University of Groningen
Biobased products from rubber, jatropha and sunflower oilBin Abu Ghazali, Yusuf
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Biobased products from
rubber, jatropha and sunflower oil
Muhammad Yusuf Abduh
Biobased products from rubber, jatropha and sunflower oil
Muhammad Yusuf Abduh
PhD Thesis
University of Groningen
The Netherlands
The work described in this thesis was conducted at the Department of Chemical
Engineering, University of Groningen and Biotechnology Research Center, Institut
Teknologi Bandung.
This Research Project was financially supported by the Agriculture beyond Food
Program of the Netherlands Scientific Organization (NWO)
Cover design by Muhammad Yusuf Abduh
Cover photo (Skudneshavn, Norway 2013) by Muhammad Yusuf Abduh
Layout by MuhammadYusuf Abduh
ISBN: 978-90-367-7644-8
ISBN: 978-90-367-7643-1 (electronic version)
Biobased products from rubber,
jatropha and sunflower oil
PhD thesis
to obtain the degree of PhD at the
University of Groningen
on the authority of the
Rector Magnificus Prof. E. Sterken
and in accordance with
the decision by the College of Deans.
This thesis will be defended in public on
Friday 27 February 2015 at 16.15 hours
by
Muhammad Yusuf Abduh Bin Abu Ghazali
born on 25 July 1983
in Jakarta, Indonesia
Supervisors
Prof. H.J. Heeres
Prof. R. Manurung
Assessment committee
Prof. S.R.A. Kersten
Prof. M.W.M. Boesten
Prof. A.A. Broekhuis
This thesis would have not been possible without knowledge and hardwork.
Hence, I dedicate this thesis for those who understand knowledge and hardwork,
especially my parents and family
Table of Contents List of Abbreviations ...................................................................................................................................... 1 Chapter 1………………………………………… ....................................................................................................... 3 Introduction………………………………………………………………………………………………………………………....3 1.1 Biobased products ............................................................................................................................................ ……….3 1.2 Biodiesel: an overview ............................................................................................................................................... 4 1.3 Biodiesel feedstock ...................................................................................................................................................... 8 1.3.1 Sunflower oil................................................................................................................................................................ 9 1.3.2 Jatropha oil ................................................................................................................................................................. 10 1.3.3 Rubber seed oil ......................................................................................................................................................... 11 1.4 Seed processing technology ................................................................................................................................... 12 1.4.1 Mechanical pressing .............................................................................................................................................. 12 1.4.2 Solvent extraction ................................................................................................................................................... 13 1.5 Biodiesel production ................................................................................................................................................. 14 1.5.1 Conventional production of biodiesel ........................................................................................................... 14 1.5.1.1 Down- stream processing of crude biodiesel......................................................................................... 16 1.5.1.2 Drying of biodiesel .............................................................................................................................................. 16 1.5.2 New developments in biodiesel technology ............................................................................................... 17 1.5.2.1 Continuous centrifugal contactor separators ........................................................................................ 17 1.5.2.2 Continuous fixed bed operation with supercritical methanol ....................................................... 18 1.5.2.3 Reactive distillation ............................................................................................................................................ 19 1.5.2.4 Membrane reactors for biodiesel synthesis ........................................................................................... 20 1.5.2.5 Ultrasonic cavitation reactors ....................................................................................................................... 21 1.6 Mobile biodiesel units ............................................................................................................................................... 21 1.7 Biobased polymers from plant oils..................................................................................................................... 21 1.8 Thesis outline ................................................................................................................................................................ 22 1.9 References ……………………………………………………………………………………………………………………25 Chapter 2 ......................................................................................................................................................... 34 Experimental evaluation and modelling of solvent assisted hydraulic pressing of dehulled rubber seeds ……………………………………………………………………………………………………………………34 2.1 Introduction ................................................................................................................................................................... 36 2.2 Theory: the Shirato model ...................................................................................................................................... 37 2.3 Materials and methods ............................................................................................................................................. 39 2.3.1 Materials ...................................................................................................................................................................... 39 2.3.2 Moisture conditioning ........................................................................................................................................... 39 2.3.3 Oil content measurement .................................................................................................................................... 40 2.3.4 Hydraulic pressing .................................................................................................................................................. 40 2.3.5 Design of experiments, statistical analysis and optimisation ............................................................ 41 2.3.6 Data analysis .............................................................................................................................................................. 41 2.3.7 Analytical methods ................................................................................................................................................. 42 2.4 Results and discussion ............................................................................................................................................. 42 2.4.1 Rubber seed characteristics ............................................................................................................................... 42 2.4.2 Non-solvent assisted hydraulic pressing ..................................................................................................... 42 2.4.3 Solvent assisted hydraulic pressing ............................................................................................................... 45 2.4.4 Data modelling using the Shirato model ...................................................................................................... 46 2.4.5 Empirical modelling of oil recoveries using design experiments for SAHP ................................ 52 2.4.6 Composition and relevant product properties of RSO .......................................................................... 56 2.5 Conclusions and outlook ......................................................................................................................................... 57 2.6 Nomenclature ............................................................................................................................................................... 58 2.7 References ……………………………………………………………………………………………………………………58
Chapter 3 ......................................................................................................................................................... 61 The influence of storage time on relevant product properties of rubber seed, rubber seed oil and rubber seed oil ethyl esters .................................................................................................................................. 61 3.1 Introduction ................................................................................................................................................................... 63 3.2 Materials and Methods ............................................................................................................................................. 65 3.2.1 Materials ...................................................................................................................................................................... 65 3.2.2 Storage conditions .................................................................................................................................................. 65 3.2.3 Determination of the moisture content of the rubber seeds ............................................................. 66 3.2.4 Determination of the oil content of the rubber seeds ........................................................................... 66 3.2.5 Hydraulic pressing of RSO .................................................................................................................................. 66 3.2.6 Synthesis of rubber seed oil ethyl esters ..................................................................................................... 66 3.2.7 Product analysis ....................................................................................................................................................... 66 3.3 Results and discussion ............................................................................................................................................. 67 3.3.1 Rubber seed characteristics ............................................................................................................................... 67 3.3.2 Effect of storage time of the moisture content of the rubber seeds ............................................... 67 3.3.3 Modelling of the moisture content of the rubber seeds versus time ............................................. 68 3.3.4 Oil content of rubber seeds and acid value versus storage time ...................................................... 70 3.3.5 Influence of storage time on the acid value of RSO ................................................................................. 71 3.3.6 Influence of storage time on the acid value of RSO ethyl esters ....................................................... 72 3.3.7 Comparison of the acid value versus time profiles for rubber seeds, RSO and RSOEE ......... 74 3.4 Conclusions and outlook ......................................................................................................................................... 75 3.5 References ……………………………………………………………………………………………………………………76 Chapter 4 ......................................................................................................................................................... 78 Synthesis and refining of sunflower biodiesel in a cascade of continuous centrifugal contactor separators…….. ……………………………………………………………………………………………………………………78 4.1 Introduction ................................................................................................................................................................... 80 4.2 Materials and Methods ............................................................................................................................................. 81 4.2.1 Materials ...................................................................................................................................................................... 81 4.2.2 Synthesis of FAME in a batch reactor ............................................................................................................ 82 4.2.3 Synthesis of FAME in a CCCS .............................................................................................................................. 82 4.2.4 Refining of FAME in a CCCS ................................................................................................................................ 82 4.2.5 Synthesis and refining of FAME in a cascade of CCCS............................................................................ 83 4.2.6 Drying procedure for refined FAME .............................................................................................................. 83 4.2.7 Statistical analyses and optimisation ............................................................................................................ 83 4.2.8 Analytical methods ................................................................................................................................................. 84 4.2.9 Definition of yield and volumetric production rate ................................................................................ 84 4.3 Results and discussion ............................................................................................................................................. 85 4.3.1 Screening experiments in a batch reactor................................................................................................... 85 4.3.2 Initial screening experiments in a CCCS device ........................................................................................ 87 4.3.3 Systematic studies on the effect of process variables on CCCS performance ............................ 88 4.3.4 Model development ............................................................................................................................................... 91 4.3.5 Crude product properties of FAME ................................................................................................................ 97 4.3.6 Refining of FAME in a CCCS ................................................................................................................................ 97 4.3.7 Synthesis and refining of FAME in a cascade of CCCS devices........................................................... 98 4.3.8 Properties of the refined FAME obtained in a cascade of two CCCS devices ........................... 100 4.4 Conclusions ................................................................................................................................................................. 100 4.5 Nomenclature ............................................................................................................................................................ 100 4.6 References………….. .................................................................................................................................................. 101
Chapter 5 ....................................................................................................................................................... 103 Experimental and modelling studies on continuous synthesis and refining of biodiesel in a dedicated bench scale unit using centrifugal contactor separator technology ................................. 103 5.1 Introduction ................................................................................................................................................................ 105 5.2 Materials and Methods .......................................................................................................................................... 106 5.2.1 Materials ................................................................................................................................................................... 106 5.2.2 Synthesis of FAME in a CCCS ........................................................................................................................... 106 5.2.3 Continuous washing of FAME in a stirred vessel and a liquid-liquid separator .................... 107 5.2.4 Continuous drying of FAME in a bubble column................................................................................... 107 5.2.5 Continuous operation of the bench scale unit ........................................................................................ 107 5.2.6 Analytical methods .............................................................................................................................................. 108 5.2.7 Aspen modelling studies for FAME refining ............................................................................................ 108 5.2.8 Definitions of FAME yield, volumetric production rate and residence time ........................... 110 5.3 Results and discussion .......................................................................................................................................... 111 5.3.1 Synthesis of FAME in a CCCS ........................................................................................................................... 111 5.3.2 Continuous washing of FAME in a stirred vessel and a bubble column .................................... 112 5.3.3 Continous drying of FAME with air in a bubble column ................................................................... 115 5.3.4 Continuous synthesis and refining of FAME in a dedicated bench scale unit ......................... 119 5.3.5 Process optimisation using Aspen ............................................................................................................... 122 5.4 Conclusions and outlook ...................................................................................................................................... 123 5.5 Nomenclature ............................................................................................................................................................ 123 5.6 References…………. ................................................................................................................................................... 124 Chapter 6 ....................................................................................................................................................... 125 Biodiesel synthesis from Jatropha curcas L. oil and ethanol in a continuous centrifugal contactor separator ........................................................................................................................................................ 125 6.1 Introduction ................................................................................................................................................................ 127 6.2 Materials and methods .......................................................................................................................................... 129 6.2.1 Materials 129 6.2.2 Synthesis of FAEE in a batch reactor .......................................................................................................... 129 6.2.3 Synthesis of FAEE in a CCCS ............................................................................................................................ 130 6.2.4 Analytical methods .............................................................................................................................................. 130 6.3 Results and discussion .......................................................................................................................................... 131 6.3.1 Experiments in a batch reactor ..................................................................................................................... 131 6.3.2 Synthesis of FAEE from jatropha oil in a CCCS....................................................................................... 134 6.3.3 Volumetric production rates of FAEE in batch and the CCCS ......................................................... 139 6.3.4 Properties of FAEE............................................................................................................................................... 140 6.4 Conclusions and outlook ...................................................................................................................................... 140 6.5 Nomenclature ............................................................................................................................................................ 141 6.6 References.. ................................................................................................................................................................. 141 Chapter 7 ....................................................................................................................................................... 145 Synthesis and properties of cross-linked polymer from epoxidized rubber seed oil using triethylenetetramine ...................................................................................................................................................... 145 7.1 Introduction ................................................................................................................................................................ 147 7.2 Materials and Methods .......................................................................................................................................... 150 7.2.1 Materials ................................................................................................................................................................... 150 7.2.2 Eperimental procedure for the epoxidation of plant oils ................................................................. 150 7.2.3 Preliminary experiments of the amidation of oil with TETA .......................................................... 150 7.2.4 Cross-linking of EO with TETA ...................................................................................................................... 150 7.2.5 Statistical analysis and optimisation .......................................................................................................... 151 7.2.6 Product Analysis ................................................................................................................................................... 151
7.3 Results and discussion .......................................................................................................................................... 153 7.3.1 Synthesis and properties of epoxidized oils .......................................................................................... 153 7.3.2 Product properties of the EOs ........................................................................................................................ 155 7.3.3 Synthesis of cross-linked polymers ............................................................................................................. 157 7.3.4 Systematic studies on the cross-linking of ERSO with TETA .......................................................... 161 7.3.5 Synthesis of cross-linked polymers with TETA at optimum conditions ................................... 167 7.4 Conclusions ................................................................................................................................................................. 170 7.5 Nomenclature ............................................................................................................................................................ 170 7.6 References.. ................................................................................................................................................................. 171 Chapter 8 ....................................................................................................................................................... 174 Preliminary techno-economic evaluations on rubber seed pressing and biodiesel production ...................................................................................................................................................... 174 8.1 Application of the biorefinery concept for rubber seeds ...................................................................... 175 8.2 Techno-economic evaluations on the valorisation of rubber seeds to rubber seed oil and biodiesel derived thereof ............................................................................................................................................. 176 8.2.1 Small scale production of RSO from rubber seeds ............................................................................... 176 8.2.1.1 Production scale ................................................................................................................................................ 176 8.2.1.2 Location ................................................................................................................................................................. 176 8.2.1.4 Mass balances ..................................................................................................................................................... 177 8.2.1.5 Estimation of capital costs ........................................................................................................................... 177 8.2.1.6 Total production cost ..................................................................................................................................... 179 8.2.1.7 Sensitivity analysis .......................................................................................................................................... 180 8.2.2 Small-scale biodiesel production using CCCS technology ................................................................ 181 8.2.2.1 Production scale ................................................................................................................................................ 181 8.2.2.2 Location ................................................................................................................................................................. 181 8.2.2.4 Mass balances ..................................................................................................................................................... 181 8.2.2.5 Capital cost estimations ................................................................................................................................ 182 8.2.2.6 Production cost.................................................................................................................................................. 184 8.2.2.7 Sensitivity analysis .......................................................................................................................................... 185 8.3 Concluding remarks ................................................................................................................................................ 186 8.4 References.. ................................................................................................................................................................. 186 Summary ........................................................................................................................................................ 188 Samenvatting ............................................................................................................................................... 202 Acknowledgement ..................................................................................................................................... 194 List of publications ..................................................................................................................................... 196 Papers………………… ......................................................................................................................................................... 196 Presentations… ................................................................................................................................................................. 197
List of Abbreviations
1
List of Abbreviations
ANOVA Analysis of variance
CCD Central Composite Design
CCCS Continuous Centrifugal Contactor Separator
CECO Commercial epoxidized soybean oil
CO Coconut oil
CP Cloud point
CSTR Continuous stirred tank reactor
DMTA Dynamic mechanical thermal analysis
DSC Differential scanning calorimetry
EO Epoxidized oil
ECO Epoxidized coconut oil
EFAR Easy fatty acid removal
EJO Epoxidized jatropha oil
EPO Epoxidized palm oil
ERSO Epoxidized rubber seed oil
ESO Epoxidized soybean oil
EU European Union
FAEE Fatty acid ethyl esters
FAME Fatty acid methyl esters
FFA Free fatty acid
FT-IR Fourier Transform-Infrared
GC-MS Gas chromatography-mass spectrometry
JO Jatropha oil
LCA Life Cycle Assessments
L-L Liquid-liquid
NMR Nuclear Magnetic Resonance
NPT No-pretreatment
NSHP Non solvent assisted hydraulic pressing
PCECO Commercial Epoxidized soybean oil based polymer
2
PECO Epoxidized coconut oil based polymer
PEJO Epoxidized jatropha oil based polymer
PEPO Epoxidized palm oil based polymer
PERSO Epoxidized rubber seed oil based polymer
PESO Epoxidized soybean oil based polymer
PFR Plug flow reactor
PI Process intensification
PO Palm oil
PP Pour point
PT Pretreatment
RD Reactive distillation
RED Renewable Energy Directive
RH Relative humidity
RSO Rubber seed oil
RSOEE RSO ethyl esters
SAHP Solvent assisted hydraulic pressing
TGA Thermogravimetric analysis
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