Catalytic Process Development for Renewable Materials E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 695

Veröffentlichungsjahr: 2013

Beschreibung

Green, clean and renewable are the hottest keywords for catalysis and industry. This handbook and ready reference is the first to combine the fields of advanced experimentation and catalytic process development for biobased materials in industry. It describes the entire workflow from idea, approach, research, and process development, right up to commercialization. A large part of the book is devoted to the use of advanced technologies and methodologies like high throughput experimentation, as well as reactor and process design models, with a wide selection of real-life examples included at each stage. The contributions are from authors at leading companies and institutes, providing firsthand information and knowledge that is hard to find elsewhere. This work is aimed at decision makers, engineers and chemists in industry, chemists and engineers working with/on renewables, chemists in the field of catalysis, and chemical engineers.

Leseprobe

Table of Contents

Related Titles

Title page

Copyright page

The Next Feedstock Transition

Preface

List of Contributors

1: The Industrial Playing Field for the Conversion of Biomass to Renewable Fuels and Chemicals

1.1 Introduction

1.2 The Renewables Arena

1.3 Renewable Fuels

1.4 Renewable Chemicals

1.5 Conclusions

2: Selecting Targets

2.1 Introduction

2.2 Target Selection Can Focus on Specific Structures or General Technologies

2.3 Previous Selection Efforts

2.4 Corroboration of the Value of Screening Studies

2.5 The Importance of Outcomes and Comparisons of Outcomes

2.6 Evaluation Processes Can be Comprised of a Variety of Criteria

2.7 Catalysis Aspects

2.8 Conclusions

3: The Development of Catalytic Processes from Terpenes to Chemicals

3.1 Introduction

3.2 Strain Engineering for the Production of Terpenes

3.3 Terpene Building Blocks of Commercial Interest

3.4 Sesquiterpenes as Chemical Building Blocks: β-Farnesene

3.5 Polymers

3.6 Lubricants

3.7 Conclusions

4: Furan-Based Building Blocks from Carbohydrates

4.1 Importance of Furans as Building Blocks

4.2 Sources of Carbohydrates

4.3 Carbohydrate Dehydration

4.4 Conclusions and Further Perspectives

5: A Workflow for Process Design – Using Parallel Reactor Equipment Beyond Screening

5.1 Introduction

5.2 The Evolution of Parallel Reactor Equipment

5.3 The Evolution of Research Methodology – Conceptual Process Design

5.4 Essential Workflow Elements

5.5 Other Examples of Parallel Reactor Equipment Applied Beyond Screening – Long-Term Catalyst Performance

5.6 Concluding Remarks

6: Braskem’s Ethanol to Polyethylene Process Development

6.1 Introduction

6.2 Ethanol and Brazil

6.3 Commercial Plants for Ethanol Dehydration

6.4 Legislation and Certification

6.5 Process Description

6.6 Polymerization

6.7 Conclusion

Acknowledgments

7: Fats and Oils as Raw Material for the Chemical Industry

7.1 Introduction – Setting the Scene, Definitions

7.2 Why Fats and Oils Need Catalytic Transformation

7.3 Catalytic Process Development – Conceptual

7.4 Fatty Alcohols: Then and Now, a Case Study

7.5 Conclusion and Outlook: Development Challenges for the Future

8: Production of Aromatic Chemicals from Biobased Feedstock

8.1 Introduction

8.2 Chemical Routes to Aromatic Chemicals from Biomass

8.3 Biological Routes to Specific Aromatic Chemicals

8.4 Lignin – The Last Frontier

8.5 Considerations for Scale-Up and Commercialization

8.6 Conclusion

9: Organosolv Biorefining: Creating Higher Value from Biomass

9.1 Introduction

9.2 Concepts and Principles of Biorefinery Technologies

9.3 Catalytic Processes Employed in Biorefining

9.4 An Organosolv Biorefinery Process for High-Value Products

9.5 Conclusions

10: Biomass-to-Liquids by the Fischer–Tropsch Process

10.1 Basics of Fischer–Tropsch Chemistry and BTL

10.2 Cobalt Fischer–Tropsch Catalysis

10.3 Fischer–Tropsch Reactors

10.4 Biomass Pretreatment and Gasification

10.5 Biomass-to-Liquids Process Concepts

10.6 BTL Pilot and Demonstration Plants

10.7 XTL Energy and Carbon Efficiencies

10.8 BTL Summary and Outlook

11: Catalytic Transformation of Extractives

11.1 Introduction

11.2 Fine and Special Chemicals from Crude Tall Oil Compounds

11.3 Fine and Special Chemicals from Turpentine Compounds

11.4 Conclusions

11.5 Acknowledgment

12: Environmental Assessment of Novel Catalytic Processes Based on Renewable Raw Materials – Case Study for Furanics

12.1 Introduction

12.2 Energy Savings by Catalytic Processes

12.3 LCA Methodology

12.4 Case Study: Energy Analysis and GHG Balance of Polyethylene Furandicarboxylate (PEF) as a Potential Replacement for Polyethylene Terephthalate (PET)

12.5 Discussion and Conclusions

13: Carbon Dioxide: A Valuable Source of Carbon for Chemicals, Fuels and Materials

13.1 Introduction

13.2 The Conditions for Industrial Use of CO2

13.3 Carbon Dioxide Conversion

13.4 Energy Products from CO2

13.5 Production of Inorganic Carbonates

13.6 Enhanced Fixation of CO2 into Aquatic Biomass

13.7 Conclusion and Future Outlook

Index

Related Titles

Xie, H., Gathergood, N.

The Role of Green Chemistry in Biomass Processing and Conversion

2013

ISBN: 978-0-470-64410-2

Tao, J., Kazlauskas, R. J. (eds.)

Biocatalysis for Green Chemistry and Chemical Process Development

2011

ISBN: 978-0-470-43778-0

Jameel, F., Hershenson, S. (eds.)

Formulation and Process Development Strategies for Manufacturing Biopharmaceuticals

2010

ISBN: 978-0-470-11812-2

Harmsen, J., Powell, J. B. (eds.)

Sustainable Development in the Process Industries

Cases and Impact

2010

ISBN: 978-0-470-18779-1

Walker, D.

The Management of Chemical Process Development in the Pharmaceutical Industry

2010

ISBN: 978-0-470-65251-0

The Editors

Dr. Pieter Imhof

Avantium

VP Strategic Account Management

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

Dr. Jan Cornelis van der Waal

Avantium

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

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The Next Feedstock Transition

The last century has witnessed the dramatic growth of the energy and chemicals industry, fueled by a steep rise in world population, exploding demand for products, breakthroughs in catalysis and polymer sciences, and finally the switch from coal to relatively cheap oil and gas as a feedstock. In the coming decades, further growth and change are to be expected, induced by a continuing rise in world population, the sustainability imperative, substantial progress in bio- and nanosciences, and a gradual switch from fossil-based resources to renewable resources.

To provide a general backdrop to the material presented in this book I should like to offer a few insights gathered during my career in one of the leading energy and chemicals companies, Royal Dutch Shell. Let us start with reminding ourselves that the golden age of chemocatalysis was brought to the fore by the availability of abundant and relatively cheap oil and gas – created by biomass decomposition over millions of years. These resources are characterized by, relative to coal, low to medium range molecular weights, high H/C ratios, and chemical stability upon storage. Over time, the industry has developed an impressive series of thermal and chemocatalytic processes to convert these resources into fuels, lube oils, and chemical building blocks, such as syngas, olefins and aromatics. In a next set of processes, the chemical building blocks are then functionalized to yield aldehydes, acids, esters, amides, aliphatic oligomers and polymers for use in manufacturing of the chemical products that enabled our modern ways of living. Molecular transformations include oxidation, amination, (de-)hydrogenation, desulfurization, denitrogenation, (hydro-)cracking, hydroformylation, polymerization, and so on. The chemical stability of the fossil resources – brought along by the predominance of C–H and C–C bonds in the feedstocks – forces the industry to apply high temperatures and pressures in (especially) the primary conversion processes. The resulting capital intensity has driven the industry to building ever larger plants enjoying very high space time yields and efficient energy management.

It is my firm conviction that the very extensive knowledge and experience base gained through the conversion and upgrading of fossil resources will be a key contributor to the technology revolution needed to move towards an economy that is based on biomass. Firstly, a number of existing conversion technologies will – with some minor adaptations – be employed for the production of alkanes and oxygenates from ‘green’ syngas, for the upgrading of biomass-derived oils and for the production of chemical intermediates from bio-alcohols and bio-acids. Secondly, a new generation of catalytic processes are or will be developed to specifically convert biomass components, such as sugars, cellulose and lignin into chemical intermediates currently employed by the industry. Thirdly, bio- and chemocatalysts will play a role in the generation of a set of ‘green’ intermediates and end products that make better use of the high oxygen contents and low aromaticity of biomass.

Frequently, the conversion of a specific source of biomass to one or more products sold to end consumers will include a series of thermal, biocatalytic and thermocatalytic transformations. The logistics of biomass accumulation, storage, and transport are very different from those of fossil resources, and this will have consequences for the choice of technology and size of plants. One might imagine that biocatalytic processes will be employed in smaller scale distributed plants that can handle the seasonality and variability of biomass, and that chemocatalytic processes will be employed in large scale central plants making full use of economies of scale. A concerted approach and extensive technology development will be essential to optimize the value chain from biomass to products to use.

In the coming years, the push for renewable feedstocks will change the landscape of the process industry. It will be fascinating to watch how bio- and chemocatalysis will complement each other in creating green value chains that displace existing value chains based on fossil resources. The authors of the contributions of this book demonstrate that many scientists and technologists will not only watch this story unfold but will actively shape its outcome by leveraging the inherent strengths of chemocatalysis in imaginative and productive ways.

Jan van der Eijk

CTO of Royal Dutch Shell (2006–2009)

Preface

The strong incentives to switch from traditional raw materials to renewable resources, as well as the requirements to come to selective and efficient conversion processes, have prompted us to compose this book. It gives an overview of several processes, either in developmental or commercial stage, to highlight the characteristics of chemical catalytic processes based on renewables, and the steps that need to be taken to come to an economically and ecologically viable, and attractive process. We have chosen to start it from an intermediate chemicals perspective, that is, those renewable products that are formed by biological or thermal conversion processes, like fermentation, pyrolysis, or selective combustion.

The renewables area is a fast developing one, in which each step of process development workflow needs to be reconsidered and is open for choice. We have striven to include all aspects of the catalytic process development workflow, that is, from idea, research and process development, up to commercialization, as well as the application of advanced methodologies and technologies. The workflow includes idea generation and concepts, design of experimentation and experimental approach, catalyst discovery and screening, catalyst optimization, process design, reaction kinetics, process optimization, reaction modeling, up-scaling, and life cycle analysis. We have chosen to include several industrial contributions, to demonstrate the current state of technologies, but also to be faced with the implications of introducing a new generation of materials and environment.

After an introduction of the industrial playing field in Chapter 1 and the selection of target molecules in Chapter 2, the subsequent chapters are devoted to various groups of target renewable molecules and processes, like terpenes (Chapter 3), furans (Chapter 4), ethanol (Chapter 6), fats and oils (Chapter 7), aromatics (Chapter 8), biorefining (Chapter 9), syngas (Chapter 10), extractives (Chapter 11), and carbon dioxide (Chapter 13). In Chapter 5 methodologies for the development of catalytic processes are described, whereas in Chapter 12 the application of life cycle analysis to renewables is covered.

This book is directed toward decision makers, chemists, and engineers in strategic, research, development, and engineering departments in renewables, petro-chemicals, fine chemicals, refining, and the biotechnology industry, as well as academic researchers and students in chemical engineering, chemistry and biology. Moreover, it is useful for policy makers, involved in the bio-based economy and biology, and industrial organizations linked to the renewables industry.

We trust that this book, dealing with the various aspects of the process development workflow, will enable the reader to make optimal choices, and select the right technologies and partners to do so, by understanding the pros and cons of the different scenarios and ways to improve the process, amongst others by parallelization of experimentation and different phases of the workflow.

We would like to sincerely acknowledge our colleagues and friends, who have contributed with passion and expertise to this book. Moreover, Dr. Martin Lok deserves special attention and recognition for his valuable contributions during the review process. And finally, our thanks go to Lesley Belfit, Stefanie Volk and Claudia Nussbeck from Wiley-VCH for their assistance in preparing this book.

Pieter Imhof

Jan Cornelis van der Waal

March 2013

List of Contributors

Paulo Luiz de Andrade Coutinho

Braskem

Av das Nacoes Unidas, 8501

25th floor

05425-070 Sao Paulo, SP

Brazil

Michele Aresta

University of Bari

Interuniversity Consortium on Chemical Reactivity and Catalysis-CIRCC

Department of Chemistry

Via Celso Ulpiani 27

70126 Bari

Italy

Joseph Bozell

University of Tennessee

Department of Forestry, Wildlife and Fisheries

Knoxville, TN 37996

USA

Luis F. Cassinelli

Braskem

Av das Nacoes Unidas, 8501

24th floor

05425-070 Sao Paulo, SP

Brazil

Angela Dibenedetto

University of Bari

Interuniversity Consortium on Chemical Reactivity and Catalysis-CIRCC

Department of Chemistry

Via Celso Ulpiani 27

70126 Bari

Italy

David Dodds

Dodds & Associates LLC

4686 Druids Glen

Manlius, NY 13104

USA

Aloysius J.J.E. Eerhart

Copericus Institute

Department of Science, Technology and Society (STS)

Room 305, Budapestlaan 6

3584 CD Utrecht

The Netherlands

Adil Fahmi

Statoil

Arkitekt Ebbels veg 10

7005 Trondheim

Norway

Bob Humphreys

PO Box 709

109 Lido Blvd

Point Lookout, NY 11569

USA

Pieter Imhof

Avantium Technologies

Zekeringstraat 14

1014 BV Amsterdam

The Netherlands

Ed de Jong

Avantium

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

Päivi Mäki-Arvela

Åbo Akademi University

Biskopsgatan 8

20500 Turku

Finland

Leo E. Manzer

LLC

Catalytic Insights

Wilmington, DE 19803

USA

Derek McPhee

Amyris, Inc.

5885 Hollis St. Suite 100

Emeryville, CA 94608

USA

Antonio Morschbacker

Braskem

Av das Nacoes Unidas, 8501

24th floor

05425-070 Sao Paulo, SP

Brazil

Dimitry Yu. Murzin

Åbo Akademi University

Biskopsgatan 8

20500 Turku

Finland

Esther Ochoa-Fernández

Statoil

Arkitekt Ebbels veg 10

7005 Trondheim

Norway

Martin K. Patel

Copericus Institute

Department of Science, Technology and Society (STS)

Room 305, Budapestlaan 6

3584 CD Utrecht

The Netherlands

Gene Petersen

Biomass Technologies Office

US Department of Energy

Golden, CO 80401

USA

Robert-Jan van Putten

Avantium

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

E. Kendall Pye

Lignol Innovations Ltd

Unit 101 – 4705 Wayburne Drive

Burnaby, V5G 3L1 BC

Canada

Erik-Jan Ras

Avantium Chemicals

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

Michael Rushton

Lignol Innovations Ltd

Unit 101 – 4705 Wayburne Drive

Burnaby, V5G 3L1 BC

Canada

Erling Rytter

Statoil

Arkitekt Ebbels veg 10

7005 Trondheim

Norway

Tapio Salmi

Åbo Akademi University

Biskopsgatan 8

20500 Turku

Finland

Deger Saygin

Copericus Institute

Department of Science, Technology and Society (STS)

Room 305, Budapestlaan 6

3584 CD Utrecht

The Netherlands

Irina L. Simakova

Boreskov Institute of Catalysis

pr. Lavrentieva 5, 630090

Russia

Ana Sousa Dias

Avantium

Zekeringstraat 29

1014 BV Amsterdam

The Netherlands

Augusto Teruo Morita

Braskem

Av das Nacoes Unidas, 8501

05425-070 Sao Paulo, SP

Brazil

Jan Cornelis van der Waal

Avantium Technologies

Zekeringstraat 14

1014 BV Amsterdam

The Netherlands

Roberto Werneck Do Carmo

Braskem

Av das Nacoes Unidas, 8501

24th floor

05425-070 Sao Paulo, SP

Brazil

James White

LLC

3RiversCatalysis

Richland, WA 99352

USA

Aalbert (Bart) Zwijnenburg

Johnson Matthey

Wardstrasse 17

46446 Emmerich am Rhein

Germany

1

The Industrial Playing Field for the Conversion of Biomass to Renewable Fuels and Chemicals

Leo E. Manzer, Jan Cornelis van der Waal, and Pieter Imhof

1.1 Introduction

The world is changing its chemistry backbone. In recent years, it has become clear that the feedstocks of choice for the chemical industry can no longer be just petrochemical-based and that alternatives from biomass will need to become readily available in the near future. This has been driven not only by rising fuel prices and the location of much of the petroleum reserves but also the developing insights as to the effects of additional CO2 on the changing climate of our planet. Many countries are now pursuing the development of new technology for the conversion to fuels and chemicals of renewable feedstocks from biomass that can be grown locally and harvested, such as wood, agricultural crops, algae, municipal waste and animal residue.

In this book we will focus in great detail, from an industrial perspective, on chemical and process technology routes, and the many challenges for these new platform chemicals, their production routes and their potential compared to biological and traditional oil-based technologies. In this chapter an overview of the most important industrial research efforts and strategies is given. The change to a biomass-based economy faces several challenges as the chemistries involved and new platform chemicals that will become available can differ radically from those used for petroleum feedstocks. In addition, it is clear to all involved that a considerable research effort still lies ahead of us.

In this, it is exemplary to consider the petrochemical industry. It has taken several decades to develop technology for the conversion of crude oil and gas into transportation fuels and chemicals and this research effort is still ongoing. In contrast to the exploration of crude oil and the production of fuels and chemicals, which typically involve cracking of carbon–carbon bonds, heterogeneous acid catalysis and hydrotreatment, the renewable feedstocks require a new collection and distribution system and the conversion of wet, highly functional carbohydrates into products that will ideally be compatible with existing refinery operations. As a result, new catalysis and biology need to be developed to convert these oxygenated feedstocks to useful products.

1.2 The Renewables Arena

Many companies are active in the emerging renewables arena. In this chapter, several of the large multinational and several of the smaller start-up companies will be discussed in more detail. A nice way to identify the key-players based in the field is by looking at the yearly Biofuels Digest polls among its readers and the list of the top 50 companies that its readers deem most active in the renewable fuels and chemicals area [1]. The top 50 companies from the 2010–2011 survey are shown in Table 1.1. It is also interesting to note that the focus of these companies differs both in feedstocks used and in products made, exemplifying that the use of biomass is a general concept and is in good agreement with environmental effort to create biodiverse, sustainable agricultural landscapes.

Table 1.1 The top 50 bioenergy companies, compiled by Biofuels Digest 2010–2011.

An alternative way is to look at the most promising bio-renewable platform chemicals derived from the various processes to see which companies have either production capacity already or have reported development of new processes. Table 1.2 shows a list of products with strong growth potential in the chemical industries and some promising ones that are well advanced in the pipeline [2].

Table 1.2 Production of platform chemicals [2].

The companies shown in Tables 1.1 and 1.2 also reveal the broad and diverse interest in biorenewable fuels and chemicals. The effort is carried by both established large multinationals and young inventive start-ups, but the diversity is also clear in other aspects. For example, renewable fuels are obtained from different feedstocks, such as algae, oils, and carbohydrates to challenging ones such as lignin, lignocellulosics and municipal solid wastes. Clearly, with such a broad range of feedstocks many different technologies need to be developed and applied. Currently fermentation of carbohydrates to ethanol is by far the biggest process, but other fermentations, like Gevo’s butanols and Amyris’s Farnesenes, are now commercialized. However, chemical catalysis will quickly pick up from there and convert the fermented products further. The announcement of The Coca Cola Company [3] of collaboration with Gevo, Virent and Avantium to develop 100% biobased beverage bottles is based on three different catalytic technologies.

One thing the tables above do not reflect well is the considerable impact that existing, well-established technologies have in the renewable area. The fermentation of carbohydrates to alcoholic beverages (6.1 l of pure alcohol per person aged over 15 year worldwide or 32 Mtonne per year total [4]), and the use of vegetable oils that can be saponified to soaps, emulsifiers and other chemicals (around 14% of world production of vegetable oils or an equivalent of 16.8 Mtonne per year [5]).

When each entry in Tables 1.1 and 1.2 is categorized by feedstock use, product made, type of processing, and geographic location, one can draw certain conclusions as to the state and the direction for the current chemicals from renewables efforts. In this analysis, no differentiation between company size and/or development/maturity state of the process is made and the numbers presented are based purely on the number of companies involved. With respect to the geographic spread of companies involved in the renewable areas (see Figure 1.1), it is clear that the United States of America, with two-thirds of the companies being located there, is leading. At first sight, the contribution of Asia appears to be small. However, many of the larger industrial conglomerates are collaborating very actively with smaller start-up companies all over the world. In addition, this survey did not include the already existing biorenewable efforts in which Asia has a long-standing tradition, especially palm oil and alternative sugar crops, such as rice and tapioca, which offer great potential as feedstocks for biorenewable fuels and chemicals (Figure 1.1).

Figure 1.1 Geographic distribution of companies in the renewable area.

With respect to the biomass feedstock used, it is clear from Figure 1.2 that carbohydrates, including lignocellulosics, make up 74% of the starting material; even more if one considers that ethanol and butanol as the starting product in most cases originate from carbohydrates by an earlier fermentation process. The concept of using intermediates derived from biomass is called secondary-derived biobased platform chemicals. Ethanol and butanol, from fermentation of sugars, are examples, but it is not restricted to this. Dohy [2] identified several groups, that is, biogas, syngas (Chapter 10) and H2, pyrolysis oils (Chapter 8), vegetable oils (Chapter 7), lignin (Chapter 9) and the C5 and C6 sugars (Chapters 4 and 8). Fermentation (Chapters 3 and 6) and catalytic conversion of the latter two (Chapter 4) gives rise to an even more diverse group of products, as was identified by Werpy [6] (Figure 1.2). In addition the use of CO2 as feedstock is addressed in Chapter 11.

Figure 1.2 Distribution of feedstock use in the renewable area by number of companies. Carbohydrates refer to readily available sugars (glucose, fructose, sucrose, xylose). Oils refer to vegetable oils.

In Figure 1.3 the distribution of renewable products is shown. From this figure it is clear that the products industry currently still focuses on ethanol and fuel production. There is a strong correlation with the size of the company and the production of these two main products. Smaller, often venture capital backed companies tend to focus on drop-in solutions, hence ethanol, biodiesel and other fuels. This probably reflects the perceived reduced risk profile for these drop-in products. The established low-key technology needed, and the small production volumes. However, one should consider that obtaining a market share can still constitute a high risk since one is competing against almost fully optimized processes employing depreciated capital.

Figure 1.3 Distribution of renewable products made scaled to reported production volume. The production volume in kt a−1 for the five largest products is also shown.

It is also very instructive to consider the type of process used to produce the biorenewable product. From Figure 1.4 it is clear that the most commonly used type of processing is a biological type of conversion, that is fermentative and/or enzymatic (43 processes, 52.1 Mtonne per year) or algae (7 processes, 0.2 Mtonne/year). Not surprisingly, a very strong correlation with ethanol can be observed here. Similarly, chemocatalytic processes are dominated by the FAME (fatty acid methyl ester) biodiesel production. If these two fuel products are excluded from the analysis, the contribution of fermentative processes to the other products is still very high (42%). The remainder of the processes used are bio-renewable chemicals divided between thermal processes and chemocatalytic processes. Especially, the overall low usage of chemocatalytic routes today is surprising as this is in stark contrast with current day petro-based chemicals production where almost all process and products involve catalysis at some point.

Figure 1.4 Distribution by type of conversion process used by number of companies.

It is also refined from our data that the more specialized products in the graph are generally produced by larger multinationals which have the financial backbone and market outlets, or by small companies that have access to a unique technology, often fermentative/enzymatic in nature. Both parties have found each other and many collaborations and joint ventures have since been announced. An overview of these collaborations is given in Table 1.3.

Table 1.3 Overview of efforts, collaborations and joint ventures of some large, multinational oil companies mid-2011.

Today’s status of the biorenewable fuels and chemicals world is one of direct drop-in replacements and thus strongly tied to fermentation of sugars to ethanol and transesterification of vegetable oils to biodiesel. What is also clear from our survey is that the use of secondary derived biobased platform chemicals is still very limited, suggesting that considerably more effort will be needed in this area for the chemical industry to be able to offer a full biomass-to-product portfolio. In Figure 1.5 the projected cumulative production volume of new biorenewable chemicals and fuels processes, based on announced production volumes employing novel technologies, is shown. The total production volume of 5.1 MTonne per year, however, is still small compared to the current total production volume for ethanol and FAME in 2010, which exceeded 80 Mtonne per year.

Figure 1.5 Prognoses of growth in biorenewable products in total kt a−1 by new technologies [1].

Though the advance of new biobased products seems small, it should be realized that these are only the front-runners of a whole new generation of materials. Many of the technologies are not yet mature enough for commercial (pilot-) plant production. At least 25 research efforts in particular bio-renewable chemicals are reported for the 2011–2015 period. In Figure 1.6 these 25 bio-renewable chemicals are shown, with the number of independent research efforts for each identified. Clearly, ethanol and fuels are still the biggest contributors, but it is without doubt that an impressive number of widely diverse chemicals will become available in the near future (Figure 1.6).

Figure 1.6 Announced research efforts until 2015 in new biobased renewable chemicals. The number in each pie indicates the number of companies researching and/or producing the renewable chemicals.

The world today is seeing more and more processes that are using bio-renewables. Certain production routes are well-established with large production volumes, such as the traditional fermentation of sugars to ethanol or the transesterification of fatty acids to FAME. However, it is clear that on the horizon a diverse spectrum of molecules will become available. Unlike the current petrochemical-based chemicals industries, which use almost exclusively chemocatalytic and thermal processes, the role of fermentation and enzymatic conversions will be much more marked in the bio-refinery of the future. Still, we have a long way to go. Today, processes are focused on drop-in replacements or on the conversion of biomass in secondary derived biobased platform chemicals. Future research will most likely start to focus on further conversions of these platform chemicals, and will make use of technology closer to the catalytic processes currently in place.

In the next two sections recent developments in the renewable fuels and in the renewable chemicals areas will be discussed. Although most players clearly state what their aim is, it is also clear that an overlap exists between the two areas. Where needed the effort of such players is divided over the two sections.

1.4 Renewable Chemicals

Several companies focus on chemicals derived from biomass, even more than for fuels, for which other clean energy sources and uses can be envisaged, such as electric cars via solar panels. The production of renewable chemicals inherently requires carbon atoms from the biomass. Several companies are working on biological, catalytic or thermochemical routes to chemicals as they generally have a higher value than fuels. In some cases the products are direct drop-in replacements, while other companies obtain new chemicals and products. An important and commonly cited report was prepared by PNNL and NREL [6], which will be discussed in detail in Chapter 3. They proposed 12 molecules (see Table 1.6) that would be attractive building blocks for future renewable chemicals. This report has stimulated a very significant amount of research within the academic and industrial communities.

Table 1.6 The top carbohydrate-derived building blocks outlined by DOE [6].

Top 12 carbohydrate-derived building blocksSuccinic, fumaric and maleicItaconic acid2,5-Furan dicarboxylic acidLevulinic acid3-Hydroxyl propionic acid3-HydroxybutyrolactoneAspartic acidGlycerolGlucaric acidSorbitolGlutamic acidXylitol/arabinitol

Several of these building blocks can be made via fermentative or enzymatic routes and are thus outside the scope of this book. Nevertheless, as was already concluded in earlier sections, the role of fermentation in bio-mass conversion will certainly be an important technology in future bio-refineries. Genencor and Rivertop describe enzymatic and thermochemical processes for the carbohydrate acids, gluconic and glucaric acids [26, 27]. Likewise, for the amino acids aspartic and glutamic acids, which are produced largely in China by a variety of companies, the Fufeng group being the largest.

The chemical synthesis and production of some of these building blocks are already well known. In the mid-1950s Roquette in France developed processes for sorbitol and xylitol. These processes are based on the hydrolysis of starches to glucose and subsequent selective hydrogenation to sorbitol and can be modified to give other polyols, that is, maltitol, mannitol, xylitol and arabinitol. The sorbitol is then further converted into the anhydride isosorbide, which is considered a potential diol building block for renewable polyesters [28].

One molecule that is receiving considerable attention is succinic acid. A number of small and large companies (BioAmber, Myriant, DSM, BASF, and others) have announced plans to commercialize biobased succinic acid by fermentation and its derivatives by chemical conversion. The world’s first commercial demo-plant of succinic acid was started in France in January 2010 by BioAmber Inc. with nominal capacity of 220 t a−1, with new full-scale plants being planned in Canada and Thailand. The petrochemical route for producing succinic acid is by hydrogenation of maleic acid, obtained via butane oxidation. A biobased source of succinic acid and its derivatives would be drop-in replacements for the petroleum-derived compound and could even be used to supply bio-maleic acid and maleic acid anhydride by selective oxidation. The markets for products derived from biobased succinic acid (polymers, plastics, solvents, adhesives, and coatings) (Figure 1.15) are significant. So it is not surprising that it has attracted the attention of so many companies.

Figure 1.15 Succinic acid as a biorenewable platform chemical [29].

First described in 1875 by Freiherrn, Grote and Tollens [30], levulinic acid has been of interest for many years as a bifunctional keto-acid but it has never been made on a commercial scale [31]. Biofine Renewables, LLC has developed a thermochemical process that produces levulinic acid, furfural, formic acid and char from a wide variety of carbohydrate-containing biomass feedstocks. The process uses two reactors: in the first the biomass is broken down into small components, such as carbohydrates and hydroxymethylfurfural, which are then further converted in the second reactor to levulinic acid. The conditions employed are extreme, with high temperatures and pressures in the presence of acid catalyst, yielding about 50% levulinic acid. With the ketone and acid group functionality, levulinic acid can be converted to a wide variety of compounds. Currently three demo-plants are operational, the largest in Caserta, Italy with a 50 t d−1 lignocellulosic feed intake. A study by Hayes [32] suggests that the production of ethyl levulinate can be competitive at a 400 kt a−1 scale, if all energy required is generated on-site from waste streams.

DuPont has disclosed a diverse portfolio of products that can be obtained such as N-alkylpyrrolidones, monomers for the preparation of thermally stable polymers, ionic liquids and nylon intermediates (Figure 1.16) [31]. While many of these materials are exciting new renewable-based chemicals, none have reached commercial production yet, due to the absence of a high volume levulinic acid production process at sufficiently low cost.

Figure 1.16 Selected derivatives of levulinic acid,

adapted from Ritter [31].

Segetis Inc., a Minnesota-based venture capital backed company, also uses levulinic acid as the basis of their product portfolio [33]. They developed a novel class of ketals formed by the reaction of diols and polyols with the ketone group of levulinic acid. In particular, by using glycerol and levulinic acid, both part of the DOE “Top 12” list (Table 1.6), new ketal products are produced which have excellent functionality and can potentially replace existing petroleum-based solvents, surfactants and plasticizers (Figure 1.17).

Figure 1.17 Segetis ketals are derived from diols and levulinic acid.

Furandicarboxylic acid (FDCA) is another of the DOE Top 12 molecules, and has potential to replace terephthalic acid [34]. It has been shown that this could be prepared by oxidation of hydroxymethylfurfural, HMF. Production of HMF has long been researched, but even with two pilot plants having been commissioned no commercial process has been established that can produce HMF at low cost [35]. Avantium is pursuing the use of HMF-ethers as renewable platform chemicals (Figure 1.18) [24] and has recently announced the start-up of a pilot-plant in the Netherlands. An advantage of forming the HMF-ether is that it is much more stable and easier to work with than HMF. Having shown that the HMF-ethers can easily be oxidized to FDCA, polymers of FDCA have now been made. Especially, the FDCA polyesters (PEF) are potential replacements for terephthalic acid esters. The new PEF polymer had a reported glass transition temperature, Tg = 86 °C versus PET with Tg = 81 °C, whereas the gas barrier properties for CO2 and O2 are at least 2 and 9 times better, respectively, compared to PET, allowing it to be used in demanding applications such as bottles and food packaging [24]. The main price drivers for biobased FDCA are the feedstock price and economy of scale. However, at a >300 kT a−1 scale the price of FDCA will be <€1000 per ton, and therefore competitive with pTA produced on the same scale.

Figure 1.18 The Avantium process for producing furanic polyesters [36].

1.5 Conclusions

The intent of this chapter was to provide examples of the creativity and innovation being developed in the field of bio-renewable fuels and chemicals. Today new start-up companies mostly lead the effort. These companies are playing a key role in the development of renewable fuels and chemicals. Not all will be successful, larger oil and chemical companies will acquire some, and some will grow into new companies. With luck, perseverance, and significant funding, a significant portion of the world’s needs for fuels and chemicals will someday be based on renewable feedstock.

In the rest of this book, it will be shown that chemical catalytic processes, in combination with fermentative processes, will play a pivotal role in creating cost-effective and sustainable production methods.

References

1 www.biofuelsdigest.com (accessed July 2011).

2 Dohy, M., de Jong, E., Jørgensen, H., Mandl, M., Philips, C., Pouet, J.C., Skiadas, I., Van Ree, R., Walsh, P., Wellisch, M., and Willke, T. (2009) Adding Value to the Sustainable Utilisation of Biomass, RRB5, Fifth International Conference on Renewable Resources and Biorefineries, Ghent.

3 Neuman, W. (2011) Race to Greener Bottles Could Be Long, Printed on December 16, 2011, on page B1 of the New York edition; Press release 15 december 2011, http://www.thecoca-colacompany.com/dynamic/press_center/2011/12/plantbottle-partnerships.html (accessed July 2011).

4 World Health Organisation (2011) Global status report on alcohol and health.

5 Rupilius, W., and Ahmad, S. (2005) The Changing World of Oleochemicals, Palm Oil Developments 44, http://www.chgs.com.my/chinese/download/Palm%20Oil%20Developments/june%202006/The%20changing%20world%20of%20Oleochemicals.pdf (accessed January 2012).

6 Werpy, T., and Petersen, G. (2004) Top Value Added Chemicals From Biomass. Pacific Northwest National Laboratory (PNNL) and the National Renewable Energy Laboratory (NREL), August 2004.

7 Giordani, M. (1939) Chim. Ind., 21, 266.

8 Bergius, F. (1937) Ind. Eng. Chem., 29, 247.

9 Kleinert, T.N. (1971) Organosolv Pulping and Recovery Process. US Pat. Appl. US 3.585.104.

10 Blanch, H.W., Simmons, B.A., and Klein-Marcuschamer, D. (2011) Biotechnol. J., 6, 1086.

11 Ramey, D.E. (2012) Butanol: The Other Alternative Fuel, http://nabc.cals.cornell.edu/pubs/nabc_19/NABC19_5Plenary2_Ramey.pdf (accessed 3 July 2012).

12 Bernacki, B. (2011) “Biobutanolpotential for biobasedmonomers and polymers” at BioPlastics, Las Vegas.

13 Keasling, J., Martin, V., Pitera, D., Kim, S.-W., Withers, S.T., Yoshikuni, Y., Newman, J., and Khlebnikov, A.V. (2011) Host cells for production of isoprenoid compounds. US Patent Appl. US 201122958, A1 (2001).

14 Phillips, S., Aden, A., Jechura, J., and Dayton, D. (2007) NREL/TP-510-41168, April, 2007.

15 Huber, G.W. (2008) Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels: Next Generation Hydrocarbon Biorefineries, National Science Foundation. Chemical, Bioengineering, Environmental, and Transport Systems Division. Washington DC, NSF.

16 (2010) Wall Street Journal, February 10, 2010.

17 Downloaded from news section www.inpbioenergy.net item “09/08/2010 Bioethanol effort gets boost in Florida” on 3 Jul 2012 and downloaded from http://www.ineos.com/new_item.php?id_press=257 on 3 July 2012.

18 Funazukuri, T., Hudgins, R.R., and Silveston, P.L. (1984) Flash Pyrolysis of Cellulose in a Micro Fluidized Bed, ACS Fuel Meeting Fall, Philadelphia, 29 (6).

19 O’Connor, P., Stamires, D., and Daamen, S. (2006) Process for the conversion of biomass to liquid fuels and specialty chemicals. US Patent Appl. US 2009090046 (A1), KiOR was formed and funded in 2007.

20 Román-Leshkov, Y., Barrett, C.J., Liu, Z.Y., and Dumesic, J.A. (2007) Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature, 447 (7147), 98.

21 Van Walsum, G.P., and Wheeler, M.C. (2009) Production of Higher Alcohols Liquid Biofuel via Acidogenic Digestion and Chemical Upgrading of Industrial Biomass Streams, http://bcsmain.com/mlists/files/biomass/obpreview2009/biochem/documents/2.3.3.1.pdf (accessed 3 July 2012).

22 Haan, R.J., and Lange, J.-P. (2007) Gasoline composition and process for the preparation of alkylfurfuryl ether. US Patent Appl. US 2011035991 (A1).

23 Lange, J.-P., Price, R., Ayoub, P.M., Louis, J., Petrus, L., Clarke, L., and Gosselink, H. (2010) Valeric biofuels: a platform of cellulosic transportation fuels. Angew. Chem. Int. Ed., 49, 4479.

24 Gruter, G.-J., and de Jong, E. (2009) Furanics: novel biofuel options from carbohydrates. Biofuels Technol., 1, 11–17; Gruter, G.J.M., and Dautzenberg, F. (2007) Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use, WO2007104515 (A2).

25 United States Department of Agriculture (2005) Biomass as a Feedstock for a Bioenergy and Bioproducts Industry: The Technical Feasibility of a Billion-Ton Annual Supply, April 2005. Updated in 2011 “U.S. Billion-ton Update, Biomass Supply for a Bioenergy and Bioproducts Industry” http://www1.eere.energy.gov/biomass/pdfs/billion_ton_update.pdf (accessed July 2011).

26 Lantero, O.J. (1995) Process for the preparation of gluconic acid and gluconic acid produced thereby. Canadian Patent Appl. CA 2240294 A1.

27 Kiely, D., Carter, A., and Shrout, D. (1995) Improved oxidation process, WO 9638402 (A1).

28 Flèche, G., Huchette, M. (1986) Isosorbide preparation, properties and chemistry sorbitol, Starch, 38 (1) 26; production started in 1954 by Roquette-Frères, in Lestrem, France. http://www.roquette.com/history (accessed July 2011).

29 Zeikus, J.G., Jain, M.K., and Elankovan, P. (1999) Biotechnology of succinic acid production and markets for derived industrial products. Appl. Microbiol. Biotechnol., 51, 545.

30 Freiherrn, A., Grote, V., and Tollens, B. (1875) Untersuchungen über Kohlenhydrate. I. Ueber die bei Einwirkung von Schwefelsäure auf Zucker entstehende Säure (Levulinsäure). Justus Liebigs Ann. Chem., 175, 181–204.

31 Ritter, S. (2006) Biorefinery gets ready to deliver the goods. Chem. Eng. News, 84, 47.

32 Hayes, D.J., Ross, J., Hayes, M.H.B., and Fitzpatrick, S. (2006) The biofine process – production of levulinic acid, furfural, and formic acid from lignocellulosic feedstocks, in Biorefineries: Industrial Processes and Products, vol. 1 (eds B. Kamm, P.R. Gruber, and M. Kamm), Wiley-VCH Verlag GmbH, Weinheim, pp. 139–164.

33 Wicks, D., Williams, C., and Selifonov, S. (2007) Ketal compounds from polyols and oxocarboxylates, WO 2009032905 (A1); Elifonov, S., Rothstein, S.D., Wicks, D., Mullen, B.D., Mullen, T., Ppratt Jason, D., Williams, C.T., and Wu Chunyong, K. (2007) Polyketal compounds, synthesis, and applications, WO 2009049041 (A2).

34 Gandi, A., and Belgacem, M.N. (1997) Prog. Polym. Sci., 22, 1203–1379.

35 van Putten, R.-J., van der Waal, J.C., de Jong, E., Rasrendra, C.B., Heeres, H.J., de Vries, H.J. (2012) Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem. Rev., in press, http://dx.doi.org/10.1021/cr300182k.

36 For more information see www.avantium.com and www.yxy.com (accessed July 2012).

2

Selecting Targets

Gene Petersen, Joseph Bozell, and James White

2.1 Introduction

The development of processes for catalytic conversion of renewable feedstocks into chemicals and materials is significantly aided by the rational selection of target products. This selection is important for two obvious reasons. First, the chemistry or biochemistry surrounding any process development is better enabled when the type of product is identified, such as an oxidized molecule, hydrocarbon or polymeric material (or its precursor). Second, the development of chemical and biological tools needed to enable these processes is more germane if the specific chemical nature(s) of the desired end-products are identified. Other factors that contribute to the need to select targets include market drivers or interest in desirable or useful properties in the renewable chemicals or materials produced. For example, the demand for biobased products generated from regenerable biomass resources appears to be growing, occasioned by both market potential and environmental concerns. In addition, some of these chemicals and materials exhibit unique properties of commercial interest currently not readily available from conventional petrochemical sources.

A historical example of the development of chemical processes to produce biobased products was found in the Chemurgy movement in the twentieth century. While the driver for the chemurgical effort was the wider use of agricultural feedstocks, the push to use plant-based carbohydrates, both in monomeric and polymeric form, and plant-based oils required some process development. Targets included replacement of petroleum-based parts in automobiles; as a result, the Ford Motor Company in the mid-twentieth century claimed that there was a bushel of soybeans used in each car manufactured [1]. The onset of World War II in the Pacific Basin limited or even cut off supplies of natural products vital to the military, in particular, rubber. This led to research and development of alternative sources of these materials, such as the isoprenoid components of the desert plant guayule and corn starch for ethanol [1]. These needs also motivated research into better catalytic processes, such as those related to vulcanizing rubber [2]. In the latter part of the twentieth century, there arose interest in biobased polymers that could substitute for petroleum-based fibers and, hence, targets for polymer precursors were sought that could be produced or derived from biomass itself. Two examples are lactic acid that is generated microbially and then chemically converted into polylactic acid (PLA) [3] and polyhydroxybutyrate derived from storage carbohydrates in microbial systems [4]. These polymeric materials have been proposed as replacements for existing plastics in areas such as packaging [5, 6], and substitutes for petrochemically derived chemical polyesters [7]. More recently, the market is being driven to find alternate sources of strategic raw materials as a hedge against potential shortages in conventional hydrocarbon feedstocks, and an interest in developing sustainable, domestic sources of chemical building blocks.

Whether driven by a desire to develop new markets or to find new uses for regenerable resources, like plant carbohydrates or oils, wood or agricultural residues, the development of biobased products faces the challenge of an overabundance of targets, regardless of whether catalysis will be employed as a process technology or not. The list of biobased products can include structures already made by the chemical industry (and therefore de facto commercial opportunities), as well as new structures that arise from the ever-expanding research efforts in carbohydrate and lignin chemistry. Accordingly, biorefinery or biobased product development will greatly benefit from robust screening processes that can maximize the value of expended research and development (R&D