Jet biofuel production from agroindustrial wastes through furfural
platform
Valentina Aristizábal Marulanda
Universidad Nacional de Colombia Sede Manizales
Instituto de Biotecnología y Agroindustria, Facultad de Ingeniería y Arquitectura,
Departamento de Ingeniería Química
Manizales, Colombia
2015
Producción de biocombustible de avión a partir de residuos
agroindustriales a través de una plataforma de furfural
Valentina Aristizábal Marulanda
Universidad Nacional de Colombia Sede Manizales
Instituto de Biotecnología y Agroindustria, Facultad de Ingeniería y Arquitectura,
Departamento de Ingeniería Química
Manizales, Colombia
2015
Jet biofuel production from agroindustrial wastes through
furfural platform
Valentina Aristizábal Marulanda
Thesis submitted in partial fulfillment of the requirements for the degree of:
Master of Science in Engineering - Chemical Engineering
Advisor:
Ph.D., M.Sc, Chemical Engineer Carlos Ariel Cardona Alzate
Co-Advisor:
M. Sc, Chemical Engineer Álvaro Gómez Peña
Research line:
Chemical and Biotechnological Processes Engineering
Research group:
Chemical, Catalytic and Biotechnological Processes
Universidad Nacional de Colombia sede Manizales
Instituto de Biotecnología y Agroindustria, Facultad de Ingeniería y Arquitectura,
Departamento de Ingeniería Química
Manizales, Colombia
2015
A Dios y a la vida… A mis padres: mi soporte…
A los que se quedaron, a los que se fueron… A la soledad
“Todo con la alegría de poder hacerlo y el placer de triunfar”
IX Jet fuel production from agroindustrial wastes through furfural platform
Acknowledgements
I would like to thank all the people who accompanied me in some way in the development
of the work described in this document. I would like to thank first to my parents who have
believed in me, they have given me support and unconditional love. I express my gratitude
to the small Isa for her hugs full of affection and happiness.
I thank to my academic advisor, Dr. Carlos Ariel Cardona Alzate who has believed in me
and has educated me with exigency and discipline. I want to thank to my co-advisor,
Professor Álvaro Gómez for his accompaniment, availability and advices. I would like to
express my deep gratitude and respect to my research group fellows and friends: Laura,
Javier, Catalina, Héctor, Carlos, Jonathan, Juan Camilo, Angela, Valentina, Miguel, Juan
David, Angela and Paola from the Amazonas who gave me in difficult moments some of
their time for an idea, information or guiding. I appreciate their laughter and long talks.
Thanks to Edu and Alan for their aid. Thanks to Pablito and Yei who have given me a true
friendship and have shared with me more than a nice dinner. Thanks to Eli (my cousin) for
his encouragement and company. I thank to IBA's people, to Denir, Natalia, Diana and
especially to Juan who always had a solution to my problems of experimental installation.
Finally, I want to thanks to institutions and persons associated to financial and operative
support of this thesis: Universidad Nacional de Colombia at Manizales, Facultad de
Ingeniería y Arquitectura, Instituto de Biotecnología y Agroindustria, Laboratorio de
Materiales Nanoestructurados y Funcionales, Laboratorio de Intensificación de Procesos
y Sistema Híbridos, Laboratorio de Magnetismo y Materiales Avanzados and Colciencias
(call 645 - 2014). I would like thank to Dr. María José Cocero Alonso for receiving me at
his laboratory during my internship in Universidad de Valladolid.
X Content
Abstract
The aim of this thesis is the design and analysis of a process to obtain ethanol and jet fuel
or jet fuel bioadditives through furfural platform from lignocellulosic biomass. The
compositional characterization of all feedstocks used is determined. The yields of
experimental procedures are obtained to produce ethanol, furan-based compounds and
derivatives using rice husk, sugarcane bagasse and coffee cut-stems as raw materials.
Simulation procedures based on literature experiences are used to evaluate the production
processes. The analysis presented in this work include techno-economic and
environmental assessments. Also, physicochemical properties of blends of ethanol-
butanol, ethanol-octanol and ethanol-biodiesel are evaluated and compared with properties
of conventional jet fuel to determine their compatibility. As extra work, fique (Furcraea
andina) bagasse is included as raw material for the same process including experimental
evaluation and the simulation procedure.
Keywords: lignocellulosic biomass, jet fuel, bioadditives, ethanol, furfural as
platform, techno-economic and environmental assessment.
Content XI
Resumen
El objetivo de esta tesis es el diseño y análisis del proceso para obtener etanol y
combustible para avión o bioaditivos para combustible a través de una plataforma de
furfural a partir de biomasa lignocelulósica. La caracterización composicional de todas las
materias primas usadas se realizó. Los rendimientos de los procedimientos
experimentales son obtenidos en la producción de etanol, compuestos furanos y derivados
usando cascarilla de arroz, bagazo de caña y zoca de café como materias primas. Se
usaron procedimientos de simulación basados en experiencias reportadas en la literatura
para evaluar los procesos de producción. También, son evaluadas y comparadas las
propiedades fisicoquímicas de las mezclas etanol-butanol, etanol-octanol y etanol-
biodiesel con propiedades de combustible de avión convencional para determinar su
compatibilidad. Como trabajo adicional, se incluyó el bagazo de fique como materia prima
para la evaluación experimental y el procedimiento de simulación.
Palabras claves: biomasa lignocelulósica, combustible para avión, bioaditivos,
etanol, furfural como plataforma, evaluación tecno-económica y ambiental.
Content
Page
Acknowledgements ....................................................................................................... IX
Abstract........................................................................................................................... X
Resumen ........................................................................................................................ XI
Content......................................................................................................................... XIII
List of figures.............................................................................................................. XVII
List of tables ................................................................................................................ XIX
List of publications...................................................................................................... XXI Research Papers ....................................................................................................... XXI Conference Papers .................................................................................................... XXI Oral ..................................................................................................................... XXI Posters .............................................................................................................. XXII Book Chapters ........................................................................................................ XXIV Participation of this Thesis in Research Projects ..................................................... XXIV
Introduction ................................................................................................................ XXV
Thesis hypothesis .................................................................................................... XXVII
Thesis objectives ..................................................................................................... XXVII General Objective .................................................................................................. XXVII Specific Objectives................................................................................................. XXVII
1. Jet biofuels and additives production from lignocellulosic biomass ................. 29 1.1 Overview ............................................................................................................... 29 1.2 Biofuels ............................................................................................................ 29
1.2.1 Bioethanol ...................................................................................................... 32 1.2.2 Biodiesel ........................................................................................................ 33 1.2.3 Biogas ........................................................................................................... 34 1.2.4 Biohydrogen .................................................................................................. 34
1.3 Jet fuels ............................................................................................................ 35 1.4 Additives for jet fuels ........................................................................................ 38 1.5 Bio-additives for jet fuels and jet biofuels .......................................................... 38
1.5.1 Alcohols ......................................................................................................... 39
XIV Jet fuel production from agroindustrial wastes through furfural platform
1.5.2 Alkanes ......................................................................................................... 40 1.5.3 Fatty acid esters ............................................................................................ 40 1.5.4 Biohydrogen .................................................................................................. 41 1.5.5 Biomethane ................................................................................................... 41
1.6 Colombian lignocellulosic biomass .................................................................... 42 1.6.1 Rice husk (RH) .............................................................................................. 44 1.6.2 Sugarcane bagasse (SCB) ............................................................................ 45 1.6.3 Coffee cut-stems (CCS) ................................................................................ 45 1.6.4 Fique bagasse (FB) ....................................................................................... 46
1.7 Final remarks .................................................................................................... 48
2. Materials, Methods and Methodology ................................................................... 49 2.1 Overview ........................................................................................................... 49 2.2 Raw materials ................................................................................................... 49
2.2.1 Rice husk (RH) .............................................................................................. 49 2.2.2 Sugarcane bagasse (SCB) ............................................................................ 50 2.2.3 Coffee cut-stems (CCS) ................................................................................ 50 2.2.4 Fique bagasse (FB) ....................................................................................... 50
2.3 Reagent and raw material characterization methods ......................................... 50 2.3.1 Sample preparation ....................................................................................... 51 2.3.2 Extractives content ........................................................................................ 51 2.3.3 Ash content ................................................................................................... 51 2.3.4 Holocellulose content .................................................................................... 52 2.3.5 Cellulose content ........................................................................................... 52 2.3.6 Lignin content ................................................................................................ 54
2.4 Experimental production of ethanol, furfural and alkane precursor .................... 54 2.4.1 Dilute-acid pretreatment ................................................................................ 54 2.4.2 Enzymatic hydrolysis ..................................................................................... 54 2.4.3 Ethanolic fermentation ................................................................................... 55 2.4.4 Dehydration reaction ..................................................................................... 55 2.4.5 Catalyst preparation ...................................................................................... 55 2.4.6 Aldol-condensation reaction .......................................................................... 56
2.5 Sample analysis ................................................................................................ 56 2.5.1 Sugars and furan-based compounds determination ...................................... 56 2.5.2 Reducing sugars concentration ..................................................................... 57 2.5.3 Ethanol determination.................................................................................... 57 2.5.4 Alkane precursor determination ..................................................................... 57
2.6 Catalyst characterization ................................................................................... 58 2.6.1 X-Ray diffraction ............................................................................................ 58 2.6.2 FT-IR ............................................................................................................. 58 2.6.3 TGA ............................................................................................................... 59 2.6.4 SEM – EDX ................................................................................................... 59
2.7 Determination of physicochemical properties .................................................... 59 2.7.1 Density .......................................................................................................... 59 2.7.2 Viscosity ........................................................................................................ 59 2.7.3 Freezing Point ............................................................................................... 60 2.7.4 Heat Capacity ................................................................................................ 60 2.7.5 Flash point ..................................................................................................... 60
2.8 Process Simulation Description ......................................................................... 61 2.8.1 Techno-economic Assessment ...................................................................... 61 Sugars extraction .......................................................................................... 64
Content XV
Ethanol .......................................................................................................... 64 Butanol .......................................................................................................... 65 Mixture of alcohols ......................................................................................... 65 Furfural .......................................................................................................... 65 HMF ............................................................................................................... 66 Octane ........................................................................................................... 66 Nonane .......................................................................................................... 66 PHB ............................................................................................................... 66 2.8.2 Environmental Assessment ............................................................................. 67
3. Characterization results of lignocellulosic biomass ............................................ 69 3.1 Overview .......................................................................................................... 69 3.2 Results and discussion experimental characterization ...................................... 69
3.2.1 Rice husk (RH) .............................................................................................. 70 3.2.2 Sugarcane Bagasse (SCB) ............................................................................ 70 3.2.3 Coffee Cut-Stems (CCS) ............................................................................... 71 3.2.4 Fique Bagasse (FB) ....................................................................................... 72
3.3 Final remarks ................................................................................................... 73
4. Results physicochemical properties of blends .................................................... 75 4.1 Overview .......................................................................................................... 75 4.2 Results and Discussion .................................................................................... 75 4.3 Final remarks ................................................................................................... 78
5. Experimental results for production of ethanol and furfural from lignocellulosic biomass ................................................................................................................... 81
5.1 Overview .......................................................................................................... 81 5.2 Results and discussion of experimental procedure ........................................... 81
5.2.1 Ethanol production ......................................................................................... 83 5.2.2 Furfural production ......................................................................................... 84 5.2.3 Catalyst characterization ................................................................................ 85 5.2.4 Alkane precursor production .......................................................................... 87
5.3 Final remarks ................................................................................................... 95
6. Techno-economic and environmental assessment for jet biofuels production . 90 6.1 Biorefineries based on coffee cut-stems and sugarcane bagasse: furan-based compounds and alkanes as interesting products ......................................................... 90
6.1.1 Overview........................................................................................................ 90 6.1.2 Biorefineries from sugarcane bagasse and coffee cut-stems ......................... 97 6.1.3 Scenarios and process description ................................................................ 99 6.1.4 Results and Discussion ................................................................................ 105 6.1.5 Conclusions ................................................................................................. 109
6.2 Design and analysis of process schemes based on coffee cut-stems coupled with gasification technology .......................................................................................110
6.2.1 Overview...................................................................................................... 110 6.2.2 Production of ethanol and octane from lignocellulosic biomass .................... 110 6.2.3 Scenarios description................................................................................... 111 6.2.4 Process description ..................................................................................... 113 6.2.5 Results and Discussion ................................................................................ 115 6.2.6 Conclusions ................................................................................................. 118
6.3 Techno-economic and environmental analysis of the processes to obtain blends as additive for jet biofuels ..........................................................................................119
XVI Jet fuel production from agroindustrial wastes through furfural platform
6.3.1 Overview ..................................................................................................... 119 6.3.2 Blends of biofuels as additive for jet fuels .................................................... 119 6.3.3 Process and scenarios description .............................................................. 120 6.3.4 Results and Discussion ............................................................................... 122 6.3.5 Conclusions ................................................................................................. 126
6.4 Lignocellulosic biomass to obtain sugars, ethanol, PHB and energy: Design and analysis of processes ................................................................................................ 127
6.4.1 Overview ..................................................................................................... 127 6.4.2 Second generation biomass to obtain interesting products .......................... 127 6.4.3 Scenarios and process description .............................................................. 128 6.4.4 Results and Discussion ............................................................................... 131 6.4.5 Conclusions ................................................................................................. 137
7. Conclusions ......................................................................................................... 139
A. Annex: Kinetic parameters for simulation procedures ..................................... 141
B. Annex: Analysis of the statics for the furfural synthesis by reactive distillation ............................................................................................................. 145
References .................................................................................................................. 154
List of figures
Page Figure 1-1 Total primary energy supply from 1973 to 2012 by fuels in the world [2], [3]. 30
Figure 1-2 Ethanol and biodiesel world production. Production and prospect (2013-2022)
[4]. .................................................................................................................................. 31
Figure 1-3 Description the feedstocks and biofuels depending on raw material generation.
....................................................................................................................................... 32
Figure 1-4 Production and consumption of ethanol in Colombia. Prospect (2013-2022)
[4]. .................................................................................................................................. 33
Figure 1-5 Production and consumption of biodiesel in Colombia. Prospect (2013-2022)
[4]. .................................................................................................................................. 34
Figure 1-6 Production and consumption of jet fuel in the world [20]. .............................. 36
Figure 1-7 Production and consumption of jet fuel in Colombia [20]. .............................. 36
Figure 1-8 Features of lignocellulosic biomass. Balance between feedstocks and
bioproducts. .................................................................................................................... 43
Figure 1-9 Production of sugarcane and rice in Colombia (2000-2014) [47], [48]. .......... 43
Figure 1-10 Production of coffee and fique at Colombia (2000-2014) [49], [50]. ............. 44
Figure 5-1 Diagram of experimental procedure to obtain ethanol, furfural and alkane
precursor. ....................................................................................................................... 82
Figure 5-2 X-ray diffraction pattern of Mg-OX and ZrO2 [76]. .......................................... 85
Figure 5-3 X-ray spectrum of MgO-ZrO2 obtained in catalyst characterization. .............. 85
Figure 5-4 FT-IR spectrum of MgO-ZrO2. ...................................................................... 86
Figure 5-5 TGA profile of MgO-ZrO2. ............................................................................. 86
Figure 5-6 SEM image of catalyst at 10μm. EDX spectrum and compositional report of
catalyst. .......................................................................................................................... 87
Figure 5-7 Aldol-condensation reaction of furfural and acetone, followed by
hydrogenation of aldol products [39], [40]. ...................................................................... 88
Figure 5-8 GC-MS chromatographs of furfural and monomer when RH is the used as raw
material. ......................................................................................................................... 89
Figure 5-9 GC-MS chromatographs of furfural and monomer when SCB is the used as
raw material. ................................................................................................................... 90
Figure 5-10 GC-MS chromatographs of furfural and monomer when CCS is the used as
raw material. ................................................................................................................... 90
Figure 5-11 GC-MS chromatographs of furfural and monomer when FB is the used as
raw material. ................................................................................................................... 90
XVIII Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-1 Catalytic pathways for furfural conversion. .................................................... 98
Figure 6-2 Catalytic pathways for HMF conversion......................................................... 99
Figure 6-3 Technological scenarios corresponding to the distribution shown in the
scenarios description. ................................................................................................... 100
Figure 6-4 Global economic margins for all scenarios evaluated from SCB and CCS. 107
Figure 6-5 Total potential environmental impact for the different scenarios according to
raw material. ................................................................................................................. 109
Figure 6-6 Process schemes to scenarios 1 and 2 from CCS. ...................................... 113
Figure 6-7 Biomass integrated gasification combined cycle system. 1. Heat exchanger, 2.
Splitter, 3. Compressor, 4. Gas turbine, 5. Dryer, 6. Gasification and combustion
chamber, 7. Cyclone, 8. LP pump, 9. Economizer, 10. LP drum, 11. Evaporator, 12.
Super-heater. ................................................................................................................ 114
Figure 6-8 Energy cost of stream requirement per tonne of CCS based on obtaining
products. ....................................................................................................................... 116
Figure 6-9 Distribution of total costs of process schemes based on CCS. .................... 117
Figure 6-10 Economic margin per scenario and obtained products for process schemes
based on CCS............................................................................................................... 117
Figure 6-11 Process scheme to obtain ethanol and butanol. ........................................ 122
Figure 6-12 Process scheme to obtain ethanol and mixture of alcohols. ...................... 122
Figure 6-13 Global economic margins to obtain ethanol and butanol (Sc. 1) from SCB
and RH.......................................................................................................................... 124
Figure 6-14 Global economic margins to obtain ethanol and mixture of alcohols (Sc. 2)
from SCB and RH. ........................................................................................................ 125
Figure 6-15 PEI per kg of product (ethanol and butanol). ............................................. 125
Figure 6-16 PEI per kg of product (ethanol and mixture of alcohols). ........................... 126
Figure 6-17 Process scheme to obtain glucose and xylose. ......................................... 130
Figure 6-18 Process scheme to obtain ethanol. ............................................................ 130
Figure 6-19 Process scheme to obtain PHB. ................................................................ 130
Figure 6-20 Process scheme to obtain octane and nonane. ......................................... 131
Figure 6-21 Economic margin per raw material of products obtained. .......................... 137
Figure B-1 Separatriz of second order and phase diagram of system .......................... 147
Figure B-2 Chemical interaction and reaction line, case 1. ........................................... 148
Figure B-3 Chemical interaction and reaction line, case 2. ........................................... 148
Figure B-4 P/W in function of pseudoinitial compositions of furfural, case 1. ................ 149
Figure B-5 P/W in function of pseudoinitial compositions of furfural, case 2. ................ 150
Figure B-6 Limit stable state (S1) and technologic scheme, case 1. ............................. 151
Figure B-7 Limit stable state (S1) and their possible trajectories, case 2. Technologic
scheme trajectory 1. ...................................................................................................... 151
Figure B-8 Limit stable state (S2) and technologic scheme, case 2. ............................. 152
Figure B-9 Scheme of process presented in the patent US 20130172583A1 [142]. ..... 152
Content XIX
List of tables
Page Table 1-1 Test flights with addition of biofuels to conventional kerosene. ....................... 41
Table 1-2 Information about geographic sources of crops producing lignocellulosic wastes
studied in this work. ........................................................................................................ 47
Table 2-1 Price/cost of feedstock, utilities and products used in the economic
assessment. ................................................................................................................... 63
Table 3-1 Rice husk composition on a dry basis. ........................................................... 70
Table 3-2 RH chemical characterization reported in literature (wt %). ........................... 70
Table 3-3 Sugarcane bagasse composition on a dry basis. ........................................... 71
Table 3-4 SCB chemical characterization reported in literature (wt %). .......................... 71
Table 3-5 Coffee cut-stems composition on a dry basis. ................................................ 72
Table 3-6 CCS chemical characterization reported in literature (wt %). .......................... 72
Table 3-7 Fique bagasse composition on a dry basis. .................................................... 73
Table 3-8 FB chemical characterization reported in literature (wt %). ............................. 73
Table 4-1 Jet A-1 aviation fuel specifications [119], [120]. .............................................. 76
Table 4-2 Experimental properties for the ethanol-butanol blend in mass fractions. ....... 78
Table 4-3 Experimental properties for the ethanol-octanol blend in mass fractions. ....... 78
Table 4-4 Experimental properties for the ethanol-biodiesel blend in mass fractions. ..... 78
Table 5-1 Results ethanol and furfural production from RH. ........................................... 91
Table 5-2 Results ethanol and furfural production from SCB. ......................................... 92
Table 5-3 Results ethanol and furfural production from CCS. ......................................... 93
Table 5-4 Results ethanol and furfural production from FB............................................. 94
Table 6-1 Scenarios description in biorefineries from SCB and CCS. ...........................102
Table 6-2 Production capacities of top and secondary products per scenario. ..............105
Table 6-3 Production cost of biorefinery products from SCB and CCS. .........................107
Table 6-4 Potential environmental impact for the different scenarios according to raw
material. Human toxicity by ingestion (HTPI), human toxicity by dermal exposition or
inhalation (HTPE), terrestrial toxicity potential (TTP), aquatic toxicity potential (ATP),
global warming (GWP), ozone depletion potential (ODP), photochemical oxidation
potential (PCOP), and acidification potential (AP). .........................................................108
Table 6-5 Scenarios description for process schemes from CCS. .................................112
Table 6-6 Production capacities of top and secondary products per process scheme from
CCS. .............................................................................................................................115
XX Jet fuel production from agroindustrial wastes through furfural platform
Table 6-7 Scenarios description from RH and SCB. ..................................................... 121
Table 6-8 Production capacities of products per scenario. ............................................ 123
Table 6-9 Production cost of products from SCB and RH. ............................................ 123
Table 6-10 Scenarios description to produce sugars, fuel, biopolymer and energy. ...... 129
Table 6-11 Production capacities per scenario from FB and RH. .................................. 132
Table 6-12 Total production cost of glucose and xylose from FB and RH. .................... 133
Table 6-13 Total production cost of ethanol from FB and RH. ....................................... 134
Table 6-14 Total production cost of PHB from FB and RH. ........................................... 135
Table 6-15 Total production cost of Octane and Nonane from FB and RH. ................... 136
Table A-1 Kinetic models used in simulation procedures. ............................................. 141
Table B-1 Boling temperatures of all compounds involved............................................ 146
Table B-2 Conditions of the azeotrope of the system.................................................... 146
Table B-3 Clasification of the fixed points of the system. .............................................. 147
Table B-4 Subregions to direct and indirect separations. .............................................. 147
Table B-5 LSS for direct separation (pseudoinitial compositions and dependence P/W)
case 1. .......................................................................................................................... 149
Table B-6 LSS for direct separation (pseudoinitial compositions and dependence P/W)
case 2. .......................................................................................................................... 150
Content XXI
List of publications
Research Papers
Aristizábal V., Cardona C. A., Gómez A. 2015. Biorefineries based on coffee cut-stems and
sugarcane bagasse: furan-based compounds and alkanes as interesting products. Status:
Submitted. Journal: Bioresource technology.
Conference Papers
Oral
Aristizábal V., Cabrera L. C., Hernández V., Cardona C. A. Producción de biocombustible
para aviones integrado en una biorefinería de bagazo de caña de azúcar. In: Colombia.
Event: Congreso Internacional de Ciencia y Tecnología de los Biocombustibles - CIBSCOL
2014.
Dávila J., Aristizábal V., Castro E., Cardona C. A. Electricity generation from agroindustrial
wastes. Economic point of view. In: Spain. 2014. Event: 4th International Congress on
Green Process Engineering.
Cardona C. A., Aristizábal V., Moncada J. Comparison jet biofuel production from first and
second generation feedstocks. In: Spain. 2014. Event: 10h International Conference on
Renewable Resources & Biorefineries.
XXII Jet fuel production from agroindustrial wastes through furfural platform
Dávila J. Aristizábal V., Moncada J., Cardona C. A. Techno-economic assessment of
hydrogen production from sugarcane waste. In: Spain. 2014. Event: 10h International
Conference on Renewable Resources & Biorefineries.
Cabrera L. C., Aristizábal V., Cardona C. A., Pisarenko Y. Analysis of the statics for the
furfural synthesis by reactive distillation. In: Colombia. 2014. Event: XXVII Congreso
Interamericano y colombiano de Ingeniería Química.
Aristizábal V., Moncada J., Cardona C. A., Gómez A. Analysis of furfural as a platform for
future biorefineries. In: United States. Event: AIChE 2014 Annual Meeting.
Cardona C. A., Aristizábal V., Moncada J., Gómez A. Bioenergy producing biorefineries:
Design and Analysis. In: United States. Event: AIChE 2014 Annual Meeting.
Aristizábal V., Dávila J., Cardona C. A., Gómez A., Aroca G. Techno-economic and
environmental analysis of the use of different biofuel blends to obtain jet biofuels. In: United
States. Event: AIChE 2014 Annual Meeting.
Daza L. Carvajal J. C., Aristizábal V., Cardona C. A. Simultaneous Pretreatment,
Saccharification, Fermentation and Separation Processes to Obtain Ethanol. In: United
States. Event: AIChE 2014 Annual Meeting.
Dávila J., Aristizábal V., Daza L., Rosenberg M., Taborda G., Cardona C. A. Analysis of
the supercritical extraction of anthocyanins. The Andes berry case. In: United States. Event:
AIChE 2014 Annual Meeting.
Posters
Aristizábal V., Carvajal J. C., Cardona C. A. Análisis tecno-ecnonómico de la producción
de biocombustibles y productos de valor agregado bajo el concepto de biorefinería a partir
de cáscara de plátano (Musa paradisiaca AAB). In: Colombia. Event: Congreso
Internacional de Ciencia y Tecnología de los Biocombustibles - CIBSCOL 2014.
Content XXIII
Aristizábal V., Carvajal J. C., Cardona C. A. Lignina como base para futuras biorefinerias
colombianas. In: Colombia. Event: Congreso Internacional de Ciencia y Tecnología de los
Biocombustibles - CIBSCOL 2014.
Aristizábal V., Forero H., Cardona C. A. Sustainable production of jet biofuels in tropical
countries. In: United States. 2014. Event: 36th Symposium on Biotechnology for Fuels and
Chemicals.
Forero H., Aristizábal V., Moncada J., Cardona C. A. Importance of optimal design of
downstream processing in biorefineries. In: Spain. 2014. Event: 10h International
Conference on Renewable Resources & Biorefineries.
Hernández V., Castro E., Aristizábal V., Cardona C. A. Production of biogas and
biofertilizer from wheat straw: A techno-economic and environmental assessment. In:
Czech Republic. Event: 21st International Congress of Chemical and Process Engineering
CHISA 2014.
Aristizábal V., Castro E., Romero-García J. M., Hernández V., Cardona C. A. Techno-
economic assessment of the jet biofuel production from olive stone. In: Czech Republic.
Event: 17th Conference on Process Integration, Modelling and Optimization for Energy
Saving and Pollution Reduction PRES 2014.
Aristizábal V., Moncada J., Cardona C. A. Jet biofuel production from lignocellulosic raw
materials: design and analysis. In: Czech Republic. Event: 21st International Congress of
Chemical and Process Engineering CHISA 2014.
Hernández V., Aristizábal V., Castro E., Cardona C. A. Análisis tecno-económico y
ambiental de la producción de biofertilizantes a partir de residuos cítricos. In: Colombia.
2014. Event: XXVII Congreso Interamericano y colombiano de Ingeniería Química.
Aristizábal V., Carvajal J. C., Dávila J., Cardona C. A. Producción de xilitol y ácido láctico
a partir de cáscara de plátano. In: Colombia. 2014. Event: XXVII Congreso Interamericano
y colombiano de Ingeniería Química.
XXIV Jet fuel production from agroindustrial wastes through furfural platform
Aristizábal V., Idárraga A. M., Carvajal J. C., Cardona C. A. Análisis de la producción de
acetato de etilo por vía química y biológica. In: Colombia. 2014. Event: XXVII Congreso
Interamericano y colombiano de Ingeniería Química.
Restrepo J. B., Aristizábal V., Cardona C. A. Modelado de un sistema bioreactor-extractor
para la producción de biodiesel. In: Colombia. 2014. Event: XXVII Congreso
Interamericano y colombiano de Ingeniería Química.
Aristizábal V., Hernández V., Cardona C. A. Producción de furfural e hidroximetilfurfural a
partir de bagazo de fique. In: Colombia. 2014. Event: XXVII Congreso Interamericano y
colombiano de Ingeniería Química.
Cardona C. A., Forero H., Aristizábal V., Gómez A. Thermodynamic analysis of a
lignocelullose-based furfural biorefinery. In: United States. Event: AIChE 2014 Annual
Meeting.
Book Chapters
Hernández V., Aristizábal V., Cardona C. A. High-cellulose agricultural residues for
biorefineries. In: Agricultural Wastes: Characteristics, Types and Management. Editorial:
Nova Science Publishers, Inc. Status: under review.
Aristizábal V., Hernández V, Cardona C. A. Economic and environmental comparison of
first, second and third generation biorefineries. In: Biorefineries: Sustainable Development,
Applications and Emerging Technologies. Editorial: Nova Science Publishers, Inc. Status:
under review.
Participation of this Thesis in Research Projects
Convocatoria Nacional Jóvenes Investigadores e Innovadores año 2014 of Departamento
Administrativo de Ciencia, Tecnología e Innovación -Colciencias-.
Programa Nacional de Apoyo a Estudiantes de Posgrado para el Fortalecimiento de la
Investigación, Creación e Innovación de la Universidad Nacional de Colombia 2013-2015.
Consultoría para desarrollo de componentes adicionales a las herramientas de evaluación
rápida sobre bioenergía y seguridad alimentaria (BEFS RA) FAO.
Introduction
Nowadays, decrease in oil sources, constant fluctuations and uncertainty of oil prices,
together with environmental concerns are the starting point for energy policies to develop
and produce sustainable, renewable, clean and energy-efficient fuels. Currently, the
population growth has caused an increase in energy demand especially in the
transportation sector. According to United States Energy Information Administration for
2010 the consumption of jet fuel in the world was of 5.2 million barrels per day
approximately. Also, International Air Transport Association (IATA) has fixed as objective
the reduction of emissions of CO2 in 50% for 2050 in aircraft industry. These data, indicate
the necessity of the inclusion of alternative fuels in the aviation industry.
In the past decade, the production of biofuels from feedstocks with low production cost
which do not compete with the worldwide food security have been studied. These
feedstocks play an important role in mitigation of environmental pollution, have high
availability and are potentially sustainable. These reasons indicate that lignocellulosic
biomass is a promising raw material for both biochemicals and fuels. Colombia as tropical
country offers abundance and big variety of raw materials. The diversity of climates zones
allows to farm and produce all type of food. From these crops can be obtained wastes that
in the past were being underused.
Ethanol, biodiesel, butanol, hydrogen and biogas are the main biofuels produced from
lignocellulosic biomass. Recent studies show other attractive possibilities to obtain jet fuels
or additives such as alkanes or mixture of alcohols. The alkanes can be synthesized
through furan-based compounds and the alcohols can be produced by fermentation of
sugars. In addition to the researches done to produce the alternative fuels also studies are
under way to assess compliance with the requirements that have aviation fuels. Some of
features are good burning, free from contaminants, low viscosity, high lubricity and good
thermal and chemical stability.
XXVI Jet fuel production from agroindustrial wastes through furfural platform
In this work, a process design to obtain ethanol and furan-based compounds from four
agroindustrial wastes is presented. Four types of lignocellulosic biomass were selected to
be analyzed as feedstocks to produce jet fuels or jet fuel additives. The chosen feedstocks
were rice husk, sugarcane bagasse, coffee cut-stems and a complimentary fique bagasse.
These residues were selected due to their high content of holocellulosic fiber and
availability. Simulation procedures based on experimental characterization were used to
evaluate the yields of process proposed using the Aspen Plus software. Process
configurations for each waste were evaluated in technical, economic and environmental
terms. In this study, experimentally also were evaluated procedures to obtain ethanol,
furan-based compounds and derivatives. Finally, the physicochemical properties of blends
(ethanol-butanol, ethanol-octanol and ethanol-biodiesel) were analyzed and compared with
properties of conventional jet fuel.
Content XXVII
Thesis hypothesis
It is possible to obtain a jet biofuel with physicochemical properties similar to conventional
jet fuel from lignocellulosic furfural and biofuel blends under biorefinery concept with
Colombian raw materials.
Thesis objectives
General Objective
To design and analyze from the technical, economic and environmental points of view jet
biofuel production from Colombian raw materials.
Specific Objectives
To physicochemically characterize rice husk, sugarcane bagasse and coffee cut-
stems.
To experimentally evaluate ethanol, furfural and intermediates production to obtain
jet biofuel blends.
To evaluate from the technical, economic and environmental point of view jet biofuel
production from biofuel blends and lignocellulosic furfural at Colombian context.
To compare based on experimental physicochemical properties, jet biofuel with
conventional jet fuel.
1. Jet biofuels and additives production from lignocellulosic biomass
1.1 Overview
Currently, there are concerns to reduce the fossil fuel dependence and therefore new
energy sources are being proposed to supply the increasing energy demand. As a
consequence, biomass appears as a promising alternative to produce biofuels, jet fuels and
additives environmentally friendly with competitive advantages over non-renewable fuels.
Among potential biofuels, bioethanol has become one of the most important biofuels as
gasoline additive and widely used in countries such as USA, Brazil and Colombia.
Alternatively, biodiesel also has been a popular biofuel, which is essentially composed of
methyl or ethyl ester of fatty acids and has been used as an additive in diesel in the
transportation sector. Another important biofuel is biobutanol that has gained visibility in
recent years as a replacement for gasoline. Nowadays, the lignocellulosic biomass is the
main source of biofuels because with its content of cellulose, hemicellulose and lignin can
be produced any amount of products including electricity. The raw materials to produce
biofuels have been developed from first generation feedstock (agricultural farming), second
generation (residuals) and third generation (microalgae).
1.2 Biofuels
According to Food and Agriculture Organization of the United Nations – Bioenergy and
Food Security (FAO-BEFS), fuel is defined as an “energy carrier intended for energy
conversion”. Biofuels are liquid fuels that are generated directly or indirectly from biological
materials. A concept that has recently been narrowed, “biofuel is a renewable source of
30 Jet fuel production from agroindustrial wastes through furfural platform
carbon” [1]. Biofuels can be considered one of the most sustainable forms of replacement
for fossil fuels. The first oil crisis (70s) made that several developed and developing
countries started to look for other sources of energy [2]. The biofuels showed up in this
context as an interesting alternative as much from an economic point of view as from the
environmental and social ones. Figure 1-1 shows the global supply of primary energy. The
substantial reduction of oil supply and considerable increase of total energy supply are
significant. Total energy supply jumped from 6106 Mtoe (Million tonnes of oil equivalent) in
1973 to 13371 Mtoe in 2012 [3].
Biofuels are the most effective and efficient option of renewable energy and are composed
of mono-alkyl esters of long chain fatty acids derived from vegetable oils, animal fats and
other non-edible oil sources. Biofuels available in the world are bioethanol, biobutanol,
biodiesel, biohydrogen, biogas, and renewable methanol. Biofuels have special features
such as, mitigation of global warming, low emissions, can provide new incomes and
employment opportunities in rural areas, and are safer.
Figure 1-1 Total primary energy supply from 1973 to 2012 by fuels in the world [2], [3].
*In these graphs, peat and oil shale are aggregated with coal. ** Includes geothermal, solar, wind, heat, etc.
Chapter 1 31
Figure 1-2 shows ethanol and biodiesel world production in 2015 and prospects until 2022.
There is an interesting linear increase of the prospect of global production for both biofuels.
The availability of feedstock and the enhancement of current techniques are the main
factors that boost this prospect of increasing production and consumption in the coming
years.
Figure 1-2 Ethanol and biodiesel world production. Production and prospect (2013-2022) [4].
Biofuels are usually classified based on feedstock sources. The figure 1-3 shows a brief
description the feedstock and biofuels depending on raw material source. According to the
above the biofuels can be of first generation (1G), second generation (2G), third generation
(3G) and fourth generation (4G) [1] - [5].
First generation (1G) biofuels face social, economic and environmental challenges because
these are derived from food crop feedstocks. Their use can lead to increase food prices
and also to create pressure on land use which makes it unlikely to be totally sustainable.
Additionally, 1G can provide controversial energy balances [1], [6], [7]. Second generation
(2G) biofuels can overcome the social, economic and environmental challenges without
hampering to food cost and creating pressure on land use because it is non-edible,
biodegradable and can grow on marginal land [1], [7], [8]. 2G feedstocks overcome the fuel
vs. food dilemma. Third generation (3G) biofuels, mainly obtained from microalgae have
some remarkable advantages such as being cultured to low-cost, high energy, eco-friendly
and entirely renewable feedstock [1], [9]. Finally, fourth generation (4G) biofuel is an
0
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32 Jet fuel production from agroindustrial wastes through furfural platform
advanced biofuel based on aromatic and sulphur-free rich fuel with a high cetane blending
value that is fully compatible with oil-derived diesel [5].
Figure 1-3 Description the feedstocks and biofuels depending on raw material generation.
A brief description of main road biofuels currently used in the world is shown below.
1.2.1 Bioethanol
Global ethanol fuel production reached 124000 million liters in 2014 [4], with the US and
Brazil as the world′s top producers, accounting together for 90% of the global production
[10]. World fuel ethanol production during last years is shown in Figure 1-2. The United
States and Brazil remain the two largest producers of ethanol [10]. Corn is the primary
feedstock for US ethanol, and sugarcane is the dominant source of ethanol in Brazil. In
Chapter 1 33
2010, Colombia was the tenth largest producer of ethanol in the world, with a production of
85 million gallons, using sugarcane juice and molasses as feedstock.
Production and consumption of ethanol in Colombia and prospect until 2022 is shown in
figure 1-4. Ethanol can be used as a fuel for vehicles in its pure form, but it is widely used
as a gasoline additive to increase octane and reduce vehicle emissions. In Colombia, the
current blend of ethanol in gasoline is 8% (E8) [1].
Figure 1-4 Production and consumption of ethanol in Colombia. Prospect (2013-2022) [4].
1.2.2 Biodiesel
The Colombian biodiesel production is chiefly based on palm oil. Some new projects
consider other crops such as cotton, soybean and other oil seeds not intended for human
consumption like castor bean and J. curcas. Colombia occupies the fifth place in palm oil
production in the world and the first place in Latin America. Biodiesel is usually used as a
diesel additive to reduce vehicle emissions. In Colombia, biodiesel is added at 7–10%,
depending on the region of the country.
Figure 1-5 shows the prospects of production and consumption of biodiesel in Colombia.
These data show the trend of a gradual increase of biofuel aiming the partial substitution of
petroleum products and reduction of the dependence on foreign energy markets.
0
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Eth
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34 Jet fuel production from agroindustrial wastes through furfural platform
Figure 1-5 Production and consumption of biodiesel in Colombia. Prospect (2013-2022) [4].
1.2.3 Biogas
Biogas is usually 50%-80% methane and 20%-50% carbon dioxide, with traces of gases
such as hydrogen, carbon monoxide, and nitrogen. Biogas can be the versatile and
sustainable energy carrier providing economic security and environmental stability. A large
share of energy crops could be converted into biogas. Compared to fossil transportation
fuels like petrol and diesel, biogas is extremely efficient in reducing overall CO2 emissions
[11]. According to European Biomass Association (AEBIOM) primary biogas production in
the European Union was in 2006 and 2007 in ktoe (thousand tons of oil equivalent) of
4898.9 and 5901.2 respectively [11]. Germany is considered a leader of biogas production.
This country is the leading European biogas producer, accounting for half of the European
primary energy output (50.5% in 2009) and half of the biogas sourced electricity output
(49.9% in 2009) [11]–[13]. Colombia has a very low biogas production at high scale. Usually
biogas is obtained at small scale in some factories.
1.2.4 Biohydrogen
Hydrogen has been identified as a molecule with highest potential as an energy carrier
because it has a higher energy density and can be converted to electricity more efficiently.
Among the biological methods of producing hydrogen, dark fermentation has some
advantages over the photosynthetic and photolytic bioprocesses because of lower net
energy input, higher rate, and moderate yields [14]. Hydrogen is believed by many experts
to be a potential major fuel for transport in the future because of its eco-friendly combustion
0
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2013 2014 2015 2016 2017 2018 2019 2020 2021 2022
Bio
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Chapter 1 35
products. However, its main potential for road transport lies in its future role for fuel cell
vehicles and thus it may largely depend on the development of this technology. The
application of hydrogen as an energy source in large scale has been limited due to the
difficulties of finding effective storage material for it. Important advances in storage,
transport infrastructure, fuel cell technology, etc, require costly investment but could
significantly improve performance. At the same time, hydrogen will have to compete with
existing alternatives, such as ethanol and natural gas [15], [16].
1.3 Jet fuels
According to EIA, jet fuel is defined as a refined petroleum product used in jet aircraft
engines. The two main types of aviation fuels are gasoline (avgas) and jet fuel (kerosene)
(C8-16). They are composed mainly of paraffins and cycloparaffins and smaller amounts of
aromatics and olefins along with some additives specified by each category of aviation fuel
[17], [18]. Jet fuels are specialized products that are manufactured according to very tightly
controlled specifications. Jet fuels have special features in comparison with fuels for land
transport. Some requirements of the fuels for aviation use are as follows: good burning
characteristics, free from contaminants, low viscosity and high lubricity, good thermal
stability/chemical stability and wide availability and acceptable cost [19].
Figures 1-6 and 1-7 show the production and consumption of jet fuel in the world and
Colombia respectively. The constant increase of air traffic over the years has increased its
demand and therefore production.
36 Jet fuel production from agroindustrial wastes through furfural platform
Figure 1-6 Production and consumption of jet fuel in the world [20].
Figure 1-7 Production and consumption of jet fuel in Colombia [20].
Today's kerosene jet fuels have been developed based on the same illuminating kerosene
used in the early gas turbine engines. These engines needed a fuel with good combustion
characteristics and a high energy content [21]. The first fuel specifications appeared in 1943
in the UK and 1944 in the EE.UU. [19]. Fuels specifications have undergone many changes,
mainly related to safety or security of supply until today. There are JP-4, JP-5 and JP-8 for
military use and Jet A-1, Jet A and Jet B for commercial use. The main specifications for
Jet A-1 and Jet A are in ASTM D1655.
2,500
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Chapter 1 37
Jet A-1
Jet A-1 is a kerosene grade of fuel suitable for most turbine engine aircraft. It has a minimum
flash point of 38ºC and a maximum freeze point of -47ºC [21], [22].
Jet A
Jet A is a kerosene grade fuel, normally only available in the U.S.A. It has the same flash
point as Jet A-1 but a higher maximum freeze point (-40°C) [21], [22].
Jet B
Jet B is a distillate covering the naphtha and kerosene fractions. It can be used as an
alternative to Jet A-1 but because it is more difficult to handle (higher flammability), there is
only significant demand in very cold climates where its better cold weather performance is
important [21].
JP-4
JP-4 used to be the primary jet fuel for the USAF but was phased out in the 1990s because
of safety problems. A few air forces around the world still use it but there is very little
production. JP-4 is the military equivalent of Jet B with the addition of corrosion inhibitor
and anti-icing additives; it meets the requirements of the U.S. Military Specification MIL-
PRF-5624S Grade JP-4 [21].
JP-8
JP-8 is the military equivalent of Jet A-1 with the addition of corrosion inhibitor and anti-
icing additives; it meets the requirements of the U.S. Military Specification MIL-T-83188D.
It is the dominant military jet fuel grade for NATO air forces [21].
JP-5
JP-5 is a high flash point kerosene meeting the requirements of the U.S. Military
Specification MIL-PRF-5624S Grade JP-5 [21].
38 Jet fuel production from agroindustrial wastes through furfural platform
Aviation turbine fuels are a complex hydrocarbon mixture consisting of different classes,
such as paraffin (C8-C15), naphthene and aromatics. Bio-aviation fuels are mainly
composed of alkanes that are used as mixing components in aviation turbine fuels, with the
largest proportion being less than 50% according to ASTM D7566.
1.4 Additives for jet fuels
Aviation fuel additives are compounds added to the fuel in very small quantities, usually
measurable only in parts per million, to provide special or improved qualities. The quantity
to be added and approval for its use in various grades of fuel is strictly controlled by the
appropriate specifications. The additive content of jet fuels varies considerably, depending
on whether the fuel is for civil or military use. A few additives in common use are as follows:
anti-knock, antioxidants, static dissipater additives, corrosion inhibitors, icing inhibitors and
metal deactivators [23]. However, it is important to note that any fuel or biofuel that can
fulfill most of the jet fuel requirements can be blended in some proportions and can be
considered jet fuel additives.
1.5 Bio-additives for jet fuels and jet biofuels
Some of the main requirements for alternative fuels are: to reduce greenhouse gas
emissions, to be compatible with conventional fuel, to be sustainable and to produce a clean
burning. However, concerns over the compatibility of the fuel with the aircraft operation
have limited the development of these fuels to date. An alternative fuel must have a number
of characteristics to be considered suitable for aviation. These include the need for a high
energy density, good atomization, rapid evaporation, an ability to be relit at altitude though
a low explosive risk on the ground, they must have a suitably low viscosity, an extremely
low freezing point, good chemical stability, be reasonably non-toxic, be widely available and
economically competitive. Below a description of fuels that can be used in aviation industry
as biofuel and/or bioadditive.
Chapter 1 39
1.5.1 Alcohols
Lignocellulosic ethanol is obtained from sources with low cost and high availability. Also,
the figures 1-2 and 1-4 indicate that the trend in ethanol production is linear for the next
years in the world and Colombia respectively. These factors make it attractive and
interesting for the use as an aviation fuel. The use of ethanol in aviation industry dates
mainly in Brazil [24]. Agricultural aviation and light aircraft, especially in single-engine
airplanes have operated using only ethanol [25]. The replacement of aviation gasoline by
ethanol caused a decrease in operating costs (up to 40%) and environmental improvement.
Monoplanes are driven by piston engines and widely used in the Brazilian agriculture,
representing 75% of sales in the sector. 25% of these aircraft run on ethanol [24], [26].
In commercial aviation, the energy concentration of the fuel is extremely important, and the
use of bioethanol is not particularly desirable for this reason. Additionally, ethanol has high
volatility and low flash point [24], [27], [28]. The growth of ethanol industry, especially in
terrestrial transport opens the door to consider the possibility of studying higher alcohols as
alternative aviation fuels. Higher alcohols offer advantages with respect to energy density,
as the carbon to oxygen ratios growth with increasing molecular mass [24], [27]. n-Butanol,
for example, may be obtained through fermentation of lignocellulosic biomass through the
Acetone–Butanol–Ethanol (ABE) fermentation pathway [6], [29], [30], whereas the use of
modified organisms gives rise to the possibility of producing n-hexanol and higher alcohols
[31]. The n-butanol is considered an attractive fuel for gasoline engines, and has interesting
characteristics for spark ignition engines, demonstrating considerable potential in reducing
GHG emissions [6], [24].
Other alternative use of alcohols in transport industry is the possibility of mixed alcohols as
a fuel additive in gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, coal,
petroleum coke or as a neat fuel in and of itself [32], [33]. The mixed alcohols formulations
can contain C1-C5 alcohols, or in the alternative, C1-C8 alcohols or higher C1-C10 alcohols
in order to boost energy content [32], [33]. The primary benefits of mixed alcohols are:
increase combustion efficiencies, reduce emissions profiles and low production costs.
According to studies, a jet fuel for use in a jet turbine engine, comprising kerosene and a
mixture of alcohols. The mixture of alcohols comprises by volume 1-30% methanol, 40-75%
ethanol, 10-20% propanol, 4-10% butanol and 1-8% pentanol [32].
40 Jet fuel production from agroindustrial wastes through furfural platform
1.5.2 Alkanes
Jet fuels range alkanes can be obtained from lignocellulosic biomass by a novel route,
wherein C6 and C5 sugars are firstly produced by hydrolysis of biomass and then converted
into 5-HMF and furfural, respectively, by dehydration step [34]–[38]. Furan-based
compounds are further reacted with acetone by aldol condensation step to produce jet fuel
intermediates, following by the generation of long chain alkanes raging from C7 to C15 via
a dehydration/hydrogenation step. Alkane products from this process have cetane
numbers, a measure of the ignition quality of diesel fuel, ranging from 63 to 97, whereas
the overall cetane number for diesel is typically from 40 to 55. The high cetane numbers for
these biomass-derived alkanes make them excellent blending agents to produce sulfur-free
diesel fuel for transportation applications [38]–[41].
1.5.3 Fatty acid esters
Fatty acid esters (FAEs) are products from the transesterification of triglycerides and fatty
acids of vegetable or animal origin. These can be obtained from raw materials rich in oil as
soybeans, peanut, sunflower, palm, jatropha, canola, microalgae and others. The
properties and characteristics of biodiesel vary considerably depending on the raw material
used and some contaminants may be harmful in the burning of engines [42].
Biodiesel as fuel shows the advantages of high flash point, good energy balance and good
miscibility with petroleum fuels. However, biodiesel is still undergoing many challenges to
become a potential jet fuel due to its high viscosity, its low lower calorific value (LCV) and
high freezing point. In order to meet the specifications required, many test flights have been
conducted with blends of biodiesel and fossil fuels targeting improvements in LCV and
freezing point properties [24], [28], [43]. Fatty acids with short-chain or even with high
number of unsaturations may decrease the problems of high freezing point. Caprylic (C8:0)
and linolenic (C18:3) acids also show an interesting behavior to be used as fuels [27].
In the last years, many tests have been carried out by military aircrafts and airlines in order
to meet the specifications required, as show the Table 1-1. Besides, to test mixture values
with the objective of finding a sustainable solution for the problem of high GHG emission
rates. Biodiesel fuel can be used as a biodiesel fuel and/or additive in other types of fuels
Chapter 1 41
or oils without , including but not limited to: jet fuel, avgas, kerosene, lubrication oil, and fuel
for any 2-stroke engine [44].
Table 1-1 Test flights with addition of biofuels to conventional kerosene.
Year Biomass Biofuel (%) Airline
2005 Soybean 50 Argentine Air Force
2007 N/A Jatropha
100 50
Czech military aircraft Air New Zealand/Boeing/Ross Royce
2008 Coconut/babassu 20 Virgin Atlantic/ Boeing/GE
2009 Algae/jatropha Algae/jatropha/camelina
50 50
Continental Airlines/Boeing/GE-CFM Japan Airlines/Boeing/Pratt & Whitney
2010 Jatropha Halophytes derivatives
50 N/A
TAM Interjet/Airbus
2011 Jatropha/camelina/animal fat
50 Lufthansa
2014 Recycled waste frying oil 20 KLM Royal Dutch Airlines
1.5.4 Biohydrogen
Since 1939 projects have been carried out in Germany aiming to use hydrogen as a fuel
for jet engines. Hydrogen cell technologies stand out among the more efficient and cleaner
ways of transforming electrical energy into transportable energy [24].
Hydrogen is a potentially viable energy source for conventional powertrain applications.
Much of the focus, however, is on pathway applications [45]. Biohydrogen is produced from
a wide range of biomass resources by following both thermal and biochemical methods[14],
[46]. Liquid hydrogen is being established as alternative jet fuel [28]. The combustion of
liquid hydrogen fuels causes low emission of greenhouse gases compared to petroleum
based jet fuels. The major problem is that the liquid hydrogen fuel cannot be used as such
in the conventional aircraft engine so the engine has to be modified [45].
1.5.5 Biomethane
Liquid methane can be used as fuel in cryogenic aircrafts, being considered interesting and
having high energy density in fuel cells. The use of carbon dioxide emission can be
decreased about 25% by the use of liquid methane fuel. Engine design is a difficulty that
42 Jet fuel production from agroindustrial wastes through furfural platform
has to be faced for the commercialization of the liquid methane fuels. To their use, changes
in engines, injection system and storage of aircrafts are required. The combustion of liquid
methane fuel emits methane, which is a major greenhouse gas [16], [24], [28].
Alternative aviation fuels are produced from renewable bioresources. In this sense, the
section 1.5 shows an overview of main lignocellulosic biomass in Colombia and the features
of raw materials used in this work.
1.6 Colombian lignocellulosic biomass
Colombia as tropical country offers abundance and big variety of raw materials. The
diversity of climate zones allows farming and producing all types of food. From tropical
crops it is possible to obtain wastes that in the past were being underused. These residues
are characterized to have a promising future; this concept implies sustainability based on
low costs and availability. Figure 1-8 shows the synergy of the features of agroindustrial
wastes in the use as raw materials to obtain techno-economic and environmentally feasible
bioproducts. A wide range of feedstocks used for the production of bioenergy, biomaterials
and biochemicals can be obtained in Colombia such as forestry residues (i.e. sawdust,
wood bark) and wastes from agriculture and food processing (i.e. rejected bananas, peel,
seed and whole of fruits, husk, seed and leaves of cotton, husk, pulp and cut-stems of
coffee, husk and straw of rice, bagasse and leaves of sugarcane, and juice and bagasse of
fique, etc).
Chapter 1 43
Figure 1-8 Features of lignocellulosic biomass. Balance between feedstocks and bioproducts.
Rice husk, sugarcane bagasse, coffee cut-stems and fique bagasse were the raw materials
evaluated in this work for the production of ethanol, furfural and alkane precursors. Then,
a brief explication and introduction over the origin, obtaining and potential of each waste.
Initially, figures 1-9 and 1-10 show the production in the last years in Colombia of the source
crops of lignocellulosic biomass studied in this work. Besides, table 1-2 indicates the main
departments and areas where are cultivated, also the wastes and quantity that are
produced.
Figure 1-9 Production of sugarcane and rice in Colombia (2000-2014) [47], [48].
1.E+06
6.E+06
1.E+07
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1999 2001 2003 2005 2007 2009 2011 2013 2015
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44 Jet fuel production from agroindustrial wastes through furfural platform
Figure 1-10 Production of coffee and fique at Colombia (2000-2014) [49], [50].
1.6.1 Rice husk (RH)
In 2014, world rice production could be reached about 501.1 million tonnes (Mt) according
to FAO [51]. The main global rice producers are China, India and Indonesia. In Latin
America, the main crops are in the southern part of the continent. Production in the region
is 19.5 million tonnes with Brazil as main producer followed by Argentina, Colombia,
Ecuador, Guyana and Paraguay [51]. Rice husk is the main waste in the rice agroindustry.
Rice processing generates around 20% rice husk by weight of the total rice production [52].
Amongst the various biomasses, with abundant and renewable energy sources, rice husk
is not only a potential source of energy, but also a value-added byproduct [53]. Rice husk
has unique characteristics in comparison with other agricultural residues, such as high silica
contents and lignocellulosic fibers, high porosity, lightweight and very high external surface
area making it a valuable material for industrial applications. Besides, rice husk can be a
raw material to obtain absorbents, rubber filler and pigments [52]–[54].
Rice husk represents an opportunity for developing projects of clean production and use of
agroindustrial wastes. In Colombia, part of husk which is produced is disposed in vacant
lots causing environmental problems. A priori estimates say that only 5% of husk produced
has an established use. It is necessary to propose integral processes to use this raw
material beginning for example with cogeneration projects to meet energy demand for rice
processing [55], [56].
5,000
7,000
9,000
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21,000
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30,000
1999 2004 2009 2014
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Chapter 1 45
1.6.2 Sugarcane bagasse (SCB)
One of the main lignocellulosic materials most abundant in tropical countries is sugarcane
bagasse [52], [57]. Brazil is the biggest producer of sugarcane in the world followed by India
and China. Colombia is the second largest producer in South America [51]. It has been
estimated for 2014/2015 that production will be around 652 million tonnes [57]. In Colombia
there are 13 processing plants of sugarcane, localized mainly at Valle del Cauca. These
plants are the higher producers of crop residues and sugarcane bagasse. Waste production
is between 46 and 50% of total production [55], [58]. One tonne of sugarcane can be
contained around of 26 to 31% of sugarcane bagasse [52], [57]. The residual fraction from the sugarcane stem after juice extraction is named bagasse.
Normally, sugarcane bagasse is used as the main source of the energy required in sugar
mills and ethanol distilleries and also for generating electricity to be sold (94%
approximately) [59]–[61]. However, an important part of the produced bagasse is
underutilized, and it could be used in more than forty different applications, such as
production of pulp and paper, boards and animal feed [62], [63]. The integral utilization of
bagasse components is desirable for both economic and environmental reasons.
1.6.3 Coffee cut-stems (CCS)
Brazil, Colombia, Vietnam, Ethiopia and Indonesia are the biggest producers of coffee in
the world. According to International Coffee Organization (ICO) global production for
2013/2014 was 145.8 million bags [64]. Colombia produced around 12 million bags [49].
Different residues such as pulp, husk, leaves, and coffee grounds are annually generated
in more than 2 million tonnes during the coffee harvesting, processing and final
consumption [65]. Coffee cut-stems is a cut above the land where the coffee plant is
cultivated of 15-20 cm of length and is obtained by crop renewal. Currently, this
lignocellulosic material has not a defined use but can be used as fertilizer, regenerator of
land and manufacture of furniture [65]. Generally the production of these residues is not
concentrated in an only place. For this reason, recent studies have been focused on raising
an optimal exploitation of energy capacity of this raw material taking into account
restrictions in logistics [55], [66].
46 Jet fuel production from agroindustrial wastes through furfural platform
1.6.4 Fique bagasse (FB)
Venezuela, Costa Rica, Ecuador, Mexico and Colombia are main producers of fique in the
world and this crop is part of his agroindustrial economy. In Colombia are grown about24
mil hectares. These crops are located in the departments of Cauca, Nariño, Caldas,
Antioquia and Santander. Fique bagasse is obtained after fiber extraction of plant. Each
tonne of fique processed generates approximately 70% is juice, 5% fiber and 17% bagasse.
In general, 20.8 tonnes of bagasse and juice are produced by 1 hectare of crop. These
wastes do not have a specific use. Hence, the residual fraction is discard into environment
causing pollution problems [50].
Chapter 1 47
Table 1-2 Information about geographic sources of crops producing lignocellulosic wastes studied in this work.
Crop Colombia grower
regions
Main wastes from
crop Cultivated area (ha)
Waste
(tonnes/year) References
Rice
Oryza sativa
Tolima, Huila, Casanare,
Norte de Santander,
Meta, Bolivar, Arauca and
Sucre
Husk and straw 455,194
(year: 2013)
Rice husk
451,085 [48], [56]
Sugarcane
Saccharum
officinarum L.
Valle del Cauca, Cauca,
Risaralda, Norte de
Santander and Caldas
Bagasse and leaves 225,560
(year: 2014)
Sugarcane bagasse
6,136,765 [47], [58]
Coffee
Coffea arabica
Huila, Antioquia, Tolima,
Cauca and Caldas.
Cut-stems, pulp,
husk, and leaves
948,511
(year: 2014)
Coffee cut-stems
22,000* [49], [66]
Fique
Furcraea andina
Cauca, Nariño, Tolima,
Antioquia and Caldas. Bagasse and juice
18,939
(year: 2011)
Fique bagasse
3,744 [50]
*Eje cafetero
48 Jet fuel production from agroindustrial wastes through furfural platform
1.7 Final remarks
In the last years, conventional feedstocks (so called first generation) have been changed
by holocellulosic biomass (cellulose and hemicellulose) rich in sugars and source of
biofuels and biofuel components. Tropical and agricultural countries as Colombia have a
potential to produce lignocellulosic biomass. Overall, these wastes do not have the best
collection and disposal system avoiding its full utilization. However, the lignocellulosic
biomass has others competitive advantages as low cost, wide variety and abundance.
Agroindustry wastes do not compete with food security and are constantly produced,
ensuring a stable supply to industry dedicated to convert these raw materials. Sugar crops,
agro and urban/industrial residues show their potential as platform to obtain alternative
energy. These residues in the framework of this thesis can be considered an interesting
feedstocks to obtain different molecules (biofuels and derivatives as those obtained from
furfural) to be blended with jet fuels.
2. Materials, Methods and Methodology
2.1 Overview
Lignocellulosic raw materials have been used in biofuels production as an alternative of
fossil fuels. This chapter describes the potential of raw materials studied in this Thesis, also
the methods used for assessing the different feedstocks and processing routes to produce
sugars, ethanol, furfural and derivatives. In this chapter the simulation procedure, including
the thermodynamic models and technical parameters is shown. On the other hand, a
description of the economic evaluation software is also shown. Finally, the environmental
evaluation packages are also explained. A brief description of the methods used for the raw
material characterization and sample analysis in the experimental setup is developed. All
this together, experimental analysis and simulation procedure help to understand and
design the process routes developed in this Thesis.
2.2 Raw materials
2.2.1 Rice husk (RH)
Rice husk (from Oryza Sativa variety) used in this study was obtained as by-product from
a rice mill company located at Tolima Department between the Magdalena and Cauca river
valleys (central zone of Colombia, 2º 52’ 59’’ and 5º 19’ 59’’ N, 74º 24’ 18’’ and 76º 06’ 23’’
W) during July 2014. Tolima has four different climate zones: one semi-wet located at the
Central and Eastern mountain ranges with an annual rainfall higher than 2,000 mm, another
small area from west to southwest is scheduled as slightly wet with an annual rainfall
between 1,500 and 2,000 mm; the area over the Magdalena river valley is considered as
subhumid with an annual rainfall between 1,000 and 1,500 mm and an average temperature
of 24°C.
50 Jet fuel production from agroindustrial wastes through furfural platform
2.2.2 Sugarcane bagasse (SCB)
Sugarcane bagasse was obtained from a farm placed at Salamina town Caldas
(5°26'02.1"N, 75°28'54.5"W) during April 2014, with altitude about 1,800 meters above
sea level and has an average temperature of 22°C with an average annual rainfall of 1,700
and 1,300 mm.
2.2.3 Coffee cut-stems (CCS)
Coffee Cut-Stems was obtained from a farm placed at La Merced town Caldas
(5°23'19.7"N, 75°32'46.1"W) during June 2014, with an altitude about 1,819 meters above
sea level and has an average temperature of 19°C with an annual rainfall of 1,700 to 1,300
mm.
2.2.4 Fique bagasse (FB)
Fique bagasse was obtained from a farm placed at Salamina town Caldas (5°22'49.2"N,
75°29'29.0"W) during mid-April 2014, with an altitude about 1,800 meters above sea level
and has an average temperature of 22°C with an average annual rainfall of 1,700 and 1,300
mm.
2.3 Reagent and raw material characterization methods
The chemical reagents used for this study were of analytical grade without further
purification. Anhydrous glucose and sodium hydroxide were purchased from Merck. Acetic
acid, sodium and potassium tartrate, sulfuric acid, and anhydrous ethanol were purchased
from Carlo Erba. 3,5-dinitrosalicylic acid (DNS) was bought from Sigma-Aldrich. Sodium
chlorite was obtained from Khemra Technologies.
The physicochemical characterization for whole agroindustrial wastes with three replicates
was carried out. Moisture contents were measured at 105ºC using Shimadzu moisture
balance MOC - 120H.
Chapter 2 51
2.3.1 Sample preparation
Materials have some impurities remaining, therefore these must be removed before their
pretreatment. Materials were dried in an oven (Thermo Precision model 6545) at 45°C
during 24 hours until constant weight. Finally, dried materials were milled (Retsch GmbH
SR200 Gusseisen) to pass 40 mesh (0.4mm) using a Wiley® Mill.
2.3.2 Extractives content
The extractives are chemical products present on cell wall mainly consisting of fats, fatty
acids, fatty alcohols, phenols, terpenes, steroids, resin acids, waxes, etc. They derive their
name as chemicals that are removed by one of several extraction procedures. These
chemicals exist as monomers, dimers and polymers.
According to National Renewable Energy Laboratories (NREL/TP-510-42619) [67], add 2-
10 g of sample to a tared extraction thimble. The height of the biomass in the thimble must
not exceed the height of the Soxhlet siphon tube. Insert the thimble into the Soxhlet tube.
Add 250mL of distilled water to the tared receiving flask with several boiling chips to prevent
bumping. Place the receiving flask on the Soxhlet apparatus. Adjust the heating mantles to
provide a minimum of 4-5 siphon cycles per hour. Carry out the extraction in an extraction
chamber for 24 h. Place them in the oven overnight at temperatures not exceeding 45°C
for 24 h. When dry, remove them to a desiccator for one hour and record the weigh. Repeat
the same procedure in the case of ethanol as solvent.
2.3.3 Ash content
The ash content was determined according to National Renewable Energy Laboratories
(NREL/TP-510-42622) [68]. The ash content of fiber is defined as the residue remaining
after temperature ramp program indicated below: Ramp from room temperature to 105°C.
Hold at 105°C for 12 minutes. Ramp to 250°C at 10°C per minute. Hold at 250°C for 30
minutes. Ramp to 575°C at 20°C per minute. Hold at 575°C for 180 minutes. Allow
temperature to drop to 105°C. Hold at 105°C until samples are removed. After ignition
carefully remove the crucible from the furnace directly into a desiccator and cool. When
cooled to room temperature, record the weigh on the analytical balance.
52 Jet fuel production from agroindustrial wastes through furfural platform
2.3.4 Holocellulose content
Holocellulose is defined as a water-insoluble carbohydrate fraction of plant materials. The
holocellulose content was determined with the chlorination method described by the ASTM
Standard D1104 [69]. For the assay, the sample should be extractive and moisture free.
To 2.5 g of sample, add 80 mL of hot distilled water, 0.5 mL acetic acid, and 1 g of sodium
chlorite in a 250 mL Erlenmeyer flask. An optional 25 mL Erlenmeyer flask is inverted in the
neck of the reaction flask. The mixture is heated on a water bath at 70°C. After 60 min, 0.5
mL of acetic acid and 1 g of sodium chlorite are added. After each succeeding hour, fresh
portions of 0.5 mL acetic acid and 1 g sodium chlorite are added with shaking. The
delignification process degrades some of the polysaccharides, and the application of
excess chloriting should be avoided. Continued reaction will remove more lignin but
hemicellulose will also be lost. Addition of 0.5 mL acetic acid and 1 g of sodium chlorite is
repeated until the fibers are completely separated from lignin. It usually requires 6 h of
chloriting, and the sample can be left without further addition of acetic acid and sodium
chlorite in the water bath overnight. At the end of 24 h of reaction, the sample is cooled and
the holocellulose content is filtered using a Buchner funnel equipment. The filtration process
is carried out until de yellow color turns into with color and the odor of chlorine dioxide is
removed. The sample is washed with acetone, vacuum-oven dry at 105°C for 24 h, place
in a desiccator for an hour and record the weigh. The holocellulose should not contain any
lignin and the lignin content of holocellulose should be determined and subtracted from the
weight of the prepared holocellulose.
2.3.5 Cellulose content
The preparation of 𝛼-cellulose is a continuous procedure from Procedure 2.3.4 in pursuit of
the ultimately pure form of fiber [69]. Thus the last fraction gives the hemicellulose content.
The sample should be extractive and moisture free.
Weigh out about 2 g of vacuum-oven dried holocellulose and place into a 250 mL glass
beaker provided with a glass cover. Measure 25 mL of 17.5% NaOH solution in a graduated
cylinder and maintain at 20°C. Add 10 mL of 17.5% NaOH solution to the holocellulose in
the 250 mL beaker, cover with a watch glass, and maintain at 20°C in the water bath.
Chapter 2 53
Manipulate the holocellulose lightly with a glass rod with the flat end so that all of the
specimen becomes soaked with the NaOH solution.
After 2 minutes, manipulate the specimen with the glass rod by pressing and stirring until
the particles are separated from one another. After the addition of the first portion of 17.5%
NaOH solution to the specimen, at 5 minute intervals, add 5 mL more of the NaOH solution
and thoroughly stir the mixture with the glass rod, until the NaOH is gone.
Allow the mixture to stand at 20°C for 30 minutes, making the total time for NaOH treatment
45 minutes. Add 33 mL of distilled water at 20°C to the mixture. Thoroughly mix the contents
of the beaker and allow to stand at 20°C for 1 h before filtering.
Filter the cellulose with the aid of suction into the tarred, alkali-resistant fitted-glass crucible
of medium porosity. Transfer the entire holocellulose residue to the crucible, and wash with
100 mL of 8.3% NaOH solution at 20°C. After the NaOH wash solution has passed through
the residue in the crucible, continue the washing at 20°C with distilled water, making certain
that all particles have been transferred from the 250 mL beaker to the crucible. Washing
the sample in the crucible is facilitated by releasing the suction, filling the crucible to within
6 mm of the top with water, carefully breaking up the cellulose mat with a glass rod to
separate any lumps present, and again applying suction. Repeat this step twice.
Pour 15 mL of 10% acetic acid (at room temperature) into the crucible, drawing the acid
into the cellulose by suction but, while the cellulose is still covered with acid, release the
suction. Subject the cellulose to the acid treatment for 3 minutes from the time the suction
is released, then apply suction to draw off the acetic acid. Without releasing the suction, fill
the crucible almost to the top with distilled water at 20°C and allow to drain completely.
Repeat the washing until the cellulose residue is free of acid as indicated by litmus paper.
Give the cellulose a final washing by drawing, by suction, an additional 250 mL of distilled
water through the cellulose in the crucible. Dry the crucible on the bottom and sides with a
cloth and then, together with the weighing bottle in which the sample was originally
weighed, place it overnight in a vacuum oven to dry at 100-105°C. Cool the crucible and
weighing bottle in a desiccator for 1 h before record the weight.
54 Jet fuel production from agroindustrial wastes through furfural platform
2.3.6 Lignin content
This procedure is a modified version of TAPPI T222 acid-insoluble lignin in wood and pulp
[69]. The sample should be extractive and moisture free.
Accurately weigh out approximately 200 mg of ground vacuum dried sample into a 100 mL
centrifuge tube. To the sample in a 100 mL centrifuge tube, add 1 mL of 72% (w/w) H2SO4
for each 100 mg of sample. Stir and disperse the mixture thoroughly with a glass rod twice,
then incubate the tubes in a water bath at 30°C for 60 minutes. Add 56 mL of distilled water.
This results in a 4% solution for the secondary hydrolysis.
Autoclave at 121°C, 15 psi, for 60 min. Remove the samples from the autoclave and filter
off the lignin, with glass fiber filters (filters were rinsed into crucibles, dried and tarred) in
crucibles using suction, keeping the solution hot. Wash the residue thoroughly with hot
water and dry at 105°C overnight. Move to a desiccator, and let it sit 1 h and record the
weigh.
2.4 Experimental production of ethanol, furfural and alkane precursor
2.4.1 Dilute-acid pretreatment
Acid pretreatment of raw materials was carried out using two operation conditions, i)
sulfuric acid solution (2 %v/v) at 110ºC as reported in [70], [71]. The solid to dilute-acid
solution ratio was 1:10 (w/w), reaction time was 5 h. ii) sulfuric acid solution (10% v/v) at
125ºC as describe in [72]–[74] .The solid dilute-acid solution ratio was 1:10 (w/w), reaction
time was 30 min.
After pretreatment, the solid fractions and liquor were separated by filtration. Solid fraction
was washed eight times using distillated water. This pretreatment was based in
methodology exposed by C. Triana, 2010 [65].
2.4.2 Enzymatic hydrolysis
Enzymatic hydrolysis of cellulose was carried out employing Celluclast 1,5L and
Viscozyme. After acid pretreatment and washing processes, the solid fraction was diluted
with water at 1:10 ratio (%w/w), pH was adjusted with a buffer solution of sodium citrate to
Chapter 2 55
0.05M and pH 4.8. Mass ratio between solid and enzyme was 10:1.5. The sample was
incubated using reciprocal shaking bath model 2870 at 100 rpm and 50ºC of temperature
during 48h. This pretreatment was based in methodology exposed by C. Triana, 2010 & J.
Quintero, 2011 [52], [65]. Finally, the enzymatic hydrolysis was stopped and the hydrolyzed
was vacuum filtrated to remove the solid fraction and the concentration of reducing sugars
was analyzed.
2.4.3 Ethanolic fermentation
Saccharomyces cerevisiae yeast was used as microorganism for ethanolic fermentation of
sugars. After enzymatic hydrolysis and vacuum filtrated, rich-glucose liquor was carried
to autoclave at 120ºC for 20 minutes to sterilize. Fermentations were carried out in 200ml
glass balloons at 32ºC with a fermentation volume of 60ml. For each gram of reducing
sugars was added 4.2 mg of urea, 0.01 mg of magnesium sulphate and ferric chloride.
Ethanol fermentation was started by inoculating the fermentation broth with 5 %v/v of S.
cerevisiae cell at semi-anaerobic conditions. Pre-inoculum was prepared with malt extract
broth.
2.4.4 Dehydration reaction
Dehydration reaction was carried out following these conditions: atmospheric pressure and
at the boiling temperature of an aqueous solution of xylose, with sulfuric acid as catalyst
plus an inorganic salt (NaCl) as promoter. The catalyst and xylose concentration were
according to the conditions of the dilute-acid hydrolysis (i.e., Condition 1: H2SO4 to 2% v/v
and Condition 2: H2SO4 to 10% v/v). The amount of NaCl as promoter was 2.4g based on
data reported by C. Rong et al., 2012 [75]. The experiment was performed by stirring the
aqueous solution with high speed for 1.5 h and was sampled at time 0 and 1.5h.
2.4.5 Catalyst preparation
Catalysts were synthesized by the sol–gel technique, starting from Mg(NO3)2·6H2O (Merck)
and ZrOCl2·8H2O (Merck) and using NaOH as the precipitation agent. Typically, 50.9 g of
magnesium nitrate and 5.2 g of zircomium oxychloride were dissolved in 1L of deionized
56 Jet fuel production from agroindustrial wastes through furfural platform
water [76]. The mixture was stirred at room temperature, and NaOH (1M) solution was
added until the pH was equal to 10. The resulting gel was aged for 72 h and separated by
vacuum filtration. The precipitate was thoroughly washed with deionized water at least four
times and dried in an oven at 120ºC from 16 to 24 h. The MgO-ZrO2 catalyst was obtained
by calcination of the resulting dry precipitate in 100ml min-1 air flow at 600ºC for 3 h with a
3 h heating ramp. A 5% Pd/MgO-ZrO2 catalyst was prepared by wetness impregnation of
Pd (using 5 %w in Palladium (II) chloride from Sigma Aldrich) onto the above-mentioned
MgO-ZrO2 support. The catalyst was dried in an oven at 100ºC overnight. It was then
calcined in 120ml min-1 air flow at 450ºC for 2 h with a 2 h heating ramp [39], [40], [77], [78].
The catalyst obtained was used for all the aldol-condensation runs, as described below.
2.4.6 Aldol-condensation reaction
Aldol-condensation reaction was carried out in batch reactor and sealed completly
employing Pd/MgO-ZrO2 as catalyst based on data reported by W. Shen et al., 2011 [77].
A 5.5ml reactant solution (55 wt. % total organics, furfural/acetone= 1 by moles,
methanol/water= 1.85 by volume) and 40 mg catalyst were added to the stainless steel
reactor with a total capacity of 11 ml. Next, reactor was heated at 120ºC and pressurized
at 7-10atm for 24h and was sampled at time 0 and 24h. The temperature and pressure
were controlled by an oven (Thermo Precision model 6545) and vapor fraction of the
reactant solution respectively.
2.5 Sample analysis
2.5.1 Sugars and furan-based compounds determination
Sugars and furan-based compounds content during acid hydrolysis, dehydration and
aldolcondensation reactions were quantified by the HPLC system (ELITE LaChrom) using
an ORH-801 Transgenomic® column. Also in aldolcondensation reaction. Sulfuric acid to
0.01N was used as mobile phase. The column oven and RID were maintained at 50ºC, and
flow rate for mobile phase was fixed at 0.8 ml min-1 [79]. The samples were centrifuged,
diluted and filtered using membrane GV (Durapore) 0.22μm of pore and 13mm of diameter
into the HPLC vials. Peaks were detected by the RI detector and quantified on the basis of
area and retention time of the standards (glucose, xylose, furfural and HMF) procured from
Chapter 2 57
Merck, Sigma–Aldrich and Acros Organics. The procedure was carried out in the
Laboratorio de Intensificación de Procesos y Sistemas Híbridos, Universidad Nacional de
Colombia sede Manizales.
2.5.2 Reducing sugars concentration
DNS method was used for determining the total reducing sugar content during enzymatic
hydrolysis and ethanolic fermentation. The reducing sugars were quantified by the 3,5-
Dinitrosalicylic acid (DNS) method with a Jenway 6405 UV/Vis Spectrophotometer. The
sample 1:20 in DNS reagent in a test tube were diluted and mixed. Tubes were placed in
boiling water bath for 9 minutes, transferred to ice to rapidly cool down for 3 minutes. Then,
absorbance was measured at a wavelength of 540 nm, against a blank. A calibration curve
was made from an anhydrous glucose standard solution (1, 2, 3, 4 and 5 g L-1) and the
blank was prepared with distilled water.
2.5.3 Ethanol determination
Ethanol were quantified by the HPLC system (ELITE LaChrom) using an ORH-801
Transgenomic® column. Sulfuric acid to 0.01N was used as mobile phase. The column
oven and RID were maintained at 35ºC, and flow rate for mobile phase was fixed at 0.8 ml
min-1 [79]. The samples were centrifuged, diluted and filtered using membrane GV
(Durapore) 0.22μm of pore and 13mm of diameter into the HPLC vials. Peaks were
detected by the RI detector and quantified on the basis of area and retention time of the
standard (ethanol) procured from Merck. The procedure was carried out in the Laboratorio
de Intensificación de Procesos y Sistemas Híbridos, Universidad Nacional de Colombia
sede Manizales.
2.5.4 Alkane precursor determination
Alkane precursor (4-(2-furyl)-3-buten-2-one) identification was based on mass spectra (EI,
70 eV) obtained with a gas chromatograph (Agilent Technologies 6850 Series II) equipped
with a mass selective detector (MSD 5975B). The injector temperature was kept at 250 °C.
The chromatographic separation was performed using a HP-5MS capillary column
(30 m × 0.25 mm i.d., 0.25 μm film thickness). Helium (99.99%) was used as the carrier
58 Jet fuel production from agroindustrial wastes through furfural platform
gas with a constant flow rate of 1 mL min-1 and a 1:100 split ratio. The GC oven temperature
was programmed from 40 °C (2 min) to 250 °C with the heating rate of 5 °C min-1, and hold
up during 2 min. The temperature of the GC/MS interface was held at 250 °C. Mass spectra
and reconstructed chromatograms were obtained by automatic scanning in the mass
range m/z 40–350 at 3.5 scan s−1. Chromatographic peaks were checked for homogeneity
with the aid of the mass chromatograms for the characteristic fragment ions. The procedure
was made according to reported by Z. Krkosová et al., 2007 [80] with some modifications
and was carried out in the Laboratorio de Instrumental of the Instituto de Biotecnología y
Agroindustria –IBA–, Universidad Nacional de Colombia sede Manizales.
2.6 Catalyst characterization
2.6.1 X-Ray diffraction
X-ray analysis of solids was carried out using a Rigaku Miniflex II diffractometer. The
patterns were run with copper radiation (λ = 1.5406 A) at 30 kV and 15 mA; the diffraction
angle 2θ between 3-70° was scanned at a rate of 5ºC min−1 [39], [76], [77]. The procedure
was carried out in the Laboratorio de Materiales Nanoestructurados y Funcionales,
Universidad Nacional de Colombia at Manizales.
2.6.2 FT-IR
The Fourier transform infrared spectrum (FT-IR) of sample was performed by means of a
spectrometer Nicolet iS5 (Thermo Scientific, Madison, US) with a Transmission iD1
accessory using KBr pellet. Data were collected over 64 scans with a resolution of 4 cm-1
in the range 4,000 to 400 cm-1 [76], [81]. The procedure was carried out in the Laboratorio
de Instrumental of the Instituto de Biotecnología y Agroindustria –IBA–, Universidad
Nacional de Colombia at Manizales.
Chapter 2 59
2.6.3 TGA
Thermogravimetric analysis was performed in a TGA Q500 TA Instruments. The TG curves
were carried out under dynamic nitrogen atmosphere (50 mL min-1). Temperature was
increased from 25 up to 800ºC at 10ºC min-1. The procedure was carried out in the
Laboratorio de Magnetismo y Materiales Avanzados, Universidad Nacional de Colombia at
Manizales.
2.6.4 SEM – EDX
Scanning electron microscopy coupled with energy dispersive X-ray (SEM/EDX)
spectroscopy analysis was carried out in a FEI, Quanta 250 with digital image acquisition
to study the surface morphology. The procedure was carried out in the Instituto de
Investigaciones en Estratigrafía, Universidad de Caldas.
2.7 Determination of physicochemical properties
2.7.1 Density
Density was determined according to Standard Test Method for Density, Relative Density
and API Gravity of Liquids (ASTM D4052) [82]. Record the weight of pycnometer of known
volume. Add the sample into the apparatus until the gauging. Insert the apparatus into the
water bath. After insertion, allows the pycnometer to reach bath temperature (15ºC). When
reaches the temperature record the weight again. Density is the result of difference between
the final and initial weight measure divided by the volume of the pycnometer.
2.7.2 Viscosity
Viscosity was determined according to Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (ASTM D445-12) [83]. 15 ml of sample were added to
Ostwald’s viscometer through the larger diameter tube and was inserted the apparatus into
the bath. After insertion, was allowed that the viscometer to will reach bath temperature (-
20ºC). When reached the temperature, the liquid was aspirated above the upper mark of
the smaller diameter tube. The time it takes the sample to pass between the gauging 1 and
60 Jet fuel production from agroindustrial wastes through furfural platform
2 was measured. Viscosity was the result of multiplying the constant parameter given by
the viscometer according to size and the measured time. Viscometer sizes were 1 and 1C
and constant respective is 0.01048 and 0.03034 mm2 s-2 (cSt s-1).
2.7.3 Freezing Point
Freezing point was determined according to Standard Test Method for Freezing Point of
Aviation Fuels (ASTM D2386-06) [84]. 15 ml of sample was transferred to a test tube. The
apparatus was inserted into the bath while the temperature descended gradually. The
sample was observed continuously until appearance of crystals. The temperature was
recorded when the crystals completely appeared.
2.7.4 Heat Capacity
The thermal treatment of samples was carried out in-situ, in DSC-Q100 TA instruments.
The MDSC curves were performed under nitrogen atmosphere (50ml min-1). Samples were
prepared in aluminum hermetic DSC capsule. Once sealed, it was allowed to equilibrate for
30 minutes to assure stabilization. An empty capsule was used as reference. The samples
were tested in MDSC ramps from 25 to 70ºC, for 5ºC min-1.
2.7.5 Flash point
Flash point was determined according to Standard Test Method for Flash Point by Pensky-
Martens closed cup tester (ASTM D93) [85]. The cup was filled with the sample being tested
up to the level indicated by filling mark. The lid was put on the cup and was left the cup
inside the stove. The thermometer was inserted into the thermometer port. The test flame
was lit with an external ignition source and was adjusted the flame. The stirrer was
connected to the stirrer motor to homogenize the sample. The stirrer motor during the
application of the test flame was turned off. The test flame was applied at each temperature
reading by turning the fiber knob clockwise. The cover assembly was opened and the test
flame was immersed into the sample cup. The temperature was recorded when the flash
point occurred. The proofs were made in K16200 flash point tester assembly (115V Model).
Chapter 2 61
2.8 Process Simulation Description
2.8.1 Techno-economic Assessment
For a given scenario, flowsheet synthesis was carried out using process simulation tools.
The objective of this procedure was to generate the mass and energy balances from which
the requirements for raw materials, consumables, utilities and energy needs are calculated.
The main simulation tool used was the commercial package Aspen Plus v8.2 (Aspen
Technology, Inc., USA). Specialized package for performing mathematical calculations
especially for kinetic analysis such as Matlab was also used. The acid and enzymatic
hydrolysis were calculated using the kinetic models reported by Huang et al. (2011) [70]
and Morales-Rodriguez et al. (2011) [86] respectively. The fermentation stage for fuel
ethanol production was calculated using the kinetic model reported by Rivera et al. (2006)
[87] when Saccharomyces cerevisiae is considered and the kinetic model reported by
Rogers et al. (2001) [88] when Zymomonas mobilis is used as microorganism. Kinetic
model for detoxification were reported by Martinez et al. (2001) [89]. The kinetic model used
for the calculation of PHB production was reported by Shahhosseini (2004) [90]. For some
products (furfural, HMF, octane and nonane) reaction conditions were adapted from
different studies [41], [89] - [91]. One of the most important issues to be considered during
the simulation procedure is the appropriate selection of the thermodynamic models that
describe the liquid and vapor phases. Non-Random Two-Liquid (NRTL) thermodynamic
model was applied to calculate the activity coefficients of the liquid phase and the Hayden-
O’Connell equation of state was used for description of the vapor phase. The most selected
model for this issue was UNIFAC-DORTMUND for liquid phase and Soave Redlick Kwong
for vapor phase.
The estimation of the energy consumption was performed based on the results of the mass
and energy balances generated by the simulation. For this purpose, the thermal energy
required in the heat exchangers and re-boilers was taken into account, as well as the
electric energy needs of the pumps, compressors, mills and other equipments. The capital
and operating costs were calculated using the Aspen Process Economic Analyzer v8.2
software (Aspen Technologies, Inc., USA). This analysis was estimated in US dollars for a
10-year period at an annual interest rate of 17% (typical for the Colombian economy),
considering the straight line depreciation method and a 25% income tax. Prices and
62 Jet fuel production from agroindustrial wastes through furfural platform
economic data used in this analysis correspond to Colombian conditions such as the costs
of the raw materials, income tax, labour salaries, among others, were incorporated in order
to calculate the production costs per kilogram of product. Table 2-1 summarizes the
economic data used in the different process configuration.
Chapter 2 63
Table 2-1 Price/cost of feedstock, utilities and products used in the economic assessment.
Item Unit Price Reference
Rice husk USD ton-1 5 [92]
Sugarcane bagasse USD ton-1 15 [92]
Coffee cut-stems USD ton-1 18 [92]
Fique bagasse USD ton-1 5.7 +
Ethanol USD kg-1 1.07 [93]
Butanol USD kg-1 1.9 [94]
Octanol USD kg-1 1.68 [94]
Furfural USD kg-1 1.7 [94]
5-HMF USD kg-1 2.0 [94]
Octane USD kg-1 7.0 [94]
Nonane USD kg-1 22.5 [94]
Sulfuric acid USD kg-1 0.094 [95]
Calcium hydroxide USD kg-1 0.07 [95]
Acetone USD kg-1 0.97 [95]
Toluene USD kg-1 0.85 [95]
Hydrogen USD kg-1 9.26 [94]
Dimethyl sulfoxide USD kg-1 1.0 [94]
Butanol USD kg-1 1.9 [94]
Glucose USD kg-1 0.8 [94]
Xylose USD kg-1 1.5 [94]
PHB USD kg-1 3.5 [94]
Mixture of alcohols USD kg-1 2.91 +
Mid P. Steam (30bar) USD ton-1 8.18 [96]
Low P. Steam (3bar) USD ton-1 1.57 [96]
Fuel USD/MEGAWatt 24.58 [97]
Water USD m-3 0.74 *
Electricity USD/kWh 0.14 *
Operator labor USD h-1 2.56 *
Supervisor labor USD h-1 5.12 *
+ Estimate.
*Typical prices in Colombia.
64 Jet fuel production from agroindustrial wastes through furfural platform
Following is in detail the description of processes used to produce glucose, xylose, ethanol,
butanol, mixture of alcohols, furfural, HMF, octane, nonane and PHB.
Sugars extraction
Lignocellulosic biomass is submitted to a process consisting in three stages as follow
described: i) size reduction and pretreatment, ii) dilute-acid pretreatment and iii) enzymatic
hydrolysis. The first stage of the process involved a size reduction stage in which the
expected final particle diameter was 1 mm. After milling and sieving, in the second stage
the hemicellulose fraction is hydrolyzed with sulfuric acid (2% by weight) based on the
kinetic expressions reported by Huang et al. (2011) [70] at 100 °C. This process is carried
out in a single reactor. The result of this hydrolysis is a non-converted solid fraction and a
rich-pentose liquor which is separated by filtration. Finally in the third stage, the solid
fraction rich in cellulose and lignin is submitted to an enzymatic hydrolysis step based on
the kinetic expressions reported by Morales-Rodriguez et al. (2011) [86] at 35°C to obtain
a rich-hexoses liquor and a solid residue rich in lignin.
As a by-product in the dilute-acid pretreatment, furfural and HMF are obtained as a result
of the decomposition reactions of sugars. Then, detoxification technology is applied [98],
[99]. This procedure is carried out to avoid poisoning and inhibition by the acids, furfural
and HMF in the fermentation stage where Z. mobilis is used as microorganism.
Ethanol
The fermentation step is carried out with Saccharomyces cerevisiae when hexoses are
considered as feedstock. On the other hand, as an alternative Zymomonas mobilis is used
as fermentation microorganism for ethanol production using pentoses as feedstock
(scenario 4). Initially rich-sugar liquor is sent to a sterilization process at 121°C in which the
biological activity is neutralized. Later the fermentation process is carried out based on the
kinetic expressions reported by Rivera et al. (2006) [87] and Rogers et al. (2001) [88], using
Saccharomyces cerevisiae at 37ºC and Zymomonas mobilis at 30ºC as microorganisms
respectively. Afterwards, cell biomass is separated from the culture broth by a simple
gravitational sedimentation technology. After the fermentation stage, the culture broth
containing approximately 5-10% (wt/wt) of ethanol is taken to the separation step, which
Chapter 2 65
consists of two distillation columns. In the first column, ethanol is concentrated nearly to 45-
50% by weight. In the second column, the liquor is concentrated until the azeotropic point
(96% wt) to be led to the dehydration step with molecular sieves to obtain an ethanol
concentration of 99.6% by weight [100].
Butanol
Rich-hexoses liquor is sent to sterilization process at 121°C in which the biologic activity is
neutralized. Then, the ABE fermentation process is carried out based on the kinetic
expressions reported by (van der Merwe 2010), at 33°C using C. acetobutylicum as
microorganism. Afterwards, cell biomass is separated from the culture broth containing
approximately 5% (wt/wt) of butanol. The resulting stream is taken to the separation zone,
which consists of three distillation columns. In the first column, some organic components
and the most of the water are removed, concentrating the butanol up to 53%. The second
column removes acetone and ethanol, obtaining butanol is at 69%. Finally, in the third
column of the mixture water-butanol is separated for obtaining butanol at a concentration
of 90% by weight (van der Merwe 2010) [101].
Mixture of alcohols
The process to obtain mixture of alcohols is composed by three stages, i) dehydration
process of ethanol to obtain ethylene at 450ºC, ii) Ziegler process in presence of oxygen
and aluminum to form triethylaluminum, and iii) oxidation process to form an alcohols mix
at 290ºC and 25bar [102].
Furfural
Furfural is obtained from rich-pentose liquor via xylose dehydration, catalyzed by aluminum
and hafnium pillared clays with 86.2% of conversion [103] and using air as stripping agent
for removing the product while is produced [91]. First the liquor is sent to a reactor at 170°C
and 10bar. Air is fed into the reactor at a ratio of 30:1 air to feed. The resulting stream is
depressurized to recover the liquid fraction. Then, the mixture is sent to a liquid-liquid
extraction process with toluene as solvent with 1:1 v/v ratio to recover the furfural from the
water. Finally, the solvent-furfural stream is submitted to a distillation process where the
furfural is obtained as bottom product [91].
66 Jet fuel production from agroindustrial wastes through furfural platform
HMF
HMF is obtained from rich-hexose liquor via glucose dehydration, through a non-catalyzed
system in water as describe Jing et al. (2008) [104]. Liquor is sent to a reactor at 220ºC
and 10MPa. The resulting stream is the depressurized. Then, the mixture is sent to a liquid-
liquid process with dimethyl sulfoxide (DMSO) as solvent with 1:0.6 molar ratio to recover
the HMF from water. Finally, the solvent-HMF stream is submitted to a distillation process
where the HMF is obtained as bottom product [105], [106].
Octane
Octane is obtained from furfural. The process to obtain octane is described in three steps:
1) aldol-condensation of furfural with acetone over MgO/NaY as catalyst at 85ºC as
describe Wang et al. (2012) [38], 2) mild hydrogenation of aldol products at 140ºC and
2.5MPa catalyzed by Pt/Co2AlO4 as describe Lu et al. (2011) [41] and 3)
dehydration/hydrogenation to liquid alkanes at 170ºC and 2.5MPa [41]. Finally, octane at
82% is obtained by distillation.
Nonane
Nonane is obtained from HMF. The process to obtain nonane is described in three steps:
1) aldol-condensation of HMF with acetone (molar ratio of 1:10) over MgO/ZrO2 as catalyst
at 50ºC as described Dumesic et al. (2007) [40] 2) hydrogenation of aldol products in
supercritical carbon dioxide in the presence of Pd/Si-Al-MCM-41 catalyst at 80ºC and
12MPa as describe Chatterjee et al. (2008) [107] and 3) dehydrogenation/hydrogenation to
liquid alkanes at 80ºC [107]. Finally, nonane at 88% is obtained by distillation.
PHB
Initially rich-hexose liquor is sent to a sterilization process at 121°C in which the biological
activity is neutralized also involving a nitrogen source ((NH4)2SO4). The ratio of the nitrogen
source to the carbon source is 0.16 wt/wt. Later the fermentation process is carried out
based on the kinetic expressions reported by Shahrokv Shahhosseini (2004) [90], using R.
eutropha at 30ºC. Afterwards, cell biomass is separated from the culture broth by a simple
gravitational sedimentation technology. After the fermentation stage, the culture broth is
Chapter 2 67
washed in order to remove impurities to finally remove water by evaporation and spray
drying to obtain PHB approximately at 98% (w/w).
Environmental Assessment
2.8.2 Environmental Assessment
The environmental analysis was carried out using the Waste Reduction Algorithm (WAR
Algorithm) designed by the Environmental Protection Agency of the United States (US EPA)
by WARGUI software. This algorithm is based on the determination of the Potential
Environmental Impact (PEI), which is a conceptual quantity representing the average
unrealized effect or impact that mass and energy emissions would have on the environment
[108]–[110] The PEI are quantified in Human Toxicity Potential by Ingestion (HTPI), Human
Toxicity Potential by Exposure (HTPE), Aquatic Toxicity Potential (ATP), Terrestrial Toxicity
Potential (TTP), Global Warming Potential (GWP), Ozone Depletion Potential (ODP),
Photo-chemical Oxidation Potential (PCOP) and Acidification Potential (AP). Some PEI’s
of compounds such as lignin, cellulose and hemicelluloses are not in database of WARGUI
software, so they were taken from several material safety data sheet, articles, among
others. The WAR algorithm is a tool to compare process configurations from the
environmental point of view.
3. Characterization results of lignocellulosic biomass
3.1 Overview
Lignocellulosic biomass consists of mainly three different types of polymers, cellulose,
hemicellulose and lignin. This chapter presents the physicochemical characterization of the
lignocellulosic biomass studied in this work as potential feedstock to produce furan-based
compounds and biofuels. In addition, the characterization provides potential information
that can be used to produce sugars (C5 and C6) in Colombia. All characterizations were
compared with previously works reported in the literature.
3.2 Results and discussion experimental characterization
Lignocellulosic biomass, mainly composed of cellulose, hemicellulose, and lignin, is the
most abundant renewable resource available for the industrial production of biochemicals.
The composition in term of major compounds is different for various plant fractions and
development stages, as well as for different types of plant cell wall. The bioconversion of
lignocellulosic materials is dependent not only on the biochemical composition of the matrix
but also on the tissues and cell wall organization and of their constituents and the interaction
between them. Thus, the information about the composition is of vital importance to
understand the mechanisms of mechanical conversion and further to optimize the utilization
of lignocellulosic materials [57], [111].
70 Jet fuel production from agroindustrial wastes through furfural platform
3.2.1 Rice husk (RH)
The tables 3-1 and 3-2 show the experimental chemical composition of rice husk and some
data reported in the literature respectively. As can see, the compositions change slightly
according to authors, holocellulosic content is less than in other raw materials but ash
content is considerably high. This lignocellulosic residue, besides to be source of reducing
sugars is raw material to obtain silica-based products. The medium content of fiber
lignocellulosic is reflected in minor yields to sugars. These results indicate the potential of
this raw material as source of different biochemicals due to compositional diversity.
Table 3-1 Rice husk composition on a dry basis.
Feature Content (wt %)
Cellulose
Hemicellulose
Lignin
Extractives
Ash
40.70 ± 1.77
15.57 ± 0.22
26.54 ± 5.86
6.28 ± 0.89
10.91 ± 0.01
Table 3-2 RH chemical characterization reported in literature (wt %).
Cellulose Hemicellulose Lignin Ash Others Reference
34.40 24.30 29.20 15-20 N.A. [53]
40.50 13.65 17.50 21.27 N.A. [54]
63.53* 35.50 N.A. 1.58 [112]
N.A.: Non-Available *Holocellulose: cellulose + hemicellulose
3.2.2 Sugarcane Bagasse (SCB)
Experimental chemical composition of sugarcane bagasse is shown in Table 3-3. Its
considerable holocellulose content confirms the important role as pioneer raw material to
produce energy, fuels and biochemicals. The results of characterization in the feedstock
are in accordance with studies reported by authors cited as shows the table 3-4. As can be
seen, SCB has a high content of cellulose that can be used as raw material to produce
reducing sugars (glucose) hence alcohols and organic acids can be obtained. Additionally,
the relatively low lignin content associated with the fiber makes technical and economically
Chapter 3 71
feasible the recovery of almost completely the total cellulose by using a suitable
delignification process.
Table 3-3 Sugarcane bagasse composition on a dry basis.
Component Content (wt %)
Cellulose
Hemicellulose
Lignin
Extractives
Ash
46.74 ± 4.40
23.62 ± 2.10
19.71 ± 0.76
8.79 ± 2.38
1.13 ± 0.01
Table 3-4 SCB chemical characterization reported in literature (wt %).
Cellulose Hemicellulose Lignin Ash Others Reference
40.6 20.9 17.4 4.0 17.1 [57]
40-45 30-35 20-30 N.A. N.A. [61]
42.2 27.6 21.6 2.84 5.63 [63]
42.3 25.1 24.7 3.5 3.7 [63]
41.2-47 25.1-26 19.5-21.7 1.4-5.4 2.3-2.9 [63]
38.0 32.0 27.0 2.3 0.7 [113]
32-45 19-24 27-32 N.A. N.A. [114]
44.94 28.24 18.93 N.A. 7.89 [115]
N.A.: Non-Available
3.2.3 Coffee Cut-Stems (CCS)
Table 3-5 shows the experimental chemical composition of coffee cut-stems. The results
indicate as the fibers that composed this residue have a mild balance in the content of
cellulose and hemicellulose that can be raw material to obtain products from xylose and
glucose equitably. Table 3-6 shows some results of compositional analysis of lignocellulosic
biomass given in the literature. As can see, the compositions change slightly according to
authors and this may be due to culture conditions, climate and/or soil characteristics. The
use of this raw material as lignocellulosic biomass is associated to some difficulties such
as storage and collecting affected mainly when the crops are at locations that are difficult
to access. These factors can compromise the availability and the price. Despite the
72 Jet fuel production from agroindustrial wastes through furfural platform
potential of CCS discovered in recent years, the issues mentioned above have not allowed
a constant in their use.
Table 3-5 Coffee cut-stems composition on a dry basis.
Component Content (wt %)
Cellulose
Hemicellulose
Lignin
Extractives
Ash
40.39 ± 2.23
34.01 ± 1.17
10.13 ± 1.29
14.18 ± 0.85
1.27 ± 0.03
Table 3-6 CCS chemical characterization reported in literature (wt %).
Cellulose Hemicellulose Lignin Ash Others Reference
37.35 27.79 19.81 2.27 12.79 [112]
33.5 24.97 17.80 N.A. N.A. [116]
40-50 20-40 18-25 N.A. N.A. [116]
N.A.: Non-Available
3.2.4 Fique Bagasse (FB)
The tables 3-7 and 3-8 indicate the results of experimental chemical composition of FB and
some data reported in the literature respectively. As can be seen, this material has a high
content of extractives represented mainly in chlorophyll. However, the cellulose content is
sufficiently representative to say that this raw material can be an additional alternative to
the well-known lignocellulosic biomass to produce bioproducts. Currently, only 4% of the
plant source of this residue is being exploited and 96% remaining is represented in juice
and bagasse. The use of bagasse as raw materials to obtain added-value products can
mitigate the self-generated pollution in crop fields.
Chapter 3 73
Table 3-7 Fique bagasse composition on a dry basis.
Component Content (wt %)
Cellulose
Hemicellulose
Lignin
Extractives
Ash
50.79 ± 3.01
14.19 ± 1.37
12.47 ± 1.05
21.84 ± 1.98
0.69 ± 0.09
Table 3-8 FB chemical characterization reported in literature (wt %).
Cellulose Hemicellulose Lignin Ash Others Reference
67-78 7-11 20-24 0.6-1 N.A. [53]
31.08 23.19 25.45 6.41 9.5 [117]
41.81 22.17 15.56 N.A N.A [118]
N.A.: Non-Available
3.3 Final remarks
This section show the results of chemical composition of lignocellulosic biomass that may
offer interesting sources to obtain energy, biofuels, biochemicals, biofertilizers, etc. The
features of biomass analyzed reflect its great potential of viability. The integrated use of
lignocellulosic biomass characterized with a process engineering concept involves
economic and environmental benefits translated in obtaining sustainable products.
Production processes from lignocellulosics can be developed in many directions and
special attention has been paid to sugar derivatives that can be used as a chemical building
block (sugars and furan-based compounds)
4. Results physicochemical properties of blends
4.1 Overview
Environmental concerns and the rising cost of crude oil have incentivized the search for
alternative aviation fuels. However, any potential alternatives must be thoroughly
characterized and tested. In this chapter, the properties of blends such as ethanol-butanol,
ethanol-octanol and ethanol-biodiesel are presented. Density, viscosity, freezing point and
heat of combustion are assessed to analyze the compatibility between blends and
conventional jet fuel (Jet A-1). Experimental results of blends are compared with properties
of jet fuel given by ASTM D1655 and DEF STAN 91-91. According to results, the blend with
the best behavior is ethanol-biodiesel (70 to 50% of ethanol) with a density of 0.82 g cm-3,
viscosity of 6.7 mm2 s-1, freezing point of -40 ºC and flash point of 56.3ºC (average values).
4.2 Results and Discussion
Table 4-1 shows some physicochemical properties of Jet A-1. These properties given a
reference point to evaluate the compatibility of blends studied with a conventional aviation
fuel.
76 Jet fuel production from agroindustrial wastes through furfural platform
Table 4-1 Jet A-1 aviation fuel specifications [119], [120].
Property Unit ASTM D1655 DEF STAN 91-91
Density (15ºC) g/cm3 0.775-0.84 0.775-0.84
Viscosity (-20ºC) mm2/s Max 8 Max 8
Freezing point ºC Max -40 Max -47
Flash point ºC Min 38 Min 38
The Jet A-1 standard stipulates that the density of a fuel must sit within the range 0.775–
0.840 g cm-3. The densities of ethanol-biodiesel blend follow a roughly linear trend all within
the values specified for Jet A-1. On the contrary, the blends between alcohols have a
decreasing trend with a maximum point slightly above of required values by standard. The
density of the fuel is important in the operation of aircraft required to fly long distances, or
in smaller aircraft where space is limited. In these cases the limiting factor on range is the
volume of the fuel tank rather than the maximum structural weight capacity of the airframe
[27].
According to the Jet A-1 specifications indicate that a fuel must have a viscosity of no more
than 8mm2 s-1 at -20ºC. The viscosities of blended fuels were ascertained at an of
temperature from -20ºC up to -22ºC to give a clearer indication of performance (tables 4-1,
4-2 and 4-3). Highly viscous aviation fuels lead to poor atomization and combustion,
pumping difficulties and in extreme cases the blocking of fuel injectors. All blends exhibit
good viscosity behavior with an approximately lineal increase with a reduction in ethanol
fraction. n-Octanol had the highest viscosity for two of alternative fuels tested in this
investigation, presumably due to the increased hydrogen bonding between the alcohol
groups. As such at 90 and 70% of blend levels, n-octanol lies outside of the required
specification. Similarly, the blend with 90% of n-butanol is also not suitable as an aviation
fuel. The blends with 90% of ethanol appear to be promising candidates for blending with
aviation fuel as additive. These blends have a similar viscosity, which is roughly half that of
Jet A-1 at -20ºC. If both blends are mixed with aviation fuel can reduce the viscosity of the
overall fuel, this could have potentially beneficial consequences in terms of better
atomization and pumping, while also reducing the viscosity of highly viscous aviation fuels.
In the measure of freezing point a limitation was presented that prevented to determine with
exactness this property. For this reason, in the results only is indicated if the blend at -40ºC
Chapter 4 77
no has changed of aggregate state as establishes the requirements. All blends tested had
a suitable freezing point compatible with of the Jet A-1.
The energy density of a potential fuel impacts on the range vs. payload and a high energy
density is vital in trying to maximize the passenger and cargo capacity while retaining range.
Where weight capacity is the limiting factor, as is the case with most civil aviation flights, it
is desirable to have a fuel that produces the most energy per unit mass whereas in
applications where range is to be maximized, the volumetric energy content of the fuel is
the most important parameter, and a higher volumetric energy content is desirable [27],
[121]. In this work the heat capacity is taken as reference to measure the energy transferred
of the blend when has a temperature change. In general, the high values are presented
when the blend is dominated for a component with high molecular weight.
The flash point of a fuel is the temperature at which an ignitable air/fuel vapor forms above
the fuel. Conventional aviation fuel is a complex mixture of a few hundred different
hydrocarbons and as such, the molecular interactions that may govern the temperature at
which the flash point occurs are difficult to predict [27]. In this work the flash points of all
the alternative fuels were determined experimentally (Tables 4-2 to 4.4). The flash point of
the blended fuels appears to be largely dictated by that of the lower flashpoint component.
In the case of ethanol-butanol blend, the flash point of pure components is considerably
low for this reason the blends is not according to established in the standard. For the blend
ethanol-octanol only when ethanol is present in 10% of blend the flash point is acceptable.
Finally, for the blend ethanol-biodiesel the flash point increases proportionally to increment
of biodiesel fraction.
78 Jet fuel production from agroindustrial wastes through furfural platform
Table 4-2 Experimental properties for the ethanol-butanol blend in mass fractions.
Ethanol
fraction
Density to
15ºC (g/cm3)
Viscosity to -
20ºC (mm2/s)
Freezing
point (ºC)
Flash
point (ºC)
Heat capacity
(J/kg K)
0.1 0.88 9.19 < to -47 30 648.58
0.3 0.87 6.29 < to -47 27 -----
0.5 0.90 5.49 < to -47 20 952.21
0.7 0.86 4.21 < to -47 17 -----
0.9 0.84 3.35 < to -47 15 649.44
Table 4-3 Experimental properties for the ethanol-octanol blend in mass fractions.
Ethanol
fraction
Density to
15ºC (g/cm3)
Viscosity to -
20ºC (mm2/s)
Freezing
point (ºC)
Flash
point (ºC)
Heat capacity
(J/kg K)
0.1 0.890 33.1 < to -47 38 1216.27
0.3 0.918 14.8 < to -47 35 -----
0.5 0.861 6.98 < to -47 34 736.11
0.7 0.864 4.84 < to -47 28 -----
0.9 0.858 4.80 < to -47 25 630.26
Table 4-4 Experimental properties for the ethanol-biodiesel blend in mass fractions.
Ethanol
fraction
Density to
15ºC (g/cm3)
Viscosity to -
20ºC (mm2/s)
Freezing
point (ºC)
Flash
point (ºC)
Heat capacity
(J/kg K)
0.9 0.725 3.79 < to -40 28 824.11
0.8 0.789 4.76 < to -40 37 -----
0.7 0.808 5.09 < to -40 47 693.18
0.6 0.817 6.65 < to -40 55 -----
0.5 0.835 8.58 < to -40 67 521.75
4.3 Final remarks
According to the results from physicochemical properties in biofuel blends can be found an
alternative additive for the oxygenation of conventional fuels. While jet fuels have
requirements for the properties to low temperatures, the blend of ethanol-biodiesel satisfies
Chapter 4 79
substantially these requests. The use of these blends as additive or biofuel from process
generally biological can help to decrease the emissions of pollutants linked to the fossil
fuels and promote the transformation and use of lignocellulosic biomass. From global point
of view the use of biofuels in aviation can present some problems such as engine
modifications, thermal stability of fuel, storage of raw materials and biofuels, and production
costs and cost effectiveness of the process related to production.
5. Experimental results for production of ethanol and furfural from lignocellulosic biomass
5.1 Overview
In this chapter, the results of the experimental evaluation to obtain ethanol, furfural and
alkane precursors through two conditions of acid hydrolysis from rice husk, sugarcane
bagasse, coffee cut-stems and fique bagasse are presented. First, the influence of
pretreatment conditions such as time and acid concentration in the yields of sugars, ethanol
and furan-based compounds are analyzed. Besides, the profiles of the ethanolic
fermentation are shown. Second, the yields obtained in each one of stages of
transformation process are discussed which are composed of steps shown in the figure 4-
1. Finally, the characterization of catalyst used in aldolcondensation reaction to obtain jet
fuel intermediates is presented. This process is made by a wide range of physical
techniques such as X-ray, FT-IR, TGA and SEM-EDX.
5.2 Results and discussion of experimental procedure
Figure 5-1 shows the schematic representation of the sequence established for the
processing of the agroindustrial wastes to obtain ethanol, furan-based compounds and
alkane precursor. Pretreatment initial of raw materials is surely a key element regarding
technical and economical features. This stage comprises material adequacy (drying and
particle size), acid hydrolysis and enzymatic hydrolysis. These procedures are made in
82 Jet fuel production from agroindustrial wastes through furfural platform
order to alter the lignocellulosic structure of feedstock and obtain sugars (xylose and
glucose) as platform to transform to interesting products.
Figure 5-1 Diagram of experimental procedure to obtain ethanol, furfural and alkane precursor.
Cond 1. 2 %v/vH2SO4, 5h y 115ºC. Cond 2. 10 %v/vH2SO4, 0.5h y 115ºC
Tables 5-1 to 5-4 indicate the results obtained in experimental procedure of conversion of
lignocellulosic biomass studied in this work to alcohol, furan-based compound and
derivatives. First, the concentrations of glucose, xylose, furfural and HMF obtained at two
operation conditions of acid hydrolysis. Second, the amount of reducing sugars generated
in cellulose transformation through of enzymatic hydrolysis. Third, the yield referred to the
mass of ethanol per mass of substrate in process fermentation. Fourth, data of dehydration
reaction as the final concentration of furfural with his respective yield per mass of xylose.
Finally, furfural consumption to produce alkane precursor in aldol condensation reaction.
Chapter 5 83
5.2.1 Ethanol production
Ethanol is a liquid biofuel with the potential to partially replace the gasoline needed for
transportation worldwide and in the last years this fuel has become one of the most studied
biofuels. It is well known that ethanol production from lignocellulosic biomass involves four
steps: mechanic pretreatment of biomass, saccharification (acid and/or enzymatic),
fermentation and distillation. Then, a brief discussion of results obtained for the first three
stages corresponding to the work developed in this thesis.
The acid hydrolysis has variables as reaction time and acid concentration that determine
the formation of products. For this reason, two operation conditions were evaluated.
According with the results for RH and SCB, the reaction time has an effect positive in
production of xylose and acid concentration helps to have higher concentration of furfural
as by-product. However, this parameters have different effect when it is CCS and FB. In
these cases, the sugar and furfural concentration has not a significant change between
hydrolysis conditions. In this sense, acid hydrolysis with operation conditions 1 are obtained
yields for xylose of 0.83, 0.81, 0.50 and 0.58 grams per grams of hemicellulose contained
in RH, SCB, CCS and FB respectively. For operation conditions 2 are obtained yields for
xylose of 0.61, 0.60, 0.51 and 0.54 grams per grams of hemicellulose for RH, SCB, CCS
and FB respectively.
When acid hydrolysis is carried out using a high concentration of acid can bring serious
implications on sugar integrity affecting the yields of reducing sugars in enzymatic
hydrolysis. Results show that for operation conditions 1 there are yields of 0.20, 0.38, 0.21
and 0.34 (grams of glucose per gram of initial cellulose) for RH, SCB, CCS and FB
respectively. On the contrary, for conditions 2 the yield for RH, SCB, CCS and FB were
0.17, 0.33, 0.19, and 0.33 respectively. Due to that the hydrolysis with 10% of H2SO4 has
not a large contact time, the yields show no a considerable reduction. Raw materials that
have high cellulose content offer high concentration of sugars reducing, it is the case of
SCB and FB.
Process fermentation is the final stage for glucose line, the availability of sugars reducing
determines the productivity in the transformation to ethanol. The conversion of sugars from
lignocellulosic biomass studied in this work indicate satisfactory results but, as was
expected the yields in conditions 1 show higher values. Data reported in literature indicate
that yields when CCS is used as raw material are 0.34, 0.23 and 0.41 grams of ethanol per
84 Jet fuel production from agroindustrial wastes through furfural platform
gram of substrate (xylose and glucose) for Candida lusitaniae, Pichia stipitis and
Zymomonas mobilis as microorganisms respectively [52], [65]. If rice husk is used as raw
material can be obtained yields of 0.29 grams of ethanol per gram of reducing sugars using
Saccharomyces cerevisiae as microorganism [52]. In the case of sugarcane bagasse using
S. cerevisiae the yield is 0.42 grams of ethanol per gram of sugars [122].
In the comparison of yields obtained with data reported can be seen that the experimental
procedures made in this work have a remarkable approach with what says the literature
using S. cerevisiae as microorganism and RH as raw material. For SCB, being the results
obtained considerably good the studies report slightly higher values. In the case of CCS,
although only glucose is considered as carbon source the yields obtained are high
compared with fermentation using P. stipitis and glucose and xylose as microorganism and
raw material respectively, as shown above. Finally, when FB is used the results are
satisfactory irrespective of little use that this feedstock has as source of ethanol.
5.2.2 Furfural production
Furfural is considered a chemical platform highly versatile and key used in the manufacture
of a wide range of important chemicals, and it is likely to be of increasing demand in different
fields, such as plastics, pharmaceutical, energy and agrochemical industries [73]–[75], [91],
[123]. C. Rong et al. 2012 reported that the production of furfural from corn stover has a
yield of 75% using as catalyst 10 %w/w of sulfuric acid. Additionally indicates that xylose
dehydration to furfural, the yield was under 10% when acid was nearly to 2.5% w/w. But
when the concentration of sulfuric acid became 12.5% w/w, the yield reduce to 51% [75].
In this work the acid concentrations were 3 and 18% w/w for operation condition 1 and 2
respectively. As can be seen, for all raw materials studied and subject to conditions 1 and
2 the average yields were 0.08 and 0.085 grams of furfural per gram of xylose respectively.
These results show a concordance slightly significant with the reported. The low yields of
furfural can be attributed to side reactions, such as xylose dehydration to other aldehydes
(e.g., formaldehyde), degradation of furfural, or polymerizations of intermediate, and furfural
[75].
Chapter 5 85
5.2.3 Catalyst characterization
X-Ray diffraction analysis
Figure 5-2 shows X-ray diffraction patterns of Mg-OX and ZrO2 and figure 5-3 shows X-ray
spectrum of MgO-ZrO2 obtained in catalyst characterization. In the comparison of both
figures can see that the X-ray pattern shows the presence of bands corresponding to MgO
(periclase) and ZrO2 (tetragonal phase) in the sample.
Figure 5-2 X-ray diffraction pattern of Mg-OX and ZrO2 [76].
Figure 5-3 X-ray spectrum of MgO-ZrO2 obtained in catalyst characterization.
FT-IR spectrum of MgO-ZrO2
Figure 5-4 shows FT-IR spectrum of MgO-ZrO2. The Fourier transform infrared spectrum
(FT-IR) of MgO–ZrO2 shows a strong absorption at 427.3 cm-1 due to the Zr–O vibration.
86 Jet fuel production from agroindustrial wastes through furfural platform
The intense bands were observed at 3405.2 and 1444.2 cm-1, it could be due to hydrated
compounds [81], [124]. The FT-IR spectrum of MgO–ZrO2 in the n(OH) region shows one
slight band around 3600–3700 cm-1, this band corresponds to –OH stretching vibrations of
surface hydroxyl groups [81], [125]. The peak observed at 1444.2 cm-1 could be due to Mg–
O interaction [81], [126].
Figure 5-4 FT-IR spectrum of MgO-ZrO2.
TGA profile of MgO-ZrO2
The thermal stability of the prepared sample was investigated by a TGA method. The
thermogram obtained for the calcined MgO–ZrO2 is presented in Figure 5-5. The TG profile
was characterized by two peaks of weight loss till 411.9ºC. The first one occurs at 38.65ºC
to 186.12ºC (3.34% weight loss). The second weight loss occurred between (4.66% weight
loss) 186.12ºC and 411.9ºC.
Figure 5-5 TGA profile of MgO-ZrO2.
Chapter 5 87
SEM-EDS Analysis
SEM images are shown in Figure 5-6 for catalyst. The EDX spectrum of catalyst clearly
indicates presence of Pd, Mg and Zr. From figure 5-6, it is evident that Pd/MgO-ZrO2
particles were obtained in a micro size range and showed uniform-sized particles.
Figure 5-6 SEM image of catalyst at 10μm. EDX spectrum and compositional report of catalyst.
Element Wt% At%
CK 669 1120 OK 3648 4583 MgK 5037 4164 ZrL 365 80 PdL 281 53
5.2.4 Alkane precursor production
MgO-ZrO2 is considered a heterogeneous catalyst and is composed by mixed metal oxides
(MMOs). MMOs can offer a modulation of surface acidity, catalytic activity and thermal
stability that leading to higher application in different fields compared to pure oxides. MMOs
88 Jet fuel production from agroindustrial wastes through furfural platform
represent one of the most important and widely employed classes of solid catalyst, either
as active phases or supports [76]. These catalyst are applied both for their acid-base and
redox properties. Important organic reactions as aldol-condensation, Cbz-protection of
amines and synthesis of 1,5-benzodiazepine are carried out in presence of this catalyst
[81].
Aldol-condensation and hydrogenation steps to form C8 to C15 alkane precursors is carried
out using a bifunctional Pd/MgO-ZrO2 catalyst that according to W. Shen et al., 2011 [77]
and C. J. Barret et al., 2006 [39] has high activity and selectivity, as well as excellent
recyclability and hydrothermal stability. It is important to note that during first reaction the
Pd on the catalyst is inert, because the performance of the Pd/MgO-ZrO2 catalyst is
identical to the performance of MgO-ZrO2 during aldol-condensation. The large compounds
obtained from this series of reactions undergo hydrodeoxygenation reactions to produce
final alkanes [39] - [41], [77]. Figure 5-7 indicates the essential features of the bifunctional
reaction pathways involved in the production of intermediates jet fuel (C8 to C15 alkane
precursors) from biomass-derived furfural from xylose.
Figure 5-7 Aldol-condensation reaction of furfural and acetone, followed by hydrogenation of aldol
products [39], [40].
Figures 5-8 to 5-11 show the appearance of precursor (4-(2-furyl)-3-buten-2-one) after
aldol-condensation reaction for operation condition 1 in acid hydrolysis of each raw
material. This product is the main intermediate or precursor to obtain jet fuels. The catalytic
performance was evaluated by the disappearance of furfural and appearance of monomer
despite that is not possible quantify the amount produced. According to results, specifically
the percentage of disappearance of furfural that indicate the tables 5-1 to 5-4 the Pd/MgO-
Chapter 5 89
ZrO2 as catalyst exhibits excellent catalytic activity with a maximum furfural conversion of
96.5% after reaction for 24h at 120ºC in a batch reactor.
When aldol-condensation reaction is carried out for operation condition 2, the formation of
interest product is not recorded for all raw materials. Taking into account that in this case
the reaction was evaluated according to following conditions, i) excess of catalyst, ii) excess
of acetone, iii) normal load of catalyst and iv) lower than normal catalyst loading. Although
were made some testing is believed that the high concentration of homogenous catalyst
(H2SO4) used in acid hydrolysis and dehydration inhibited to the heterogeneous catalyst
(Pd/MgO-ZrO2) or have been encouraged unwanted reactions forming sulfates of
magnesium, palladium and/or zirconium.
The data reported in literature indicate a disappearance percentage of 66% in the same
conditions that the procedure developed in this work [77]. When compared to results
obtained it is possible to say that the experiments made in this work are excellent and
shown clearly the potential of furfural as platform product to obtain great amount of
chemicals.
Figure 5-8 GC-MS chromatographs of furfural and precursor when RH is the used as raw material.
90 Jet fuel production from agroindustrial wastes through furfural platform
Figure 5-9 GC-MS chromatographs of furfural and precursor when SCB is the used as raw material.
Figure 5-10 GC-MS chromatographs of furfural and precursor when CCS is the used as raw
material.
Figure 5-11 GC-MS chromatographs of furfural and precursor when FB is the used as raw material.
Chapter 5 91
Table 5-1 Results ethanol and furfural production from RH.
Dilute-acid hydrolysis
Condition Temperature (ºC) Reaction time (h) H2SO4 (%v/v) Glucose (g/L) Xylose (g/L) Furfural (g/L) HMF (g/L)
1 115 5 2 2.64±0.02 14.76±0.42 1.09±0.02 0.05±0.0
2 115 0.5 10 4.01±0.15 10.84±0.28 1.74±0.02 0.04±0.0
Enzymatic hydrolysis
Acid Hydrolysis Condition Reducing sugars (g/L)
1 9.43±0.55
2 8.31±0.25
Ethanolic fermentation
Acid Hydrolysis Condition Yield (g ethanol/g glucose)
1 0.26±0.02
2 0.20±0.01
Dehydration reaction
Acid Hydrolysis Condition Furfural (g/L) Yield (g furfural/g xylose)
1 3.03±0.06 0.13±0.005
2 3.59±0.05 0.17±0.02
Aldol-condensation reaction
Acid Hydrolysis Condition Furfural (g/L) % disappearance
1 1.25±0.08 58.7±0.02
92 Jet fuel production from agroindustrial wastes through furfural platform
Table 5-2 Results ethanol and furfural production from SCB.
Dilute-acid hydrolysis
Condition Temperature (ºC) Reaction time (h) H2SO4 (%v/v) Glucose (g/L) Xylose (g/L) Furfural (g/L) HMF (g/L)
1 115 5 2 5.75±0.11 22.10±0.05 1.48±0.01 0.09±0.0
2 115 0.5 10 7.03±0.26 16.21±0.16 1.89±0.15 0.05±0.0
Enzymatic hydrolysis
Acid Hydrolysis Condition Reducing sugars (g/L)
1 20.65±1.77
2 18.12±0.83
Ethanolic fermentation
Acid Hydrolysis Condition Yield (g ethanol/g substrate)
1 0.27±0.005
2 0.24±0.013
Dehydration reaction
Acid Hydrolysis Condition Furfural (g/L) Yield (g furfural/g xylose)
1 2.83±0.06 0.06±0.008
2 2.85±0.05 0.06±0.057
Aldol-condensation reaction
Acid Hydrolysis Condition Furfural (g/L) % disappearance
1 0.80±0.12 71.7±0.018
Chapter 5 93
Table 5-3 Results ethanol and furfural production from CCS.
Dilute-acid hydrolysis
Condition Temperature (ºC) Reaction time (h) H2SO4 (%v/v) Glucose (g/L) Xylose (g/L) Furfural (g/L) HMF (g/L)
1 115 5 2 2.89±0.08 19.41±0.61 0.92±0.05 0.07±0.0
2 115 0.5 10 3.07±0.15 19.58±0.02 0.86±0.05 0.05±0.0
Enzymatic hydrolysis
Acid Hydrolysis Condition Reducing sugars (g/L)
1 9.66±0.40
2 8.83±0.10
Ethanolic fermentation
Acid Hydrolysis Condition Yield (g ethanol/g substrate)
1 0.25±0.06
2 0.19±0.003
Dehydration reaction
Acid Hydrolysis Condition Furfural (g/L) Yield (g furfural/g xylose)
1 2.16±0.21 0.063±0.02
2 2.17±0.15 0.067±0.005
Aldol-condensation reaction
Acid Hydrolysis Condition Furfural (g/L) % disappearance
1 0.074±0.02 96.5±0.014
94 Jet fuel production from agroindustrial wastes through furfural platform
Table 5-4 Results ethanol and furfural production from FB.
Dilute-acid hydrolysis
Condition Temperature (ºC) Reaction time (h) H2SO4 (%v/v) Glucose (g/L) Xylose (g/L) Furfural (g/L) HMF (g/L)
1 115 5 2 9.14±0.21 9.34±0.13 0.30±0.02 0.51±0.01
2 115 0.5 10 9.14±0.21 8.55±0.21 0.27±0.01 0.21±0.01
Enzymatic hydrolysis
Acid Hydrolysis Condition Reducing sugars (g/L)
1 19.69±1.25
2 18.69±1.55
Ethanolic fermentation
Acid Hydrolysis Condition Yield (g ethanol/g substrate)
1 0.24±0.03
2 0.23±0.02
Dehydration reaction
Acid Hydrolysis Condition Furfural (g/L) Yield (g furfural/g xylose)
1 1.16±0.08 0.092±0.009
2 0.66±0.09 0.045±0.052
Aldol-condensation reaction
Acid Hydrolysis Condition Furfural (g/L) % disappearance
1 0.082±0.04 92.9±0.008
5.3 Final remarks
In this study the performance and influence of the operating conditions for acid hydrolysis
on processes RH, SCB, CCS and FB were compared. The overall data presented here
increase the understanding of the effects of acid concentration on raw materials when
are submitted to the enzymatic hydrolysis and fermentation process to obtain ethanol,
dehydration to produce furfural and aldol-condensation to generate monomer. Besides
knowing the excellent features that have the lignocellulosic biomass as availability and
low commercial value to produce biofuels as ethanol this work presents a new
perspective for biomass conversion from catalysis point of view to obtain precursors of
jet fuel range alkanes.
Also, has been shown that Pd/MgO-ZrO2 catalyst prepared by a simple and green
method exhibits excellent performance and is an active catalyst for aldol-condensation
over basic sites (MgO-ZrO2). This bifunctional catalyst allows to carbohydrate-derived
compounds, like furfural and HMF, to be converted in a single reactor to large water-
soluble intermediates for further aqueous phase processing to produce liquid alkanes.
6. Techno-economic and environmental assessment for jet biofuels production
The raw materials assessed can be used to obtain not only jet fuel additives, but also to
generate other products of added-value as demonstrated in Chapter 5. In this chapter
different cases are presented including biorefineries and no biorefineries approaches.
6.1 Biorefineries based on coffee cut-stems and sugarcane bagasse: furan-based compounds and alkanes as interesting products
6.1.1 Overview
This work presents a techno-economic and environmental assessment for a biorefinery
based on sugarcane bagasse and coffee cut-stems. Five scenarios were evaluated at
different levels, conversion pathways, feedstock distribution and technologies to produce
ethanol, octane, nonane, furfural and hydroxymethyl furfural (HMF). These scenarios
were compared between them according to raw material and economic and
environmental characteristics. A simulation procedure was used in order to evaluate
biorefinery schemes for all the scenarios, using Aspen Plus software. The results showed
that the configuration with the best economic and environmental performance for
sugarcane bagasse and coffee cut-stems is the one that considers ethanol, furfural and
octane production (scenario 1). The global economic margin was 62.3% and 61.6% for
SCB and CCS respectively. The results have shown the potential of these types of
biomass to produce fuels and building block products (furfural). The environmental
assessment revealed that the scenario that considers the production of ethanol and
octane (scenario 1) was the most environmentally friendly given their lower consumption
of chemical reagents. In contrast, the scenario that considers the production of furfural
97 Jet fuel production from agroindustrial wastes through furfural platform
and HMF (scenario 5) had a major potential environmental impact due to the use of large
volume of solvents and toxicity of furan-based compounds.
6.1.2 Biorefineries from sugarcane bagasse and coffee cut-stems
According to International Energy Agency (IEA) Bioenergy Task 42 a biorefinery is
defined as “A sustainable processing of biomass into a spectrum of marketable products
and energy” [127], [128]. A biorefinery is a network of facilities that integrates biomass
conversion processes and equipments to produce biofuels, power and chemicals from
biomass. This concept is analogous to today's petroleum refinery, which produces
multiple fuels and chemicals from petroleum [127], [128]. A biorefinery can take
advantage of the different biomass constituents and intermediates and maximize the
value derived from the feedstock. In this respect, the most effective and efficient
utilization of renewable biomass resources is through the development of an integrated
biorefinery. Through this strategy the processes included on biorefinery concept can be
economically profitable and environmentally sustainable.
Second generation raw materials (lignocellulosic biomass) are generally considered a
promising feedstock due to its availability in large quantities, its relatively low cost and
its potential sustainability [52], [92], [112]. Sugarcane bagasse is a fibrous residue
obtained after extracting the juice from sugarcane in the sugar production process.
Coffee cut-stems is a cut above the land where the coffee plant is cultivated of 15-20 cm
of length and is obtained by crop renewal. These lignocellulosic wastes are found
especially in tropical countries as Colombia, Brazil, Cuba and Indonesia [52], [65]. In
Colombia, around 5 and 7 million tons of sugarcane bagasse and coffee cut-stems
respectively were generated at 2014 [47], [49]. While, the comparison between these
raw materials is made because if SCB is a well-known lignocellulosic biomass, instead
CCS is born as an alternative that can be as competitive as the aforementioned.
Ethanol is highly commercial and is used as a large-scale transportation fuel.
Hemicellulose present in biomass undergoes an acid hydrolysis to form xylose, and then
xylose is dehydrated to form furfural. Furan-based compounds are a highly versatile and
key derivatives used in the manufacture of a wide range of important chemicals and can
serve as precursors for production of jet fuels substitutes or additives (alkanes C7-C15)
[41], [129].
Chapter 6 98
Several pathways for conversion of furan-based compounds are considered in Figures
6-1 and 6-2 [34]. Biomass-derived sugars can be upgraded to conventional fuels through
the combination of aldol-condensation reactions and hydrogenation/dehydration
reactions. Dumesic et al. [39], [40], [105], [129] have done intense work in this area,
applying molecular engineering concepts to formulate catalytic strategies and
transformation routes of biomass for the production of renewable fuel components and
chemicals. Considering the rapid progress on the catalytic conversion of biomass, this
work concentrates mainly on describing of a feasibility study through simulation
strategies.
In this section, two lignocellulosic materials were considered in order to evaluate the
viability of the production of ethanol, furfural and HMF (furan-based compounds), octane
and nonane (alkanes) over biorefinery concept. These consist in sugarcane bagasse
(SCB) and coffee cut-stems (CCS). The five evaluated scenarios were as follows: i)
production of ethanol from hexoses and octane, ii) production of ethanol, octane and
nonane, iii) production of same products of scenario ii but ethanol and nonane from 40%
and 60% of glucose respectively, iv) production of ethanol from pentoses and nonane,
and v) production of furfural and HMF. The comparison of the evaluated scenarios was
performed using modern process-engineering tools. Each scenario was evaluated from
a technical, economic and environmental point of view. The chemical composition of
SCB and CCS was determined experimentally. The chemical composition of raw
materials was also used as the starting point in the processes simulation.
Figure 6-1 Catalytic pathways for furfural conversion.
99 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-2 Catalytic pathways for HMF conversion.
6.1.3 Scenarios and process description
For the evaluation of the biorefineries from SCB and CCS five scenarios were included
per each raw material. The scenarios consider integrated production of ethanol, octane
and nonane as main products and building block products as furfural and HMF (furan
compounds). For all scenarios, the feedstock was 5 tons/h (equivalent to 40,000
tons/year). This feedstock value is a minimum amount that represents approximately
0.05 % of biomass in the country for 2014 [49], [93]. The raw materials composition was
shown in the chapter 3.
The scenarios are based on distributions and technologies for the same amount of SCB
and CCS as feedstock. In this way, a description of biorefineries from SCB and CCS
included in this study is shown in Table 6-1. This description indicates the distribution of
materials across the processes and also technologies for each product. The aim of the
evaluation of the five scenarios from two raw materials is basically done in order to
compare each other in terms of performance from the techno-economic and
environmental point of view. This comparison is the basis to decide which could be the
best alternative for biorefinery configuration according to raw material. Figure 6-3 shows
four technological scenarios corresponding to the distribution of raw material and the
products formation (scenarios 1, 2, 4 and 5). The description of production processes to
obtain sugars, ethanol, furfural, HMF, octane and nonane are shown above in the section
2.8.1.
Chapter 6 100
Figure 6-3 Technological scenarios corresponding to the distribution shown in the scenarios
description.
101 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-3 (Continued).
Chapter 6 102
Table 6-1 Scenarios description in biorefineries from SCB and CCS.
Scenario Products
Technology Distribution Top Secondary
Sc. 1 Ethanol
Octane Furfural
Hemicellulose hydrolysis Sulfuric acid 2% v/v.
Cellulose hydrolysis Enzymatic hydrolysis.
Ethanol production Continuous Bioreactor.
Saccharomyces Cerevisiae.
Furfural production Xylose dehydration
Octane production
Aldolcondensation with acetone.
Hydrogenation. Dehydration/Hydrogenation.
Ethanol production
100% of glucose from cellulose.
Furfural production
100% of xylose from hemicellulose.
Octane production
100% of furfural from xylose.
Sc. 2
Ethanol
Octane
Nonane
Furfural
HMF
Hemicellulose hydrolysis Sulfuric acid 2% v/v.
Cellulose hydrolysis Enzymatic hydrolysis.
Ethanol production Continuous Bioreactor.
Saccharomyces Cerevisiae
Furfural production Xylose dehydration.
Octane production Aldolcondensation with acetone.
Hydrogenation. Dehydration/Hydrogenation.
HMF production Glucose dehydration.
Nonane production Aldolcondensation with acetone.
Hydrogenation. Dehydrogenation/hydrogenation.
Ethanol production
60% of glucose from cellulose.
Furfural production
100% of xylose from hemicellulose.
HMF production
40% of glucose from cellulose.
Octane production
100% of furfural from xylose.
Nonane production
100% of HMF from glucose.
103 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-1 (Continued)
Scenario Products
Technology Distribution Top Secondary
Sc. 3
Ethanol
Octane
Nonane
Furfural
HMF
Hemicellulose hydrolysis Sulfuric acid 2% v/v.
Cellulose hydrolysis Enzymatic hydrolysis.
Ethanol production Continuous Bioreactor.
Saccharomyces Cerevisiae.
Furfural production Xylose dehydration.
Octane production
Aldolcondensation with acetone. Hydrogenation.
Dehydration/Hydrogenation.
HMF production Glucose dehydration.
Nonane production Aldolcondensation with acetone.
Hydrogenation. Dehydrogenation/hydrogenation.
Ethanol production
40% of glucose from cellulose
Furfural production
100% of xylose from
hemicellulose.
HMF production
60% of glucose from cellulose.
Octane production
100% of furfural from xylose.
Nonane production
100% of HMF from glucose.
Sc. 4 Ethanol
Nonane HMF
Hemicellulose hydrolysis Sulfuric acid 2% v/v.
Cellulose hydrolysis Enzymatic hydrolysis.
Ethanol production Continuous Bioreactor.
Zymomonas mobilis
HMF production Glucose dehydration.
Nonane production Aldolcondensation with acetone.
Hydrogenation. Dehydrogenation/hydrogenation.
Ethanol production 100% of
xylose from hemicellulose.
HMF production 100% of glucose
from cellulose.
Nonane production 100% of
HMF from glucose.
Chapter 6 104
Table 6-1 (Continued)
Scenario Products
Technology Distribution Top Secondary
Sc. 5 Furfural
HMF
Hemicellulose hydrolysis Sulfuric acid 2% v/v.
Cellulose hydrolysis Enzymatic hydrolysis.
Furfural production Xylose dehydration. Liquid-liquid
extraction with toluene and distillation.
HMF production Glucose dehydration. Liquid-liquid
extraction with DMSO and distillation.
Furfural production
100% of xylose from
hemicellulose.
HMF production
100% of glucose from cellulose.
105 Jet fuel production from agroindustrial wastes through furfural platform
6.1.4 Results and Discussion
Simulation results for ethanol, liquid alkanes and furan compounds production from SCB
and CCS are shown in Table 6-2. Higher cellulose content in SCB has allowed to obtain a
higher sugars yield and consequently a higher ethanol, HMF and nonane yield than in the
case of CCS. On the contrary, CCS present higher hemicellulose content and hence a
higher furfural and octane production. The overall yields according to kinetics studied for
conversion of lignocellulosic material to sugars were 0.71 grams of xylose per grams of
hemicellulose and 0.64 grams of glucose per grams of cellulose. In the case of ethanol
production, the yields obtained were 0.54 grams per grams of glucose and 0.45 grams per
grams of xylose.
Table 6-2 Production capacities of top and secondary products per scenario.
Scenario Raw
material
Ethanol
(kg/h)
Octane
(kg/h)
Nonane
(kg/h)
Furfural
(kg/h)
HMF
(kg/h)
Sc. 1 SCB 786.08 644.18 ----- 681.52 -----
CCS 664.79 925.65 ----- 979.30 -----
Sc. 2 SCB 471.27 644.18 265.95 681.52 398.18
CCS 406.01 925.65 232.03 979.30 347.58
Sc. 3 SCB 310.24 644.18 398.85 681.52 597.27
CCS 270.66 925.65 339.74 979.30 521.38
Sc. 4 SCB 366.01 ----- 664.66 ----- 995.45
CCS 527.99 ----- 549.17 ----- 868.97
Sc. 5 SCB ----- ----- ----- 674.00 1048.0
CCS ----- ----- ----- 703.37 863.06
Economic assessment
According to the results obtained from Aspen Process Economic Analyzer package
adapted to Colombian parameters, the feature that contributes with a higher proportion on
the total production costs are operating costs that includes various aspects inherent to the
production process such as raw materials, utilities, labor and maintenance, general plant
costs and general administrative costs. For most industrial processes the raw materials
represent approximately more than 50% of total production cost.
Chapter 6 106
Distribution and technologies included in the chosen products directly affect yields and the
production costs. Table 6-3 shows production costs of products in each scenario depending
of raw material. Higher cellulose content in SCB is translated in economic terms to a low
cost of ethanol, HMF and Nonane compared with CCS as raw material. Thus, considerable
content of hemicellulose in CCS reflects in low production costs of furfural and octane.
When all glucose is destined to produce ethanol (scenario 1) from SCB and CCS the
economic margins are 61.6% and 51.4%, respectively. If the xylose is the substrate to
ferment (scenario 4) the economic margins are -71.03% and -22.43% for SCB and CCS,
respectively. This difference could be explained by the dependence of the product to the
amount of substrate available and yields in pretreatment (acid hydrolysis) and enzymatic
hydrolysis. In the scenarios 1, 2 and 3 both the building block product (furfural) and the
octane have good profitability with an average economic margin of 75% and 62.7%
respectively. In the same way, the scenarios 2, 3 and 4 have positive economic margin for
HMF and nonane of around 81.5% and 36.3% respectively. In these scenarios there is a
difference in distribution of raw material (cellulose) equivalent to 4.5% of the economic
margin. The scenario 5 shows the production of furfural and HMF following by stages of
pretreatment of raw material, reaction and separation that in others scenarios the process
arrives only to reaction stage. In the case of SCB, this implies an increase in the production
cost of 0.44 and 0.6 USD/kg of furfural and HMF respectively and for CCS the increase is
0.47 and 0.59USD/kg for furfural and HMF respectively.
Figure 6-4 shows the global economic margins for all scenarios evaluated from SCB and
CCS. According to these results, the scenario 1 to SCB and CCS, have the highest
economic margin consequently the best profitability followed by the scenario that considers
the production of furfural and HMF (scenario 5). The results have shown the potential of
these types of biomass to produce fuels and building block products (furfural and HMF).
107 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-3 Production cost of biorefinery products from SCB and CCS.
Item Sc. 1 Sc. 2 Sc. 3 Sc. 4 Sc. 5
Total production cost Ethanol (USD/kg)
SCB 0.41 0.58 0.84 1.83 -----
CCS 0.52 0.68 0.84 1.31 -----
Total production cost Octane (USD/kg)
SCB 2.63 2.63 2.63 ----- -----
CCS 2.58 2.58 2.58 ----- -----
Total production cost Nonane (USD/kg)
SCB ----- 10.46 10.27 10.22 -----
CCS ----- 10.80 10.51 10.24 -----
Total production cost Furfural (USD/kg)
SCB 0.47 0.47 0.47 ----- 0.91
CCS 0.38 0.38 0.38 ----- 0.85
Total production cost HMF (USD/kg)
SCB ----- 0.40 0.35 0.32 0.94
CCS ----- 0.47 0.39 0.37 0.96
Figure 6-4 Global economic margins for all scenarios evaluated from SCB and CCS.
Environmental assessment
The results of the potential environmental impact per kilogram of products are presented in
Table 6-4 and Figure 6-5. The results showed that for all the evaluated scenarios, the
impacts that contribute the most to the PEI were photochemical oxidation potential (PCOP)
Sc 1 Sc 2 Sc 3 Sc 4 Sc 5
SCB 62.33 43.79 43.50 30.43 50.00
CCS 61.59 54.01 54.43 51.00 51.08
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
Econom
ic M
arg
in (
%)
SCB CCS
Chapter 6 108
due to organic load of effluents as vinasse and solvent purge and gas emission. Besides
Human toxicity potential by ingestion (HTPI) and terrestrial toxicity potential (TTP), that are
highly related because both are calculated in function of lethal dose by ingestion (LD50).
Chemical reagents involved on processes are direct contributors to these categories.
Table 6-4 Potential environmental impact for the different scenarios according to raw material.
Human toxicity by ingestion (HTPI), human toxicity by dermal exposition or inhalation (HTPE),
terrestrial toxicity potential (TTP), aquatic toxicity potential (ATP), global warming (GWP), ozone
depletion potential (ODP), photochemical oxidation potential (PCOP), and acidification potential
(AP).
Scenario Raw
materials
Impacts
HTPI HTPE TTP ATP GWP ODP PCOP AP
Sc. 1 SCB 2.53e-1 1.52e-1 2.53e-1 1.16e-2 6.02e-3 2.24e-8 5.81e-1 6.13e-2
CCS 5.16e-1 1.33e-1 5.16e-1 1.54e-2 5.95e-3 2.23e-8 8.37e-1 6.09e-2
Sc. 2 SCB 4.79e-1 1.28e-1 4.79e-1 1.30e-2 4.92e-3 1.84e-8 7.65e-1 5.02e-2
CCS 5.19e-1 1.24e-1 5.19e-1 1.44e-2 5.54e-3 2.07e-8 8.82e-1 5.67e-2
Sc. 3 SCB 2.59e-1 1.20e-1 2.59e-1 1.15e-2 4.73e-3 1.77e-8 5.60e-1 4.84e-2
CCS 5.20e-1 1.20e-1 5.20e-1 1.61e-2 5.37e-3 2.02e-8 8.65e-1 5.51e-2
Sc. 4 SCB 4.38e-1 7.91e-2 4.38e-1 8.77e-3 3.48e-3 1.19e-8 4.56e-1 3.24e-2
CCS 6.65e-1 5.42e-2 6.65e-1 1.87e-2 9.01e-3 3.30e-8 6.97e-1 9.02e-2
Sc. 5 SCB 6.14e-1 1.42e-1 6.14e-1 1.03e-2 1.92e-3 7.30e-9 9.22e-1 1.99e-2
CCS 7.17e-1 1.63e-1 7.17e-1 1.65e-2 8.39e-3 3.18e-8 1.16 8.70e-2
From the raw material point of view, the first scenario was the most environmentally friendly
given their lower consumption of chemical reagents. In contrast, the fifth scenario had a
major potential environmental impact due to the use of large volume of solvents and toxicity
of furan compounds.
109 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-5 Total potential environmental impact for the different scenarios according to raw
material.
6.1.5 Conclusions
According to the techno-economic results, CCS is a lignocellulosic raw material that if it is
not well known have a potential and can be as competitive as sugarcane bagasse. As a
general conclusion, this work demonstrated that it is technically possible to convert SCB
and CCS to produce ethanol, jet fuels range alkanes and furan-based compounds under a
biorefinery scheme. These compounds show interesting properties and are precursors for
the synthesis of products in the same way as the sugars (C5-C6).
0.00E+00
1.00E+00
2.00E+00
3.00E+00
4.00E+00
Sc 1 Sc 2 Sc 3 Sc 4 Sc 5
To
tal (P
EI/k
g P
rod
uc
t)
SCB CCS
Chapter 6 110
6.2 Design and analysis of process schemes based on coffee cut-stems coupled with gasification technology
6.2.1 Overview
In this section, a techno-economic assessment for process schemes to obtain alcohol and
alkane from coffee cut-stems are presented. Four scenarios were evaluated at different
levels for ethanol, furfural and octane production. These scenarios were compared between
them according to use of cogeneration system and economic behavior. A simulation
procedure was used in order to evaluate process schemes for all the scenarios, using
Aspen Plus software. The results showed that the configurations with the best economic
performance are the one that consider the cogeneration system (scenarios 3 and 4). The
global economic margin for scenarios 1 and 2 was 38.4% and 62.7% respectively. For
scenarios 3 and 4 was 46.3% and 64.1% respectively. The results shown the positive
impact in economic terms that can have a cogeneration system on a process scheme to
obtain fuel and biochemicals from CCS.
6.2.2 Production of ethanol and octane from lignocellulosic biomass
The uncertainty on oil reserves, oil prices as well as the climate change have become in
important reasons to search new alternatives to produce valuable chemicals and fuels
[130], [131]. In this sense, biomass appears as a source to produce environmentally friendly
biofuels and biobased materials with promising substitution capacity of petrochemical
sources. Renewable biomass resources are considered promising and particularly
attractive, and worldwide many efforts have been devoted to its conversion [34], [36], [37],
[41]. Especially, the derivation of biofuel from the catalytic conversion of lignocellulosic
biomass has become one of the trendiest research subjects in the world.
Bioethanol is one biofuel well known for its competition commercial, calorific properties and
sustainable production. Recently, studies report that jet fuels range alkanes could be
obtained from lignocellulosic biomass by a novel route, wherein C5 sugar was firstly
produced by hydrolysis of biomass and then converted into furfural by a dehydration step;
furfural was further reacted with acetone by an aldol condensation step to produce jet fuel
111 Jet fuel production from agroindustrial wastes through furfural platform
intermediates, following by the generation of long chain alkanes ranging from C7 to C15 via
a dehydration/hydrogenation step. Furfural offers an important and rich source of
derivatives that have potential use as biofuel components [35]–[37].
In this section, CCS as lignocellulosic material was considered in order to evaluate the
viability of the production of ethanol, furfural and octane. The following four scenarios were
evaluated: i) production of ethanol from hexoses and furfural from pentoses, ii) production
of ethanol and octane, iii) production of same products of scenario i with cogeneration
system and iv) production of same products of scenario ii with cogeneration system. The
comparison of the evaluated scenarios was performed using modern process-engineering
tools. Each scenario was evaluated from a technical and economic point of view. The
chemical composition of CCS was determined experimentally. The chemical composition
of raw materials was also used as the starting point in the processes simulation.
6.2.3 Scenarios description
For the evaluation of the processes from CCS four scenarios were included. For all
scenarios, the amount feedstock was 5 tons/h (equivalent to 40,000 tons/year). This
feedstock value represents approximately 0.05 % of biomass in Colombia for 2014. The
raw material composition was shown in the chapter 3.
The scenarios are based on inclusion of cogeneration system in scenarios 1 and 2. In this
way, a description of processes from CCS included in this study is shown in Table 6-6. This
description indicates the distribution of materials across the processes and also
technologies for each product. The first and second scenario described the production of
ethanol and furfural, ethanol and octane respectively, without cogeneration system. In the
third and fourth scenario are obtained the same products corresponding to scenarios 1 and
2 respectively, but with system cogeneration. In these scenarios, the cogeneration
generated low pressure steam that was able to supply the heat requirements in processes.
The aim of the evaluation of the four scenarios is basically done in order to compare each
other in terms of performance from the techno-economic point of view. This comparison is
the basis to decide which could be the best alternative of process. Figure 6-6 shows two
technological schemes corresponding to the scenarios 1 and 2 and formation of the
respective products.
Chapter 6 112
Table 6-5 Scenarios description for process schemes from CCS.
Scenario Products
Technology Distribution Top Secondary
Sc. 1
Sc. 3
Furfural
Ethanol
Electricity
(Sc. 3)
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Ethanol production
Continuous Bioreactor.
Saccharomyces Cerevisiae.
Furfural production Xylose
dehydration. Liquid-liquid
extraction with toluene and
distillation.
Cogeneration (Sc. 3)
Combined cycle
Ethanol production
Glucose from cellulose.
Furfural production
Xylose from hemicellulose.
Cogeneration
Residual lignocellulosic
biomass from hydrolysis
Sc. 2
Sc. 4
Ethanol
Octane
Furfural
Electricity
(Sc. 4)
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Ethanol production
Continuous Bioreactor.
Saccharomyces Cerevisiae
Furfural production
Xylose dehydration.
Octane production
Aldolcondensation with
acetone. Hydrogenation.
Dehydration/Hydrogenation.
Cogeneration (Sc. 4)
Combined cycle
Ethanol production
Glucose from cellulose.
Furfural production
Xylose from hemicellulose.
Octane production
Furfural from xylose.
Cogeneration
Residual lignocellulosic
biomass from hydrolysis
113 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-6 Process schemes to scenarios 1 and 2 from CCS.
6.2.4 Process description
The description of production processes to obtain sugars, ethanol, furfural and octane are
shown above in the section 2.8.1.
Cogeneration system
For this section the technology used for cogeneration is the biomass integrated gasification
combined cycle (BIGCC) as described Rincon et al. (2013) & Balat et al. (2009), [132],
[133]. Basic elements of BIGCC system include biomass dryer, gasification chamber, gas
Chapter 6 114
turbine and heat steam recovery generator (HRSG). Gasification is a thermo-chemical
conversion technology of carbonaceous materials (coal, petroleum coke and biomass), to
produce a mixture of gaseous products (CO, CO2, H2O, H2, CH4) known as syngas added
to small amounts of char and ash. Gasification temperatures range between 875-1275 K
[59]. The gas properties and composition of syngas changes according to the gasifying
agent used (air, steam, steam-oxygen, oxygen-enriched air), gasification process and
biomass properties [59]. Syngas is useful for a broader range of applications, including
direct burning to produce heat and power or high quality fuels production or chemical
products such as methanol [134], [135]. A gas turbine is a rotator engine that extracts
energy from a flow combustion gas. It is able to produce power with an acceptable electrical
efficiency, low emission and high reliability. The gas turbine is composed by three main
sections: compression (air pressure is increased, aimed to improve combustion efficiency),
combustion (adiabatic reaction of air and fuel to convert chemical energy to heat) and
expansion (obtained pressurized hot gas at high speed passing through a turbine
generating mechanical work) [136]. The HRSG is a high efficiency steam boiler that uses
hot gases from a gas turbine o reciprocating engine to generate steam, in a thermodynamic
Rankine Cycle. This system is able to generate steam at different pressure levels.
According to process requirements a HSRG system can use single, double or even triple
pressure levels. Figure 6-7 shows the processing steps for the BIGCC technology. This
process scheme was added to the scenarios 3 and 4. The price of low pressure steam used
in this study was 1.57 USD per tonne.
Figure 6-7 Biomass integrated gasification combined cycle system. 1. Heat exchanger, 2. Splitter,
3. Compressor, 4. Gas turbine, 5. Dryer, 6. Gasification and combustion chamber, 7. Cyclone, 8. LP
pump, 9. Economizer, 10. LP drum, 11. Evaporator, 12. Super-heater.
115 Jet fuel production from agroindustrial wastes through furfural platform
6.2.5 Results and Discussion
In the present study were analyzed process schemes from CCS to obtain ethanol, furfural,
octane and energy. Particularly, for setting up the four different scenarios with their
respective technical-economic calculations. CCS is considered a second generation
feedstock to obtain biofuel (ethanol), bioproducts (furfural and octane) and bioenergy
(referred as co-generation).
Simulation results for ethanol, furfural and octane production from CCS are shown in Table
6-6. The mass flow of ethanol is the same in all scenarios since is used the same amount
of hydrolyzed cellulose. Furfural flow is different due to obtaining conditions. The scenarios
1 and 3 include separation system to obtain furfural at 95% as final product. On the contrary,
the scenarios 2 and 4 do not take into account this stage since the furfural is a platform
product to obtain octane as final product. The inclusion of octane as a final product is a
promising strategy due to a sustainable production and a high selling price of this alkane in
the market.
Table 6-6 Production capacities of top and secondary products per process scheme from CCS.
Scenario Ethanol (kg/h) Furfural (kg/h) Octane (kg/h) Electricity* (kWh)
Sc. 1
Sc. 3 665.15 739.31 ----- 73.49
Sc. 2
Sc. 4 665.15 984.98 931.023 30.24
* Electricity obtained corresponding to Sc. 3 and Sc. 4.
Economic Assessment
One of the best alternatives for reducing production costs is to decrease the energy
consumption during the production process by implementing more energy-efficient and
better-performing technologies. The energy consumption resulted from the simulations was
used to assess the implication of the process distribution choices and technologies
according to energy consumption and the effect of energy savings on production cost.
The economic analysis of the process schemes based on CCS was focused on the
influence of cogeneration system. In this way, one of the main priorities in the economic
evaluation was the determination of the energy requirements according to the description
of the different proposed scenarios. For all scenarios, the process that represents the larger
Chapter 6 116
energy consumption is the pretreatment stage (sugars production). This could be explained
because this is one of the stages which has more processing units and materials
conditioning operations.
Figure 6-8 shows the total costs for both the heat and power requirements per tonne of
biomass for the scenarios 1 and 2. The second scenario showed the higher energy
consumption in comparison with scenario 1 due to the addition of octane process.
Figure 6-8 Energy cost of stream requirement per tonne of CCS based on obtaining products.
The scenarios 3 and 4 corresponding to the addition of cogeneration system to scenarios
1 and 2 respectively. Power requirements of simple process schemes are satisfied by
cogeneration system. Remaining power flows are shown in the table 6-6 and are taken as
secondary product that generated economic gains to process schemes. Additionally, the
low pressure steam produced by cogeneration system meets the demand of scenarios 1
and 2 in a 96.78% and 46.92% respectively. These positive results represent an economic
advantage reflected in the reduction of production cost and demonstrates that scenarios 3
and 4 proposed are feasible.
The total cost distributions of the process schemes based on CCS are shown in Figure 6-
9. The highest cost corresponds to feedstock with 60-70% of the total cost followed by the
total utility costs and the capital depreciation with 15% and 26%, respectively. The addition
of the cogeneration system slightly increases the distribution to raw material costs (water
used in steam generation) and capital depreciation (number of equipments) but decreases
considerably the percentage of utilities.
0
10
20
30
40
50
60
70
80
Sc.1 Sc. 2
US
D p
er
ton
ne (
heat
an
d
ele
ctr
icit
y r
eq
uir
em
en
ts)
Low P. Steam (USD/ton) Electricity (USD/ton)
117 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-9 Distribution of total costs of process schemes based on CCS.
The economic margins for all scenarios are shown in Figure 6-10. For all the studied
scenarios, the economic margin of all products was positive. This result could be explained
by the fact that the sale prices of these products are higher than their production costs.
Then, the economic margins for furfural in scenarios 1 and 3 are slightly positive but the
considerably high economic margins for ethanol can subsidize this product. Overall, by
including cogeneration system for scenarios 1 and 2, production costs and gains are
minimized and maximized, respectively.
Figure 6-10 Economic margin per scenario and obtained products for process schemes based on
CCS.
0% 10% 20% 30% 40% 50% 60% 70% 80%
Total Raw Material Cost
Operating Labor Cost
Maintenance Cost
Total Utilities Cost
Operating Charges
Plant Overhead
G & A Cost
Capital Depreciation
Sc. 1 Sc. 2 Sc. 3 Sc. 4
0
10
20
30
40
50
60
70
80
90
Ethanol Furfural Octane
Econom
ic m
arg
in (
%)
Sc 1 Sc 2 Sc 3 Sc 4
Chapter 6 118
6.2.6 Conclusions
According to results obtained, scenarios proposed for CCS for the production of ethanol,
furfural, and octane were feasible. However, given the analysis developed, the scenario
that considers cogeneration system was the most recommended from economic point of
view. Furfural as a chemical platform to obtain bioproducts and biofuels can contribute to
the development of new catalytic conversion processes of furfural and its derivatives, which
in the future can lower the cost of their production. This could increase the scale of
production, which will result in the launch on the production of alternative fuels, which will
replace for conventional fuel.
119 Jet fuel production from agroindustrial wastes through furfural platform
6.3 Techno-economic and environmental analysis of the processes to obtain blends as additive for jet biofuels
6.3.1 Overview
Sugarcane bagasse and rice husk are one of the main agroindustrial wastes in Colombia.
The content of lignocellulosic material makes them attractive and interesting materials to
transform them into biofuels. In this section, the possibility to obtain alcohol mixtures as
biofuel additive or biofuel from SCB and RH was evaluated. The production processes were
designed and analyzed from techno-economic and environmental point of view. Raw
materials were compared to produce ethanol-butanol, and ethanol-alcohol mixture.
According to the economical results, SCB is the best raw material to obtain alcohols with
global economic margins of 44.1 and 66.8% for scenario 1 and 2 respectively. The
processes that considered SCB as raw material are the most environmentally friendly with
a potential environmental impact per kg product of 1.97 and 2.1 for scenarios 1 and 2
respectively.
6.3.2 Blends of biofuels as additive for jet fuels
Currently, there are concerns to reduce the fossil fuel dependence and therefore new
energy sources are being proposed to supply the increasing energy demand. As a
consequence, biomass appears as a promising alternative to produce environmentally
friendly biofuels with competitive advantages over non-renewable fuels [137]. Nowadays,
the lignocellulosic biomass is the main source of biofuels because with its content of
cellulose, hemicellulose and lignin can be produced any amount of products including
electricity [92]. The raw materials to produce biofuels have been developed from first
generation feedstocks (agricultural farming), second generation (residuals) and third
generation (algae) [138].
Among potential biofuels, bioethanol has become one of the most important biofuels as
gasoline additive and widely used in countries such as USA, Brazil and Colombia.
Alternatively, biodiesel also has been a popular biofuel, which is essentially composed of
methyl or ethyl ester of fatty acids and has been used as an additive in diesel in the
Chapter 6 120
transportation sector [138]. Another important biofuel is biobutanol that has gained visibility
in recent years as a replacement for gasoline. Butanol has unique properties as a fuel. The
energy content of butanol (99,840 Btu per gallon) is 86% of the energy content of gasoline.
Other alternative of fuels, is use of mixed alcohol formulas that can be used as a fuel
additive in gasoline, diesel, jet fuel, aviation gasoline, heating oil and bunker oil. The
formulation of mixed alcohols can contain C1-C5 alcohols, or in the alternative, C1-C8
alcohols or higher C1-C10 alcohols in order to boost energy content. Alcohol fuel additives
have been found as oxygenate for internal combustion engines, reducers of emissions and
increasers combustion efficiencies [32], [33].
In this section, two lignocellulosic materials were considered in order to evaluate the viability
of the production of ethanol, butanol and mixture of alcohols. These consists in sugarcane
bagasse (SCB) and rice husk (RH). The following two scenarios were evaluated: i)
production of ethanol and butanol and ii) production of ethanol and mixture of alcohols
(butanol, octanol, hexanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol
and eicosanol). Each scenario was evaluated from a techno-economic and environmental
point of view. The chemical composition of SCB and RH was determined experimentally.
The chemical composition of raw materials was also used as the starting point in the
processes simulation.
6.3.3 Process and scenarios description
SCB and RH are the feedstock to assess the production of ethanol-butanol and ethanol-
mixture of alcohols. Two scenarios were studied per each raw material. The feed for all
processes was 5 tons/h (equivalent to 40000 tons/year). The raw material compositions
were shown in the chapter 3. The description of scenarios and process schemes are
presented in the table 6-7 and figures 6-11 and 6-12 respectively. The description of
production processes to obtain ethanol, butanol and mixture of alcohols are shown above
in the section 2.8.1.
121 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-7 Scenarios description from RH and SCB.
Scenario Products Technology Distribution
Sc. 1
Ethanol
Butanol
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Ethanol production
Continuous Bioreactor.
Zymomonas mobilis.
Butanol production
ABE fermentation
Clostridium beijerinckii.
Ethanol production
100% of xylose and
20% of glucose.
Butanol production
80% of glucose from
cellulose.
Sc. 2
Ethanol
Mixture of
alcohols
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Ethanol production
Continuous Bioreactor.
Zymomonas mobilis.
Alcohols production
Dehydration of ethanol to
ethylene.
Ziegler process to obtain alcohol
C2-C20.
Ethanol production
Glucose and xylose
Alcohols production
40% of ethanol.
Chapter 6 122
Figure 6-11 Process scheme to obtain ethanol and butanol.
Figure 6-12 Process scheme to obtain ethanol and mixture of alcohols.
6.3.4 Results and Discussion
Techno-economic assessment
SCB and RH are composed by 70% and 56% of holocellulosic material respectively,
distributed in 46% and 40% of glucose 15% and 23% of xylose for SCB and RH
respectively. Evidently, the high availability of glucose and xylose in SCB leads to higher
123 Jet fuel production from agroindustrial wastes through furfural platform
flow of products of interest. Ash content in RH exceeds the normal levels leading to a
displacement of the material to convert in sugars. For this reason the flows of products for
RH decrease substantially in comparison with SCB as shows the table 6-8. The yields
associated to processes developed in this section are 0.47 grams of ethanol per gram of
sugars, 0.22 grams of butanol per gram of glucose and 0.56 grams of mixture of alcohols
per gram of ethanol. The mixture of alcohols is composed by 0.02 of butanol, 0.13 of
octanol, 0.06 of hexanol, 0.19 of decanol, 0.21 of dodecanol, 0.18 of tetradecanol, 0.13 of
hexadecanol, 0.08 of octadecanol and 0.04 of eicosanol in mass fraction (C4 to C20).
Table 6-8 Production capacities of products per scenario.
Scenario Raw material Ethanol (kg/h) Butanol (kg/h) Mix alcohols (kg/h)
Sc. 1 SCB 531.67 309.26 -----
RH 329.89 249.22 -----
Sc. 2 SCB 575.80 ----- 258.94
RH 530.40 ----- 178.93
The production costs for SCB and RH to obtain ethanol, butanol and mixture of alcohols
are shown in the table 6-9. In economic terms, the behavior respect to the raw materials is
the same, that is to say, the production costs for SCB are lower due to high flows of products
compared with RH. In spite of greater production cost of products for RH, this material
continues to maintain a positive economic margin as show the figures 6-13 and 6.14.
Table 6-9 Production cost of products from SCB and RH.
Item Sc. 1 Sc. 2
Total production cost Ethanol (USD/kg)
SCB 0.54 0.78
RH 0.9 1.1
Total production cost Butanol (USD/kg)
SCB 1.12 -----
RH 1.74 -----
Total production cost Mix alcohols (USD/kg)
SCB ----- 0.42
RH ----- 0.47
Chapter 6 124
Individual economic margins for ethanol are 49.5 and 27.1% for SCB and RH respectively.
For butanol are 41.1 and 8.4% for SCB and RH respectively. Global economic margins are
indicated in figure 6-13, the gains for RH are affected mainly by availability of holocellulosic
material to transform and the limitations in the process to obtain butanol, related with yield
of ABE fermentation and purification of final product.
Figure 6-13 Global economic margins to obtain ethanol and butanol (Sc. 1) from SCB and RH.
Figure 6-14 shows the global economic margins of 66.8 and 60.3% to produce ethanol and
mixture of alcohols from SCB and RH respectively. As can be seen, there is a brief
difference respect to raw materials due to individual economic margins for ethanol that are
15.9 and -3.74% for SCB and RH respectively. These results, are directly affected by the
content of holocellulose. In the case of rice husk this content is minor since ash content
exceeds normal values of any lignocellulosic biomass. Ash content of RH can be source of
silica-based products but in this work are not considered.
0.0
10.0
20.0
30.0
40.0
50.0
Eco
no
mic
marg
in (
%)
SCB RH
125 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-14 Global economic margins to obtain ethanol and mixture of alcohols (Sc. 2) from SCB
and RH.
Environmental assessment
The results of the potential environmental impact per kilogram of products are presented in
Figure 6-15 and 6-16 for scenarios 1 and 2. The results show that the process that
considered as SCB as raw material are the most environmentally friendly due to the fact
that this biomass contains less lignin and therefore has low deposition of solid waste to the
outside. For all the evaluated scenarios, the impacts that contribute the most to the PEI
were the photochemical oxidation potential (due to the gases emissions in fermentation
process) and the terrestrial toxicity potential (due to the emissions of solid material). The
PCOP for scenario 1 is higher than for 2 due to scenario 1 account with two fermentation
processes.
Figure 6-15 PEI per kg of product (ethanol and butanol).
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00E
co
no
mic
marg
in (
%)
SCB RH
0.00E+00
5.00E-01
1.00E+00
1.50E+00
2.00E+00
2.50E+00
3.00E+00
HTPI HTPE TTP ATP GWP ODP PCOP AP Total
PE
I/k
g o
f p
rod
uc
t
SCB RH
Chapter 6 126
Figure 6-16 PEI per kg of product (ethanol and mixture of alcohols).
6.3.5 Conclusions
This work brings on to the table an interesting discussion about the design and analysis of
potential technological schemes to produce promising jet biofuel blends. Special attention
is paid to the use of second generation feedstocks in countries from tropical regions. The
economic evaluation indicates that the production cost of the two blends studied, although
are economically viable, when SCB is used as raw material there is a high economic
margin, product of a higher holocellulosic fiber content convertible to reducing sugars.
0.00E+00
5.00E-01
1.00E+00
1.50E+00
2.00E+00
2.50E+00
3.00E+00
HTPI HTPE TTP ATP GWP ODP PCOP AP Total
PE
I/k
g o
f p
rod
uc
t
SCB RH
127 Jet fuel production from agroindustrial wastes through furfural platform
6.4 Lignocellulosic biomass to obtain sugars, ethanol, PHB and energy: Design and analysis of processes
6.4.1 Overview
This section presents a techno-economic assessment for obtain sugars, fuel, biopolymer
and energy from fique bagasse and rice husk through four scenarios per each raw material.
The two lignocellulosic raw materials are compared to obtain glucose, xylose, ethanol, PHB,
octane and nonane according cellulose and hemicellulose content transformable. Designed
processes were analyzed to produce an only product and determine its economic viability.
The results showed an average economic margin for glucose, xylose, ethanol, PHB, octane
and nonane of 50.3, 15.8, 25.7, 63.1, 53.6 and 82.3% respectively.
6.4.2 Second generation biomass to obtain interesting products
Currently, there are concerns to reduce the oil dependence, and therefore new feedstock
sources are being proposed to supply the increasing products demand. Then, biomass
appears as a promising alternative to produce bioproducts and environmentally friendly
biofuels with competitive advantages over non-renewable fuels. Countries such as
Colombia, located in tropical regions have an important production of raw materials and
specifically a large amount of biomass. Some of them are of first and second generation:
First generation raw materials are designed to obtain multiple products of added value,
while second generation feedstocks are generally residues obtained from the processing
of first generation feedstocks. Both raw materials are excellent platforms for obtaining
biofuels, biochemicals and biopolymers and energy.
Sugars as glucose and xylose are the initials products that can be obtain from
lignocellulosic biomass. These products are considered a platform to generate alcohols,
organic acids, among others biochemicals. Biofuels as ethanol, this alcohol has become
one of the most important biofuels as gasoline additive and widely used in countries such
as USA, Brazil and Colombia. Biopolymers as PHB, the use of PHB as biodegradable
plastic is desirable since the non-biodegradable plastics disposal, after they are used,
causes significant ecological problems. PHB has many potential applications in medicine,
Chapter 6 128
veterinary practice and agriculture due to its biodegradability. Bioenergy as alkanes
components of biofuels (octane and nonane) and jet fuels.
In this section, two lignocellulosic materials were considered in order to evaluate the viability
of the production of sugars, alcohol, polymer and energy. These consists in fique bagasse
(FB) and rice husk (RH). The following two scenarios were evaluated: i) production of
glucose and xylose ii) production of ethanol, iii) production of PHB and iv) production of
octane and nonane. Each scenario was evaluated from a techno-economic point of view.
The chemical composition of FB and RH was determined experimentally. The chemical
composition of raw materials was also used as the starting point in the processes
simulation.
6.4.3 Scenarios and process description
For the evaluation of the proposed processes from FB and RH four scenarios were included
per each raw material. The scenarios consider the production of sugars (glucose and
xylose), fuel (ethanol), biopolymer (PHB) and energy (octane and nonane). For all
scenarios, the feedstock was 20 tons h-1 (equivalent to 160,000 tons per year). The raw
material compositions were shown in the chapter 3.
The scenarios are based on design and analysis to obtain interesting products for the same
amount of FB and RH as feedstocks. In this way, a description of processes from FB and
RH included in this study is shown in Table 6-10. This description indicates the distribution
of materials across the processes and also technologies for each product. The aim of the
evaluation is analysis of four scenarios from two raw materials that is basically done in order
to compare each other in terms of performance from the techno-economic point of view.
This comparison is the basis to decide which could be the best alternative of process
according to raw material. Figures 6-17, 6-18, 6-19 and 6-20 show the four processes from
lignocellulosic biomass designed, analyzed and evaluated to obtain sugars, fuel,
biopolymer and energy respectively. The description of production processes are shown
above in the section 2.8.1.
129 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-10 Scenarios description to produce sugars, fuel, biopolymer and energy.
Scenario Products Technology Distribution
Sc. 1 Glucose
Xylose
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Glucose production
100% of cellulose
Xylose production
100% of hemicellulose
Sc. 2 Ethanol
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Ethanol production
Continuous Bioreactor.
Z. mobilis.
Ethanol production
100% glucose and xylose
Sc. 3 PHB
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
PHB production
Continuous Bioreactor.
Ralstonia eutropha
PHB production
100% glucose and xylose
Sc. 4 Octane
Nonane
Hemicellulose hydrolysis
Sulfuric acid 2% v/v.
Cellulose hydrolysis
Enzymatic hydrolysis.
Furfural production
Xylose dehydration.
Octane production
Aldolcondensation with acetone.
Hydrogenation.
Dehydration/Hydrogenation.
HMF production
Glucose dehydration.
Nonane production
Aldolcondensation with acetone.
Hydrogenation.
Dehydrogenation/hydrogenation.
Furfural production
100% of xylose from
hemicellulose.
HMF production
100% of glucose from
cellulose.
Octane production
100% of furfural from xylose.
Nonane production
100% of HMF from glucose.
Chapter 6 130
Figure 6-17 Process scheme to obtain glucose and xylose.
Figure 6-18 Process scheme to obtain ethanol.
Figure 6-19 Process scheme to obtain PHB.
131 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-20 Process scheme to obtain octane and nonane.
6.4.4 Results and Discussion
Simulations of both feedstock were used to generate their respective mass and energy
balances, which are the basic input for the technical and economic analysis. Table 6-11
shows the production of each product per 20 tons of raw material fed (FB and RH). As can
see FB has a slight advantage over RH for the cellulose content, but RH has a greater
content of hemicellulose. These raw materials have a composition very similar of
holocellulosic fibers. Their difference is that FB exhibits high amount of extractives
associated with high chlorophyll content. On the contrary, RH is characterized for their
considerable content of ashes referred to the silica content.
The yields do not change between the different processes to each raw material. The overall
yields according to kinetics studied for conversion of lignocellulosic material to sugars were
0.71 grams of xylose per grams of hemicellulose and 0.64 grams of glucose per grams of
cellulose. In the case of ethanol production, the yield obtained was 0.47 grams per gram of
glucose and xylose. For PHB, the yield obtained was 0.12 grams per gram of glucose.
Finally, for octane and nonane were obtained an average yields of 0.08 and 0.13 grams
per gram of fresh raw material respectively.
Chapter 6 132
Table 6-11 Production capacities per scenario from FB and RH.
Scenario 1
Raw material Glucose (kg/h) Xylose (kg/h)
FB 5664.65 2060.61
RH 5259.35 2253.59
Scenario 2
Raw material Ethanol (kg/h)
FB 3686.14
RH 3371.54
Scenario 3
Raw material PHB (kg/h)
FB 811.1
RH 649.8
Scenario 4
Raw material Octane (kg/h) Nonane (kg/h)
FB 1566.48 2902.03
RH 1698.11 2327.45
A goal of the economic assessment is to evaluate the total production cost and the income
by product sales. In this way, the total production cost of sugars, fuel, biopolymer and
energy were calculated for the all schemes. Hence, Table 6-12 to Table 6-15 shows the
production cost of the product considered in this work. The main factor that affect the
production costs is the availability of cellulose and hemicellulose content in the feedstock.
When the base of the products is the glucose, the FB is the ideal material due to lower
production costs but if the base of the products is the xylose, RH is the best raw material.
In all scenarios, the items that contribute in high proportion to production cost are: raw
material costs, utility costs and depreciation. Raw material costs are related with the costs
of enzymes, reagents and solvents. Utility costs involve cooling and heating fluids and
electricity. Finally, depreciation implies the periodic decrease in the value of the equipment.
133 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-12 Total production cost of glucose and xylose from FB and RH.
Item Cost and
Share (%)
Glucose (USD/kg) Xylose (USD/kg)
FB RH FB RH
Raw materials Cost
Share
0.074
0.203
0.072
0.166
0.929
0.728
0.875
0.685
Operating Labor cost Cost
Share
0.005
0.013
0.006
0.014
0.016
0.012
0.014
0.011
Maintenance cost Cost
Share
0.002
0.006
0.003
0.007
0.007
0.006
0.007
0.006
Utilities cost Cost
Share
0.218
0.597
0.272
0.629
0.194
0.152
0.243
0.195
Operating charges Cost
Share
0.001
0.003
0.002
0.004
0.004
0.003
0.004
0.003
Plant overhead Cost
Share
0.004
0.010
0.011
0.005
0.011
0.009
0.011
0.009
General &
Administration cost
Cost
Share
0.027
0.073
0.078
0.034
0.085
0.067
0.079
0.063
Depreciation Cost
Share
0.034
0.094
0.093
0.040
0.030
0.024
0.036
0.029
Total Cost 0.37 0.43 1.28 1.25
Share 100.0 100.0 100.0 100.0
Chapter 6 134
Table 6-13 Total production cost of ethanol from FB and RH.
Item Cost and Share
(%)
Ethanol (USD/kg)
FB RH
Raw materials Cost
Share
0.176
0.233
0.186
0.221
Operating Labor cost Cost
Share
0.005
0.006
0.005
0.006
Maintenance cost Cost
Share
0.005
0.006
0.006
0.007
Utilities cost Cost
Share
0.471
0.624
0.534
0.634
Operating charges Cost
Share
0.001
0.002
0.001
0.002
Plant overhead Cost
Share
0.005
0.006
0.005
0.006
General & Administration
cost
Cost
Share
0.053
0.070
0.059
0.070
Depreciation Cost
Share
0.040
0.053
0.045
0.053
Total Cost 0.75 0.84
Share 100.0 100.0
135 Jet fuel production from agroindustrial wastes through furfural platform
Table 6-14 Total production cost of PHB from FB and RH.
Item Cost and Share
(%)
PHB (USD/kg)
FB RH
Raw materials Cost
Share
0.296
0.291
0.476
0.298
Operating Labor cost Cost
Share
0.032
0.031
0.059
0.037
Maintenance cost Cost
Share
0.071
0.070
0.110
0.069
Utilities cost Cost
Share
0.079
0.077
0.131
0.082
Operating charges Cost
Share
0.008
0.008
0.015
0.009
Plant overhead Cost
Share
0.051
0.050
0.084
0.053
General & Administration
cost
Cost
Share
0.086
0.084
0.070
0.044
Depreciation Cost
Share
0.396
0.389
0.654
0.409
Total Cost 1.02 1.56
Share 100.0 100.0
Chapter 6 136
Table 6-15 Total production cost of Octane and Nonane from FB and RH.
Item Cost and
Share (%)
Octane (USD/kg) Nonane (USD/kg)
FB RH FB RH
Raw materials Cost
Share
2.157
0.670
2.108
0.645
2.201
0.842
2.736
0.844
Operating Labor cost Cost
Share
0.008
0.003
0.008
0.003
0.004
0.002
0.006
0.002
Maintenance cost Cost
Share
0.015
0.005
0.014
0.004
0.008
0.003
0.010
0.003
Utilities cost Cost
Share
0.629
0.195
0.744
0.228
0.186
0.071
0.217
0.067
Operating charges Cost
Share
0.002
0.001
0.002
0.001
0.001
0.000
0.002
0.000
Plant overhead Cost
Share
0.012
0.004
0.011
0.003
0.006
0.002
0.008
0.003
General &
Administration cost
Cost
Share
0.291
0.090
0.279
0.085
0.157
0.060
0.203
0.063
Depreciation Cost
Share
0.105
0.033
0.102
0.031
0.050
0.019
0.060
0.019
Total Cost 3.22 3.27 2.61 3.24
Share 100.0 100.0 100.0 100.0
A criteria to calculate the feasibility of a process, is the combination of the total production
cost of products directly related with the sales of them. Thus a profit margin can be included
as the relation of sales and total production cost. In this way, Figure 6-21 shows the profit
margin for all products for each raw material. As can be seen the processes that considered
the glucose as basis for their obtaining have higher rates of viability. The high content of
cellulose in FB makes stand out against RH. On the contrary, both materials have a similar
hemicellulose content that does not do very different the economic margins for the products
obtained from xylose.
137 Jet fuel production from agroindustrial wastes through furfural platform
Figure 6-21 Economic margin per raw material of products obtained.
6.4.5 Conclusions
The versatility of lignocellulosic biomass to obtain a great amount of products is remarkable.
However, in some case the process technologies are not sufficiently adequate to allow that
the biological processes are as competitive as conventional. Given the above, can be
proposed an optimization work to improve processes related to operating conditions,
genetic modification of microorganisms and separation and purification technologies.
0
10
20
30
40
50
60
70
80
90
Glucose Xylose Ethanol PHB Octane Nonane
Eco
no
mic
marg
in (
%)
FB RH
7. Conclusions
In the last years it has been suggested that lignocellulosic biomass could be used as an
ideal source of biofuels and biochemicals. It was briefly showed the potentiality of Colombia
to produce these products due to its location in tropical region and its diversity. In this work
is indicated the great opportunity of obtain jet fuel range alkanes through the catalytic
transformation of lignocellulosic biomass. The results given an encouraging response and
open an additional possibility to the use of agroindustrial wastes to produce jet biofuels and
subsidize the dependency of oil sources. Also, according to the study developed is possible
suggest additives, compounds by conventional biofuels for the use in aircraft industry that
in general comply with the requirements of international standards in physicochemical
properties.
The success in the obtaining of interesting products in this work is based in the initial yields
of sugars which in turn depends of efficiency and the operation conditions in the extraction
process in pretreatment step. Moreover, it was shown that most of the biomass has a high
potential towards conversion to bioproducts in spite of their limitations relating the content
of holocellulosic fiber, collecting, storage and initial conditioning. This work contributes to
implementation of simultaneous processes from agroindustrial wastes for obtaining
ethanol, furan-based compounds and alkane precursor to obtain jet biofuel, focusing on the
comprehensive utilization of raw materials and achieving considerable yields. Also, this
work promotes the combination and feedback between chemical and biological processes
due to use of mixed metal oxides and microorganisms as catalysts for conversion of the
same raw material.
Chapter 7 140
Colombia as a tropical country has the potential to produce multiple crops that are source
of great amount of residues. This wastes can be used as feedstock to produce fuels,
fertilizers, chemicals. However, the catalytic conversion of agroindustrial wastes to produce
biochemicals in this country has a substantial deficiency. In this thesis, four residues were
selected according to national production and availability to assess the possibility of obtain
sugars, alcohol, furan-based compounds and alkane precursor. According with the results,
the raw materials used are defined as promising feedstock for the strengthening of this
industry. The integral use of biomass allows creating high profitability processes focused
on the growing biorefinery concept where individual processes are supported, provided with
feedstock and also economically subsidized. This increase on economic sustainability has
an effect on the competitiveness of industries based on these kinds feedstock.
A. Annex: Kinetic parameters for simulation procedures
Table A-1 Kinetic models used in simulation procedures.
Acid hydrolysis
Kinetic model Parameters Conditions Ref
𝐻𝑒𝑚𝑖𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 𝑡𝑜 𝑥𝑦𝑙𝑜𝑠𝑒
𝑘1𝑟 = 𝐴1 ∗ 𝐶𝐴𝑛1 ∗ 𝑒𝑥𝑝 (
−𝐸𝑎1
𝑅𝑇)
𝑋𝑦𝑙𝑜𝑠𝑒 𝑡𝑜 𝑓𝑢𝑟𝑓𝑢𝑟𝑎𝑙
𝑘2𝑟 = 𝐴2 ∗ 𝐶𝐴𝑛2 ∗ 𝑒𝑥𝑝 (
−𝐸𝑎2
𝑅𝑇)
𝐶𝐴 = 𝑎𝑐𝑖𝑑 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (%𝑤𝑡)
𝐵𝑎𝑙𝑎𝑛𝑐𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛𝑠
𝛾ℎ𝑒𝑚 = −𝑘1𝑟 ∗ 𝐶ℎ𝑒𝑚
𝛾𝑥𝑦𝑙 = (𝑘1𝑟 ∗ 𝐶ℎ𝑒𝑚) − (𝑘2𝑟 ∗ 𝐶𝑥𝑦𝑙)
𝛾𝑓𝑢𝑟 = 𝑘2𝑟 ∗ 𝐶𝑥𝑦𝑙
𝑡 =1
𝜏 𝑡𝑖𝑚𝑒
𝑑ℎ𝑒𝑚 = 𝑡 ∗ (𝐶ℎ𝑒𝑚𝑓 − 𝐶ℎ𝑒𝑚𝑖) + 𝛾ℎ𝑒𝑚
𝑑𝑥𝑦𝑙 = 𝑡 ∗ (𝐶𝑥𝑦𝑙𝑓 − 𝐶𝑥𝑦𝑙𝑖) + 𝛾𝑥𝑦𝑙
𝑑𝑓𝑢𝑟 = 𝑡 ∗ (𝐶𝑓𝑢𝑟𝑓 − 𝐶𝑓𝑢𝑟𝑖) + 𝛾𝑓𝑢𝑟
𝑅 = 8.314 𝐽 𝑚𝑜𝑙−1𝐾−1
𝐴1 = 1.4𝑒14 𝑚𝑖𝑛−1
𝐴2 = 3.3𝑒10 𝑚𝑖𝑛−1
𝐸𝐴1 = 111600 𝐽 𝑚𝑜𝑙−1
𝐸𝐴2 = 95700 𝐽𝑚𝑜𝑙−1
𝑛1 = 0.68
𝑛2 = 0.4
𝜏 = 20ℎ
𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑡𝑦𝑝𝑒:
𝐶𝑆𝑇𝑅
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒:
373.15𝐾
𝐴𝑐𝑖𝑑 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛:
2% 𝑤𝑡/𝑤𝑡
[70]
Enzymatic hydrolysis
Kinetic model Parameters Conditions Ref
𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 𝑡𝑜 𝑐𝑒𝑙𝑙𝑢𝑏𝑖𝑜𝑠𝑒
𝛾1 =𝑘1𝑟𝐶𝑒1𝑏𝑅𝑆𝐶𝑆
1 +𝐶𝑔2
𝑘1𝑖𝑔2+
𝐶𝑔
𝑘1𝑖𝑔+
𝐶𝑥𝑦
𝑘1𝑖𝑥𝑦
𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 𝑡𝑜 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
142 Jet fuel production from agroindustrial wastes through of furfural platform
𝛾2 =𝑘2𝑟(𝐶𝑒1𝑏 + 𝐶𝑒2𝑏)𝑅𝑆𝐶𝑆
1 +𝐶𝑔2
𝑘2𝑖𝑔2+
𝐶𝑔
𝑘1𝑖𝑔+
𝐶𝑥𝑦
𝑘2𝑖𝑥𝑦
𝐶𝑒𝑙𝑙𝑢𝑏𝑖𝑜𝑠𝑒 𝑡𝑜 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝛾3 =𝑘3𝑟𝐶𝑒2𝑓𝐶𝑔2
𝑘3𝑀 (1 +𝐶𝐺
𝑘3𝑖𝑔+
𝐶𝑥𝑦
𝑘3𝑖𝑥𝑦) + 𝐶𝑔2
𝐸𝑛𝑧𝑦𝑚𝑒 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
𝐶𝑒𝑖𝑏 =𝐸𝑖𝑚𝑎𝑥𝑘𝑖𝑎𝑑𝐶𝑒𝑖𝑓𝐶𝑆
1 + 𝑘𝑖𝑎𝑑𝐶𝑒𝑖𝑓
𝐸𝑛𝑧𝑦𝑚𝑒
𝐶𝑒𝑖𝑡 = 𝐶𝑒𝑖𝑓 + 𝐶𝑒𝑖𝑏
𝑆𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒
𝑅𝑆 =𝐶𝑆
𝑆0
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑐𝑒
𝑘𝑖𝑟 = 𝑘𝑖 ∗ 𝑒𝑥𝑝 (−𝐸𝑎
𝑅(
1
𝑇1
−1
𝑇2
))
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑘𝑖𝑛𝑒𝑡𝑖𝑐
𝑑𝐶𝑆 = −𝛾1 − 𝛾2 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒
𝑑𝐶𝑔2 = 1.05𝛾1 − 𝛾3 𝑐𝑒𝑙𝑙𝑢𝑏𝑖𝑜𝑠𝑒
𝑑𝐶𝑔 = 1.111𝛾2 + 1.053𝛾3 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝑅 = 8.314 𝐽 𝑚𝑜𝑙−1𝐾−1
𝑘1 = 22.3 𝑔 𝑚𝑔−1ℎ−1
𝑘2 = 7.18 𝑔 𝑚𝑔−1ℎ−1
𝑘3 = 285.5 𝑔 𝑚𝑔−1ℎ−1
𝐸𝑎 = −23190 𝐽𝑚𝑜𝑙−1
𝑘1𝑖𝑔2 = 0.015 𝑔𝐿−1
𝑘1𝑖𝑔 = 0.1 𝑔𝐿−1
𝑘1𝑖𝑥𝑦 = 0.1 𝑔𝐿−1
𝑘2𝑖𝑔2 = 132 𝑔𝐿−1
𝑘2𝑖𝑔 = 0.04 𝑔𝐿−1
𝑘2𝑖𝑥𝑦 = 0.2 𝑔𝐿−1
𝑘3𝑖𝑔 = 3.9 𝑔𝐿−1
𝑘3𝑖𝑥𝑦 = 201 𝑔𝐿−1
𝑘3𝑀 = 24.3 𝑔𝐿−1
𝐸1𝑚𝑎𝑥 = 0.06 𝑔𝑔−1
𝐸2𝑚𝑎𝑥 = 0.01 𝑔𝑔−1
𝑘1𝑎𝑑 = 0.4 𝑔𝑔−1
𝑘2𝑎𝑑 = 0.1 𝑔𝑔−1
𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑡𝑦𝑝𝑒:
𝐶𝑆𝑇𝑅
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒:
308.15𝐾
[86]
Fermentation to ethanol from glucose
Kinetic model Parameters Ref
𝐵𝑖𝑜𝑚𝑎𝑠𝑠
𝛾𝑥 =𝜇𝑚𝑎𝑥𝑆
𝐾𝑆 + 𝑆exp (−𝐾𝑖𝑆) (1 −
𝑋
𝑋𝑚𝑎𝑥 +)
𝑚
(1 −𝑃
𝑃𝑚𝑎𝑥
)𝑛
𝑋
𝐸𝑡ℎ𝑎𝑛𝑜𝑙
𝛾𝑝 = 𝑌𝑝𝑥𝛾𝑥 + 𝑚𝑝𝑋
𝐺𝑙𝑢𝑐𝑜𝑠𝑒
𝛾𝑠 =𝛾𝑥
𝑌𝑥
+ 𝑚𝑥𝑋
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑘𝑖𝑛𝑒𝑡𝑖𝑐
𝑑𝑋 = 𝑡(𝑋𝑓 − 𝑋𝑖) + 𝛾𝑥 𝑏𝑖𝑜𝑚𝑎𝑠𝑠
𝑑𝑆 = 𝑡 ∗ (𝑆𝑓 − 𝑆𝑖) − 𝛾𝑆 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝑑𝑃 = 𝑡 ∗ (𝑃𝑓 − 𝑃𝑖) + 𝛾𝑝 𝑒𝑡ℎ𝑎𝑛𝑜𝑙
𝜇𝑚𝑎𝑥 = 0.426ℎ−1
𝐾𝑖 = 0.002
𝑃𝑚𝑎𝑥 = 86.072
𝑋𝑚𝑎𝑥 = 54.474
𝑌𝑝𝑥 = 0.03831
𝐾𝑠 = 4.1
𝑚𝑝 = 0.1
𝑚𝑥 = 0.2
𝑚 = 1
𝑛 = 1.5
𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑡𝑦𝑝𝑒:
𝐶𝑆𝑇𝑅
[87]
Annex A. Kinetic parameters for simulation procedures 143
𝑡 =1
𝜏 𝑡𝑖𝑚𝑒
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒: 310𝐾
𝑀𝑖𝑐𝑟𝑜𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚:
𝑆𝑎𝑐𝑐ℎ𝑎𝑟𝑜𝑚𝑦𝑐𝑒𝑠 𝑐𝑒𝑟𝑒𝑣𝑖𝑠𝑖𝑎𝑒
𝜏 = 40ℎ
Fermentation to ethanol from glucose and xylose
Kinetic model Conditions Ref
𝑀𝑖𝑐𝑟𝑜𝑏𝑖𝑎𝑙 𝑔𝑟𝑜𝑤𝑡ℎ 𝑓𝑜𝑟 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝛾𝑥1 = 𝜇𝑚𝑎𝑥1 (𝑠1
𝐾𝑠𝑥1 + 𝑠1
) (1 −𝑝 − 𝑃𝑖𝑥1
𝑃𝑚𝑥1 − 𝑃𝑖𝑥1
) (𝐾𝑖𝑥1
𝐾𝑖𝑥1 + 𝑠1
)
𝑀𝑖𝑐𝑟𝑜𝑏𝑖𝑎𝑙 𝑔𝑟𝑜𝑤𝑡ℎ 𝑓𝑜𝑟 𝑥𝑦𝑙𝑜𝑠𝑒
𝛾𝑥2 = 𝜇𝑚𝑎𝑥2 (𝑠2
𝐾𝑠𝑥2 + 𝑠2
) (1 −𝑝 − 𝑃𝑖𝑥2
𝑃𝑚𝑥2 − 𝑃𝑖𝑥2
) (𝐾𝑖𝑥2
𝐾𝑖𝑥2 + 𝑠2
)
𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝛾𝑠1 = 𝑞𝑠𝑚𝑎𝑥1 (𝑠1
𝐾𝑠𝑠1 + 𝑠1
) (1 −𝑝 − 𝑃𝑖𝑠1
𝑃𝑚𝑠1 − 𝑃𝑖𝑠1
) (𝐾𝑖𝑠1
𝐾𝑖𝑠1 + 𝑠1
) 𝑥
𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝑥𝑦𝑙𝑜𝑠𝑒
𝛾𝑠2 = 𝑞𝑠𝑚𝑎𝑥2 (𝑠2
𝐾𝑠𝑠2 + 𝑠2
) (1 −𝑝 − 𝑃𝑖𝑠2
𝑃𝑚𝑠2 − 𝑃𝑖𝑠2
) (𝐾𝑖𝑠2
𝐾𝑖𝑠2 + 𝑠2
) 𝑥
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝛾𝑝1 = 𝑞𝑝𝑚𝑎𝑥1 (𝑠1
𝐾𝑠𝑝1 + 𝑠1
) (1 −𝑝 − 𝑃𝑖𝑝1
𝑃𝑚𝑝1 − 𝑃𝑖𝑝1
) (𝐾𝑖𝑝1
𝐾𝑖𝑝1 + 𝑠1
)
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑥𝑦𝑙𝑜𝑠𝑒
𝛾𝑝2 = 𝑞𝑝𝑚𝑎𝑥2 (𝑠2
𝐾𝑠𝑝2 + 𝑠2
) (1 −𝑝 − 𝑃𝑖𝑝2
𝑃𝑚𝑝2 − 𝑃𝑖𝑝2
) (𝐾𝑖𝑝2
𝐾𝑖𝑝2 + 𝑠2
)
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑘𝑖𝑛𝑒𝑡𝑖𝑐
𝑑𝑋 = [𝛼𝛾𝑥1 + (1 − 𝛼)𝛾𝑥2]𝑥 𝑏𝑖𝑜𝑚𝑎𝑠𝑠
𝑑𝑆1 = 𝛼𝛾𝑠1𝑥 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝑑𝑆2 = 𝛼𝛾𝑠2𝑥 𝑥𝑦𝑙𝑜𝑠𝑒
𝑑𝑃 = [𝛼𝛾𝑝1 + (1 − 𝛼)𝛾𝑝2]𝑥 𝑒𝑡ℎ𝑎𝑛𝑜𝑙
𝛼 = 0.65
𝑞𝑠𝑚𝑎𝑥1 = 10.9
𝑞𝑠𝑚𝑎𝑥2 = 3.27
𝑞𝑝𝑚𝑎𝑥1 = 5.12
𝑞𝑝𝑚𝑎𝑥2 = 1.59
𝜇𝑚𝑎𝑥1 = 0.31 𝜇𝑚𝑎𝑥2 = 0.1
𝐾𝑠𝑥1 = 1.45 𝐾𝑠𝑥2 = 4.91
𝑃𝑚𝑥1 = 57.2 𝑃𝑚𝑥2 = 56.3
𝐾𝑖𝑥1 = 200 𝐾𝑖𝑥2 = 600
𝑃𝑖𝑥1 = 28.9 𝑃𝑖𝑥2 = 26.6
𝐾𝑠𝑠1 = 6.32 𝐾𝑠𝑠2 = 0.03
𝑃𝑚𝑠1 = 75.4 𝑃𝑚𝑠2 = 81.2
𝐾𝑖𝑠1 = 186 𝐾𝑖𝑠2 = 600
𝑃𝑖𝑠1 = 42.6 𝑃𝑖𝑠2 = 53.1
𝐾𝑠𝑝1 = 6.32 𝐾𝑠𝑝2 = 0.03
𝑃𝑚𝑝1 = 75.4 𝑃𝑚𝑝2 = 81.2
𝐾𝑖𝑝1 = 186 𝐾𝑖𝑝2 = 600
𝐾𝑖𝑝1 = 42.6 𝐾𝑖𝑝2 = 53.1
𝑇𝑦𝑝𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟: 𝐶𝑆𝑇𝑅
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒: 308𝐾
𝑀𝑖𝑐𝑟𝑜𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚:
𝑍𝑦𝑚𝑜𝑚𝑜𝑛𝑎𝑠 𝑚𝑜𝑏𝑖𝑙𝑖𝑠
[88]
Fermentation to butanol from glucose
Kinetic model Conversion Conditions Ref
𝐶6𝐻12𝑂6 + 𝐻2𝑂 → 𝐶3𝐻6𝑂 + 3𝐶𝑂2 + 4𝐻2
𝐶6𝐻12𝑂6 → 𝐶4𝐻10𝑂 + 2𝐶𝑂2 + 𝐻2𝑂
𝐶6𝐻12𝑂6 → 2𝐶2𝐻6𝑂 + 2𝐶𝑂2
𝐶6𝐻12𝑂6 → 𝐶4𝐻8𝑂2 + 2𝐶𝑂2 + 2𝐻2
𝐶6𝐻12𝑂6 → 3𝐶2𝐻4𝑂2
0.1554
0.5556
0.0071
0.0217
0.0106
𝑇𝑦𝑝𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟:
𝐶𝑆𝑇𝑅
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒:
306𝐾
𝑀𝑖𝑐𝑟𝑜𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚:
[101]
144 Jet fuel production from agroindustrial wastes through of furfural platform
𝐶6𝐻12𝑂6 + 6𝑂2 → 6𝐻2𝑂 + 6𝐶𝑂2
𝐶6𝐻12𝑂6 + 1.1419𝑁𝐻3 → 6.055𝐶𝑒𝑙𝑙 + 0.2857𝐶𝑂2 + 2.5714𝐻2𝑂
0.1471
0.0627
𝐶𝑙𝑜𝑠𝑡𝑟𝑖𝑑𝑖𝑢𝑚
𝑏𝑒𝑖𝑗𝑒𝑟𝑖𝑛𝑐𝑘𝑖𝑖
Fermentation to PHB from glucose
Kinetic model Parameters Conditions Ref
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑘𝑖𝑛𝑒𝑡𝑖𝑐
𝐵𝑖𝑜𝑚𝑎𝑠𝑠
𝛾𝑥 = 𝜇𝑚
𝑆𝑟
𝑆𝑟 + 𝐾𝑠𝑟
[1 − (𝑆𝑟
𝑆𝑚
)𝑛
] 𝐶𝑥
𝛾𝑠𝑐 = −𝑘4𝛾𝑥 − 𝑘5𝐶𝑥 𝑔𝑙𝑢𝑐𝑜𝑠𝑒
𝛾𝑐 = −𝑘3𝛾𝑥 𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛
𝛾𝑝 = 𝑘1𝛾𝑥 + 𝑘2𝐶𝑥 𝑃𝐻𝐵
𝑆𝑟 =𝐶𝑠𝑛 (𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛)
𝐶𝑠𝑐 (𝑐𝑎𝑟𝑏𝑜𝑛)
𝜇𝑚 = 0.78ℎ−1
𝐾𝑠𝑟 = 0.29
𝑆𝑚 = 0.3
𝑛 = 0.24
𝑘1 = 0.2604
𝑘2 = 0.0301
𝑘3 = 0.6511
𝑘4 = 4.503
𝑘5 = 0.0001
𝑇𝑦𝑝𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟:
𝐶𝑆𝑇𝑅
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒:
303.15𝐾
𝑀𝑖𝑐𝑟𝑜𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚:
𝑅𝑎𝑙𝑠𝑡𝑜𝑛𝑖𝑎 𝑒𝑢𝑡𝑟𝑜𝑝ℎ𝑎
[90]
Gasification process
Kinetic model Conditions Ref
Combined cycle
Gasification based on stoichiometric approach using
free Gibbs energy minimization method taking into
account components as CH4, CO, CO2, H2O, NOx,
SOx, N2O, O2, N2
Reactor type: gasified
PBR to 60bar
[132],
[133]
B. Annex: Analysis of the statics for the furfural synthesis by reactive distillation
Furfural is a well-known platform chemical derived from lignocellulosic biomass to produce
resins, pharmaceuticals, agrochemicals and biofuels [104], [123]. In order to overcome the
concern related to the separation of the furfural from the aqueous solution produced after
the biomass digestion, numerous investigative work have been performed to assess the
application of reactive distillation (RD). Due to the presence of an azeotrope of minimum
boiling several concerns may exist related with the separation of furfural. For that reason
RD should be analyzed in depth for this particular mixture to generate optimal flow sheets
to ensure not only the required product quality, but also to provide savings in capital and
energy costs and to keep environmental safety.
As consequence, RD is analyzed as an interesting alternative to isolate the furfural from
the mixture. RD has remarkable characteristics because of the mass selective exchange,
which offers positive influence in chemical transformation. Besides, presence of chemical
reaction to certain conditions can "break up" the azeotropes [139]. The thermodynamic
topological analysis (TTA) has been applied as a tool that quantitatively predicts the
thermodynamic possibilities and limitations of the operation. When the reaction is taken into
account the analysis is called “analysis of the statics” and as a final point, alternative
separation sequences can be investigated and compared in order to select the best one
[140], [141].
Methodology
Static analysis was used to select the limit steady states (LSS) which represent the
maximum conversion and selectivity due that they are cataloged according to optimization
criteria as the most important in the schemes in these processes. The procedure of the
146 Jet fuel production from agroindustrial wastes through of furfural platform
analysis is cited by Pisarenko et al. 2001 and López & López 2003). The chemical reaction
is the dehydration of xylose (X) to produce furfural (F) and water (H2O) according to
equation (1).
𝐶5𝐻10𝑂5 → 𝐶5𝐻4𝑂2 + 𝐻2𝑂 (1)
𝑋𝑦𝑙𝑜𝑠𝑒 → 𝐹𝑢𝑟𝑓𝑢𝑟𝑎𝑙 + 𝑊𝑎𝑡𝑒𝑟
Table B-1 shows the boiling temperatures at atmospheric pressure of the compounds
involved. The system has one azeotrope and their composition and boiling temperatures
are shown in table 2.
Table B-1 Boling temperatures of all compounds involved.
Compound Xylose Furfural Water
Boling point (ºC) 301.78 161.35 100.02
Table B-2 Conditions of the azeotrope of the system.
Azeotrope Boiling point (ºC) Composition
X F H2O
F- H2O 97.68 0.000 0.0938 0.9062
Static analysis
Analysis of the structure of the distillation diagram to the reactive system
Figure B-1 shows the separatriz of second order and the phase diagram of the system from
information indicated on tables B-1 and B-2. The geometric separatriz of the ternary system
is a projection of the geometry limiting of the ternary system X – H2O. Separatriz of second
order does not represent thermodynamic limitations. Blue lines represent the residue
curves which are above and below to the separatriz formed by the azeotrope F - H2O.
Figure B-1 indicates that only exist one distillation region and the residue curves begin in
the azeotrope F – H2O and end in the X point.
Annex B: Analysis of the statics for the furfural synthesis by reactive distillation 147
Fixed points characterization and subregions of distillation
From the information of figure B-1 the fixed point characterization was made and is shown
in table B-3. For both cases, direct and indirect separation exist one subregion of distillation
and are present in table B-4.
Figure B-1 Separatriz of second order and phase diagram of system
Table B-3 Clasification of the fixed points of the system.
Fixed Point X F H2O Az H2O-F
Type Stable node Saddle Saddle Unstable node
Table B-4 Subregions to direct and indirect separations.
Direct separation Indirect separation
Az F - H2O – F – X Az F - H2O - H2O - X
Chemical interaction and reaction lines
Chemical interaction line form depending on the stoichiometric reaction. For furfural
production chemical interaction line is shown in Figure B-3. Direction of reaction lines is
given by the reaction pole as shown equation (2) where L1 is the necessary distance to find
148 Jet fuel production from agroindustrial wastes through of furfural platform
the pole, L2 is the distance from the stoichiometric feeding to the point of product formation,
NP is the number of produced moles and NR is the number of reactant moles.
𝐿1 = 𝐿2
𝑁𝑃
𝑁𝑅 − 𝑁𝑃 (2)
Case 1 When the reaction line is below the azeotrope
Figure B-2 Chemical interaction and reaction line, case 1.
Case 2 When the reaction line is above the azeotrope
Figure B-3 Chemical interaction and reaction line, case 2.
Annex B: Analysis of the statics for the furfural synthesis by reactive distillation 149
Results and Discussion
Case 1. Limit steady states (LSS)
The reaction line for case 1 is built by four pseudoinitial compositions considering the direct
separation as the most important because the furfural is interest product. P/W is calculated
for the type separation, reaction line and pseudoinitial composition. LSS for direct
separation is shown clearly in table B-5 and figure B-4 (marked by S1).
Table B-5 LSS for direct separation (pseudoinitial compositions and dependence P/W) case 1.
Initial composition Pseudoinitial composition P/W
X H2O F X F H2O
0.08 0.92 0
0 0.03 0.05 0.07
0.05 0.03 0.02 0.01
0.95 0.94 0.93 0.92
1.2 0.67 0.28 0.12
Figure B-4 P/W in function of pseudoinitial compositions of furfural, case 1.
Case 2. Limit steady states (LSS)
The reaction line for case 2 is built by five pseudoinitial compositions considering the direct
separation as the most important because the furfural is interest product. P/W is calculated
for the type separation, reaction line and pseudoinitial composition. LSS for direct
separation is shown clearly in table B-6 and figure B-5 (marked by S1 and S2).
0
0.4
0.8
1.2
1.6
0.00 0.02 0.04 0.06
P/W
Pseudoinitial composition of furfural
S1
150 Jet fuel production from agroindustrial wastes through of furfural platform
Table B-6 LSS for direct separation (pseudoinitial compositions and dependence P/W) case 2.
Initial composition Pseudoinitial composition P/W
X H2O F X F H2O
0.4 0.6 0
0.020 0.044 0.056 0.054 0.069
0.211 0.141 0.109 0.095 0.074
0.769 0.815 0.835 0.851 0.857
7.25 14.0 15.0 14.0 4.25
Figure B-5 P/W in function of pseudoinitial compositions of furfural, case 2.
Feasible steady states
Case 1
In this case only one steady state is feasible with a maximum conversion. Figures 5 and 6
present the trajectory and separation scheme for the steady state. The trajectory is not
developed in the simplex concentracional completely for this reason the furfural obtained
in distillate made is not totally pure.
0
2
4
6
8
10
12
14
16
18
0 0.05 0.1 0.15 0.2 0.25
P/W
Pseudoinitial composition of furfural
S1 S2
Annex B: Analysis of the statics for the furfural synthesis by reactive distillation 151
Figure B-6 Limit stable state (S1) and technologic scheme, case 1.
Case 2
Figure B-7 Limit stable state (S1) and their possible trajectories, case 2. Technologic scheme
trajectory 1.
The steady stable feasible S2 has a maximum conversion. The trajectory and balance line
have an overlap which leads to the tower-packing is possible from geometrical point of view
but physically is not possible because in this zone trajectory there is not presence of
reagent.
152 Jet fuel production from agroindustrial wastes through of furfural platform
Figure B-8 Limit stable state (S2) and technologic scheme, case 2.
The scheme obtained in the case 2, LSS S1 and the trajectory 1 is compared with the
diagram shown in the figure B-9 published in the patent "Process for the production of
furfural US 20130172583A1" indicating that the analysis made in this study can arrive to a
successful approach for this technological configuration.
Figure B-9 Scheme of process presented in the patent US 20130172583A1 [142].
Annex B: Analysis of the statics for the furfural synthesis by reactive distillation 153
Conclusions
This analysis shows that short-cut based on thermodynamics, specifically in topological
thermodynamics are a powerful and essential tool before of design and even experiment
with reactive distillation towers, note for example that the cited patent was almost certainly
the work of many years and here by a simple method gets to establish which is the
technological diagram should be proposed to carry out this process.
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