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C G Editorial I am delighted to be able to welcome Jim Bashkin to the Green Chemistry editorial team as our Associate Editor for the Americas. Jim has considerable industrial and academic experience of environmentally benign chemistry and of educational development and won one of the1998 Presidential Green Chemistry Challenge Awards. He is currently based at Washington University St Louis Missouri USA. In the front section of this issue Jim has an article on ‘taking green chemistry from laboratory to chemical plant’(see p. G41) in which he describes the new commercial route to 4-aminodiphenylamine based on nucleophilic substitution for hydrogen. This is an excellent example of a successful nucleophilic aromatic substitution reaction that does not involve dehalogenation.Traditional chemistry of this type involves the introduction into an aromatic nucleus of a halogen which is subsequently displaced. Thus all of the halogen ends up as waste typically in the form of salt (the problem is made worse by any waste produced in the initial halogenation stage e.g. hydrogen halide). Of course halogenation is more commonly used to introduce useful properties as a substituent in the final product and there is considerable scope for improving the efficiency of and reducing the waste from halogenation processes (see the article by Smith et al. p. 83). Bashkin’s article should encourage us to think of greener reaction chemistry not only in terms of better catalysis solvent substitution and new techniques but also in terms of the synthetic route.The established routes that we learn about from text books and practice as students in the teaching laboratory are not necessarily the best—especially in these environmentally-conscious days! If the production of a chemical product is environmentally unacceptable because of the nature or quantity of waste generated then we should first consider if we need to make that particular product (product substitution) then consider the route (alternative routes) and Green Chemistry April 1999 G29 C G then seek the best conditions for maximum efficiency in the selected route. Product substitution is likely to play an increasingly important role in green chemistry. As we are carried along by the euphoria of the approaching new millennium it is perhaps sobering to realise that fossil fuel-based hydrocarbon feedstock will cease to be the major raw material for the chemical and allied industries long before the end of its first century.The good news is that we can grow enough to provide the raw materials for these industries. The challenge is to make effective use of the molecules that nature provides us with in crops and to develop new products based on these. This will certainly lead to a considerable level of product substitution. One less direct environmental benefit of using crop-derived feedstocks is that while we currently invest considerable energy and generate considerable waste in oxidising hydrocarbons so as to give them functionality the building blocks of the future already have high oxygen content courtesy of nature! As with halogenation oxidation in the future will largely be carried out so as to introduce specific functionality in the product rather than to facilitate its synthesis. Alternative feedstocks is the subject of a review (p. 107) and an article about an on-going initiative (p. G39). I look forward to seeing more articles for Green Chemistry on both sustainable feedstocks and product substitution. James Clark York March 1999 Green Chemistry April 1999 G30

ISSN:1463-9262    

DOI:10.1039/gc990g29

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Several companies are developing new cleaner fuels Cleaner fuels As controls on exhaust emissions are becoming tighter producers are meeting the challenge to develop cleaner fuels. Elf Elf has launched a new fuel (Europe Environment 530 p II.4) which is claimed to reduce emissions by up to 25% as well as reduce fuel consumption by up to 5%. Shell Shell has launched an improved diesel (Shell UK Focus 10 27) which has a sulfur content at least 90% lower than standard diesel and produces fewer particulates and less smoke. The Rentech gas-to-liquids process Rentech Rentech based in Denver Colorado is currently promoting its patented technology which it claims produces fuels which exceed all current and proposed US federal and state diesel emission requirements.The process is based on Fischer-Tropsch technology which does not involve sulfur making the fuels sulfur-free. Furthermore the fuels produced contain no aromatics (making them devoid of carcinogens) burn with 80-90% less smoke than other diesels and emit less CO and NOx. For more information see http://www.gastoliquids.com. C G N EWS BP Amoco BP Amoco has announced that its service stations in the UK are to be the first in its worldwide network to move to selling an ultra-low-sulfur diesel. The new fuel already available at 75% of the company’s 1600 sites across Britain will soon be available to the remainder. BP Greener Diesel as the fuel is known emits 90% less sulfur dioxide and nearly a third less particulates and black smoke than standard diesel.This is the first phase of a much larger investment which the company plans over the next 6 years to produce a range of cleaner fuels that maximise performance but minimise exhaust emissions. A high-activity HDS catalyst for diesel fuel Cosmo Oil and Petroleum Energy Center (PEC) have developed a new hydrodesulfurization (HDS) catalyst of high activity C-603A to produce clean diesel fuel whose sulfur content is less than 0.05 mass %. The preparation of this catalyst combines the use of zeolite technology and impregnation technology to provide excellent HDS activity [Catalysis Today 45(1-4) 307-312]. C-603A possesses significantly higher activity than conventional Co-Mo/alumina catalysts.Industrial operation with this catalyst has successfully proven its high performance. New industrial processes 7-ADCA DSM will be commissioning its new 7-ADCA (7-aminodeacetoxycephalosporinic acid) plant at Delft at the end of 2000. The new facility which will create several dozen new jobs will manufacture this semisynthetic antibiotic raw material using a new green process involving genetically modified strains of Penicillium. According to the company this innovation will substantially reduce the cost of production cutting energy consumption by 35% doing away with the need for toluene (30 tonnes/year) and reducing the use of other solvents from 25 tonnes/year to just several kg/year. The new facility will have a capacity of several 100 tonnes/year Green Chemistry April 1999 G31 N EWS C G which is roughly the same as DSM's existing 7-ADCA unit; this will eventually be used for other purposes.For further information see http://www.dsmr.com. Ethyl acetate A team from the Qingdao Institute of Chemical Technology in China has developed a novel process for the production of ethyl acetate from ethanol and acetic acid. In this process sulfuric acid is replaced by zeolite H-ZSM5. Despite the fact that the conversion is slightly lower than with the conventional process the new route reduces waste and corrosion to plant is also less extending plant lifetime (Xiangdai Huagong 18(11) 49). VAM BP Amoco has announced a new technology (called LEAP) which is being used to produce Vinyl Acetate Monomer (VAM).The new process involves the same raw materials—acetic acid ethylene and oxygen as the current process. However the benefits derive from advanced reactor design and process engineering. The new system relies on a fluidised bed reactor incorporating new reactor and catalyst design and allows substantial downsizing of the plant. The new plant will be situated at the company’s site in Hull UK and will be commissioned at the end of 2000. Production volumes will be 250 000 tonnes/year. For further information see http://www.bp amoco.com. and for an article on the impact of the intensive processing on green chemistry see Green Chemistry 1(1) G15-G17.Pigment intermediate Wakayama Seika Kogyo a Japanese manufacturer has announced a new process for the preparation of its dichlodine-H yellow pigment intermediate. The technique produces the pigment with a drainage volume of virtually zero while reducing the output of wastes to 40%. Global demand for the final pigment is ca. 20,000 tonnes/year. 3 Bn Yen will be invested in the new technology at its Kainan site in Wakayama Prefecture. The first material is due to be produced in 2000 [Japan Chemical Week 39(2004) 3]. Potassium dithiocarbamate-derived oil additives A newly developed clean technology developed at the National Ukrainian Academy of Sciences at Kiev for production of a highly pure potassium Filaments of the nitrogen-fixing cyanobacterium Nostoc 73102 forming heterocysts (h; site of nitrogen fixation) and vegetative cells (v; harbouring a complete photosynthesis) G32 Green Chemistry April 1999 dithiocarbamate additive (used as oxidation inhibitor in lubricating oils) consists of synthesis of 3-aminothiolane- 1,1-dioxide from butadiene sulfur dioxide and ammonia in isopropanol (yield 85 to 90% by butadiene mass) and subsequent conversion of the resulted amine with hydrogen sulfide and potassium hydroxide in water-ethanol medium at 30 to 40°C for 3.5 h to potassium (1,1-dioxothiolan-3-yl)dithiocarbamate (yield 80.8% by amine mass) and potassium ethylxanthogenate by-product.Neither wastewaters nor solid wastes were formed. The process has been implemented in a commercial plant (capacity 150 tonnes/year) (Khim.Tekhnol. Topl. Masel 4 19-20). Renewable resources Cyanobacteria as producers of molecular hydrogen—a clean and renewable energy source 2 Hydrogen is a potential renewable replacement for fossil fuels. An attractive possibility is the direct splitting of water for generation of H2 using solar radiation. This splitting can be achieved either in photochemical fuel cells or by applying photovoltaics which directly utilizes solar radiation for electrolysis of water into H and O2. The third and most challenging option according to Dr Peter Lindblad (Department of Physiological Botany Uppsala University Sweden) is the 2 2 production of hydrogen by photosynthetic microorganisms.For photobiological H production cyanobacteria are among the ideal candidates since they have minimal nutritional requirements. They can thrive on air (N2 and CO2) water (electrons and reductant) and mineral salts with light as the only energy source. Cultivation is therefore simple and relatively inexpensive. In N2-fixing cyanobacteria H2 is mainly produced by nitrogenases but its partial consumption is quickly catalyzed by a unidirectional uptake hydrogenase. In addition a bidirectional (reversible) enzyme may also oxidize some of the molecular hydrogen. Filamentous cyanobacteria have been used in bioreactors for the photobiological conversion of water to hydrogen. However the conversion efficiencies achieved are low because the net H2 production is the result of H2 evolution via a nitrogenase and H2 consumption mainly via an uptake hydrogenase.In order to achieve significant H production rates over long time the following need to be considered l the strains used must be selected for their specific hydrogen metabolism. l the selected strains must be genetically engineered in order to produce large amounts of H2 (e.g. to increase the H2 evolution by nitrogenase and/or by the bidirectional hydrogenase as well as through the production of mutants deficient in H2 uptake activity). l the overall conditions for cultivation in bioreactors must be improved. Symbiotic cells are of fundamental interest since they in situ ‘function as a bioreactor’—high metabolism transfer of metabolite(s) from symbiont to host (‘bioreactor’) but almost no growth.Moreover international coordination is necessary and at present two major initiatives can be recognized l IEA (http://www.iea.org) Agreement of the Production and Utilization of Hydrogen Annex 14. l COST 8.18 (continues as COST 8.41) (http://www.cordis.lu/cost/). More information see Hansel A. and Lindblad P. (1998) Mini-Review Towards optimization of cyanobacteria as biotechnologically relevant producers of molecular hydrogen a clean and renewable energy source. (Applied Microbiology and Biotechnology 50 153-160) and http://www.fysbot.uu. se/fysbot/Cyano/Cyanomain5.html Monsanto stops Biopol project Scientists at the U.S.Department of Agriculture have developed wheat-based concrete C G 1996. Though significantly below today’s costs for biodegradable polymers the cost of Biopol production is still estimated to be 25-50% higher than conventional commodity polymers such as polyethylene and polypropylene. Moreover the earliest time to market is 2005. This expected cost premium of the future product and the length of time to commercialisation has limited large-scale conversion away from conventional polymers to Biopol. Facing these challenges Monsanto have over the past year sought a strategic alliance or investment partner to participate in further development of Biopol. It is as a result of failing to find such a partner that Monsanto have decided to stop the Biopol project.Wheat-based concrete Lightweight concrete products such as exterior panels for high-rise office buildings may soon be made with an unusual ingredient—wheat starch. The Agricultural Research Service (ARS) chief research agency of the U.S. Department of Agriculture and Artlo Industries Inc. of Perris California have entered into a Cooperative Research and Development Agreement today in Washington D.C. to develop test and commercialize wheat-based concrete. Artlo Industries provides concrete products for some of the world's largest construction corporations as well as for other architectural design and engineering firms. Under the new agreement ARS scientists in Albany California will provide samples of wheat-based aggregate for making the concrete to Artlo Industries.Artlo Industries will test various mixes of the concrete for strength and durability and will also determine cost-effective ways to manufacture lightweight pre-cast wheat starch-based concrete products for indoor and outdoor uses. At the ARS Western Regional Research Center in Albany plant physiologist Gregory Glenn will help develop specifications for commercial products. Glenn holds a patent for wheat-based concretes. For further information contact Martha B. Steinbock Technology Transfer Coordinator Pacific West Area Agricultural Research Service USDA 800 Buchanan St. Albany CA 94710 USA. Tel. (510) 559-5641 Fax (510) 559-5963 E-mail msteinbock@pw.usda.gov With the Biopol project Monsanto has been working on the twin objectives of delivering low-cost polymer in plants through biotechnology and winning acceptance in the market for the compostable materials based on renewable resources. Today this product is being produced through fermentation technology acquired with the purchase of the Biopol business from Zeneca in N E WS Green Chemistry April 1999 G33

ISSN:1463-9262    

DOI:10.1039/gc990g31

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G industry voluntary initiative designed to improve the performance of the chemical industry in the fields of health safety and environment (Chemical Industries Association 1992). Future predictions of world scenarios invariably foretell increased population increased economic development and extrapolated associated pollution loads upon the planet. It will fall largely to the engineering profession to come up with the means of continuing to produce the goods and services society requires whilst reducing the net output of pollutant per unit of product. The greening of engineering F E AT U R E Sue Haile1 the Environmental Co-ordinator Why the environment? The advantages to industry of implementing environmental improvements are often quoted although there is still much reluctance particularly on the part of smaller companies to tackle the issue.Many companies world-wide are going further than this and are seeking formal recognition of their achievements by applying for accreditation to one of the environmental management standards such as the International Standard BS EN ISO14001 or EMAS the Eco Management and Audit Scheme (93/1836/EEC) the European Environmental Standard. Those companies that are taking a positive attitude towards the environment are also demanding the same high standards from their suppliers and thus the pressure is pushed on down the supply chain. For example Volvo in Sweden recently asked 850 of their suppliers for a copy of their environmental policy.Reasons given by industry for initiating environmental management schemes include the need to ensure current and future compliance with legislation—there are currently 400 EC draft or established regulations dealing with environmental topics! By being proactive and taking an anticipatory approach companies may give themselves market edge and find new market opportunities. The value of the market for new environmental services and technologies has been estimated as in excess of $3.5 billion dollars world-wide and is predicted to grow to $640 billion by 2010 (Environment Council 1998). Financial savings are also an invariable result of improved environmental management either through reduced costs for raw materials utilities waste disposal or being cynical in reduced fines for at the University of Newcastle-upon-Tyne UK ing world awareness and concern for environmental issues.In fact the chemical industry is deeply concerned with reducing its environmental impact and has been at the forefront of initiative development. For example the Responsible Care programme originally set up in 1989 is an international chemical discusses the green engineer Ask any school child which colour they associate with engineering and they will inevitably say grey or brown certainly not green. The concept of the chemical engineer as a net polluter is often still an integral part of public perception and one which needs to be addressed particularly with the grow- 1 Dr Haile is Course Director of the MSc course in Clean Technology at the Department of Chemical and Process Engineering at the University of Newcastle-upon-Tyne G34 Green Chemistry April 1999 housekeeping’ or improved monitoring and targeting.Cleaner production techniques are concerned with the concept of getting more value and use from a product or service with less resulting environmental impact. Some so-called ‘green’ products have been traditionally criticised as giving less from less (e.g. a ‘green’ washing product which doesn't wash as clean). Techniques Four approaches may be mentioned in the identification of a cleaner technology although these are not definitive but are given as examples. ‘Natural Step’ Devised by Dr.Karl-Henrik Robèrt in 1988 this approach is based upon society striving to operate according to four basic rules which should not be broken (Robèrt et al. 1997). Implemented throughout Sweden with every household being given a copy! The principles are used by IKEA a major international company in the day-to-day planning and running of their operations. ENVOP Developed in 1993 by BP/Costain using a similar methodology to Hazop (Potter and Isalski 1993). Env(ironmental) Op(timisation) involves a systematic review of a process driven by key words wherein a team of specialists familiar with the process plant ask at each step what would be the effect of certain changes to the operation of the plant.Key words used for example include raised or lowered temperature pressure flow rate recycled water etc. At each stage the question is asked as to whether this would improve the environmental performance without compromising production. The desired environmental improvements are categorised with the following six areas Why the environment? Requirements for Environmental Management Certification Compliance with increasing legislation Cost saving on raw material utilities waste disposal and treatment Pressure from the public and stake holders Increased legal liability Environmental impairment insurance requirements Market advantage and opportunities Supply chain pressure non-compliance. Figures of 10% reduction in cost savings for companies during the first year of an environmental action are well documented and often result from simple good housekeeping measures.The UK Environment Council estimates that a £70 saving per employee could be made by adopting simple resource-conserving strategies. Clean technologies Recently much has been made of the move away from traditional ‘end of pipe’ solutions and the drive towards clean technology a rather definitive concept with the target of zero emissions and of cleaner production techniques which are a comparative improvement on current technologies. Implementation of clean technology usually involves product modification such as changes in raw materials or processing improvements by for example process intensification.Lower down in the hierarchy of environmental improvement methodology comes waste minimisation which should not be disregarded as it is frequently achievable at zero cost through ‘good Clean technology opportunities can apply to all stages in the life cycle F E AT U R E C G l Vapour emission reduction l Liquid emissions reduction l Solid disposal reduction l Utility consumption reduction l Noise reduction l Reduction of odiferous discharges The procedure then results in the compilation of list of potential changes to the production process and an assessment of the relative environmental benefits or drawbacks in each of the six areas listed above. This is then followed by a cost benefit analysis of the suggested options.Principles of Natural Step l Substances extracted from the earth’s crust must not systematically increase in nature. We should not extract fossil fuels and metals from the Earth’s crust at a faster rate than they are replenished. We need to decrease the use of fossil fuels and reduce mining recycle oils and metals etc. l Substances produced by society must not systematically increase in nature. Substances should not be produced at a faster rate than they are broken down. We should phase out substances that cannot be biodegraded and are persistent in the environment e.g. PCBs. l The physical basis for the productivity and diversity of nature must not be systematically deteriorated (diminished).Don’t use resources beyond the ability of sustainable development i.e. so they are replenished at the same rate as their use. This for example will effect sustainable fisheries forestry and agriculture. l We must be efficient enough to meet all basic human needs or humans must achieve the just and efficient use of energy and other resources. People must be able to meet their needs (as opposed to their wants) and resources should be equally distributed. Green Chemistry April 1999 G35 F E AT U R E C G Life Cycle Assessment Life Cycle Assessment (LCA) looks at each stage in a service or product life cycle from cradle to grave (manufacture use and disposal) and pinpoints areas of greatest environmental impact which may then be targeted for improvement.The process may also be used to compare the environmental burdens of two competing products. The concept has developed very rapidly in its application over the last decade and is widely used by companies such as Proctor and Gamble (White et al. 1995). It is now covered by an international standard (ISO14040). LCA can be used to establish criteria for Eco-Labelling of products to bolster the market of an existing product to assess whether a proposed new product will produce a real environmental improvement in product defence and to reduce the impact of an existing product. LCA is a relatively new field but with great potential for growth and application although there are still relatively few practitioners.Eco-Efficiency Fitness Compass The Eco-Efficiency Fitness Compass originated from Dow Chemicals in 1993 (ENDS 1996). It consists of a six-point compass that allows comparison of a proposed product with an existing one based on consideration of six criteria. The compass uses six dimensions of eco-efficiency. Any new product is judged against the six criteria based on achieving a maximum rating of 5. Existing products are given a hypothetical rating of two to enable the new product to achieve either a better or worse rating in comparison. Eco-efficiency criteria l Amount of energy used l Amount of materials used l Resource conservation l Ecotoxicity l Waste to landfill l Durability and functionality Conclusions The approaches described vary in the stage in the production process in which they apply.The Natural Step is a philosophical approach relying on the four thermodynamic and ecological based rules. Industry should see adherence to these rules as the guiding light in the development of all of their operations. Green Chemistry April 1999 G36 ENVOP acts very much at processing stage once the product has already been decided upon. LCA may be carried out on all or some stages in the life cycle of a product or service but should be concentrated where the environmental burden is felt to be the greatest. For example in a washing machine this would be in the ‘use’ phase due to the water and energy requirements and resultant emissions.Whilst the concept is based on a ‘cradle to grave’ assessment of environmental impact in practice the scope of the undertaking is often so vast that clearly defined system boundaries must be applied. The Eco-Efficiency Fitness Compass essentially acts as a form of life cycle assessment but with the equivalent of LCA impact criteria being placed into one of six categories. It may be used to compare an existing product with a proposed one at the design stage or to compare two or more existing products. Which tools are used to ensure less environmentally damaging products and services is a decision that should be made at the planning and design stage although as we have seen methodologies exist that are applicable further along the production and processing chain.The challenge to industry to meet the environmental requirements of the future has been issued. The engineering community has the tools and increasingly the expertise to ensure we are able to meet that challenge and will be at the forefront of the drive towards achieving sustainable development. The Eco-Efficiency Fitness Compass References BS EN ISO 14001. Environmental Management Systems Specifications with Guidance for use 1994. BS ISO 14040 Life Cycle Assessment General Principles and Practices 1994. Chemical Industries Association (1992). Responsible Care Management Systems publication CIA July 1992 ISBN 0 900 623 853. Environment Council Business and Environment Programme Handbook October 1998 Background p20. Environmental Data Services (ENDS) Report 252 January 1996 16-19 European Commission 93/1836/EEC Regulation allowing voluntary participation by companies in the industrial sector in a community eco-management and audit scheme (OJ L168 10 July 1993). Potter N.; Isalski W. H. Environmental Optimisation The ENVOP Technique Environmental Protection Bulletin 1993 26 17. Robert K.-H.; Daly H.; Hawkins P.; Holmberg J. Journal of Sustainable Development and World Ecology 1997 4 79-92. White P.; Franke I.; Hindle I. Integrated Solid Waste Management A Lifecycle Inventory Publication Chapman & Hall 1994.

ISSN:1463-9262    

DOI:10.1039/gc990g34

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

The team at the Green Chemistry Network. Left to right Helen Coombs Mike Lancaster and James Clark Green Chemistry Network As you are probably aware The Royal Society of Chemistry announced last October that it was funding the establishment of a Green Chemistry Network (GCN) based at the University of York under the Directorship of James Clark. The full team is now in place at York with the appointment of Mike Lancaster as the Network Manager and Helen Coombs as part-time Administrative Assistant. The aim of the GCN is to promote awareness and facilitate education training and practice of Green Chemistry in industry universities and schools. With this in mind we are in the final stages of putting together a Technical Advisory Panel (TAP) consisting of representatives of Trade Associations Professional Organisations Government Departments and Funding Bodies.The TAP will advise and hopefully contribute to the programmes and initiatives we develop. We are also busy recruiting network members so please copy and fill in the registration form in the back of this issue. We are producing a database of network members highlighting areas of interest and expertise and this will eventually be available to members on our GCN web site as well as in hard copy. The web site is currently being set up (hopefully it will be accessible within the next two months and will be hosted on the chemsoc.org site). So please pay us a visit and let us know how you would like to see this site developed.As we only have a very small core of people working on network activities we need to rely heavily on member volunteers. We are keen to start working on providing educational material for schools and universities. If anyone ‘copy and fill in the GCN registration form at the back of this issue’ out there has examples of processes or reactions suitable for use as simple experimental exercises which highlight green chemistry concepts please let us know. Still on the topic of education we have got together a series of articles on green chemistry for publication in Chemistry Review (Philip Allan Publishers ISSN 0959 8464) we are now looking for people to write articles for the RSC magazine Education in Chemistry aimed at 'A' level and undergraduate students.If you have any suitable topics please get in touch (email greennet@york.ac.uk). F O R U M C G Sustainable production and use of chemicals The UK Royal Commission on Environmental Pollution (RCEP) has responded to the UK Department of the Environment Transport and the Regions (DETR) consultation document on Sustainable Production and Use of Chemicals. In it the RCEP points out that it believes that the management of risks from new chemical substances is generally effective but that there is a need for an improved system for assessing the risks posed by chemical substances in use prior to 1981. In the Royal Commission’s view the solution lies in industry taking greater responsibility for the substances it produces and markets subject to appropriate safeguards.This approach should build on the existing initiatives started by the UK’s Chemical Industries Association (CIA) and legislation should reflect the greater responsibility taken by industry aim for consistency between the regulations controlling different chemicals and preserve accountability. It also points out that policies should have an international focus. In the context of self-assessment the pursuit of greater eco-efficiency should play a very important role and it was noted that the CIA already has an agreement with the DETR on energy efficiency. For further information on this consultative document see the Feature Article on page G47 of this issue of Green Chemistry.Chemicals in the European environment low doses high stakes? In the European Environment Agency (EEA) and United Nations Environment Programme (UNEP) Annual Message 2 the subject of Chemicals in the Environment is considered. The statements are aimed at raising public and political awareness on critical or emerging issues to facilitate preventative action by governments and others. The EEA/UNEP survey reveals that we may face serious if hard-to-identify risks but also that measures to reduce these risks are available. The search for greater eco-efficiency in the production and use of chemicals is partly driven by concern over the possible effects on humans and ecology of many combinations of chemicals.The weaknesses in present policies for managing chemicals in the EU will be clarified and addressed by the current European Commission review. The Green Chemistry April 1999 G37 F O R U M Environmental taxes on energy and pesticides are under active consideration in Europe C G statement makes it clear that the aim must be to strike the right balance between different approaches to the risks of chemicals and to the benefits and costs of their use. It is recognised that there is still great room for improvement since even the best chemical plants in Europe are still believed to be inefficient in their use of energy and in their production of wastes. The full text of the EEA/UNEP Annual Message 2 on the State of Europe’s Environment can be viewed at http://www.eea.eu.int/document/brochure/ chemicals/index.html.Industry uneasy about taxes The European Union seems likely to introduce an energy tax in an effort to reduce carbon dioxide emissions. However the chemical industry in Europe is very concerned about the effects such a tax would have on its global competitiveness. With energy costs in Europe already higher than those in the US and Asia CEFIC (the European Chemical Industry Council) fears that such a tax could have a very negative impact on its members. However Germany (currently holding the EU Presidency) France and the UK are considering energy taxes. A few industrialists such as Rodney Chase president of BP-Amoco are in favour of energy tax as a valid instrument in the drive for energy efficiency.Other proponents of the tax point to the possibility that the tax could be balanced by other incentives which would leave the overall tax burden essentially unchanged (Chemistry and Industry 1999). The UK Department of the Environ- G38 Green Chemistry April 1999 ment is also considering a pesticide tax (Crops 1998 extra issue 6). Such a tax is already in place in Denmark where tax on insecticides is 56% and 33% on other agrochemicals. Additionally the Danes have banned several agrochemicals in common use in many other countries. The British Agrochemicals Association (BAA) is strongly opposed to the introduction of such pesticide taxes in the UK and British farmers are worried about the consequences with many farms already in a precarious economic situation.Many farmers may decide to bring every square metre of their land into full production to stay in business reversing the great strides made in habitat creation and pollution control on farmland over the past 5 years. Environmental groups are generally in favour seeing the revenues of such a tax potentially being available for environmental projects. Sustainable development in the OECD Sustainable development was one of the five priority areas for future work of the OECD identified by the Secretary General. In the 1997 report of the high level advisory group on the environment Guiding the transition to sustainable development ; a critical role for the OECD it was noted that governmental policies on the environment and economic matters were not well connected and it was recommended that the OECD should become the leading international organisation analysing how best to harmonise policies in these areas.In response to this challenge the OECD has developed a strategy for work that should be undertaken up to the year 2001. This strategy has been endorsed by the OECD Ministers and it is intended that there will be major report to one of their meetings in 2001. A number of intermediate studies and reports will be produced in the interim and will be available on the OECD website (http://www.oecd.org/) Chemical testing programme to speed up The US Chemical Manufacturers Association (CMA) along with the White House the EPA and the Environmental Defense Fund has announced a major testing programme for 2800 industrial chemicals.These chemicals are all produced in quantities in excess of The EPA is conducting a major chemical testing programme 1 Mlb/year [Soap Cosmetics Chemical Specialities 1998 74(12) 12]. This 6-year testing programme will investigate environmental fate eco- and human toxicity and is estimated to cost $700M. The programme is in response to the finding that the majority of chemicals produced worldwide (around 100,000) have not been subjected to a full risk assessment. Audits carried out in Europe have indicated that ca. 75% of the highest production volume chemicals do not have enough toxicity data for even a preliminary assessment to be made.This mirrors surveys carried out in the US. CEFIC (the European Chemical Industry Council) has agreed to the principle of a global voluntary initiative and will aim to produce a list of around 1000 priority chemicals as well as contribute to a worldwide research programme (European Chemical News - Chemscope 1998 21-23). In an additional measure the CMA has initiated a five-year research programme costing $100M which is designed to examine the basic mechanisms of interaction of chemicals with the environment rather than assess specific chemicals individually (Chemistry and Industry 1999 131). The major areas of the project can be divided into five themes—exposure assessment risk measurement carcinogenicity respiratory toxicology and hormone disruption.Other themes are how chemicals affect the immune system the nervous system ecosystems and the atmosphere. The work will be based predominantly at the Chemical Industry Institute of Toxicology in California. Results will be disseminated on a website. New funding opportunity for water and watersheds research A EPA/NSF/USDA Partnership for Environmental Research will provide grants for research on water and watersheds. Approximately $7 million will be awarded with an award range of $100,000 to $300,000 per award per year and an approximate duration of 2-3 years. Applications may be made up to May 28 1999 and awards will be made in early Fiscal Year 2000.Further information is available from the website http://es.epa.gov/ncerqa/rfa/water.html. Additional information on this and other calls for proposals are available in HTML and PDF formats on the NCERQA Web site at http://es.epa.gov/ncerqa/ The greening of government The UK House of Commons Environmental Audit Committee has produced a report entitled ‘The Greening of Government’ which applauds sustainable development but regards achievements as being disappointing. It is the intention of the Committee to audit the governments green performance on the basis of annual departmental reports which should state what has been done in practical terms.The Chairman of the Committee John Horam MP has stated that they would like to see a high profile debate in parliament on environmental matters led by the Deputy Prime Minister. He recognises that environmental debates get driven by the big issues such as climate change and that targets for emissions cuts for example can be over-ambitious. He pointed out that while the big issues need to be examined so do the more immediate concerns of greening government (Business Standards November 1998). IENICA The Interactive European Network for Industrial Crops and their Applications IENICA is a project funded by DGXII of the European Commission. It has been running since 1997 under the coordination of Melvyn Askew at the Central Science Laboratory Sand Hutton York UK.The project has 14 partners in the EC which includes all member states IENICA internet home page http://www.csl.gov.uk/ienica with the exception of Luxembourg the project also has a new partner in Hungary and has close links with Poland. The IENICA project has four targets l Establishment of an interactive network to promote industrial and scientific collaboration between science and industry and between member states. l Preparation of individual state reports on potential / challenges / opportunities for industrial crops in individual member states and EU overall. This will be available during 1999. l Development of an interactive database of industrial plants and products available free of charge on the internet at http://www.csl.gov.uk/ienica l Three seminars for industry and research w Natural Fibres Performance Forum—Needs Challenges Opportunities May 1999.Copenhagen Denmark. w Vegetable Oils—Meeting the Needs of Industry. June 1999. Rotterdam Netherlands. w Speciality Chemicals for the 21st Century. September 1999. Nice France. IENICA publishes a regular Newsletter with articles on Europeanwide developments in industrial crops; authors range from project partners to industry contacts to officers at the European Commission. We welcome suggestions for contributions from our readers. The newsletter also has information on forthcoming industrial crops events including IENICA seminars.To receive copies of the newsletter or add your name to the mailing list please contact s.hugo@csl.gov.uk. IENICA launched its internet site in February 1998 it is accessed directly at http://www.csl.gov.uk/ienica. The website has a database of crops information F O R U M C G on forthcoming industrial crops events and background details of the project. The crops database provides information on a wide range of plants with novel applications in industry. Crops listed are for example those which yield alternatives to oils normally derived from the petrochemical industry for use as lubricants fuels plastics detergents paints; plants which can be used to provide energy when burned; plants which yield quality fibres which can substitute for carbon- or petrochemicalderived sources.There is also information on plants which are sources of therapeutic chemicals dyes carbohydrates paper or pulp and traditional food crops for which non-traditional uses have been developed. Environmental benefits accrue from the use of these bio-renewable products. Entries are described botanically and in terms of quality characteristics constraints on production market potential crop production statistics agronomy pests and diseases also useful contacts and links to EC funded projects It is proving to be a useful tool to producers end-users industry and academia alike. Another feature of the website is a ‘Contacts’ page where we have direct links with useful websites in UK Europe and worldwide including contacts with industry. For further information on the project or to submit information to the website please contact s.hugo@csl.gov.uk or telephone + 44 (0)1904 462259. Chemical Education Foundation The Chemical Education Foundation (CEF) has developed a range of publications and videos on chemical product stewardship regulatory training and safe chemical handling. Many of these publications are free. The CEF was formally known as The Natural Association of Chemical Distributors Educational Foundation (NACDEF) and is a non-profit educational organisation that serves as a primary worldwide resource for educational outreach and training for businesses communities and individuals served by the chemical industry. The CEF website address is http://nacdef.com/ and the contact is Jennifer Aleknavage (Fax +1 703 527 7747). Green Chemistry April 1999 G39

ISSN:1463-9262    

DOI:10.1039/gc990g37

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G James Bashkin and his wife Shelley Shray with the 1994 Thomas and Hochwalt Award which he shared with Michael Stern P R O F I L E James K. Bashkin was born in Iowa City USA in 1958 but spent most of his early years in Tucson Arizona. After attending the University of Arizona for a year he transferred to the University of California at Irvine. After graduating in 1977 he went to Oxford to do his graduate work with Malcolm L. H. Green. His graduate work involved primarily the structural and synthetic chemistry of molybdenocene dimers. He obtained a D. Phil. in organometallic chemistry in 1982 and then moved to R. H. Holm’s group at Harvard where he was an NIH postdoctoral fellow. In the Holm Group he worked on synthetic models for the iron-molybdenum cofactor (FeMoco) of nitrogenase iron thiololate species and a soluble cobalt sulfide that contains the Co8S6 cluster unit found in the mineral pentlandite.James Bashkin– patents. He has remained active in the green chemistry arena as a consultant for Flexsys and through a new program to broaden the scope of his original NASH reaction so that it can serve as a general method for halide-free bond formation. Recently Professor Jim Bashkin was chosen as one of 125 scientists and engineers world-wide to contribute to a document to help define environmentally sustainable technologies for the Institute for Prospective Technological Studies in Seville an institute of the EC’s Joint Research Centre.The final report is to be delivered to European Policy makers. Information on Professor Bashkin’s green chemistry research can be found at http://wunmr.wustl.edu/Faculty/Bashkin/ jkbgreen.html. Contact information Tel.+1 (314) 935-4801. Fax +1 (314) 935-4481. Email bashkin@wuchem.wustl.edu our Associate Editor for the Americas He then took a position at Monsanto in the Chemical Sciences Department of Corporate Research. During this time (1985-91) he developed programs on solid-state reference electrodes a new green chemistry version of nucleophilic aromatic substitution and catalytic chemotherapy based on functional mimics of ribozymes. The green chemistry was recently commercialized in Europe by Flexsys; it is an example of nucleophilic aromatic substitution for hydrogen (NASH).Flexsys is a joint venture between Solutia (formerly Monsanto’s chemical company) and Akzo Nobel. In 1994 Professor Bashkin and co-inventor M. K. Stern shared Monsanto’s highest science and technology award the Thomas and Hochwalt prize for this chemistry and in 1998 they and a group of colleagues received the President’s Green Chemistry Challenge Award for Alternative Synthetic Pathways (http://www.epa.gov/opptintr/greenchemistry/ past.htm). Professor Bashkin was appointed to the Editorial Advisory Board of Chemical Reviews in 1991 co-chaired the NSF Organometallic Workshop (1988-1990) and served on an NSF review panel for SBIR grants. In 1991 Professor Bashkin joined the chemistry faculty at Washington University as an Assistant Professor. He has continued to pursue bio-organic and - inorganic approaches to catalytic drugs and to study the mechanism of RNA transesterification and hydrolysis. In 1998 he guest-edited a thematic issue of Chemical Reviews on ‘RNA/DNA Cleavage Chemistry’ and contributed the article on ribozyme mimics. Professor Bashkin has published more than 45 papers and is an inventor on 6 U.S. G40 Green Chemistry April 1999

ISSN:1463-9262    

DOI:10.1039/gc990g40

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Taking green chemistry from laboratory to chemical plant Cl James Bashkin Roger Rains and Michael Stern give a personal perspective on We sought to reach this objective by eliminating the use of chlorobenzenes altogether thereby avoiding any salt disposal issues. Our process which was designed to impact the rubber chemicals industry is best described as nucleophilic substitution for hydrogen. One version of the key reaction is shown overleaf F E AT U R E developing a new route to 4-aminodiphenylamine (4-ADPA) Over the past several years we and a team of talented colleagues have had the opportunity to follow a new green chemistry process from the stage of problem definition to initial laboratory discovery through pilot-scale studies and on into commercial practice.The chemistry was initiated at Monsanto Company and finalized at Flexsys with participation of Solutia in the latter stages. Here we describe how this work evolved while offering some personal perspectives that may aid other chemists and engineers in the discovery and implementation of their own green chemistry. A green process has been developed for the synthesis of 4-ADPA an important intermediate in the synthesis of antioxidants/antiozonants for automobile tyres Cl (1) + HCl Cl NO2 + (2) NO2 PNCB (3) NO2 + KCl + CO + CO2 + organics NH NH2 + H2O (4) 4-ADPA The traditional chemistry process catalyst + Cl2 + HNO3 NH 4-NDPA H2 catalyst for 4-ADPA synthesis The chemistry previously employed by Monsanto to make ADPA involved the synthesis of 4-nitrodiphenylamine (4-NDPA) as shown in the following sequence of reactions Cl NHCHO K2CO3 PNCB + xylene 185 °C 4-NDPA The above chemistry requires p-nitrochlorobenzene (PNCB) which must be separated from its ortho isomer after synthesis.The p-chloro group is only introduced so that it can later be removed to be discarded in an aqueous waste stream containing KCl. The green chemistry process for 4-ADPA synthesis A new process was therefore developed with the objective of the dramatic reduction or elimination of as much inorganic organic and aqueous waste as possible. C G Starting Materials for 4-ADPA Synthesis Traditional chemistry aniline formic acid nitrobenzene chlorine K2CO3 (consumed) xylene (solvent for final step) Green chemistry aniline nitrobenzene tetramethylammonium hydroxide (reusable catalyst) Green Chemistry April 1999 G41 C G –O N+ H O H2O –O F E AT U R E H N OH– HN H N+ –O OH– ON NH The indicated (nitroso) compound is the predominant product formed and is subsequently hydrogenated to form 4- ADPA an important intermediate in the synthesis of antioxidants/antiozonants for automobile tyres.It turned out that the project was able to achieve its environmental goals and also reduce the total manufacturing cost of 4-ADPA enough to justify the decision to invest in the commercialization of a new chemical plant.This new chemical plant demonstrates the long-term commitment of Flexsys to the rubber chemicals business and has solved many of tomorrow’s environmental problems. Success factors of the green chemistry approach Certain features are unique to this project but others can be generally applied to the commercial development of new green chemistry. ‘green chemistry is not solely process engineering – it can encompass entirely new chemical reactions’ l It was essential to know the appropriate chemical literature but not to pay it too much homage. In fact clues to our new chemistry were found in the literature from the turn of the century,1,2 and inspiration came from the recent work of Stahly3 and Makosza.4,5 However we found our success by defining the ideal result and working backwards rather than by collating what was known and attempting to rework it.The ideal result in this case was the simple and direct coupling of nitrobenzene and aniline G42 Green Chemistry April 1999 and this turned out to be the exact solution to the problem. l It was essential that the discovery team did not insist on redefining the problem into one that was readily solved without regard for the main goals. Certainly redefining the problem can be a valid strategy but it is a luxury that is not always available in an industrial setting especially when the chemical compound under investigation is already a welldefined product with an established sales base.This again can provide difficulty at the academic/industrial interface in academics a solution to any important problem is inherently valuable while in industry one is constrained to solve the current problem of actual commercial (and environmental) importance. For example our initial laboratory success occurred with DMSO used as a solvent and NaH as the base; Successes of the green 4-ADPA process In comparison to the process traditionally used to synthesize 4-ADPA the Flexsys process generates 74% less organic waste 99% less inorganic waste and 97% less waste water. In global terms if just 30% of the world’s capacity to produce 4-ADPA were converted to the Flexsys process chemical waste would be reduced by 74 million lb./year and waste water would be reduced by 1.4 billion lb./year.this demonstrated the concept of NASH chemistry applied to 4-ADPA synthesis but would be impractical for an industrial process. In our interactions between discovery and production teams it was helpful for the discovery teams to learn about the full manufacturing and business context of the problem and the constraining parameters imposed by this context during the process of formulating potentially new synthetic routes. l It was essential to have clear communication between those who best understood the nature of the waste problem and those who worked on discovering solutions to the problem. Potential problems that can derail or impede such communication are political or ‘turf’ considerations and issues of secrecy.The latter can be a particular stumbling block for academic/industrial collaborations because it may be difficult for companies to reveal their largest environmental problems to outsiders. It may be helpful to note that all three present authors were employed at Monsanto Company when our project was started. To be successful it helped to have a team with a broad professional background incorporating both experts in the field and scientists new to this area. We benefited from excellent coworkers in synthetic chemistry physical and analytical sciences and chemical engineering and from invaluable management support. Of course many of our coworkers appeared as coauthors of papers6-10 and coinventors of patents.11-21 The special contributions of Chi Chao Chieng James M.Allman Brian T. Kirtley Frederick D. Hileman Karen A. Andreshak Ralph A. Genetti and Larry C. McCune were also recognized by designating them as cowinners with ourselves of our Presidential Green Chemistry Challenge Award administered by the United States Environmental Protection Agency (for more information on this important program see http://www.epa.gov/ opptintr/greenchemistry). l The synergy of our team was essential to its success as was the courage of management to commit the funds for a pilot plant and subsequent full-scale chemical plant. This required a successful crossing of many borders initially within Monsanto (MTC) central research and operating units and then between Monsanto and Akzo Nobel (AKZO) during the creation of Flexsys a joint venture comprising the combined the rubber chemicals businesses of the two parent companies.To further complicate matters Monsanto divested itself of its chemical business during the final stages of the project to create the new company Solutia (SOI). It would have been easy for the program to fail simply due to complex and shifting alliances but the importance of green chemistry and the combined financial and environmental benefits of the new process were kept clearly in mind by those involved. We are certainly grateful to all of our colleagues named and un-named who contributed to this process.‘the enormous power of chemistry to do good (and make money) should not be overlooked’ Conclusions There are several aspects of this program that we hope will become general descriptors for the field of green chemistry. l It is clearly possible to develop green chemistry that actually decreases associated process costs even in the absence of any accounting for environmental costs. l Green chemistry is not solely process engineering it can encompass entirely new chemical reactions discovered tomorrow that were unknown today. l As successful as traditional chemical synthesis has been in providing the reactions upon which today’s industry and modern society depend there is ample room for new paradigms even in seemingly simple bond-forming reactions.l Excellent communication amongst research process and business groups is vital for the continued development of relevant green chemistry. l The enormous power of chemistry to do good (and make money) should not be overlooked amongst the flood of new technologies from other fields and the negative connotations sometimes associated with the ‘central science’. Chemistry can prevent pollution not just create or measure it all while providing truly essential goods for modern society. Creative new chemistry and engineering are we suspect far less likely without strong industrial and academic research labs and strong ties between them. References 1 A.Wohl and W. Aue Chem. Ber. 1901 34 2442-2450. 2 A. Wohl Chem. Ber. 1903 36 4135-4138. 3 G. P. Stahly and D. R. Bell J. Org. Chem. 1989 54 2873-2877. 4 M. Makosza and A. Kwast J. Phys. Org. Chem. 1998 11 341-349. 5 M. Makosza and K. Sienkiewicz J. Org. Chem. 1990 55 4979. 6 M. K. Stern F. D. Hileman and J. K. Bashkin J. Am. Chem. Soc. 1992 114 9237-9238. 7 M. K. Stern and B. K. Cheng J. Org. Chem. 1993 58 6883-6888. 8 M. K. Stern B. K. Cheng F. D. Hileman and J. M. Allman J. Org. Chem. 1994 59 5627-5632. 9 M. K. Stern B. K. Cheng and J. Clark New J. Chem. 1996 20 259-268. 10 J. K. Bashkin ‘Benign Organic Synthesis’ Environmental Protection Agency document EPA/600/ R-94/125 Cincinnati Ohio 1994. 11 M. K. Stern and J.K. Bashkin Method of preparing 4-aminodiphenyl amine U. S. Patent 5,117,063. 12 M. K. Stern and B. K. Cheng Process for preparing N-aliphatic substituted p-phenylenediamines U. S. Patent 5,252,737. 13 M. K. Stern and J. K. Bashkin Process for preparing p-nitroaromatic amides and products thereof U. S. Patent 5,331,099. 14 M. K. Stern and B. K. M. Cheng Process for preparing p-nitroaromatic amides and products thereof U. S. Patent 5,380,946. 15 M. K. Stern and B. K.-M. Cheng Process for preparing substituted aromatic amines U. S. Patent 5,382,691. 16 M. K. Stern and B. K. Cheng Process for preparing p-nitroaromatic amides and products thereof U. S. Patent 5,436,371. 17 M. K. Stern and J. K. Bashkin Method of preparing 4-aminodiphenyl amine U.S. Patent 5,453,541. 18 M. K. Stern and B. K.-M. Cheng Process for preparing substituted aromatic azo compounds U. S. Patent 5,552,531. F E AT U R E C G 19 M. K. Stern J. M. Allman J. K. Bashkin and R. K. Rains Method of preparing 4-aminodiphenylamine U.S. Patent 5,608,111. 20 M. K. Stern and B. K.-M. Cheng Process for preparing substituted aromatic amines U. S. Patent 05618979. 21 M. K. Stern and J. K. Bashkin Method of preparing 4-aminodiphenyl amine U. S. Patent 05623088. Biographies From 1985 to 1991 James Bashkin (Email:bashkin@wuchem.wustl. edu) worked for Monsanto and during that period he initiated programs on solid-state reference electrodes a new green chemistry version of nucleophilic aromatic substitution and catalytic drugs based on functional mimics of ribozymes.In 1991 he joined the chemistry faculty of Washington University in St Louis as an Assistant Professor. Following a career of 27 years with Monsanto Roger Rains (Email rkrains@flexsys.com) joined Flexsys when it was created by Monsanto (now Solutia) and Akzo Nobel. he has been involved for many years in process development process improvement cost reduction and quality improvement from lab to pilot plant to commercial scale. Michael Stern (Email michael.k.stern@monsanto.com) joined Monsanto in 1988 and has been involved in a variety of research programmes relating to the development of novel chemical processes and pharmaceutical processes. He is currently Director of Technology and Senior Science Fellow within Monsanto's Agricultural Sector's Chemical Herbicide Business. James Bashkin and Michael Stern were co-recipients of the Monsanto Thomas and Hochwalt Science and Technology Award in 1994 for their roles in the discovery of the aromatic substitution chemistry used in the development of Monsanto's new process to 4-ADPA. Green Chemistry April 1999 G43

ISSN:1463-9262    

DOI:10.1039/gc990g41

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G P E R S P E C T I V E S reaction 1 to give the ether and a molecule of HX RX + ROH " ROR + HX reaction 1 HX + ROH " RX + H2O reaction 2 (X can be bromide or iodide but bromide is the ideal candidate). The clever step is that under the reaction conditions chosen the HX reacts with a molecule of alcohol to regenerate the alkyl halide (reaction 2). Thus the catalytic cycle is established and reaction 1 can take place again. This cycle continues until HX is lost from the system or until a phase separation occurs which limits the efficiency of the reaction considerably. However selectivity is very high in all cases studied. Even 2-phenylethanol derived ethers and halides reacted cleanly without the expected competing elimination to give styrenes.Cyclopropylmethanol also reacts cleanly without acid-catalysed rearrangement further indicating the applicability of the process. Chiral alcohols are racemised suggesting that an SN1 mechanism operates (at least for secondary alcohols). New clean etherification Methods to prepare ethers generally involve the use of strong acids or bases. For example the classical Williamson synthesis involves alkoxides and alkyl halides generating an equivalent of salt. Other routes involve strong acids to either protonate an alkene which is captured by an alcohol or to dehydrate an alcohol to give a carbocation followed by reaction with an alcohol. In both cases the acid must be separated and neutralised again leading to salt formation.Chris Strauss and his research team at CSIRO Molecular Science in Clayton Australia have come up with a simple and elegant route to symmetrical ethers which avoids these harsh wastegenerating procedures (Chem. Commun. 1999 283). Their approach uses an alkyl halide as catalyst. The alkyl halide reacts with an alcohol molecule according to New epoxidation methods Improved methodologies for the preparation of epoxides are the subject of much effort. Two contrasting pieces of work have recently been published in Chemical Communications. The first (1998 p 2211) by Corma et al. describes improvements to the mesoporous titanium silicate Ti-MCM-41. This is a large pore version of the industrially important TS-1 zeolite and can be used to epoxidise larger alkenes than the zeolitic material.Corma and his co-workers describe two methods that improve the efficiency of epoxidation using tert-butyl hydroperoxide. One method is to silylate the surface of the material leading to a very hydrophobic material; the second is to remove water from the reaction media. Both approaches are thought to work due to the more efficient separation of water from the catalyst reducing the amount of diol formed. The diol is a catalyst poison and suppressing its formation results in an Epoxidation of alkenes can be carried out using hydrophobic Ti-MCM-41 with t-BuOOH or (n-C7F15)2CO with H2O2. increase in selectivity to epoxide from ca. 90% to almost 100% in the case of cyclohexene.A second quite different approach is that of Sheldon et al. (Chem. Commun. 1999 263) who have used the fluorous biphase technology pioneered by Horvath in the mid-90s. (For a recent review see I. T. Horvath Acc. Chem. Res. 1998 31 641) This approach is centred round the remarkable ability of some heavily fluorinated compounds to be totally immiscible with organics at one temperature but mix completely at a slightly higher temperature. Thus many catalysts can be made with long perfluoro ‘pony tails’ such that they are soluble in fluorous phases. Raising the temperature slightly allows them to mix with an organic phase containing reactants and carry out catalysis. Following this the temperature is dropped and the fluorous phase containing the catalyst is removed.Sheldon has applied this concept to the hexafluoroacetone / hydrogen peroxide system a known epoxidising mixture. Whereas hexafluoroacetone is a very volatile compound and requires extreme measures to efficiently condense it and keep it in the reactor longer chain perfluoroketones do not suffer this G44 Green Chemistry April 1999 drawback. Catalytic quantities of perfluoroheptadecanone were used with hydrogen peroxide to efficiently epoxidise a range of alkenes in high yield. The only co-product is water making this process very environmentally acceptable. Remarkable pressure-dependent changes in diastereoselectivity in supercritical carbon dioxide A further example of the remarkable utility of supercritical fluids was recently published by Christopher Rayner and his co-workers at Leeds University in the UK (Chem Commun.,1999 247).This time the supercritical medium was carbon dioxide. This is easily made supercritical and there is a great deal of scope for variation in both temperature and pressure both of which can change the properties of the fluid. Their latest article demonstrates the benefits of having the ability to tune the fluid to suit the reaction. The oxidation of chiral sulfides such as those derived from the sulfur-containing amino acids cysteine and methionine using tert-butyl hydroperoxide and an Amberlyst ion exchange resin leads to sulfoxides which are themselves chiral centres.Thus a pair of diastereomers is possible. In a remarkable piece of work they have managed to show that variations in pressure during the reaction can change the diastereoselectivity from 0% up to a maximum of 95%. Such diastereoselectivity is possible in conventional solvent systems but only with very careful choice of bulky substituents on the substrate as opposed to the simple S-methyl and methyl ester substituents used in this work. Up to 50 bar pressure no d.e. was observed. Increasing the pressure further resulted in a steady increase up to 95% d.e. at pressures of just under 200 bar. Higher pressures led to a drop in d.e. to about 40%. The origin of these effects is still not known and is under investigation by the Leeds group.Whether these effects are general is not yet clear but would have enormous implications for synthetic chemistry where the achievement of high levels of control over diastereoselectivity is vitally important on many cases but can often only be achieved with the use of complex directing groups if at all. However Rayner has indicated that other as yet unpublished results indicate that the phenomenon may be quite widespread. For more information on supercritical carbon dioxide see Chem. Eng. News 15 February 1999 12 and Chem. Br. April 1999. Fluorous biphasic catalysis with metal-centred catalysts This fluorous catalysis approach has been used by other workers recently in a variety of catalytic applications.Mikami et al. (Synlett 1998 1347) have developed a perfluoroalkyl sulfonamide complex of a lanthanide. This represents an interesting twist as lanthanides are usually used as catalysts because of their ability to function as Lewis acids even in the presence of water. They have shown that the lanthanide species is capable of remarkably efficient catalysis using benzotrifluoride as solvent in a monophasic system. For example anisole could be acylated in essentially quantitative yield in 2 hours at only 40 oC. This compares very favourably with conventional methods which require significant quantities of catalyst and generate a great deal of waste. Alcoholysis of anhydrides and Diels–Alder reactions are also discussed. Other organometallic catalytic systems have also been investigated.Sinou e t a l. (Tetrahedron Lett. 1998 9439) have used Pd complexes of polyfluorinated phosphines to carry out allylic alkylations in perfluorinated solvents/ THF biphasic mixtures. The mixtures became monophasic at around room temperature. Substitutions were typically complete in a few minutes and the catalyst could be separated from products by cooling to 0oC. P E R S P E C T I V E S Curran and co-workers (Tetrahedron Lett. 1998 8691) have effected catalytic enantioselective protonation of Sm enolates using fluorous proton sources. They achieved ee’s of up to 90%. Shift towards green practices in crop protection In a press release from Frost and Sullivan the international marketing consultancy company (http://www.frost.com) the results from a new study on the European market for crop protection are summarised.Research and development has enabled better and more environmentallyfriendly products to be launched onto the market and there will always be demand for crop protection. The shift towards green practices has led to the development of new low-dose products with better pest-targeting capacities. New active ingredients which are less harmful to the environment and better able to target pests can earn high revenues for manufacturers thus stimulating the market. Traditionally crop protection has proved an excellent method for minimising costs while maximising yields and some farmers have been reluctant to reduce the volume of crop protection used per hectare.However this attitude is declining as concern for the environment heightens and farmers have the option of adopting integrated crop management as a positive step towards Pesticides are now being applied in lower doses using improved application methods Green Chemistry April 1999 G45 C G improving the environment. It is believed that farmer’s reliance on crop protection will over time decline. Vapour-free dissolution There is increasing pressure for the chemical industry to avoid volatile organic solvents especially chlorinated compounds. The problem is to find alternatives. A little known area of chemistry ionic liquids could soon provide at least one way to carry out reactions without volatile solvents.Chemists at several centres around the world have found that they can turn a solid into liquid simply by tweaking their ions so that the crystalline form is less stable than the liquid. Important work particularly relevant to petrochemicals is being carried out at the French Petroleum Institute France. The team have recently developed an ionic liquid system for converting feedstock alkenes using hydrogenation isomerization and hydroformylation reactions. They also have a process available for licensing that uses ionic liquids to dissolve transition metal catalysts for converting butenes into iso-octenes one of the raw materials for PVC plasticizers. The Queen's University of Belfast UK have another group leading the way to clean reactions.The team have raised more than £2 M (Euro 2.9 M) of support from industry and elsewhere. This funding will help develop ionic liquids for clean syntheses of linear alkyl benzenes the regioselective alkylations of aromatic amines and alcohols for epoxidations the low-temperature reduction of aromatics to alicyclics and the oligomerization of butenes for making synthetic lubricants such as polyisobutene. [The European Chemist (January 1999) 1 22]. P E R S P E C T I V E S the lost oxygen atom and puts a pincer grip on the CO fragment. This doesn’t last long however because the hold is so loose that the pincer can be rapidly pushed aside by the carbon atom of an additional compound mixed into the reactor by the researchers.Once the pincer is completely forced away the carbon dioxide is transformed to a molecule with three carbon atoms—acetone [Angewandte Chemie International Edition 1999 38(3) 362-363]. C G Terephthalic acid production The synthesis of terephthalic acid from p-xylene is one of the largest scale processes in the chemical industry. The hydrocarbon is currently oxidised using air in acetic acid as solvent some of which is lost by ‘burning’ under the forcing conditions of the oxidation. The process is run at high temperatures and in the presence of metal bromides leading to potentially severe corrosion problems. R. L. Holliday and his co-workers B. Y. M.Jong and J. W. Kolis (J. Supercritical Fluids 1998 12 255) have found that water at very high temperatures (close to supercritical and supercritical) is an excellent medium for the reaction. They have successfully oxidised a range of alkyl aromatics with oxygen as the oxidant—the high temperature water being an excellent solvent for oxygen. They required a catalyst for reaction to occur—as in the traditional process MnBr2 and CoBr2 were found to be the best with other metal salts giving large quantities of char and coupling reactions. Converting the greenhouse gas carbon dioxide into acetone Koji Tanaka and co-workers from the Institute for Molecular Science in Myodaiji Japan have developed a ruthenium naphthyridine complex that transforms carbon dioxide into acetone an important feedstock for the chemical industry.In an electrolysis apparatus the Japanese team force the CO2 to give away one carbon atom by transferring it to another carbon dioxide molecule which is thus transformed into an electrically charged carbonic acid molecule. The remaining CO fragment is recompensed for its loss by the addition of a ruthenium compound to the reaction mixture. The compound takes the place of G46 Green Chemistry April 1999 Biodiesel The British Association for Bio Fuels and Oils (BABFO) believes that oilseed rape could supply 10% of the UK’s diesel requirements for 2020 if the tax on its purchase was reduced to 10% of that on fossil-sourced diesel.The use of rape oil could be increased by blending it into fossil diesel at 5% as is done in France and Sweden. Biodiesel is cleaner than fossil diesel; its carbon dioxide emissions are balanced by its fixation in the plant and it requires no added sulfur lubricant. Bob Fox and Dan Ginosaur from Idaho National Engineering and Environmental Laboratory have discovered a chemical process to turn waste food-grade French fry oil into a higher quality biodiesel fuel faster less expensively and with less waste than current processes. The new process uses a solid catalyst and eliminated the need for a base liquid which also eliminates the need for acid to neutralise the base and water to rinse away the acid—a problem of current processes.The process is continuous and produces food-quality glycerol as a byproduct. Sales of the glycerol to the food and beverage industry could pay for the entire process bringing the price of the biodiesel down to the same price as regular petrodiesel. Glyphosate 1999 is the 25th anniversary of glyphosate—the enormously successful nonselective herbicide developed by Monsanto but now off-patent in all countries except the USA where is does not come off-patent until 2000. Traditionally the key intermediate disodium iminodiacetate (DSIDA) in glyphosate production has been synthesised by the Strecker process which requires ammonia formaldehyde hydrochloric acid and hydrogen cyanide. The last of these chemicals is acutely toxic and requires special handling.Furthermore since the process exothermically generates potentially unstable intermediates special care must be taken to prevent runaway reactions. The overall process also generates up to 1 kilogram of waste for every 7 kilograms of product and this waste must be treated prior to disposal. The new Monsanto process for DSIDA production relies on the copper-catalyzed dehydrogenation of diethanolamine. The raw materials have low volatility and are less toxic. Process operation is inherently safer because the dehydrogenation reaction is endothermic and therefore does not present the danger of runaway reaction. In addition this ‘zero-waste’ route to DSIDA produces a product which after filtration of the catalyst is of such quality that no purification or waste removal is necessary for subsequent use in the manufacture of glyphosate. Superabsorbent polymers for pesticide application Helmut Brueggemann received the Huels Innovations Prize for 1998 for his application of superabsorbent polymers (used in hygiene products) to pesticide application. The pesticides are incorporated into the superabsorbent polymers which are then fixed in the root area of the crops to achieve a controlled release of the substance over a long period of time. Pesticides will have to be applied only once a year with this new Culigel technology. Active substance requirements can be reduced by 90% and crop yield can be increased— e.g. by 20% in the case of potatoes. Further information can be obtained on http://www.huels.de. Read any green chemistry papers? If you have read any items relating from your literature reading which could be in the ‘Perspectives’ section of Green Chemistry please send them to James Clark or Duncan Macquarrie [email greenchem@york.ac.uk; Fax +44(0)1904 434533 or +44(0)1904 423559]

ISSN:1463-9262    

DOI:10.1039/gc990g44

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

UK Government consultation paper on sustainable production and use of chemicals1 Becky Allen reports on a paper which has been attacked by some sections of the chemical industry be needed to fund the basic research the RSC argues. ‘Industry is unlikely to do this [basic research] on its own. Latest figures for the UK chemicals industry show a declining spend on all research and development as a percentage of sales,’ the RSC points out. for not being radical enough In its submission to the Department of the Environment Transport and the Regions (DETR) the IChemE says ‘We are concerned that the focus [of the consultation paper] on extending current legislative regimes fails to encourage the radical approaches required to drive sustainability .. . Sustainability will only be achieved by a quantum change in approach by both industry and Government and this message is sadly lacking.’ According to the IChemE ‘Very urgent action is needed by the chemical industry to set in motion profound structural changes which can only flow from a reexamination of the chemistry fundamentals which underpin it and the development of the process technologies to bring about the changes.’ These sentiments are echoed in the Royal Society of Chemistry’s comments on the consultation paper. As well as needing ‘step changes that go well beyond good housekeeping’ the RSC says that the sustainable production and use of chemicals requires invention and development of new chemical science and technology.‘a step change is needed within academia and industry’ (IChemE and RSC) According to the RSC this ‘step change’ will depend on a new approach by many academic and industrial chemists as well as business managers ‘Sustainable performance can be a real commercial opportunity and worth the investment.’ But Government money will ‘Government money will be needed to fund basic sustainable production research’ The Government’s consultation paper says that a review of policy on chemicals in the environment is necessary because of factors like public attitudes towards chemicals and the slow progress of risk assessing existing chemicals. In its response to Government the Chemical Industries Association (CIA) says ‘A review is clearly needed.Despite industry's demonstrable improvements in performance there has been a change in the degree of risk acceptable to society from chemicals in the environment and this must be addressed.’ Many consultees support the Government’s suggestion of using a stakeholder forum to improve dialogue between industry and the public although` some doubt the impact it can have. According to the CIA:‘Transparency is essential in chemicals management [but] broadening public involvement will be difficult given the practical obstacles to genuine public dialogue.’ Room for agreement? As well as the IChemE CIA and RSC over 100 other organisations and individuals responded to the consultation paper C G F E AT U R E that posed several questions about the legal and policy framework (see box).The comments will form the basis of a White Paper due for publication in April. Comments came mainly from the chemical industry—including companies trade associations and professional societies but a significant number of environmental and health groups also responded. As a result there are divergent views among consultees on how to effect change although most agree that change is necessary. Differences of opinion are pronounced on several issues including risk assessment voluntarism and substitution. ‘There are large differences between consultees’ views on the proper scope of the review effective methods for speeding up assessments the correct rationale for controlling chemicals and information exchange with the public,’ says the DETR.Most environmental groups that responded to the consultation paper are signatories to the Friends of the Earth (FoE) Joint statement on chemicals and health. The statement calls for a phase- Key questions l How effective is current legislation and is framework legislation on chemicals needed at European or international level? l How might an eco-efficiency programme be advanced in the chemical industry? l How can the risk assessment process be accelerated? l How can the decision-making process be made more transparent? Green Chemistry April 1999 G47 F E AT U R E C G out of persistent or bioaccumulative chemicals and a move towards a positive licensing system for chemicals placing the onus to prove that a chemical is safe on industry.Consultees from the chemical industry reject such proposals. ‘We are specifically opposed to a regulatory approach based on the ‘reverse burden of proof’ comparative assessment and hazard substitution,’ says the CIA. Risk assessment substitution and the carrot or the stick? Despite widespread agreement among consultees that risk assessment under the Existing Substances Regulation must be speeded up there is no consensus about how to achieve this. Environmental groups also regard the risk assessment process as deeply flawed. But many consultees from industry agree that new schemes are not the way forward.‘We have severe doubts about a duplicative scheme being created in the UK and firmly believe that no new national schemes should be started for the testing and assessment of chemicals. Global resources for chemicals management are already scarce and those that do exist must be focused on the key issues,’ says CIA. Italian green chemistry recognition program ‘change must be based on the voluntary principle’ (CIA) ‘regulatory action is essential’ (Friends of the Earth) Although most responses from the chemical industry stress that any change must be based on voluntary principles environmental groups say that the stick must accompany the carrot. According to FoE ‘The crucial role of Government [is] in transforming industry and stimulating innovation through technology-forcing regulation rather than voluntary agreements which tend to reduce innovation .. . Friends of the Earth does not consider that a voluntary approach is adequate either to protect human health or to promote innovation. Regulatory action is essential.’ G48 Green Chemistry April 1999 Environmental organisations favour a positive licensing system for chemicals Greenpeace also thinks that innovation can be stimulated by a greater emphasis on substitution. The group’s submission argues that substitution will create new markets for the replacement of hazardous chemicals by less hazardous alternatives. According to Greenpeace ‘Substitution of hazardous chemicals is I TA LY C G Green chemistry in Italy On February 22nd Italy's National Interuniversity Consortium of Chemistry for the Environment (INCA) launched a annual recognition program of industrial contributions in ‘Green Chemistry’ / ‘Clean Chemical Production Processes.’ The formal recognition program was part of the annual INCA meeting in Venice Italy where representatives of some 30 Italian universities gathered to discuss their programs in chemistry for the environment and to map out research and education strategies for the Consortium over the next 5 years.INCA recognized three companies this year. The first award went to Lonza Intermediates and Additives S.A. for its ‘Process Optimization of the Oxidation of o-Xylene to Phthalic Anhydride by the Selective Transformation of Reaction Intermediates.’ The second company honored was Mapei S.p.A.for its development of ‘Very Low VOC Emitting Adhesives ‘and the third Solvay Italia for its process ‘Recovery of Residues from Fume Purification Plants and their Reutilization as Feedstocks.’ Each of the 1999 INCA recipients received a dish engraved citing their specific contribution. Participants in the recognition program included representatives from the Italian Ministry for Industry the Italian Institute for Health the Venetian Regional Program for the Modernization of Industry in Porto Marghera and the U. S. Environmental Protection Agency's Green Chemistry Program. The INCA recognition program is the first OECD country to formally implement an awards program as one of the recommendations contained in the OECD Working Party for Sustainable Chemistry report of October 1998. The OECD recommendation for member countries to implement industrial recognition programs was based on the highly successful Presidential Green Chemistry Challenge Awards program now in its fourth year in the United States. For further information contact Professor Pietro Tundo University of Venice tundop@unive.it or the INCA website hydra.unive.it/inca one feature of a new policy that has real potential to move the chemicals sector onto a more sustainable path.’ 1Sustainable Production and Use of Chemicals Consultation Paper on Chemicals in the Environment. Department of the Environment Transport and the Regions (1998). (http://www.environment.detr.gov.uk/sustainable/ chemicals/consult/index.htm).

ISSN:1463-9262    

DOI:10.1039/gc990g47

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G F E AT U R E out of persistent or bioaccumulative chemicals and a move towards a positive licensing system for chemicals placing the onus to prove that a chemical is safe on industry. Consultees from the chemical industry reject such proposals. ‘We are specifically opposed to a regulatory approach based on the ‘reverse burden of proof’ comparative assessment and hazard substitution,’ says the CIA. Risk assessment substitution and the carrot or the stick? Despite widespread agreement among consultees that risk assessment under the Existing Substances Regulation must be speeded up there is no consensus about how to achieve this. Environmental groups also regard the risk assessment process as deeply flawed. But many consultees from industry agree that new schemes are not the way forward.‘We have severe doubts about a duplicative scheme being created in the UK and firmly believe that no new national schemes should be started for the testing and assessment of chemicals. Global resources for chemicals management are already scarce and those that do exist must be focused on the key issues,’ says CIA. Italian green chemistry recognition program ‘change must be based on the voluntary principle’ (CIA) ‘regulatory action is essential’ (Friends of the Earth) Although most responses from the chemical industry stress that any change must be based on voluntary principles environmental groups say that the stick must accompany the carrot. According to FoE ‘The crucial role of Government [is] in transforming industry and stimulating innovation through technology-forcing regulation rather than voluntary agreements which tend to reduce innovation .. . Friends of the Earth does not consider that a voluntary approach is adequate either to protect human health or to promote innovation. Regulatory action is essential.’ G48 Green Chemistry April 1999 Environmental organisations favour a positive licensing system for chemicals Greenpeace also thinks that innovation can be stimulated by a greater emphasis on substitution. The group’s submission argues that substitution will create new markets for the replacement of hazardous chemicals by less hazardous alternatives. According to Greenpeace ‘Substitution of hazardous chemicals is I TA LY C G Green chemistry in Italy On February 22nd Italy's National Interuniversity Consortium of Chemistry for the Environment (INCA) launched a annual recognition program of industrial contributions in ‘Green Chemistry’ / ‘Clean Chemical Production Processes.’ The formal recognition program was part of the annual INCA meeting in Venice Italy where representatives of some 30 Italian universities gathered to discuss their programs in chemistry for the environment and to map out research and education strategies for the Consortium over the next 5 years.INCA recognized three companies this year. The first award went to Lonza Intermediates and Additives S.A. for its ‘Process Optimization of the Oxidation of o-Xylene to Phthalic Anhydride by the Selective Transformation of Reaction Intermediates.’ The second company honored was Mapei S.p.A.for its development of ‘Very Low VOC Emitting Adhesives ‘and the third Solvay Italia for its process ‘Recovery of Residues from Fume Purification Plants and their Reutilization as Feedstocks.’ Each of the 1999 INCA recipients received a dish engraved citing their specific contribution. Participants in the recognition program included representatives from the Italian Ministry for Industry the Italian Institute for Health the Venetian Regional Program for the Modernization of Industry in Porto Marghera and the U. S. Environmental Protection Agency's Green Chemistry Program. The INCA recognition program is the first OECD country to formally implement an awards program as one of the recommendations contained in the OECD Working Party for Sustainable Chemistry report of October 1998. The OECD recommendation for member countries to implement industrial recognition programs was based on the highly successful Presidential Green Chemistry Challenge Awards program now in its fourth year in the United States. For further information contact Professor Pietro Tundo University of Venice tundop@unive.it or the INCA website hydra.unive.it/inca one feature of a new policy that has real potential to move the chemicals sector onto a more sustainable path.’ 1Sustainable Production and Use of Chemicals Consultation Paper on Chemicals in the Environment. Department of the Environment Transport and the Regions (1998). (http://www.environment.detr.gov.uk/sustainable/ chemicals/consult/index.htm).

ISSN:1463-9262    

DOI:10.1039/gc990g48

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Cleaner synthesis seminar On 19 January this year a half-day meeting was held at Lancaster University’s conference centre on the topic of ‘Cleaner Synthesis’. I hope I need not write of the importance of this area to readers of this journal since green chemistry is of course primarily concerned with minimizing the impact our activities have upon our ever more fragile environment. Clean synthesis is of course a multifaceted area that covers chemical aspects such as strategies for the synthesis of chemicals and immobilization strategies through to engineering-based approaches such as new technologies for reactor design monitoring of effluent and energy usage etc. We decided however in this meeting to focus on the chemical/materials aspects of the subject with a view to providing a tight focus for the afternoon.At this point I should mention the input of Lancaster Synthesis whose generous sponsorship made the meeting possible. Owing to our tight schedule we began proceedings rather earlier than usual and kicked off with an enthusiastic talk from Steve Howdle of Nottingham University. Steve told us how his group are using supercritical fluids such as carbon dioxide in polymer synthesis and processing. An unusual aspect of the work appears to be the effect of stirring on the progress of these radically initiated polymerization reactions. Steve discussed the observed poor performance of reactions carried out with efficient stirring in terms of interactions of the reactor vessel wall with the polymerization system.We also heard how polymers processed with supercritical fluids are being used to imbibe drugs and possibly even produce Green Chemistry April 1999 G49 C G E V E N T S new artificial bone materials. Next to speak was Ron Grigg of Leeds who discussed some new cascade cycloaddition reactions based mainly on 1,3-dipolar additions with nitrones. As well as producing some exciting new synthetic chemistry we heard how cascade-type processes can provide cleaner synthetic alternatives to traditional stepwise synthesis by reducing the number of work-up steps required both in the laboratory and on a larger scale. Continuing with this theme of waste minimization and ease of work-up our next speaker James Clark from York discussed a large range of silicaimmobilized catalysts that are finding uses in an ever more numerous areas of chemical manufacture.New catalysts included solid bases and acids and new oxidants. The alternative support materials to inorganics such as the silicas are synthetic polymers. Work began in this area back in the 1970s but oddly it’s only recently that the chemical community has begun to appreciate the advantages of polymer-supported strategies. Our next speaker David Sherrington has been at the forefront of research in this area continuously from the initial 1970s burst of interest through E V E N T S C G to the current renaissance in the field. His talk centred on polyimide support materials and included descriptions of how the nature of the polymer support can effect the course of the reaction.The advantage of polyimides over the conventional polystyrenes is of course superior thermal stability. Our final speaker David Gani broadened the scope of the meeting by describing how the design of drug molecules can be achieved by careful examination of active sites in the relevant enzymes. He also described his groups preliminary work on using functionalized polytetrafluoroethylene another candidate for a support that has good chemical and thermal stability. Yale Corporate Environmental Leadership Seminar Yale University are running a Corporate Environmental Leadership Seminar in New Haven Connecticut between June 6 and June 17 1999.The course is intended to offer state-of-the-debate assessments of contemporary issues to sharpen tools needed for environmental management and to enhance the strategic thinking of participants. The course is delivered by a distinguished group of faculty members from Yale’s Law Medical Management and Forestry and Environmental Studies Schools as well as outside experts through a mix of discussions problemsolving exercises and case studies. A mix of professionals from various industries as well as government and non-governmental organisations are invited to enhance discussion and interaction across sectors. The 1999 Seminar will place emphasis on international issues public and private roles practical implications of industrial ecology and leadership activities.Further information can be obtained from Janet Testa or Marion Chertow at the Yale School of Forestry and Environmental Studies 205 Prospect Street New Haven Connecticut 06511- 2189 USA email:janet.testa@yale.edu or via the web site www.yale.edu/cels. G50 Green Chemistry April 1999 Clearly supports based on this stable and tough polymer could in the future revolutionise supported synthesis. Thus we brought the proceedings to a close and retired to our apres-seminar discussion groups lubricated by generous sponsorship from Lancaster Synthesis in Cartmel College’s bar! Overall the event was well attended with a good number of people who had travelled some distance.Those of you who missed the event can all look forward to the sequel in due course. Steve Rimmer The Polymer Centre Lancaster University Green 'swap shop' The University of Sheffield's Environmental Business Network in conjunction with the RSC Green Chemistry Network and Yorkshire and Humberside Chemicals Sector are organizing a 'Swap Shop' on the theme of ‘Waste Minimization and Measurement’. The Swap Shop will be held on 17 May at the Tankersley Manor Hotel in Barnsley UK. The morning session will include several presentations on relevant legislation together with examples from industry on Best Practice. The afternoon will take the form of poster session with participants able to display information on 'Technology Offered and Wanted' There will also be a series of surgeries in the afternoon where participants will be able to 'drop in' and discuss issues with relevant experts. For more information contact Angela Bottom on (0114) 222 4600 E.mail:EBN@sheffield.ac.uk or greennet@york.ac.uk Visit the GREEN CHEMISTRY homepage...... l FREE electronic access to news articles l FREE electronic access to full contents of Issue 1 http://www.rsc.org/greenchem Arranging or attending any green chemistry events? If you have any items about conferences seminars etc. which could be included in the events or conference diary sections of Green Chemistry please send them to James Clark or Duncan Macquarrie [email greenchem@york.ac.uk; Fax +44 (0)1904 434533 or +44 (0)1904 423559]

ISSN:1463-9262    

DOI:10.1039/gc990g49

出版商:RSC    

年代:1999

数据来源: RSC