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Participants Sweden Centre for Environment and Sustainability, Chalmers University and University of Gothenburg Katarina Grdfeldt Oliver Lindqvist Emma Rex DanStrmberg Maria Svane

Volvo Car Corporation Polymer Centre Mikael Fransson

Chalmers University of Technology Dept of Chemical and Biological Engineering Magdalena Svanstrm Hans Theliander Center for Intellectual Properties Studies Bo Heiden Andrew Telles

Innventia AB Karin Lindgren

Sdra Louise Staffas

Akzo Nobel Surface Chemistry AB Natalija Gorochovceva Bengt-Arne Thorstensson

Denmark Novozymes A/S Rasmus Devantier Katja Salomon Johansen Sven Pedersen

resund Org Jacob Juul Gade

Finland University of Helsinki Dept of Applied Chemistry and Microbiology Annele Hatakka Pekka Maijala Petri Oinonen

VTT Technical Research Centre Sami Alakurtti Tuulamari Helaja

Latvia SA Latvian State Institute of Wood Chemistry Anna Andersone Galina Telysheva Alexandrs Volperts

Norway Borregaard Martin Andresen Bernt Myrvold Gudbrand Rodsrud

Title: LigniMatch Lignin as raw material for chemicals

Nordic Innovation Centre (NICe) project number: 06246

Author(s):Maria Svane

Institution(s): Centre for Environment and Sustainability, GMV

Abstract: The LigniMatch project has explored the possibilities to use various lignin structures as chemical precursors for chemical substances with a potentially high commercial value for the Nordic and Baltic industry. By compiling methods for processing the lignin, characterizing potential yield and potential market values, the possibility of replacing fossil based products by upgraded lignin materials has been explored. By using lignin as the raw material, the results from the project have three important advantages for the society:

Making better use of the raw materials produced Providing materials from renewable sources Substitute for chemicals produced from fossils

The general outcome of this project is a roadmap which will guide major actors in the field towards the launching of lignin based products on the international market. During the project, a vast amount of potential value-added products and/or process routes was collected and listed. From these lists, three products have been identified as most interesting for future implementation; Activated carbon - not innovative but easy to produce and a high quality can be achieved; Carbon fibers for replacement of PAN or steel in automotive applications - a new application that can become very profitable; Phenol as a building block for chemicals - in order to replace oil based phenol.

Topic/NICe Focus Area: Environmental Technology

ISSN: Language: English Pages: 136

Key words: Lignin, renewable sources, activated carbon, carbon fiber, phenol Distributed by: Nordic Innovation Centre Stensberggata 25 NO-0170 Oslo Norway

Contact person: Maria Svane Centre for Environment and Sustainability, GMV Aschebergsgatan 44 SE-412 96 Gteborg, Sweden Tel: +46 31 7724973 www.chalmers.se/gmv/

http://www.chalmers.se/gmv/

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Executive summary

LigniMatch was initiated by actors within academia, research institutes and industry with common interests in forest research and biotechnology. The project have addressed environmental challenges and at the same time explored the economic potential of lignin, a raw material that is abundant in the Nordic and Baltic countries. The rationale was to find innovative routes to by-pass mother-natures slow process of forming oil by using the lignin that can be extracted from the pulp and paper industry. Lignin as a raw material could offer a potential future source for further upgrading into value added product and might substitute current fossil-based alternatives. Lignin can be isolated through different extraction methods, resulting in various types of lignin with different characteristics. A large number of lignin modification methods make it possible to derive a range of substances and materials from this precursor. The purpose of the study was:

The aim of the project was to evaluate the potential market for upgrading of lignin into value-added products, identify the most promising alternatives and reveal drivers and barriers for such eco-innovation systems. Development of lignin as a potential source for value-added products has several possible benefits for the environment as well as for the economy. With a market for lignin-based products, fossil derived raw materials can be replaced at the same time as energy efficiency measures in the pulp and paper sector are encouraged. Hereby an excess of energy can be taken out from the mills as lignin. Economically, lignin can be the basis of new innovation systems in the Nordic/Baltic region. Method:

Data collection has been performed through surveys (peer reviewed literature, patents and other available sources), but also through knowledge transfer between project participants. Being a knowledge creation, dissemination and transfer project, the most important data sources have therefore been available literature as well as project partner expertise. The LigniMatch consortia comprises know-how from different levels in potential innovation chains (researchers and developers, industry and authorities), to cover the competence and achieve new insights on how to use lignin as a resource for chemicals and new products. A wide range of products and routes were identified during the initial data collection phase. These products were considered possible candidates for future use in the chemical industry. Some groups of products are already being produced from lignin in commercial scale, while other products hold varying potential for being manufactured from upgraded lignin fractions. The wide range of commercialized products on the market today, such as binding agents, dispersants, emulsifier and sequestrants, reflects the potential of utilizing different lignin properties.

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Extensive lists of potential products were discussed and evaluated during repeated partner meetings. These lists were iteratively refined and ultimately generated the product ideas, including potential niche markets that were selected for thorough studies. Based on pre defined selection criteria and the interests among the project partners, three product systems were isolated for further investigation through e.g. a system analysis. These systems include: production of activated carbon, production of carbon fiber, and production of phenol. The system analysis aimed at revealing more details on aspects for the selected products. Finally, the innovation system, including manufacturing processes surrounding these preferred routes, was analyzed. The most important task in the LigniMatch project has thus been to facilitate the turning of promising ideas into successful implementation while avoiding less promising routes. For the system analysis, the goal and scope was decided through discussions among the partners, taking place at project meetings and over e-mail. Main results

LigniMatch has highlighted promising routes for implementation of new lignin-based products on the international market. It excludes applications that are already commercially available today, and focuses on applications that can be developed into new markets.

A wide range of products can be produced from lignin. This project have identified and evaluated prospective groups of products, as well as technologies and manufacturing processes. In a process including studies of literature and patents, repeated partner meetings and electronic surveys, we have identified products with future potential for utilizing upgraded lignin fractions. The products were grouped with respect to the exploited lignin property:

Binding and filling capacity of lignin as bulk material in soil and materials (asphalt, bitumen)

Binding of special molecules, such as metals, nutrients and toxins Utilization of the polarity of the molecule (complexing agents, destabilization,

flocculation, granulation) Barrier properties Materials (carbon fiber and phenolic resins) Energy production Plastics (polyurethanes, bloc copolymers, polyesters, polyolefins,

biodegradables) Agricultural use (fertilizers, ground improvement, composting) High value compounds (insecticides, antibacterials and antioxidants)

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Three products were identified as the most appropriate alternatives to study further within the LigniMatch consortia:

Activated carbon Carbon fibers Phenols

In-depth analysis of these three product systems in terms of energy and environment, market potential, and the innovation system was performed. Other aspects of major importance for the future markets of these products are e.g. political decisions, environmental awareness and shortage of oil. It was concluded that activated carbon products are easy to produce, and it is already possible to make activated carbon from lignin, thus this route is not innovative. High quality products can be achieved, and the market potential is believed to be good. Due to the existing range of qualities and precursor alternatives, further studies are needed to see whether there exists a profitable niche market for lignin-based alternatives, for example use in supercapacitors. Producing carbon fibers for replacement of PAN or steel in automotive applications is a new application that has the potential to become very profitable. Manufacturing processes are still immature, but huge research efforts are devoted to develop the technology. Carbon fibers are expected to see a large market growth if the prices of the material can be reduced. Lignin is very promising in providing this less expensive precursor, as soon as large volumes can be produced at acceptable quality. Higher oil prices and carbon taxes can also drive this development. Phenol can be used as a building block for chemicals in order to replace oil based phenol. Therefore lignin-based phenols are of great interest as lignin is the only known natural biological aromatic polymer. However, the technology to produce phenols from lignin is not fully developed and the cracking of lignin results in a wide variety of aromatics. The separation of those molecules into pure compounds is a challenge and thus the cost to produce current quality demands is expected to be too high for a profitable market in the coming years. Possibly, this will change with a high increase in oil prices, or legal restrictions. It was concluded that carbon fiber production for the automotive sector is presently regarded the most interesting route. Apart from a possibly large market growth, lignin-based carbon fibers are also of interest because the properties and production processes of the material are similar to the PAN-based carbon fibers used today. This limits the investments needed, and makes the risk reasonable also for smaller actors. Another benefit of lignin-based carbon fibers is that it is used in high-value products, making it an interesting application for investments. Typical early applications within the automotive industry can be found within interior details of cars; seat casings, or as components in the floorpan. These details can be introduced as soon as the lignin-based material is available on the market. When the

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technology to produce carbon fibers from lignin is fully developed and the material can be further processed and manufactured at reasonable prize, this application will see a huge market. It offers incentives for the automotive industry to substantially reduce weight (and thereby also fuel consumption) of consumer cars, and at the same time minimizing the carbon footprint from this sector. The following conclusions can be drawn from the results:

Dependency on world market for oil and biomass The preferred use of lignin is likely to depend largely on the world price of both biomass and of oil. Lignin is an excellent source of bio-energy and can always be traded on the basis of its energy content. At the same time, its competitiveness in replacing fossil based raw materials in various applications is highly dependent on the prize and supply of oil.

The importance of environmental awareness and political initiatives Environmental awareness and political actions are important aspects influencing the potential market for lignin-based products. Political initiatives, such as strategies, large investment programs in environmental technology, and policy instruments that add costs or other burdens to fossil-derived products, may have a large impact on the market development.

Potential environmental benefits The potential environmental benefits from finding alternative uses of lignin are extensive, and with a double effect. Lignin can be used to replace fossil based raw materials in a wide range of products, from plastics to individual chemical products and carbon fibers. Furthermore, if there is a market for lignin for such value-added products, the mills will also have an additional economic incentive to take measures for higher energy efficiency.

Roadmap to guide development in the Nordic/Baltic region A roadmap has been created to provide guidance on how to select and prepare for successful development and production of lignin-based products in the Nordic/Baltic region. The starting point has been the replacement of fossil-based products with lignin-based alternatives, of benefit for Nordic/Baltic actors, as well as for the environment. The roadmap is directed towards potential actors in future innovation systems around value-added products from lignin in the Nordic/Baltic region, such as industry partners, network organizations, researchers and policymakers. The focus of the roadmap is on applications that can provide high value to the actors in the LigniMatch project. The roadmap contains a short summary of outcomes from the LigniMatch project. Details on the technological, economical and ecological aspects in connection with the innovation system can be found in sections 6.1 and 6.2 of the technical report.

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Recommendations for future innovation systems

It is recommended that a consortium is formed to further explore the potential of implementing carbon fiber produced from a lignin raw material in the automotive industry. Presently, the global conventional carbon fiber industry (PAN; pitch) is dominated by a handful of companies, based in Japan, Europe, the U.S. and Taiwan. Currently no lignin-derived carbon fiber producer exists in the Nordic/Baltic region, but the region holds many actors, also outside the LigniMatch consortia, with an interest in participating in an innovation system around lignin-based carbon fibers for the automotive industry. Examples of roles in a consortium for further development of the carbon fiber application include actors within:

Lignin production The LignoBoost technology is under introduction in large scale, and will probably be established in the Nordic/Baltic region within a few years.

Carbon fiber production There is currently no carbon fiber producer in the region, but actors with expertise in various steps in the innovation chain have been identified (e.g. fiber production, spinning).

Material production In production of the composite and in refining of the material, several actors with different competences might be needed. The technique to weave large tows of carbon fibers exists; a technique that reduces quality requirements on individual fibers (e.g. in Nordic patents). Actors with competences in specific segments have yet to be identified in order to complete the potential innovation system chain (e.g. production of moulds and composites).

Automotive industry Car manufacturers have shown interest in using lignin-based carbon fibers in future vehicles. The interest from vehicle parts manufacturers need to be further investigated.

Research, networks and policymaking The Nordic/Baltic region holds several important research milieus for research and testing as well as related networks and centras of excellence. Actions by policymakers and governmental bodies are also important and can constitute barriers as well as drivers for the innovation system.

Anticipated environmental and quality directives will have a large impact depending on design and interpretation. Funding for research, demonstration and full-scale plants is another powerful tool. For the supply of lignin, political incentives for general energy efficiency measures at the plants may also be of importance.

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Lignin as raw material for chemical

Contents 1. Background .......................................................................................................................................... 2

2. Description of the LigniMatch Project ................................................................................................. 2

2.1. Outline of the LigniMatch report ................................................................................................. 4

2.2. Introduction .................................................................................................................................. 4

2.3. The products and innovation systems ......................................................................................... 7

3. Summary and conclusions ................................................................................................................. 10

4. The consortium .................................................................................................................................. 12

4.1 Industrial partners ....................................................................................................................... 12

4.2 Universities and research institutes ............................................................................................ 13

4.3 Network organizations ................................................................................................................ 15

5. References ......................................................................................................................................... 15

6. Appendix ............................................................................................................................................ 26

6.1. WP3 New chemicals, replacements of plastics and new macro-molecular products............. 27

6.2. WP4 Market possibilities and the innovation system ............................................................. 83

6.3. Road Map ................................................................................................................................. 119

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1. Background Forest industry is, and has traditionally been, a cornerstone in Nordic economies. During industrial processing of the wood at pulp and paper mills, large quantities of lignin are separated from the raw material. As lignin is the second most abundant bio polymer, the use of lignin as raw material holds a large economical potential for the Nordic-Baltic chemical industry. Furthermore, lignin is a renewable material while oil is not. Thus, replacing oil based products with products manufactured from a lignin precursor would be one important step towards a sustainable society. The Nordic-Baltic region holds a strong position in biotechnology, and research within the field is world leading, Therefore the region therefore has extremely high potential to lead the development of sustainable solutions and eco-innovation, in particular for production of chemicals using lignin as precursor material.

This project will explore the possibilities to use various lignin structures as chemical precursor for chemical substances with a potentially high commercial value. It will compile methods for processing the lignin, characterize potential yield and potential market value, explore the possibility of replacement of fossil based products by upgraded lignin material, and create a road-map for the future to launch new lignin based products.

Common products, such as plastics, glue and washing powder, are today produced from fossil oil. Fossil oil is the result of natures extremely slow process of converting plants. In LigniMatch, forest research and biotechnology work together using new techniques that can by-pass this million-year conversion of plants to oil and enable a direct use of lignin, which is a main component of wood, as a source for many of the above products.

The use of lignin include production of, e.g. biosorbents, soil amendments, bioregulators, antioxidants, conservation agents, composites, dyes, plastics and various pharmaceuticals.

The LigniMatch consortia will cover the competence to achieve new insights on how to use lignin as a resource for chemicals and new products. By bringing actors and stakeholders together from all levels of the innovation chain (i.e. researchers and developers, industry and authorities) in various networking activities to form cluster for co-working, sharing of resources and define common research agendas, we will bridge the gap between innovation and commercialisation in the field.

The general outcome of this project will be a roadmap which will guide major actors towards the launching of lignin based products on the international market.

2. Description of the LigniMatch Project The LigniMatch project is a spin off project from the ScanBalt Campus Knowledge Network Environmental Biotechnology. The project is financially supported by the Nordic Innovation Centre (NICe) and industry. Furthermore, it is one of the 5 projects constituting NICes focus area of Environmental technology. By combining know-how from two industrial sectors, the forest and the chemical industry, with knowledge within academia, LigniMatch is a good example of how knowledge can be combined to solve environmental challenges and at the same time exploit economic potential in raw material that the Nordic countries have great resources of.

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The LigniMatch project is a knowledge collection, dissemination and transfer project, and is thus not a traditional research project. Data collection has been performed through surveys of e.g. peer reviewed literature, patents and other available sources, but also through knowledge transfer between project participants. The most important data sources are therefore the available literature and the project partners. The LigniMatch project as a platform for innovation was also discussed - to use the knowledge within the group to create value for the partners - with the purpose of preparing for eco-innovation. This is seen as a major driver behind the project.

The various tasks within the project were grouped into consecutive Work Packages (WPs). Figure 1 shows a flowchart of the WPs, and the corresponding tasks. A responsible WP leader was assigned to each WP. WP1 and WP2 were concerned with the management of the project, and WP5 and WP7 arranged workshops for dissemination of results. (Responsible WP leaders were Centre for Environment and Sustainability, VTT Technical Research Centre, and resund Org, respectively) The work with data collection and analysis was performed in WP3 and WP4. Integration of results in a preliminary roadmap, updates of the roadmap, and initiation of the implementation of the roadmap were the responsibilities of WP6, WP8 and WP9, respectively. The corresponding WPLs were the Department of Chemical and Biological Engineering at Chalmers University (WP6&8) and Akzo Nobel Surfave Chemistry AB (WP9).

Figure 1. An illustration of the different phases in the LigniMatch project.

WP3 in the LigniMatch project aims to identify interesting products and routes for the up-grading of lignin fractions for use in the chemical industry. The work in WP3 was further divided into three sub groups, with specific areas to cover. WP3a (WPL University of Helsinki) was focused on new chemicals from lignin, and WP3c (WPL Latvian State Institute of Wood Chemistry) investigated new macro-molecular products from lignin. The initial task for WP3b (WPL Centre for Environment and Sustainability) was replacement of plastics. During the survey of available literature, it became

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obvious that this track was of less interest, and the focus of WP3b shifted to look at other applications. These were production of activated carbon and carbon fiber, respectively. WP3 generated the product ideas (see appendix 6.1), including potential niche markets that would be used in the later WPs. A selection of routes to study further was then made based on the interests among the project partners.

Selected products and routes from WP3 were further analyzed through e.g. system analysis in WP4 (see appendix 6.2) (WPL Department of Chemical and Biological Engineering at Chalmers University), before the integration of results in a roadmap (see appendix 6.3). The system analysis in WP4 aimed at revealing more details on some aspects for the selected options, and finally, the innovation system surrounding selected routes was to be analyzed.

The most important task in the LigniMatch project is thus to facilitate the turning of promising ideas into successful implementation while avoiding less promising routes.

For the system analysis, the goal and scope was decided through discussions among the partners, taking place at project meetings and over e-mail. Among other things, project partners were asked to grade different alternative lignin product options according to their preferences. The inventory of data for the analysis of the selected options was done partly as a literature study and partly by asking for information from the project partners and other identified data sources.

2.1. Outline of the LigniMatch report This report summarizes the main conclusions from the work within the LigniMatch project. It gives a background to the project, and provides supplementary information on the project consortia composition and competence. A more thorough description of the work performed during the data collection and analysis phases in WP3 and WP4 are reported separately in appendix 6.1 (WP3; New chemicals, replacements of plastics, and new macro-molecular products) and appendix 6.2 (WP4; Market possibilities and the innovation system). The general outcome of the project is summarized in a roadmap entitled: Future use of lignin in value added products a roadmap for possible Nordic/Baltic innovation (appendix 6.3.). The reference list in section 5 is comprehensive, and also includes the references from sections 6.1. and 6.2., respectively.

2.2. Introduction Lignin is one of the main constituents in wood, and is the second most abundant bio polymer on earth. Lignin is a three dimensional amorphous polymer consisting of methoxylated phenylpropane structures (Chakar and Ragauskas, 2004).Three monolignols: p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, constitute the building blocks in the lignin structure, see Figure 2. The proportion of these basic units differs in various species, (e.g. hardwood, softwood, annual crops). The lignin structure is complex, and not fully understood, although considerable work has focused on the detailed structural characterization of these complex natural polymers through e.g. spectroscopy coupled with oxidation/reduction, ozonation, photochemical degradation, thermogravimetic analysis, and computational studies (Chakar and Ragauskas, 2004, Holmgren et al, 2006, Parkas et al, 2007, Akiyama et al, 2005, Wang et al,2004, Crestini and DAuria,1997, Xie et al,2009, Beste and Buchanan, 2009). As a result, understanding of both structure and function is growing. An example of softwood structure is given in Figure 3. Despite the chemical complexity of lignin, the use of lignin as

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raw material for value added products hold a large economical potential for the chemical industry in the region.

Figure 2. The three monolignols, the building blocks of lignin, and their corresponding structures in lignin polymers (from Brodin, 2009)

Substitution of fossil-derived products with lignin-based alternatives would be beneficial for the environment, as well as for future actors in this sector.

Figure 3. Example of softwood lignin structure (Henriksson, 1998)

The global wood pulp production in 2000, considering the top producing countries, was about 160 million tonnes1. The pulp industry in Sweden and Finland contributed 15% of this, or 24 million tonnes. From this, a theoretical number of the total amount of lignin that could be extracted can be

1 http://www.greenamericatoday.org/programs/woodwise/consumers/stats/index.cfm

http://www.greenamericatoday.org/programs/woodwise/consumers/stats/index.cfm

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calculated; approximately 8 million tonnes of lignin could be available for reprocessing in the Nordic Countries, annually, provided that pulp mills are provided with the necessary equipment (e.g. LignoBoost technology in Kraft pulping).

However, the pulp mills already use a lot of the lignin as internal energy input at the mills, and even combined with energy efficiency measures at the pulp mills, the mills would need to find alternative sources to supply some of this process energy if all this lignin was removed. On the other hand, already today, excess energy that exists at some locations is sometimes hard to find use for since it is in the form of heat. If some of this excess energy could be taken out as lignin instead, this would provide a much more flexible and valuable source of energy than heat, and also a potential raw material for different products. Programs towards higher energy efficiency or increased capacity at the pulp mills could provide a substantial amount of lignin. The recovery boiler is sometimes a bottle-neck when capacity increases are planned at the mills, and then, one possible solution is to extract lignin in order to reduce the pressure on the boiler. If the market price for lignin is high enough, investments for extraction of lignin from the mills will be profitable. If lignin products become valuable enough to result in changes at the Nordic pulp mills, it is not unlikely that around 800,000 tonnes of lignin could be produced each year in the Nordic countries (Staffas, 2010). Based on the energy content of lignin and the price for energy, a reasonable price for lignin today could be about $330 per tonne (Staffas, 2010).

Lignin appears in different form in different types of pulp mills:

Kraft lignin (in black liquor) at the Kraft pulp mills. This type of lignin could in the near future be extracted in large quantities at Nordic pulp mills and therefore has a large potential

Sulphite lignin, or lignosulphonates, (in red liquor) at the sulphite pulp mills. This type of lignin appears in lower quantities and is already to some extent extracted (about 1 million tonnes globally)

Hydrolysis lignin from hydrolysis pulp mills

LignoBoost is a technology that extracts lignin from the chemicals used in the pulping process (Wallmo et al, 2009). This system was invented and patented in Sweden. If implemented at pulp and paper mills to extract lignin from Kraft black liquor, it has the potential to increase lignin availability on the market. The LignoBoost separating process is based on precipitation and separation by filtration. The results are lignin-lean black liquor that is returned to the pulping process, and pure lignin that can be used for numerous applications. It thus offers a new potential to increase production and reduce costs and at the same time create new sources of income for the mills.

Lignin is used as raw material in a range of commercialized products on the market today. The utilizing of different properties has allowed these lignins to be used in a variety of products, such as binding agents, dispersants, emulsifier and sequestrants. Figure 4 illustrates the vast array of products that are currently produced from lignin.

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Figure 4. Examples of products and product groups already produced from lignin.

2.3. The products and innovation systems Initial surveys for suitable product and/or route candidates for further analysis resulted in a wealth of information (see appendix 6.1. for more details). The most interesting products were summarized and a list of product groups emerged. Figure 5 lists the products that were considered most attractive by the LigniMatch consortia.

Figure 5. Potential groups of future products from a lignin precursor material

A discussion was then held on how to make the selection of routes to study further in the system analysis. It was clear from the discussion that the different companies involved had different interests. A first list of selection criteria to base the selection on was created:

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Lignin products should be relevant to active partners Technical processes should be relevant to active partners Raw materials (lignin and others) could be available in required amounts Capacity of existing production lines should be considered, as should the requirement of new

investments Intellectual property rights should be manageable

Nordic lignin potentially produced in connection to the Kraft pulping process (using LignoBoost) should be considered as a starting point. It was also decided that a global market for the lignin products should be studied. A selection of standard aspects (primary energy, fossil resources, global warming, acidification, eutrophication, toxicity, ecotoxicity and product value) was discussed, and the following list of relevant aspects were identified:

Function: The lignin product should have better function than available competing product (at the time of implementation)

Energy consumption: The energy consumption in production of the lignin product should be lower than available competing product (at the time of implementation)

Price: The price for the customer in relation to the function should be lower than available competing product (at the time of implementation)

Environment: The lignin product should be environmentally friendly, taking the whole life cycle into account

Based on discussions of the selection of criteria, and evaluation of the lists of products that was created in WP3 sub groups, five different lignin products were selected for a more thorough study:

Activated carbon Carbon fiber Dispersant Phenolic compounds Sorbent for removal of toxic metals

A preliminary screening of the product systems and process routes indicated that two of the selected products were of less interest. It was decided to not proceed with sorbent for removal of toxic metals, since this requires large amounts of chemicals and only has been tested in lab scale, and dispersant, which is produced already today and therefore not interesting as a new niche market. Discussions were therefore continued only for three options:

Carbon fibers for replacement of PAN or steel in automotive applications - a new application that can be very profitable and of specific interest to one of the partners (Volvo)

Activated carbon which is not innovative but easy to produce and can be of high quality Phenolic compounds as building blocks for chemicals - in order to replace oil based phenolics

A comprehensive system analysis (see appendix 6.2. for more details) on the technical system should focus primarily on four aspects: Energy, Environment, Safety and Costs. These aspects can be described quantitatively or qualitatively depending on the availability of data. Four other aspects

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should be discussed in more generic terms for a larger system: Raw material availability - are required amounts available at present?; Market - How large are different markets and how large is the market in comparison to what could potentially be produced?; Function/quality - in comparison to competing products and in relation to the needs of the market; and Lignin source flexibility - Can this route and product be chosen for lignin from several different sources or only specific sources? The two remaining aspects, Property rights and REACH, should only be briefly discussed in relation to the innovation system.

According to the goals of the LigniMatch project, a life cycle perspective should be used in the basic system analysis. In a standard life cycle assessment (LCA), a product system describes the activities in the life cycle of the product. Although a full LCA is not intended to be made within this project, a generic product system was outlined as a guide for discussions. This outline is shown in Figure 6. This structure was going to be used as far as possible in the collection and analysis of the information. For each of the three studied products, the following activities are therefore of interest:

Production of the lignin product Use of the lignin product Waste management of the lignin product Transports - means and distances Replaced product - all activities mentioned above for the lignin product

Figure 6. Generic product system for the system analysis

For the activities, the following four aspects were analyzed and discussed when relevant and as far as access to information allowed:

Kraft process+ LignoBoost

ligninSystem boundary

Materials

Production oflignin product

Use oflignin product

Trsp

Wastemanagement

Trsp

Trsp

Chemicals

Replaced product

Heat

Electricity

Fuel

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Energy (heat, electricity, transportation fuel) Environment (use of chemicals and materials, emissions to air, water, and soil, and

generation of waste) Safety Costs

For an even broader societal system, issues related to the physical resource basis were then discussed for each alternative. The raw material availability was discussed and related to the size of potential markets. The function of the products in terms of their quality in relation to market demands and existing alternatives was also discussed, as well as the flexibility of the process to different sources of lignin. Finally, the innovation system around each product system was analyzed and discussed.

3. Summary and conclusions From a chemical point of view, there are several possibilities of producing materials from a lignin base. If the demand is large enough for some special application, e.g. biodegradable plastics, it might be possible to further develop a lignin based plastic material. However, no major commercial breakthrough has been recognized for plastics manufactured from lignin. The idea of producing carbon fibers and activated carbon from lignin seems much more promising. Furthermore, the technology for production of macro-molecular products is rather simple, and e. g. medical enterosorbents can be produced from lignin using standard equipment.

From an environmental and resource efficiency view, different time perspectives must be considered to successfully replace raw material of fossil origin with lignin based biomaterial. In the very long time perspective (~50 years), biomass and other bio-resources might be too valuable as raw materials or as being allocated for food production. However, in a shorter time perspective, the role for biomass during energy conversion and for fuel in the transportation sector will be of great importance, at least in certain regions.

Another argument is that economic considerations of different types could alter the picture. Chemicals, plastics and other similar materials are more valuable products compared to fuels, at least in terms of value per tonnes. Therefore, extra development costs could be better absorbed within the value added material sector. Micro-economic considerations for the producers of lignin are of course also of great importance, e.g. the investment situation for soda-boilers at the plants, the energy price situation, and incomes that could be gained from the production. Considering the intensive climate change debate, it is realistic to assume several niches application for bio-based chemicals/plastic/material. In addition to improving the carbon balance, those niche applications also represent an economic opportunity for the lignin producers.

Furthermore, along with efficiency improvements in major sectors such as energy production, steel, cement, and transportation, also the plastic/material and chemical sectors will most certainly grow to be an increasingly interesting object for policy efforts. The fact that a situation might occur, where no really vast environmental benefit from a system perspective could be anticipated, stresses the

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point that the production chain must be optimized at all stages, in order to avoid the criticism that has occurred for ethanol as a fuel in the transportation sector.

Much of current research is focused on lignin structure; e. g. degradation kinetics, compositional modifications, thus it is realistic to anticipate that deeper understanding of such lignin properties will augment technology development towards high performance material production once the know-how is established. Bio-plastic production is advantageous as the process does not require toxic chemical adhesives and the resulting products are produced from biological components. An enhanced biodegradability is an extra plus for some lignin containing plastics, which could be of great value for special applications.

Although lignin is abundant, and considered a rich source for potentially significant bio-product candidates, a challenge remains to find environmentally friendly and economically viable processes to disintegrate the precursor lignin material into value-added products. Production of chemicals, plastics, carbon fibers and macro-molecular products from lignin might be a solution for the future if an efficient production with the sought qualities could be established. It fits well with a wise allocation of biomass resources in the long term perspective. To be able to develop the needed technologies, the use of niche markets is, of course, a possible strategy. There are signs that such markets could be available already today. In the short term perspective, no major obstacle other than the common economic-technological challenges could be anticipated, if the efficiency and quality challenges are met. The environmental perspective could work as one of the drivers for such a development, considering the current focus on climate issues.

Establishment of a production of lignin based products will most likely be driven by the demand from niche market actors in combination with microeconomic considerations of the lignin producers/companies active in the area of refining of lignin into products.

By using lignin as the raw material, three product systems have been identified as most interesting for future implementation. These products are: Activated carbon - not innovative but easy to produce and a high quality can be achieved; Carbon fibers for replacement of PAN or steel in automotive applications - a new application that can become very profitable; and Phenol as a building block for chemicals - in order to replace oil based phenol. The results from the project will have key advantages for the society:

Making better use of the raw materials produced

Providing materials from renewable sources

Substitute for chemicals produced from fossils

The conclusions from LigniMatch have resulted in a roadmap to provide guidance for future lignin-based innovation systems in the Nordic and Baltic region. The use of lignin as raw material for carbon fiber production in automotive applications was identified as an attractive route to pursue for actors in the region. The roadmap highlights important aspects concerning products and technologies, in order to select and prepare for a successful implementation of chosen routes, and will guide major actors in the field towards the launching of lignin based products on the international market. The

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results were presented during a final workshop with partners and invited stakeholders. The general outcome from the concluding discussion resulted in agreement on recommendations to initiate the formation of a consortium to further explore the potential of lignin for carbon fiber production.

4. The consortium The LigniMatch consortium consists of Nordic and Baltic partners representing a broad range of business and research competences. These competences are represented by industrial actors from different parts of future value chains of lignin products, universities and research institutes with a wide range of interests and expertise in relevant areas, and two network organizations that bring in connections to other important parts of potential innovation systems (see Figure 7). The added value gained from the mixture of member roles and functions of the LigniMatch consortia is used when potentials of future innovation systems are discussed.

Figure 7. Three different types of actors can be identified within the LigniMatch consortium: industry, universities and research institutes, and networks organizations that provide platforms for collaboration.

4.1 Industrial partners Industrial partners involved in the consortium include many different parts of the value chain, from the producers of the lignin, including forest owners, the wood processing and separation of lignin, companies that produce or are interested in producing different lignin products, or in providing chemicals for these processes, to companies that see opportunities in the use of these new products for different applications.

Sdra is a major actor in the Swedish forestry sector, with business areas ranging from forestry management and environmental conservation to accounting, sales and product development. Products include sawn and planed timber goods, interior products, pulp and biofuel. Efficient production at the pulp mills results in excess energy, and Sdra is therefore a large producer of electricity. Further increases in efficiency or capacity may give

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opportunities to take out some excess energy in the form of lignin, and selling it or using it for different purposes. Research and development are essential parts of Sdras competitive vision. Strong resources and partnerships with universities and research institutes create opportunities for the entire value chain, from forest improvement to the marketing of new products to customers.

Borregaard Industries is the world's leading supplier of wood-based chemicals, and other related niche markets. Through strong innovation efforts and investments in R&D and pilot plants, the companys four business areas cover a wide range of increasingly specialized products, within segments such as Ingredients, Fine Chemicals and Energy in Borregaard LignoTech, Borregaard ChemCell, Borregaard Ingredients and Borregaard Synthesis. These value added products, based on different components in wood, range from omega-3 and vanilla for food stuff through high purity specialty cellulose for chemical-technical applications, to lignin-based binding and dispersing agents. Borregaards global presence increases the value added to the products.

Novozymes A/S produce enzymes for use in different sectors, e.g. transformation of starch into sugars or in wastewater treatment. Development, production, and distribution of enzymes form the core business idea. Two major segments, Enzyme Business and BioBusiness, will provide sustainable solutions through optimized production technology. Products, such as technical enzymes, are used in the transformation of starch into different kinds of sugars where the functionality is used in the starch and fuel industries. Novozymes microorganisms are used in industrial and municipal wastewater treatment, as well as in the cleaning of surfaces.

AKZO Nobel Suface Chemistry AB is a leading supplier of surfactants, a class of chemicals that have the power to change the surface properties of a variety of materials. These surface-active agents are used in hundreds of commercial applications. The products range from formulations for industrial and household cleaning and paint and building additives to emulsifiers for many applications, including systems for road paving and flotation agents for the purification of minerals.

Volvo Cars is a well known manufacturer of commercial vehicles, in a wide range of segments. The company is working hard towards reducing the environmental impact from production and use of their products. Intense R&D is focused on developing engines that consume less fuel and have emission levels close to zero for nitrogen oxides and particulate matter. Reduced fuel consumption as well as vehicle performance is also incentives for looking at weight reduction measures from alternative construction materials.

4.2 Universities and research institutes University and research institute partners cover a broad area of relevant research expertise, ranging from wood chemistry, to construction of plant equipment and innovation.

The Department of Chemical and Biological Engineering at Chalmers University of Technology, is focused on research within the whole span from pure and basic chemistry and

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bioscience via applied chemistry to biotechnology and chemical engineering. The interaction with industry is very strong, ranging from pharmaceutical and food industry to pulp and paper, automotive and steel industries. The Department has successfully attracted funding for centers within the areas of catalysis, high temperature corrosion, supramolecular biomaterials, wood-based materials and plastics for a sustainable society. The department initiated ideas on the LignoBoost. Research and development of the technique is performed in cooperation with Innventia AB.

The Lignin group (Environmental Biotechnology and Biotechnology of Renewable Natural Resources) at University of Helsinki focuses on basic as well as applied research on a wide range of topics related to lignin. Basic research areas include microbiological and enzymatic degradation of lignin, degradation of lignin by white-rot and litter-decomposing fungi, production and properties of ligninolytic and cellulolytic enzymes, and catalytic mechanisms of peroxidases. Within the applied field of research, the group is working with projects related to biopulping (use of fungi to treat wood chips to decrease chemical or energy consumption in pulping and to remove pitch (extractives) from wood chips); degradation of polycyclic aromatic hydrocarbons (by litter-decomposing fungi in soil); removal of organic material from soil (contaminated with dioxins and dibenzofurans) and degradation of lignin and lignocellulose in compost.

The Latvian Institute of Wood Chemistry, IWC, is focused on research related to chemical and thermochemical processing of wood, in particular on wood chemistry and other aspects related to biomass. Areas of studies include energy production, modification of properties of wood and its components, as well as the chemistry of lignin. One focus area is investigation of the properties of lignin and lignin derivatives as components of disperse systems; another is lignin and silicon containing lignin products in biogeocenosis. Technologies for development of novel products for environmental, industrial and agricultural use are also being tested.

Innventia AB(former STFI-Packforsk) provides research and development within a large number of different fields relating to pulp, paper, graphic media, packaging and biorefining. Being a link between academia and industry, Innventia translates research into innovative products and processes. By carrying out research at the highest international level, results can be implemented in commissions and in consultancy and training services. Innventia also provide state-of-the art laboratory and pilot plant equipment. Have developedLignoBoost in cooperation with Chalmers University of Technology.

VTT Technical Research Centre of Finland is a global and multi-technological contract research organization. VTT provides high-end technology solutions and innovation services within a wide range of field. The technology focus areas cover: applied materials, bio-and chemical processes, energy, industrial systems management, information and communication technologies, microtechnologies and electronics, services and the built environment, and business and innovation research.

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4.3 Network organizations The networks organizations aim at contributing to innovation within the cleantech and sustainability area and constitute connections to other universities, institutes and industries but also to authorities on different levels and different organizations.

The Centre for Environment and Sustainability, GMV, is a network organization at Chalmers University of Technology and University of Gothenburg. GMV promotes research and education for sustainable development, and creates and encourages research projects and multidisciplinary initiatives. Cooperation with the business community as well as the provision of information and education to the general public are part of GMV's brief. Almost 500 scientists and about 500 representatives from industry, local authorities and other environmental organisations are involved in GMV's research network.

resund Org (formerly resund University) is a Danish-Swedish organisation, founded in 1997 by the universities in the region. As an engine for growth and development in knowledge-intensive areas, the organisation facilitates cross-border networks and projects in areas such as clean tech, food science, logistics, ICT and material science. By bringing universities, businesses and major authorities together, resund Org supports entrepreneurship and innovation to ensure recognition of the resund Region as a regional and international triple helix collaboration arena also in the future.

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6. Appendix The appendix includes three reports from LigniMatch.

The technical reports from WP3; New chemicals, replacements of plastics and new macro-molecular products, and WP4; Market possibilities and the innovation system, provide detailed information on literature surveys, products, selection critera, innovation system, etc.

The Road Map provides an executive summary with conclusions and recommendations.

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6.1. WP3 New chemicals, replacements of plastics and new macro-molecular products

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New chemicals, replacements of plastics, and new macro-molecular products

Contents 1. Purpose and deliverables .................................................................................................................. 30

2. Method .............................................................................................................................................. 30

3. Definition of Work Package (WP3); three parallel sub groups.......................................................... 33

3.1. WP3a: New Chemicals from lignin ............................................................................................. 34

3.2. WP3b: Activated carbon, carbon fiber and plastics produced from lignin ................................ 36

3.2.1. Activated carbon ................................................................................................................. 36

3.2.2. Carbon fiber ......................................................................................................................... 37

3.2.3. Plastics ................................................................................................................................. 39

3.3. WP3c: New macro-molecular products from lignin ................................................................... 40

4. Results: Products selected for further analysis ................................................................................. 43

5. Lists of lignin-to-product applications from WP3 sub groups ........................................................... 44

5.1. List of new chemicals from lignin ............................................................................................... 45

5.2. List of activated carbon, carbon fiber, and plastics from lignin ................................................. 53

5.3. List of macro-molecular products from lignin ............................................................................ 63

6. References ......................................................................................................................................... 72

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New chemicals, replacements of plastics, and new macro-molecular products

This report describes the work that has been performed within Work Package 3 of the LigniMatch project. It reports on the process to identify and collect prospective products and routes with potential for upgrading from lignin to value added products. The most promising alternatives will be selected for further analyses through e.g. system analysis in a later stage in the project (see WP4 report; appendix 6.2), before the integration of results in a roadmap (see Roadmap; appendix 6.3).

1. Purpose and deliverables Work Package 3 (WP3) in the LigniMatch project aims at identifying interesting techniques and products for the up-grading of lignin fractions, in order to distinguish routes with great potential for future use in the chemical industry in the Nordic and Baltic region. WP3 has the following deliverables:

D3 a I: A list of chemicals to be produced from the lignin fractions coming from paper pulp industry, ethanol production, and other industrial processes

D3 a II: Document describing the specific requirements and challenges for the Nordic-Baltic actors respectively, in the lignin to chemicals production chain

D3 b I: A list of applications of lignin based plastics*2 D3 b II: Document describing the specific requirements and challenges for the Nordic-Baltic

actors respectively, in the lignin to plastic* materials production chain D3 c I: A list of applications of macro-molecular products based on lignins from ethanol

production D3 c II: Document describing the specific requirements and challenges for the Nordic-Baltic

actors respectively, in the lignin to macro-molecular products manufacture chain

2. Method The work in WP3 has focused on finding potential routes for production of value added products from a lignin precursor. The working strategy was to collect, categorize and analyze available information on products and technologies with a potential for future development. The first action was to explore the research field in order assess lignin upgrading routes of most interest for the LigniMatch project partners. In order to meet the deliverables of WP3, the work was divided in four parts:

LigniMatch questionnaire survey Patent database analysis Scientific publication review Analysis and discussion of the criteria for the routes

2 Within WP3a I&II, focus shifted from lignin-to-plastics applications to lignin-derived activated carbon and carbon fiber applications, respectively, during the course of the survey

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A questionnaire survey was executed in a password protected electronical form. The industrial partners of the LigniMatch project (Volvo Car Corporation, Novozymes A/S, Borregaard Industries, Sdra, Akzo Nobel Surface Chemistry AB) and research institute partners (Innventia AB, VTT) were asked to answer questions related to their expectations about the research area, about problems related to current technologies and about market expectations for the future. The emphasis of the questionnaire was to highlight the most appealing products for further analysis within the project. The information was confidential, but has been used as a guideline to illustrate the requirements for some products and what product groups the research should be focussed on. Products that are considered to have the greatest potential for tomorrows market are expected to be renewable, readily biodegradable or multifunctional. The information was shared with the other project partners after all the data has been gathered and analysed.

Searches in database services (espacenet and epoline) were performed to find existing patents concerning the extraction of lignin from various sources and the production of materials derived from lignin. The emphasis was on the methods and product groups originally stated in the deliverables of the WP3. The relevant patent publications were summarized with a few sentences, categorized by a few keywords and put to a refworks database (www.refworks.com) for further use. The aim is to use this database in designing the routes for systems analysis work.

Scientific publications were studied to give a more solid basis to the design of the routes. In comparison to the patent database analysis, the scientific publications were studied in detail to discover attractive techniques for future and innovative manufacturing and upgrading of lignin material, and not only to locate the current techniques.

Based on the information gathered during these surveys, a wide range of products were listed. On the second project partner meeting within LigniMatch (M2), held in Espoo, Finland, on January 24-25, 2008, a presentation of the preliminary results from WP3a-c was given. As a background for the selection of prospective products, the currently most dominating lignin sources and already commercialized products from lignin were discussed. Figure 1 show a summary of lignin sources, products and handling schemes.

Figure 1. Summary of current lignin sources, products and handling schemes

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A discussion was then held on how to make the selection of routes to study further in the system analysis. It was clear from the discussion that the different companies involved had different interests. A first list of selection criteria to base the selection on was created:

Lignin products should be relevant to active partners Technical processes should be relevant to active partners Raw materials (lignin and others) should be available in required amounts Capacity of existing production lines should be considered, as should the requirement of new

investments Intellectual property rights should be manageable

An initial list of potential future product groups emerged from partner discussions. Figure 2 lists the products that were considered most attractive by the LigniMatch consortia.

Figure 2. Initial list of products/product groups

The plan was to continue the discussion on the following project partner meeting, when the results from WP3 were closer to completion. It was clear that the project partners had to be engaged in the selection procedure in order for their interests to be considered.

The third partner meeting (M3) took place in restad, Denmark, on March 31, 2008. It was agreed that based on the lists of potential products that resulted from WP3, all project partners were going to be asked about their preferred products and process routes to be studied further in WP4.

On May 27, 2008, an e-mail was sent to all project partners with the lists of lignin products that had been identified in WP3. Project partners were asked to select a maximum of 10 lignin applications from the lists and send it back by June 10th. In order to select only a few products to study further in the system analysis, th