摘要:

C G G U E S T E D I TOR I A L C G Green Chemistry— one year on Alook back on the s its second year we can Green Chemistry enters successful launch of this new journal. The timing for this venture appears to have been just right since in 1999 there have been numerous international conferences devoted to the topic. This has generated considerable discussion with regard to what green chemistry embodies and even whether or not the name itself is appropriate. Although it is not easy to succinctly describe what green chemistry encompasses the following is a reasonable working definition Green chemistry efficiently utilises (preferably renewable) raw materials eliminates waste and avoids the use of toxic and/or hazardous reagents and solvents in the manufacture and application of chemical products.Green chemistry eliminates waste at source i.e. it is primary pollution prevention. Waste remediation (end-of-pipe solutions) may be very useful and necessary particularly for the short-term but it does not constitute green chemistry. Industry appears to prefer the terms sustainability or sustainable development defined as development that meets the needs of the present without compromising the ability of future generations to meet their needs. The word ‘green’ apparently has too many political associations in many countries. This is a pity because green chemistry is probably more meaningful to the general public. Moreover perhaps the two terms are not mutually exclusive sustainability is the goal and green chemistry is the means to achieve it.Green chemistry embodies two components. One is concerned with efficient utilisation of raw materials and the elimination of waste. The other focuses on the health and safety aspects of chemical manufacturing. The two aspects were admirably illustrated by Guy Ourisson President of the French Academy of Sciences and doyen of synthetic organic chemistry in his opening address at a conference entitled “Clean Processes and the Environment The Catalytic Solution” which was held in Lyon from 6-8 December 1999. He invoked the terms black chemistry and red chemistry to describe these two shortcomings of many traditional Green Chemistry February 2000 G1 Green Chemistry Professor Roger Sheldon This journal is © The Royal Society of Chemistry 2000 G U E S T E D I TOR I A L processes.Black chemistry stands for waste = pollution and conjures up images of the industrial revolution black smoking chimneys and Blake’s “dark satanic mills”. Red chemistry on the other hand denotes danger and evokes associations with incidents such as Bhopal and Seveso. Many chemical processes in use today are black or red or both. Hence the goal of the chemical industry is or should be the replacement of red and/or black chemistry with green alternatives. Ourisson suggested that the following chemicals should in addition to the desired product be allowed to leave a chemical plant O2 N2 H2O (potable) NaCl and CaCO3 (and presumably CO2). It is worth noting however that a salt such as NaCl although quite innocuous can be a problem depending on the scale.If 10 kg of NaCl is produced per kg of product this is not likely to be a problem in the production of ten tons per annum of a pharmaceutical. The concomitant production however of one million tons of NaCl with 100,000 tons of a bulk chemical is a different matter. Subsequent lectures at the conference in Lyon generated considerable discussion with regard to what does and does not fall within the scope of green chemistry. This was perfectly illustrated by two back-to-back lectures on phosgene chemistry and dimethyl carbonate presented by J. P. Senet (SNPE) and F. Rivetti (Enichem) respectively. In the production of polycarbonates for example phosgene is reacted with bisphenol A and NaOH to give a polycarbonate and NaCl.If the latter is recycled via electrolysis to NaOH and Cl2 and the Cl2 is used to regenerate COCl2 then the process is in principle waste-free. Is this green chemistry? Not really. Even if we stretch our definition of primary pollution prevention to include recycling (always better than remediation) phosgene chemistry remains red. However phosgene can be converted to 1,1-dichloromethyl ether (Chloromyl®) by reaction with methylformate. If a pharmaceutical company uses Chloromyl® as a non-hazardous phosgene substitute is this green rather than red chemistry? The answer obviously depends on the vantage point from which we are looking. Most people would agree that the use of dimethyl carbonate as a phosgene substitute constitutes a greener solution.Dimethyl carbonate is produced by catalytic carbonylation of methanol and is a non-toxic substitute for phosgene and dimethyl sulfate in carbonylations and methylations respectively. Moreover no salt is produced; the coproducts are methanol and CO2 and the former can be recycled. But does recycling of methanol and emission of CO2 better qualify as primary pollution prevention than recycling of NaCl? Well for one thing methanol is a lot easier to recycle and recycling of NaCl is only viable on a very large scale. And is carbon monoxide green red or possibly pink? These examples illustrate that it is neither simple nor clearcut to define what is or is not green. The problem is that black red and green are relative rather than absolute descriptors.What is needed as was noted in a lecture by M. Misono is a semi-quantitative measure of the greenness of a process that is the environmental impact based on energy and raw materials consumption waste generation and health and safety aspects. This is easier said than done. As reflected in the title of the conference the solution to replacing black and/or red chemistry with green alternatives is often a catalytic one. This and other issues within the context of clean processes and the C G G2 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 environment were underlying themes in the lectures and poster sessions homogeneous or heterogeneous catalysis 4 new trends in polymerisation and depolymerisation 4 new solvents and reaction media 4 alternative feedstocks be possible to achieve these objectives via a cyclohexanone oxime-based route.An evaluation of different routes led to the following choice The key to success was the development of a highly efficient C G G U E S T E D I TOR I A L 4 selective catalytic organic chemistry 4 waste minimisation by selective catalysis and waste treatment 4 enhanced atom utilisation 4 replacement of stoichiometric or hazardous reagents by use of Apart from the words “waste treatment” this looks very much like a list of topics suitable for publication in Green Chemistry. One of the highlights of the conference was the lecture by J. P. Brunelle of Rhodia on a new eco-friendly caprolactam process in the session on enhanced atom utilisation.Caprolactam (CPL) is mainly produced from cyclohexanone via oximation and Beckmann rearrangement of the oxime a process that generates ca. 4.5 kg of ammonium sulfate per kg of CPL (E factor = 4.5). Rhodia’s objectives were ambitious a new process that was salt-free had lower costs than the existing process gave CPL of high quality and was ready for commercialization in 2000. To cut a long story short they rapidly concluded that it would not (>99.5% selectivity at >99% conversion) hydrolysis/cyclization of the intermediate aminonitrile to CPL and NH3 over an alumina catalyst in the vapour phase at 300 °C. The ammonia is not produced as a salt and can be re-used.The raw material adiponitrile is produced by DuPont via catalytic hydrocyanation of butadiene giving an overall stoichiometry The process meets the objectives set by Rhodia. It is salt-free lower cost and quality approval was achieved on a 60-ton scale in 1999. The current goal is a 100,000 ton plant in Europe in 2003. A truly elegant example of high atom utilisation thanks to catalysis. This is surely the quintessence of green chemistry. But what about HCN? Does its use not constitute red chemistry? Here again it depends on your vantage point. From the viewpoint of Rhodia the process is green as the Green Chemistry February 2000 G3 This journal is © The Royal Society of Chemistry 2000 G U E S T E D I TOR I A L starting material is adiponitrile. If one looks further upstream however the process begins to take on a red tinge. The situation is similar to the phosgene/Chloromyl® story (see above). Alternative processes based on catalytic carbonylation would in principle be greener since CO is less red (and less expensive) than HCN. For the quintessential green route to caprolactam what about a costeffective glucose (biomass)-based route? Perhaps this is a challenging goal for the new millennium. And so it goes. The discussion of technological and social aspects of green chemistry continues on a broad basis and Green Chemistry is an ideal forum for this discussion. A happy and green new year to all our readers. Roger Sheldon (Chairman Green Chemistry Editorial Board) Delft University of Technology The Netherlands C G G4 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000

ISSN:1463-9262    

DOI:10.1039/b000153h

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

New processes …niacinamide Alusuisse Lonza has commissioned a niacinamide plant in Guangzhou China which will use a new technology that combines traditional chemical processes with an enzymic step and is said to be environmentally friendly and lowenergy. The continuous process converts methylpentane diamine to 3-cyanopyridine which is then subjected to a highly selective bio-hydrolysis with immobilized enzymes to yield niacinamide. This is the water-soluble form of the B-vitamin niacin. …trimethylolpropane (TMP) BASF AG is to erect a 20,000 tonne per year plant for TMP for commissioning in 2001. The plant will use a patented BASF process that produces no by-products. The first step is the base-catalysed aldol addition of formaldehyde to n-butyraldehyde and then hydrogenation of the product to TMP.The current process produces around 50 kg of sodium or calcium formate byproduct per 100 kg of TMP. …key polyester ingredient from glucose Genencor International (Genencor) and DuPont on 22 Nov 1999 announced the achievement of another important milestone on the path to manufacturing a critical component for a high performance polyester from glucose a renewable raw material; Genencor and DuPont scientists have successfully combined enzymes from two different micro-organisms into one production strain and in so doing achieved greater than a five-hundred-fold improvement in productivity. The final goal of using fermentation technology to manufacture this ingredient for performance polyester is now in sight.The companies celebrated the first milestone only 20 months ago. Once commercialized by DuPont in the next few years the patented technology will represent a breakthrough in “green chemistry”. The well documented technology is a bioprocess to 1,3-propanediol (3G or PDO) a monomer precursor to the 3GT polyester (http://www.genencor.com). C G N EWS …palm oil separation Concept Engineering Malaysia in collaboration with the Palm Oil Research Institute of Malaysia has developed a cleaner more efficient method of separating palm oil. The membrane-filter press separates oil water and solid waste. The system is known as Zero Effluent Discharge Technology. It recycles 95% of the waste into fertilizers or animal feed.Malaysia produced 8.3 M tonnes of palm oil in 1998 mainly using steel presses and centrifuges. …from NOx to fertilizer A recent technology developed at NASA’s John F Kennedy Space Centre and available for licensing is the Nitrogen Oxides (NOx) Waste Conversion to Fertilizer. This converts NOx into potassium nitrate. Prior to the development of this new technology the NOx gas stream was absorbed by sodium hydroxide with produced sodium nitrate sodium nitrite and nitric oxide. The disposal cost for this waste stream was about 23 c/lb or $700,000/year. Benefits of the new technology include the elimination of hazardous waste disposal expenses; reduction of facility fertilizer expenses; and improved scrubbing efficiency.…coatings In spring 2000 a production facility for three monomers is due to be completed by Nippon Kasei Chemical in Onahama. The monomers are used in the production of environmentally friendly coatings. The development of the monomers has been undertaken in conjunction with Nippon Kasei Chemical’s parent company Mitsubishi Chemical. This is the first commercial application of dimethylol butyric acid (DBC) which is being used in production of water-based polyurethanes. The other two monomers are dimethylol propionic acid also used for water-based polyurethanes and diacetone acrylamide. …continuous processing Kvaerner Process Technology of Stockton-on-Tees UK has developed a continuous process for chemical transformations that are traditionally carried out on a batch basis The process is economically and environmentally beneficial and can achieve clean and efficient esterification.The process uses a novel counter-current reactor for undertaking diphasic and triphasic reactions. The process should be of interest to all sectors of the industry e.g. butanediol from maleic anhydride. Green Chemistry February 2000 G5 This journal is © The Royal Society of Chemistry 2000 N E W S C G Green moves at Unique Images Unique Images part of Hallmark Europe’s largest suppliers of gift wrapping paper (120 million metres per year) is now using water-based inks instead of inks based on organic solvents as part of company policy to reduce or even eliminate VOCs (volatile organic compounds).The problem of paper dampening from use of such water-based ink has been overcome by incorporation of a steam heat drying unit. In fact Unique Images are getting 6–10% faster printing with the new ink. Unique Images has also installed Salter Weigh-Tronix electronic weighing equipment to monitor waste in its greetings card business (again Europe’s largest producer at 1.2 billion cards per year); the company is targeting a reduction in waste to a 1% level. Mattel turns from traditional plastics Mattel Inc. is bringing together a consortium of the world’s most innovative materials developers and consultants to formally begin investigating newly developed environmentally friendly and organically based materials for its products and packaging.Mattel’s mandate to these firms is to identify materials that are derived from organic and renewable sources while maintaining the safety and structural integrity of the company’s products. The company intends to begin the introduction of products produced from organically derived materials as early as the year 2001 based on extensive research in the year 2000. As the viability of these new technologies is confirmed their use will be expanded into all brand categories and product lines. Mattel says its decision is based more on the use of environmentally friendly materials than current pressure throughout the industry to phase out the use of phthalates in toys which Mattel has already stopped using in its teething toy products.Headquartered in El Segundo California USA Mattel has offices and facilities in 36 countries (http://www.mattel.com). Catalysts …for alkylbenzene synthesis Fushun Petrochemical Corporation G6 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 Dalian Institute of Chemistry and Physics and the Chinese Academy of Sciences have developed a new catalyst for the production of linear alkylbenzene (LAB) which they have developed. This is a solid catalyst which is not corrosive to replace hydrofluoric acid. This means that savings can be made in plant costs such as acid generators re-generators and pipelines.The new catalyst is environmentally friendly and its record for reuse is good. …chiroporphyrins A CNRS-CEA research team at a university in Grenoble has discovered a new family of chiral molecules chiroporphyrins. The user would be able to make either chiral form by changing the metal (iron or manganese). Alternative uses of tobacco India produces about 600 M kg of cured tobacco and the entire production is used for conventional smoking and chewing applications. The Central Tobacco Research Institute (CTRI) Rajahmundry is trying to find alternative uses of tobacco. Proteins can be extracted from the green tobacco leaves and these proteins can be used to manufacture various animal feeds. About 381 kg of protein/hectare crop can be extracted.The resulting residue in the process can be used for solvent extraction of solanesol which is a high value alcohol used in the synthesis of products like the cardiac drug co-enzyme Q9 and vitamins K and E. India exports crude solanesol worth Rup 20 M/y to Japan. The scientists at CTRI are aiming to extract 95% pure solanesol which is valued at $500/kg in the global markets. It is possible to extract about 18.3 kg of solanesol/hectare of tobacco crop. Also from tobacco waste the scientists have developed technology to extract nicotine sulfate of 40% purity an environmentally friendly insecticide effective against a wide range of insect pests. Biodegradable firefighting foam French company Bio-Ex has developed a new range of environmentally friendly fire-fighting foams.These foams are biodegradable and are resistant to variations in external temperatures. Their low viscosity means that Bio-Ex foams put out fires quickly and can function at low pressure and low temperatures. These foams create a film on hydrocarbon matter and a thin gel on polar and special products preventing any risk of re-ignition or the release of gases or toxic fumes. The high performance of Bio-Ex foams exceeds current European standards. Bio Filmopol 3 and Bio Newpol 3S are multipurpose foams for fighting hydrocarbon and polar solvent fires. Their single concentration application rate of 3% means they are long-lasting and easy to store. Bio For C on the other hand an additive for class A fires (forests towns homes cars gas paper mills) is a foaming/wetting agent for use at very low concentrations from 0.1% to 0.6%.So as well as providing significant cost savings and water selfsufficiency which enables a higher number of turnarounds Bio For C also limits water damage in urban environments so reducing the clearing time by firemen. Bio-Ex is the leading supplier to prestige chemical industries. It is an ISO 9001 certified European leader thanks to services like centralised 24 h emergency services and its product development. Bio-Ex is looking for distribution for its products in the UK. Green burial Green chemists can now take the “cradle to grave” approach a little further.Green Burials (http://www.green-burial.co.uk) offers corrugated cardboard flatpack biodegradable coffins which can be assembled in less than 10 minutes. The coffins are suitable for burial or cremation are available in plain or woodgrain effect finishes. A variety of other eco-coffins are available e.g. a British store called Green Undertakings sells biodegradable body bags and wicker burial stretchers and in California Biofab offers coffins made of 99% biodegradable straw available in a range of colours. For further information on green burial see http://www.world trans.org/naturaldeath.html or http://www. funeral.com/casket. Recycling …polyester bottles Eastman Chemical Co. have developed and patented a new polyester bottle recycling technology in which the depolymerization process is independent of dyes coatings or barrier plastics and is energy-efficient.The resulting polyester is admissable for food contact. The depolymerization involves glycolysis methanolysis and ‘supercleaning’ each of which is patented. The attributes of the methanolysis glycolysis and hydrolysis processes are tabulated. Eastman expect the new process to deal with all colours of beverage bottles and with regulated compositional variants and to tolerate some PVC contamination but does not expect it to compete economically with mechanical recycling for clean clear monolayer bottles for general use. …nylon carpets A joint venture between AlliedSignal Inc. and DSM Engineering Plastics has been set up to recycle old carpets into high quality grade caprolactam.The joint venture Evergreen Nylon Recycling is located in Augusta Georgia will produce 100 M lbs/y of caprolactam and 100 M lbs/y of virgin nylon 6. To generate this quantity the Evergreen facility will have to process 200 M lbs/y of nylon carpet. The joint venture uses patented technology the Infinity nylon process developed jointly by AlliedSignal and DSM Engineering Plastics. The recycling process will have energy savings of 4.4 M BTUs/y. DSM will launch its new nylon 6 products Akulon Renew early in 2000. The products contain 25% caprolactam and the range includes standard unreinforced glass reinforced and glass/mineral compounds.Solvents .corn-derived green solvent NTEC Inc and Archer Daniels Midland USA have signed an agreement to jointly develop and commercialize new markets for ethyl lactate a biodegradable solvent made from corn. Under the auspices of this arrangement all North American sales of ethyl lactate manufactured by Archer Daniels Midland will be handled under the umbrella of a strategic relationship between NTEC and Archer Daniels Midland. This product already being shipped to several customers in the US is sold under the “Versol” brand name. Ethyl lactate is a high performance environmentally friendly green solvent that can successfully replace hundreds of millions of pounds of toxic petroleum based chemical compounds used in the world today.Ethyl lactate is 100% biodegradable it simply decomposes into carbon dioxide and water. Archer Daniels Midland based in Decatur Illinois is engaged in the business of procuring transporting storing processing and merchandising agricultural commodities and products (http://www.admworld.com). .“Solvents for Green Chemistry” report US industry uses more than 3.8 M tons/y of solvents most of them designated as toxic. A new Futuretech report from Technical Insights a unit of John Wiley & Sons Inc. “Solvents for Green Chemistry” shows how industry can replace toxic solvents with safer more efficient materials how to minimize solvent use recycle solvents and optimize design of processes to use solvents more efficiently.Demand for chemical solvents is expected to reach 12.4 bn lb valued at $4 bn by the year 2003. Several polychlorinated solvents have already been eliminated while coatings inks and adhesives have undergone reformulation to reflect new regulations. Green solvents are poised to grab market share with demand for ether solvents alcohol solvents ester solvents and other solvents growing modestly over the next five years. The market for ether solvents is expected to grow 1.6% between the years 1998 and 2003 as will the market for alcohol solvents. Ester solvents will see growth projected at 3.7% and demand for other solvents will grow by 4.7%. However market projections based on conventional technologies do not factor in such advances as ethyl lactate near critical water room temperature ionic liquids and phytosols all promising new technologies that are just now edging their way into commercialization.New emission limits from power stations The UK Environment Agency has announced new limits to protect the environment from excessive emissions of sulfur dioxide nitrogen oxides and particulate matter from coal- and oilfired power stations. The Agency will require that by September 2005 the total amount of sulfur dioxide to be released from the stations in England and Wales is less than 398,000 tons – a reduction of about 60% over 1996/7 rates. For further information see http://www.environmentagency. gov.uk. C G N E W S Resolving pollution David Lewis a microbiologist who has worked at the US EPA for 30 years has warned regulators that world-wide data on pollution are flawed because they do not account for the effect of chirality on toxicity.It has been shown through laboratory and field tests that environmental changes in soil can alter the risk posed by chemicals in pollutants because of chirability. Lewis points out that the pharmaceutical industry has been aware of the chirality– toxicity link for many years and that the same could be done in the manufacture of plastics pesticides and herbicides. Environmentally friendly credit cards The world’s first plant-based biodegradable credit card has been launched by the UK’s Co-operative bank. The card is made from biopol which was first made by Zeneca using a carbohydrate-based fermentation process.Subsequently Monsanto acquired the technology and have subsequently produced a thermoplastic copolymer in plants. The Co-operative Bank is committed to replacing all of its existing 2 million credit cards with the new ones before the end of the year 2000. Insecticide-treated mosquito bed nets The Academy for Educational Development (AED) will utilize its experience in social marketing to lead an ambitious alliance of public and private organizations aimed at reducing the risk of malaria deaths among children and pregnant women in Africa. NetMark a five year Africa regional project funded by the US Agency for International Development seeks to create a commercially sustainable market for insecticide treated materials such as bed nets.The $15.4 M NetMark project will be managed by AED a nonprofit organization that has implemented development projects in more than 100 countries. AED has formed a collaborative relationship with private and public partners. Technical expertise on malaria and insecticide treated materials research will be provided by Johns Hopkins University’s Department of International Green Chemistry February 2000 G7 This journal is © The Royal Society of Chemistry 2000 N E W S C G Health and The Malaria Consortium a joint venture of the London School of Hygiene and Tropical Medicine and the Liverpool School of Medicine. The sales promotion effort will be supported by Group Africa and other African consumer product promotion groups (http://www.aed.org).Tin as an environmentally friendly alternative to lead .The UK Department of Trade and Industry (DTI) has announced a collaborative project between the National Physical Laboratory and ITRI (the tin research organisation) on replacement of lead in solders used in the assembly of printed circuit boards. Lead-based solders are the subject of legislation around the world. Japan has already banned leadbased solders by the end of 2001óMatsushita has announced that four of its home electronic products will be lead-free by 2001. Hitachi will stop using lead solder by 2001. In October 1999 ITRI launched SOLDERTEC the Lead- Free Soldering Technology Centre to meet the rising demand for lead-free soldering information and research.All lead-free solders can now be found on the SOLDERTEC website at http://www.lead-free.org along with much other information on lead-free soldering. .Several major US police departments now use tin bullets on their practice shooting ranges as an answer to the lead fumes generated by firing large numbers of lead bullets in such confined spaces. There is also an increasing concern over hazards to wildlife resulting from deposition of toxic lead shot on wetlands. Voluntary and regulatory bans on lead shot are being introduced worldwide and various nontoxic alternatives are proposed. .A new technological development from the Advanced Lead Acid Battery Consortium (ALABC) has highlighted the benefits of increasing the tin content of alloy grids used in lead-acid batteries.Originally applied to Electric Vehicle technology manufacturers worldwide are applying this technology in the SLI battery sector. .Other applications are tin wine capsules (the traditional lead and more recently plastic covers over corks) tin-zinc based flame-retardants as replacements for G8 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 antimony/bromine based compounds and tin weights to replace lead weights to balance car wheels. For further information on tin see http://www.itri.co.uk/home.htm. Green glue .USA The “feet” of mussels produce an epoxy with adhesive-like properties that rivals any “super” glue on the market.Unfortunately it takes about 10,000 mussels or molluscs to produce just one gram of adhesive resulting in a prohibitive cost. So molecular biologists at the DOE’s Idaho National Engineering and Environmental Laboratory (INEEL) are developing methods to clone the mussel’s genes through DNA technology that will allow them to economically produce large quantities of the adhesive protein for use as a strong cementing element for manufacturing plywood oriented strand and other building materials. The dental industry is also looking for a better safer adhesive for dentures. The INEEL in collaboration with scientists at the University of California Santa Barbara is identifying five proteins that go into the thread makeup that constitutes the “glue.” Cloning the mussel proteins is expected to be the crucial step in opening doors for developing this amazing epoxy.The ability to remain intact in sea water is only one advantage the “mussel glue” offers. It doesn’t require high temperatures to activate its cementing qualities as do other conventional waterproof glues and it’s also environmentally safe (http://www.home.doe.gov/mussels.htm). .UK Simon McQueen-Mason from the Biology Department at York UK is leading a team developing ìgreen glueî from genetically engineered tobacco plants. McQueen-Mason is exploiting the strong glues produced by mussels to anchor themselves to rocks by transferring the gene for the mussel protein into tobacco plants where they are expressed in plant cell wall proteins (extensins) with similar properties to the mussel glues. The advantage of the tobacco extensins similarly crosslinked oxidatively through a key tyrosine residue is that easily extracted from the plants in high yield. Snippets …India will encourage the use of secondary lead and zinc provided they are recycled using environmentally safe processes. There is growing use of lead and zinc in railway electrification road transport and agriculture and this is leading to a national shortage. …CK Witco is to allocate $70 M to the expansion of its green tyre activities and to its trimethoxysilane process to produce organofunctional silanes. $50 M is to be spent doubling sulfur silane capacity at Termoli Italy by mid-2001. The remaining $20 M will be used to develop the TMS process in North America with particular emphasis on intermediates. Full production is scheduled for mid-2001.

ISSN:1463-9262    

DOI:10.1039/b000154f

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

Moves towards greener cars Introduction Pick up any journal from the popular scientific press or even any quality daily newspaper and you are likely to come across at least one article on cars and pollution. In the UK the topic is a current political ‘hot potato’ with the Government trying to introduce policies to reduce traffic congestion and pollution without alienating the motorist. Elsewhere particularly in developing countries governments are starting to introduce legislation which will help control pollution as the growth in car ownership continues to rise. Industry particularly in the US and Europe is meanwhile putting more and more research efforts into finding alternative cleaner technologies whilst at the same time pushing existing technology to the limits of energy efficiency.In this article some of the recent developments which have made the headlines throughout the world are pulled together to give an overview of the area. Mike Lancaster reports on several recent developments around the world towards making cars both more energy efficient and less polluting the gasoline used to fuel them. “This is a big deal taking 2 million tons of air pollution from the air,” said Rebecca Stanfield of the US Public Interest Research Group. The rules will become part of “the lasting White House legacy on the environment,” she said. The cleaner gasoline and tougher tailpipe emissions standards would be phased in over five years beginning in 2004.The current level of sulfur in gasoline which nationally now averages 330 parts per million would be reduced by 90% over 5 years to 30 ppm under the new rules. High sulfur levels in gasoline are blamed for clogging vehicles’ catalytic converters which control tailpipe emissions and reduce pollution. At the same time minivans trucks and sport utility vehicles (SUVs) would have to reduce their emissions of nitrogen oxides which cause smog. Bigger SUVs would have until 2009 to comply. EPA and White House officials have stressed the health benefits of cutting smog-forming pollution notably stopping what the administration says is an explosion in child asthma cases around the country. ARB bans MTBE and modifies rules for cleaner burning gasoline The California Air Resources Board (ARB) approved a new set of gasoline rules that will ban the additive methyl tert-butyl ether (MTBE) while preserving all the air-quality benefits obtained from the state’s cleaner-burning gasoline programme.The new rules known officially as the Phase 3 gasoline regulation prohibit the formulation of USA Effect of changes in US rules on emission levels In order to reduce the effects cars have on the environment the Clinton administration has announced sweeping new rules to cut car emissions and sulfur levels in gasoline a twin effort aimed at keeping 2 million tons of smog-forming pollution out of the air. The new rules from the Environmental Protection Agency will for the first time address not just pollution from automobiles but also from All the major car companies are researching cleaner cars N EWS R E V I EW gasoline with MTBE after 31 December 2002.To better enable refiners to costeffectively produce non-MTBE gasoline the new regulation changes several ARB cleaner-burning gasoline specifications that have been in effect since 1996. The regulation establishes more stringent standards for two major gasoline pollutants sulfur and benzene while relaxing two standards for distillation temperatures. The new standards will improve the ability of refiners to make non-MTBE gasoline while ensuring motor vehicle emissions do not increase. These new standards will also take effect on 31 December 2002 (http://www.arb.ca.gov).Powerball Technology A report prepared by Energetics Inc. for the Department of Energy (DOE) Office of Power Technologies Hydrogen Programme shows that Powerball Technology can be competitive as a future infrastructure fuel. The report predicts that the future cost of powerballs may be $1.56/gallon of gasoline equivalent and perhaps much lower when produced in high volume using efficient conversion technologies. Additionally the DOE funded report points out that “the application of the Powerball Technology in the chemical industry represents an attractive option”. The estimated plant gate manufacturing cost of sodium metal via Powerball Industries’ thermochemical process could be as much as ten times less than the current commodity price for sodium produced via electrolysis.Powerballs can be produced from plentiful and clean Green Chemistry February 2000 G9 C G This journal is © The Royal Society of Chemistry 2000 N EWS R E V I EW North America during the 1999 model year. There are now over 1000 Ranger EVs in use in the United States and Canada. Electric vehicles have failed to catch on with consumers because of limited driving ranges frequent required recharges and a weak infrastructure that offers limited locations for recharging. They have proven more popular for fleets like that of the postal service Ford’s other alternative fuel vehicles include the Prodigy a diesel-electric hybrid family saloon capable of 80 mpg ; this vehicle was previewed at the North American International Auto Show in Detroit in January 2000.DaimlerChrysler Hundreds of thousands of air travellers will experience electric vehicle technology in traveling to and from Los Angeles World Airport as the first 10 DaimlerChrysler Electric Powered Interurban Commuter (EPIC) minivans join the fleet of Xpress Shuttle. The five-passenger minivans which represent DaimlerChrysler’s state-of-theart electric vehicle presence in California are being added to the shuttle company’s fleet each expected to log up to 100,000 miles of service per year an unprecedented workout for an electric vehicle. The breakthrough comes thanks C G natural gas energy. The fuel pellets are easy to transport store and use and are ideal as an energy carrier since they produce zero point-of-use emissions.Each gallon of powerball fuel pellets stores an impressive 17.8 kWh of energy in the form of clean environmentally friendly hydrogen. Powerball Technologies LLC is a joint venture between Powerball Industries and Natex Corp. focused on innovative hydrogen distribution. At the heart of their technology is the proprietary hydride pellets which dramatically increase the storage density and distribution efficiency for hydrogen through incremental and on-demand production to portable fuel cell systems (http://www.powerball.net). Ford Motor Co. Ford Motor Co. has received the single largest electric-vehicle order in US history.The world’s no. 2 carmaker said the US Postal Service is purchasing an initial order of 500 electric mail-delivery vehicles based on the Ford Ranger EV pickup truck. The postal service also has the option to order a total of 6000 vehicles. Production of the 500 vehicles will begin in the autumn and continue through next year said Ford which is working in partnership with Baker Electromotive of Rome NY Ford said the bulk of the electric pickups will be used for mail delivery in California with the rest being used in the Washington DC metro area. The Ranger EV is the national leader in electric vehicle sales with 561 sold in G10 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 Ford Ranger EV Ford Postal EV Photo credits Ford Motor Co.to EPIC’s unique fast-charging capabilities that allow the minivans to quickly refuel with electricity and return to the road. The EPIC can carry a payload of 925 lbs—about five passengers and 175 lbs of cargo. The current model is powered by twenty-eight 12-volt advanced nickelmetal-hydride batteries that deliver up to 80–90 miles per charge. AeroVironment Inc. of Monrovia California is providing the fast-chargers for this project. Where a traditional charger delivers six-to-seven kilowatts and recharges an electric vehicle in 5–7 hours the EPIC fastcharger operates at much higher power (60–150 kilowatts) and has the minivan back at close to full charge within a halfhour.General Motors Corp. Meanwhile General Motors Corp. have taken strides to make the more conventional combustion engine more energy efficient when it recently unveiled the Precept an experimental teardropshaped sedan capable of 80 miles per gallon. The car was developed under the federally sponsored Partnership for a New Generation of Vehicles (PNGV). Members of the industry–government collaboration,launched in 1994 are committed to building by 2004 production-ready prototypes that can offer triple the fuel economy of a typical family sedan without sacrificing performance. Company officials say the Precept will probably never go into mass production because of their high costs. But some of the advanced fuel-economy technology could wind up in consumerready cars and trucks.The hybrid-electric Precept is driven by a battery-powered electric traction system that moves the front wheels and a lightweight 1.3 litre 3 cylinder diesel engine in the rear. The direct-injection engine featuring turbocharged compression ignition was developed by Isuzu Motor Co. Ltd. one of GM’s Asian affiliates. GM has developed the electric motor to run off either a nickel metal hydride battery like the kind used in the new version of its EV1 electric car or a lithium polymer battery. The electric traction system also captures energy from braking and sends it back to the battery. Designers of the Precept took their overall design cues from the EV1 and constructed the car to be as aerodynamic as possible.Exterior door handles have been eliminated and outside mirrors were replaced by a camera system. Because front-facing grills create wind drag the Precept has special air openings behind the rear wheels (http://www.gm.com/). Honda Honda has introduced their new gasoline-electric hybrid car the twodoor Insight into the California auto market. It has a 65 mpg fuel efficiency which will substantially reduce emissions that contribute to global warming. However the vehicle will certify to a level of smog-forming pollution ten times greater than the standard set by California for Super Ultra Low Emissions Vehicles. Some of Honda’s model year 2000 Accords and Toyota’s forthcoming Prius hybrid will meet this higher standard.The FCX concept vehicle unveiled at the Detroit International Auto Show in January 2000 features Honda’s innovative fuel cell unit powertrain. Honda has announced its intentions to put fuel cell-powered vehicles on the road in 2000 and is researching both methanol and hydrogen fuel cell prototypes. In the FCX concept vehicle the fuel cell unit located below the floor of the passenger cabin employs a methanol-type fuel cell. Power is achieved when a methanol and water mixture moves from a storage tank located in the rear of the unit through a “fuel processor” where hydrogen is extracted. The hydrogen is then mixed with oxygen within the cell stack (part of the fuel cell system) to produce electricity.This in turn powers the electric drive motor. Buyer’s Guide to Cleaner Cars The California Air Resources Board (ARB) has a buyer’s guide to cleaner cars on its web site at http://www.arb.ca.gov/ msprog/ccbg/ccbg.htm. This site gives a lot of information on the models of cars fit into the various categories of cleaner cars as defined in California [transitional low-emission vehicles (TLEVs) lowemission vehicles (LEVs) ultra-lowemission vehicle (ULEVs) super-ultralow-emission vehicles (SULEVs) and zero-emission vehicles (ZEV)] to help the environmentally conscious purchaser to choose. The Environmental Health Center (part of the National Safety Council) has a very useful Cleaner Cars Module on its website (http://www.nsc.org/EHC/ mobile/intro.htm).Sections include 4 background to air pollution 4 buying a cleaner car 4 alternatively fueled vehicles 4 cleaner refueling and energyefficient driving 4 responsible recycling of motor vehicle fluids N EWS R E V I EW Germany Sales of biodiesel a renewable fuel from oilseed rape have doubled in Germany since 1996 to 100,000 tonnes in 1998. 800 German petrol stations now sell the green fuel. A study by the International Economic Platform for Renewable Energies (IWR) at the University of Munster indicates that the area dedicated to the growth of the rapeseed used in the fuel’s manufacture is also increasing. However the fuel still remains a niche market amounting to less than 1% of total German diesel sales.Saudi Arabia The move towards unleaded petrol is also gaining momentum in other parts of the world. Saudi Arabia the world’s biggest oil producer will introduce unleaded gasoline in 2001. Arab News daily quoted Essam Tawfiq manager of Saudi Aramco’s public relations department as saying the cleaner fuel would hit the domestic market on January 1 2001. Like other Gulf Arab states which sit on nearly half of the world’s oil reserves Saudi Arabia is struggling to introduce unleaded gasoline to a population unfamiliar with the cleaner burning fuel. Gulf Arab states will need to perform major upgrades on refineries across the region to produce unleaded gasoline.Vietnam Vietnam have announced that they will develop an action plan to phase out leaded petrol as the first step to completely stopping the use of such fuel. At present only leaded petrol is currently used in the country. India The Union Ministers for Petroleum & Gas and Environment & Forests met to discuss a long-term plan to supply cleaner and better quality fuel to the auto sector that will reduce the levels of pollution. The aim is to achieve compliance norms more stringent than Euro II in the auto sector. There is a proposal to supply low-sulfur diesel not only in the National Capital Region but also in other metros. The Supreme Court has directed the Government of India to ensure supply of high-speed diesel with Green Chemistry February 2000 G11 Europe European Automobile Manufacturers’ Association (ACEA) At the same time European car manufacturers have called on the European Commission to support German moves to introduce sulfur-free diesel and petrol.The European Automobile Manufacturers’ Association (ACEA) said the Commission should encourage European Union states to introduce tax incentives similar to those planned in Germany to bring the sulfur content of fuels down to 10 ppm. “We’ve written to the Commission to ask it to support the German government,” said Giovanni Margaria emissions and fuels director of ACEA. “Lower-sulfur fuels would improve environmental conditions and help European carmakers catch up technologically with their Japanese counterparts” Margari said.The average sulfur content of petrol sold in Japan is already below 10 ppm. ACEA said it would be wrong to renegotiate recently agreed laws under which the sulfur content of petrol and diesel will fall to 50 ppm by 2005. But it said the EU should back countries which introduce tax incentives to encourage reductions in sulfur which causes pollution by dangerous particulates as well as nitrous oxides which produce harmful ground-level ozone. Germany introduced tax incentives in August last year for the introduction of so-called “sulfur-free fuels”—containing no more than 10 ppm—which will be effective from January 2003. Meanwhile as a ban on leaded petrol in Europe comes into force the European Commission said it had given Italy Spain and Greece until January 1 2002 to enact the new laws two years later than the rest of the European Union.“The main justification for this is to ensure that they have adequate time both to time the transition to unleaded petrol and to ensure a good public information campaign,” said an EU official. In making the decision the Commission C G said it rejected the governments’ claims that the move to unleaded petrol would force older cars to be scrapped and bring severe socio-economic problems for the countries involved (http://www.acea.be/). This journal is © The Royal Society of Chemistry 2000 N EWS R E V I EW manufactured and serviced by ONSI Corp. has accumulated more than 3 M hours of in-service operation breaking its own world record.ONSI has produced more than 200 of the power plant systems which are operating in 84 cities throughout the US as well as 11 countries in Europe Asia and North America. The fleet’s previous record 2 M hours of operation was set in June 1998. Each PC25 power plant provides 200 kilowatts of power operating on a variety of fuels. While most use natural gas some use methane from anaerobic digesters at waste water treatment plants or landfills others use propane butane pure hydrogen or methane. The PC25 system contains the fuel cell itself and the components to make it commercially viable including the fuel processing equipment and the devices needed to convert the direct current from the fuel cell into the alternating current normally used in homes and businesses.International Fuel Cells and its manufacturing arm ONSI both of South Windsor Connecticut are world leaders in fuel cell production (http://www.internationalfuelcells.com). New US hydrogen fuel cell station Energy and motor companies are to set up a dedicated hydrogen filling station and fuel-cell vehicle centre in 2000 at Sacramento California at the headquarters of the California Fuel Cell Partnership—a group including the state government energy firms and vehicle manufacturers. The fuelling facility jointly funded by Shell International Arco (Atlantic Richfield Co.) and Texaco Inc. will dispense liquid and compressed hydrogen fuel for 16 fuel-cell powered passenger vehicles.“Refuelling is one of the key issues for enabling fuel-cell vehicles to reach the mass market,” said Don Huberts chief executive of Shell Hydrogen. Automobile companies involved in the venture include DaimlerBenz AG Ford Motor Co. Honda Motor Co. Ltd. and Volkswagen AG and each will have garage bays at the centre for servicing repairs and diagnostics (http://www.drivingthefuture.org). Ballard Power Systems Ballard have produced a new fuel cell the Mark 900 which was included in the new Ford prototype fuel-cell vehicle the TH!NK FC5 presented at the North American International Auto Show in Detroit in January 2000 (http://www.ballard.com and http://www.thinkmobility.com).C G sulfur content of less than 0.05% by 1 April 2000. Efforts are being made to achieve this by commissioning nine diesel hydro-desulfurisation plants that would bring down the sulfur content in high-speed diesel to 0.25%. Brazil The government in Brazil has abandoned subsidies for fuel alcohol distilled from sugarcane. They argue that this is no longer appropriate when alcohol is now much cheaper than gasoline. Hydrous alcohol which has been subsidised by the State is used by less than 1% of new cars in Brazil. Anhydrous alcohol which has also been State-subsidised is added to all gasoline sold in Brazil at a rate of 24%. The combined annual savings to the government will be $175M. Developments in fuel cell technology Fuel cell project at Houston Advanced Research Center (HARC) Two utility companies a major energy company and a major supplier of engine components and automotive products have joined forces to power up a fuel cell demonstration and evaluation project at HARC.The three-year $7 M project seeks to test and determine the various conditions under which fuel cells can be put to use as a clean reliable and affordable energy source. The four companies participating in this initial project of HARC’s newly created Center for Fuel Cell Research and Applications are Dana Corp. Texaco Southern Co. and Salt River Project. The project’s objective is to demonstrate the value of stationary near-zero emission proton exchange membrane fuel cell units in both small and large-scale applications.HARC plans to operate fuel cells from multiple US and foreign-based manufacturers first looking at a large 250 kW fuel cell system. Based in Toledo Ohio Dana Corp. is one of the world’s largest independent suppliers to vehicle manufacturers. Salt River Project is the third largest public power utility in the US. Southern Co. based in Atlanta is an international energy company. Texaco Energy Systems Inc. is exploring business opportunities in fuel cells hydrocarbons-to-liquids and alternative fuels (http://www.harc.edu). Record 3 M hours of ‘green’ power A fleet of PC25 commercial fuel cell power plant systems developed by International Fuel Cells Inc.and G12 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 DaimlerChrysler DaimlerChrysler have stated that they believe it will take another 10 years to produce fuel-cell-powered vehicles that are truly competitive with conventional cars. Despite this the company plan to start selling such cars by 2004 and they believe that the market for them will reach 25% of the global market for vehicles in 2020. Popular Science magazine in its 1999 “Best of What’s New” issue awarded the DaimlerChrysler NECAR 4 the Grand Prize as the year’s best achievement in science and technology. For more information on developments in the application of fuel cells to transportation see the Online Fuel Cell Information Centre developed by Fuel Cells 2000 at http://www.fuelcells.org/ the Fuel Cells Network (http://www.keele.ac.uk/deps/ch/fuelcell/ network/board/htm) and http://evworld.com. Future outlook Most people involved in the industry now agree that fuel cell technology will play an important role in the future of transport. The only real question is over how long this will take before a significant impact is made 10 20 or 30 years? There are still several key technical and economic questions to be answered but with the sheer volume of high quality research going on it is surely only a question of a few years before we start to see fuel cell powered cars on the forecourt. In the meantime as the article on the Ford EV pick-up highlights existing clean technology solutions will continue to find niche markets but even the most ardent enthusiast does not believe the electric battery powered car will become widely used. Whilst the world waits for the new clean technologies to come on stream small but valuable incremental improvements can still be made. Leaded gasoline will soon be phased out in many parts of the world and more stringent control of levels of sulfur in both diesel and gasoline are being introduced. Designers are still striving for the perfect aerodynamic shape but for all practical purposes we must surely be near the limit of where this area of research can have a significant impact on fuel efficiency.

ISSN:1463-9262    

DOI:10.1039/b000156m

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

A novel continuous reactor for UV irradiated reactions Bill Dunk and Roshan Jachuck from Newcastle University UK describe how use of a spinning disc reactor allows bulk polymerisations under UV irradiation The reduction of organic solvent use in several industries is a topic of great concern to environmentalists and throughout the world efforts are being made to bring about drastic reductions in their use. In the chemical industry an important advance in this direction would be the introduction of means whereby many of the reactions currently conducted in solvents could be conducted at or near to 100% reactant concentration. In the synthetic polymer industry the free-radical mechanism is favoured for the preparation of addition polymers since the robust nature of the reaction lends itself to a variety of reaction conditions.However the properties of most monomers having commercial importance require that their polymerisation be carried out at relatively low concentrations very often in organic solvent solution. High heats of polymerisation combined with rapid rates of propagation dictate against the use of 100% monomer unless bulky and complex installations are available. The patent literature contains numerous disclosures of plant for bulk polymerisation but only methyl methacrylate and styrene have been polymerised in this way in the liquid phase on an industrial scale. Multi-unit tubular reactors and heat exchange zones that utilise heat exchange fluids are typical for these monomers whilst a variety of other systems e.g.conveyor belts or hollow shafts1 have been disclosed for a wider range of polymerisation procedures. None of these approaches seem to have reached industrial realisation. Only in recent years has any concerted effort been expended to reduce the scale of chemical plant not only for conventional chemical reactions but also for polymerisation. At Newcastle University the process Intensification and Innovation Centre (PIIC) has been at the forefront of such endeavours and amongst several novel reactor designs and concepts has introduced spinning disc The spinning disc reactor which can be seen in Figure 1 produces thin highly sheared films. It has been shown that the hydrodynamics of such films encourages high heat and mass transfer rates whilst providing excellent mixing (Figure 2).The centrifugal force created by the rotation of the reactor surface is used to produce very thin sustainable films of 100–300 mm. As the film is thin it is possible to maintain good and uniform penetration of UV radiation. The reactor studied and developed is 180 mm in diameter and has the ability to produce approximately 40 kg h–1 of polymer on a continuous mode. Currently even smaller reactors are being developed for laboratory-scale studies. Since the reactor has very good heat transfer characteristics it is particularly suitable for performing fast exothermic reactions. The use of photoinitiation was chosen for a number of reasons not least the wide temperature range available for effective initiation.In addition there were other advantages technology to both organic and polymer synthesis. A very recent development in which a spinning disc reactor (SDR) has been applied to the bulk polmerisation of ethylenically unsaturated monomers using UV radiation initiation has been pioneered by Dr Bill Dunk and Dr Roshan Jachuck who believe that the procedure has great potential for processes based on green chemistry. 4 Novelty. Little progress has been made in the use of photochemistry for the synthesis of linear high-molecularweight polymers. Green Chemistry February 2000 G13 F EAT U R E C G Figure 1. Spinning disc reactor.Figure 2. View of the surface waves in a spinning disc reactor. This journal is © The Royal Society of Chemistry 2000 F EAT U R E C G 4 Control of polymerisation since the free-radical initiator could only give initiating species when the UV lamp was turned on. 4 The zero activation energy for the free-radical initiator decomposition means that there would be little effect of temperature on the rate of polymerisation. 4 Rapid rate of initiation under SDR conditions would be expected to be comparable to rate of propagation thus polydispersity of the formed polymer should be low. We may remark that the use of UV radiation in polymerisation chemistry is far from new Hoffmann having reported the formation of a glassy solid when styrene was exposed to sunlight (1849) whilst as long ago as 1912 Ciamician2 foresaw possible applications of photochemistry in industry.However in 1927 IG Farbenindustrie rejected the suggestion that sunlight be used to polymerise vinyl acetate on the ground that “there would not be sufficient sunlight and they could only operate on a small scale with other light sources”.3 Little progress was made in this direction and some 35 years later we read of a photo-polymerisation of isopropyl acrylate on a 500 ml scale which required four identical UV lamps positioned around the reactor.4 Subsequently patents appeared,5 disclosing conveyor belts moving under banks of UV lamps but problems of plant size and homogeneity of light source have hindered exploitation of these procedures.For the purposes of exploiting the advantages of excellent micro mixing short residence times and effective heat exchange that are features of the spinning disc reactor the use of photo-initiation seemed most attractive particularly as polymerisations could be conducted at or near to ambient temperatures. The monomer chosen was n-butyl acrylate which is transparent to the radiation to be used with a heat of polymerisation of 77.4 kJ mol–1 and a rate coefficient for propagation of 16300 l mol-1 s–1 at 30 °C. Benzoin methyl ether or dimethoxyphenyl acetophenone were used as photoinitiators the latter proving more effective at a UV wavelength of 365 nm. Polymerisations were carried out with nitrogen purged monomers in the temperature range 30–60 °C.As a control static film polmerisations were conducted under similar conditions. G14 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 The results of the experiments indicated that there is a definite potential for adaptation to photo-initiated polymerisations. A particular observation concerning polymer micro structure was that even at 66% conversion there were no signs by NMR of any branching. As is well known this is a common feature in conventionally prepared poly(n-butyl acrylate). As a result of these results it is hoped to develop a predictive model for this polymerisation procedure and extend investigations to other monomers and other polymerisation mechanisms e.g.cationic. We believe that the characteristic features of the SDR which have been described earlier in this article have proved to be of importance in the performance of UV-initiated polymerisation reactions. However the enhanced degree of mixing at the molecular level (micro-mixing) should lead to improvements in reaction times and efficiencies of currently utilised photochemical reactions even where production costs are already reduced by using photoreactions e.g. the synthesis of caprolactam for nylon-6 production. The synthesis of vitamin D components by application of the photo-Cope reaction might benefit from the use of SDR characteristics as may other organic reactions that involve UV-irradiated steps e.g.Rose oxide from citronellol. In any photochemical reaction that involves appreciable conversion of reactants to products it is very likely that the absorbance of the system will change significantly as the reaction proceeds consequently the validity of the Beer–Lambert Law is in question since the presence of a time-dependent concentration gradients do not allow one to assume the law to be valid. The thin film regime on the spinning disc may well reduce these problems. The use of UV radiation in the sterilisation of water represents an area of technology where increased efficiency may be achieved where the water is present in a thin film. A similar area of water treatment makes use of semiconductor photocatalysts (R)6 for the removal by oxidation or reduction of trace toxic chemicals e.g.phenol or chlorinated solvents present in industrial water effluents. The economic viability of slurry reactors has been questioned for such use and although some progress has been reported by the use of fixed bed catalysts (R),7 low surface area to volume ratios and inefficiency due to absorption and scattering of the applied radiation by the reaction medium seem to be limiting factors in their adoption. Conditions on a spinning disc should reduce these drawbacks considerably perhaps using immobilised semiconductor catalysts. References 1. (a) M. A. Latham US Patent 2750320 (1954); (b) G. Weickert Eng. Chem.Res. 1998 37 799. 2. G. Ciamician Science 1912 36 385. 3. H. Morawetz Polymers The Origins and Growth of a Science. John Wiley & Sons New York (1985) p.125 4. C. F. Ryan and J. J. Gormley Macromolecular Synthesis 1st edn. Ed. C. G. Overberger John Wiley & SonsNew York 1963 pp. 30–37. 5. (a) P. J. Arndt et al. German Patent DE 3208369 to Rohm GmbH 1983; (b) J. Boutin and J. Neel German Patent DE 2716606 to Rhone- Poulenc 1977; (c) J. Boutin et al. European Patent EU 8246 to Rhone-Poulenc 1980. 6. M. R. Hoffman et al. Chem. Rev. 1995 95 69. 7. D. W. Balmenann et al. in Photocatalytic purification and treatment of water eds. D. W. Ollis and H. Al-Ekabi Elsevier Amsterdam 1993 pp. 313–319. Since retiring from Courtaulds Coatings Bill Dunk (Tel. +44 (0)191 222 5206) has collaborated with the Process Intensification & Innovation Centre (PIIC) at Newcastle University UK to develop polymerisation techniques for use in novel reactors with special reference to photo-initiation. Roshan Jachuck (r.j.j.jachuck @ncl.ac.uk; Tel. +44 (0)191 222 5202) a Lecturer in the Department of Chemical & Process Engineering at Newcastle University is involved in promoting the concepts of Process Intensification through his involvement with PIIC. Visit the Green Chemistry homepage 4 FREE electronic access to news articles 4 FREE electronic access to full contents of 1999 Issue 1 http://www.rsc.org/greenchem

ISSN:1463-9262    

DOI:10.1039/b000158i

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

University of Oregon Green Chemistry Laboratory Anew teaching laboratory which focuses on reducing waste and chemical hazards in organic chemistry has been opened at the University of Oregon USA. Professors Jim Hutchison and Ken Doxsee have developed the “green” organic chemistry curriculum over the last few years. Their experiments teach the same principles as a traditional organic laboratory but use solvents and reagents that are less toxic and teach students to consider the environmental cost of the chemistry they are learning. Students learn how to evaluate potential hazards of chemical processes and suggest creative ways to minimise their human and environmental impact. Students substitute less-toxic solvents and reagents and minimise waste by recycling the products into future experiments.One experiment soon to be published in Journal of Chemical Education teaches students how to synthesise adipic acid a chemical used to make nylon. Typically nitric acid is used as the oxidant. An unfortunate byproduct of the experiment is nitrous oxide a chemical that contributes to ozone depletion and global warming. Instead students substitute hydrogen peroxide and a simple catalyst significantly reducing the hazard. Because green chemistry focuses on using environmentally benign chemicals students can perform experiments using the larger quantities typical of industrial and research settings; hence green chemistry allows the student to move closer to reality in their chemical experiments.Professor Hutchison believes that the new laboratory will prepare students to contribute environmentally responsible solutions to chemical problems in their future careers. “They will act,” he says “as green ambassadors when they enter the job market”. Many companies are now focusing attention on green considerations as they struggle to keep abreast of regulations and satisfy environmentally aware consumers and Student working in the green chemistry laboratory at the University of Oregon USA. Professors Jim Hutchison (left) and Ken Doxsee (right) developers of the green organic chemistry curriculum at the University of Oregon USA. C G FOR U M investors; examples include Intel 3M and DuPont who are all seeking to phase out harmful chemicals reduce water consumption reduce waste generation etc.To further promote green chemical education Professor Hutchison hopes to see the University of Oregon become a national centre for green chemical education where educators from colleges universities and high schools learn green methods and curriculi to take back to their schools and laboratories. For further information contact Lynde Ritzow Graduate Recruiting Coordinator Chemistry Department 1253 University of Oregon Eugene OR 97404-1253 USA. Email lynde@oregon.uoregon.edu Sustainable development report A report has been presented by UNICE the union of industrial and employers’ confederations of Europe called Agenda for Promoting Sustainability to the EU environment commissioner and the president of the European environment council.In the report European businesses reiterate their commitment towards taking a growing role in promoting sustainable development. Commissioners are to receive a paper containing more focused suggestions in the near future once UNICE’s directors give approval. According to UNICE sustainable development is only possible through the integration of environmental economic and social policies and urges clearly defined European environmental objectives involving both producers and Green Chemistry February 2000 G15 This journal is © The Royal Society of Chemistry 2000 F O R U M C G consumers. Its recommended approach is for more scope for companies’ own environmental initiatives more emphasis on partnership agreements and more costeffective legislation (http://www.unice.org).Power plants from short-rotation coppice Several UK companies are building new power plants utilising renewable energy resources such as short-rotation coppice. RRBRE is building the first at Eggborough Yorkshire to be completed in March 2000 to produce 10 MW of electricity from wood chips 75% from short-rotation coppice grown on 2000 ha within 40 miles of the plant. Others include Border Biofuels whose Carlisle plant producing 20 MW in the first phase and a further 10 MW in the second is due to start up in spring 2002; plans for a second plant at Newbridge on Wye await planning permission.Ambient Energy plans to open 5.5 MW plants at Eye Suffolk and at Cricklade Wiltshire by June 2001. Green Chemistry in Japan Japan will launch an Alliance for Green and Sustainable Chemistry in spring 2000. This will include a new centre for a Green/Sustainable Chemistry Network. There will be a strong emphasis on international collaboration. These initiatives follow from the workshops on green chemistry in Tokyo held in November 1999 along with a survey of the news of academic and industrial chemists. The workshop involved 67 invited delegates from academia industry and other interested organisations. The survey on green chemistry revealed a number of interesting points 4 71% recognised the term “green chemistry” 4 the majority of respondents believe that the major driver towards the greening of chemical processes is societal 4 11 key areas of development were identified including alternative reagents and renewable feedstocks The importance of recognising the declining public image of chemistry was also highlighted by another survey among 5th grade elementary schoolchildren.This revealed that while the majority (57%) G16 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 believed that science and technology improved their quality of life a majority (53%) also believed that science and technology cause many problems for society. A major initiative to promote chemistry at school level “Dream Chemistry 21” (Chemistry will make our dreams come true in the 21st Century) is now running with sponsorship from several organisations.EU to clamp down on hormone-mimicking chemicals The EU has pledged to clamp down on a group of chemicals believed to damage both animal and human health by mimicking the effects of hormones in the body. So-called endocrine disruptors have been linked to a range of health problems in animals including the development in fish of both male and female reproductive organs. They have also been linked to hormone-related cancers lowered sperm counts and birth defects in humans. Some of the chemicals suspected of having these effects include those used in certain paints and in some pesticides as well as the phthalates used to soften plastics.Environment Agency joins forces with Fire Service A new partnership has been formed in the UK between the Environment Agency the Fire Service and Local Authorities. This will ensure that all fire-fighters are properly trained and equipped to reduce the environmental impact of an accident before Environment Agency officers are able to attend to provide technical support and assistance. The early actions of firefighters at a pollution incident are very important and can significantly limit the environmental impact of many incidents such as fires and road traffic accidents. (Environment News Service December 1999). Centre of excellence for the UK chemical industry A major boost for Britain’s largest export industry was launched on 19 October 1999 by Yorkshire Forward.The Chemical Industries Regional Centre of Excellence (CIRCE) is a unique facility within the UK provided to help new and established businesses and universities. The £3M facility has been built beside Hickson & Welch’s site in Wheldon Road Castleford but will operate independently to encourage innovation and improve the business performance of companies in the chemical and related sectors. It has been funded by a £685,000 grant from the Department for Education and Employment’s Centre of Excellence Fund and £665,000 from European Regional Development Funds. Hickson has also donated a building. Although the public funding is earmarked for small and medium enterprises within the Yorkshire & Humberside Region CIRCE can also carry out work for clients based across the UK.The opening of the centre marked a major milestone in offering help to Britain’s chemicals industry which has an annual trade surplus of £4 bn. In Yorkshire & Humberside it employs more than 30,000 people about 11% of the UK total. CIRCE offers an independent testing and analysis service to businesses throughout the UK. This includes chemical analysis including method development process safety testing and environmental impact testing. A broad range of training courses focused towards the chemical industry is also being offered. In addition the centre has available specialist business incubation units for small chemical companies including startup and spinoff companies.Competition from developing countries has increased the need to modify develop and manufacture high quality products faster and more cheaply. CIRCE will concentrate on enhancing the technical skills of those already in the industry help attract new business and retain graduates by providing unparalleled opportunities for training research and development (E-mail keith.crane@yorkshireforward. com). Sustainable chemistry in Europe The European Chemical Industry Federation CEFIC organised a symposium on Sustainable Chemistry as part of its 10th Sustech meeting in Brussels in December 1999 (http://www.cefic.be/sustech/sustech10/ programme.htm).The symposium included presentations about the sustainable and green chemistry activities in the US and Japan (given by Nhan Nguyen and Masao Kitajima respectively) as well as an overview of green chemistry and its importance to chemistry and the chemical industry (James Clark). It was interesting to note the similarities in the various initiatives around the globe and common goals that were shared notably the drive towards more environmentally friendly products and processes and the recognition of the need to improve the image of chemistry and to attract more able young people into the area. The meeting also included a poster session largely designed to promote technology transfer. The Japanese initiative is relatively new.Their “New Sunshine Project” will focus on key areas including carbon dioxide fixation catalysis biodegradation and supercritical fluids. It is based on an alliance between industry government and academe. The plans for a European Green and Sustainable Chemistry award scheme were described by Allan Astrup. Plans are at an advanced stage and involve the Green Chemistry Network who are likely to be involved in administering the awards. David Bricknell highlighted the concerns of the European industry. These included the word “green” and ill-defined labelling which can promote one product as being greener than others. He also stated the view that the industry was already heading down the road towards sustainability and did not need outside intervention to drive this.Further information on the Sustech programme can be found on http://www.cefic.org/sustech. Non-food crops …the new Food Chain and Crops for Industry Foresight panel has set up 6 task forces including “Unlocking the potential of industrial crops”. For more information contact David Rawlins on (0171) 215 6703. …the House of Lords Select Committee Report on Non-Food Crops (NFCs) was published on 9 December 1999. The main points in the report were 4 NFCs have significant potential to make an impact both on sustainable land use and economic activity particularly those intended for use in energy production or as sources for fibres in biocomposites.4 NFCs used for the production of speciality chemicals notably pharmaceuticals are also likely to become increasingly economically viable although this will depend greatly on quality and the development of new processing techniques. 4 The use of genetic modification techniques increases the number of potential applications for non-food crops. However it is important to continue to address potential environmental concerns during the development of such crops. 4 Few incentives either from taxation or subsidies promote long-term development of potentially important non-food crops. The Committee recommended increased co-ordination and availability of research funding in order to take advantage of a rapidly developing area.…ACTIN is organising a seminar ‘Industrial uses of wheat’ on 22 March 2000 at Chilford Halls near Cambridge UK. The subjects to be discussed include 4 thermo-mechanical pulping of wheat straw 4 packaging materials from wheat flour 4 wheat straw in construction materials On the preceding day 21 March 2000 ACTIN is also organising a workshop for all those interested in the LINK Programme ‘Competitive Industrial Materials from Non-Food Crops’ (CIMNFC); this workshop will comprise a number of papers followed by discussion on the topic of Extraction Technologies. For further information contact Ms. Saija Nakari at the ACTIN Help Desk (Tel. +44 (0)1372 802054; email info@actin.co.uk) “The UK a long way from sustainability” An environmental think tank Forum for the Future (founded by three prominent environmental activists Paul Ekins Sara Parkin and Jonathon Porritt) has published a report entitled “Estimating Sustainability Gaps in the UK.” The gaps identified include 4 air pollution—where the report says emissions of CO2 SO2 and NOx continue at unsustainable levels.It estimates that on current trends it will take 126 years for the UK’s emissions F O R U M C G to reach sustainability. 4 water pollution—where abstraction is a number of areas is above sustainable levels and for a number of pollutants quality standards for surface waters are still being exceeded. 4 generation and disposal of waste— where the gap between the current situation and the various policy targets that have been adopted is substantial and in some cases growing.The report written by Paul Ekins and Sandrine Simon from the Department of Environmental Social Sciences at Keele University criticises the UK Government’s own sustainable development indicators which although welcome in themselves fail to identify sustainability standards and UK environmental performance in relation to them. For more information see http://www.forumforthefuture.org.uk/ UK Government’s Chemicals Strategy paper On 16 December 1999 the Department of Environment Transport & the Regions (DETR) published its Chemicals Strategy paper following its consultation document “Sustainable Production and Use of Chemicals” (Green Chemistry 1 G47).The main goals of the strategy are to 4 make full information publicly available about the environmental risks of chemicals 4 continue reduction of risks presented by chemicals to the environment and human health—while maintaining the competitiveness of industry 4 phase out early those chemicals identified as representing an unacceptable risk to the environment The Strategy proposes measures to speed up assessment of the environmental risks posed by chemicals. The Strategy also proposes that a Stakeholder Forum with representatives of all those groups with an interest in chemicals should be set up to help build consensus on future policy on chemicals and the environment. For more information on the Strategy consult http://www.environment.detr.gov.uk/ chemistrat/ The UK Chemical Industries Association (CIA) has welcomed the publication of the strategy paper by the DETR endorsing the goal of sustainable development and welcoming the manner in Green Chemistry February 2000 G17 This journal is © The Royal Society of Chemistry 2000 F O R U M C G which the industry’s Confidence in Chemicals initiative has been recognised.However the CIA states that the targets set out in the paper are challenging and it intends to work with its member companies and government to ensure it delivers its commitments on a voluntary basis. Appeal for pesticide reduction In an open letter addressed to European Environment Commissioner Margot Wallstrom on 28 October 1999 the Pesticide Action Network Europe (PAN Europe) criticises the EU for failing in its commitment to substantially reduce chemical pesticide use throughout Europe by the year 2000 despite heightened consumer anxiety over food production methods.Around 300,000 tonnes of pesticide active ingredients are released into the European environment each year. The EU’s Fifth Environmental Action Programme had promised a significant shift from pesticide dependence towards sustainable pest control methods. Two months before the programme expires nothing at all has been achieved. Some EU countries such as the Netherlands Sweden Denmark and Finland have recognised the urgency of the situation by adopting their own successful pesticide reduction programmes.PAN Europe is asking the rest of the EU to follow their lead. CIA welcomes Government paper on chemicals management The UK Chemical Industries Association (CIA) has welcomed the UK Government’s strategy paper on chemicals management issued on December 16 1999 by the Department of the Environment Transport and the Regions (DETR); it is entitled “Sustainable Production and Use of Chemicals. A Strategic Approach. The Government’s Chemical Strategy”. The paper’s goal is sustainable development which is welcomed by the CIA although it is also seen as being challenging. The CIA intends to work with member companies and the government to ensure it delivers its commitments on a voluntary basis.The paper represents a new approach from the UK Government which G18 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 recognises stakeholder involvement and can be viewed at http://www.environment.detr.gov.uk/ sustainable/chemicals/strategy/ New Green Chemistry Newsletter in the US The first newsletter from the newly formed Green Chemistry and Engineering Subdivision of the ACS I&EC Division recently appeared (http://green.chem.umb.edu/greenchem/). This results from the meeting of interested professionals at the ACS National meeting in New Orleans in the summer of 1999. The meeting concerned the future of the Practical Pollution Prevention subdivision and led to the proposal for its replacement by the new subdivision.This was approved and a number of volunteers have agreed to assist with programming with the first session from the new subdivision scheduled for the San Francisco ACS meeting in the spring of 2000 (Green Chemistry for the Reduction of Greenhouse Gases). At the Washington meeting in August 2000 there will be sessions on Clean Solvents and Green Chemistry Applications in Academia and Industry. The draft mission statement for the subdivision is “The Green Chemistry and Engineering Subdivision focusses on activities related to waste minimization the development of green manufacturing processes and the minimization of environmental and manufacturing costs. Chemists and engineers involved in green manufacturing waste minimization and chemical process optimization are encouraged to participate” The Programming chair is Martin Abraham (University of Toledo) Membership co-Chairs are Dan Tedder (Georgia Tech daniel.tedder@che.gatech.edu) and Michael Gonzalez (EPA gonzalez.michael@epamail.epa.gov).The Public Relations officer is Mary Kirchoff (EPA) and the web site is being looked after by John Warner (University of Massachusetts Boston). The future’s green Two leading chemists have highlighted the importance of green chemistry to the future of chemistry and the chemical industry. The ACS President Professor Wasserman has said that “The major concern of the chemical industry will be green chemistry.” He has also stated that the greatest impact will come as a result of improvements in catalysis.Joe Blaker former Group technical director at Glaxo- Wellcome and now Chair of the UK Government’s Technology Foresight Chemicals Panel has said that environmental concerns will transform the face of the chemical industry by 2010. He sees for example chemical plants the size of garages becoming commonplace and new chemical plants being more environmentally friendly. He believes that the public attitude towards the chemical industry will improve as a result of industry moving towards lower energyconsuming less wasteful and nonenvironment threatening plants and processes (Chemistry and Industry December 20 1999). Green Chemistry Network .the Green Chemistry Network website (http://wwwchemsoc.org/gcn) is proving very popular with spot checks indicating over 900 hits per month. The site has been extensively updated and hence is well worth a visit or a re-visit. A members’ area has been added which will initially contain a database of members and their areas of interest and expertise. It is hoped to extend this to include a comprehensive database on green chemistry including who is doing what industry examples educational materials etc. .remember that the closing date for nominations for the UK Green Chemistry Awards to be administered by the Green Chemistry Network [with support from Salters’ Company The Jerwood Foundation Department of Trade and Industry (DTI) Department of the Environment Transport and the Regions (DETR) and the Royal Society of Chemistry (RSC) is now 31 May 2000; there will be an award of £10,000 for a young academic and two awards for industry. For further information on these awards see Green Chemistry 1999 G136-G137.

ISSN:1463-9262    

DOI:10.1039/b000160k

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

Eco-labelling legal decent honest and truthful? Becky Allen reports on the rise of eco-labelling its scientific basis and the operation of key national Coverage Eco-label EU Eco-label EU member states plus Norway Liechtenstein and Iceland Norway Sweden Iceland and Finland 1989 Sweden Germany France Netherlands Austria Nordic Swan Good Environmental Choice (Bra Miljoval) Blue Angel NF Environnement Stichting Milieukeur Umweltzeichen Bäume AENOR Medio Ambiente Spain USA Canada Japan Green Seal Programme Environmental Choice Eco-mark Eco-labels from around the world. Clockwise from top left Nordic Swan* (Scandinavia); Green Seal (USA); Blue Angel (Germany); AENOR Medio Ambiente (Spain); EU Eco-label (EU); Eco-mark (Japan).*The paper for this journal has been awarded the Nordic Swan Label. and international schemes The phenomenon of “green consumerism” emerged during the 1980s on the back of increasing publicity and public concern about environmental issues like global warming. Manufacturers and suppliers of many consumer products saw this rising concern as an opportunity to market new and existing products on the back on environmental claims and policy-makers viewed both developments as a chance to stimulate production and consumption of goods that were less damaging to the environment. The 1980s and early 1990s saw the launch of dozens of national—as well as two international—eco-labelling schemes. Although some have overlapping jurisdictions most of the schemes share similar objectives and operate in the same way.Eco-labelling is a market-based instrument with dual aims to enable consumers to make environmentally informed purchasing decisions; and to encourage manufacturers to produce more environmentally friendly products. With the exception of the US Green Seal and Sweden’s Good Environmental Choice all major eco-labelling schemes are overseen by public bodies. Voluntarism transparency independence and stakeholder participation are central tenets of most eco-labelling schemes. Most eco-labelling schemes are based on the principles of “life-cycle assessment” (LCA). A methodological heir to the global modelling studies and energy audits of the 1960s and 1970s LCA can been seen as part of a general trend towards risk assessment in other spheres such as health and safety.Life-cycle assessment LCA’s primary function is to compare life cycles of alternative processes products or services designed to achieve similar C G Key eco-labelling schemes Date of inception 1992 1990 1977 1992 1992 1991 1993 1989 1988 1989 F EAT U R E Green Chemistry February 2000 G19 This journal is © The Royal Society of Chemistry 2000 F EAT U R E C G objectives in order to discover which is the most environmentally sound.1 As the name suggests LCAs take a “cradle-to-grave” approach to assessing environmental impact (both positive and negative) looking at the raw materials resources manufacturing processes and disposal methods of a given product process or service.While some elements of the assessment—such as energy water and resource consumption— are relatively straightforward to represent numerically others—such as pollution—are more subjective and inevitably involve value judgements. The EU eco-label One of the two major international schemes the European Union (EU) eco-label examines five stages of a product in its LCA 4 pre-production 4 production 4 packaging and distribution 4 use 4 disposal At each stage a number of environmental effects are considered including waste; noise; air contamination; water contamination; ecosystem effects; energy consumption; natural resource consumption; and soil pollution.Apart from the impact of noise most other criteria draw heavily on chemistry and the expertise of chemists in these fields. The EU eco-label has been in operation since 1992 and aims to provide a single authoritative and widely recognised guide to consumers on products which are less harmful to the environment than their alternatives. However the EU eco-label has been only a qualified success. The scheme was one of the first of its kind to award labels on the basis of a serious assessment of the environmental impact of products throughout their life cycle and although it has done much to raise the profile of LCA as a policy and product management tool its visibility and impact on the market have been disappointingly low.By March 1999 only 250 products had been awarded the EU eco-label. Covering all consumer goods except food drink and medicines the EU ecolabel’s criteria are adopted by qualified majority voting among member states which had set criteria for 15 product groups—from toilet paper and light bulbs to washing machines and laundry detergents—by 1999. The following are the product groups for which the EU has already set criteria G20 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 4 footwear 4 textiles 4 light bulbs 4 bed mattresses 4 refrigerators 4 dishwashing detergents 4 laundry detergents 4 washing machines 4 dishwashers 4 copying paper 4 soil improvers 4 personal and portable computers 4 tissue paper 4 paints and varnishes 4 bed linen and T-shirts The criteria are revised every three years.2 While the criteria are set by the European Commission eco-labels themselves are awarded by the competent national bodies.The EU scheme has been criticised from several quarters. Small- and medium-sized enterprises (SMEs) say that obtaining an EU eco-label is prohibitively expensive (applications cost 500 ECU plus 0.15% of annual volume sales in the EU of the eco-labelled product) and even large retailers have been far from enthusiastic. In its submission to the UK’s Environment Select Committee in 1999 major UK food retailer Sainsbury’s plc said “From the beginning Sainsbury’s was supportive of the principles behind the EU eco-labelling scheme.However we became increasingly disappointed with the lack of progress and in our opinion the following reasons contributed to its recent demise within the UK high cost; assessment criteria [which] took far too long to be agreed; and lack of consumer interest.”3 Despite Sainsbury’s views the UK Government remains committed to the EU eco-label even though it wound up the UK eco-labelling board in 1998. For more information about the EU Eco-label contact the European Commission DGXI-E.4 Rue de la Loi 200 – B1049 Brussels Belgium. Tel +32 (2) 295 77 55. Fax +32 (2) 295 56 84. Email ecolabel@dg11.cec.be Revising the EU eco-label The EU published a proposal to revise its eco-labelling scheme in December 1996 cautiously admitting that the scheme has suffered from “certain difficulties” not least of which have been delays in setting criteria.The proposal also concedes that the EU eco-label’s visibility on the European market is still low but says that it is still too early to judge the scheme’s impact “It is premature to assess the market effects of the Community scheme given that the Community eco-label has not yet gained sufficient visibility in the market place because of its still relatively early stage of development. The potential of eco-labels for market influence has already been demonstrated by national and other schemes. However the Community scheme has encountered particular obstacles to the full development of its market potential.”4 As well as slow progress in setting criteria and poor visibility the eco-label has also been hampered by differences in market structures and consumer expectations between member states and the applicability of criteria to non-EU producers.As a result the proposal suggests that a revised eco-labelling scheme should be more flexible. “It would help to introduce a graded label allowing for greater flexibility in setting the criteria and providing information to consumers on the level of ‘environmental performance’ of each labelled product,” the proposal says. One route towards greater flexibility may be the award of between one to three eco-label flowers instead of the current “pass or fail” regime.The proposal also acknowledges that the scheme is too expensive for industry and the proposed revision suggests the introduction of a ceiling on annual fees as well as reduced rates for SMEs and manufacturers from developing countries. A measure of success As well as the operational criticisms levelled at the EU scheme there are more fundamental critiques of LCA and hence all eco-labelling schemes. Measuring the environmental impact of eco-labelling is extremely problematic. Most schemes have operated for too short a time to be analysed but even for more established schemes quantifying the environmental impact of eco-labelling—as opposed to other environmental policy tools—is difficult.Success therefore tends to be measured in terms of consumer awareness manufacturers’ demand for eco-labels and market information although the latter is also difficult to measure due to commercial confidentiality. Market share is not intrinsically indicative of an eco-label’s success as criteria are generally set (and revised) so that only around 5–30% of products in any one category can obtain an eco-label but market power conferred on producers with eco-labels (i.e. whether a product can command a higher price or market share) is an indication of success. Manufacturers’ demand for eco-labels as with the Blue Angel in Germany (over 4100 products in 76 categories had been awarded the Blue Angel by 1996) is also an indicator of a scheme’s success.In 1997 the Organisation for Economic Co-operation and Development (OECD) produced a report on the impact of selected eco-labelling schemes.5 The report found that consumer awareness was a key indicator of a scheme’s success. Thus the success of the Nordic Swan in Sweden—which is recognised by 95% of the population—is attributable to high levels of consumer awareness. In contrast to Sweden consumer awareness in Japan is relatively low with only 47% of those questioned in a 1997 survey recognising the Japanese Ecomark. As a result says the OECD report “In Japan a wide variety of environmentally preferable products is available. However their sales have been negligible with the exception of recycled copy paper.” Although there are no data on the consumer awareness of the Green Seal in the USA it might be expected to be higher than that of the Eco-mark in Japan.The OECD attributes the Green Seal’s limited success to its rather different operation in that it is privately administered by a nonprofit making organisation “The success of the Green Seal scheme has been rather limited so far in part due to the reluctance of industry to engage in third party ecolabelling.” In Germany too there seems to be a problematic relationship between consumer awareness and buying patterns. Historically high levels of awareness appear to have fallen and the OECD report suggests that this may be partly due to consumers becoming confused by the proliferation of eco-labelling schemes.“Overall eco-labelling has been at best moderately successful with individual consumers. The proliferation of all types of environmental labels on products has created confusion among consumers and official eco-labelling programmes have not succeeded in avoiding this problem,” the OECD says. The German experience also highlights the fact that in general ecolabelled products have only had a significant impact on the market in certain product categories and that green products need to be competitive on price and performance to succeed in the marketplace. Where schemes have had a greater impact however it has been when eco-labels become a requirement imposed by retailers and/or used for government and institutional purchasing decisions.Although little direct evidence is available on the environmental impact of eco-labels a Nordic Council of Ministers evaluation gives a flavour of the effect of the Nordic Swan. In detergents for example eco-labelling has resulted in an end to the use of optical brighteners certain surfactants and chelates and ecolabelling of detergents has played a major part in product development in the sector. Green claims code The UK Government remains committed to eco-labelling as a policy tool although it believes the scheme should be repositioned and used primarily for key products traded across the EU. The Government was also concerned that consumers were not getting the information they needed and launched the Green Claims Code in 1998 to give manufacturers guidance on making accurate environmental claims on product labels.6 “The principles set out in this code should help create a level playing field where good claims are able to command the credibility they deserve,” the Government said.Although the code is voluntary Environment Minister Michael Meacher warned manufacturers “Where voluntary measures don’t succeed we are looking to crack down on the problem through the use of the Control of Misleading Advertisements (COMA) Regulations. This will be helped by a new and international standard [ISO14021] which for the first time defines good and bad practice in green claims making.” The uptake and impact of the code has been monitored since its launch by the National Consumer Council (NCC) but its report on the code’s first year of operation is not encouraging.7 According to the NCC report the code has only been successful among a few large retailers and manufacturing sectors.The report is critical of a number of sectors including the paper products group saying “The overall picture for paper products is of a plethora of conflicting and confusing claims a wide range of logos and several breaches of the code. Claims have changed over the first year of the code but mostly not for the better.” Overall the NCC is not optimistic and suggests that to be effective the code must be legally enforceable. “When the code was launched we were doubtful that as a voluntary code it would be credible uniform in its application and effective.Our experience in monitoring its first year of operation has reinforced this view. The C G code lacks a strong sanction and this is a serious barrier to its effectiveness,” says the NCC. The NCC supports Government plans to enforce the code via the COMA Regulations but it says that to be effective the Regulations must be amended to give the Director of Fair Trading greater power to act against transgressors. Even well-policed eco-labelling however can only be expected to achieve so much and there is a growing realisation that it is only one among many policy tools that can be used to secure environmental improvements.At an EU level this realisation is taking form in the “market transformation” approach which is using a combination of measures—including the EU energy label negotiated sectoral agreements incentive schemes and procurement initiatives—to achieve aims that it was probably unrealistic to believe that eco-labelling alone could achieve. F EAT U R E References 1. Life cycle assessment The Royal Society of Chemistry Environment Health and Safety Committee 1998. 2. http://europa.eu.int/comm/ environment/ecolabel/ 3. Memorandum by the Department of the Environment Transport and the Regions (EL 14) http://www.publications.parliament. uk/pa/cm199899/cmselect/cmenvtra/ 149/149mem27.htm 4. Proposal for a Council Regulation establishing a revised Community eco-label award scheme European Commission COM (96) 603 - EN 1996 http://europa.eu.int/comm/ environment/ecolabel/proprev.htm 5. Eco-labelling actual effects of selected programmes Organisation for Economic Cooperation and Development 1997 http://www.oecd.org 6. The Green Claims Code Department of Transport Environment and the Regions 1998 (http://www. environment.detr.gov/gcc/ and http://www.environment.detr.gov.uk/ greening/greenpro/gcode.htm) 7. The Green Claims Code is it working? National Consumer Council 1999. Further reading Swedish Society for Nature Conservation and Eco-labelling website. http://www.snf.se.hmv/hmveng/ ecolabelling.htm. Global Ecolabelling Network (http://www.gen.gr.jp/whats.html) Green Chemistry February 2000 G21 This journal is © The Royal Society of Chemistry 2000

ISSN:1463-9262    

DOI:10.1039/b000161i

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

F EAT U R E C G Green chemistry resources on the Internet Hamish Kidd from the Royal Society of Chemistry reviews some Research sites UK Centre for Clean Technology York † Websites are constantly changing and hence some of the websites mentioned in this article may have been discontinued. (http://www.york.ac.uk/depts/chem/ staff/Clark-home.html) seduced by what the web has to offer may gain an insight into the type of information that could be available to them. The usefulness of websites varies considerably because some organisations put up web pages merely as advertisements and image builders (often rarely updated) while other actually supply hard data or information links to other sites of interest photo libraries etc. The Internet is continually being updated both with the arrival of new sites and an updating of existing ones—this review can provide no more than a snap-shot of sites currently available.Searching The Internet can be searched using a search engine which employs an index to the material on the Web. Having entered a key word or phrase search engines compile lists of what they regard as potentially relevant sites usually in a perceived order of relevance. There are several available search engines (Box 1) each using a different index and hence giving different results from the same search terms. Metasearch engines give a more comprehensive search as they automatically search several of the major search engines at the same time. One drawback of searching using search engines is that too many hits are retrieved many of which are irrelevant and the user finds it time consuming and unrewarding to plough through a long list of websites of possible interest.On the other hand since less than 10% of all websites are indexed and therefore retrievable using the common search engines many relevant sites are missed by standard searching techniques. the websites† which might be of interest to a ‘green chemist’. Introduction The Internet is one of the most significant revolutions in computing and communications in recent years. The Internet was originally developed about 25 years ago to allow academic and military communities to transfer data between computers. However the creation of the World Wide Web about 5 years ago was the driving force in moving the Internet into mainstream culture with rapid growth in Internet users (an estimated 1 million new users go online every week).There has been a simultaneous increase in the number and diversity of Internet sites with just about every organisation and company as well as thousands of individuals having their own presence in cyberspace. Data G22 Green Chemistry February 2000 available now include text graphics audio and video these being generally assembled onto a ‘page’ which the user can access. Internet users can not only download files but also use the Internet to access various online publications and databases (often requiring the payment of a subscription fee).One advantage of Internet sites over more traditional publishing methods is that they can be rapidly updated and data can be easily copied and incorporated into other applications. This short article seeks to point readers toward some of major websites which might be useful to the ‘green chemist’. Experienced web users may be directed to some undiscovered sites whereas those who haven’t yet been This journal is © The Royal Society of Chemistry 2000 http://www.excite.com http://www.excite.co.uk http://www.altavista.com http://www.altavista.telia.com http://www.infoseek.com http://www.lycos.com http://www.lycos.co.uk http://www.thunderstone.com http://webcrawler.com http://www.yahoo.com http://www.yahoo.co.uk http://www.euroferret.com http://www.hotbot.com http://www.ukindex.co.uk Search engines SINGLE SEARCH ENGINES Excite Excite UK AltaVista AltaVista – Europe Infoseek Lycos Lycos UK Thunderstone Webcrawler Yahoo Yahoo UK Euroferret HotBot UK Index METASEARCH ENGINES Go2 (Metacrawler) DogPile Metafind Internet Sleuth Google (http://www.chemsoc.org/gcn).Institute for Applied Catalysis (http://www.iac.org.uk) Centre for Alternative Technology (CAT) (http://www.cat.org.uk) Questor The Questor Centre was the first industry–university cooperative environmental research centre outside the USA. It was set up in May 1989 in The Queen’s University of Belfast with nine founder industry members and five participating university departments (http://questor.qub.ac.uk/).From this website one can move to QUILL the Queens University Ionic Liquids Laboratory (http://quill.qub.ac.uk/) University of Nottingham – Clean Technology Research Group This grouped is headed by Professor Martyn Poliakoff and is particularly interested in supercritical liquids http://www.go2net.com http://www.dogpile.com http://www.metafind.com http://www.sleuth.com http://www.google.com This is the group headed by Professor James Clark and is particularly interested in catalysis. Professor Clark and Dr Duncan Macquarrie are the scientific editor of this journal and Professor Clark is also the Director of the Green Chemistry Network University of Reading – Catalysis Research Centre (http://www.nottingham.ac.uk/ ~pczsp/clnthome.html) (http://www.chem.rdg.ac.uk/ dept/catrg/catrg.html) Centre for Sustainable Design at the Surrey Institute of Art & Design (Farnham Surrey UK) (http://www.cfsd.org.uk) Cardiff School of Biosciences – Clean Technology Group (http://www.cf.ac.uk/uwc/biosi/ associates/ctgroup/) Italy Interuniversity Consortium of Chemistry for the Environment (http://www.unive.it/inca.html) Italian Group of Catalysis (http://www.fci.unibo.it/gic/) Netherlands Netherland Institute of Catalysis Research (http://www.chem.tue.nl/niok/) Australia Murdoch University Perth (http://wwwscience.murdoch.edu.au/te aching/m234/recycle32.htm) Monash University Clayton (http://www.monash.edu.au/).A new Green Chemistry Centre has been established with substantial funding by F EAT U R E C G the Australian Research Council. For further information contact Colin Raston (c.raston@sci.monash.edu.au) Greece http://www.chemeng.upatras.gr The Department of Chemical Engineering of the University of Patras has several ongoing projects of interest to green chemists. http://www.cperi.forth.gr The Chemical Process Engineering Research Institute (FORTH) in Thessaloniki is particularly interested in reformulated fuels and hydrocarbons energy conservation and renewable resources polymer reaction engineering solid fuels and environmental processes and aerosol and particle technology http://www.iceht.forth.gr The Institute of Chemical Engineering and High-Temperature Chemical Processes (FORTH) in Patras in particularly interested in surface science catalysis and reaction engineering materials science and technology environment and biochemical engineering modeling and computeraided simulation and development of new analytical and diagnostic instruments.http://cheng.auth.gr/cheng_uk The Department of Chemical Engineering of the University of Thessaloniki has several on-going research activities which could be of interest to the green chemist. USA Centre for Clean Technology (University of California) (http://cct.seas.ucla.edu) National Center for Environmental Research and Quality Assurance (NCERQA) (http://es.epa.gov/ncerqa/) National Center for Clean Industrial and Treatment Technologies (CenCITT) (http://es.epa.gov/ncerqa/cencitt/cenci tt.html) Centre for Green Manufacturing—a new centre being built as part of the Alabama Institute for Manufacturing Excellence at the University of Alabama (http://bama.ua.edu/~cgm/) Regulatory and funding sites European Commission A number of EU sites contain information relevant to green chemistry both regulatory information and also Green Chemistry February 2000 G23 This journal is © The Royal Society of Chemistry 2000 F EAT U R E C G information on funding.The following are the principal websites of interest DG III (Environment Nuclear Safety & Civil Protection) http://www.europa.eu.int/comm/dg03/ index_en.htm DG IX (Industry) http://www.europa.eu.int/comm/dg11/ index_en.htm DG XII (Science Research and Development) http://www.europa.eu.int/comm/dg12/ index_en.htm Fifth Framework Programme Energy Environment and Sustainable Development (http://www.cordis.lu/eesd/) European Environment Agency (EEA) – the bulk of the information available on this recently redesigned website is electronic versions of all EEA publications including the Agency’s main environmental assessment reports.(http://www.eea.eu.int) UK Environment Agency England and Wales (http://www.environmentagency. gov.uk) Scottish Environment Agency (http://www.sepa.org.uk) Department of the Environment Transport and the Regions (http://www.detr.gov.uk) (http://www.sourcerer.co.uk/html/ G24 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 Health & Safety Executive (http://www2.dti.gov.uk) (http://www.dti.goc.uk/ost) (http://www.open.gov.uk/hse/) Department of Trade and Industry Office of Science and Technology (OST) National Environment Research Council (NERC) (http://nerc.ac.uk) Engineering & Physical Sciences Research Council (EPSRC) (http://www.epsrc.ac.uk) Biotechnology & Biological Sciences Research Council (BBSRC) (http://www.bbsrc.ac.uk) USA EPA Green Chemistry Program (http://www.epa.gov/opptintr/dfe/ and http://www.es.epa.gov/partners/chem istry/chemistry.html).The EPA organises the annual Presidential Green Chemistry Awards [Green Chemistry 1999 1(4) G88; 1(5) G124; 1(6) G174]. Green Chemistry Institute (http://www.lanl.gov/greenchemistry) National Center for Clean Industrial and Treatment Technologies (CenCITT) (http://cpas.mtu.edu/cencitt/) Industry sites Practically all the major (and most of the minor) chemical manufacturers have their own websites e.g. DuPont Zeneca Monsanto Dow Bayer BASF Novartis etc. Some of these sites are simply designed as image builders but others do give news and some information on R&D. In addition several trade associations have their own websites such as the Alternative Crops Technology Interaction Network ACTIN (http://www.actin.co.uk) (Green Chemistry 1999 1(1) G6) and the Interactive European Network for Industrial Crops and their Applications (IENICA) hosted by the UK Central Science Laboratory (http://www.csl.gov.uk/ienica) (Green Chemistry 1999 1(2) G39) Confederation of British Industries (CBI) (http://www.cbi.org.uk) The Chemical Industry Homepage (http://www.neis.com) SORIS english/soris.htm) (Green Chemistry 1999 1(3) G63) The Greening of Industry Network—this is an international partnership focusing on issues of industry environment and society and dedicated to building a sustainable future (http://www.greeningofindustry.org) Learned Professional and Charitable Societies USA The American Chemical Society (ACS) has a general chemistry website (http://www.acs.org/) American Institute of Chemical Engineers (http://www.aiche.org/) UK Royal Society of Chemistry (RSC) Green chemistry on the Royal Society of Chemistry website (http://www.rsc.org) consists mainly of the journal Green Chemistry (http://www.rsc.org/ greenchem).The RSC also provides The Chemistry Societies Network (http://www.chemsoc.org.uk) which has a variety of information of general chemistry including hosting the Green Chemistry Network (http://www.chemsoc.org/gcn); this network based at the Chemistry Department of the University of York UK was launched in 1999 (Green Chemistry,1999 1(5) G134) (http://www.chemsoc.org/gcn). The main aim of the GCN is to promote awareness and facilitate education training and practice of green chemistry in industry academia and schools.Its website provides a wealth of information on what is going on within green chemistry (news events publications etc.). One useful feature on this website is a list a recent journal articles with a green chemistry theme drawn from the published literature. Society for Chemical Industry (SCI)— details of its meetings several of which cover green chemistry related subjects such as catalysis (http://sci.mond.org/) Institution of Chemical Engineers (http://icheme.chemeng.ed.ac.uk/) Environmental organisations Friends of the Earth (FoE) FoE (http://www.foe.co.uk) in particular have a Factory Watch Website (Green Chemistry 1999 1(3) G61) at http://www.foe.co.uk/factorywatch/ where factories are league-tabled on the basis of their pollution they cause.Greenpeace The Greenpeace site (http://www.greenpeace.org) is another comprehensive site which contains information reports and press releases on all the organisation’s campaigns. WWF Global Network (http://www.panda.org) UNEP–Cleaner Production Program (http://www.unepie.org/cp2/about/ home.html) EnviroNET Australia—Eco-efficiency and Cleaner Production (http://www.environment.gov.au/epg/ environet/eecp/tools11.html) Environmental News Network—deals with all aspects of environmental concerns to the public (http://www.enn.com) Going for Green is a UK environmental awareness campaign funded by both the Government and the private sector which encourages people to live in a sensible way that reduces damage to the environment.The Going for Green website (http://www.gfg.iclnet.co.uk) contains a downloadable green calculator program called EcoCal which allows the user to calculate how green their household is EcoCal is fun to use and gives helpful suggestions on how to improve the environmental impact of your household. Publications Green Chemistry (http://www.rsc.org/greenchem) Journal of Chemical Technology & Biotechnology (http://www.wiley.com/journals/jctb/) Journal of Environmental Monitoring (JEM) (http://www.rsc.org/jem) Journal of Clean Products & Processes (http://link.springer.de/link/servoce/ journals/10098/index.htm) The first newsletter from the newly formed Green Chemistry and Engineering Subdivision of the ACS I&EC Division recently appeared (http://green.chem.umb.edu/greenchem/). This results from the meeting of interested professionals at the ACS National meeting in New Orleans in the summer of 1999. Electronic Green Journal - a journal on international environmental information (http://egj.lib.uidaho.edu) Journal of Industrial Ecology - an international multi-disciplinary quarterly designed to foster both understanding and practice in the emerging field of industrial ecology (http://mitpress.mit.edu/journalhome. tcl?issn=10881980) Educational resources Chemical Industry Education Centre UK (http://www.york.ac.uk/org/ciec/) Network for Chemistry Teaching (http://science.ntu.ac.uk/chph/net chemteach/) National Pollution Prevention Center for Higher Education (http://www.umich.edu/~nppc/) University of York Science Education Group (http://www.york.ac.uk/depts/chem/seg) Chemical Education Foundation—an article on this US organisation which produced a wide variety of educational resources (Green Chemistry 1999 1(3) G60).Their website is http://www.chemed.org) Linksites University chemistry departments worldwide (http://chemdex.org) ChemWeb (http://chemweb.com) WWW Virtual Development Library – Sustainable Development (http://www.ulb.ac.be/ceese/meta/ sustvl.html). This site which is updated every 3 months and gives a vast number of useful links is maintained by the Center for Economic and Social Studies on the Environment located at the Université Libre de Bruxelles Belgium.Internet resources on Cleaner Production in Industry (http://www.marietta.edu/~spilatrs/ cln_prod.html) Links to Cleaner Production Sites (China–Canada Cooperation Project in Cleaner Production) (http://www.chinacp.com/eng/ cplinks.html) Pollution Prevention and Clean Production Europe (http://www.rec.org/poland/wpa/p2cpeu. htm) C G Solstice – an online resource from the Centre for Renewable Energy and Sustainable Technology (CREST) F EAT U R E (http://solstice.crest.org) Environment News Service (ENS) (http://gallery.uunet.be/internetpress/ head101.htm) The GreenWeb Guide—a Danish link site to a wide variety of green sites e.g.those on sustainable development ethical business product life cycle design. There are also university links related book titles research articles and a database of educational programs and sustainable designers (http://home5.inet.tele.dk/nyboe/green web.htm) The Online Fuel Cell Information Center developed by Fuel Cells 2000 (http://www.fuelcells.org/) (available in English and Spanish) gives information on all the latest development in fuel cell development for transportation stationary power etc. together with a huge number of links to organisations involved. Conclusion The sites discussed here give an overview of some of the diverse resources on the Internet available to the ‘green chemist’. With a subject as broad as green chemistry there are a large number of sites of potential interest many of which are difficult to identify by keyword searching. Hence this article is only a starting point for the “green chemistry surfer”. Do you use the Internet? This article is our first attempt to identify green chemistry resources on the Internet and we realise that it is far from comprehensive and will be quickly outdated. We would like to build on the information in this article in future issues. Hence if you have information on any useful green chemistry-related web sites not mentioned in this article please send details to the editor (minhash@rsc.org) so that readers of Green Chemistry can be alerted. Green Chemistry February 2000 G25 This journal is © The Royal Society of Chemistry 2000

ISSN:1463-9262    

DOI:10.1039/b000162g

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

F EAT U R E C G Figure 1 SO2 and NOx emission abatement Soghomon Boghosian of the University of Patras in Greece describes new catalytic and 2+2 0.12 99.995 electrochemical processes which have earned a NATO “Science for Peace” grant Calls for more stringent measures to ban the release of sulfur dioxide and nitrogen oxides are becoming more strident as international concern over their health hazards has grown markedly in recent years. Ultimately it seems that legislative pressures from the European Union and the United States will dictate that emission of SO2 and NOx must be controlled; similar control in the countries of Eastern Europe is anticipated. Catalytic process Researchers from the Boreskov Institute of Catalysis (Novosibirsk) have devised a method (“the reverse process”) which is promising for the attainment of extremely low emission levels with significant capital and operating cost savings.The research will be carried out by Professor Bair Bal’zhinimaev and Dr. Andrey Zagoruiko and is based on non-stationary G26 Green Chemistry February 2000 reaction kinetics mathematical modelling and process engineering. Figure 1 shows the concept of the process in a simplified flow-sheet pertaining to the sulfur dioxide process for sulfuric acid production. The installation (actually the second stage of a Double Contact/Double Absorption system) consists of two catalyst beds. One of the beds is fed with the reaction mixture which contains SO2 (flow line shown solid).SO2 is absorbed in the liquid film on the surface of the catalyst partly oxidising to SO3. In the beginning of the cycle no SO2 is detected in the outlet gas which is discharged to the SO3 adsorber. Meanwhile the second bed is blown by air in the counter-current direction (dotted line). Thus SO2 and SO3 are being desorbed and the catalyst is being oversaturated with dioxygen. When the SO2 content in the outlet of the first bed eventually reaches 50 ppm the gas Figure 2 flows are reversed and the first bed is blown by air while the second operates under catalytic reaction conditions. It should be noted that the oversaturation of the catalyst melt with dioxygen during the first step of the cycle favours the equilibrium.The following table summarises some data which are based on preliminary studies. Number of catalysts beds Loading of Catalyst/ m3 per ton of H2SO4/year SO2 content at the outlet/ ppm <50 Total conversion/ % Electrochemical process Furthermore scientists at the Georgia Institute of Technology (Atlanta USA) led by Professor Jack Winnick have indicated the potential for a novel electrochemical membrane desulfurisation process (EMD) for efficient and economic removal of SO from flue gas. The operation of EMD in a coal-burning power plant is shown in Figure 2. The gas is fed to the cathodes at about 400 °C. While the chemical and electrochemical reactions are somewhat complex the net effect is one of dioxygen reduction and sulfate ion production This journal is © The Royal Society of Chemistry 2000 2 SO3 + 1/2O2 + 2e-? SO4 2- The sulfate ions migrate in the applied electric field across the electrolyte-filled membrane to the anodes where the sulfate is oxidised producing concentrated SO3.4 SO 2- ? SO3 + 1/2O2 + 2e- The net effect is one of continuous in situ concentration of the sulfur oxides from sub-percentage levels in the wet flue gas to 60% or so in the dry process stream available for economic oleum manufacture. A consortium (see box) under the coordination of Soghomon Boghosian has now been awarded a substantial NATO “Science for Peace” grant ($325,000) to help develop the catalytic and electrochemical methods for SO2 and NOx emission abatement.The consortium is in close collaboration with Professor Kenneth R. Seddon (Queen’s University Belfast UK) who acts as a consultant appointed by NATO and two expert/advisors Professor Chris Adams of the Institute of Applied Catalysis (UK) and Dr Paul Anastas of the Environmental Protection Agency (USA). This journal is © The Royal Society of Chemistry 2000 MEMBERS OF THE CONSORTIUM working to develop catalytic methods for SO2 and NOx emission abatement FORTH/ICE-HT Patras Greece Technical University of Denmark Lyngby Denmark Georgia Institute of Technology Atlanta USA Professor Jack Winnick Boreskov Institute of Catalysis Novosibirsk Russia University of Bucharest Romania Byisk Oleum Plant Byisk Russia NATO “Science for Peace” programme The objective of the “Science for Peace” programme is to offer support to Partner countries1 in their transition towards a market-oriented environmentally-sound economy (http://www.nato.int/science/sfp.htm) 1Albania Armenia Azerbaijan Belarus Bulgaria Estonia Georgia Kazakhstan Kyrghyz Republic Latvia Lithuania Moldova Romania Russian Federation Slovak Republic Slovenia Tajikistan Macedonia Turkmenistan Ukraine Uzbekistan.Dr Soghomon Boghosian (Coordinator) Professor Rasmus Fehrmann Professor Bair Bal’zhinimaev Professor Vasile Parvulescu Dr Yurii N. Zhukov Coordinator Soghomon Boghosian holds an M.Sc. (1984) and a Ph.D. (1988) in Chemical Engineering from the University of Patras Greece. After two years as a postdoctoral fellow at the Technical university of Denmark and at the Norwegian Institute of Technology he became lecturer (1995) and assistant professor (1999) in chemical engineering at the University of Patras. His research interests include spectroscopic studies of high temperature molten salts and vapours and spectroscopic studies of systems. Green Chemistry February 2000 G27 F EAT U R E C G

ISSN:1463-9262    

DOI:10.1039/b000163p

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

P E R S P E C T I V E S C G Green oxidations A group led by Ryoji Noyori from Nagoya University in Japan has published a very detailed and thorough paper on their work on green oxidations (Bull. Chem. Soc. Jpn. 1999 72 2287). In this work they have taken sodium tungstate and hydrogen peroxide and used this to oxidise secondary alcohols to ketones a quite difficult task to carry out in a green manner. They run the reaction without solvent. Under these conditions the system is biphasic and they use a phase transfer catalyst methyl trioctyl ammonium sulfate. Yields are excellent with a range of alcohols and competitive experiments show that a large number of functional groups (including epoxides and nitriles) are tolerated. Primary amides do interfere probably by blocking the alcohol coordination site at the metal.A further very impressive feature is that the turnover numbers (mol product/mol catalyst) are extremely high in the range of 79 000 to 179 000 over 100 times better than other systems. The reaction has been carried out with 100 g of bulk substrate indicating that the reaction at this scale presented no difficulties whatsoever. Further uses of this system include the oxidation of primary alcohols to carboxylic acids and the oxidation of benzylic alcohols to aldehydes in good yields can also be achieved. A second example of green oxidation from Japan has been published by Michio Higashijima of Mitsubishi. (Chem. Lett. 1999 1093) He reports the preparation of a ruthenium-substituted heteropolyanion [SiW11O39RuIII(H2O)]5- which is very active as a water soluble catalyst for the oxidation of p-xylene to terephthalic acid.One of the problems of current manufacturing processes for this important product is the corrosive medium (acetic acid Co Mn and Br) in which the reaction takes place. Not only is the bromide very corrosive but the G28 Green Chemistry February 2000 reaction leads to the destruction of significant amounts of the solvent. The new catalyst functions in water at 200 oC and give a good conversion to terephthalic acid (58.8%) after five hours. Other products are partially oxidised compounds such as toluic acid as well as a significant amount of CO2 from over oxidation.Green total synthesis Contributions to green total synthesis from the groups led by Alois Fürstner at the Max Planck Institut für Kohlenforschung in Mannheim have recently been summarised in a very interesting short review (A. Fürstner Synlett 1999 1509). The concept of using catalytic alternatives to improve efficiency and reduce the length of synthetic pathways through novel transformations is well illustrated. The article illustrates how clever use of strategy and innovative methodology can be used to make the synthesis of many complex target molecules more efficient and less wasteful. In particular novel approaches to the formation of heterocyclic rings are discussed. Illustrated are two examples of catalytic processes which are highly efficient and increase the complexity of the molecule This journal is © The Royal Society of Chemistry 2000 significantly.Other processes include a sonochemically assisted SN2 reaction at a sterically hindered secondary position on a mannose residue. Green route to aromatic amines Researchers at Hoechst Marion Roussel have published a route to aromatic amine involving the displacement of aryl triflates with piperidines (L. Schio G. Lemoine and M. Klich Synlett 1999 1559). This work demonstrates that efficient palladium-catalysed coupling of the two reagents takes place under relatively mild conditions (up to 110 oC) in the absence of solvent. Good yields were obtained for a variety of triflates (themselves prepared from phenols with triflic anhydride).The activity of the triflate was correlated with its softness with the reactants with the lowest energy LUMO being the most reactive. Very good yields could be obtained with reaction partners with reactive functional groups. Two limitations were discussed. The hard nucleophile octylamine reacts preferentially with the harder electrophilic sulfur centre in preference to the ring carbon leading to formation of the phenol rather than the coupling product. Bulky amines such as diisopropylamine do not react. Supported aqueous-phase catalysts Glass beads continue to provide interesting opportunities for supported aqueous phase catalysts. Jonathan Williams and Matthew Leese of the University of Bath (Synlett 1999 1645) have shown that guanidinium-substituted phosphines can be used as water soluble ligands for Pd complexes.They claim that the synthesis of these ligands is much easier and more reliable than the synthesis of the more usual water soluble phosphine (TPPTS containing aryl sulfonates as solubilising groups). The resultant catalysts were found to be very active for Heck reactions Sonogashira couplings and allylic substitutions (see scheme below). Very little Pd leaching was noted and reuse was possible. P E R S P E C T I V E S Organometallic catalysis in aqueous biphasic media Roger Sheldon and co-workers have published a very accessible review on “Organometallic Catalysis in Aqueous Biphasic Media” which details recent work on a range of catalytic systems such as organometallics with water soluble ligands (e.g.sulfonated triphenylphosphines). The review (Chemtracts – Organic Chemistry 1999 12 777) discusses applications of these systems in a wide variety of reactions including hydroformylation hydrocarboxylation copolymerisation ring opening metathesis polymerisation (ROMP) hydrogenation and oxidation and Heck coupling reactions. Heterogeneous catalysis in scCO2 Groups led by Martyn Poliakoff at the University of Nottingham and Thomas Swan Ltd. have published details of their work using heterogeneous catalysts in a supercritical CO2 (scCO2) flow reactor (J. Am. Chem.Soc. 1999 121 10711). Deloxan ASP and Amberlyst were used as the solid catalysts and the reactions studied were dehydration of alcohols to ethers and acetal/ketal formation. Generally results were impressive but some unusual effects were also noted. For example large ring ethers can be made in very good selectivity which is in contrast to what is found in the conventional systems where rearrangement to smaller rings predominates. Similarly excellent selectivity towards monomethyl ether formation is seen even with diols which C G otherwise cyclise and with a threefold excess of methanol. Acylation of aromatics The acylation of aromatics remains a formidable challenge for chemists trying to replace aluminium chloride. New research carried out by Wolfgang Hölderich and Alfred Heidekum at the RWTH in Aachen and by Mark Harmer at DuPont Wilmington Delaware has shown that Nafion/silica composites are very promising systems for such chemistry (J.Catal. 1999 188 230). The acylation of anisole with acid chlorides was shown to proceed much more readily with the composites than with the simple Nafion resins themselves. Conversions up to 100% and selectivities up to 97% have been obtained using this system. Formation of 5-membered heterocyclic systems Atom transfer radical cyclisation is an atom efficient method for the formation of 5-membered heterocyclic systems. A group led by Andrew Clark at the University of Warwick has described supported CuI catalysts which are efficient at carrying out this reaction cleanly and in high yields (J.Org. Chem. 1999 64 8954) Green Chemistry February 2000 G29 This journal is © The Royal Society of Chemistry 2000 Materials Chemistry (J. Mater. Chem. 2000 10 P E R S P E C T I V E S Green chemistry reviews in RSC and processing using supercritical carbon dioxide (scCO2) by Andrew Cooper you may be interested to know that Dr Cooper has recently written a much more extensive review of this topic in Journal of journals Useful reviews on broad areas of green chemistry can be found in recent issues of other RSC journals The latest issue of Dalton (J. Chem. Soc. Dalton Trans. 2000 101–110) Professor James Clark along with his colleagues at York (Peter Price and Duncan Macquarrie) has written a perspective entitled “Modified silicas for clean technology”.A wide variety of novel materials can be prepared through the chemical modification of silica gels with organic and inorganic functionalities. In addition to their use in chromatographic separations they have been increasingly used as catalysts in liquid phase organic reactions. It is the application of these materials as viable more environmentally friendly alternatives to traditional homogeneous catalysts that forms the main body of the perspective. Their use as efficient materials for the selective preconcentration of trace metals from aqueous systems is also discussed. If you read the recent article in Green Chemistry (Green Chem.1999 G167–G168) on clean polymer synthesis 207–234). This 28-page review highlights the wide range of opportunities available to the materials chemist through the use of scCO2. The synthetic techniques discussed include homogeneous solution polymerisation precipitation polymerisation dispersion and emulsion polymerisation and bulk polycondensation. The use of scCO2 in polymer processing is fully discussed with examples such formation of microcellular polymer foams polymer particle formation spray coating and microlithography. C G The catalyst could be used twice without leaching of the Cu but with a reduction in rate on the last reuse indicating some deactivation. Yields were still high and only slightly lower than the first use. Fluorous BINOL-Ti complex Groups led by Dennis Curran and Seiji Takeuchi have prepared a fluorous soluble BINOL-Ti complex (Tetrahedron Lett. 2000 41 57) and demonstrated that it is a very active and reusable catalyst for the addition of diethylzinc to benzaldehyde. The fluorous phase could be recovered and reused five times without loss in either activity or enantioselectivity. The preparation of the fluorous BINOL was achieved in four steps from the dibromo derivative in high yield. G30 Green Chemistry February 2000 This journal is © The Royal Society of Chemistry 2000 Read any green chemistry papers? If you have any items from your literature reading which could be included 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/b000165l

出版商:RSC    

年代:2000

数据来源: RSC

摘要:

Conference Diary March 5–9 March 22 March 23–24 March 25 March 26–31 March 2000 Process Design and Operation for Sustainable Development The Hilton Hotel Atlanta (http://www.cpe.surrey.ac.uk/staff/aa.htm) Renewable Raw Materials - March 9 Chemicals from Agricultural Crops University of Wales Aberystwyth UK (http://www.rsc.org/lap/rsccom/locsecs/localsec77.htm) Green Chemistry March 15 University of York UK (http://www.chemsoc.org/events/_events/00002021.htm) Biocatalysis as a tool for organic synthesis March 20–22 Crowne Plaza Hotel Amsterdam The Netherlands (http://www.scientificupdate.co.uk/pages/ biocatalysis/biocat.html) Industrial Uses of Wheat Cambridge UK (http://www.actin.co.uk/newsletter/ index.htm#anchor.events) INBIO Europe 2000 Biocatalysis - New Science and Applications Crowne Plaza Hotel Amsterdam The Netherlands (http://www.scientificupdate.co.uk/pages/ inbio/inbio.html) Teaching the Environmental Sciences in the Millennium Including a session on Green Chemistry Scientific Lecture Theatre Burlington Place London UK (greennet@york.ac.uk) ACS National Meeting Including Green Chemistry for Reduction of Greenhouse Gas Emissions San Francisco California USA (http://www.lanl.gov/greenchemistry/conf.html) April 3–5 April 4–6 April 2000 GreenTech® 2000 - Sustainable Raw Materials Royal Dutch Jaarbeurs Utrecht The Netherlands (http://www.europoint-bv.com/) Hazards XV.The process its safety and the environment—getting it right UMIST Manchester UK (http://www.chemsafety.gov/info/IchemE1.pdf) (mikeadams@valrichardson.com) G31 Green Chemistry February 2000 5th International Symposium on Supercritical Fluids “Supercritical Fluids for Sustainable Technology” Westin Atlanta North Hotel Atlanta Georgia USA (http://www.issf2000.org) Wood and Cellulose Building Blocks April 9–12 for Chemicals Fuels and Advanced Materials SUNY-EST Syracuse New York USA (http://www.epa.gov/opptintr/greenchemistry/calendar.htm) Rapid Process Development and Safe April 12 Process Scale-Up North London UK (http://www.helgroup.co.uk/index.cfm/page,news) CAPoC5 – 5th International Congress on Catalysis and Automative Pollution Control Université Libre de Bruxelles Belgium (http://www.ulb.ac.be/sciences/surfcat/CAPoC5/) 9th International (and 4th European) Symposium on Supercritical Fluid Chromatography and Extraction.In cooperation with Analytica Conference 2000 Munich Germany (sfc2000@mx.uni-saarland.de) RSC Annual Congress including Symposium “Towards Sustainability” UMIST Manchester UK (http://www.rsc.org/lap/confs/sciprog.htm) InLCA The International Conference and Exhibition on Life Cycle Assessment Cincinnati USA (InLCA.CI@epamail.epa.gov) May 2000 Synthetic Methodology and Total Synthesis May 16 New Horizons in NaturalProduct Chemistry University of Glasgow UK (http://www.rsc.org/lap/rsccom/dab/perkidiv.htm) 3rd International Workshop on Green May 16–20 Chemistry in China Guangzhou China (jhf@mail.gic.accn) 16th Canadian Symposium on Catalysis Banff Alberta Canada (http://www.gch.ulaval.ca/~sayari/16csc/) Green Chemistry Symposium University of Leicester UK (greennet@york.ac.uk) This journal is © The Royal Society of Chemistry 2000 C G D I A R Y April 8–12 April 12–14 April 13–14 April 16–20 April 25–27 May 23–26 May 24 D I A R Y September 26–27 June 5–9 Chemsource Clean Technology for Manufacture of Speciality Chemicals New Century House Manchester UK (http://www.chemsoc.org/events/_events/00002188.htm) December 14–19 December 2000 Pacifichem 2000 including Symposium on Environmental Chemistry Honolulu Hawaii (http://www.acs.org/meetings/pacific2000/) April 3–6 April 2001 Green Chemistry Sustainable Products and Processes University of Wales Swansea UK (greennet@york.ac.uk) July 1–7 July 2001 CHEMRAWN XIVWorld July 9–13 Conference on Green Chemistry Toward Environmentally Benign Chemical Products and Processes University of Colorado-Boulder USA (http://www.lanl.gov/greenchemistry/chemrawn.html) July 2–6 July 16–21 August 20–25 September 25–28 C G June 2000 R’2000 Recovery Recycling Re-integration.5th World Congress with Trade Show Toronto Ontario Canada (barrage@peak.ch) Gordon Conference on Industrial Ecology June 11–16 New London New Hampshire USA (ballenby@att.com) 4th Annual Green Chemistry June 26–29 and Engineering Conference “Sustainable Technologies From Research to Industrial Implementation” National Academy of Sciences Washington DC USA (http://www.epa.gov/opptintr/greenchemistry/ calendar.htm#4thGC&EC) July 2000 World Renewable Energy Congress Brighton UK (asayigh@netcomuk.co.uk) 4th International Symposium - Supported Reagents and Catalysts in Chemistry St Andrews University UK (http://ch-www.st-andrews.ac.uk/conferences/) 12th International Congress on Catalysis July 9–14 Granada Spain (http://lcpb00.lc.ehu.es/12icc/index.html) 5th Gordon Conference on Green Chemistry Connecticut College New London CT (http://www.grc.uri.edu/00sched.htm) IEX 2000 Ion exchange at the Millennium July 16–21 Organised by the SCI.Churchill College University of Cambridge UK (http://sci.mond.org/conference/meetings/IEX.HTM) August 2000 ACS 220th National Meeting including Green Chemistry - Applications in Academia and Industry Symposium Washington DC USA (williamson.tracy@epa.gov) September 2000 The 4th International Conference on the Scale-Up of Chemical Processes Including Safety and Environmental Issues Hotel de France St Helier Jersey Channel Islands (http://www.scientificupdate.co.uk) G32 Green Chemistry February 2000

ISSN:1463-9262    

DOI:10.1039/b000167h

出版商:RSC    

年代:2000

数据来源: RSC