University of Groningen Biobased products from rubber, jatropha and sunflower oil Bin Abu Ghazali, Yusuf IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2015 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Bin Abu Ghazali, Y. (2015). Biobased products from rubber, jatropha and sunflower oil [S.l.]: [S.n.] Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 03-10-2018
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 List of Abbreviations ANOVA CCD CCCS CECO CO CP CSTR DMTA DSC EO ECO EFAR EJO EPO ERSO ESO EU FAEE FAME FFA FT-IR GC-MS JO LCA L-L NMR NPT NSHP PCECO Analysis of variance Central Composite Design Continuous Centrifugal Contactor Separator Commercial epoxidized soybean oil Coconut oil Cloud point Continuous stirred tank reactor Dynamic mechanical thermal analysis Differential scanning calorimetry Epoxidized oil Epoxidized coconut oil Easy fatty acid removal Epoxidized jatropha oil Epoxidized palm oil Epoxidized rubber seed oil Epoxidized soybean oil European Union Fatty acid ethyl esters Fatty acid methyl esters Free fatty acid Fourier Transform-Infrared Gas chromatography-mass spectrometry Jatropha oil Life Cycle Assessments Liquid-liquid Nuclear Magnetic Resonance No-pretreatment Non solvent assisted hydraulic pressing Commercial Epoxidized soybean oil based polymer 1
PECO PEJO PEPO PERSO PESO PFR PI PO PP PT RD RED RH RSO RSOEE SAHP TGA Epoxidized coconut oil based polymer Epoxidized jatropha oil based polymer Epoxidized palm oil based polymer Epoxidized rubber seed oil based polymer Epoxidized soybean oil based polymer Plug flow reactor Process intensification Palm oil Pour point Pretreatment Reactive distillation Renewable Energy Directive Relative humidity Rubber seed oil RSO ethyl esters Solvent assisted hydraulic pressing Thermogravimetric analysis 2