Separation and Purification Technologies in Biorefineries
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List of Contributors xix
Preface xxiii
PART I INTRODUCTION 1
1 Overview of Biomass Conversion Processes and Separation and Purification Technologies in Biorefineries 3
Hua-Jiang Huang and Shri Ramaswamy
1.1 Introduction 3
1.2 Biochemical conversion biorefineries 4
1.3 Thermo-chemical and other chemical conversion biorefineries 8
1.4 Integrated lignocellulose biorefineries 14
1.5 Separation and purification processes 15
1.6 Summary 27
References 28
PART II EQUILIBRIUM-BASED SEPARATION TECHNOLOGIES 37
2 Distillation 39
Zhigang Lei and Biaohua Chen
2.1 Introduction 39
2.2 Ordinary distillation 40
2.3 Azeotropic distillation 45
2.4 Extractive distillation 48
2.5 Molecular distillation 54
2.6 Comparisons of different distillation processes 55
2.7 Conclusions and future trends 58
Acknowledgement 58
References 58
3 Liquid-Liquid Extraction (LLE) 61
Jianguo Zhang and Bo Hu
3.1 Introduction to LLE: Literature review and recent developments 61
3.2 Fundamental principles of LLE 62
3.3 Categories of LLE design 65
3.4 Equipment for the LLE process 67
3.5 Applications in biorefineries 70
3.6 The future development of LLE for the biorefinery setting 74
References 75
4 Supercritical Fluid Extraction 79
Casimiro Mantell, Lourdes Casas, Miguel Rodríguez and Enrique Martínez de la Ossa
4.1 Introduction 79
4.2 Principles of supercritical fluids 81
4.3 Market and industrial needs 83
4.4 Design and modeling of the process 84
4.4.1 Film theory 88
4.5 Specific examples in biorefineries 89
4.6 Economic importance and industrial challenges 93
4.7 Conclusions and future trends 96
References 96
PART III AFFINITY-BASED SEPARATION TECHNOLOGIES 101
5 Adsorption 103
Saravanan Venkatesan
5.1 Introduction 103
5.2 Essential principles of adsorption 104
5.3 Adsorbent selection criteria 110
5.4 Commercial and new adsorbents and their properties 111
5.5 Adsorption separation processes 116
5.6 Adsorber modeling 123
5.7 Application of adsorption in biorefineries 124
5.8 A case study: Recovery of 1-butanol from ABE fermentation broth using TSA 136
5.9 Research needs and prospects 142
5.10 Conclusions 143
Acknowledgement 143
References 143
6 Ion Exchange 149
M. Berrios, J. A. Siles, M. A. Martín and A. Martín
6.1 Introduction 149
6.1.1 Ion exchangers: Operational conditions-sorbent selection 150
6.2 Essential principles 151
6.3 Ion-exchange market and industrial needs 153
6.4 Commercial ion-exchange resins 154
6.5 Specific examples in biorefineries 156
6.6 Conclusions and future trends 164
References 164
7 Simulated Moving-Bed Technology for Biorefinery Applications 167
Chim Yong Chin and Nien-Hwa Linda Wang
7.1 Introduction 167
7.2 Essential SMB design principles and tools 171
7.3 Simulated moving-bed technology in biorefineries 191
7.4 Conclusions and future trends 197
References 197
PART IV MEMBRANE SEPARATION 203
8 Microfiltration, Ultrafiltration and Diafiltration 205
Ann-Sofi Jönsson
8.1 Introduction 205
8.2 Membrane plant design 207
8.3 Economic considerations 210
8.4 Process design 213
8.5 Operating parameters 216
8.6 Diafiltration 222
8.7 Fouling and cleaning 224
8.8 Conclusions and future trends 226
References 226
9 Nanofiltration 233
Mika Mänttäri, Bart Van der Bruggen and Marianne Nyström
9.1 Introduction 233
9.2 Nanofiltration market and industrial needs 235
9.3 Fundamental principles 236
9.4 Design and simulation 238
9.5 Membrane materials and properties 241
9.6 Commercial nanofiltration membranes 245
9.7 Nanofiltration examples in biorefineries 246
9.8 Conclusions and challenges 256
References 256
10 Membrane Pervaporation 259
Yan Wang, Natalia Widjojo, Panu Sukitpaneenit and Tai-Shung Chung
10.1 Introduction 259
10.2 Membrane pervaporation market and industrial needs 260
10.3 Fundamental principles 261
10.4 Design principles of the pervaporation membrane 265
10.5 Pervaporation in the current integrated biorefinery system 283
10.6 Conclusions and future trends 288
Acknowledgements 289
References 289
11 Membrane Distillation 301
M. A. Izquierdo-Gil
11.1 Introduction 301
11.2 Membrane distillation market and industrial needs 304
11.3 Basic principles of membrane distillation 308
11.4 Design and simulation 313
11.5 Examples in biorefineries 315
11.6 Economic importance and industrial challenges 317
11.7 Comparisons with other membrane-separation technologies 319
11.8 Conclusions and future trends 321
References 322
PART V SOLID-LIQUID SEPARATIONS 327
12 Filtration-Based Separations in the Biorefinery 329
Bhavin V. Bhayani and Bandaru V. Ramarao
12.1 Introduction 329
12.2 Biorefinery 330
12.3 Solid-liquid separations in the biorefinery 335
12.4 Introduction to cake filtration 336
12.5 Basics of cake filtration 336
12.6 Designing a dead-end filtration 340
12.7 Model development 346
12.8 Conclusions 348
References 348
13 Solid-Liquid Extraction in Biorefinery 351
Zurina Zainal Abidin, Dayang Radiah Awang Biak, Hamdan Mohamed Yusoff and Mohd Yusof Harun
13.1 Introduction 351
13.2 Principles of solid-liquid extraction 352
13.3 State of the art technology 356
13.4 Design and modeling of SLE process 357
13.5 Industrial extractors 363
13.6 Economic importance and industrial challenges 368
13.7 Conclusions 371
References 371
PART VI HYBRID/INTEGRATED REACTION-SEPARATION SYSTEMS-PROCESS INTENSIFICATION 375
14 Membrane Bioreactors for Biofuel Production 377
Sara M. Badenes, Frederico Castelo Ferreira and Joaquim M. S. Cabral
14.1 Introduction 377
14.2 Basic principles 381
14.2.1 Biofuels: Production principles and biological systems 381
14.3 Examples of membrane bioreactors for biofuel production 390
14.4 Conclusions and future trends 403
References 404
15 Extraction-Fermentation Hybrid (Extractive Fermentation) 409
Shang-Tian Yang and Congcong Lu
15.1 Introduction 409
15.2 The market and industrial needs 410
15.3 Basic principles of extractive fermentation 412
15.4 Separation technologies for integrated fermentation product recovery 413
15.5 Examples in biorefineries 426
15.6 Economic importance and industrial challenges 428
15.7 Conclusions and future trends 431
References 431
16 Reactive Distillation for the Biorefinery 439
Aspi K. Kolah, Carl T. Lira and Dennis J. Miller
16.1 Introduction 439
16.2 Column internals for reactive distillation 441
16.3 Simulation of reactive distillation systems 446
16.4 Reactive distillation for the biorefinery 451
16.5 Recently commercialized reactive distillation processes for the biorefinery 458
16.6 Conclusions 458
References 459
17 Reactive Absorption 467
Anton A. Kiss and Costin Sorin Bildea
17.1 Introduction 467
17.2 Market and industrial needs 468
17.3 Basic principles of reactive absorption 468
17.4 Modelling, design and simulation 469
17.5 Case study: Biodiesel production by catalytic reactive absorption 470
17.6 Economic importance and industrial challenges 482
17.7 Conclusions and future trends 482
References 482
PART VII CASE STUDIES OF SEPARATION AND PURIFICATION TECHNOLOGIES IN BIOREFINERIES 485
18 Cellulosic Bioethanol Production 487
Mats Galbe, Ola Wallberg and Guido Zacchi
18.1 Introduction: The market and industrial needs 487
18.2 Separation procedures and their integration within a bioethanol plant 488
18.3 Importance and challenges of separation processes 490
18.4 Pilot and demonstration scale 498
18.5 Conclusions and future trends 500
References 500
19 Dehydration of Ethanol using Pressure Swing Adsorption 503
Marian Simo
19.1 Introduction 503
19.2 Ethanol dehydration process using pressure swing adsorption 504
19.3 Future trends and industrial challenges 510
19.4 Conclusions 511
References 511
20 Separation and Purification of Lignocellulose Hydrolyzates 513
G. Peter van Walsum
20.1 Introduction 513
20.2 The market and industrial needs 516
20.3 Operation variables and conditions 517
20.4 The hydrolyzates detoxification and separation processes 519
20.5 Separation performances and results 524
20.6 Economic importance and industrial challenges 525
20.7 Conclusions 527
References 527
21 Case Studies of Separation in Biorefineries-Extraction of Algae Oil from Microalgae 533
Michael Cooney
21.1 Introduction 533
21.2 The market and industrial needs 534
21.3 The algae oil extraction process 539
21.4 Extraction 540
21.5 Separation performance and results 546
21.6 Economic importance and industrial challenges 548
21.7 Conclusions and future trends 549
References 550
22 Separation Processes in Biopolymer Production 555
Sanjay P. Kamble, Prashant P. Barve, Imran Rahman and Bhaskar D. Kulkarni
22.1 Introduction 555
22.2 The market and industrial needs 556
22.3 Lactic acid recovery processes 559
22.4 Separation performance and results of autocatalytic counter current reactive distillation of lactic acid with methanol and hydrolysis of methyl lactate into highly pure lactic acid using 3-CSTRs in series 561
22.5 Economic importance and industrial challenges 564
22.6 Conclusions and future trends 565
Acknowledgements 566
References 566
Index 569
Chapter 1
Overview of Biomass Conversion Processes and Separation and Purification Technologies in Biorefineries
Hua-Jiang Huang and Shri Ramaswamy
Department of Bioproducts and Biosystems Engineering, University of Minnesota, USA
1.1 Introduction
There has been an increasing interest in conversion of biomass to biofuels, energy and chemicals due to increase in global demand, price and decrease in potential availability of crude oil, the need for energy independence and energy security, and the need for reduction in greenhouse gases emission from fossil fuel contributing to global climate change, and so forth.
Biomass feedstock suitable for producing biofuels, energy and co-products can be starchy biomass (e.g., corn/wheat kernel, cassava), sugarcane and sugar beet, ligocellulosic biomass including agricultural residues (e.g., corn stover, crop residues such as wheat straw and barley straw, and sugar cane bagasse), forest wastes, fast-growing trees such as hybrid poplar and willow, fast-growing herbaceous crops such as switchgrass and alfalfa, oily plants such as soybean and rapeseed, microalgae, waste cooking oil, animal manure, as well as municipal solid waste. The total amount of biomass feedstock available is huge. In the United States, based on the estimation by U.S. Department of Energy (U.S. Department of Energy 2011), total potential biomass resource is about 258 (baseline)–340 (high-yield scenario) million dry tons in 2012. Potential supplies at a forest roadside or farmgate price of $60 per dry ton range from 602 to 1009 million dry tons by 2022 and from about 767 to 1305 million dry tons by 2030, depending on the assumptions for energy crop productivity (1% to 4% annual increase over current yields). This estimate excludes resources that are currently being used, such as corn grain and woody biomass used in the forest products industry. Worldwide, the biomass availability is also significantly high of the order of 5.0 billion tons per year (Bauen et al. 2009; U.S. Department of Energy 2011).
Biofuels made from starchy crops, sugar plants as well as vegetable oils are usually called first-generation biofuels; for example, bioethanol produced from maize, starch, or sugar via fermentation, biodiesel from soybean oil, rapeseed oil, palm oil, or other plant oil by transesterification. Biogas from anaerobic digestion of waste streams also belongs to the first-generation biofuels. As the first-generation biofuels produced from food crops competes with food production and supply, and biogas can only be produced in small quantities, the first-generation biofuels alone generally cannot meet our energy requirements. Biofuels such as cellulosic ethanol made from lignocellulosic biomass such as woody crops, fast-growing trees and herbaceous crops, agricultural residues and forestry waste are referred to as the second-generation biofuels. The focus for second-generation biofuels was primarily ethanol. Unlike the first-generation biofuels, the second-generation biofuels are based on non-food crops and other lignocellulosic biomass; it can also bring about significant reduction in greenhouse gas emissions as well as reduction in fossil fuel use. The third-generation biofuels are made from genetically modified energy crops that may be carbon-neutral, biofuels from algae, or biofuels directly produced from microorganisms or using advances in biochemistry. Fourth-generation biofuels have also been suggested, which are carbon negative—they consume more carbon than they generate during their entire life cycle. Examples of this could be carbon-fixing plants such as low input high-diversity perennial grasses (Tilman, Hill, and Lehman 2006).
A biorefinery is a facility to convert biomass to bioproducts including bioenergy (fuels, heat and power) and diverse array of co-products (including materials and chemicals) (Huang et al. 2008; Huang and Ramaswamy 2012). The biorefinery concept is similar to today's petroleum refinery, which produces multiple fuels and products from petroleum (http://www.nrel.gov/biomass/biorefinery.html). Biorefinery can be divided into two basic conversion platforms: biochemical conversions, and thermo-chemical conversions. A biorefinery can also be a combination of both biochemical and thermo-chemical conversion approaches. Biochemical conversions of biomass using enzymes and microorganisms (yeast and bacteria) are often referred to as “sugar-platform” conversions, where biomass is firstly pretreated and hydrolyzed to mono-sugars: glucose, xylose, arabinose, galactose, and mannose, and so forth. The mono-sugars are then fermented or digested to biofuels such as bioethanol and biobutanol, or chemicals such as lactic acid and succinic acid, depending on the biocatalysts used. Thermo-chemical conversion of biomass includes biomass combustion for heat and power, pyrolysis for bio-oil and biochar, hydrothermal liquefaction to bio-oils as major product, and biomass gasification to syngas. Syngas (mainly CO and H2) from biomass gasification can be further synthesized into a wide range of different fuels and chemicals under different catalysts and operating conditions; biomass gasification or “syngas platform” represents the major thermo-chemical platform. In addition to these basic thermo-chemical conversions, there are a variety of other chemical conversion processes such as conversion of oil-containing biomass such as soybean and microalgae for biodiesel, and the conversion of building block chemicals such as lactic acid to its corresponding commodities, chemicals, polymers and materials.
This chapter provides an overview of the separation and purification technologies in biorefineries for producing bioproducts including biofuels, bioenergy, biochemicals and materials, with more emphasis on lignocelluose biorefineries.
1.2 Biochemical conversion biorefineries
In the biochemical conversion biorefineries or “sugar platforms,” biomass is subjected to hydrolysis and saccharification and then the resulting sugars, including hexoses (glucose, mannose, and galactose) and pentoses (xylose, arabinose) are converted to biofuels such as ethanol and butanol, chemicals, and materials.
As an example, the basic process for conversion of cellulosic biomass to fuel ethanol is shown in Figure 1.1, which mainly consists of the following eight major process areas (Aden et al. 2002):
1. Feedstock handling including biomass storage and size reduction (shredding). 2. Pretreatment and hydrolyzate conditioning or detoxification. Here, the shredded biomass is pretreated with dilute sulfuric acid at a high temperature (using steam), and thus most of the hemicellulose is hydrolyzed to fermentable monosugars (mainly xylose, mannose, arabinose, and galactose) while glucan in the hemicellulose and a small fraction of the cellulose are converted to glucose. In addition, the hydrolysis reaction produces acetic acid liberated from acetate in biomass, furfural and hydroxymethyl furfural (HMF) from degradation of pentose and hexose sugars respectively. These compounds are inhibitory to the subsequent fermentation so, following the pretreatment, the prehydrolysys slurry is flashed to remove a portion of the acetic acid, and most of the furfural and HMF. The hydrolyzate, after being separated from the solids, is then overlimed to pH 10 by adding lime to remove the remaining inhibitors, followed by neutralization and precipitation of gypsum. After filtering out the gypsum, the detoxified hydrolyzate and the solids (cellulose) are sent to the saccharification and co-fermentation area. This step also solubilizes some of the lignin in the feedstock and make the cellulose accessible to subsequent enzymatic hydrolysis. 3. Saccharification and co-fermentation. The cellulose is biochemically hydrolyzed or saccharified to glucose by cellulase enzyme in the continuous hydrolysis tanks. The co-fermentation of the detoxified hydrolyzate slurry is carried out in anaerobic fermentation tanks in series using the microorganism Zymomonas mobilis. With several days of separate and combined saccharification and cofermentation, most of the cellulose and xylose are converted to ethanol. 4. Product separation and purification. Beer is firstly preconcentrated by distillation, followed by vapor-phase molecular sieve separation for ethanol dehydration. The postdistillation slurry from the distillation bottom is separated into the solids and liquid. The liquid is then evaporated and separated into the concentrated syrup, and the condensed water is recycled in the process. The solids and the syrup obtained are sent to the combustor. 5. Wastewater treatment. Part of the evaporator condensate, together with the wastewater from pretreatment area, is treated by anaerobic digestion. The biogas (rich in methane) from anaerobic digestion is sent to the combustor for energy recovery. The treated water is recycled for use in the process. 6. Product storage. 7. Combustion of solids (lignin) for heat (steam) and power. The solids from distillation, the concentrated syrup from the evaporator, and biogas from anaerobic and aerobic digestion are combusted in a fluidized bed combustor to produce high-pressure steam for electricity production and process heat. Generally, the process produces excess steam that is converted to electricity by steam turbines for use in the plant and for sale to the grid. 8. Utilities.Figure 1.1 Simplified process block diagram of basic lignocellulose to ethanol biorefinery (Aden et al. 2002; Huang et al....
