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