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ANNUAL REPORT 2006 Speciality Chemicals from Renewable Resources Greenche m

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Page 1: Greenchem · esters, surfactants, epoxides) products for specifi c mar-ket segments of interest to the companies have been identifi ed for continued development, scale-up, envi-ronmental

ANNUAL REPORT 2006

Speciality Chemicals from Renewable Resources

Greenchem

Page 2: Greenchem · esters, surfactants, epoxides) products for specifi c mar-ket segments of interest to the companies have been identifi ed for continued development, scale-up, envi-ronmental

The Swedish research programmeGreenchem focuses on develop-ment and application of clean proc-

esses based on biocatalysis for production of chemical products from renewable raw materials. The programme aims to demon-strate the feasibility of robust biotechnology tools and processes to establish a technology link between the renewables sector and the chemical producer/user industry. Green-chem has its academic base at Lund Uni-versity, Sweden.

A range of industries, representing renew-able raw material providers as well as pro-ducers and users of chemicals, participate in the programme, and help to identify the products for which the environmental effect is critical from the manufacturing and appli-cation perspective. In some cases, it implies the replacement of an existing manufactur-ing process while in the others that of the fi nal product. The participating industries are:

• AarhusKarlshamn• ACO HUD NORDIC

The Greenchem programme• Akzo Nobel Industrial Coatings• Akzo Nobel Surfactants• AstraZeneca• IKEA of Sweden• Perstorp• Protista

The programme further involves the evalu-ation of the environmental impact of the products from a life-cycle perspective and also the analysis of critical factors for intro-duction of new technologies in the chemi-cal industry. The chemicals chosen for study within Greenchem are of interest to both Swedish and international industry, and are targeted for application in environmental-friendly surface coatings, lubricants, con-sumer care and cleaning. The product ex-amples include:

• Epoxides (fatty epoxides, glycidyl ethers)

• Acrylates (acrylated polyesters and oils)

• Branched fatty acids • Alkyl glycosides• Alkanolamides

PHOTOS AND ILLUSTRATIONS:Illustrations on cover and page 20 by Ullrika TörnvallPhoto on page 11 is published with permission from PerstorpPhoto (right), page 15 is published with permission from Akzo NobelAll other photos and illustrations are made by Greenchem (except otherwise indicated)

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16

Greenchem Annual Report 2006 3

ContentsA few words from... The board .................................................................4 The management group ...........................................4 The industrial partners ..............................................5

GREENCHEM – a perspective on the fi rst phase ..................6

Integrating chemicals and energy production in a biorefi nery...........................................................7

Land use in life cycle assessment of green chemicals...........8

Back to the roots – Chemicals from renewables..................10

Green product development in a societal context...............12

Towards environment-friendly coating reagents– epoxides and acrylates.............................................14

Synthesis of Alkanolamide Surfactants................................16

Enzymatic synthesis of sugar based surfactants...................16

Development of novel biocatalysts......................................18

Greenchem - External communication................................20

Publications ......................................................................22

Staff ..................................................................................24 20

18

16

10

7

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4 Greenchem Annual Report 2006

The year 2006 was a critical one for Greenchem when the programme was evaluated and deci-sion was taken for funding the programme for

THE MANAGEMENT GROUP

A few words from...

The year 2006 was the last of the fi rst phase of the Greenchem Programme. Looking back at the results of the activities, the decision by

Mistra to support the Programme for another four years is the best proof of its success so far. In addition, the Board has been able to observe a growing inter-est from the participating companies for the develop-ment within the Programme which with regard to the Programme targets is of great importance. From the originally chosen product types for development (wax-esters, surfactants, epoxides) products for specifi c mar-ket segments of interest to the companies have been identifi ed for continued development, scale-up, envi-ronmental testing and market evaluation during phase two. Targets for the development are now products for surface coating, adhesives and lubricants as well as products for personal care and cleaning.

To a great extent the work of the Board in 2006 has been directed by the evaluations of the Programme ini-tiated by Mistra for the phase two decision. The com-pany engagement, international benchmarking and the continued innovation study has then been in the foreground.

With the new, market-directed product development within the Programme, it is natural to give the com-panies greater responsibility for the specifi c selection of products to aim for. Only they can tell if there is a market potential or not. Such responsibility change is achieved by introducing application management groups for the different market areas with the com-panies as leaders, and to have them decide about the priority for products to be developed. In order for such priorities to work the companies will have to keep a very close contact with the development and take ac-tive part in it, i.e to be more engaged.

In the last few years, industrial biotechnology has won great recognition, not the least through the growing interest for the production of ethanol from lignocel-lulosic raw materials. The 7th framework program for research within EU does also give the development of

industrial biotechnology a crucial importance for the sustainable and competitive position of the European Industry. In many EU-countries technology platforms and development programs similar to Greenchem have therefore been started. The Board has urged the Green-chem management to keep in contact with these and to invite them for exchange of experiences and discus-sions of cooperation. It is with great pleasure we note the interest shown to Greenchem nationally and also internationally.

In the fi rst phase of Greenchem, an innovation system study was an integral part of the Programme. The pur-pose of that study was to examine the prerequisites and likelihood for the paradigm shift within the chemi-cal industry, what the changeover to environmentally benign and sustainable biotechnology would mean. Major parts of the study remain however to be car-ried out during phase two. This is especially the case for questions of what the society knows about the new technology and its possibilities as well as the interest and preparedness of the market to accept its products. The Board has assisted the Greenchem management in looking for ways to perform these tasks.

For the new phase of Greenchem, the character of is-sues to be solved will be different from those in the fi rst phase. Scale-up and evaluation of the feasibility for the processes developed during phase one will need knowledge other than that of the researchers. As many of the companies also lack experience of biotechni-cal productions, there will be great demands on the Greenchem Board and management to fi nd ways to bridge that knowledge gap. This shall be the greatest challenge for the Greenchem Board in phase two of the Programme.

Harald SkogmanChairperson of the Board

THE BOARD

a second phase. The evaluation indicated that Green-chem fared rather well during the fi rst phase with respect to the scientifi c results, management, co-op-

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Greenchem Annual Report 2006 5

During any transition from one phase to an-other there are, and indeed should be, rather hectic activities related to the evaluation of

previous activities and planning of future ones. In the case of Greenchem, the primary goal of these activities has certainly been to determine if the results so far mo-tivate further support, or not. However, the outcome in terms of conclusions and advice for the future serves as a valuable complement to the continuous internal work, and allows us to optimise the activities and fur-ther concretise the path to the goal. Before such a re-view there can for natural reasons be mixed feelings due to increased workload, but during the process of evaluation and afterwards, pride evolves together with a sense of pleasure to spread the word.

At our latest annual meeting I refl ected on the change in mode of interaction between the people working within Greenchem, from the start of the project up to now. The individuals in a project of this type dif-

THE INDUSTRIAL PARTNERS

eration and communication. However, some recom-mendations were provided in order for the programme to make an impact on the innovation system and the industrial sector.

The research within Greenchem has been driven more by the need to develop a product for the market, as a result of which there is a deeper appreciation among the academic group about the product requirements for the various applications and also of the market and the main actors at an international level. This ex-posure has been rewarding for the research students. The programme has been successful in attracting other international undergraduate and graduate students to be involved in the projects. There has however been a delicate balance for the academicians between the need to publish and the possibility of delay in publishing in case of industrial interest in a particular product.

A number of scientifi c publications have resulted so far, some even of interdisciplinary nature. Greenchem has also been represented at different conferences ranging from biocatalysis and green chemistry to utilization of vegetable oils. At the national level, information about Greenchem activities has been communicated to the Swedish industry and society at seminars and exhibi-tions, such as the conference arranged by the Swedish Federation of Plastics and Chemicals, Green Chem-istry session at Sustainable innovation fair, and the seminar “Swedish Industrial Biotechnology – today

and tomorrow” co-sponsored by Bioteknik Forum and the Greenchem Board. For a more scientifi c audience, we arranged a very successful seminar day in Novem-ber 2006 on “Effi cient biocatalytic routes for selective introduction of oxygen”, co-sponsored by the Swedish Research Council, for which leading researchers from other countries in Europe were invited as lecturers.

With a mission to bring at least one of our products close to the market, it has been decided that during Phase 2 industry partners will be closely involved along with the management group in setting the product priorities. The management group will further stream-line its efforts towards building a scientifi c platform for green chemistry and industrial biotechnology in Lund and also establish co-operations with Centers of excellence and industries outside Sweden to bring in increased know-how into the programme.

With an increasing interest in EU and also other countries in setting up biorefi neries, the management group sees Greenchem as a natural link to these devel-opments.

Rajni Hatti-KaulProgramme director

fer in background and qualifi cations, as well as their daily working environments. The piece that each per-son brings into the Greenchem jigsaw puzzle consists of experience, knowledge or capability in one or more of the key fi elds. However, each individual is also less knowledgeable in fi elds where others instead can con-tribute. It takes a well-developed ability to listen, a humble attitude as well as respect, to make the most out of a mixed collaborative environment like this. It is with great pleasure that I note the progress that has and continuously is taking place in this respect. It promises well for the future.

Johanna Brinck, ACO HUD NORDICChairperson of the Industrial Reference

Group

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6 Greenchem Annual Report 2006

GREENCHEM – a perspective on the fi rst phase

Greenchem is not just any research programme. Its ultimate goal is to transform an entire in-dustrial sector and its adjacent academic sys-

tem, by developing, introducing and disseminating environmental-friendly technologies.

The obstacles the programme faces are enormous. The capital-intensive chemical industry is reluctant to make drastic changes in its technological systems and production lines. Consumers, while increasingly aware of the long-term instability of the fuel-based economy, still primarily react to price signals. The academic system – both in terms of education and research – is still to a large extent focused on fos-sil-based processes. Government regulation navigates between environmental and economic goals, and still tends to favor corporate short-term interest.

To succeed, Greenchem needs to achieve four goals at the same time. First, it must capture the interest of the chemical industry and turn bio-based processes from a peripheral interest (at best) to a central part of R&D and production planning. Second, it needs to be based on realistic assumptions regarding market demand for environmentally-friendly products. Third, it needs to mobilize a wide variety of academic specialties in the quest for economically viable products and processes. Fourth, it needs to be integrated with public regula-tion.

So far, has Greenchem reached its goals? The answer is necessarily both in the affi rmative and in the negative.

Greenchem’s design is both a virtue and a liability. Greenchem is clearly an academic programme, al-beit with a strong role for industry in its governance. Greenchem’s priorities refl ect the long-standing tradi-tions of the Department of Biotechnology in Lund. Greenchem has had a very important effect in unit-ing and connecting fi elds of activity in the area. It has, however, not yet resulted in broader attempts to form a scientifi c platform for green chemistry, neither in Lund nor in Sweden as a whole. However, an innovative ele-ment in Greenchem is the collaboration between the Department of Biotechnology and environmental sys-tems and innovation studies, which has contributed to a broadening of the perspective of technological change in the chemical sector. An important limiting factor for an even more inclusive approach is resources. Greenchem, while not being insignifi cant fi nancially,

is minute in comparison with similar initiatives out-side Sweden. Another weakness is that money has been allocated on the basis of company interest. Areas where no corresponding industrial interest (yet) exists have been excluded, which also means that some exciting avenues have not been pursued.

Greenchem is heavily oriented towards feasible re-search, where results can be expected to be of use to in-dustry. Change-oriented programmes need to include

at least a fraction of support for “fringe projects” with more uncertain applications but with larger potential for renewal and breakthroughs.

Greenchem lacks a risk fund for research of cutting-edge qualities: it is (overly) focused on feasible projects with industrial legitimacy.

Greenchem has therefore been shaped by the priorities of industry. The companies have become increasingly important in the design not only of the programme as a whole but also for individual projects. Some projects are clearly very tightly related to the research and de-velopment strategies of individual companies, and rep-resentatives of these fi rms have played a decisive role in critical moments of these projects. On the overarching level, industry has gained from the programme – and in particular the marketing effect of showing that there actually exists change-oriented programmes within the chemical industry. Hence, Greenchem has functioned as a window and exemplar to the rest of the chemi-cal sector, important not least to companies operating on the interface between biotechnology and chemistry. However, a major impediment to the successful imple-mentation of Greenchem’s goals is the relative lack of fi nancial contributions from companies. Programmes with a focus on industrial transformation are in need of committed partnerships between academia and in-dustry. Company commitment and fi nancial support not only secures implementation but also widens the fi nancial support of the programme. If Greenchem is to succeed, sustainable support from industry is neces-sary. An important goal is clearly to fi nd a long-term fi nancial and organizational model for the fi eld, in-volving industry as well as funding agencies and uni-versities.

Greenchem’s relationship to consumers and markets have been the real weak part so far. The programme is clearly driven by technological opportunities, and little attention has been paid to market acceptance of

Greenchem’s design is botha virtue and a liability.

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Greenchem Annual Report 2006 7

biotechnology-based products, attitudes towards the chemical industry and similar issues. Biotechnology is still an area viewed with skepticism within the general public, and much more attention needs to be focused on attitudes towards new technologies, but also to questions of price elasticity and the willingness of con-sumers to pay more for more environmentally-benign products. Relationship to public regulation is another critical issue. While parts of the state apparatus have been involved in the governance of the programme, connections to the fi elds of technology policy and en-vironmental policy have been limited so far. It seems clear that the future development of the chemical in-dustry is not highly prioritized within industrial policy in Sweden today, and the programme must contribute to a new mindset in this respect.

To sum up, Greenchem has made progress during its fi rst phase, has produced a signifi cant amount of sci-entifi c publications, many of great industrial interest, and has functioned as a meeting spot for academicians, industrialists and policy makers. It is a pilot project in this respect, indicating the long-term effects of net-working and collaboration to develop new products and processes. What is needed now is a “tiger jump” from pilot project to transformative initiative. This will be a challenge, but also a possibility to turn Green-chem into more than an ordinary research project. The stakes are high!

Mats Benner, Project leader, Lund University

Integrating chemicalsand energy production in a biorefi nery

has now raised concern regarding land availability, competing land use options (see subsequent article), and increasing cost of food due to increasing food de-mand in the future. The alternative raw material op-tions that are being considered are non-food biomass from forestry, grasses or wastes. The possibility to use wastes as raw material makes biogas as an attractive fuel and is being developed in some countries like Swe-den (Department of Biotechnology at Lund University has an active research group in this area). It is defi nitely more useful to plan bio-based production in terms of a biorefi nery for producing multiple products, so as to take advantage of the natural complexity and differ-ence in biomass components and intermediates, and hence maximize the value derived from the biomass. This will also provide substantially higher economic profi ts for the farmers.

Currently, only about 10 % of the entire chemicals production is bio-based. Shifting the resource base for chemicals production requires radical changes in the technologies used in the industry. Some companies like DuPont and Cargill have already taken the lead and are developing important platform intermediates for speciality products like polymers. These companies have further shown the advantages of integration of modern biotechnology and chemistry in production processes. Linking the chemicals production to the rapidly emerging bio-energy industries, from which important bio-platform molecules are becoming avail-

Climate change and global warming are popular expressions in today´s world. The looming dis-asters for the planet Earth as a result of these

climatic changes are attributed to the human activities coupled to the fossil carbon. A major part of fossil oil after refi ning goes to the energy sector; hence the need for alternative, clean energy has been given the high-est priority world wide to reduce the dependence on fossil raw materials. Although only a minor fraction of the refi ned petroleum (less than 10 %) is used for the production of chemicals and materials, this provides substantially greater value-added economic activity to a nation.

Substantial efforts are currently being made to use renewable biomass to produce energy primarily for transportation purposes. This is being promoted by ap-plying various policy incentives at different levels. The alternative bio-fuels are bioethanol, biodiesel, biogas, BTL (biomass to liquid) and biobutanol (through new BP-DuPont process). Much attention is currently fo-cused on bio-ethanol and bio-diesel, the former from carbohydrate rich feedstock and the latter from oilseed crops. European Union is leading in biodiesel market, contributing about 3.375 million tonnes to a total glo-bal production of 4.1 million tonnes.

However, using biomass for energy production only is not a solution to sustainable development. For exam-ple, production of the biofuels from agricultural crops

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8 Greenchem Annual Report 2006

Land use in life cycle assessmentof green chemicals

The production and utilisation of green chemicals are normally associated with the twelve princi-ples of green chemistry which can be summa-

rised to entail use of renewable feedstocks, substitution of hazardous chemicals, and reduced consumption of chemicals and energy. However, the implications of applying these principles in practice are not fully known today. Life cycle assessment (LCA) is one way of gaining more knowledge and bringing them closer to application. Results from the life cycle assessments carried out under the Greenchem programme show, for example, that the principle of introducing biocata-lyst in the production of chemicals normally leads to signifi cant energy and environmental benefi ts. How-ever, the principle of using renewable feedstock is not necessarily favourable in all situations and concerning all the various environmental aspects. For example, the benefi ts of reduced emissions of carbon dioxide when using renewable feedstock instead of fossil feedstock may be off-set by emissions of various greenhouse gas-es during the production of the biomass, such as rape seed. The cultivation of feedstock crops may also lead to eutrophication and acidifi cation due to leaching of nitrate, emission of ammonia etc. Similar fi ndings have been reported in other environmental systems studies of green chemicals based on renewable feedstock. Fur-thermore, the need of including the aspect of land use in LCA of green chemicals has been highlighted also from another perspective, the competing utilisation of biomass resources in reducing greenhouse gases.

Ways to account for land use impacts in LCA have been explored since the early methodological guides for this tool. However, there is to date no consensus as to how land use impacts may be incorporated in

LCA. Accounting for land use in LCA can be seen as inherently problematic because land represents a scare resource, yet it is not simply consumed like mineral or fossil energy resources, in the sense that it is not ex-tracted and dissipated. There exist some suitable tools for the assessment of land use impacts in specifi c life cycle stages, which use appropriate and detailed in-dicator sets. However, there is a confl ict between the level of detail and the life cycle coverage that can be attained. Thus, a strictly performed LCA using cur-rent guidelines is not an appropriate tool to guide land management. It will be valuable in comparing systems which differ quite substantially (e.g. bio-based versus fossil-based products considering emission of carbon dioxide emissions), but it should also be able to high-light substantive differences in land quality measures caused by different management and crop cultivation systems (e.g. comparing various feedstock crops con-sidering nutrient leaching, soil carbon accumulation, biodiversity etc). This lack calls for a further meth-odological development in LCA, and/or using a more broad environmental assessment approach in, for ex-ample, the analyses of green chemicals based on vari-ous agricultural biomass resources.

Land use effi ciency is one fundamental parameter which should be included when analysing various biomass feedstock options in the production of green chemi-cals. Depending on which crop that is cultivated, how and where it is produced, the biomass yield per hectare and the energy input required may differ substantially. In Figure 1, the biomass yield, gross energy yield and net energy yield are shown for some agricultural crops cultivated on good soils in southern Sweden. As can be seen in the fi gure, the output of biomass per hectare

able, can be a good starting point for establishing bi-orefi neries. For example, production of inexpensive glycerol, as a by-product during biodiesel production, is a good motivation for its use as precursor for other organic molecules in the chemical industry. To pro-mote the development of biorefi neries, the existing policy instruments need to be extended beyond bio-energy to chemical industry.

The research program, Greenchem is developing products for coating, lubricant and consumer care and cleaning applications from renewable resources. The programme is a useful starting point for further expan-sion into a biorefi nery where production of chemicals can be integrated with bio-energy production from the waste streams.

Rajni Hatti-Kaul, Programme DirectorBo Mattiasson, Project leader, Lund University

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Greenchem Annual Report 2006 9

0

50

100

150

200

250

Wheat Rape seed Sugar beet Ley crops Maize Energyforest

GJ

per h

ecta

rer p

er y

ear

Net energy yield Gross energy yield

(6,4)

(2,8)

(11)

(7,5)

(9,5)(9,5)

(Dry tonne per hectare per year)

Figure 1. Gross energy yield, net energy yield (gross energy yield minus energy input in cultivation) and bio-mass yield per hectare and year for some vari-ous crops cultivated in southern Sweden on good soils.

and year may differ by roughly a factor three depend-ing on what crop that is cultivated. The energy effi -ciency in the biomass production, expressed as gross energy yield divided by the energy input required in cultivation (e.g. diesel fuels, mineral fertilizers etc), may vary between approximately 20 (energy forestry) and 6 (rape seed). In general, the production of peren-nial crops requires less energy input than cultivation of annual crops. A lower input of energy in form of diesel fuels, mineral fertilizers produced by fossil fuels etc, will also lead to lower emissions of greenhouse gases and other air pollutants. Furthermore, cultivation of perennial feedstock crops may reduce the risk of nutri-

ent leaching, erosion and loss of soil organic matter etc, compared with the cultivation of annual crops, due to reduced soil tillage and that the soil is covered all year around. Altogether, this results in better life cycle per-formance of high yielding perennial crops produced with low energy input compared with low yielding an-nual crops produced with high energy input.

The agricultural crops included in Figure 1 are, how-ever, not completely comparable as feedstock options in the production of green chemicals. Ley crops and energy forest, for example, represent biomass rich in lignocellulose, whereas wheat and maize are rich in starch and sugar beet in sugar. Rape seed can be used to produce vegetable oil which is a potential feedstock in a wide range of green chemical applications. Today, there are a limited number of alternative domestic pro-duction options of vegetable oil. The alternatives that exist are often importing of, for example, soy oil from

Brazil and palm oil from Malaysia. When comparing these three different vegetable oil crops, other impact categories associated with land use are also relevant to consider, such as landscape values and biodiversity. Concerning biodiversity, erasing diversifi ed vegetation and replacing it with mono-culture crops is always violation against it, but the consequences appear as site-specifi c factors, such as the number of species af-fected by cultivation. Today, the expansion of soybean production in Brazil is mainly located on the cerrado having a natural vegetation rich in biodiversity. The cerrado soils are also poor in nutrients leading to a high input of mineral fertilizers in soybean cultivation. The

expansion of oil palm plantations in Malaysia during the last decades has to a large extent been as a shift of rubber trees to oil palms, but also in form of new oil palm plantations in the tropical rain forest.

Assessing the environmental impact of using renew-able feedstock in the production of green chemicals thus calls for an inclusion of land use aspects in a broad perspective. Although there are many obstacles on the way towards an appropriate method for land use evalu-ation in LCA, it is highly desirable to continue to seek solutions since sustainable use of farm land is essential in sustainable development, while e.g. chemical pro-ducers and policy makers need direction in their eve-ryday decisions.

Pål Börjesson, Project leader, Lund University

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10 Greenchem Annual Report 2006

Back to the roots – Chemicals from renewables at Perstorp

Perstorp’s vision is to be the recognized global leader in realizing resource-effi cient and envi-ronmentally sustainable solutions in selected

niches of organic and polymer chemistry.

In 1881, when Wilhelm Wendt began building his fi rst small plant for the carbonization of beech wood, many people shook their heads and questioned his idea of “making money from smoke”. Squire Carl Wendt’s son, Wilhelm, had decided to convert beech wood from the forests on his father’s estate to acetic acid. At that time, no one could possibly imagine that during the course of the next 125 years his fi rst small retort at Stensmölla in Perstorp would grow and develop into Perstorp Holding AB, one of the world’s leading spe-cialty chemicals companies [1].

Attaining sustained development, or sustainability, is an important goal today for the chemicals industry and for Perstorp. It seems more than just a coincidence that the RME (rapeseed methyl ester) investment is con-nected to the company’s beginnings. Perstorp started in 1881 with the beech forests as raw material and the forests were then called Skåne’s green mine. Now the circle is closed with Perstorp’s large-scale investments in chemical production based on renewable resources from cultivated rapeseed.

The building of the factory for the production of rape methyl ester in Stenungsund with production sched-uled to start around middle of 2007 is thus particularly interesting. Rapeseed methylester, or RME, is used in renewable fuel. Perstorp’s ambition with the plant is to cover Sweden’s entire need for RME as a 5% mixture in automotive diesel fuel. The investment is made within the framework of a partnership agreement with Preem Petroleum AB, Sweden’s largest oil company, and the intention is to expand operations as the demand for biodiesel increases [2].

Most of Perstorp’s speciality chemicals are intermediate products used in the production operations of other industrial companies, primarily in the chemicals, coat-ing and plastic processing industries, as well as con-struction, automotive and engineering industries.

Nearly two-third of sales are booked in the chemicals industry, with the coatings industry via the resin in-dustry as the largest single user. Other application ar-eas include the agricultural, food and other industrial sectors.

The main products and application areas are:• Basic and speciality polyols• Formalin technology (production plants and catalysts for formalin production)• Organic acids• Oxo alcohols and plasticizers• Feed acids and other agricultural chemicals (Food & Feed)

The largest product groups are basic and speciality polyols and oxo alcohols and plasticizers, which ac-count for more than 70% of sales. Approximately two-thirds of raw materials are based on crude oil or natural gas, the most widely used include formalin, methanol, natural gas, propylene, ethylene, butyralde-hyde and acetaldehyde. The main auxiliary chemicals include sulphuric acid, sodium hydroxide and formic acid. Most production is supported by effective, envi-ronmentally compatible processes that are developed within the Group. Several key raw materials for propri-etary production, with special emphasis on aldehydes such as formaldehyde, butyraldehyde and propionic aldehyde, are produced internally, which contributes strongly to the Group’s competitiveness and opportu-nities to develop new products [3].

In addition to the current favourable business trend, the world is characterized by rapid price increases for all sorts of raw materials, which, for Perstorp and the chemical industry in general mainly means very sharp cost increases for oil and natural gas based products. Moreover, signifi cant price increases for energy also in-fl uenced raw-material prices and increased production costs. In addition investments have been made in bio-fuel-based energy production at the plant in Perstorp for the use of Biomal, which is based on offal as energy raw materials [4].

There is enormous interest today in the possibilities of producing chemicals that are biodegradable and thus environmentally adapted. This comes under the area

Quotations from company reports…

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Greenchem Annual Report 2006 11

of green chemistry, which Perstorp has, in practice, been involved in since 1881, when beech wood was used as a raw material for, among other things, ace-tic acid production. Like many other players, Perstorp feels that relying on fossil fuels is unsustainable in the long term, and rising oil prices are a main driving force behind the development of today’s chemicals industry.

The key to success in the modern chemicals industry is to secure a supply of the requisite raw materials at a reasonable price, in order to stay profi table and com-petitive. One solution is to produce them from renew-able raw materials such as agricultural waste (crops and forestry).

Perstorp is active in several areas relating to green chemistry. Among other things, Perstorp participates in the Greenchem program at the Lund University, aimed at producing biodegrad-able chemicals from re-newable raw materials. Perstorp’s interest in the program is to de-velop environmentally-adapted chemicals for coating resins and help shape future develop-ment.

Perstorp maintains continuous external contact and alliances through numerous close and broad collab-orations with the aca-demic sector in many areas. Perstorp is also a member of several national and interna-tional consortia in both industry-specifi c and more diversifi ed inter-est areas. These collab-orations span develop-ment areas in Perstorp’s sphere of interest, and include activities in the fi elds of renewable raw materials, green- and white chemistries

(Greenchem, Chemicals from forest industry-Biore-fi nery, EcoBuild, and CHRISGAS), computerised kinetic calculation models (Åbo Akademi University), catalysts (University of Cardiff ), and organic cataly-sis of small organic molecules (TEKES, and Berzelius centre, Stockholm University). Perstorp funds and su-pervises industrial PhD students and thesis work for M Sc. students in close collaboration with university de-partments in Sweden and abroad. Perstorp also collab-orates with customers in specifi c projects for develop-ing products with properties specifi c to their intended applications, for instance waterborne coating systems (alkyd emulsions, polyurethane dispersions and water-borne polyester), radiation curing technology, powder coatings, foams and fi re-retardant coatings.

Many projects for reducing raw material consumption are in progress at the plants. All the plants register dis-ruptions that lead to increased raw material consump-tion, and perform measures to minimise these disrup-tions. Ongoing optimisation efforts include charting of raw material consumption and exchange. The plants also conduct various process improvement and optimi-sation measures to reduce the amount of raw material per ton of fi nished product. The catalyst plant in Per-storp accepts used catalysts for recycling from its cus-tomers. Molybdenum and ceramic rings are also recy-cled. In total, the catalyst plant recycles approximately 65% of all catalysts supplied to customers [5].

References

(1) Making money from smoke, Perstorp AB 1881-1981, 1981(2) The good circles and the bad, Perstorp AB, Rahmberg, R., 2006(3) Perstorp Holding AB, Annual Report, 2005(4) Perstorp Holding AB, Year-end report, 2006(5) Environmental Report, Perstorp Holding AB, 2005

Contribution from

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12 Greenchem Annual Report 2006

Green product development in a societal context

The market development of environmentally be-nign chemical products is, among other things, a social system stimulated by societal values,

norms and expectations, which in turn are enforced by public actors. In the case of ANIC (Akzo Nobel Indus-trial Coatings) and IKEA of Sweden we can see how the interaction between policy-makers, NGOs, the media, consumers and the public have strengthened and shaped the demand for green chemical coating products. This is especially clear during IKEA’s involve-ment in two formaldehyde crises, which took place in the 1980s and 1990s. The social tumult surrounding these crises set a snowball in motion in that it increased the com-pany’s capability and motivation to inte-grate environmental considerations in the development of their products.

The later of these formaldehyde crises, referred to by the industry as the “Big Bang”, occurred in IKEA’s largest market Germany, with one of its biggest sellers, the “Billy bookshelf ”. International media communicated the public’s fear of health risks caused by formaldehyde emission and together with environmental organiza-tion a growing uncertainty and lack of trust in IKEA was made visible. Characteristic headlines were for ex-ample: “Buying Billy is like playing Russian roulette” or “Ill because of Billy”. This period had an intense im-pact on the furniture industry as a whole and resulted in business collaboration between IKEA and ANIC with the purpose to change from a coating system based on acid curing lacquer to something more environmen-

tally benign. In the aftermath of the “Big Bang” a test-ing laboratory was set up for the purpose of developing new coating techniques. Additionally IKEA commit-ted itself to the framework of a non-governmental organization called The Natural Step. The framework provided the company with environmental knowledge and has been an important driving force for structural changes benefi cial for the development of green prod-ucts in a broad sense and in extension for chemical products as well. Nevertheless, the two formaldehyde crises and the societal pressure aimed at IKEA repre-

sent a rather practical level of understand-ing how a company is shaped over time and how it becomes in-fused with value dur-ing that process.

When analyzing these empirical incidents more thoroughly we see that both the cor-porate identity features and the organisational self-understanding of IKEA constitute an im-portant platform from which green strategies could take off. In other words: IKEA’s under-standing of “who we

are”, (for example close to the “Swedish healthy way of life” and the “Swedish reputation for safety”), helps to explain its capability to be environmentally receptive. The similar value system between The Natural Step and IKEA eased a knowledge-transfer in that it har-monised diverse ideas and ways of thinking about the environment. In this sense, corporate identity and the maintenance of certain values, has been supportive for orientating IKEA towards collaboration with ANIC and towards environmental strategies aimed at chemi-cal products.

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Greenchem Annual Report 2006 13

The marketdevelopment ofenvironmentallybenign coatingproducts

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(Policy-makers, NGOs, public opinion and the media)

Beatrice Bengtsson, Research Policy Institute

Furthermore, we argue that the downbeat public im-age and reputation of IKEA (perceptions and beliefs about the company) represent a legitimacy gap. The consumers’ perception of bad product quality and fear of health risks when buying IKEA products jeopardized its legitimacy as a trustworthy company and imposed a direct threat to their competitiveness on the market. That is how a challenged corporate identity and cor-porate image promptly motivated IKEA to raise the environmental criteria in chemical coating products. Because of this, industry regulations such as IWAY and IOS-MAT and the participation of ANIC and IKEA in GREENCHEM need to be viewed in relation to past societal legitimacy crises. With this model I want to summarize a few concluding remarks.

IKEA’s past experience of the formaldehyde crises is of great relevance for explaining its attitudes towards, and efforts of, green product development. The company’s self-understanding and the image problem supported an active interpretation process of present challenges that resulted in business collaboration with ANIC and commitment to the framework of TNS, for the pur-pose of raising the environmental criteria in products. We argue that an important overall driving force be-hind this process is the desire to maintain social legiti-macy. The need for IKEA to reconstruct a contract to society, consumers and the public facilitated the devel-opment of environmentally benign coating products, and this process appeared very important to retain a competitive position on the market.

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14 Greenchem Annual Report 2006

Nearly all wood surfaces are treated with some kind of surface coating prior to use. This treatment can take the form of oils, waxes,

paints, varnishes and so on. The function of these coat-ings can be both to protect the wood material and to enhance its aesthetic properties. The level of protection which a coating must provide obviously depends on the application, but for furniture it is desirable to have a certain level of resistance towards stains from water, grease and coffee. It can also be of interest to make the surface harder to improve scratch resistance.

Lacquers are coatings which can cross-link after appli-cation on the intended surface. By cross-linking, the coating is turned into a continuous fi lm, essentially covering the surface in plastic. This type of coating gives considerably better chemical and mechanical re-sistance than more traditional alternatives such as oils and waxes, but has the drawback of giving the surface a glossy and less natural look.

A surface coating is normally a complex mixture of components with different functions. In a lacquer, the basis for the coating is a cross-linkable binder, often a polymer. Several binders can be combined in a coat-ing to achieve the desired properties. Since the binders

Towards environment-friendly coatingreagents – epoxides and acrylates

often are highly viscous solvents or reactive diluents (solvents which can be incorporated into the hardened lacquer) are needed. For many binders, some form of catalyst is needed to enable the cross-linking after ap-plication. Wetting agents are often used to aid in the application of coating to the wood surface. Other ad-ditives alter the appearance of the coating with respect to texture and colour. All of these components affect the properties of the coating in the application and in the fi nished product.

Within Greenchem the focus in the coatings area has been on synthesising the cross-linkable binders for lac-quers; more specifi cally, the generation or introduction of cross-linking functionality in target molecules. The two main projects have been epoxidation of vegetable oil and synthesis of polyester acrylates (fi gure 1). Prod-uct evaluations have been conducted in collaboration with Akzo Nobel Industrial Coatings in Malmö. In the evaluation, products were applied to wood substrates and cured, after which they were subjected to tests of chemical resistance and hardness. The curing rate of the fi lm should preferably be higher than 20 metres per minute. The fi lm must exhibit little or no change after exposure to coffee or alcohol for one hour, or water or grease for 24 hours.

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Greenchem Annual Report 2006 15

Acrylates are esters of acrylic acid and are widely used within the coatings industry, both as binders and as reactive diluents. Cross-linking of the acrylic function-alities takes place by radical polymerisation of the dou-ble bond, initiated by UV-radiation and catalysed by photo-initiators. The synthesis of acrylates tradition-ally involves esterifi cation at 80 - 100 °C using met-al or acid catalysis. Handling of acrylic acid at these temperatures requires polymerisation inhibitors and is problematic because of its high vapour pressure and corrosive nature. Enzymatically catalysed acrylation is therefore interesting, since it can be carried out at much lower temperatures.

Mathias Nordblad, Ph. D. student, Lund UniversityUllrika Törnvall, Ph. D. student, Lund University

The target products within this project have been pol-yester acrylates, synthesised by enzymatic acrylation of hydroxyl-functional polyesters (which were produced chemically). These polyesters have a relatively high viscosity at the desired temperatures, necessitating the use of solvents or reactive diluents. While the ultimate goal is a solvent-free process, the present process is sol-vent-based and involves stepwise addition of acrylic acid at 50 °C reaction temperature. With this proc-ess, we have successfully introduced acrylic acid into hydroxyl-functional polyesters with molecular weights in the range of 1000 to 2000. In the evaluation, these polyester acrylates were able to achieve adequate curing rates and good resistance to water, grease and alcohol.

As an alternative to acrylates, environmentally benign cationic UV curable coatings can also be based on epoxidized oils. Epoxidation is one of the most impor-tant reactions for functionalization of the C-C double

bond, giving vegetable oils and fatty acids a more re-active group than the unsaturation. Fatty epoxides in the market today are produced by a chemical process using a peracid for oxygen transfer to the double bonds in the fatty acid. The peracid is usually formed in situ from hydrogen peroxide and acetic or formic acid with a strong mineral acid or ion exchange resin as catalyst. The peracid can also be generated using enzyme cata-lysed peroxygenation of carboxylic acid, and within

Greenchem we have developed a solvent-free chemo-enzymatic process, which is milder and generates fewer by-products. Both soybean and linseed oil have been successfully epoxidized using this process.

The epoxidation reaction rate depends on the choice of raw material, the amount of enzyme catalyst, the hydrogen peroxide concentration and the reaction temperature. At high hydrogen peroxide concentra-tion and a temperature of 40˚C, the reaction is com-pleted within 24 hours for linseed oil. Unfortunately, these conditions are not optimal for lipase stability. For an economical process, the lipase stability in presence of hydrogen peroxide has to be improved. There are several possible approaches for achieving this, for ex-ample by fi nding other more stable lipases, by protein engineering or by changing the enzyme preparation. These options are currently being evaluated within Greenchem.

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16 Greenchem Annual Report 2006

Surfactants are substances that have one water-soluble part and one fat-soluble part. Because of this structure they tend to accumulate at inter-

faces: at an organic-aqueous interface their fat-soluble part will be in the organic phase and the water-soluble part in the aqueous phase. Because of this behavior surfactants are very useful when making emulsions of an organic phase in water or of an aqueous phase in oil.

Enzymatic synthesis of sugar based sur-factants

Emulsions of both types are common components of food, and emulsions are formed when organic dirt is removed with water and surfactants. Still other appli-cation examples of surfactants include action as help-ing substances in pharmaceutical preparations and as additives in concrete to improve its ability to fl ow into the molds.

Alkanolamides are environmentally friendly surfactants present in many products we use in our daily lives such as shampoos, soaps,

dishwashers, hard surface cleaners and rust inhibitors. They are widely used and have become very popular due to their high skin tolerance, good biodegradability and low toxicity.

Alkanolamides are chiefl y produced from coconut oil, by reacting coconut fatty acids with alkanolamines and there are several chemical procedures available using either high temperature or chemical catalysts to achieve the desired reac-tion. Recent efforts in alkanolamide synthesis have focused on improving product quality in terms of purity, col-our and odour. Several strategies have been tried, e.g. the use of an alkaline chemical catalyst together with post treatment, or the addition of deodor-izers and anti-oxidants to the process.

Within Greenchem we attempt a differ-ent approach; that of using an immobilized enzyme (a lipase) for alkanolamide production. Lipases are highly versatile catalysts that are widely used to produce fats and oils for food applications. The reactions are typi-cally carried out in an organic solvent, such as hexane. However, the use of organic solvents is undesirable in processing of food and personal care products. There-fore we decided to optimize the lipase-based process in a reaction system containing only a liquid mixture of the reactants. This approach is very attractive since it

both makes the process more environmentally benign and improves process economy.

Our efforts resulted in a very simple process set up which looks promising for implementation in indus-try. Shortly, an enzyme reactor, as depicted in Figure 1 is loaded with fatty acid and enzyme and brought to reaction temperature (about 90 ºC). Then half of the alkanolamine is added to initiate the reaction and the

rest of the alkanolamine is added step-wise within 2 hours. The reaction is then allowed to proceed for two more hours under vacuum and fi nally termi-nated by fi ltering off the enzyme.

The product obtained was highly pure alkanolamide in the form of slightly off-white solid, free from any unpleas-ant odour. Post treatment was thus unnecessary. The physical appearance and chemical composition of the prod-uct was found to be comparable to that of the so-called super amides, the best quality products currently avail-

able. Our study clearly shows that enzymatic synthe-sis provides an attractive and environmentally benign alternative to the conventional chemical approaches currently used for the production of high quality al-kanolamides.

Dietlind Adlercreutz, Research Associate, Lund UniversityPär Tufvesson, Ph.D. Student, Lund University

Annika Karlsson, Akzo Nobel Surfactants

Synthesis of Alkanolamide Surfactants

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Greenchem Annual Report 2006 17

In order for a surfactant to be useful, its physico-chem-ical properties must be suitable: they must be effective in making emulsions, solubilising different products, etc. In the past it was enough that the surfactant had good technical performance and an acceptable price. However, nowadays surfactants are evaluated also with respect to biodegradability and environmental impact. Surfactants made from renewable resources and having low environmental impact are gaining in importance and in the Greenchem programme we are very active in this development.

We have chosen to make surfactants belonging to the alkyl glycoside group. In these, the water soluble part is a carbohydrate, which can originate from a large variety of renewable raw materials. Typically it can be glucose, derived from starch. The fat-soluble part of the alkyl glycoside is a fatty alcohol that can be obtained from a vegetable oil by hydrolysis followed by reduction. The key step in the synthesis of alkyl glycosides is to cou-ple the water-soluble carbohydrate and the fat-soluble alcohol. A major obstacle is that the two reactants are very poorly soluble in each other, which makes it dif-fi cult to make them react.

The enzymes that we use to couple carbohydrates with alcohols are glycosidases. In their normal function, these enzymes catalyze the cleavage of bonds between

The effi cient preparation of alkyl glycosides is a chal-lenging task. Although there is still a long way to an industrially viable process, important steps on the way have been taken by combination of a good synthesis strategy, better enzymes and process engineering.

Patrick Adlercreutz, Project leader, Lund University

Figure: Process scheme for the enzymatic synthesis of hexyl glucoside from glucose and hexanol. The reaction occurs in the aqueous phase in the reactor on the left. Extraction with water is used to remove unreacted glucose from the organic phase. The re-sulting hexyl glucoside is recovered by adsorption. After desorption and evaporation, a pure product is obtained.

carbohydrates and alcohols in aqueous reaction me-dia. However, by using a reaction medium contain-ing mainly alcohol and carbohydrate and only small amounts of water, the reaction can be reversed. The challenge is to fi nd an enzyme that works effi ciently under those conditions. Previously described enzymes did not work so well and therefore other options were evaluated. Good performance was discovered for gly-cosidases originating from thermophilic microorgan-isms. These enzymes have been cloned and produced within the Greenchem programme and are now used for synthesis of alkyl glycosides.

Even with the new, better enzymes relatively moderate product concentrations were achieved and only with relatively short alcohols. Different engineering ap-proaches are thus applied to improve the process. In the direct reaction between glucose and an alcohol, the reaction stops because it comes close to the chemical equilibrium position. In order to obtain more product, it was proven benefi cial to remove the product initially formed, thereby shifting the equilibrium. Product re-moval was achieved by adsorption in a column con-taining aluminium oxide or a similar absorbent. In order to recover the product, it was eluted from the absorption column. This procedure for in situ product recovery considerably improves the process. A process scheme for the entire process is shown below:

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18 Greenchem Annual Report 2006

Development of novel biocatalysts

Discovery of novel enzymes from organisms growing in many different ecological niches, in combination with gene isolation and re-

combinant production have erased some of the fi rst identifi ed hinders, e.g. limited access, for use in indus-trial biocatalysis. The availability of genes, and pos-sibilities to produce the encoded enzymes combined with the improved possibilities to determine struc-tures, further facilitate our understanding of the mol-ecules and our possibilities to develop them further by site-directed and random mutation strategies.

Thermostable enzymes and adaptationsThe reasons to choose thermostable enzymes for de-velopment is related to their intrinsic thermostabil-ity, possibilities for pro-longed storage, increased tolerance to organic solvents, as well as low activity losses during processing, which are relevant arguments for choosing these enzymes as stable scaffolds for development into ro-bust biocatalysts. In the Greenchem program we have, after an initial da-tabase screening, selected thermostable candidates for development in or-der to create good pos-sibilities for optimizing function in already stable enzymes.

An enzyme or protein can be called thermosta-ble when it is shown to have an unfolding temperature (Tm), or a long half-life at a temperature above the thermophile boundary for growth [>55 °C]. Most, but not all proteins from thermophiles are thermostable. Extracellular enzymes, e.g. many polysaccharide modi-fying glycoside hydrolases (GH) show high thermosta-bility, as they cannot be stabilized by cell-specifi c fac-tors like compatible solutes.

Adaptations of the biomolecules to extreme conditions, like high temperature (Figure 1), involve a compro-mise of stability and fl exibility in order to optimise the functional state of proteins rather than to maximize stability. The free energy of stabilization of unrelated globular proteins of mesophilic origin correspond to a few weak interactions, and the difference between a thermostable protein and a protein of mesophilic origin, corresponds to only a few additional interac-tions. In addition, despite several statistical studies of primary sequences, no general strategies in terms of preferred amino acid exchanges are to be expected and very small 3D-structural alterations may hence suffi ce to cope with the various extreme conditions. (For more information of use and development of thermostable

enzymes, see the recent review by P. Turner, G. Mamo & E. Nordberg Karlsson, on “Potential and utilization of ther-mostable enzymes in bi-orefi ning” , accepted for publication in Microbial Cell Factories.)

Strategies for en-zyme improvementIn vitro mutation and evolution strategies, uti-lize site-specifi c, random or semi-random changes in the protein coding sequence. The random strategies were originally often used to increase sta-bility of non-thermosta-ble enzymes with desired activities, using the tem-

perature of the screening assay as selection pressure.

Development of specifi city has got increased attention (as the natural selection is not expected to prioritize variants suitable for artifi cial industrial conditions). With time, semi-random strategies are often selected over random as the methods of choice, as this reduces the library size needed for successful screening. To select interesting regions for diversifi cation, in a semi-random

Figure1. Hot environments can be used for isolation of microor-ganisms and/or novel genes

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Greenchem Annual Report 2006 19

strategy, structural knowledge is demanded, and in line with this trend, we have within Greenchem, chosen to structure determine one interesting novel enzyme can-didate (Figure 2), allowing use of both semi-random and site-specifi c development strategies.

Development of a screening method can bea challengeFrancis Arnold, one of the pioneers, in random mu-tagenesis, coined the expression “you get what you screen for”, which states the necessity of using a rel-evant screening assay in order to improve enzymatic

Figure 2. Two views of the experimental electron density maps of the beta-glucosidase Bgl3B from Thermotoga neapolitana. a) shows a well-fi tting alpha-helix (yellow) superimposed on the experi-mental electron density map (light blue). b) shows, in addition to the map, the heavy atom substruc-ture (green), corresponding to the positions of methionine residues, allowing phasing statistics.

performance. Direct measurement of the product of interest is however not always straightforward, and for easy quantifi cation the methodology should ideally in-clude both easy quantifi cation of high enough accuracy, and allow high (or at least high enough) throughput, as well as take into account that enzyme variants might show different expression levels. During the year, an assay for screening of alkyl-glucoside production has been developed within the Greenchem programme (Figure 3), taking advantage of the possibility to use coupled enzyme reactions.

Detection: Synthesis Hydrolyses

Liquid culturesPrescreen

org. phaseaq. phase

Reverse hydrolyses

Figure 3. Overview of the main steps in the screening method (left) decribed in the thesis of M. Gräber (right)

Eva Nordeberg Karlsson, Project leader, Lund University

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20 Greenchem Annual Report 2006

Greenchem - External communication

Greenchem has a general goal to promote the use of white (industrial) biotechnology when-ever environmental benefi ts can be foreseen.

We see it as our task to communicate with the outside world to bring out the results generated in the pro-gramme, to proliferate the knowledge and to stimulate the creation of national and international networks concerning green chemistry, industrial biotechnology and bio-based production. In order to do this, we com-municate with other scientists, politicians, the general public and business people in different ways.

As most scientists we use scientifi c journals and exter-nal seminars and conferences to publish and get hold of new results. We organize international scientifi c conferences and seminars that are promoted through direct e-mails, university news channels and our home-page. The lectures from our seminars are also available on the Greenchem homepage.

Coverage in public media is important to reach politi-cians and a wider public. In these media we promote the great potential of white biotechnology as an envi-ronmental friendly alternative to traditional chemistry production. To reach out with this message we also take an active role in conferences directed to a wide audi-ence. On our homepage we have a general presentation about Greenchem that has encouraged journalists and others to contact us.

The industry partners of Greenchm play an important role to reach other companies that might have an inter-est in white biotechnology. The Greenchem newsletter is used to inform about the latest news and this infor-mation is often spread to business associates outside the Greenchem sphere. Giving lectures about Green-chem at conferences and seminars has also been an ef-fective way to get in personal contact with interested business people.

Josefi n Ahlqvist, Programme secretary, Technology coordinator

GREENCHEM IN MEDIAJournals and magazinesProduce ethanol and biogas in the same process. Original titel: Tillverka etanol och biogas i samma process. Column by Bo Mattiasson, Miljö & Utveck-ling, No. 2, May 2006

Green processes with Greenchem Original title: Grö-na processer med Greenchem. Interview with Annika Karlsson, Axplock (Newsletter from Akzo Nobel), No. 5, 2006

Green chemistry gives results. Original title: Grön kemi ger resultat. Interview with Glenn Svensson, Stefan Ulvenlund and Erik Andersson, Process Nordic No. 5, 2006

Slumbering chemical production can be roused to a green life. Original title: Slumrande kemikalieproduk-tion kan väckas till ett grönt liv. Interview with Harald Skogman, Biotech Sweden No. 9, October, 2006

Establishing an acters group - a new initiative within Inudstrial Biotechnology. Original title: Bil-dande av aktörsgrupp – nytt initiativ inom industriell Bioteknik, Report from the seminar ‘Swedish Indus-trial Biotechnology – today and tomorrow’, Bioteknik (Newsletter from SIK - The Swedish Institure for Food and Biotechnology), No. 4, December 2006

Greenchem is approaching industrial scale. Origi-nal title: Greenchem närmar sig industriell skala. In-terview with Josefi n Ahlqvist, Mistra (Newsletter from Mistra), No. 5, October 2006

Can agriculture replace the oil? Original title: Kan jordbruket ersätta oljan? Interview with Pål Börjesson, LTH-Nytt (Magazine from Lund University, Faculty of Engineering), No. 2, 2006

Success for Green Chemistry. Original title: Succé för grön kemi. Interview with Rajni Hatti-Kaul, LTH-Nytt, No. 2, 2006

RadioMore knowledge in a smaller worldOriginal title: Mer vetande i en mindre värld. Inter-view with Rajni Hatti-Kaul in Vetandets värld, Swed-ish Radio P1, 14th of November 2006

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Greenchem Annual Report 2006 21

Lunch break at the Greenchem symposium Effi cient biocatalytic routes for selective introduction of oxygen.The invited lecturer Vlada Urlacher, Stuttgart University, Ger-many, is talking to Bo Mattiasson, Maria Viloria-Cols, Protista Fer-mentation (at the end of the table) and three German students.

INVITED LECTURESGreenchem has been presented in a number of invited lectures held during the year, in Sweden and abroad, for example by:

Rajni Hatti-Kaul at Cairo University, Cairo, Egypt (21 February); National Chemical Laboratory, Pune, India (28 June); Indian Institute of Technology Kan-pur, Kanpur, India (17 July); Birla Institute of Tech-nology & Sciences Goa Campus, India (21 July); Bhabha Atomic Research Centre, Mumbai, India (26 July); Universidad Mayor de San Simón, Cochabam-ba, Bolivia (12 September); Universidad Mayor de San Andrés (21 September), La Paz, Bolivia; KILU dagen, Institute of Chemistry, Lund University (14 October); seminar on Swedish Industrial Biotechnology – today and tomorrow, Malmö, Sweden (8 November)

Patrick Adlercreutz at Kemikaliedagarna 2006, Tylösand, Sweden (28 September)

Bo Mattiasson at Oil Crops seminar at Swedish Uni-versity of Agricultural Sciences, Alnarp, Sweden (14 November)

Josefi n Ahlqvist at a course on Energy Crops, arranged Biogas Syd and Agellus, Eslöv, Sweden (6 December)

GREENCHEM SEMINARSBulk Chemicals by Industrial Biotechnology, Environmental and Economic aspectsA Greenchem seminar by Assoc. Prof. Dr Martin Patel, Department of Science, Technology and Society at Utrecht University, The Netherlands. Date and place: 7th November 2006, Environ-mental and Energy Systems Studies, Lund Uni-versity

Swedish Industrial Biotechnology - today and tomorrowA BioteknikForum seminar in cooperation with Greenchem. Date and place: 8th November 2006, Elite Savoy Hotel, Malmö

Effi cient biocatalytic routes for selective intro-duction of oxygenA highly specifi c Greenchem symposium with in-ternational lecturers. Date and place: 9th Novem-ber 2006, Elite Savoy Hotel, Malmö

Green ChemicalsGreenchem hosted one of the parallel sessions dur-ing Sustainable Innovation Fair. Date and place: 21st November 2006, Skandinvium, Göteborg

Lennart Holm, Chairman of the Board, Perstorp AB at the parallel session Green Chemicals

GREENCHEM HOMEPAGEDuring 2006 the Greenchem webpage had 3 000 visi-tors. Since Greenchem started the homepage in 2003 there have been totally 10 000 visitors.

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22 Greenchem Annual Report 2006

PublicationsPh.D. THESESOrellana-Coca, C. 2006. Chemo-enzymatic epoxida-

tion of unsaturated fatty acids. Department of Bio-technology, Lund University, Sweden

PEER-REVIEWED PAPERSPublished 2006Crennell, S.J., Cook, D., Minns, A., Svergun, D.,

Andersen, R.L., Nordberg Karlsson, E. (2006)Dimerisation and an increase in active site aromat-ic groups as adaptations to high temperatures: X-ray solution scattering and substrate-bound crystal structures of Rhodothermus marinus endoglucanase Cel12A. Journal of Molecular Biology 356, 57-7187

Nilsson, C., Nilsson, F., Turner, P., Sixtensson, M., Nordberg Karlsson, E., Holst, O., Cohen, A., Gorton, L. (2006) Characterization of two novel cyclodextrinases using microdialysis sampling on- line with HPAEC-PAD. Analytical and Bioanalyti-cal Chemistry 385, 1421-1429

Ramchuran, S. O., Vargas, V., Hatti-Kaul, R., Nord-berg Karlsson, E. (2006) Production of a lipolytic enzyme originating from Bacillus halodurans LBB2 in the methylotrophic yeast Pichia pastoris. Applied Microbiology and Biotechnology 71, 463-472

Sjöström, J. (2006) Green chemistry in perspective – models for GC activities and GC policy and knowledge areas. Green Chemistry 8, 130-137

Sjöström, J. (2006) Fysikifi erat och biofi erat. Kemivärlden Biotech med Kemisk Tidskrift no. 1, s. 22-24. (related publication in Swedish)

Turner, C., Turner, P., Jacobson, G., Waldebäck, M., Sjöberg, P., Nordberg Karlsson, E., Markides, K. (2006) Subcritical water extraction and beta-glu-cosidase-catalyzed hydrolysis of quercetin in onion waste. Green Chemistry 8, 949-959

Accepted 2006Gustafsson, L.M., Börjesson, P. (2007) Life cycle

assessment in Green Chemistry - A comparison of various wood surface coatings, International Journal of Life Cycle Assessment. DOI: 10.1065/lca2006.11.280

Hatti-Kaul, R., Törnvall, U., Gustafsson, L.M., Börjesson, P. (2007) Industrial biotechnology for the production of bio-based chemicals – a cradle-to-grave perspective. Trends in Biotechnology 25, 119-124

Lathi, P., Mattiasson, B. (2007) Green approach for the preparation of biodegradable lubricant base stock from epoxidised vegetable oil. Applied Cataly-sis B: Environmental 69, 207-212

Orellana-Coca, C., Billakanti, J.M., Mattiasson, B., Hatti-Kaul, R. (2007) Lipase mediated simultane-ous esterifi cation and epoxidation of oleic acid for the production of alkylepoxystearates. Journal of Molecular Catalysis B: Enzymatic 44, 133-137

Petersson, A.E.V., Adlercreutz, P., Mattiasson B. A water activity control system for enzymatic reac-tions in organic media. Biotechnology & Bioengi-neering DOI: 10.1002/bit.21229

Tufvesson, P., Annerling, A., Hatti-Kaul, R., Adler-creutz, D. Solvent-free enzymatic synthesis of fatty alkanolamides. Biotechnology & Bioengineering DOI: 10.1002/bit.21258

Turner, P., Mamo, G., Nordberg Karlsson, E. Poten-tial and utilization of thermophiles and thermosta-ble enzymes in biorefi ning. Microbial Cell Factories(accepted for publication)

Turner, P., Svensson, D., Adlercreutz, P., Nordberg Karlsson, E. A novel variant of Thermotoga neapol-itana ß-glucosidase B is an effi cient catalyst for the synthesis of alkyl glucosides by transglycosylation. Journal of Biotechnology (accepted for publication)

Törnvall, U., Orellana-Coca, C., Hatti-Kaul, R., Adlercreutz, D. (2007) Stability of immobilized Candida antarctica lipase B during chemo-enzy-matic epoxidation of fatty acids. Enzyme and Mi-crobial Technology 40, 447-451

CONFERENCE ABSTRACTS and POSTERSAdlercreutz P. Grön Kemi – Vad är det? Oral pres-

entation at Kemikaliedagarna 2006, organised by the Swedish Plastics and Chemicals Federation, Tylösand, 26-28 September 2006

Hatti-Kaul, R., Orellana-Coca, C., Törnvall, U., Adlercreutz, D., Mattiasson, B. Lipase mediated production of epoxides and alkylepoxystearates. Poster presented at Environmental Biocatalysis: From Remediation with Enzymes to Novel Green Processes, Cordoba, Spain, April 23-26, 2006

Klintman, M., Sjöström, J. The chemical enteprise, the public, and the environment: toward a better

chemistry? Presented at the XVI ISA World Con-gress, Durban, South Africa, 23-29 July 2006 (in a section about paradigm change in public image of science and technology)

Lathi, P.S., Mattiasson, B. Biodegradable lubricant base stock from epoxidised vegetable oil. Poster presentation at Gordon Research Conference, Ox-ford, UK, August 27-31, 2006

Lathi, P.S., Mattiasson, B. Green approach for the preparation of biodegradable lubricant base stock from epoxidised vegetable oil. Oral presentation

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Greenchem Annual Report 2006 23

at 10th Annual Green Chemistry & Engineering Conference: Designing for a Sustainable Future: Resources & Renewables, Washington DC, June 26-29, 2006

Nordberg Karlsson, E., Turner, P., Svensson, D., Logan, D., Adlercreutz, P. Use and development of ß-glucosidases from Thermotoga neapolitana, for alkyl-glycoside production. Poster presented at the International Congress on Biocatalysis, Hamburg, Germany, September 3-7, 2006

Nordberg Karlsson, E., Turner, P., Svensson, D., Logan, D., Adlercreutz, P. Use of a novel variant of Thermotoga neapolitana ß-glucosidase B for the synthesis of alkyl glucosides by transglycosylation. Poster presented at Extremophiles 2006, Brest, France, September 17-21, 2006

Petersson, A. Wax esters produced by solvent-free energy-effi cient enzymatic synthesis and their ap-plicability as wood coatings. Oral presentation at World Conference and Exhibition on Oilseed and Vegetable Oil Utilization, Istanbul 14-16 August,

2006, Abstract page 4Törnvall, U., Adlercreutz, D., Hatti-Kaul, R. Fatty

epoxides produced with industrial biotechnology. Poster presented at World Conference and Exhibi-tion on Oilseed and Vegetable Oil Utilization, Is-tanbul, August 14-16, 2006

MASTER THESESAmadi, E.I. (2006) Optimization of chemo-enzymat-

ic epoxidation of allyl ethers. Master thesis, Depart-ment of Biotechnology, Lund University

Badenes, S. (2006) Chemo-enzymatic epoxidation of oils. Master thesis, Department of Biotechnology, Lund University

Cui, Y. (2006) Site-directed mutagenesis of a cycloma-ltodextrinase of thermophilic origin, and evaluation of the effect on hydrolytic and transglycosylating activity. Master thesis. Department of Biotechnol-ogy, Lund University

Ekwe, E. (2006) Site-directed mutagenesis of ß-glu-cosidase-A from Thermotoga neapolitana (TnBglA) for alkylglycoside synthesis. Master Thesis. Depart-ment of Biotechnology, Lund University

Megyeri, M. (2006) Molecular design of a thermosta-ble ß-glucosidase originating from Thermotoga nea-politana for alkyl glycoside synthesis applications. Master thesis. Dept. of Biotechnology, Lund Uni-versity

Pohl E. , Prahl M. (2006) Enzymatic production of polyester acrylates. Master thesis. Dept. of Biotech-nology, Lund University

Graeber, M. (2006) A novel direct screening method for evaluation of alkyl glucoside producing ß-glu-cosidases. Master Thesis. Dept. of Biotechnology, Lund University

Rundbäck F. (2006) Reaction conditions for produc-tion of alkyl glucosides by reversed hydrolysis using BglB from Thermotoga neapolitana in a two-phase system. Master Thesis. Dept. of Biotechnology, Lund University

Cecilia Orellana-Coca defended her theses in January 2006. On the top pictures we see the opponent Prof. John Woodley and Cecilia herself. Below, Prof. Bo Mattiasson announces in the presence of the opponent and the commitee member Prof. Sten Stymne that Cecilia now is Ph D. On the last picture we see Maria Andersson, Di-etlind Adlercreutz and Rajni Hatti-Kaul shar-ing the moment with Cecilia.

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24 Greenchem Annual Report 2006

StaffThe Board, from the left: Karl Hult, Agne Svanberg, Torbjörn Brorson, Harald Skogman (chairman), Britt Marie Bertilsson (Mistra) and Kirsti Siirala.

The Board

Industry

Annelise LarsenIKEA of Sweden

Ralph NussbaumIKEA of Sweden

Hans JungvidProtista Fermentation

Johanna BrinckACO HUD NORDIC

Christer MartinssonAarhusKarlsahmn/Binol

Ulf ÅkerströmACO HUD NORDIC

Torbjörn WärnheimACO HUD NORDIC

Annika KarlssonAkzo Nobel Surfactants

Ingegärd JohanssonAkzo Nobel Surfactants

Eva ÖsterbergAkzo Nobel Surfactants

Daniel RömePerstorp Speciality Chemicals

Merja LämsäAarhusKarlshamn/Binol

Maria Viloria ColsProtista Fermentation

Stefan JeppssonAkzo Nobel Industrial Coatings

Joachim RonnermarkAkzo Nobel Industrial Coatings

Glenn SvenssonAkzo Nobel Industrial Coatings

Stefan UlvenlundAstraZeneca

Katarina EkelundAstraZeneca

Stefan LundmarkPerstorp Speciality Chemicals

Mircea ManeaPerstorp Speciality Chemicals

PHO

TO: M

ATS N

YG

REN

PHO

TO: PR

IVA

TE

PHO

TO: PR

IVA

TE

PHO

TO: PR

IVA

TE

PHO

TO: PR

IVA

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PHO

TO: PR

IVA

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PHO

TO: PR

IVA

TE

PHO

TO: PR

IVA

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PHO

TO: PR

IVA

TE

PHO

TO: PR

IVA

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PHO

TO: PR

IVA

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Erik DahlinAarhusKarlshamn/Binol

PHO

TO: PR

IVA

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Greenchem Annual Report 2006 25

Anna PeterssonPh.D. Student Bioprocess set-up

Eva Nordberg KarlssonProject leader Biocatalyst screening, Enzyme production

Mathias NordbladPh.D. Student Acrylates

Jing LiuResearch Associate Bio-process set-up

Josefi n AhlqvistProgramme secretary, Technology coordinator

David SvenssonPh.D. Student Biosur-factants

Patrick AdlercreutzProject leader Alkyl glyco-sides, Acrylates, Bio-process set-up

Erik AnderssonProgramme secretary, Technology coordinator

Mats BennerProject leader Techno-logical Innovation Systems Analysis

Pål BörjessonProject leader Environ-mental Systems Analysis

Rajni Hatti-KaulProgramme director, Project leader Epoxides, Alkanolamides, Bio-catalyst screening

Olle HolstProject leader Enzyme production

Mikael KlintmanPost doc Technological Innovation Systems Analysis

Piyush LathiPost doc Branched fatty acids, Bioprocess set-up

Jesper SjöströmPost doc Technological Innovation Systems Analysis

Pär TufvessonPh.D. Student Epoxides, Alkanolamides

Pernilla TurnerPh.D. Student Biocatalyst screening, Enzyme production

Ulrika TörnvallPh.D. Student Epoxides, Biocatalyst screening

Ana CorreiaProject worker Alkanol-amides

Linda GustafssonPh.D. Student Environ-mental Systems Analysis

Lars J. NilssonProject leader Environ-mental Systems Analysis

Dietlind AdlercreutzResearch Associate Al-kanolamides, Epoxides

The Greenchem participants during the autumn meeting 2006Örenäs Slott, Höör

Lund UniversityStaff

Beatrice BengtssonProject worker Techno-logical Innovation System Analysis

Sangita KasturePost doc Epoxides

Bo MattiassonProject leader Epoxides, Branched fatty acids, Bioprocess set-up

Suzanne LethProject worker Alkanolamides

Gashaw MamoPost doc Biocatalyst screening and develop-ment

Fabian RundbäckProject worker Alkyl-glycosides

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26 Greenchem Annual Report 2006

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Research with practical benefi ts

The Swedish Foundation for Strategic Environ-mental Research – Mistra - supports research of strategic importance for a good living environ-ment and sustainable development.

It invests in research groups who, working alongside users, are able to contribute to solving major environmental problems.

Mistra’s programmes cut across disciplinary boundaries, and the results are intended to fi nd practical applications in companies, public agencies and non-governmental organizations.

Mistra provides funding for some twenty major programmes, each extending over six to eight years. All of them have the aim of building bridges, both between disciplines and between researchers and users.

The Foundation’s strategy is to seek to ensure that its funds produce a threefold return: strong research environments that create value for us-ers, asset management in support of sustainable development, and active communication to make the results known.

Further information can be found on Mistra´s web site: www.mistra.org.

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Contact information

Programme director Rajni Hatti-KaulDept. of Biotechnology, Lund UniversityP.O. Box 124, SE-221 00 Lund, SwedenPhone: +46 46 222 48 40Fax: +46 46 222 47 13E-mail: [email protected]

Programme secretary Josefi n Ahlqvist Dept. of Biotechnology, Lund UniversityP.O. Box 124, SE-221 00 Lund, SwedenPhone: +46 46 222 48 38Fax: +46 46 222 47 13E-mail: josefi [email protected]

For more information on Greenchem:

www.greenchem.lu.se

Speciality Chemicals from Renewable Resources

Greenchem

ANNUAL REPORT 2006Editor and layout: Josefi n Ahlqvist. Printing: Ljungbergs tryckeri AB, Klippan, 2007.