was modified in 1960 by Gullio Natta who also received a Nobel
Prize. Instead of the homogenous aqueous solution Gullio Nattas research showed that it was better for Ti
particles, in term of dispersibility, to be loaded onto MgCl2 support. This catalytic system consisting of Ti
loaded MgCl2
105is referred to as the second generation polymerization catalyst. 10 The

catalytic activity for the
second generation catalyst was approximately 6 times the activity of the first generation catalyst. One
drawback to the second generation catalyst is that it is very difficult to control the molecular structure of the
product from 1-propylene polymerization. Therefore, the second generation catalyst was modified further by
adding internal donor and external donor. Formation of a highly isotactic structure polymerization is possible
by adding these donors as shown in Figure 2.2. The internal donor and external donor that is used widely for
polymerization reaction is isobutyl phthalate and alkoxysilane. a) Isotactic b) Syndiotactic c) Atatic Figure 2.2
Three typical molecular structure of polymers from polymerization; isotactic a), syndiotactic b), and atactic c)
An active Ziegler-Natta catalyst for polymerization has to be activated first by mixing it with an
organometallic substance, which belong to a family of air-sensitive substance known to ignite when exposed
to air. In most text books and literature, organometallic substances are referred to as co-catalyst. When
co-catalyst is mixed with Ziegler-Natta catalyst, its alkyl group will be linked to the titanium metal located on
the Ziegler-Natta catalyst. In 11 general, the first step is the formation of active center. According to the
polymerization mechanism proposed by Cossee 21, this bond between titanium metal and an alkyl group will
create a vacant site (or empty coordination site) that is ready to be attached by olefin molecules 13. This
formation of the vacant site caused a reduction in titanium metal. Once the olefin is attached to the titanium
metal center (vacant site) it establishes a bridge where other olefins can be inserted creating larger
molecules in the propagation step. In this propagation step, olefin is inserted repeatedly until hydrogen gas
is added into the system. This termination step is also known as -hydrogen elimination. It is when the
polymerized olefin is cleaved away from the titanium metal site. The mechanism for polymerization on
heterogeneous MgCl2 can be described by Figure 2.3. As shown in Figure 2.3a, Ti metals are dispersed on
MgCl2 support and interacted with the added organometallic (AlR3)12. This interaction causes the Ti metal
to be reduced from Ti4+ to Ti2+ and relocated to Mg2+ as shown in Figure 2.3b. Next, Ti2+ bonded with
olefin molecule through oxidative addition which convert Ti2+ to Ti4+ while the olefin molecule become
M+-CH=CH2 (Figure 2.3c). In Figure 2.3d the branch +-CH=CH2 was exchanged with the alkyl groups
which belong to the organometallic molecule (AlR3). The formation of active center is shown in Figure 2.3e.
There are many different organometallic molecules available in the market as shown in table 2.1. 12
Reduction reaction Oxidative addition
98(a) (b) (c) Active Center (d) (e) Figure 2. 3 Mechanism of
38 105 7/6/2560 7:43

polymerization over Ziegler-Natta heterogeneous catalyst; Ti dispersed on MgCl2 a), incorporation of Ti2+ in
MgCl2 structure b), interaction between olefins molecule and Ti2+ site c), addition of hydrogen d), and
formation of active center e). 22 13 Table 2.1 Information on different organometallic available in the market
Organometallics Abbreviation Structure Code Theoretical amount Al (%wt) Triethylaluminum TEAL
(C2H5)3Al 7-93-8 9 23.6 Dimethylaluminum chloride DMAC (C2H5)3AlCl 18-58-3 1 29.2 Diethylaluminum
chloride DEAC (C2H5)3AlCl 6-10-6 9 22.4 2.2.2.2 Chromium-silica (Phillips catalyst) A chromium-silica or
Phillips catalyst is a heterogeneous catalyst where chromium metal is supported on silica. Therefore, instead
of titanium metal as an active center, Phillips catalyst uses chromium as an active center. Generally,
chromium-silica can be prepared by incipient impregnation of chromium metal (in form of chromium trioxide
or chromium (III) acetate) on to silica 11. Only 1% of chromium metal is used in order to obtain catalyst with
the highest catalytic activity. As shown in Figure 2.4, polymerization of ethylene gas at 100oC over 1%
chromium-silica (calcined at 800oC) gave activity as high as 9 PE/gcat. In order for the chromium metal to
be attached to the silica support, it has to be oxidized to the oxidation state of Cr+6 (chromate) first in the
presence of oxygen, as shown in Figure 2.5a 23. Similar to Ziegler-Natta catalyst, the chromium metal on
silica has to be activated first, in order for it to be active for polymerization reaction. This is accomplished by
following the oxidation process with the reduction process, in which oxidation state of chromium metal is
reduced from Cr+6 to Cr+2. One research pointed out that the color of a properly reduced chromium metal is
blue 24. So far the most successful reduction of chromium is done by heating the catalyst at 500oC under
the presence of carbon monoxide gas (Figure 2.5b). Some researchers suggested that alkane hydrocarbon
and hydrogen gas can also be used to reduce chromium metal, but their results show that they are less
effective than CO gas. Reduction of 14 chromium metal using ethylene gas was also documented.
According to a X-ray photoelectron spectroscopy of chromium metal after it is exposed to ethylene gas,
there are only 12.9 % of Cr+2 the rest are unconverted Cr+6 and Cr+3. When CO gas was used to reduce
the chromium-silica catalyst instead of ethylene, it was found that there are as high as 63% of Cr+2 on silica
25. Moreover, it was reported that the reduction of chromium was more effective on silica than on alumina
26. Figure 2.4 Effect of chromium loading (during impregnation onto silica) on the activity of the catalyst. (a)
(b) 15 Figure 2.5 Oxidation of chromium trioxide (Cr+3) on silica at 500oC to Cr+6 (a) and reduction of Cr+6
to Cr+2 in the presence of CO gas. 2.2.3 Heterogenous acid catalyst Natural sources that can be converted
to either energy or transportation fuel included vegetable oil, methane gas, and biogas as shown in table
2.2. Additionally, wind power, geothermal heat, waves and sunlight have been successful harvested for
electricity generation. Each chemical reaction that governs the transformation of sustainable raw materials
into desirable products is unique and required the use of a specific type of catalyst. Therefore, in pursuit of a
novel reaction route we will need to decide which type of catalyst should be used and understand the
mechanism of the reaction that is dictated by the catalyst. Table 2.2 Summary of the source and reaction
required for the generation of sustainable and alternative fuel and energy. Sustainable raw materials
Reactions Products Application Transesterfication Bio-diesel/glycerol Fuel (Diesel engine) Vegetable Oil
Deoxgenation Bio-hydrogenated diesel Fuel (Diesel engine) Hydrogenation +dehydration (Alpha-decene)
Use to produce synthetic diesel and lubricant Alpha-olefins Oligomerization Dimers/Trimmers Fuel (diesel
engine) and Lubrication Sugar cane Fermentation Bio-ethanol Blend with gasoline Input into the dehydration
process to produce olefins Lignocellulosic material Hydrolysis + fermentation Bio-ethanol Blend with
gasoline Input into the dehydration process to produce olefins Bio-ethanol Catalytic reforming Synthetic
gases (Hydrogen+CO) Input into fuel cell to produce electricity 16 Glycerol (by-product) Plasma Synthetic
gases (Hydrogen+CO) Input into fuel cell to produce electricity H2 Electrocatalysis (fuel cell) Electricity
Transportation (Tesla motor) Organic waste/high BOD slurry Anaerobic digestion Methane gas Electricity
and compressed to produced transportation fuel (NGV) Catalyst
183plays a significant role in the production of energy and
39 105 7/6/2560 7:43

fuels from these sustainable sources of raw material, which lowers our demand for crude oil.Generally, the
field of catalysis is divided into three main areas: homogeneous, heterogeneous, and enzyme catalyst.
Heterogeneous catalysts are present in a phase that is different from the reactant. Therefore, they are
usually in solid phase because most reactant is either in aqueous or gaseous phase. Being in a solid phase
is advantageous compared to other form of catalyst mentioned above because they can be easily removed
from the products after the chemical reaction have taken place. The heterogeneous catalysts can existed in
either acidic form which is when the catalyst surface is saturated with brnsted acid site that is capable of
donating proton to the adsorbed molecule (in some cases lewis acid site with electron accepting behavior is
present) orin basic form 27,28. For this reason heterogeneous catalysts are frequently desired for various
chemical reactions that are operated at high pressure and temperature such as oligomerization,
isomerization, hydrogenation, and deoxygenation. Currently, utilization of solid catalysts has been hindered
due to our lack of knowledge on how their performance or catalytic activity is affected by their physical and
chemical properties. Therefore the main focus of most research is to observe in detail the impact of solid
material characteristic on the outcome of the chemical reaction. An interesting chemical reaction that has a
potential to solve the energy crisis is the oligomerization reaction over heterogeneous acid catalyst, which is
defined as the combination of alpha-olefins molecule to form larger molecule via carbenium mechanism
29,30. Dimmers (containing hydrocarbon with 20 carbon atoms) generated from the oligomerization reaction
of alpha-decene can be hydrogenated and transformed to synthetic diesel 31-35. Meanwhile, trimmers
(containing hydrocarbon with 30 carbon atoms) can be used as synthetic lubricant (after hydrogenation
reaction). 17 Various researches have demonstrated that it is possible to oligomerize olefin using
heterogeneous acid catalyst, such as zeolite, tungstated-zirconia and monmorillonite clay. For
heterogeneous acid catalyst, the active center responsible for oligomerization reaction is the brnsted acid
site. This is why in most cases the catalytic activity for oligomerization
243is proportional to the concentration of acid site on the
catalyst. Researches have shown that the degree of branching in the oligomers molecular structure is
related to the pore size of the catalyst as shown in Figure 2.6a. The degree of branching increases as the
catalysts pore site increases. Therefore, omega zeolite with the largest pore size will create oligomer with
the higher degree of branching. As shown in Figure 2.6b, an increase in
232pore size of the zeolite catalyst also increases the catalytic activity of
the oligomerization reaction 36. 2.2.3.1 Zeolite catalyst In 1987, a group of Mobil Oils scientist led by
Catherine S.H. Chen, received a patent for the production of synthetic lubricant oil
200over H-ZSM-5 and modified H-ZSM-5 catalyst.
135Modification of H-ZSM-5 was performed by doping the exterior surface of

H-ZSM-5 with
a pyridine molecule that is
40 105 7/6/2560 7:43

238larger than the pore size of the catalyst. The
catalyst was doped only onto the exterior
266surface of H-ZSM-5 because
surface acid site was assumed to cause isomerization of oligomers. An increase in degree of branching of
oligomers is what cause viscosity index to decrease 37,38. Adding a pyridine solution to the H-ZSM-5
catalyst will cause acid site on the surface of the catalyst to become inactive. However, the size of the
pyridine molecule has to be larger than the size of the catalyst pore. As shown in the replica of a HZSM- 5
catalyst, the dimension of the pyridine needs to be larger than 0.55 x 0.51 nm (Figure 2.7c). This is to
ensure that the acid sites inside the pore of the catalyst remain active for oligomerization reaction, while acid
site on the surface is inactive. As anticipated, an increase in viscosity index of the synthesize lubricant oil
was observed when the modified H-ZSM-5 catalyst was used 39. 18 Figure 2.6 Influence of textural
characteristic on degree of branching (a) and catalytic activity for oligomerization reaction (b). Figure 2.7
Model of the Faujasite zeolite catalyst (a), H
260-ZSM-5 catalyst (b) and the pore structure of the HZSM -5
catalyst (c). As shown in Figure 2.8, 13c-nmr (carbon 13 nuclear magnetic resonance) is a very convenient
technique that can be
223used to investigate the molecular structure of long-chain oligomers. A
13c-nmr spectrum of high viscosity index in Figure 2.8a is compared with the spectrum of low viscosity index
lubricant. Each peak on the spectrum is a representation of a specific configuration or the environment of the
carbon atoms. Therefore, the
68degree of branching is reflected in the noisiness of the spectrum in
Figure 2.8b. 19 Figure 2.8 13C-NMR analysis of lubricant derived from oligomerization of 1-decene using
H-ZSM5 as a catalyst at 473 K: Oligomerization reaction over modified H-ZSM5 (a), oligomerization reaction
over unmodified H-ZSM5 (b). Catalyst deactivation, during oligomerization reaction, is a serious problem
that had been studied intensively, especially in the realm of heterogeneous acid catalysts with micropores.
There are four main causes of catalyst deactivation; sinstering or accumulation of metal particles on catalyst
surface at high reaction temperature, coke deposition, poisoning and leaching 40 . Most of the time, zeolite
catalyst from an oligomerization reaction would be deactivated by coke deposition. The reason is that it is
hard for large molecules that are
16formed during the oligomerization reaction, to diffuse away from the micropores
of the catalyst.
41 105 7/6/2560 7:43

In some cases, catalyst may be deactivated when it is exposed to poisons, such as sulfur and nitrogen,
contained in feedstock. An example of olefinic feedstock that contain sulfur and nitrogen poisons is light
naphtha stream produced from the fluidized cracking. R. Van Grieken et al. observed a dramatic decrease in
oligomerization activities at 200oC over H-ZSM-5 when 1- hexene mixed with thoiphene (contained 7000
ppm of sulfur) and n-butylamine (contained 250 ppm of nitrogen) was used as a feedstock. However, it was
revealed that Al-MTS catalyst do not deactivated as fast as H-ZSM-5 when exposed to poisons. This is
because, unlike H-ZSM-5, Al- MTS contain larger pores, higher surface area and medium acidic sites which
do not bond as strongly with poisons in the feedstock 41. 20 In 2013 Corma et al. investigated the
deactivation of H-ZSM-5 from oligomerization of propylene and 1-pentene olefin. As anticipated, the
untreated H-ZSM-5 deactivated rapidly within 5-6 hours of time-on-stream due to coke formation.
254However, when H-ZSM-5 was modified through the
desilication process,
194an increase in pore size was observed along with an increase in
conversion and stability of the catalyst. Desilication is a process in which the catalyst is impregnated with
alkaline solution such sodium hydroxide at elevated temperature (90oC). It was also found that the catalyst
activity increases with the concentration of brnsted acid on the catalyst and decreases with the average
crystal size42. A short summary of different types of catalysts used are shown in table 2.3. 2.2.3.2 Metal
loaded zeolite catalyst As described previously it can be summarized that zeolite is a group of catalyst that
has high activity toward oligomerization reaction. However, one of the drawbacks of a plain zeolite catalyst is
that the surface of zeolite is usually very acidic. This property causes some part of the reactant to be
cracked into gas (ethane, propane and butane) resulting in a loss in the product form. Furthermore, due to
the micropores inside zeolite catalyst it is very easy for reactant to form coke deposit which cause the
lifetime of a zeolite to be very short. One of the solutions to this problem is to dope or load a specific type of
metal onto the zeolite surface
166in order to reduce the density of brnsted site on the zeolite catalyst.
Incorporation of zeolite
catalyst with nickel metal through both incipient impregnation and ion-exchange method has been studied
for ethylene oligomerization. This is usually referred to as a bi-functional catalyst because the catalyst
system contained brnsted sites in the shaped of hydroxyl group (belonging to the zeolite catalyst) and the
nickel active sites27,43. The best operating condition for oligomerization to achieve ethylene conversion of
80% can be conducted over 2.5wt% nickel on Beta zeolite
131in a fixed-bed reactor at
120oC, ethylene
42 105 7/6/2560 7:43

40pressure of 2.5 MPa and weight hourly space velocity
equaled to 2.1 h-1. It was revealed through pyridine-FTIR method that the density of brnsted acid site
decreased from 160 to 45 mol/gas as the amount of nickel metal located change from 1wt% to 10wtD In
order to increase the size of pore inside the framework of a catalyst, nickel was specifically incorporated in
an MCM-41 catalyst. Oligomerization of ethylene over Ni-MCM-41 was investigated in a pilot-scale
continuous stir tank reactor at 30oC and ethylene pressure of 3Mpa. The ethylene conversion of 95% was
obtained after 170 hours of operation. The 21 composition of the product contained roughly 55% dimers.
Dimerization reaction was found to decrease as the temperature increases. On the other hand, formation of
trimer and tetramer was found to increase with temperature 45. N2 sorption of Ni-MCM-41 illustrated an
isotherm with multiple-layer adsorption and a hysteresis loop, which suggested the presence of mesoporisty.
Investigation of the effect of the amount of metal loading on oligomerization of propylene has been
conducted by various researches46. Results obtained pointed out that nickel metal dispersion on catalyst
surface is very important. There are two ways to enhance the dispersibility of metal loading; the first way is
by decreasing the Ni loading and the second way is to increase the Si/Al ratio of the support. At high Si/Al
ratio it was revealed that adsorbed dimer on a neighboring site cause the activation energy of the
trimerization to decrease47. Additionally
122it was revealed that a reduction in space surrounding Ni active site
cause a reduction in catalyst activity. It was found that
122an increase in pore size also cause the
propylene oligomerization activity per Ni site to increase48. From this experiment it was also found that the
maximum nickel loading was 2.21% wt.%. An increase in nickel loading higher than this point will cause a
reduction in conversion. Furthermore, it was reveal that formation of higher oligomer, such as pentamers
(C15) and hexamers (C18), was also increased due to a higher metal loading. Hydrocarbons obtained in this
range can be used for transportation fuel. A stable oligomerization propylene can be conducted over
2.21Ni%wt./ZSM-5 in fixed-bed at 270oC, 4Mpa, and WHSV of 4.03 h-1 49. 2.2.3.3 Doped metal oxide Plain
-alumina contained high density of lewis acid site that is capable of effectively facilitating reaction such as
the elimination of hydroxide functional group from alcohol molecule or the dehydration reaction50-52.
However, plain -alumina does not contain enough brnsted site to induce formation of carbenium-ion
necessary for oligomerization reaction. Brnsted sites must be increase either by fluorination or sulfation of
the plain metal oxide. Fluorination is usually conducted simply by stirring the alumina support with aqueous
solution of NH4F. Fluorinated alumina was found to be effective for oligomerization of 1- hexene. However it
was found that fluorinated ZrO2 and TiO2 are not active for the oligomerization reaction53. Temperature
program desorption of ammonia revealed an increased in concentration of acidic as the percentage of F
loading increases. However, it was also found 22 that the desorption temperature decrease as the %F
content increase, which mean a reduction in acid strength of the analyzed catalyst54. 2.3 Heterogenous
Catalyst Characterization Techniques One of the important questions that researchers worldwide are trying
to investigate and answer is the relationship between the characteristic of heterogeneous catalysts and their
catalytic performance in terms of conversion, selectivity and yield. A strong fundamental knowledge of how
catalyst characteristics affect the productivity or the outcome of the reaction is an important step for the
43 105 7/6/2560 7:43

engineer to be able to design and customize catalyst that is most appropriate for a certain process.
Characterization of heterogeneous catalyst can be divided into physical and chemical properties. For
instance, physical properties included
3surface area, pore volume, average pore size, atom arrangement in the
crystalline structure, and image of catalysts surface. Chemical properties are usually referred to acidity of
catalyst surface. Physical properties can be observed using XRD, SEM, N2 sorption and ICP as shown in
table 2.3. Table 2.3 Different type of characterization techniques for heterogeneous catalysts Catalysis
characterization Purpose of analysis A. X-ray diffraction (XRD) Interpretation of XRD pattern can lead to
understanding of the type of crystalline and atomic arrangement of the solid sample. B.
137X-ray photoelectron spectroscopy (XPS) XPS is used to identify and measure

the elemental composition of the
heterogeneous surface. C. N2 sorption Leads to calculation of
144surface area (BET method), pore volume, and average pore size.
Interpretation of the
generated isotherm can visualization of pore structure. D.
261Scanning electron microscopy (SEM) Captured images of the solid surface
through high magnification apparatus. E. Induced-couple plasma Measure content of different type of
metals. F. Ammonia temperature program desorption (TPD- Measure the concentration of acidity on catalyst
surface (mmol/g) and acid strength (desorption temperature). 23 NH3) G. Thermo gravimetric analysis
(TGA) Measure the weight loss of heterogeneous catalyst due to thermal and gas flow (Oxygen). H.
Temperature program oxidation (TPO) Measure the amount of coke deposition on catalyst surface. I.
Hydrogen temperature program desorption (TPR) Find the optimized reduction conditions (Temperature and
flow rate of hydrogen). There are many methods available for the synthesis of solid support, including
traditional precipitation 51, co-precipitation, sol-gel 55,56, and ultrasonic spray pyrolysis 57. Some reaction
required only the presence of solid support. For instance, zeolite containing acidic surface are usually
employed for isomerization of bio-hydrogenated diesel (BHD) to improve the cold-flow property of BDH,
dehydration of primary alcohol to alpha-olefins and
38oligomerization of olefin for the production of synthetic diesel and
lubricant. However, for some other applications, only the presence of solid support is not adequate58. For
instance, gamma-alumina support can be doped with a variety of metals through the incipient impregnation.
These catalysts are required by reaction such as hydrogenation of olefins to saturated molecule (Nickel and
44 105 7/6/2560 7:43

Molybdenum metals doped on gamma-alumina)59-61, liquefaction of synthetic gas to transportation fuel in

the Fischer-Tropsch synthesis (Cobalt metal doped on metal oxide such as gamma-alumina, silica and
titanium oxide)62-64 and deoxygenation of linoleic acid to stearic acid to green diesel (Ruthenium or
Palladium on gamma-alumina support) 4,49,65-68. In addition to impregnation of metals, some reaction
required the support to be modified prior to a successful catalysis activity. For instance, the oligomerization
of dicyclopentadiene required the presence of acidic catalyst such as Beta zeolite. However, beta zeolite
contains small micropores which posed a problem regarding reactant and product internal diffusion.
3In order to increase the size of the pore inside Beta zeolite,
a bottom-up modification method where beta zeolite is mixed with soft-template (CTAB), was proposed. After
modification, an increase of pore size from 0.74nm to 3.5nm was observed by the N2 sorption technique as
shown in Figure 2.9a69. However, it was revealed
60by ammonia temperature- programmed desorption (NH3 -TPD) that the

modified beta zeolite
contained lower amount of 24 acidic site (Figure 2.9b).Additionally, X-ray diffraction pattern of the modified
beta zeolite in Figure 2.9c demonstrated an absence of the two peaks which represent [100] and [310]
atomic planar. Catalyst testing results, shown in Figure 2.9d, indicate an increase in productivity of the
catalyst after Beta zeolite was modified in spite of its lower in acidic content. This clearly suggested the
significant of the average pore size relative to the concentration of acidic site on catalysts surface69.
3(a) (b) (c) (d) Figure 2. 9 Characterization of modified (MMZ-H) and
unmodified (H) Beta zeolite from N2 sorption a), NH3-TPD b) and XRD c). Catalyst testing of modified and
unmodified Beta zeolite through oligomerization of dicyclopentadiene d). 25 Apart from zeolite catalyst,
gamma-alumina as both a support and a catalyst are also used frequently in the petrochemical industry.
Although gamma-alumina is mesoporous, meaning that its average pore size is within the range of 2 to
50nm, some process required the catalyst to have larger pore size. Similar to the modification of Beta
zeolite, modification of gamma-alumina also depend on a soft-template. However, for gamma-alumina, a
non-ionic surfactant is used as a soft-template along with a hydrophobic solution as a swelling agent.
Calcination temperature was shown to slightly affect the average size of the pore as shown by the
transmission electron microscopy (TEM) images in Figure 2.10. An increase in pore size can be observed
from TEM images. Moreover, it was also shown that an increase in the ratio between the swelling agent and
surfactant will cause an increase in average pore size 70. (a) (b) (c) Figure 2.10 Characterization of modified
gamma-alumina calcined at 400oC a) and 500oC b). Pore size distribution of gamma-alumina modified with
different ratio of swelling agent to surfactant c) 70. Acidity of the support can be increased through the
ion-exchange method. For instance, the acidic concentration of gamma-alumina can be increased by doping
with sulfuric acid[28].The sulfate loading in each gamma-alumina supported ion-exchanged with sulfuric acid
was successfully determined gravimetrically on a thermal characterization technique. Analysis of the
prepared sample using NH3-TPD revealed two major peaks at 220oC, indicating weak acidic sites and
400oC indicating strong acidic sites. Integral of both peaks increases clearly as the concentration of sulfuric
solution increases. X-ray diffraction pattern of gamma-alumina with different loading of sulfuric solution is
45 105 7/6/2560 7:43

shown in Figure 2.11. The crystalline structure of modified gamma-alumina remained the same up to sulfuric
loading of 2.4M.
1An increase in the 26 concentration of sulfuric solution above 2.
4M will result in formation of a new phase (2 = 26) identified as Al2(SO4)3. Apart from gamma-alumina,
Beta zeolite can also be modified by treating with ammonium fluoride through a process known as
fluorination. Characterization of modified Beta zeolite showed
3a decrease in surface and pore volume compared to the
plain Beta zeolite. Analysis of the modified Beta zeolite by Hydrogen Nuclear Magnetic Resonance (H-
NMR) indicated an increase in the strength of the brnsted site compared to plain beta zeolite. (a) (b) Figure
2.11 Characterization of sulfated-alumina using X-ray technique a) and NH3-TPD for acidity analysis b). 27
The relationship between nickel loading (Ni %wt.) and oligomerization reaction over Beta zeolite was studied
using ethylene as a feedstock. Nickel loading was sometimes performed on zeolite catalyst to block some of
the highly acidic site that can cause side-reaction such as cracking and isomerization which in this case is
undesirable. Zeolite loading with different amount of nickel metal was analyzed using X-ray diffraction
technique as shown in Figure 2.12a. Ethylene conversion was found to increase linearly as nickel content
increase as shown in Figure 2.12b. However, an increase of nickel content above 4%wt. has very little
impact on the ethylene conversion. This is because the adsorption site on catalysts surface have already
been saturated at nickel content of 4%wt. Therefore, excess nickel metal was transformed to NiO, as shown
in the X-ray diffraction pattern, and did not participant in the oligomerization reaction 44.
247(a) (b) Figure 2. 12 X-ray diffraction patterns of
Beta catalyst contained different nickel content a) and conversion of ethylene b) 2.4 Product
Characterization Techniques 28 2.4.1 Theory on spectroscopy techniques Light is a kind of wave that
consists of a magnetic field and an electric field. The energy of the wave is proportional to the frequency of
the wave as shown in equation 2.1, but varied inversely with respect to the wavelength as shown in equation
2.2 E ? hv (2.1) E ? hc ? (2.2)
112where h is the Plancks constant, v is the frequency of the wave and is

the
wavelength in lambda. It is known that a molecule can exist in different energy levels, for instance a bond in
the molecule may be stretched, bent, rotated or the electrons can shift from one orbital to another orbital.
These processes are proven to exist in a specific energy level with a specific frequency. The differences in
energy content of each process can be detected by different spectroscopy techniques. The Figure below
depicted the general characteristic of a spectroscopy where a molecule is exposed to a certain type of wave.
If the molecule does not interact with the wave, then the energy input will be completely collected by the
detector. On the other hand, if the input energy is high enough to transform the molecule from energy level 1
46 105 7/6/2560 7:43

to energy level 2 (through bending, stretching or movement of electrons to a different orbital), then the
energy that passed through the molecule will be reduced. Since each transition required different amount of
energy input, it is very important to choose an appropriate type of wave based on its frequency. In general
there are three major types of spectroscopies with different type of wave sources as shown in table 2.4;
139Nuclear Magnetic Resonance (NMR), infrared spectroscopy (IR) and

ultraviolet-visible spectroscopy (UV-Vis).
29 Table 2.4 Characteristic of different types of spectroscopy; NMR, IR and UV-VIS Type of Spectroscopy
Source of wave Waves characteristic Type of transition UV-VIS Visible or ultraviolet 7 150 3Electronic
state 0.4x1015 1.5x1015 Frequency (Hertz) 2.0x10-7 8.0x10-7 Wavelength (meter) Energy (kcal/mol) IR
Infrared wave 0.2x1014 1.2x1014 0.6x104 8.0x104 2.0x10-3 2.5x10-6 0.6 8.0 x 10-4 -12 2Molecule
vibration NMR Radio wave 0.5 5 Nuclear spin 2.4.1.1 Principle of 13C-NMR Nuclei will spin continuously
because it has a charge. While spinning the charge will create a magnetic field and will behave like a small
magnet. For NMR spectroscopy there are two important nuclei that need to be consider; 1H and 13C. It is
important to note that 12C and 16O existed abundantly in nature but cannot be used to create a spectrum
because it does not spin (spin=0). When the spinning nuclei are exposed to a magnetic field, they will be
arranged in the direction or the opposite of the magnetic field as shown in Figure 2.13b below. When energy
in the form of a radiofrequency wave
212is applied to the nuclei in the low energy level (oriented in the
same direction as the magnetic field), the nuclei will be activated to a higher energy level (can be referred to
as a flip or a resonance). For each analysis, the liquid sample is dissolved in a CCl4 reference solvent and
then it is inserted into a radiofrequency coil. The frequency that the coil generated is usually constant, but
the
226strength of the magnetic field is increased until the energy reaches the
threshold where molecule undergoes a transition. The strength required for this transition is converted and is
then plotted in a spectrum. In general, the strength of the magnetic field is increased from left to right of the
spectrum. The frequency that initiates each resonance or flip is different for different 1H or 13C in the
molecule. This is because each 1H or 13C in the molecule is located in different environment. The chemical
shift is calculated as the ratio between the distance of the peak relative to the reference peak (TMS) and 30
the frequency of the spectrometer in MHz. The range of chemical shift () for 1H is 0-10 ppm, while the
range for 13C is 0-200 ppm.
98(a) (b) (c) Figure 2.13 Movement of nuclei in the absence of
magnetic field a), movement of nuclei under the presence of the magnetic field b) and activation of nuclei
from low energy level to high energy level by applying radiofrequency wave c). C13-NMR technique analyze
the structure of molecule by detecting the photon energy released by activated nuclei of carbon atom. Since
47 105 7/6/2560 7:43

the structure of different molecule contained carbon in different location and some carbons may be attached
to a specific function group (such as halogen and aromatics, each carbon will release different amount of
quantified photon energy. For this reason a spectrum as shown in Figure 2.14 can be created. The area
under C13-NMRs peak can be used to calculate the short-chain branching (%) and the branch ratio by
using equation
56C.1 and C.2 shown in Appendix C.
31 Figure 2.14 Chemical shift of carbon atom attached to different function group 71 Calculation of chemical
shift is an important technique that can be used to study the structure of an unknown molecule, especially
lubricant with a variety of molecule with branched structure. The first step to revealing the unknown molecule
is to guess the kind of molecule involved. The next step
258is to find out the chemical shift of the carbon atoms in the
structure of the molecule. The third step is to analyze the unknown sample with C13-NMR device. Ultimately,
the chemical shift spectrum obtained from the device is compared with the calculated chemical shifts. If the
chemical shifts from the device and the calculation is the same then the unknown matches the guessed
molecule.. There are many reasons why the value of chemical shifts for lubricant oil is deviated from the
chemical shifts of carbons in normal linear hydrocarbons. For instance, the chemical shift of linear
hydrocarbon can be influenced by the substitution of metal with hydrogen in the structure, the presence of
branched hydrocarbon and double bond. Figure 2.15 below showed the symbol of carbons that are located
in different part of the molecular structure. The value of chemical shifts of each carbon in different location as
shown in Figure is tabulated in Table 2.5. 32 4 3 n 2 2 4 4 2 * 1 3 n n 3 (a) 1 1 (b) (c) (d) 1
1712 3 4 n n n 4 3 2 1
C 1 C2 ' ' ' (f) (e) Figure 2.15 Symbols represent carbons in different part of the molecular structure with long
chain (a), molecular structure with short branched chain (b)-(d), longchain hydrocarbons (e) and alkene (f).
33 Table 2.5 Chemical shift of carbon location in different position of a long-chain molecule.72,73 Carbon
location Chemical Shift (ppm) Carbon location Chemical Shift (ppm) 37.1 1 13.6 27.6 2 22.7 30.2 3
32.1 29.7 40.5 24.5 41.2 Chemical shifts of different carbon atoms in molecules structure can
be estimated by using the Grant-Cheney technique. The first step is to use equation 2.3 for alkane molecule
and equation 2.4 for alkene molecule. These two equations consisted of two parameters; n which represent
the number of carbon adjacent to the subjected carbon and Sij which represent the deviation of chemical
shift due to steric effect caused by branching of the molecule. The value of Sij depends on the configuration
of the subject carbon as shown in table 2.6. Chemical shifts alkane = ?2.3 ? 9.1n1 ? 9.4n2 ? 2.5n3 ? 0.3n4 ?
? Sij (2.3) Chemical shifts alkene =?123.3?10.6n1 ?7.2n2 ?1.5n3 ?7.9n1' ?1.8n2' ?1.5n3' ??S (2.4) Table
2.6 The value for different carbon configuration Carbon adjacent to subject carbon Subject carbon
192Primary (1o) Secondary (2o) Tertiary (3o) Quaternary (4o) Primary
(1o) 0 0 -1.1 -3.4 Secondary (2o) 0 0 -2.5 -7.5 Tertiary (3o) 0 -3.7 -9.5 -15.0 Quaternary (4o) -1.5 -8.4 -15.0
48 105 7/6/2560 7:43

-25.0 34 Sample 1:74 1 2 H3C CH2 3 CH3 C 4 CH3 H3C A.Carbon position 1: Adjustment of chemical due
to steric corrections: a. The subject carbon has a primary configuration and the adjacent carbon is a
secondary configuration. The value of Sij = 0 according to table.) Chemical shift of carbon#1 = ?2.1? 9.1(1)
? 9.4(1) ? 2.5(3) ? 0 ? 8.9 (2.5) B.Carbon position 2: Adjustment of chemical due to steric corrections: a. The
subject carbon has a secondary configuration and the adjacent carbon has a quaternary configuration.
Therefore the Sij value is equaled to -7.5. Chemical shift of carbon# 2 = ?2.1? 9.1(2) ? 9.4(3) ? 0 ? 7.5 ?
36.8 (2.6) C.Carbon position 3: Adjustment of chemical due to steric corrections: a. The subject carbon has
a quaternary configuration and the adjacent carbon has a secondary configuration. Therefore the Sij value is
equaled to -8.4. b. The subject carbon has a quaternary configuration and the adjacent carbon has a primary
configuration. Therefore the Sij value is equaled to 1.5. Chemical shift of carbon#3 = ?2.1? 9.1(4) ? 9.4(1) ?
8.4 ? 3(1.5) ? 30.8 (2.7) D.Carbon position 4: a. The subject carbon has a primary configuration and the
adjacent carbon has a quaternary configuration. Therefore the Sij value is equaled to -3.4. Chemical shift of
carbon#4 = ?2.1? 9.1(1) ? 9.4(3) ? 2.5(1) ? 3.4 ? 29.3 (2.8) 35 2.4.1.2
196Fourier transform infrared spectroscopy (FTIR) Fourier transform infrared

spectroscopy
114(FTIR) is a method employed to obtain an infrared spectrum of emission and

adsorption of a solid, liquid or gas.
In general, the infrared radiation is sent through the sample. The infrared radiation is partially adsorbed by
the molecules of the sample. This adsorbed energy will cause the molecule to vibrate either in the form of
stretching (alternative in the bond length) and bon angle bending. In the case of stretching, the molecule can
either stretched in-phase (referred to as symmetrical) or out-of- phase (asymmetric) as shown in Figure
2.16.
248O H C H H O H R O H
Symmetric stretching Bending Asymmetic stretching Figure 2.16 Stretching and bending of molecule in FTIR
The energy required for the adsorption of each kind is different. Therefore a spectrum obtained from FTIR is
like a fingerprint of a molecule. As shown in the table below each type of functional group has its own
location on the FTIR spectrum. For instance the presence of a C=C bond in alkene molecule is represented
as a peak associated with molecule stretching located around 1750 cm-1. Additionally, an alkene sp2
bending of a C-H bond is seen as the peak around 650 to 1000 cm-1. 36 Figure 2.17 FTIR spectrum of
different functional group72. 2.4.2 Calculation of Viscosity Index (ASTM D2270) Calculation of VI is divided
into different cases. The first case required that the viscosity at 40oC(U) is higher than the H constant
(equation 2.9). The second case required that the viscosity at 40oC (U) is lower than H constant. For the
second case Y constants, which is the viscosity of the sample at 100oC, is used as shown in equation 2.10.
The value of L and H can be obtained from Table 2.7. Case 1 (U>H) Case 2 (U<H) VI ? L ?U ?100 L ? H
(2.9) VI ? 10N ? 1 ? 100 (2.10) 0.00715 N ? log H ? logU logY L ? ( Y2 ? Y Y2 ? Y1 ) L1 ? ??? YY2 ??YY11
??? L2 37 H ? (YY22 ??YY1 )H1 ? ??? YY2 ??YY11 ??? H2 Table 2.7 The value of L and H for calculation
of VI 2.5 Micro-kinetic for heterogenous catalyst 2.5.1 Theory on catalytic surface reaction A reaction
involving heterogeneous catalyst consist of three major interactions; adsorption of feedstock reactant that is
49 105 7/6/2560 7:43

dissolved on contact with the surface, reaction on catalyst surface and desorption of the products
45in the bulk phase. The rate of the reaction can be
improved under the presence of a catalyst only if the energy barrier of the noncatalytic path is higher than
the energy barrier offered by the catalytic path. Over the past few decades, accelerated improvement in the
field of heterogeneous have concluded that the catalyst activity has a strong affected by the atomic structure
of the catalyst. Atomic arrangements can be divided into basic configuration which are referred to as
124face-centered cubic, body-centered cubic, and hexagonal
as
184shown in Figure 2. 18. 38 (a) (b) (c) Figure 2. 18 Different configuration of
the atomic structure;
124face-centered cubic a), body- centered cubic b), and hexagonal
c). Most chemical process required the active atoms to be dispersed on the surface of metal oxide or a
support, because most active species, such as transition and precious metals are usually too expensive to
be used alone. Before the reactant molecules can react with other chemical species on the catalytic surface,
it is important for the molecule to be strongly absorbed on the surface first. This type of adsorption is known
as chemisorption, required an enthalpy between 80 and 400 kJ mol-1. Additionally, chemisorption is also
characterized by a single layer or monolayer type. Therefore, once the surface is completely occupied then
the catalyst is saturated meaning no more molecule could be chemisorbed. If the molecule interacted weakly
with either the catalytic surface or another molecule, the adsorption is referred to as physisorption which
required an enthalpy of lower than 40 kJ mol-1 through the van der waals force. Unlike chemisorption, more
than one layer of molecules can be adsorbed through physisorption. Adsorption of a species (A) on catalyst
surface by chemisorption type can be illustrated using the equation 2.11 below. A ? S ??kkaddess?? A ? S
(2.11) where A is the adsorbed molecule and A-S is the complex between A molecule and the active site on
the surface through chemisorption 75. The overall rate for the adsorption and desorption can be written by
the equation below. Since the overall rate is equal to zero then the equilibrium relationship can be
constructed as shown in equation 2.12 and 2.13. 39 rads ? kads [
67A][S ] ? kdes [ A ? S ] (2. 12) Kads ? ads ?[A?S] k
(2.13) kdes [A][S] Fractional surface coverage of specie i (i) is an important value that will be discussed
and use for derivation of rate equation from micro-kinetic modeling. The number density of all adsorption
sites (ST)can be calculated as the sum of density of available site [Sv] and the density of the site occupied
by specie A (SA) as shown in the equation 2.14. Since fractional surface coverage is defined
50 105 7/6/2560 7:43

110as the ratio between the number of adsorption sites occupied and the
number of adsorption sites vacant, then the
following equation can be calculated by combining with equation 2.15. [ST ] ? [S ] ? [ A ? S ] (2.14) [Sv ] ? 1
? [KSaTd ]s[ A] (2.15) Kads[A] ?A ? 1? Kads[A] (2.16) This fractional surface coverage is referred to as the
Langmuir adsorption isotherm (equation 2.16). The equation indicated that the factional surface coverage is
independent of the concentration of A at high concentration of A. However, at low concentration the
fractional surface coverage is proportional to [A] as shown in Figure 2.1976. 40 A = 1 A = Kads[A] Figure
2.19 Langmuir adsorption isotherms The Langmuir adsorption equation changes as the number of reactant
increases due to competition between the different reactants. For instance if one more reactant (specie B) is
involved in the reaction, the fraction surface coverage needed to be change to equation 2.18. For the new
equation contained two adsorption constants, one for specie A and another for specie B.
70[ST ] ? [S]?[A? S]?[B ? S] ?A ? Kads ,A[
A] 1? Kads,A[A]? Kads,B[B] (2.17) (2.18) The above scenario assumed that one molecule is adsorbed on
one available active site. In reality there are atoms that can be adsorb dissociatively, which attached
themselves to two empty active sites. Atoms that adsorbed dissociatively are, for instance, H2 and O2
atoms. Therefore, if this is the case then the rate of adsorption has to be changed to account for the two
pairs of empty site that is occupy as shown below. [A? A]? 2[S]??kkadddeesss??[A? S ? S ? A] (2.19) 41
where 2[S] refers to the two adjacent emptied active sites and the [A-S-S-A] represents the two occupied
adjacent sites. The overall rate equation of the dissociative adsorption then is changed to: r ? kads[A?
A]?kdes[A?S ?S ? A] (2.20) dissociative molecule can be derived as: After substitution and combination with
the above equations, the rate of adsorption of r ? kads[A? A][S]2 ? kdes[A? S ? S ? A]2 [ST ] [ST ] (2.21)
The fractional coverage of the dissociative atom can therefore be calculated as shown in equation 2.22. This
equation is derived from the assumption that the total rate in equilibrium condition is zero. Kads[A? A]1/2
?A?A ? 1? Kads[A]1/2 (2.22) According to the equation, it can be concluded that the fractional coverage of
the dissociative atom varied proportionally to the concentration of [A-A]1/2. One of the simplest types of
reaction is the unimolecular conversion reaction where the adsorbed specie is converted into a produce
molecule. The following reaction is shown in equation 2.23. A ? S ?k??C ? S (2.23) where A-S is the
adsorbed A specie on the catalyst site, C is the product and S is an empty catalyst site. The concentration of
adsorbed A specie is equaled to the product of the concentration of vacant and fractional coverage of specie
A. Therefore, the rate of consumption (RDS) of A can therefore be written as
181shown in equation 2. 24. r ? k[A? S] ? k[ ST ]?A
(2.24) The fraction coverage of specie A (Langmuir adsorption isotherm)
109can be substituted into equation 2.24 to produce the following
rate reaction. 42 r ? kKads[ST ][A] 1? Kads[A] (2.25) Furthermore, if the reaction involve another reactant
then the rate equation of the reaction can be derived by considering two reactions for adsorption (adsorption
51 105 7/6/2560 7:43

of A and B) and another surface reaction as shown in equation 2.26. A? S ? B ? S ?k?2?C ? 2[S] (2.26) This
is the reaction of two species that are adsorbed on the catalyst (A-S and B-S), which is often categorized as
bimolecular reaction or the Langmuir-Hinshelwood step77. The rate equation of the bimolecular reaction is
controlled by the concentration of adsorbed A molecule and the concentration of the adjacent B molecules
adsorbed
45on the surface of the catalyst. The rate
equation for this reaction is as follow: r ? k2[A? S][B ? S] ? k2[ST ]?A?B (2.27) The fractional coverage of
specie A and B as described by Langmuir equation
109can be substituted into equation 2.27 to obtain the following
equation: r ? k2 (1k2?KKadasd,sA,A[aAds],B?[AK]a[dBs,B][[BST])]2 K (2.28) As shown in equation 2.28, the

denominator is squared which represent a bimolecular surface reaction. The number of the exponent on the
denominator
204is the number of sites that are involved in the RDS reaction. In addition to the
simple unimolecular and bimolecular type of reaction, there is also another reaction known as Rideal-Eley
reaction78. This reaction can be described as the reaction between the adsorbed specie (A-S) and another
specie B in bulk solution79. Therefore according to Rideal-Eley the reaction can be written as follow: A ? S ?
B ?k?3?C ? S (2.29) 43 There are many examples of the usage of Rideal-Eley reaction in kinetic modeling
simulation. For instance, W.O Haag reported the micro-kinetic formulation of isobutene dimerization using
Rideal-Eley mechanism 80. The adsorption of isobutene on acidic resin (polystyrene-sulfonic acid) and the
surface reaction (RDS), can be described as shown in equation 2.30 and equation 2.31. The vacant site (S)
is the brnsted acidic site containing proton. IB ? S ?k?ads,I?B? IB ? S (2.30) IB ? S ? IB ?k?r,IB?? IB ? IB
? S (2.31) The rate of consumption of IB and the concentration of the adsorbed IB specie can then be
described by equation 2.32 and equation 2.33. r ? kr,IB[IB ? S][IB] (2.32) [IB ? S] ? Kads,IB[ST ][IB]2 1?
Kads,IB[IB]
195(2.33) When substituting equation 2.33 into equation 2.
32, the rate of consumption can be obtained as: r ? kr,IBKads,IB[ST ][IB]2 1? Kads,IB[IB} (2.34) The last
step of the heterogeneous catalyst reaction is the desorption reaction where the adsorbed product is
desorbed from the active site into the main bulk solution. The rate of desorption of produce C can be
described in equation 2.35. C ? S ??kdes??C ? S , rdes ? kdes[B ? S] (2.35) Assuming a unimolecular
surface reaction equation where the equilibrium constant is K2 (= [B-S]/[A-S]) then the rate of desorption can
be written as follow. rdes ? kdesKads[A? S] (2.36) The equilibrium constant for adsorption reaction (Kads) is
used to find the concentration of A-S. The concentration of A-S can be described as equation 2.37. 44 [ A ?
S ] ? Kads [ A][S ] (2.37) However, it is still not possible to derive a useful rate equation if the concentration
of the vacant sites is unknown. In order to derive the concentration of the vacant sites the total site balance
method was applied as shown below assuming two reactants (A and B) necessary for the reaction are
52 105 7/6/2560 7:43

present. (Noted that according to the RDS [B-S] is equaled to [A-S].
70[ST]?[S]?[A? S ]?[B? S] [ST]?[S]?[ A?S]?K2 [A? S] [ST]?[S]? K1 [A][S]? K2K1

[A][ S] [S] ? [ST ] K1 [A]? K2K1 [A]
The equation for the concentration of the vacant site is then substitute into the equation 2.36. The final
micro-kinetic rate equation can then be described as shown in equation. r ? kdesK2K1[A][ST ] 1? (K1 ?
K2K1)[A] (2.38) To summarize all LHHW can be generalized into rate equation consisting of three significant
parts as shown in equation 2.39. r ? (Kinetic )(Potenetial ) (Adsorption)n (2.39) For equation the n term
represent
88the number of active sites that are involved in the catalysis reaction 81. The
Langmuir-Hinshelwood-Hougen-Watson technique for micro-kinetic modeling of reaction required 4 steps to

be taken82. 1. The first step is to propose a reaction mechanism considering Langmuir adsorption, surface
reaction and desorption. For this step it is important to establish assumption and scope of the reaction
model. Any information or prior knowledge given about the mechanism should be carefully review and apply
in this step. 45 2. The second step is to choose the part of the reaction that has the lowest rate of reaction or
rate constant. This reaction with the lowest rate of reaction is usually referred to as the rate determination
step (RDS). 3. The third step is to write the complete rate equation by substituting the concentration of
adsorbed
113species on the catalyst s surface into the rate equation for the
RDS.
113The adsorption and desorption reactions are assumed to be in equilibrium.
4. The last step is to write down a balance for the total concentration of sites, which consisted of the
concentration of adsorbed species and the vacant site available on the catalytic surface. As mentioned
previously a catalytic reaction is consisted of many reaction steps. First the molecules have to be adsorbed
onto the catalyst, activated and the product has to desorb from the molecule. The catalytic center is then
usually regenerated after undergoing a reaction. According to the Sabatier principle the
31rate of the reaction reaches a maximum when the
rate of activation is in equilibrium with the rate of product desorption. A volcano plot can be constructed to
illustrate the analysis of catalytic reactions. In this graph, the adsorption energy or reactant
174is plotted on the x -axis while the y -axis is the rate of
53 105 7/6/2560 7:43

reaction over a specific catalyst per unit surface area as shown in Figure 2.20. Low adsorption energy
indicated a weak
31interaction between the molecule and the catalytic surface.
In this case if the adsorption
31energy is really low, then the rate of reaction
can be increased by increasing the adsorption energy (positive order). However, beyond the maximum point
the adsorption is too strong meaning the adsorbed reactants are now blocking other molecule from reacting
with active sites. 46 Catalysty Acitivity (mmol O2 m-2 s-1) 10 1 0.1 adsorption Ni Weak Cu Pt Ag Au Strong
adsorption TiO2 100 -100 0 100 200 Binding Energy (kJ mol-1) 300 400 Figure 2.20 Catalyst of different
metal incorporated catalysts demonstrating the Sabatier principle 83. Surface reaction is the next step that
occurs after the adsorption of reactant on the catalysts surface. In most cases, the
6surface reaction is considered as the rate determination step
(RDS), which means that this surface reaction determinate the rate of the reaction compared to adsorption
and desorption step. In order words, if the RDS is present then other steps are considered as quasi-
equilibrate. Kinetic modeling techniques that consider both adsorption theory and surface reaction
mechanism is usually referred to as the Langmuir-Hinshelwood kinetics. Dr.Langmuir received a Nobel Prize
in 1932 for revealing the adsorption isotherm, while Dr. Hinshelwood received a Nobel Prize in 1956 for his
exhibition of the kinetics of catalytic reactions. The L-H method are used to simulate simple unimolecular
and bimolecular reactions. Later, Hougen and Wason improved the accurateness of the model by
considering the possibility of a reserve reaction in the rate equation 84. 2.5.2 Internal and external diffusion
Before conducting the experiment and collecting data for micro-kinetic considerations it is important to make
sure that the resistance to external and internal diffusion is insignificant. As shown in Figure 2.21, External
diffusion is the movement of molecules from bulk solution to the pore entrance of the catalyst (step 1) and it
is governed mainly either by the agitation speed of the reactor (stirred reactor) or flow rate of the reactant
(fixed-bed reactor). 47 Internal diffusion is the movement of molecules inside the pores of the catalyst to the
active site (step 2 and 6) and it is strongly affected by the particle size of the catalyst. For oligomerization of
n-butene the particle size of the H-mordenite used should be lower than 90 m in order to avoid internal
diffusion limitation 85. However it was discussed that the internal diffusion is strongly
185affected by the type of catalyst used. If the catalyst is
very acidic and promoted intensive coke deposition then the particle size of the catalyst should be very small
in order to avoid the diffusional limitation which can
4cause a significant decrease in the activity of the catalyst.
54 105 7/6/2560 7:43

For instance, for macroreticular acid resin (Amberlyst 15), the maximum
146particle size of the catalyst is
1 mm 86. Furthermore,
146the particle size of the H-ZSM-5 catalyst
for reaction involving C3-C7 olefins should be between 0.125 mm to 149 mm 87. On the other hand, the
external diffusion is not really affected by the type of catalyst used. A safe range for the agitation speed for
oligomerization of C4 to C5 olefins was found to be between 300 rpm to 900 rpm 85,88. For ethylene the
oligomerization over Ni/Al2O3 catalyst an appropriate agitation speed was also found to be higher than 300
rpm88. However, it is noteworthy to point out that the agitation speed for oligomerization of 1-propylene over
amorphous mesoporous silica-alumina (MSA) should be above 800 rpm 58. Figure 2.21 Illustration of the 6
steps involved in the reaction on heterogeneous catalyst; 1.external diffusion, 2. 1st internal diffusion, 3.
Adsorption, 4.Surface reaction, 5.Desorption and 6. 2nd internal diffusion. 2.5.3 Previous work on kinetic
modeling of Oligomerization 48 Recently many researchers have investigated the reaction mechanism of
olefins oligomerization over heterogeneous acid catalysts. Micro-kinetic modeling of the oligomerization of
2632-methyl-2-butene over macroreticular acid
resin (Amerberlyst-15) revealed that formation of the trimers occurred by combination of one monomer with
a dimers. The rate equation should consider that the number of unoccupied sides as negligible. One active
site is for dimerization and two active sites are for trimerization 86.
6In order to optimize the selectivity of the dimerization reaction,
Cruz et al. add ethanol to the feedstock as selectivity enhancer. Results from a batch stirred tank reactor
suggested that an increase in ratio of ethanol causes the selectivity of dimer to increase. The optimized ratio
of RIA/EtOH is equaled to 20; at this condition the selectivity toward dimers is 93%. The rate equation was
formulated by assuming that there are three active sites involved during the dimerization reaction and that
the unoccupied sites are negligible. This research also addressed the isomerization reaction as part of the
dimerization network of reaction. According to the GC-MS analysis, 5 different type of isomers are present in
the final product 87. The rate constant for formation of 3,4,4,5-tetramethyl-2-hexene oligomer was found to
be the highest compared to formation of other isomers. In addition to the oligomerization and isomerization,
another reaction that can inevitably occur at higher temperature over brnsted active sites is the cracking
reaction. Similar to oligomerization and isomerization reaction, cracking reaction also started by forming a
carbenium-ion with the hydrogen proton on the catalysts surface. Three main modes existed for the
cracking reaction; monomolecular, bimolecular and trimolecular cracking. Lower molecular weight olefin
such as 1-propylene and 1-butene mainly undergo bimolecular and trimolecular cracking, while pentene
undergo monomolecular cracking 43. Although Al2O3 does not have dominating brnsted site compared to
zeolite catalyst, it can be used for oligomerization after it is loaded with nickel. Simulation of the
oligomerization of isobutene over Ni/Al2O3 from the rate equations, acquired from micro-kinetic modelling,
55 105 7/6/2560 7:43

showed a conversion of 98.64% and selectivity of 84.19% toward isooctane. Isooctane can be used to
substitute methyl tert-butene ether (MTBE) 88. A more detailed investigation of the isobutene
oligomerization was conducted
67on a NiSO4/alumina in a stirred batch
reactor. The catalyst was prepared by loading 1wt% nickel onto -alumina using nickel (II) sulfate
hexahydrate as a precursor. The kinetic model suggested that isobutene 49 oligomerization is limited by
internal diffusion. The estimate value of the activation energy indicated the dominating surface migration
reactions 89. Thyrion et al. investigated the oligomerization of n-butene and found out that the reaction is
first-order and follow an Eley- Rideal- type mechanism 85. A catalyst system consisting of mesoporous
silica-alumina and -alumina as a binder was used to oligomerize propylene olefin in a semi-batch reactor. It
was found from the reaction and the Arrhenius equation that the apparent activation energy required for the
propylene oligomerization was 18 kJ/mol 58. Similarly, for
262ethylene oligomerization over nickel loaded sulfated alumina catalyst
the apparent
18activation energy was found to be 16.3 kJ/mol 90. Borges et al.
investigated that the kinetic model for oligomerization of light olefins over H-ZSM- 5 consisted two main
steps; the adsorption of olefin on vacant active site and the second step is the carbocation chain growth.
Three different light olefins were used in this research for oligomerization between 473 K and 723 K;
ethylene, propylene and 1-butene olefins. It was found by assuming the
12model site with a general formula of SiCl3OHAlCl3, that the
heat of adsorption on modeled acid site does not depend on the molecular size of the olefins. This is the
same for the heat of oligomerization reaction (combination of olefin with the pre-adsorbed olefin on acid
site). The heat of adsorption for these molecules calculated was -77.8 kJ/mol. This is very close to the heat
of adsorption of propylene
12on USY zeolite which is -90.0 kJ/mol
91. An interesting pathway for the production of high-quality diesel is through a two- step procedure
consisting of the trimerization of furan molecules over brnsted acidic zeolite site and hydrodeoxygenation
of the obtained trimer over platinum on carbon support in hydrogen atmosphere. Nikbin et al. discussed the
catalytic activity and the micro-kinetic mechanism of the conversion of biomass-based 2-methylfurun to
6-butylundecane. In terms of micro-kinetic mechanism the proposed oligomerization consisted of six steps;
hydrolysis, 1st Electrophilic attack, 1st deprotonation, dehydration, 2nd electrophilic attack and 2nd
deprotonation. The first electrophilic attack and deprotonation correspond to the dimerization reaction while
56 105 7/6/2560 7:43

the second reactions are for addition of another furan molecule to complete the trimerization reaction. Micro-
kinetic modeling pointed out that hydrolysis reaction
31is the rate-limiting step of the trimerization. Therefore this reaction
suggested that an increase in temperature and reduction of the pH level will improve the rate of reaction.
Additionally, insertion of an electron-donating 50 groups
205(such as, alkyl, phenyl or alkoxy) into an alpha carbon position of the
furan molecule was found
190to increase the rate of proton transfer which ultimately increase the rate
of the reaction 92. 51 Table 2.8 Rate equation from oligomerization over different type of catalysts Catalyst
Reactant Dimerization rate equation Trimerization rate equation Ref Amberlysttm 15 Amberlysttm 35
Isoamylenes (IA)/ n-hexane (HX) as solvent r DI ? k1cI2A (KIAcIA ? KDIAcDIA ? KHXcHx) rTI ? (KIAcIA ?
KkD2IcAIcADcIDAIA? KHXcHx)3 86 Isoamylenes(IA)/ 5% ethanol rDI ? (KIAaIAk?1SKaI2DAIAaDIA)3 - 87
Ni/Al2O3 Isobutene (IB)/ n-pentane (NP) as solvent rDI ?
(cIBk?1cK2IBD?IBkc2DKIBD?IBcKIBTcIBDcITBIB)2 rTI ? (cIIB ? KDIBcDIB ? KTIBcTIB)2 k2KDIBcIBcDIB
88 NiSO4/ Al2O3 Isobutene (IB) rDI ? (ckI1Bc?I2BK?DkI2BKcDIBIBK?DKIBcTIIBBccTDIBIB)2 rTI ?
k(2cKIIBD?IBcKIBDcIDBIcBD?IBk?3KKTTIIBBccITBIcBT)I2B 89 52 Catalyst Reactant Reactor system
Activation energy Kinetic constant (mol g-1 h-1) Adsorption Coefficients Ref kJ/mol Amberlysttm-15
Macroreticular acid resin 86 (Acidity = 4.81 eq H+ kg-1, MPoDa = 31.8, MPaDb = 0.74, PVc = 0.33, Sgd =
42) Amberlysttm 35 2-Methyl-2-butene (94wt.%) /n-hexane solvent Type: 120mL autoclaved Temp.e: 323K
to 393K Pres.f: 1.5 MPa RFRg: 10 mL/min CWh: 2 gram DI: 37 2 TI: 89 2 DI: 0.51KIA TI: 302.7KIA (384
K) DI: 2.20 KIA TI: 1.50 KIA (384 K) 87 (Acidity = 5.32 eq H+ kg-1, MPoDa = 32.9, MPaDb = 0.51,PVc=0.62,
Sgd = 34) 2-Methyl-2-butene with ethanol as dimer selectivity enhancer (RIA/EtOH = 20) Type: Batch stirred
tank Temp.e: 333K to 373K Pres.f: 1.9 MPa CWh: 4 gram DI: 65 3 DI: 0.58 KIA (373 K) DI: 6.22 KIA (373
K) 88 Ni/Al2O3 (MPoDa = 5 7, PVc=0.5 0.7, Sgd = 34) Isobutene/n- pentane as solvent Type: Reactive
distillation (35 stages) Temp.e: 338K to 383K DI: 24 TI: 12 DI: 50.4 TI: 1.8 (353 K) DI: 0.58 TI: 180.15 (353
K) 53 Pres.f: 1.4 MPa Mesoporous silica-alumina (MSA; MPoDa = 2/100, Sgd = 550) Propylene/propane as
solvent (30:70 to 70:30) Type: Semi-batch Temp.e: 373K to 474K Pres.f: 2 4 MPa WHSVi: 1 20 h-1 18 - -
90 58 Ni/sulfated alumina Ethylene/ n- heptane Type: Glass reactor Temp.e: 278K to 323K Pres.f: 0.17 MPa
RFRg: 70 mL/min CWh: 1 gram 16.3 - - 91 H-ZSM-5 Ethylene Propylene 1-Butene Type: Glass reactor
Temp.e: 278K to 323K Pres.f: 0.17 MPa RFRg: 70 mL/min CWh: 1 gram 45.0 1.6 45.4 1.3 18.2 2.2 4.2
0.1 (x10
12-3 mol h-1 g-1) 648K 16.7 0.
4 (x10
57 105 7/6/2560 7:43

12-3 mol h-1 g-1)
648K 66.7 2.7 (x10
12-3 mol h-1 g-1) 648K 1.9 0.
2 54 NiSO4/alumina (PV = 0.55 cm3 g-1, Sgd =204) Isobutene Type: Stir autoclave Temp.e: 323K to 363K
Pres.f: 2.1MPa DI: 23 27 TI: 20 25 mol/s(kg-cat) x (m3/mol)-2 TI: 4.2 x 10-10 1.471 x 10-9
mol/s(kg-cat) x (m3/mol)-2 DI: 5.6 x 10-10 1.5 x 10-9 89 H-Mordenite (Si/Al = 38, MPoD = 0.7 nm/5-20nm)
n-butene/pentane Type: Stir autoclave Temp.e: 373K to 488K Pres.f: 2 MPa 53 TE:13 TE: 1.4 x 10-10
mol/s(kg-cat) x (m3/mol)-2 91 a: MPoD = Mean pore diameter (nm) , e: Temp. = Temperature (K) , i = WHSV
= weight hourly space velocity b: MPaD = Mean particle size (nm) , f: Pres. = Pressure (MPa) , DI =
Dimerization reaction c: PV= Pore volume (cm3/g) , g: RFR = Reactant flow rate (mL/min) , TI =
Trimerization reaction d: Sg = Surface area (m2/g) , h: CW = catalyst weight (g) , TE = Tetramerization
reaction 55 CHAPTER 3 RESEARCH METHODOLOGY 3.1 Concept outlined As stated in the objective this
research aims to produce usable hydrocarbon diesel for transportation fuel and higher molecular weight
hydrocarbon with lubricating properties. Therefore, even in laboratory-scale this research contains a
complete system
1for the production of real transportation fuel and lubricant oil.
This system consisted of an oligomerization reactor for the synthesis (production of oligomers from olefins),
distillation column (separation of olefin residual and diesel fuel), and hydrogenation unit (for hydrotreating of
produced oligomers). The liquid products obtained are analyzed with gas chromatography (composition),
C13-NMR, viscosity bath and FTIR as shown in Figure 3.1. The catalysts used for this research included,
zeolite, modified zeolite, modified alumina and modified zirconia. Plain zeolites, alumina and zirconia are
contained from the companies. Modification of each support is conducted in the laboratory using technique
such as ion-exchange (using NH3F), incipient impregnation (Nickel nitrate) and desilication (alkaline
solution;
51in order to increase the size of the catalytic pore).
Most reactions are conducted at atmospheric pressure. However, for modified zirconia the reaction needed
to be conducted in a confined stainless-steel vessel under pressure. The heterogeneous catalysts are
characterized using techniques such as N2 sorption, thermogravimeter analysis and ammonia temperature
programed desorption. Some used catalysts (zeolite and tungstate- zirconia) are regenerated using the
conditions obtained from thermogravimeter analysis. 55 56 Figure 3.1 Framework for production of fuel and
lubricating oil. 57 3.2 Experimental setup 3.2.1 Solid catalysts, apparatus and chemicals All zeolite catalysts
such as Beta (CP814C* and CP811C-300), HY (CBV 400, CBV 720, and CBV 760) and Mordenite (CBV
21A) were obtained from Zeolyst International. Alumina (-phase) was obtained from Sasol Germany GmbH.
Tungstated-zirconia (SZ 31152) is obtained from Saint-Gobain NorPro. The chemical reagent, gas and
equipment used in this research are tabulated
58 105 7/6/2560 7:43

118in Table 3.1, Table 3.2 and Table 3.3. Table 3.1
Chemical reagents used in this research Item Chemical Concentration Company 1 1-decene 95% Acros 2
n-tetradecane 99% Sigma-Aldrich 3 Boiling Point Calibration Sample 100% Agilent 4 Nickel nitrate
hexahydrate (NiNO3)2 6H2O Solid Qrec 5 Sodium Hydroxide (NaOH) Solid Merck 6 Ammonium fluoride
(NH4F) Solid Merck Table 3.2 Gases used in this research Item Chemical Purity Company 1 Nitrogen gas
99.998% Praxair (Thailand) 2 Hydrogen gas 99.95% Praxair (Thailand) 3 Air zero 100% Praxair (Thailand)
Table 3.3 Equipment and apparatus Item Chemical Company 1 Heating Mantle Mtops korean 2 Mass flow
meter Brooks Instrument 3 Back pressure regulator TescomTM 4 High pressure pump Eldex laboratory 5
Vacuum pressure pump Rocker Scientific Co., Ltd 58 3.2.2 Catalyst pretreatment and modification Before
use every zeolite catalysts are calcined under the presence of 270 mL/min of air for at least 3 hours. The
temperature ramp was 10oC/min and the calcine temperature was 550oC. 3.2.2.1 Ion-exchange The two
different types of modification method used to enhance the activity of zeolite solid are ion-exchange and
incipient impregnation. Ion-exchange was performed using NaOH solution to increase the pore size of the
Beta (CP814C*, Si/Al = 30). An aqueous solution of NaOH was prepared by dissolving 15g of NaOH in
76.5g deionized water. Beta zeolite (35 grams) was mixed with 35 grams of deionized water.
Cetyltrimethylammonium bromide (CTAB) solution was prepared by dissolving 69 gram of CTAB into 1L of
deionized water. The first step is to add the zeolite solution to the NaOH solution and then add CTAB
solution. Stirred vigorously for 24 hours at ambient temperature. The
224pH of the mixture was adjusted to 10 using
a 50wt% solution of acetate. The solution was transferred to an oven and dried at 100oC for 12 hours. The
solution is
3washed with deionized water and ethanol and then dried again for
12 hours at 100oC. The white material was then calcine at 550oC for 3 hours to decompose the soft
template (surfactant CTAB). 3.2.2.2 Incipient impregnation Nickel nitrate is used as a precursor for incipient
wetness impregnation of the zeolite catalyst. A solution of 2.5% wt. nickel was prepared by mixing nickel
nitrate with deionized water. The volume of deionized water used is equaled
108to the total pore volume of the sample. The
green solution of nickel was slowly added it to the calcined zeolite using a glass dropper. The mixed solid
and liquid was stirred continuous at ambient temperature. The nickel load catalyst is then
3transferred to an oven to be heated at 110oC for 12 hours.
After heating the dried solution is then calcined at 550oC for 8 hours and kept in the dehumidifier for further
use. 59 3.2.3 Oligomerization reaction Each oligomerization reaction will be conducted either in a batch
59 105 7/6/2560 7:43

glass or
3a stainless steel autoclave batch reactor equipped with a
temperature and agitator speed controller as shown in Figure 3.2. The operating condition and the activation
process depend on the type of catalyst used. Zeolite catalysts can be used right away without any
pre-treatment process. Oligomerization over zeolite catalyst is carried out under atmospheric pressure and
inside a 3-necked glass batch. Catalyst modification can be performed by wet impregnation of alkaline
solution for 6 hours. Alkaline solution included large molecule pyridine such as 2,6-di-tert-butylpyridine,
polymer- bound pyridine and NaOH. Unlike zeolite catalysts, the tungstated-zirconia catalysts need to be
activate first
39under the presence of hydrogen gas (flow rate = 80mL /min,
100 psi) and inside a Parrs stainless steel autoclave. A filtration and distillation step is performed after the
oligomerization reaction. The distillation step is performed to remove unreacted olefins (1-decene; C10) and
dimers (hydrocarbons with 20 carbon atoms). The temperature of each cuts are illustrated in Figure 3.3. The
transportation fuel is referred to as C20, while the lubricant oil is coded as HC20 (stood for molecular weight
higher than C20). (a) (b) 60 Figure 3.2. Oligomerization reaction of 1-decene using a rounded bottom flask
(a) and the Parrs stainless steel autoclave Cut 1: 250oC C10 Oligomerization Product Cut 2: 250 - 350 oC
C20 Residual: 250 - 350 oC HC20 Figure 3.3 Boiling point and cut ranges for distillation of oligomer product
3.2.4 Catalyst regeneration Regeneration of zeolite and tungstated-zirconia was performed in an oven and
under the presence of air. The temperature was ramp up from 30oC to 600oC
150at a rate of 10oC /min and held at 600oC for 6 hours. The
air flow over the catalyst was set at 270 mL/min. The regenerated catalyst was found to be completely fresh
in their appearance (white). The regeneration of Pt/Al2O3 was also conducted at these conditions. However,
after testing the regenerated Pt/Al2O3 through the hydrogenation reaction it was found that the catalyst no
longer perform as well as it did when it was fresh. Therefore, the option of regenerating the catalyst for
hydrogenation was discarded. 3.2.5 Hydrogenation reaction The catalyst for hydrogenation reaction is
conducted over 1%Pt/Al2O3 which was prepared by incipient impregnation using chlorophlatinic acid
hydrate as a precursor and gamma-alumina as support (-Al2O3: 250m2/g, 7nm, 1.05m3/g) as shown in
Figure 3.4. Before treatment the support is calcined at 500oC for 2 hours under air (270 mL/min). After
incipient impregnation the doped alumina was dried at 120oC under air atmosphere for 15 hours. The
finished catalyst, as shown in Figure 3.5, is kept in a dehumidify box. 61 Figure 3.4 Preparation 1%Pt/Al2O3
through incipient impregnation using chlorophlatinic acid hydrate solution Figure 3.5 Finished solid catalyst
ready to be used for hydrogenation reaction The bottom residual (HC20; molecules that has higher
molecular weight than hydrocarbon with 20 carbon) is then separated and fed into the hydrotreating unit at
200oC, 1.2 WHSV h-1, 290 psi and
45in a fixed-bed reactor as shown in Figure 3. 6. The
60 105 7/6/2560 7:43

hydrotreated oligomer products, referred to as THC20 (treated oligomer with molecular weight higher than
C20 hydrocarbons; lubricant product) can therefore be characterized by FTIR, C13-NMR and the viscosity
bath. 62 d
228c b e a j k g h f
i p l m n o Figure 3.6 Fix-bed reactor setup for hydrogenation of oligomers product. Hydrogen gas a), Mass
flow controller b), check valve c), vent gas #1 d), fixed-bed stainless steel reactor e), split-furnace f),
high-pressure pump g), feedstock solution h), back-pressure regulator i), temperature controller j),
thermocouple k), condenser l), water circulator m), sampling vessel n), collecting samples (o) and vent gas
#2 p). 3.3 Catalyst Characterization Ammonia temperature-programmed-desorption or NH3-TPD is
performed to measure the concentration and the strength of acidity on catalysts. Catalyst acidity was
measured in mmol per catalyst, while the strength of acid is measured in terms of the desorption
temperature. This technique is conducted by flowing excess NH3 gas over the catalyst sample and then
increasing the temperature of the system in order to allow chemisorbed NH3 to desorb.
191A thermal conductivity detector is employed to 63 measure the quantity of

NH3 desorbed. The
area under the curve can be used along with calibration data to convert the amount of NH3 desorbed into
the acid concentration of a catalyst. Another important catalyst characterization technique is the nitrogen
sorption, which used nitrogen gas as an adsorbate. This technique is used to calculate the textural
properties, such as
154surface area (m2/g), pore volume (mL/g), and pore size (nm) distribution of a
catalyst. The nitrogen sorption isotherm can be used to deduce the shape of the internal pores of the
catalyst. According to IUPAC there are 4 kinds of hysteresis loops, which indicate four different shapes of
the internal pores.
268X-ray diffraction patterns for some zeolites and
tungstated-zirconia catalysts
201were obtained by using the a PANalytical (XPert pro) diffractometer (with
CuK
4radiation 40 kV, 40 mA) at a scanning speed of 2o /min
61 105 7/6/2560 7:43

from 20 to 80o. Before use the catalyst has to be grounded to particle size below 300 m and put on a glass
collector. Thermogravimetric analyser from Mettler-Toledo instrument was used to investigate the
regeneration condition of the used catalyst. Used catalyst was approximately 30 mg. 3.4 Product
Characterization Carbon 13 nuclear magnetic resonance or C13-NMR is a technique used widely for
structural elucidation of long-chain hydrocarbon molecule in lubricant oil and polymer.
15NMR spectra of oligomers were obtained using a Bruker AVANCE III 400
spectrometer at frequencies of 400 and
100 Hz. For each analysis the liquid sample was dissolved in CDCl3 and in the ordinary ampoules with
diameter of 5mm. According to the C13-NMR spectrum, peaks that correspond to carbons in alkane
molecule are located between 5 ppm 50 ppm. Each peak in the C13-NMR spectra corresponds to a
particular unique carbon structure. Therefore the C13-NMR spectra of a molecule with higher degree of
branching will show more peak than linear molecules. This is because branching affects the electron density
of each carbon atoms, while linear molecular contained symmetric carbon atoms which appears at the same
chemical shift. The degree of branching can be relatively calculated by obtaining area under the C13-NMR
spectra. 64
214Fourier transformed Infrared Spectroscopy (FTIR) was also employed to

observed the
structure of the collected product. Specifically, in the research, FTIR was conducted using the PerkinElmer
Spectrum 100.The
72spectrum is recorded every 9 seconds in the range between 4000 and 650
cm-1 with a resolution factor of 4 cm-1.
A 2 mg liquid sample mixed with 100 mg KBr before analyzed. Viscosity index is one of the very important
characteristics of lubricant oil.
242In order to calculate the viscosity index of the lubricant oil the
viscosity of the oil at 40oC and 100oC need to be measured by using a cannon-fenske viscometer (ASTM
D445). The water bath to control the temperature of each analysis is shown in Figure 3.7a. The first step is
to fill the liquid sample into position A as shown in Figure 3.7b. The sample will be collected in position B.
Immerse the cannon-fenske glass containing the liquid sample for at least 10 minutes before being the
analysis. Apply vacuum at the end of position E to draw the sample liquid from position B to position D. Next,
release the vacuum and start the stopwatch. Stop the stopwatch when the sample liquid reaches position C.
The time took for the liquid to flow down by gravity from point D to point C is usually referred to as the
effluent time (unit: second). The viscosity (unit: centistokes mm2/s) of the liquid sample can be calculated by
multiplying the effluent time with a constant (depending on the size of cannon-fenske glass) as shown in the
equation below. Viscosity (cSt) = effluent time (s) x constant (mm2/s) Eq. 3.1 A E D C B (a) (b) 65 Figure 3.7
62 105 7/6/2560 7:43

Measurement of viscosity using the cannon-fenske technique with a water bath (a) and the important parts
of the canon-fenske glass (b) The constant used for each calculation depended on the temperature (either
40oC or 100oC) and the size of the canon-fenske glass as shown in Table 3.4. For analysis of lubricant oil
the size of canon-fenske are usually 100, 150 or 200. The viscosity of liquid sample should fall in the
viscosity range Table 3.4 Constant and the range of viscosity for different sizes of canon-fenske glass Size
of canon-fenske Constant (mm2/s2) Range of viscosity (cSt) 75 0.008 1.6 - 8 100 0.015 3 - 15 150 0.038 7 -
35 200 0.1 20 - 100 300 0.25 50 - 250 66 CHAPTER 4 OLIGOMERIZATION OF 1-DECENE AND MIXED-
DECENE OVER ZEOLITE CATALYSTS 4.1 Introduction Development of an industrial catalyst is a very
difficult task even for a company with a strong research and development background. In most cases the
development of an effective catalyst, starting from laboratory-scale to pilot-scale and ultimately to the
industrial-scale, require intensive investment in terms of both time and money. Nevertheless, this process is
necessary for a company to maintain its integrity and competitiveness. In order for a catalyst to be effective,
it needs to exhibit the four important characteristics. First of all the catalyst needs to be active, which means
that it needs to give high conversion of the reactant. The second criterion, which is as equally important, is
that the catalyst needs to be selective. An active catalyst is worthless if it gives mostly undesired products.
The third criterion is related to the recyclability of the catalyst. We should be able to use and reused an
effective catalyst again after regeneration process in order to reduce the cost of operation. The fourth
criterion is the catalytic stability. The rate of deactivation of an effective catalyst need to be as low as
possible. Generally, there are four major causes of heterogeneous catalytic deactivation; poison,
agglomeration, sinstering and coke formation. A catalyst that does not pass these four criteria should not yet
be used in an industrial scale. Zeolite catalysts have been employed intensively in both laboratory and
industrial scale for reaction such as isomerization34,69,93-96, dehydration52,97-99, transesterification100,
biomass pyrolysis37,101,102 and oligomerization44,45,49,103-107. Other applications including gas phase
separation, waste water treatment and air treatment. An increase in awareness of global warming and the
energy crisis have driven many oil companies to try
1to optimize their production of transportation fuel and lubricant oil
through environmental friendly approaches. Zeolite is considered as environmental friendly compared to

lewis acid catalyst such as boron trifluoride and 66 67 aluminum chloride. Additionally, zeolite catalysts can
also be prepared by treating different types of biomass in highly acidic solution. This is also a good use of
residual agricultural waste that is generated worldwide. Generally, zeolite catalysts consisted of MO4 linked
in 3-dimentional network (M can be either Al or Si atom) which can be seen as a layer or chains. One of the
most important characteristic which defined the application of a zeolite catalyst is the Si/Al ratio. Apart from
Si/Al ratio, zeolite catalysts differ greatly in their pore structure. The types of catalysts used for this
experiment belong to three different families of zeolite catalyst including BEA, FAU and MOR. The structure
of these zeolite catalysts are shown in the Appendix E. 4.2 Experiment setup As described in chapter 3,
oligomerization of olefins over zeolite catalyst is performed inside a glass reactor heated with a mantle at
atmospheric pressure and for 3 hours of reaction. The reaction temperature required for the oligomerization
is between 150oC to 210oC, the agitation speed is 300 rpm and the amount of catalyst is varied from 5% to
15%. The zeolite is heated under the presence of air at 550oC for 3 hours. The plain zeolites used for
oligomerization are Beta-38, HY-30 and Mordenite-20. The regeneration process was conducted in a calcine
oven using compressed air as carrier gas to facilitate oxidation of the coke on catalyst surface. Beta catalyst
was modified through the ion-exchange and incipient impregnation technique. 4.3 Results and discussion
The first section of the results and discussion will be devoted to observing the physical characteristic of
Beta-38, HY-30 and Mordenite-20. The second part will discuss about how the
63 105 7/6/2560 7:43

249reaction temperature and the amount of catalyst used effect the catalytic
activity
for oligomerization reaction. The third part of this section aim
230to investigate the influence of feedstock composition on the oligomerization

reaction.
The last part is related to the regeneration of used HY-30 and Beta-38 catalyst. 68 4.3.1 Catalysts
chracterization The physical characteristics,
202such as surface area, pore volume and pore sizes of a
zeolite catalyst are significant in determining the types of application a zeolite catalyst can be used for.
Results from N2 sorption analysis of catalyst samples are shown in table 4.1. HY-30
264catalyst with Si/Al ratio of
30
158was found to have the largest surface area, pore size and pore volume
compared to Mordenite and Beta catalyst. Figure 4.1a shows isotherm of different zeolite catalysts that are
also obtained from the N2 sorption technique. According to IUPACs classification of physical adsorption, the
isotherm of zeolite catalyst can be classified as type I, which corresponded to a Langmuir isotherm of a
microporous adsorbent. The pore
220size distribution of each zeolite catalysts are shown in Figure
4.1b and the average
81pore size are recorded in Table 4.1. The desorption of NH3 profiles and
acidities of each type of zeolite catalyst are shown in Figure 4.2 and Table 4.2. The desorption profile for
HY-30 and mordenite catalysts contained two peaks centered around 200oC and 320oC. The first peak
represented the desorption of NH3 molecule from weak acidic sites, which have also been referred to as
lewis acid sites. The second peak suggested the desorption of NH3 molecule from strong acidic sites or
bronsted acidic sites. After integration of the area under NH3 desorption profiles, it was revealed that HY-30
64 105 7/6/2560 7:43

catalyst contained the most amount of weak and strong acidic sites. These acidic sites really helped
increase the catalytic activity during the reaction, which will be explained in detailed in the next section.
However, the total amount of Beta-38 zeolite catalyst was only 0.40 mmol/g which is the lowest among the
zeolite catalysts compared in this research. There were only weak acidic sites located on the Beta-38 zeolite
catalyst. Table 4.1 N2 sorption characterization of zeolite catalysts Catalyst Form Si/Al Code
186Surface area Pore Volume Average pore size cm2 /g cm3 /g nm
Mordenite-20 H-MOR 20 CBV 21A 500 0.159 2.1-2.7 HY-30 HY 30 CBV 720 780 0.591 3.1-3.6 69 Beta-38
H-Beta 38 CP814C 680 0.361 1.7-2.0 300 Beta-38: Adsorption Morenite: Adsorption HY-30:Adsorption
Beta-38: Desorption Morenite: Desorption HY-30: Desorption V olume adsorbed (cm3
27/g) 250 200 150 100 50 0 0 0.2 0.4 0.6 0.8 1 P/Po
(a) 0.8 BHeYta--3380 dV/d logd (cm3g-1/nm) 0.7 0.6 Mordenite-20 HBYet-a3-038 0.5 0.4 0.3 0.2 0.1 0 0 2 4
6 8 10 12 14 Pore size (nm) (b) Figure 4.1 N2 sorption isotherm a) and pore size distribution b) of zeolite
catalysts. 70 TCD Intensity (a.u.) HY-30 Mordenite-20 Beta-38 100 150 200 250 300 350 400 450 500
Temperature (oC) Figure 4.2 NH3-TPD results for zeolite catalysts Table 4.2 Calculation of the acidity of
catalyst sample obtained from TCD area Acidity concentration
79(mmol/g) Total acidity (mmol/g) Weak acid Strong acid
HY-30 0.551 0.232 0.784 Beta-38 0.404 - 0.498 Mordenite-20 0.422 0.094 0.555 4.3.2 Effect of temperature
and amount of catalyst The catalytic activty of zeolite catalyst can be observed by conducting the
oligomerization reaction at different temperature under atmospheric pressure. With 10%wt. catalyst and an
agitation speed of 400 rpm it was found that HY-30 zeolite gave the highest conversion compared with
Beta-38 and Mordenite-20.
25An increase in reaction temperature was also found to cause an increase in

conversion of
1-decene.
152As shown in Figure 4. 3a, an increase in temperature from 150oC to
210oC caused the conversion of 1-decene over HY-30 catalyst to increase from 60% to 87%. For Beta- 38
an increase from 32% to 63% was realized. 71 Figure 4.3b demonstrated the composition of oligomers
product obtained from oligomerization reaction over HY-30, Beta-38 and Mordenite-20 zeolite. It was found
that at a reaction temperature of 150oC HY-30 gave roughly 57 wt%. dimer, while Beta-38 and Mordenite-20
gave approximately 42 wt%. and 32 %wt dimer. The dimers obtained from oligomerization contained 20
carbon atoms which can be used as diesel transportation fuel. However, the oligomer product needs to be
65 105 7/6/2560 7:43

distilled first in order to eliminate the residual 1-decene and to separate the dimers from the heavier
oligomers (hydrocarbon with 30 to 40 carbons). The distillated cut consisting of dimers and heavier
hydrocarbons was hydrogenated first over 0.5% platinum on alumina catalyst to increase their thermal
stability. An incline in reaction temperature resulted in an increase in formation of dimer, trimer and tetramer.
Heavier oligomers including hydrocarbon with 30 and 40 carbon atoms can be used as lubricating oil for
vehicles. The composition of trimers and tetramer is shown in Figure 4.3c and Figure 4.3d. The amount of
C30 produced over HY-30 at 150oC is only 5.5 wt%. However when the temperature increased to 210oC the
amount of C30 also increased to 19 wt%. 100 HY-(3S0i/Al=30) 90 Beta-38 Conversion (%) 80 Mordenite-20
70 60 50 40 30 20 150 160 170 180 190 200 210 Temperature (oC) (a) 72 70 Amount of C20 (%wt.) 65 60
55 50 45 40 35 30 25 20 HY-(3S0i/Al=30) Beta-38 Mordenite-20 150 160 170 180 Temperature (oC) 190
200 210 (b) 20 18 Amount of C30 (%wt.) 16 14 12 10 8 6 HY-(3S0i/Al=30) 4 Beta-38 2 Mordenite-20 0 150
160 170 180 190 200 210 Temperature (oC) (c) 73 Amount of C40 (%wt.) 5 HY (Si/Al=30) 4 Beta-38 3
Mordenite-20 2 1 0 150 160 170 180 190 200 210 Temperature (oC) (d) Figure 4.3
9Effect of temperature on the conversion of 1-decene over zeolite catalyst a),

amount of C20 b),
amount of C30 c) and amount of C40 d) formed. Reaction conditions: Reaction time = 3 hours, atmospheric
pressure, agitation speed =400 rpm and 10wt% catalyst As mentioned previously, the heavier oligomers with
C30 and C40 can be used as lubricant oil for vehicles. These heavier oligomers are actually the residual that
remained in the still pot after distillation. Similar to the dimer product, the heavier oligomer had to be
hydrogenated over 0.5% platinum on alumina first
182in order to improve the thermal stability of the synthesized lubricant. One of
the
most important characteristic of the lubricant oil is the viscosity at 40oC, 100oC and the viscosity index. The
viscosity of the heavier oligomer obtained from zeolite catalyst measured at 100oC and 40oC is
approximately between 5.1 to 5.5 cSt and between 27 to 35 cSt. The viscosity index of heavier oligomer
decrease
209with an increase in reaction temperature. The viscosity index of the
liquid product produced over HY-30 at 150oC is approximately 117 as shown in Figure 4.4. A decrease in
viscosity index to 107 occurred when the reaction temperature increase to 210oC. However the viscosity
index of oligomer products obtained from Beta-38 are relatively higher than that of HY-30.
219An increase in reaction temperature from 150oC to 210oC caused the
74 viscosity index of oligomer product to decrease from 148 to 142 as shown in Figure 4.5. 40 35 Viscosity
(40oC, 100oC) 30 25 20 15 10 5 0 40oC 100oC Viscosity Index 150 175 200 210 Temperature (oC) 118 116
114 112 110 108 106 Viscosity Index 104 102 Figure 4.4 Influence of reaction temperature on viscosity and
66 105 7/6/2560 7:43

viscosity index of oligomers product from oligomerization over HY-30. Reaction conditions: Reaction time 3
hours, Atmospheric pressure, agitation speed =400 rpm and 10wt% catalyst 35 149 Viscosity (40oC, 100oC)
30 25 20 15 10 5 0 40oC 100oC Viscosity Index 148 147 146 145 144 143 142 141 140 139 Viscosity Index
150 175 200 Temperature (oC) 210 Figure 4.5 Influence of reaction temperature on viscosity and viscosity
index of oligomer product from oligomerization over Beta-38. Reaction conditions: Reaction time = 3 hours,
atmospheric pressure, agitation speed = 400 rpm and 10 wt% catalyst 75 The effect of the amount of HY
and Beta catalyst are
213shown in Figure 4. 6 and Figure 4. 7. For HY catalyst,
1an increase in the amount of catalyst from 5 wt% to 15 wt% causes the
conversion of 1-decene to increase tremendously from 40% to
80%. The composition of C20 increased slightly as the amount of catalyst increase. Additionally, the
compositions of C30 also increase clearly from approximately 1% to 18 wt%. Similar to HY catalyst,
oligomerization activity over Beta catalyst also increases with the amount of catalyst. The conversion of
1-decene increases from 20 % to roughly 48 %. The composition of C20 and C30 also increases clearly as
the amount of catalyst increases as shown in Figure 4.7. 100 C10 C20 C30 C40 Conv.(%) 90 Product
Distribution (%) 90 80 70 60 50 40 30 20 10 0 80 70 60 50 40 30 20 10 0 5 10 15 Catalyst Amount (%) (a)
Conversion (%) 76 100 Product Distribution (%) 90 80 70 60 50 40 30 20 10 0 C10 C20 C30 Conversion (%)
5 10 15 Catalyst Amount (%) 90 80 70 60 50 40 30 20 10 0 Conversion (%) (b) Figure 4.6
6Effect of the amount of catalyst on the oligomerization reaction
for HY-30 a) and Beta-38 b). Reaction conditions: Reaction time =3 hours, temperature = 200oC, , agitation
speed = 300 rpm and atmospheric pressure. Viscosity (40oC, 100oC) 30 25 20 15 10 5 0 40oC 100oC
Viscosity Index 112 111 110 109 108 107 106 105 35 113 5 10 15 Catalyst amount (%) Viscosity Index
Figure 4.7 Influence of the amount of catalyst on viscosity and viscosity index of oligomer product from
oligomerization over HY-30. Reaction conditions: Reaction time = 3 hours, temperature = 200oC,
atmospheric pressure, and agitation speed =400 rpm. 77 Viscosity (40oC, 100oC) 35 30 25 20 15 10 5 0
40oC 100oC Viscosity Index 140 120 100 80 60 Viscosity Index 40 20 0 40 160 5 10 Catalyst amount (%) 15
Figure 4.8 Influence of the amount of catalyst on viscosity and viscosity index of oligomer product from
oligomerization over Beta-38. Reaction conditions: Reaction time = 3 hours, temperature = 200oC,
atmospheric pressure, and agitation speed =400 rpm. 4.3
211.3 Effect of feedstock composition (1-decene content) The effect of feedstock

composition on
catalyst activity was conducted over HY-5 (Si/Al=5) and HY-30 (Si/Al=30) zeolite catalysts. Three different
feedstock compostions were used; the first composition contained 45.3 wt% 1-decene (54.7%wt. internal
olefin), the second composition which is purchased commercially from Aldrich contained 95% 1-decene and
the third composition contained 96% 1- decene. The oligomerization reaction was conducted at 200oC using
67 105 7/6/2560 7:43

10 wt% catalyst. A gas chromatograph of the composition with 45.3 wt% 1-decene and 95 wt% 1-decene is
shown in Figure 4.9. The oligomer product is passed through the vacuum distillation to be separated into
three cuts; residual 1-decene, C20 hydrocarbons (transportation fuel) and hydrocarbon higher than C30
which is in the range of lubricant oil (the lubricant oil usually consists of C30, C40 and C50 hydrocarbons).
78 Figure 4.9 GC analysis of feedstock containing 45.3 wt% 1-decene a) and 96 wt% 1-decene b). Results
obtained revealed that an increase in internal olefin content will cause the conversion of 1-decene to
increase. According to Figure 4.10a, for the oligomerization reaction over HY-5 catalyst, an increase in
conversion from 20% to 55% was achieved when the 1-decene content decrease from 95%wt. to 45.3 %wt.
However for oligomerization over HY-30 catalyst, the feedstock composition does not have an impact on the
conversion. It was found that a decrease in 1-decene content from 95 wt% to 45.3 wt% in the feedstock
composition cause the production of C20 hydrocarbons to decrease from 55 wt% to as low as 1 wt% for
HY-5 catalyst as shown in Figure 4.10b. Furthermore, it was found that the content of 1-decene in the
feedstock does not have an effect on the amount lubricant oil (HC20) in the product as shown in Figure
4.10c. After separation of the oligomers product using a vacuum distillation unit, the viscosity of the lubricant
cut (C30+ or residual product; boiling point higher than 350oC) was measured using the ASTM D445
specification. The viscosity of lubricant oil at 40oC and 100oC was used to calculate the viscosity index.
According to Figure 4.10d, it was found that the content of 1-decene in the 79 feedstock
206has a positive effect on the viscosity index of the lubricant oil.
For both HY-5 and HY-30, an increase in 1-decene purity (content of 1-decene in the feedstock) causes the
viscosity index to increase. The viscosity index increased from 100 to as high as 122 for HY-5 and from 92 to
116 for HY-30 catalyst. 45.3% 95% 95.8% 90 80 Conversion (%) 70 60 50 40 30 20 10 0 80 HY-5 45.3% (a)
95.0% HY-30 95.8% Amount of C20 (%wt.) 70 60 50 40 30 20 10 0 HY-5 HY-30 (b) 80 16 45.3% 95.0%
95.8% Amount of HC20 (%) 14 12 10 8 6 4 2 0 HY-5 HY-30 (c) 45.3% 95.0% 95.8% 130 120 Viscosity Index
110 100 90 80 70 60 50 HHYY1-5 HHYY-230 (d) Figure 4.10 Effect of feedstock composition on conversion
a), amount of C20 b), amount lubricant oil (C30+C40) c) and viscosity index d). Reaction conditions:
Temperature =200oC, agitation speed = 400 rpm, atmospheric pressure, and 10wt% catalyst. 4.3.4 Catalyst
deactivation and regeneration As mentioned previously, regeneration is an important process that can help
reduce the operation cost of the production process. The conditions used to regenerate a catalyst are
usually found in the laboratory-scale stage using analytical devices such as temperature-programed
oxidation and thermogravimetric (TGA). A picture of fresh catalysts (zeolite and tungstated-zirconia) and
used catalysts are 81 shown in Figure 4.11. It can be observed that both type of catalysts (tungstate-
zirconia and zeolite) turned brown after being used in the oligomerization reaction. However when
comparing the color of used zeolite catalyst, it can be observed that used HY has a brown color that is
obviously darker than used Beta zeolite. Figure 4.12 demonstrates the weight loss of used HY-30 and
Beta-38 while heating the samples from 30oC to 800oC under air atmosphere. Weight loss that occurred
between the temperatures of 30oC to 300oC is usually from the decomposition of moisture (H2O), residual
reactant/products (C10+) and soft coke. Weight loss that occurred at temperature higher than 300oC is from
decomposition of hard coke. It can be observed that roughly 53% of the weight loss from used HY-30 is
attributed to the decomposition of soft coke. This suggested that some hydrocarbon with the number of
carbon atoms between 20 and 30 are trapped inside the pores of the catalyst. These products are trapped
because the pores of the zeolite are respectively small For Beta catalyst, weight loss due to decomposition
of soft coke, is smaller than HY catalyst. This is because Beta zeolite catalyst produced lower amount of
heavier oligomers. However, since the pore structure of a Beta zeolite is linear, it is very difficult for the
generated highly-branched oligomer to diffuse out of the catalyst. Consequence, some oligomer may be
68 105 7/6/2560 7:43

trapped, reabsorbed and reacted with another olefins to form larger molecule. This process could be
repeated until coke with very large molecular weight is formed (hard coke). It can be observed from Figure
4.12 that used Beta catalyst contained more hard coke than HY zeolite catalyst. Fresh Beta-38 Fresh HY-30
82 Fresh Tungstated-Zirconia (TZ) Used Beta-38 Used HY-30 Used Tungstated-Zirconia (TZ) Figure 4.11
Fresh and used Beta, HY and tungstated-zirconia catalyst from oligomerization reaction 100 Percentage
weight loss (wt%) 90 80 70 60 50 40 30 HY-30 Beta-38 HY-30 Beta-38 Soft coke % 53 32 Hard coke % 9 13
0 100 200 300 400 500 600 700 800 Temperature (oC) Figure 4.12 Percentage weight loss during TGA
analysis of HY-30 and Beta-30 zeolite catalysts. Treatment condition: O2 flow rate = 100 mL/min and sample
weight = 0.1gram. 83 The regeneration conditions can be derived from the TGA analysis as shown in Figure
4.12. For this experiment the regeneration was conducted at 600oC and air flow rate of 270 mL/min. The
used catalysts that are regenerated are HY-30 and Beta-38. After regeneration of these catalysts, they are
tested by the oligomerization reaction at 200oC, reaction time of 3 hours and 10%wt. catalysts as shown in
Figure 4.13. The used catalyst was regenerated and then brought out to test again. Cycle 1 is referred to as
the catalytic testing of the regenerated catalyst from the first oligomerization reaction (Fresh unit). Cycle 2 is
referred to as the catalytic testing of the regenerated catalyst from Cycle 1 reaction. Figure 4.14
demonstrated the catalytic testing of fresh and regenerated HY-30 zeolite. It was revealed that the
regeneration of HY-30 was found to be effective in restoring the catalytic activity. The conversion of
1-decene remained at approximately 80% even after regeneration from the third cycles. Additionally, the
product composition also remained constant even after the third cycles (Dimers = 60 wt%, Trimers = 20
wt%, and Tetramers = 3 wt%). However, for Beta-38 catalyst the conversion of 1-decene dropped from 17.5
wt% to 11.7 wt% after the first regeneration cycle. The composition of dimers and trimers obtained from used
and recycled Beta-38 decreased significantly as well as shown in Figure 4.15. Figure 4.13 Regeneration
stage for zeolite catalysts and catalytic testing 84 90 Conversion / composition (%) 80 70 60 50 40 30 20 10
0 Conversion (%) C20 ((w%tw%t).) C30 ((w%tw%t).) C40 ((w%tw%t).) 0.7 Fresh 1.7 Cycle 1 2.7 Cycle 2 3.7
Cycle3 Figure 4.14 Catalytic activity testing of fresh HY-30 catalyst compared with the regenerated catalysts
(cycle 1, cycle 2 and cycle 3). Reaction conditions: Reaction time = 3 hours, temperature = 200oC, agitation
speed = 300 rpm and 10 %wt. catalyst. 20 Conversion (%) C20 ((w%t%wt).) C30 ((w%t%wt).) Conversion/
composition (%) 18 16 14 12 10 8 6 4 2 0 0.7 Fresh 1.7 Cycle 1 2.7 Cycle 2 3.7 Cycle3 Figure 4.15 Catalytic
activity testing of fresh Beta compared with the regenerated Beta catalysts (cycle 1, cycle 2 and cycle 3).
Reaction conditions: Reaction time = 3 hours, temperature = 200oC, agitation speed = 300 rpm and 5 %wt.
catalyst. 85 4.3.5 Modification of zeolite catalyst Two different type of modification techniques were studied
in this part of the research; incipient impregnation and ion-exchange. Beta-38 zeolite catalyst was used as
the parent support, which was then either ion-exchanged with ammonium fluoride or sodium hydroxide and
CTAB surfactant. As shown previously, Beta-38 zeolite catalyst can produce lubricant oil with very high
viscosity index. The drawback is that Beta-38 gave low conversion compared to other zeolite catalyst.
Therefore, the aim of this section is to employ ion-exchange technique to replace silicon in Beta-38 zeolite
framework with fluoride, which have been found by other research to improve activity of silicon-based
catalyst108. Another agent used for modification of Beta-38 was sodium hydroxide. In this case, sodium
hydroxide was used with CTAB as a soft template to expand the pore of Beta-38 as it was also assume that
Beta-38s low conversion may be due to its pore size which is typically smaller than other kind of catalyst.
Additionally, this section also examine the usage of nickel metal for blocking brnsted site located on HY-30
zeolite catalyst. It was pointed out from observation in the previous chapters that HY-30 was active
compared to other zeolite catalyst. However, lubricant products obtained from HY-30 have low viscosity
index which indicate that the brnsted sites on HY-30 zeolites surface are initiating very fast isomerization
reaction. Isomerization reaction causes the linear molecule of the hydrocarbon to be transformed to
branched molecule, which resulted in the reduction in viscosity index or thermal stability of the lubricant oil.
The incipient impregnation of HY-30 zeolite was conducted using nickel nitrate hexahydrate precursor. The
69 105 7/6/2560 7:43

amount of Ni metal loaded on HY catalyst varied from 1 wt% to 2.5 wt% as shown
189in Table 4.3. 86 Table 4.3 Summary of
the modification of Beta-38 through ion-exchange and incipient impregnation. Code Modification agent
Concentration Remark Beta-38 - - Plain Beta-38 zeolite catalyst BF(0.1M) Ammonium fluoride 0.1M
Ion-exchange BF(0.2M) Ammonium fluoride 0.2M Ion-exchange BF(0.3M) Ammonium fluoride 0.3M
Ion-exchange BF(0.4M) Ammonium fluoride 0.4M Ion-exchange MB Sodium hydroxide/CTAB -
Ion-exchange Figure 4.16 shows an increase in the amount of lubricant oil (HC20) produced from 2 wt% to 7
1wt% as the concentration of ammonium fluoride increased from 0 to 0.2M.

However an increase
from 0.2M to 0.4M caused the formation of HC20 to be reduced significantly. The viscosity of the lubricant oil
at 100oC was observed to increase gradually as the content of heavier hydrocarbon increases. On the other
hand, the viscosity index of the lubricant product was found to decrease with
145an increase in the concentration of ammonium fluoride solution from 0 to

0.2M. An increase in the
concentration of ammonium fluoride from 0.2M to 0.4M does not have a significant effect on the viscosity
index. In previous experiments the viscosity index of the lubricant oil is usually higher when there is a
reduction in the amount of HC20 produced (reduction in catalytic activity). However, in this experiment
viscosity index does not increase when the amount of HC20 produced decreased. This is because an
addition of ammonium fluoride beyond 0.2M promoted formation of active sites on the catalyst surface which
selectively increased the isomerization reaction. Therefore instead of the combination of olefins through
oligomerization reaction, the products are isomerized into branched molecule and potentially reabsorbed on
the active site to be transformed to a molecule with more short-chain branches. Figure 4.17 shows a gradual
decrease in the amount of lubricant oil (HC20) produced from approximately 13.6 wt% to 9.2 wt% as the
amount of Ni metal loaded 87 onto HY zeolite increased from 0 to 2.5 wt%. The viscosity at 100oC was
found to gradually decrease from 5.023 cSt to 3.947 cSt. The viscosity index does not change significantly
as the Ni metal loading increased. 10 180 9 HC20 ((%wwt%t.)) cSt ((1400o0Co)C) VI 160 HC20 (wt%), cSt
(100oC) 8 140 7 120 6 5 4.465 100 4 4.105 4.624 5.266 80 4.045 60 Vicosity Index 3 2 40 1 20 0 0 Beta-38
BF(0.1M) BF(0.2M) BF(0.4M) MB Figure 4.16 Effect of the ammonium fluoride concentration and
modification agent on the amount of HC20 produced and the viscosity of lubricant products. Reaction
conditions: 88 16 HC20 (wt%) Cst (100oC) VI 120 HC20 (wt%), Cst (100oC) 14 12 10 8 6 4 2 0 5.023 4.198
4.116 3.947 100 80 60 40 Viscosity Index 20 0 HY-30 1%Ni/HY-30 1.5%Ni/HY-30 2.5%Ni/HY-30 Figure 4.17
Effect of the Ni metal on the amount of HC20 produced and the viscosity of lubricant product. 4.4 Conclusion
From the experimental data obtained in this section it is evident that zeolite is an active catalyst for
oligomerization reaction. The pore structure, chemical and physical characteristic of the zeolite
234catalyst have a strong significant effect on the amount and the characteristic of
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the oligomers produced. HY-30 zeolite was used in the oligomerization to represent a catalyst with cage-like
pores.
240On the other hand, Beta-38 zeolite has linear pore structure.
A detailed physical characterization of the two active catalysts indicated that HY-30 has the highest surface
area and displayed a certain degree of mesoporosity. In contrast, modenite and beta has lower surface area
and contained mostly micropores. The acidity of HY was higher than modernite-30, which was higher than
Beta-38. Due to its high acidity content and cage-like structure, HY zeolite gave the highest conversion of
1-decene and produced oligomers that consisted of the highest amount of C20, C30 and C40. An
207increase in reaction temperature and the amount of catalyst was found to
increase the
1conversion of 1-decene and the oligomer products. The viscosity of the
product obtained from zeolite is approximately at 40oC and at 89 100oC. The viscosity index of the heavier
oligomer C30+ fraction decreases as the reaction temperature increases. An
176increase in the amount of catalyst was also shown to increase the viscosity
index of
the heavier oligomer C30+ fraction. A decrease in the content of 1-decene molecule in the feedstock
(replaced by internal olefins) caused conversion and dimer formation over HY-5 catalyst to increase
significantly. However, for oligomerization over HY-30 it was found that the amount of 1-decene in the
feedstock does not have an impact on the conversion and product composition. The viscosity index of the
heavier oligomer C30+ is strongly influenced by the content of 1-decene. An increase in 1-decene content
cause the viscosity index from both catalyst to increase, vice versa an increase in internal olefins content
caused the viscosity index to drop significantly. Catalyst deactivation was found to take place due to
formation of soft and hard coke in the pores of the catalyst. TGA technique was used to find the most
appropriate conditions used to regenerate used HY-30 and Beta-38 catalyst. The performance of HY-30
catalyst,
108in terms of catalytic activity and the composition of oligomer product, was
found to remain the same even after the third cycle (the catalyst was used 3 times and regenerated for 2
times). On the other hand, Beta-38 catalyst was found to give lower conversion after it is regenerated. This
suggested the irreversible deactivation of active sites on Beta-38 due to formation of hard coke. Modification
of Beta zeolite using ammonium fluoride was found to increase the formation of lubricant oil product but
reduced the viscosity index. Expansion in the pore size of Beta zeolite using sodium hydroxide and CTAB
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was found to have very little effect on the formation of HC20 product and the viscosity index. Loading of HY
zeolite with Ni metal was found to slightly decrease the formation of HC20, but viscosity index remained
almost constant. 90 CHAPTER 5 OLIGOMERIZATION OF 1-DECENE AND MIXED-DECENE OVER
MODIFIED ZIRCONIA 5.1 Introduction Tungstate-zirconia is a highly acidic heterogeneous catalyst for many
application such as hydrocracking109, dehydration110-112 and isomerization96,109,113. This type of
catalyst is also referred to as a bi-functional catalyst with two groups of site; brnsted acid site and the
metallic site27. In addition to the acidic characteristic, zirconium oxide has received remarkable attention
because it interacts strongly with reactant, exhibited high thermal stability and low volume expansion. The
two major phases existed for zirconia metal oxides are tetragonal and monoclinic. In the case of tetragonal-
structured zirconia, the lattice contained octaoordinated Zr4+ and tetracoordinated O2-. In contrast, the
monoclinic lattice contained heptacoordinated Zr4+ cation and tri/tetracoordinated O2-. Tetragonal structured
zirconia have only lewis acidic site, while monoclinic structured zirconia possesses both brnsted acid and
lewis acid site. For isomerization reaction it was reported that a zirconia with tetragonal form is 2 to 5 times
more active than zirconia with monoclinic form. Apart from isomerization it was also found that tetragonal
zirconia is more active than monoclinic zirconia for the synthesis of methanol. Addition of tungstated metal
on zirconia was found to significantly reduce the undesired transformation of tetragonal formed zirconia to
monoclinic formed. 90 91 5.2 Experimental setup For tungstated-zirconia the oligomerization was carried out
in an autoclave at temperature between 150oC to 210oC, amount of catalyst between 5 wt% and 15 wt%
and under the presence of nitrogen (40 psi). The reaction was conducted under inert atmosphere to prevent
the catalyst that is in a reduced state to be in contact with oxygen which could cause the catalyst to be
deactivated.
179In order to activate the catalyst, tungstated-zirconia has to be reduced under
hydrogen atmosphere at 100 psi,
218flow rate of 80 mL/min for 15 hours. The oligomerization was
conducted for 11 hours. Approximately 0.3mL of sample was collected every 30 minutes and 1 hour of the
reaction. For this part of the research, external and internal diffusion is considered. It was found that an
agitation speed of higher than 400 rpm and catalyst particle size between 0.1mm 0.3mm was required in
order to avoid external and internal resistance. The product composition of the oligomer was monitored
using gas chromatograph as described in the appendix.
575.3 Results and discussion 5.3.1 Catalyst characterization
An adsorption/desorption isotherm of tungstated-zirconia was found through N2 sorption technique as

shown in Figure 5.1a. The isotherm represented type VI according to IUPAC standard, which indicate that
the analyzed tungstated- zirconia contained mostly mesopore. The hysteresis loop belong to H1 group
which mean that the pores are cylindrical in shape. It was also found that tungstated- zirconia contained two
different pore sizes, which are roughly 9 nm and 100 nm. 92 500 3 Volumn absorbed (cm
90/g) 400 300 200 100 0 0.0 0.2 0.4 0.6 0.8 1.0 P/Po
72 105 7/6/2560 7:43

(a) 1.0 0.8 dV/dlogD (cm3g-1nm-1) 0.6 0.4 0.2 0.0 1090800700006005004000300200 10908070060504030
20 1098765 4 3 2 Pore diameter (nm) (b) Figure 5.1 Physical characterization of tungstated-zirconia
revealing adsorption and
100desorption isotherm a) and pore-size distribution b). As
shown in Figure 5.2a, XRD pattern revealed six diffraction peaks which corresponded with the tetragonal
phase zirconia. According to the miller 93 index, these peaks indicated the existence of crystallized plane
arrange with (111), (200), (220), (311) and (222) configuration. It was revealed by various researches that
the tetragonal phase is relatively stable compared to the zirconia in the monoclinic phase110,112,114.
Furthermore, it was also reported that the presence of tungstate during the calcination step help prevent the
transformation of tetragonal to monoclinic phase110. Apart from tungstate, it was documented that addition
of both cation and anion such as aluminum and manganese also help preserved the tetragonal phase during
calcination of zirconia catalyst115. NH3 desorption profile of tungstate-zirconia revealed the presence of only
180weak acidic sites on the catalysts surface. These weak acidic sites
or sometimes referred to as lewis acid site are represented by the desorption of NH3 molecule at
temperature between 100oC to 300oC as shown in Figure 5.2b. The acidity concentration was calculated to
be 0.415 mmol per gram catalyst, which is smaller than HY-30 and Mordenite-20 but higher than Beta-38
zeolite. It is expected that an increase in the amount of brnsted acid site on tunstated-zirconia will occur
during the reduction of tungstated-zirconia under the presence of hydrogen gas. This is why the catalytic
activity in terms of 1-decene conversion over tungstated-zirconia was very close to that of HY zeolite even
though the amount of acidity on tungstated- zirconia is significantly lower than HY catalyst. Tungstate metal
on zirconia surface will interact with hydrogen molecule (dissociative adsorption) to form strong acid sites
known as brnsted acid. 94 600 (111) 500 400 Intensity 300 200 (220) (200) (311) 100 (222) 0 10 30 50 70
2 theta (degree) (a) TCD
129intensity (a.u.) 100 150 200 152050 300 350 240000 450 500 255500 600 300
350 Temperature (oC) (b) Figure
5.2 X-ray diffraction pattern profile of tungstated-zirconia a) NH3 desorption profile of tungstated-zirconia b)
95 5.3
136.2 Effect of reaction temperature The effect of reaction temperature on

oligomerization reaction over a period of
11 hours was monitored by gas chromatography. The oligomer products were sampled from the autoclave
every 30 minutes to 1 hour. The consumption of 1-decene at different temperature is shown from 150oC to
210oC. The rate of consumption is fast until 4 hours after the start of the reaction. After 4 hours the rate of
consumption seemed to be steadier and does not change as much over time Figure 5.3a. Figure 5.3b
73 105 7/6/2560 7:43

91show the effect of reaction temperature on the formation of
dimer products. A rapid increase in C20 was found during the first 4 hours of the oligomerization reaction.
For the product collected after 4 hours of reaction, an increase in temperature from 150oC to 210oC was
found to increase the formation of dimers from 11 wt% to 47 wt%. An increase in temperature was found to
cause the formation of trimer to significantly increase as well as shown in Figure 5.3c. A trend line was
constructed based on the experimental data from each operating condition. The equations obtained from
these trend lines are shown from Table 5.1 to Table 5.3. These equation are differentiated to obtain the rate
of reaction at each specific reaction time and used in the next section (simulation of the production of dimers
and trimmers). 96 100
12590 80 Amount of C10 (%) 70 60 50 40 30 20 10 0 150 C 175 C 200 C
210C 60 Amount of C20 (%) 50 40
25330 20 10 0 150 C 175 C 200 C 210 C 70 0
2 4 Retention time (h) (a) 6 8 10 12 0 2 4 6 Retention time (h) 8 10 12 (b) 97 30 150C 25 175C Amount of
C30 (%) 20 200C 210C 15 10 5 0 0 2 4 6 8 10 12 Retention time (h) (c) Figure 5.3
9Effect of temperature on the conversion of 1-decene over tungstated- zirconia

a), amount of C20 b),
and amount of C30 c) at different temperature between 150oC to 200oC. Reaction conditions: Atmospheric
pressure, agitation speed = 400 rpm and 10wt% catalyst 98 Table 5.1 Trend lines equation for the
consumption of C10 used to find the rate of reaction. Curve for Trend lines equation r2 C10: 150oC y =
0.0829x2 - 2.392x + 93.184 0.9929 C10: 175oC y = 0.2327x2 - 5.5729x + 88.649 0.9691 C10: 200oC y =
0.0148x4 - 0.4303x3 + 4.5367x2 - 22.348x + 84.092 0.9986 C10: 210oC y = -13.66ln(x) + 55.228 0.9968
Table 5.2 Trend lines equation for the generation of C20 used to find the rate of reaction. Curve for Trend
lines equation r2 C20: 150oC y = 8.4564ln(x) + 33.69 0.9869 C20: 175oC y = 7.169ln(x) + 26.55 0.9777
C20: 200oC y = 6.548ln(x) + 14.835 0.9446 C20: 210oC y = 2.0487ln(x) + 9.4845 0.939 Table 5.3 Trend
lines equation for the generation of C30 used to find the rate of reaction. Curve for Trend lines equation r2
C30: 150oC y = 10.527x0.3585 0.9665 C30: 175oC y = 9.2276x0.3823 0.9842 C30: 200oC y =
4.6539x0.4897 0.9949 C30: 210oC y = 2.7642x0.6007 0.992 99 5.3.3 Effect of catalyst amount The amount
of tungstated-zirconia used was varied from 5 wt% to 15 wt% while the reaction remained constant. The
consumption of 1-decene was found to be affected by the amount of catalyst after 6 hours of reaction as
shown Figure 5.4 a. Oligomerization reaction conducted with 5 wt% catalyst caused the rate of 1-decene
consumption to decrease after 6 hours of reaction. The amount of dimers are also affected by the amount of
catalyst. Formation of dimers over 5wt% yielded the most dimers. A reduction in the amount of dimers
molecule in the product collected 8 hours after reaction from approximately 57 wt% to 47 wt% when the
amount of catalyst increase from 5
74 105 7/6/2560 7:43

257wt% to 15 wt% as shown in Figure 5.4b. On the
other hand,
1an increase in the amount catalyst from 5 wt% to 10 wt% caused the
formation of trimmers to increase significantly from 17.8 wt% to 26.8 wt% as shown in Figure 5.4c. 70 60 5
(wt%) Amount of C10 (%) 50 10 (wt%) 15 (wt%) 40 30 20 10 0 0 2 4 6 8 10 12 Retention time (h) (a) 100 60
Amount of C20 (%) 50 40 30 20 10 5 (wt%) 10 (wt%) 15 (wt%) 37 0 2 4 6 Retention time (h) (b) 8 10 12
Amount of C30 (%) 32 27 22 17 12 7 2 5 (wt%) 10 (wt%) 15 (wt%) 0
1622 4 6 Retention time (h) 8 10 12 (c) Figure 5. 4 Effect of the
amount of tungstated-zirconia on the conversion of 1-decene a), amount of C20 b), and amount of C30 c) at
different temperature between 150oC to 200oC. Reaction conditions: Temperature = 200oC, atmospheric
pressure, agitation speed = 400 rpm and 10wt% catalyst 101 A trend line equation for each curve is
obtained by fitting with various mathematical model such as linear, quadratic and decay and shown in Table
5.1 to 5.3. 5.3.4 Product characterization 5.3.4.1 Viscosity measurement The heavier oligomers fraction or
the lubricant oil samples obtained after distillation were analyzed by ASTM D2270 standard. The viscosities
of lubricant samples were analyzed at 40oC and 100oC in order to calculate the viscosity index.
91Figure 5. 3 shows the relationship between the viscosity index and the amount
of
heavier oligomers fraction (HC20 = C30 + C40) oligomerization reaction over zeolite catalysts and
tungstated-zirconia. The raw materials used are commercial olefins with 95% 1-decene and synthesized
olefins with 45% 1-decene (55% internal decene). Results, as shown in Figure, suggested that that viscosity
index of the lubricant oil is inversely proportional to the amount of heavier oligomers (HC20) produced over
zeolite catalysts. A reduction in the composition of 1-decene
198(increase in the amount of internal decene) also resulted in a decrease
in viscosity index as shown by the red dash line curve. Similar to the 95% 1-decene feedstock, a decrease in
viscosity index from 45% 1-decene feedstock was accompanied with an increase in HC20 composition. In
contrary to the results obtained from zeolite catalysts, the amount of HC20 produced over tungstated-
zirconia was not affected by the viscosity index of the lubricant. According to Figure 5.3, the viscosity index
of HC20 fraction remained around 107 even though the amount of HC20 (wt%) over tungstatedzirconia
catalyst increased from 20 wt% to almost 50 wt%. 102 160 150 =Zeolite catalysts =Zeolite catalysts (Feed
95% and 98%) (Feed 45%) 140 =Tungstated-zirconia VI Index 130 (Feed 95.0%) 120 110 100 90 80 0 10 20
30 40 50 HC20 (%wt.) Figure 5.5 Relationship between the VI index and the amount of HC20 (wt%.) in the
product from oligomerization over zeolite and tungstated-zirconia. 5.3.4.2 FTIR analsysis In addition to the
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viscosity measurement, the oligomer products in the range of lubricant oil (HC20) before and after
hydrogenation were analysis by the FTIR method. This method is used to detect the structural changes in
the oligomer molecule after the hydrogenation reaction over 1%Pt on alumina catalyst. The analysis is to
observe whether there are any olefin molecule remaining in the oligomer product or not after the
hydrogenation
241process. As shown in Figure 5. 4, the oligomer product
before hydrogenation contained peak at approximately 1,750 cm-1 and 900 cm-1. These two peaks
represented the presence of C=C alkene stretch and alkene sp2 bend bond inside the oligomer molecule. A
clearer images of these peaks are depicted in Figure 5.5a and 5.5b. 103 TZ after Hydrogenation T (%) TZ
Before Hydrogenation C=C Alkene sp2 Stretch alkene C-C
149bend 4000 3600 3200 2800 2400 2000 1600 1200 800 400 v (cm-1) Figure
5.6 FTIR analysis of the oligomer product from TZ catalyst before and after hydrogenation reaction. The
dashed box are zoom and depicted in Figure 5.5 a and b. Before hydrogenation After hydrogenation T (%)
C=C T (%) C=C
1032000 1600 1200 v (cm-1) 800 400 2000 1600 1200 v (cm-1) 800 400 (a) (b)
Figure
5.7 Zoomed image of oligomer product before hydrogenation (a) and after hydrogenation (b). 104 5.3.4.3
Structural investigation using C13-NMR technique The molecular structure of olefins feedstock and the
oligomer products are analyzed by C13-NMR. As shown in Figure 5.6, each peak on the C13- NMR
spectrum correspond to carbon atoms that is part of different kind of molecular with different structure. A
C13-NMR spectrum of the 1-decene feedstock obtained from Aldrich Company is shown in Figure 5.7. It can
be observed that the carbon attached to a double bond is presented by the peaks at 115 ppm and 140 ppm.
However, for the analyzed product obtained from dehydration reaction, the C13-NMR spectrum contained a
peak representing an alcohol molecule as shown in Figure 5.8. This corresponded to the residual 1-decanol
that was not converted during the previous dehydration reaction. Figure 5.9 demonstrated a C13-NMR
spectrum of linear hydrocarbon with 15 to 18 carbon atoms. The five peaks corresponded to the long chain
linear structure without any short or long structural branches. Peak number 1 represent the terminal carbon.
These peaks also appeared on the spectrum of C13-NMR analysis on other oligomerization products.
According to the C13-NMR spectrums of different lubricant oil shown in Figure 5.10 to Figure 5.12, it is
revealed that the lubricant oil synthesized from heterogeneous acid catalyst contained more peaks
compared to results from the commercial polyalpha-olefin (PAO). This indicated the complex structure of the
lubricant oil synthesized over solid acid catalyst. The major peaks that appear in each spectrum are the
peaks located at 14 ppm (First position ; representing the carbon in the R-CH3 or the methyl group), peak
at 22.6 ppm (second position ; representing the carbon in the CH2 or the methylene group) and the peak
at 32 ppm (third position ; also representing the carbon of a methylene group). However, the peak at 32
ppm is deviated from 22.6 ppm because the electrons inside carbon are shifted toward the adjacent
carbon. Other peaks on the synthesized lubricant oil spectrum such as 19.8 ppm (Figure 5.6c,d and e), 24.5
ppm (configuration or as shown in Figure 5.6f) and 37 ppm (carbon adjacent to the short branch). These
76 105 7/6/2560 7:43

peaks are the location of the peak that represents branched-chain in the molecule. 105
172(a) (b) (c) (d) (e) (f) (g) Figure 5.8
Correlation between location of peaks on the spectrum and structure of the molecule for iso
76-1 (a) , iso -2 (b) iso -3 (c) iso -4 (d) iso -5 (e)
iso-6 (f) and iso-7 (g) 116 In addition to the peaks shown above which indicate various structural
configuration, another piece of important information that can be observed from these spectrum is the
presence of naphthenic acid in the product. The range of chemical shifts that correspond to this naphthenic
acid is between 25 to 40 ppm. As shown in the C13-NMR spectrum below it can be observed that the
baseline of the curve does not touch the x-axis116. A research was conducted to eliminate the presence of
naphthenic acid through the decarboxylation reaction over different alkaline catalyst such as ZnO, MgO and
CaO at 300oC 117. 106 I-Decene.001
24.001.1r.esp 0.45 C= 0.40 Normalized Intensity 0.
35 Alkane group 0.30 0.25 C= 0.20 0.15 0.10 Reference 0.05 140 130 120 110 100 90 80 70 60 50 40 30 20
10 Chemical Shift (ppm) Figure 5.9 C13-NMR of the commercial 95% 1-decene. AlSa-D.001.001.1r.esp C=
0.45 0.40 Alkane group Normalized Intensity 0.35 0.30 C = 0.25 0.20 Refe rence 0.15 0.10 Alcohol 0.05 140
130 120 110 100 90 80 70 60 50 40 30 20 10 Chemical Shift (ppm) Figure 5.10 C13-NMR of product
obtained from dehydration reaction (containing 1- decene and 1-decanol). 107 n-BHD.001.001.1r.esp n 0.45
0.40 Normalized Intensity 0.35 0.30 0.25 0.20 3 2 1 0.15 0.10 0.05 40 35 30 25 20 15 10 Chemical Shift
(ppm) Figure 5.11 C13-NMR of linear hydrocarbon with 15 to 18 carbon atoms TZ200.001.001.1r.esp 2 0.45
3 n 1 0.40 Normalized Intensity 0.35 0.30 0.25 0.20 0.15 0.10 0.05 40 35 30 25 20 15 10 Chemical Shift
(ppm) Figure 5.12 C13-NMR product collected from oligomerization over 10%wt. tungstated-zirconia at
200oC and atmospheric pressure. 108 PN17TFLC20.001.001.1r.esp 3 n 0.45 2 1 0.40 Normalized Intensity
0.35 0.30 0.25 0.20 0.15 0.10 0.05 40 35 30 25 20 15 10 Chemical Shift (ppm) Figure 5.13 C13-NMR
product collected from oligomerization over 10%wt. HY-30 at 200oC and atmospheric pressure. n 2 1 3
Figure 5.14 C13-NMR of the product collected from oligomerization over 10%wt. Beta-38 at 200oC and
atmospheric pressure. The structure of the lubricant molecule has
252a significant influence on the viscosity index of the lubricant oil. The
two important parameters obtained from C13-NMR are the short-chain branching (%) and the branching
ratio, which can be calculated by equation Eq
56.C.1 and Eq .C.2 as shown in Appendix C.
The relationship between viscosity index and branching ratio and short-chain branching is shown in Figure
5.13 and Figure 5.14. It was revealed that the increase in the percentage of 109 short-chain branching
77 105 7/6/2560 7:43

cause the viscosity index of lubricant oil to decrease linearly. Additionally, an increase in branching ratio also
causes a decrease in viscosity index. This corresponded to other literature which suggested that an increase
in branching structure cause the viscosity to decrease significantly29. 150 140 143.0 VI Index 130 123.7
124.0 123.0 120 122.0 110 107.8 100 104.0 25.0 30.0 35.0 40.0 45.0 50.0 Short-chain branching (%) Figure
5.15 Relationship between the VI index of the lubricant product and short- chain branching (%). 150 140
143.0 VI Index 130 123.0 123.7 120 124.0 122.0 110 107.8 104.0 100 0.04 0.06 0.08 0.10 0.12 0.14
Branching ratio Figure 5.16 Relationship between the VI index of the lubricant product and branching ratio.
110 5.4 Conclusion Oligomerization of 1-decene over tungstated zirconia inside an autoclave was found to
be effective in the production of heavier hydrocarbons. Similar to zeolite catalyst,
1an increase in temperature and the amount of catalyst was found to increase
the conversion of
1-decene and the amount of oligomer in the products. The trend lines equation of the
1conversion of 1-decene and product formation
over time can be obtained and used to calculate the rate of reaction. An increase in conversion of 1- decene
was found to decrease the viscosity index of the oligomer products. When FTIR was used to analyze the
oligomer product, two peaks representing C=C bond were detected. These two peaks disappeared almost
completely after the oligomer products (heavier oligomers) were subjected to the hydrogenation reaction
over 0.5Pt/Al2O3. The structure of the oligomer molecule was also investigated by the C13-NMR method. It
was revealed that an increase in the percentage of short-chain and branch ratio caused the viscosity index
of the oligomer product to significantly decrease. 111 CHAPTER 6 MICRO-KINETIC MODELLING
OLIGOMERIZATION REACTION OVER HETEROGENEOUS REACTION 6.1 Introduction Oligomerization
reaction combined monomers into higher molecular weight oligomer. In the field of the petrochemical
industry oligomerization has been employed to increase the size of small
250olefins such as 1-butene, 1-petene and 1- hexene
for
132transportation fuels such as gasoline and diesel.
The smaller olefins are undesirably generated
132from the catalytic cracking unit. A
successful production of oligomer from these smaller olefins would mean an increase in desirable products,
which can increase the income of the refineries. However, in order for the process to be successful on an
industrial-scale, a model that reflect and simulate the mechanism of the oligomerization reaction should be
78 105 7/6/2560 7:43

derived first. Since oligomerization reaction is carried out over a heterogeneous acid catalyst, a kinetic
model representing the adsorption, surface reaction and desorption have been formulated. This model is
usually described by the Langmuir-Hinshelwood-Hougen-Watson mechanism. The interaction between
reactant and the active sites can be found by setting up different rate equations with different set of
assumptions. The rate equation that gives the closest rate compared to experimental data is the one with
the higher R2 value. This also means the interaction that is being modeled by this rate equation is very
accurate. Apart from revealing the interaction between the reactant and the active sites, kinetic modeling
also provide the value of coefficients that are necessary 111 112 for performing simulation of the reaction.
The value of coefficients are found by performing non-linear regression of the experimental data with the
rate equations. The arrenhnius equation (equation 6.1) was used to calculate the apparent activation energy
for the dimerization and trimerization reaction. As shown in Figure 6.1, the arrenhnius plot revealed
56a linear relationship between rate of reaction and the reciprocal of

temperature.
ln r ? Ao ? Ea ( ) 1 R T Eq.6.1 The
6apparent activation energy derived for dimerization reaction was found to be

210.5 kJ/mol. For trimerization the
96apparent activation energy was found to be 33 0. 6 kJ/mol.
4.0 3.8 Dimerization Trimerization 3.6 3.4 Ln(ri) 3.2 y = -4029.1x + 12.001 R = 0.9929 3.0 2.8 2.6 y =
-2536.6x + 8.421 2.4 R = 0.9994 2.2 2.0 0.0021 0.0021 0.0022 0.0022 0.0023 0.0023 0.0024 0.0024 1/T
(K) Figure 6.1 Activation energy for dimerization and trimerization 6.2 Kinetic modeling formation Formation
of the rate equation is an essential part of the kinetic modeling or the simulation of a specific type of
reaction. Apart from finding out the rate equations, kinetic modeling also offers an understanding into the
mechanism of the 113 reaction over heterogeneous catalyst. For this catalyst the micro-kinetic modeling can
be described by the
88Langmuir-Hinshelwood-Hougen-Watson mechanism (LHHW), which involved

the adsorption, surface reaction and desorption of
reactant and oligomer products. The derivation of rate equation is performed assuming the follow condition
to be true. a) The rate of adsorption and desorption happened very fast compared to the reaction that is
occurring on the catalyst surface. Consequently, the rate of
6surface reaction is considered as a rate- determining step and irreversible. The
desorption and adsorption are assumed to be quasi-equilibrated and shown from Eq.6.2 Eq.6.4. b) For this
kinetic-modeling 1-decene (C10=) is used as the feedstock. The products are residual 1-decene, dimers
79 105 7/6/2560 7:43

hydrocarbon (C20), and trimers hydrocarbon (C30). c) Two different types of reaction existed. The first type
assumed that the amount of empty site suitable for reaction is very small. Consequently, the denominator of
the rate equation will not have a unity. This first type of reaction is referred to as group a. d) The maximum
number of active sites involved for dimerization reaction was set up to three sites. Consequently, the
exponent n in the denominator can be either 1, 2 or 3. e) In the case of trimerization, the maximum number
of active acidic site was assume to be from one to four. Consequently, the exponent n in the denominator
can be either 1, 2, 3 or 4. 114 f) Dimerization reaction occurred through the combination of 1-decene as
shown in equation 6.5. This reaction is assumed to follow the eley-rideal mechanism where the adsorbed
1-decene reacted with another 1-decene in the bulk system. g) For this experiment two distinct surface
reaction models were proposed. The first model assumes that the trimerization reaction happen through
combination of three 1-decene molecules (C10= + C10= + C10=). The second model assumes that a
reactant molecule is reacted with a dimer (C10= + C20). h) Two surface reaction models were proposed to
understand how trimerization reaction takes place over acid heterogeneous catalyst. Trimerization reaction
can occur through either the combination of three reactant molecules (mechanism 1 which is referred as T1
in equation 6.6) or one reactant molecule with a dimer (mechanism 2 which is referred as T2 in equation
6.7). 1. Absorption M10= + E M10=E , [10= E] = [10=][] (6.2) 2. Desorption DiE Di + E ,
, = [[][]] , , = 1 , (6.3) TiE Ti +
255E , , = [][ ] [ ] , , = 1 ,
(6.4) 3. Dimerization 10= E + 10= DiE , 1 = 1[10= ][10=] (6.5) 4. Trimerization T1: M= E +
2(10=) TE , 2.1 = 2.1[10= ][10=] 2 (6.6) T2: DiE + 10= TiE , 2.2 = 2.2[ ][10=]
(6.7) 115 The rate of equation for the dimerization and trimerization reaction assuming either mechanism 1
and mechanism 2 can be calculated by the equation whitening
153in Table 6.1 and Table 6.2. Table 6.1
Rate equations derived from the assumption above for dimerization over tungstated-zirconia. Only one
mechanism is assumed for the dimerization: C10=+C10= DI n=1,2 or 3 Mechanism 1 a 1[10=]2
,1 = (1 + [10=] + ,[] + ,[]) b 1[10=]2 ,1 = ([10=] + ,[] +
,[]) (D1a) (D1b) Table 6.2 Rate equations derived from the assumption for trimerization over
tungstated-zirconia (Mechanism 1: C10= + C10= + C10= Ti, Mechanism 2: DI + C10= Ti) n = 1,2,3 or 4
Mechanism 1 2.1[10=]3 a 1 = (1 + [10=] + ,[] + []) (T1a) b ,1 ([10=]
+ ,[] + ,[]) = 2.1[10=]3 (T1b) Mechanism 2 a 2.2,[10=] [] ,2 = (1 +
[10=] + ,[] + ,[]) b 2.2,[10=] [] ,2 = ([10=] + ,[] + ,[
(T2b) (T2b) ( ( 116 The parameters for kinetic consideration can be obtained for each model by non-linear
regression employing the Levenberg-Marquardt algorithm. This algorithm was used to minimize the
objective function shown in equation 6.8. LA ? ?(ri,texperiment ? ri,tequation )2 t Eq 6.8 where ri,texperiment
and ri,tequation are the data from experiment and calculated (from equations in Table 6.1 and Table 6.2)
reaction rate, i is either dimer or trimer and t is the reaction time. The measurement of fitness between
experimental data and the equation from each kinetic model is calculated to by the level of fitness which
included the coefficient of determination (R2) and the variance (S2N) as shown in equation 6.9. R2 Level of
fitness = S2N Eq. 6.9 The coefficient of determination (R2) as shown above, demonstrate a general concept
of the number of experimental data point that is similar to the one calculated by the rate equation formula.
Variance is also used in the level of fitness to evaluate the deviation of the experimental data from the
80 105 7/6/2560 7:43

calculated data. n r ? i?1 ? ri,texperiment n Eq. 6.10 5 Eq. 6.11 S2N ? 1 n n ?1 i?1 ? (ri,tequation ? r) Eq.
6.12 6.3 Kinetic modelling results 117 In order to calculate the rate of dimerization and trimerization, the
derivative of the amount of dimers and trimer formed within a period of time was taken (specifically the
derivatives are taken from the curve equations in Table 5.1 to 5.3).These curve equations were initially
obtained by plotting and fitting the concentration of products collect using various mathematic functions such
as exponential quadratic, decay, and linear. The level of fitting for the dimerization reaction revealed that the
unity on the denominator should be eliminated, which indicate that the emptied site should not be
considered in the model. The negative sign on top of some columns ine Figure 6.2 indicate that the model
gave a negative kinetic equilibrium constant, which is physically impossible, therefore they are discarded.
The highest level of fitness for oligomerization reaction that gave positive kinetic coefficients at 150oC and
175oC belonged to the model that assumed that two active sites are required; this model is referred to as
the D1b(n=2) as shown in Figure 6.2. At higher temperature (200oC and 210oC) three available sites are
required during surface reaction. This increase in the number of site from 2 to 3 may have occurred because
at higher temperature the rate of coke or polyaromatic formation is also higher. Consequently, formation of
245coke is the main reason for the catalyst
deactivation. Therefore, an additional site needs to be available immediately if deactivation takes place. As
shown in Figure 6.2, some models exhibited very high level of fitness, which implied that the value of R2 for
these models have to be very close to 1. However, these models contained negative kinetic equilibrium so
they are discarded. 118 0.50 0.45 421530KoC 414785KoC 0.40 472030KoC 482310KoC Level of Fitness
0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 D1a
142(n=1) D1a (n=2) D1a (n=3) D1b (n=1) D1b (n=2) D1b (n=3)
Model Figure 6.2 Level of fitness corresponding to the estimation of the rate of equation for dimerization
assuming mechanism 1 (D1). D1a (group a) also assumes that the unoccupied sites available for
dimerization reaction are relatively small compared to the site that is occupied. There are two models
considered for trimerization reaction over tungstated-zirconia. The level of fitness shown in Figure 6.3 and
Figure 6.4 suggested that mechanism 2, where a dimer interacted with a monomer, is the most accurate
model. The trimerization reaction also assumed that the free sites on the catalyst are negligible, which is
why the adsorption unity in the denominator is eliminated. According to Figure 6.4, the model equation for
reaction at 150oC and 175oC gave the highest level of fitness when n=3.
231On the other hand, the trimerization reaction operated at higher temperature
(200oC and 210oC) required active site to increase from three to four. An increase in active site required at
150oC and 175oC from two for dimerization reaction to three for trimerization reaction was also observed by
other researchers. After performing non-linear regression of the experimental data and the calculated data,
the kinetic constant and equilibrium results are obtained and shown in Table 6.3 for dimerization reaction
and in Table 6.4 for trimerization reaction. For both reactions
203it can be observed that the kinetic constant increased with reaction 119
81 105 7/6/2560 7:43

temperature.
For dimerization reaction the equilibrium constant of adsorption also increase with temperature. The result
indicated that adsorption of olefin feedstock is favorable at higher temperature. This explained why the
3increase in temperature cause an increase in catalytic activity. For trimerization

reaction, the
mechanism that is most accurate involved the reaction between dimer oligomers and 1-decene monomer.
According to Figure 6.3 and Figure 6.4, the level of fitness derived from mechanism 2 is clearly higher than
the level of fitness obtained from mechanism 1. After non-linear regression of the experimental data with the
rate equation, it was found that three active site is required for the oligomerization reaction at lower
temperature. The number of active sites required for oligomerization at higher temperature increases from
three to four. According to Table 6.4,
237rate constant for the trimerization reaction increases with temperature. On the
other hand, an increase in temperature cause the equilibrium constant of adsorption and desorption to
decrease continuously. A reduction in the equilibrium constant of desorption suggested that there is rapid
formation of soft and hard coke during the oligomerization. The experimental data were plotted with the
calculated data obtained from the rate equation that is derived from mechanism 2. As shown
210in Figure 6. 5 to Figure 6. 8, the calculated data (based on the
assumption that trimerization reaction occur through combination of a dimer and a monomer) correlated well
with the data obtained from the experiment. The value of R2 for each non-linear regression is higher than
0.99. 120 0.40 0.35 421350KoC 424080KoC 471375KoC 428130oKC Level of Fitness 0.30 0.25 0.20 0.15
0.10 0.05 0.00 T1a
35(n=1) T1a (n=2) T1a (n= 3) T1a(n=4) T1b(n=1) T1b (n= 2) T1b (n= 3) T1b (n=4)
Model Figure 6.3 Level of fitness corresponding to the estimation of the rate of equation for trimerization
assuming mechanism 1 (T1). T1a (group a) also assumes that the unoccupied sites available for
trimerization reaction are relatively small compared to the site that is occupied. 1.40 1.20 412530KoC
414875KoC Level of Fitness 1.00 427030KoC 428130KoC 0.80 0.60 0.40 0.20 0.00 T2a
35(n=1) T2a (n=2) T2a (n= 3) T2a (n=4) T2b (n=1) T2b (n= 2) T2b (n= 3) T2b (n=4)
Model Figure 6.4 Level of fitness corresponding to the estimation of the rate of equation for trimerization
assuming mechanism 2 (T2). T2a (group a) also assumes that the unoccupied sites available for
trimerization reaction are relatively small compared to the site that is occupied. 121 Table 6.3 Estimated
82 105 7/6/2560 7:43

parameters and equilibrium constant from D1b(n=2) at lower temperature (150oC and 175oC ) and
D1b(n=3) at higher temperature (200 oC and 210 oC) for dimerization reaction Parameters 150 oC 175 oC
200 oC 210 oC k1 1.031 ? 0.052 6.441 ? 0.149 7.827 ? 0.190 16.598 ? 0.397 KAD 0.016 ? 0.004 0.029 ?
0.007 0.050 ? 0.010 0.061 ? 0.003 KDi 13.70 ? 0.184 3.759 ? 0.154 3.472 ? 0.414 2.506 ? 0.595 Table 6.4
Estimated parameters and equilibrium constant from T2b(n=3) at lower temperature (150 oC and 175 oC)
and T2b(n=4) at higher temperature (200 oC and 210 oC) for trimerization reaction. Parameter s 150 oC 175
oC 200 oC 210 oC k2.2 15.15 ? 0.369 20.91 ? 1.170 28.17.012?5 0.207 31.48 ? KAD 0.016 ? 0.004 0.029 ?
0.007 0.005.000?3 0.010 0.061 ? KDi 13.70 ? 0.184 3.759 ? 0.154 3.472 ? 0.414 2.506 ? 0.595 KTi 0.117 ?
0.053 1.066 ? 0.151 1.263 ? 0.073 4.525 ? 0.015 122 90 Rate of dimerization (mol/g-h) 80 70 42135K0oC
60 44187K5oC 50 40 30 20 10 0 2 2.5 3 3.5 4 4.5 5 5.5 Concentration [M10=] Figure 6.5 Plotting
experimental data (symbol) with the calculated rate of dimerization (dash line) at lower temperature range. r
=k1*KAD*[M10=]2/(KAD*[M10=]+[Di]*KDi+KTi*[Ti])2 300 Rate of dimerization (mol/g-h) 250 472300KoC
482310KoC 200 150 100 50 0 0 1 2 3 4 5 Concentration [M10=] Figure 6.6 Plotting experimental data
(symbol) with the calculated rate of dimerization (dash line) at lower temperature range r=k1*KAD*
[M10=]2/(KAD*[M10=]+[Di]*KDi+KTi*[Ti])3 123 45 Rate of dimerization (mol/g-h) 40 42135K0oC 35
44187K5oC 30 25 20 15 10 5 0 2 2.5 3 3.5 4 4.5 5 5.5 Concentration [M10=] Figure 6.7 Plotting
experimental data (symbol) with the calculated rate of trimerization (dash line) at lower temperature range r
=k2.2*KDi*[DI]*[M0=]/(KAD*[M10=]+[Di]*KDI+KTi*[Ti])3 300 Rate of dimerization (mol/g-h) 250 472300KoC
200 482310KoC 150 100 50 0 1 1.5 2 2.5 3 3.5 4 4.5 5 Concentration [M10=] Figure 6.8 Plotting
experimental data (symbol) with the calculated rate of trimerization (dash line) at higher temperature range r
=k2.2*KDI*[Di]*[M10=]/(KAD*[M10=]+[Di]*KDi+KTi*[Ti])4 124 6.4 Conclusion After conducting the
experiment over tungstated-zirconia, it was found that the apparent activation energy for was 21 ? 0
244.5 kJ/mol and 33 ? 0.6 kJ/mol for dimerization and trimerization. The
results of the kinetic modeling of 1-decene oligomerization reaction revealed that there are two sites
involved during the reaction conducted at lower temperature (150oC and 175oC) and three sites at higher
reaction temperature (200oC and 210oC). For trimerization it was found that the mechanism involving the
combination of a dimer and a monomer gave the rate equation that can obtain results that are closest to the
experimental data. Three active sites are required for trimerization at lower temperature and four active sites
are required at higher temperature. The model suggested that the vacant sites should not because included
in the equation. This is because
155the number of vacant sites is very small compared to the number of
active sites that are occupied by 1-decene and oligomer products. The formulated rate equations for
oligomerization of 1-decene over tungstated-zirconia can be used to simulate production of oligomers in the
future. 125 CHAPTER 7 CONCLUSION An increase in demand for transportation fuel, lubricant oil with
better quality and awareness of the environmental impact, was discussed in chapter 1. These goals can be
accomplished through oligomerization of 1-decene to dimer and trimmers. Dimers hydrocarbon with 20
carbon atoms fall in the range of diesel oil, which can be used as transportation fuel. Trimers or heavier
hydrocarbon can be used as lubricant oil for vehicle engines. Although the usage of heterogeneous acid
catalyst for oligomerization of alpha olefins have been studied by many researchers, very
259little is known about the oligomerization of
83 105 7/6/2560 7:43

higher olefin, such as 1-decene. Additionally, the
217effect of operating conditions on the catalytic activity for oligomerization of
higher olefin have not been explored. Furthermore, the mechanism regarding oligomerization of 1-decene
on catalysts surface is also not fully understood. There are only some researches on kinetic modelling of the
oligomerization reaction. However, as described in Chapter 2, these researches provided only information
on the mechanism of olefin with smaller molecule. Chapter 2 also compared kinetic data, such as rate
constant and equilibrium, obtained from modelling over zeolite catalyst. A detailed literature review on
zeolites and characterization of heterogeneous catalyst in general was also provided in Chapter 2. In prior to
the usage of zeolite for oligomerization reaction, the zeolite catalyst need to be calcined first. Tungstated-
zirconia was reduced first under the presence of hydrogen before used for oligomerization. The
oligomerization reaction was conducted in either a batch glass reactor or an autocalve. Physical and
chemical characterization revealed that Beta and Mordenite- 20 catalyst belong to group I according to
IUPAC standard, which indicate that they are microporous. On the other hand, HY zeolite catalyst was found
to contain a certain degree of mesoporsity, which is indicated
51by the presence of a hysteresis loop in the adsorption/desorption isotherm.
NH3 desorption profiles
3revealed the existence of both lewis and brnsted acid
site on HY and Mordenite-20 catalysts surface. HY zeolite catalyst contained the highest value of total
acidity, while Beta zeolite catalyst contained the lowest value of total acidity. The effect of catalysts 125 126
acidity was also revealed in chapter 4. An increase in acidic was found to improve the catalytic activity of the
catalyst. For this reason, HY zeolite catalyst with the highest total acidity gave the highest conversion of
1-decene. Oligomerization of 1- decene at various reaction temperature and various amount of catalyst were
also conducted. It was revealed that the reaction temperature and the amount of catalyst has a significant
effect
1on the conversion of 1-decene and composition of the oligomer products.
25An increase in temperature was found to cause an increase in conversion of
1-decene over the three different catalysts. Oligomerization of 1-decene over tungstate-zirconia was
investigated and reported in chapter 5. Characterization of tungstated-zirconia through x-ray diffraction
revealed that zirconia is in tetragonal phase. Adsorption and desorption isotherm of tungstated-zirconia
suggested that the pores are mesopores. Pore size distribution profile revealed two remarkable peaks
representing pores with 7 nm and 100 nm diameter.
84 105 7/6/2560 7:43

25An increase in temperature was also found to increase the conversion of
1-decene and composition of heavy oligomer in the product. The experimental data was used to obtain the
rate equation through non-linear regression in chapter 6. Trimerization reaction was found to occur through
the combination of dimer and monomer molecules. Dimerization at
147low and high reaction temperature required
2 and 3 active sites. Trimerization at
147low and high reaction temperature required
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43APPENDICES Comment [m12]: Using 14 point bold font wi an uppercase in

each alphabet 136 APPENDIX A
101 105 7/6/2560 7:43

Gas chromatography analysis A1. Analysis of production using gas chromatography (GC) The purpose of a
gas chromatography is to find the composition of the oligomer product obtained from oligomerization
reaction. Therefore, the standard solution or the boiling point calibration sample #1 kit, obtained from Agilent
Company, need to be analyzed first. The standard solution contained from hydrocarbon with five carbon
atoms (n-pentane; C5) to hydrocarbon with forty carbon atoms (n-tetracaontane; C40). The standard
solution (0.05g) is then mixed with the 1mL of stock solution, consisting of isopropanol and C13 hydrocarbon
as internal standard (concentration 10mg/mL). The combined solution is then injected into the GC. The
analysis of the standard solution is shown in the gas chromatogram in Figure. The area of each peak that is
obtained from the GC profile of the standard solution is shown in Table. The certificate of analysis offered by
the company contained the composition of each hydrocarbon as shown in table. The response factor of
each hydrocarbon is obtained by equation A
5.1. Comment [m13]: Using 14 point bold font wi an uppercase in each

alphabet
Rf ? Area(Ci)?Mass(Ci) Area(I)?Mass(I) Eq.A.1 136 137 C5 C6 C7 C12 C16 C8 C9 C10 C14 C17 C11 C15
C18 C20 C24 C28 C3 C36 C40 2 Figure A.1 Gas chromatogram of the boiling point calibration sample #1
Kit (Agilent) Table A.1 List of hydrocarbon and the area according to the gas chromatogram No. Compound
Carbon Retention Time Area% 1 n-pentane C5 1.378 4.83071 2 n-hexane C6 1.497 3.41351 3 n-heptane
C7 1.823 4.00905 4 n-octane C8 2.65 4.28878 5 n-nonane C9 4.119 4.61932 6 n-decane C10 5.476
9.76781 7 n-undecane C11 6.337 4.99657 8 n-deodecane C12 7.416 21.84291 9 n-tetradecane C14 8.666
10.88089 10 n-pentadecane C15 9.19 5.4494 11 n-hexadecane C16 9.879 11.32794 12 n-heptadecane C17
10.353 5.61567 13 n-octadecane C18 10.783 2.40621 14 n-eicosane C20 11.671 1.43126 15 n-tetracosane
C24 13.311 1.03475 16 n-octacosane C28 14.746 1.05291 17 n-dotriacontane C32 15.998 1.0395 18
n-hexatriacontane C36 17.101 0.96817 19 n-tetracontane C40 18.093 0.90443 138 Figure A.2 Gas
chromatography analysis of standard hydrocarbon mixed with the stock solution Table A.2 Summary of the
response factor of each hydrocarbons contained in the Boiling Point Calibration Sample#1 mixed with stock
solution ( 0.5g n-tridecane isopropanol 50mL) Compound Carbon Retention Time Area Mass Rf
n-heptane C7 1.6640 7200.6011 0.0020 0.9018 n-octane C8 2.3560 8235.5859 0.0021 0.9642 n-nonane C9
3.8320 9059.9727 0.0023 0.9848 n-decane C10 5.1520 19175.2000 0.0049 0.9857 n-undecane C11 6.1340
9915.0352 0.0025 0.9964 n-dodecane C12 7.0300 44319.6000 0.0109 1.0188 n-tridecane C13 7.7530
39831.5000 0.0100 1.0000 n-tetradecane C14 8.3780 20470.0000 0.0054 0.9446 n-pentadecane C15
8.9590 10234.0000 0.0027 0.9430 n-hexadecane C16 9.5540 20531.4000 0.0057 0.9101 n-heptadecane
C17 10.0700 10189.1000 0.0028 0.9110 n-octadecane C18 10.5600 4403.2398 0.0012 0.9188 n-eicosane
C20 11.5020 2550.4102 0.0007 0.8947 n-tetracosane C24 13.1700 1749.2870 0.0005 0.8488 n-octacosane
C28 14.6000 1798.6823 0.0005 0.8578 n-dotriacontane C32 15.8550 2412.0818 0.0005 1.1651
n-hexatriacontane C36 16.9670 2587.1726 0.0005 1.3418 n-tetracontane C40 17.9610 2480.5559 0.0005
1.3771 139 C10 18.15 % Product Collected C20 H-C20 H-C20 65.86% 15.99% Figure A.3 Gas
chromatography analysis of the oligomer product obtained from oligomerization at 200oC over 10 wt%
HY-30 Table A.3 Calculation of the oligomer product composition obtained by GC analysis Alkane Retention
Time Area Rf Composition (%) C10 5.073 25336.3 0.9857 18.15 C18 - C20 10.748 85707.8 0.9188 65.86
C24 - C28 14.004 19420.6 0.8578 15.99 Total 100 140 APPENDIX B Micro-kinetic simulation The rate of
1-decene consumption, production of dimers and production of trimers are obtained from taking the
derivative of the trend line equations shown in Table 5.1 to 5.3. Table B.1 Rate of 1-decene (C10)
consumption obtained by taking derivative of the trendlines equation at reaction temperature between
150oC to 210oC. Time 150oC 175oC 200oC 210oC 0 -0.225 -0.560 -2.281 0.5 -0.217 -0.535 -1.860 -2.756
102 105 7/6/2560 7:43

1 -0.208 -0.510 -1.497 -1.378 1.5 -0.200 -0.485 -1.188 -0.918 2 -0.191 -0.461 -0.929 -0.689 2.5 -0.183
-0.436 -0.716 -0.551 3 -0.174 -0.411 -0.544 -0.459 3.5 -0.166 -0.386 -0.409 -0.393 4 -0.157 -0.362 -0.306
-0.344 4.5 -0.149 -0.337 -0.231 -0.306 5 -0.141 -0.312 -0.181 -0.275 5.5 -0.132 -0.287 -0.150 -0.250 6
-0.124 -0.263 -0.135 -0.229 6.5 -0.115 -0.238 -0.130 -0.212 7 -0.107 -0.213 -0.132 -0.1968 7.5 -0.098 -0.188
-0.137 -0.1837 8 -0.090 -0.164 -0.139 -0.1722 8.5 -0.081 -0.139 -0.135 -0.1621 9 -0.073 -0.114 -0.121
-0.1531 9.5 -0.065 -0.089 -0.091 -0.1450 10 -0.056 -0.065 -0.043 -0.137 10.5 -0.048 -0.040 -0.015 -0.1312
11 -0.039 -0.015 -0.005 -0.1252 140 141 Table B.2 Rate of dimer formation (C20) obtained by taking
derivative of the trendlines equation at reaction temperature between 150oC to 210oC. 150oC 175oC
200oC 210oC 0.1 0.404 2.884 3.655 3.655 0.5 0.166 0.417 0.731 0.858 1 0.114 0.208 0.366 0.429 1.5
0.091 0.139 0.244 0.286 2 0.078 0.104 0.183 0.215 2.5 0.069 0.083 0.146 0.172 3 0.062 0.069 0.122 0.143
3.5 0.057 0.060 0.104 0.123 4 0.053 0.052 0.091 0.107 4.5 0.050 0.046 0.081 0.095 5 0.047 0.042 0.073
0.086 5.5 0.044 0.038 0.066 0.078 6 0.042 0.035 0.061 0.072 6.5 0.040 0.032 0.056 0.066 7 0.039 0.030
0.052 0.061 7.5 0.037 0.028 0.049 0.057 8 0.036 0.026 0.046 0.054 8.5 0.035 0.025 0.043 0.050 9 0.034
0.023 0.041 0.048 9.5 0.033 0.022 0.038 0.045 10 0.032 0.021 0.037 0.043 10.5 0.031 0.020 0.035 0.041 11
0.030 0.019 0.033 0.039 142 Table B.3 Rate of trimers formation (C30) obtained by taking derivative of the tr
end lines equation at reaction temperature between 150oC to 210oC. Time 150oC 175oC 200oC 210oC 0.1
0.179 0.300 0.498 0.773 0.5 0.082 0.139 0.233 0.289 1 0.059 0.100 0.168 0.189 1.5 0.048 0.082 0.139
0.147 2 0.042 0.072 0.121 0.124 2.5 0.038 0.064 0.109 0.108 3 0.035 0.059 0.100 0.096 3.5 0.032 0.055
0.093 0.088 4 0.030 0.051 0.088 0.081 4.5 0.028 0.049 0.083 0.075 5 0.027 0.046 0.079 0.071 5.5 0.026
0.044 0.075 0.067 6 0.025 0.042 0.072 0.063 6.5 0.024 0.041 0.070 0.060 7 0.023 0.039 0.067 0.057 7.5
0.022 0.038 0.065 0.055 8 0.022 0.037 0.063 0.053 8.5 0.021 0.036 0.061 0.051 9 0.020 0.035 0.060 0.049
9.5 0.020 0.034 0.058 0.048 10 0.019 0.033 0.057 0.046 10.5 0.019 0.032 0.056 0.045 11 0.019 0.032 0.054
0.044 143 APPENDIX C C13-NMR analysis The oligomer products were distillated to separate the lubricant
fraction from the dimers and unreacted olefins. The operating conditions used to prepare each lubricant
sample are shown in Table C.1. After distillation the heavier molecules containing C30 and C40 were taken
to be analyzed by C13-NMR. These values are related to the viscosity index of the lubricant oil as shown in
Table C.2. The integral found under the peaks of each C13-NMR analysis can be used to calculate the value
of branching ratio and short-chain branching (%) by using equation C.1 and equation C.2. BR= 15?
(?11-17ppm) [15? (?11-17ppm)]+[14 ? (?18-44ppm) Eq.C.1 SB(%)= ?short-chain methyl ?11-17ppm ?100
Eq.C.2 Table C.1 Operating condition for the production of lubricant oil to be analyzed by C13-NMR No.
Catalyst Amount of catalyst Temperature Reaction time 1 Beta-38 10% 200oC 5 h 2 Beta-38 15% 200oC 5h
3 HY-30 10% 200oC 0.25 h 4 HY-30 15% 200oC 0.25 h 5 Tungstated- zirconia 15% 200oC 11 h 6 Yubase-4
Commercial lubricant 7 Ultra-S4 Commercial lubricant 8 PAO 6 Commercial lubricant 9 PAO 4 Commercial
lubricant 143 144 Table C.2 Integral from C13-NMR analysis of synthesized lubricant oil obtained from
oligomerization reaction (operating conditions shown in Table C.1) No. 11-17ppm 18-44ppm Short-chain
methyl Branching Ratio Short-chain branching VI Integral Integral Integral BR SB (%) 1 1.9 22.7 0.7 0.08
38.1 124.0 2 2 20.3 0.91 0.10 45.5 120.1 3 3.1 27.1 1.45 0.11 46.8 111.5 4 3.4 3.4 25.3 1.6 0.13 107.8 5 8.2
66.5 3.7 0.12 44.5 104.0 6 5.9 110.8 2.6 0.05 44.7 122.0 7 5.9 107.7 2.6 0.06 44.5 123.0 8 1.2 13.5 0.4 0.09
29.4 143.0 9 4.3 43.4 1.5 0.10 35.1 123.7 PAO4.001.001.1r.esp n 0.45 2 1 0.40 Absolute Intensity 0.35 3
0.30 eailz0.20 d0.25 N0.15 mro 0.10 0.05 40 35 30 25 20 15 10
227Chemical Shift (ppm) Figure C.1 C13 -NMR of
commercial group 4 lubricant oil from PTT company 145 Yubase4.001
24.001.1r.esp 0.45 n 0.40 Normalized Intensity 0. 35 0. 30 0. 25 0.
103 105 7/6/2560 7:43

20 3 2 1 0.15 0.10 0.05 40 35 30 25 20 15 10 Chemical Shift (ppm) Figure C.2 C13-NMR of commercial
group 3 lubricant oil from Yubase Company. Ultra-S4.001
24.001.1r.esp 0.45 n 0.40 Normalized Intensity 0. 35 0. 30 0. 25 0.
20 3 2 1 0.15 0.10 0.05 40 35 30 25 20 15 10 Chemical Shift (ppm) Figure C.3 C13-NMR of commercial
group 3 lubricant oil from Ultra Company. 146 APPENDIX D Estimation of acidic using NH3 TPD 1.
Calibration NH3 TPD Table D.1 Calibration of acidity using 4 different loops. Loop volume Micro liter Peak
area Acidic concentration mmol/g 50 2.4134 0.00201 100 8.0507 0.00402 250 28.1741 0.01005 1000
65.6808 0.04022 NNH3 (8.205?1loo0p??5P)?T ?Wcat ? V where NNH3 is the mmol of acidity per weight of
the catalyst, Vloop volume of the loop used for calibration, P is the pressure of the system (1atm),
197T is the temperature of the system and Wcat is the weight of
catalyst sample. A. 50 micro liter Area obtained from the 50 micro litre loop is 2.4134 147 The temperature
used is the room temperature and pressure is 1 atm NNH3 (8.205?5010??150)??9303?0.1 ? 0.02010 mmol
? g B. 100 micro liter Area obtained from the 50 micro litre loop is 8.0507 The temperature used is the room
temperature and pressure is 1 atm NNH3 (8.2051?0100??51)0??3903?0.1 ? ? 0.0402 mmol g C. 250 micro
liter 146 Area obtained from the 50 micro litre loop is 28.1741 The temperature used is the room
temperature and pressure is 1 atm NNH3 (8.2052?5100??51)0??3903?0.1 ? ? 0.1005 mmol g D. 1000
micro liter Area obtained from the 50 micro litre loop is 65.6808 The temperature used is the room
temperature and pressure is 1 atm NNH3 ? 1000?10?9 mmol (8.205?10 )?303?0.1 ?5 ? 0.4022 g 148 0.450
0.400 Acidity concentration (mmol) 0.350 0.300 0.250 0.200 0.150 0.100 0.050 0.000 y = 0.000559x -
0.027790 R = 0.951559 0.0 100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0 TCD Area Figure D.1
Calculation of the acidity of catalyst sample obtained from TCD area 2. Calculation of samples acidity A. HY
catalyst Weak acid area: 851.12 Concentration of acidity is calculated by putting the area value in the trend
line equation shown in Figure D.1 NNH3 ? 0.000056?(Warceata.)- 0.002779 0.00056 (851.12) 0.002779
3 = 0.1 = 0.45 Strong acid area: 424.23 NNH3 0.000056?(Warceata.)- 0.002779 ? 0.00056
(424.23) 0.002779 3 = 0.1 = 0.21 149 Table D.2 Calculation of the acidity of catalyst sample
obtained from TCD area TCD Area Acidity concentration
79(mmol/g) Total acidity (mmol/g) Weak acid Strong acid
Weak acid Strong acid HY 851.12 424.23 0.45 0.21 0.66 Beta 764.02 - 0.40 - 0.40 Mordenite 791.17 108.35
0.42 0.09 0.51 APPENDIX E Zeolite catalyst There are many types of zeolite catalyst with different porous
structure, such as BEA, FAU and MOR. (a) (b) (c) Figure E.1 Modeled framework of FAU (HY), MOR
(mordenite) and BEA (Beta) zeolite catalyst. 150 Table E.1 Structural characteristic of zeolite catalyst Space
Group: Cell Parameters: Channel system a b c BEA P4122 12.632 (90o) 2.632 (90o) 26.186 (90o)
3-dimensional FAU Fd-3m 24.345 (90o) 24.345 (90o) 24.345 (90o) 3-dimensional MOR Cmcm 18.256
(90 o) 20.534 (90 o) 7.542 (90 o) 1-dimensional 149 150 BIOGRAPHY Name Date of Birth
Educational Attainment Mr.Snunkhaem Echaroj March 11, 1988 2017 Comment [m14]: Using 12 point
normal font Scholarship 2015-2017: Researcher assissant Publications 1. Snunkheam Echaroj, Malee
Santikunaporn, Kinetics of 1-decene oligomerization to synthetic fuels and lubricant over a tungstated-
zirconia catalyst. (In progress) 2
104 105 7/6/2560 7:43

1Snunkheam Echaroj, Malee Santikunaporn, Sumaeth Chavadej,
1Oligomerization of 1-decene over sulfated alumina catalysts for the

production of synthetic fuels and lubricants: modelling and verification,
187Reaction Kinetics, Mechanisms and Catalysis. 2016. doi:10.1007/s11144-
017-1164-4
393. Snunkheam Echaroj, Malee Santikunaporn, Sumaeth Chavadej,
32Micro-kinetic modeling of the catalytic dehydration of 1-decanol over

precipitated -Al2O3,
Reaction, Kinetics, Mechanisms and Catalysis. 2015; 114: 75-91.
105 105 7/6/2560 7:43

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