C G Green Chemistry August 1999 G89 N E W S Cleaner fuels Gas-to-liquids technology ...Chevron and Sasol in gas-to-liquids joint venture Chevron and Sasol have signed an agreement to create a new global joint venture founded on gas to liquids (GTL) technology, one of the most promising prospects for clean fuel development in the 21st century. The application of GTL technology to the enormous gas reserves located throughout the world could become the preferred method to commercialize such natural gas resources, many of which are remote and cannot easily be made commercial.A proposal was announced in April 1998, in which Chevron and Sasol outlined plans to build a GTL products plant in Nigeria. Design and engineering continue on the GTL facility, which will be capable of converting natural gas into synthetic crude oil for further processing into commercial products, principally high quality diesel and naphtha.The initial feasibility study has recently been expanded to increase target production from 20000 to 30000 barrels per day. The plant is expected to come on stream in 2003. The global joint venture would build on the foundation laid by Sasol, based on their Fischer–Tropsch technology and would utilize proprietary technologies of both companies— Chevron’s ISOCRACKING and Sasol’s Slurry Phase Distillate Process (http://www.chevron.com)....Rentech agreement with Texaco agreement Texaco and Rentech announced the signing of a Technical Services Agreement to research the integration of Rentech’s Fischer–Tropsch technology with Texaco’s gasification process.The goal is to produce a clean burning, sulfurand aromatic-free diesel fuel. The new Agreement calls for technical and developmental work to be carried out at the Rentech research and development facilities in Denver. The companies will work to maximize the hydrocarbon yield from synthesis gas produced by the Texaco gasification process.Rentech Inc. has also completed an agreement with Republic Financial Corp by which Rentech and Republic will jointly develop projects utilizing Rentech’s proprietary Fischer–Tropsch technology. The agreement represents a milestone for Rentech in its efforts to commercialize this technology (http://www.gastoliquids.com). New US sulfur specifications for gasoline On 1 May 1999, President Bill Clinton personally announced newly proposed federal standards for sulfur levels in gasoline that promise to allow automobiles to run 80% cleaner.The tough new specifications call for 30 ppm sulfur in gasoline, down from the The search for cleaner fuels is a major element of the drive to reduce the environmental impact of transport. Many approaches are being taken to reduce the pollution from vehicles.N E W S G90 Green Chemistry August 1999 C G current average of 340 ppm.The US Environmental Protection Agency estimates that this would take 3 million tonnes of pollution out of the air. The oil industry estimates that meeting the new sulfur targets using existing technology will require more than $6 bn in new US refinery investment. Refiners argue that the cost may be too high to meet the new sulfur standards.Biotechnological route to desulfurisation of fuels Energy BioSystems Corp is currently developing its $3 M biocatalytic technology to desulfurize gasoline at a target cost of 1 cent/gallon to 2 cents/gallon of gasoline. Energy BioSystems has already licensed its first unit for diesel fuel biodesulfurization to Petro Star Inc., a subsidiary of Arctic Slope Regional Corp, for their Valdez, AL, refinery.Energy BioSystems Corp of Houston is developing and commercializing biotechnology based processes for the petroleum refining and production industries. The company’s focus to date has been on developing biocatalytic desulfurization, a proprietary process involving the use of enzymes to remove sulfur from petroleum, including gasoline, diesel, and heavy and crude oils, while operating at mild temperature and pressure.The company is also pursuing opportunities to apply the principles of biocatalysis to the chemical industry, initially by developing a line of organosulfur products that are derived from its biodesulfurization process (http://www.energybiosystems.com). Shell Pura Diesel According to Shell, its Pura Diesel meets tough European emissions regulations six years early.A positive response from a London-based trial meant that the national launch was brought forward. Shell claims that Pura Diesel, with its unique formulation, helps meet growing demands from both the public and the government for cleaner fuels, and does so without compromising performance.The good news for the environment is that it contains 90% less sulfur than standard diesel, which means smoke and particulate pollution from exhaust pipes is greatly reduced. Further benefits for motorists arise because its additive package helps prevent carbon deposits building up in the engine, and gives improved combustion and protection against corrosion.Additionally, Pura Diesel is claimed to improve the fuel economy of a vehicle by up to 5–6% (http://www.shell.co.uk). Ultra-low-sulfur diesel Total Oil GB (Watford, Herts) is the producer of Ultra Low Sulfur Diesel (ULSD), which is being produced at its Lindsey Oil Refinery (LOR). Total Oil GB was the first oil company in the UK to introduce the modern cleaner diesel fuel when they introduced ‘City Diesel’ to tackle urban pollution, smoke and particulates (sooty particles) etc.ULSD was defined in the 1998 UK budget and Total Oil GB now produces it at LOR. It offers all the advantages of City Diesel, specifically in the following areas: 90% reduction in sulfur emissions, virtual elimination of black smoke, airborne particulate reduction greater than 30% and reduction of carbon dioxide and carbon monoxide emissions.Total ULSD is designed to be compatible with the latest catalyst equipped vehicles and those which qualify for the reduction in Vehicle Excise Duty. Bus company London United, an existing Total Oil GB customer, has recently announced that it is expanding its use of ULSD by switching its Kingston buses from conventional diesel to the new, green fuel.Low sulfur diesel in India The Indian Oil Corporation has just become the first in India to produce lowsulfur diesel via a hydrodesulfurization process. The capacity is 1.2 million tonnes per year and the refinery at Gujarat cost $127M. There are plans to set up further hydrodesulfurization units at three other refineries. Replacing MTBE Great West Energy and Exploration Inc.of Dallas, TX has entered into an agreement with Millennium Fuels USA that conveys the exclusive right to capitalize and participate in the only plants capable of producing one of the premier alternative replacements for the current refining industry standard additive, methyl-tertbutyl ether (MTBE). MTBE and other ether-type additives, utilized each day by the refining industry as octane enhancers and/or oxygenates, have come under attack due to their ground water contamination, harmful emissions and more importantly their possible effects on the human body.In March 1999, California became the first state in the US to ban the use of MTBE owing to its significant environmental risks. It is predicted that other states such as Massachusetts, New Hampshire, Connecticut, New York and New Jersey among others, will follow suit to ban the use of MTBE by 2000. The additive is produced from various natural hydrocarbons and raw ethanol through a patented process that produces an environmentally friendly octane additive/enhancer and oxygenate.New Fuels E85 from Ford The Twin Cities of Minneapolis/St Paul and Chicago will become test beds for efforts aimed at building sustainable ethanol (E85) infrastructure, and will also be part of a Ford coupon programme aimed at promoting the use of ethanol in flexible fuel vehicles (FFVs).FFVs allow drivers to run their vehicles on any combination of E85 and unleaded gasoline in the same tank. Ford Motor Co. plans to spend at least $1 M on developing retail alternative fuel infrastructure to help increase the use of these environmentally friendlier fuels.Ford is in partnership with the US Department of Energy to develop infrastructure in two pilot areas. In these test cities, Ford will provide eight $5 coupons to every purchaser of a 3 litre Ford Ranger pickup, which has FFV capability, targeting owners living within 15 miles of an E85 outlet.The E85 coupon programme is designed to encourage drivers of the Ranger FFV to visit the 10 E85 refuelling stations opening in Chicago and the up to 30 E85 stations planned for the Twin Cities area. By providing drivers with incentives to purchase E85 rather than gasoline, the Ford Motor Co. hopes to stimulate the use of E85 as an alternative to gasoline (http://www.ford.com). Ethanol blends ...in the US Ethanol currently accounts for less than 1% of US gasoline volume.Gasoline blending provides a market for 1.4 bn lbs/y of ethanol capacity and generates ethanol sales of $1.3 bn/y. The target of 10% ethanol content in gasoline by 1990 has never been approached owing to the price of ethanol and logistical constraints. Its use in hot weather is limited, and there are special requirements for storage and delivery of ethanol-containing gasoline which have led to marketing problems.The ethanol lobby portrays it as the longterm solution for reformulated gasoline, but gasoline producers and analysts do not agree. However, they do see a role for ethanol as a discretionary octane improving additive, and as an oxygenate in some markets. If the US subsidy on ethanol were removed it would probably not beGreen Chemistry August 1999 G91 NEWS C G used at all.It also receives additional subsidies in some US states. ...and in Brazil Brazil was one of the pioneers of the ethanol car, using ethanol derived from the sugar cane industry. In the 1970s and 1980s there were hundreds of thousands of ethanol-powered cars in the country; nowadays there are only a couple of thousand.However, the price of sugarcane ethanol in Brazil is very low at the moment, and pollution fears combined with the risk of substantial job losses in the sugar industry have led the government to persuade General Motors and Ford to restart production of alcohol cars. Fiat and Volkswagen are already producing them in Brazil.The government has announced that it will increase the amount of alcohol added to petrol from 24% to 26% and that taxi drivers will no longer enjoy tax breaks on petrol-fuelled cars, but will continue to do so if they use ethanol as a fuel. Fuel cells Fuel cells for Canada Petro-Canada, Ballard Power Systems and Methanex have announced the signing of a Memorandum of Understanding under which the three companies will work together to prepare for the establishment of a commercially viable fuel distribution network to meet the expected market demand for fuel cell vehicles.Petro-Canada, Ballard and Methanex will collaborate in laying the groundwork for a pilot project involving the supply and distribution of appropriate fuel, starting with methanol to facilitate the introduction of fuel cell vehicles (http://www.petro-canada.ca).Shell Hydrogen Shell is the first of the major oil companies to state its commitment to bringing fuel cells to market, with its formation of Shell Hydrogen. Shell has reached an agreement with a subsidiary of Daimler Benz involving co-operative research into fuel cell power for motor vehicles (http://www.shell.co.uk).Delphi and BMW announce fuel cell developments Delphi Automotive Systems (Troy, Michigan, USA) and BMW have signed a development agreement to produce vehicles that use a solid oxide fuel cell as an auxiliary power unit and that have the potential of being clean, high power generation vehicles. Under the development agreement, BMW and Delphi are jointly developing a fuel cell system that will be used as an auxiliary power unit for gasoline engines.This will allow BMW to offer more features more efficiently with the potential to reduce the emissions of an internal combustion engine. Delphi will develop the fuel cell system and BMW will integrate the unit into a vehicle. The solid oxide fuel cell unit will provide more energy into the vehicle to enhance the electrical systems.Delphi and BMW plan to produce the solid oxide fuel cell unit in the near future. The solid oxide fuel cell unit has the ability to increase the electric power within a vehicle to offer more features in the most efficient way. Additionally, it provides tremendous potential to reduce the emissions of the internal combustion engine (http://www.delphiauto.com).Hydrogen fuel cell vehicles Zevco, a British manufacturer of hydrogen fuel cell powered vehicles, has announced that it will become listed on the Easdaq and Nasdaq stock exchanges this year. This will allow the company to meet the expected increase in demand. The company is negotiating a contract to supply some vans to the UK Royal Mail, and has recently introduced the first zeroemission taxi to New York following its launch of the zero emission London Millennium Taxi.Other tests for short journey vehicles (e.g. taxis to and from airports) are being held, and the company expects to start manufacturing in the US soon. More on cars Automatic shut-off Honda has announced that it will market a scooter, the Giorno Crea DeLuxe, which automatically shuts off when stopping.The price will be around £1000. The scooter emits about half the levels of pollution allowed in Japan, and is also claimed to be more fuel-efficient than similar scooters. Germany stalls car recycling The European Union has been working on a plan to make car producers bear the cost of recycling old cars. However, the European Automobile Manufacturers Association (ACEA) have been lobbying strongly against this proposed law.The law has finally been defeated amidst accusations of Germany buckling under pressure from its powerful car lobby. ‘It is quite clear that the way the German presidency handled the end-of-life car directive was nothing less than a disgrace,’ Peter Jorgensen, spokesman for Environment Commissioner Ritt Bjerregaard, told a news briefing.The legislation would only have added 0.5% to the price of a new car, Jorgensen added. German Chancellor Gerhard Schroeder said recently that an appeal from Volkswagen AG had prompted his country to think again. Schroeder is a former member of VW’s supervisory board. Britain and Spain, both with significant car manufacturing capacity, said they were sympathetic to the Fuel cell taxi cab (London) from Zevco First generation fuel cell transit bus from Ballard Power SystemsNEWS C G G92 Green Chemistry August 1999 German position.It will now be up to the next EU president, Finland, an enthusiastic supporter of the proposals, to find a compromise. Environment ministers next meet in October, though Finland has said it would consider dealing with the proposal before then.CO2 deal between EU and Korea, but not yet with Japan The European Commission has struck a deal with Korea to reduce pollution from cars in a voluntary scheme. This would mean that average fuel consumption would be reduced from the current average of 7.7 litres/100 km to around 6. The European Commission has said that it is seeking to achieve this by 2008, the Koreans by 2009.Japan has not yet agreed, claiming that it has a different balance of the large and small car markets to the other countries, and that the target will affect it differently. The European Union has threatened to impose restrictions if a voluntary agreement is not reached soon. New products Coalescent solvent for specialist coatings Chemoxy International plc, of Middlesbrough, UK, has launched a new coalescent solvent which has been formulated to assist the film formation properties of speciality wood coatings, finishes, varnishes and lacquers.The low VOC (volatile organic chemical) content, low odour solvent is also well suited for use in decorative paints and coatings, adhesives, screen printing inks and leather coatings.Called Estasol BG, the coalescent solvent is the latest addition to Chemoxy’s rapidly expanding range of low toxicity solvents. The new high purity solvent is biodegradable, colourless and has a high flash point of 75°C. Compatible with a wide range of resins including polyvinylacetate, nitrocellulose and polyvinylbutyrate, Estasol BG is ideal for formulators looking to produce the ‘next generation’ of quick evaporation, environmentally friendly coating products.Forming and stamping fluids Solutia Inc., St Louis, USA, is introducing a new series of water-based forming and stamping fluids, the Glacier 5000 series, as new members of its metalworking fluid family. These unique products provide the benefits of oil in a water-based fluid, and serve as an alternative to the oil-based forming that currently dominates the market.Developed from breakthrough protein technology, Glacier 5000 is designed for both ferrous and non-ferrous metals. The bright and clear amber liquid uses water-based chemistry and does not contain oil. As a result, it can be easily cleaned or washed off parts using water or traditional cleaning systems.Glacier 5000 works in a wide range of applications with a broad array of applicators. It also helps parts and dies stay cooler. In addition, Glacier 5000 promotes a cleaner, safer work environment. Glacier 5000, and all Glacier fluids, are thoroughly tested for health effects. Glacier 5000 holds the safest rating for toxicity, and has a low odour. In addition, the fluid is biodegradable and recyclable, and contains no hazardous waste constituents (http://www.solutia.com).High-temperature carbon dioxide-absorbing ceramics Toshiba, Japan, has developed a ceramic material that can absorb carbon dioxide at 450–700°C through a chemical reaction after contact. This material is made from lithium zirconate which can absorb 400 times its volume of carbon dioxide— 10 times better than conventional materials.Thus, it is possible to absorb carbon dioxide from high-temperature high-pressure gases, applicable for example in coal-burning power generation plants, manufacturing sites and cars. The recovered carbon dioxide can also be utilized. Research is underway to lower the production cost and widen the applications. New processes Copper sulfate by nitric acid-catalyzed air oxidation A process for making copper sulfate has been developed by a group from the Northwest University, China, that does not evolve sulfur dioxide during the process to pollute the environment.Waste copper wire or other copper waste is heated with water, sulfuric acid and a catalytic amount of nitric oxide at 85°C and 8 kPa, with four air inlets to give an even and ample oxygen supply.The crystalline product is collected by filtration, and the mother liquor is recycled for another run of the production. A water-based process for manufacturing optical brighteners Optical brighteners have been traditionally manufactured by dissolving cyanuric chloride in a volatile solvent such as acetone and reacting this with a sulfonated amine.Ultimately the solvent which is required to effectively get the water-insoluble cyanuric chloride in an active form, is recycled but it can be avoided altogether in some cases through the use of surfactants. Hickson and Welch have recently extended the cleaner technologies to the manufacture of optical brighteners for the detergent industry. The major reasons for this are removing solvent costs, avoiding handling flammable solvents, avoiding VOC containment costs and adding value through the exploitation of more environmentally friendly technologies. Hickson and Welch now operate a water-based manufacturing process which eliminates the use of some 3000 tonnes/year of solvent (Environmental Business Magazine, May 1999).Awards ICI wins environmental award ICI’s newly formed Synetix business has won the Queen’s Award for Environmental Achievement for Hydecat, its unique process for treating sodium hypochlorite produced from waste chlorine streams.The Hydecat process, as it is known, converts sodium hypochlorite (bleach) from a potentially harmful mixture to a benign common salt solution and oxygen. Hydecat technology is essentially automatic and guaranteed for at least three years.ICI’s first commercial units were installed in 1993 and since then further improvements have been made both to the process and to the catalyst. More than 20 customers in 9 countries have successfully applied the Hydecat technology. Customer savings are impressive: one customer has reduced the cost of destruction of hypochlorite from £300000/y to £30000/y.Dexter recognized with five 1999 patent awards Dexter Electronic Materials (Industry, California, USA) received five 1999 patent awards for patents issued in 1998. The patent for stabilized nitric acid compositions claims a stabilizer that reduces the decomposition of acid when used to strip tin or tin/lead solder from printed circuit boards.Benefits to Dexter customers include dramatically extended bath life and ease of waste treatment relative to competitive processes. The patent for propargyl ether-containing compositions useful for underfill applications claims the use of aromaticC G Green Chemistry August 1999 G93 N EWS propargyl ethers as an underfill resin chemistry. The described resins can be cured to produce hydrophobic, high glass transition thermosets with no evolution of volatiles.The patent for perfluorinated hydrocarbon polymer-filled adhesive formulations and uses claims the use of perfluorinated hydrocarbon filler in die attach adhesives. Products based on this technology provide customer value in the form of reduced potential for radio frequency cross talk and ease of application.The patent for maleimide-containing formulations and uses claims the use of hydrophobic resin combinations useful in the preparation of high temperature, blister resistant laminates for printed wiring boards. The patent for bleed resistant cyanate ester-containing compositions claims the use of novel bleed reduction additives in cyanate ester-based attach adhesives. Products based on this technology provide improved reliability and productivity. Catalysts Second-generation titanium dioxide photocatalyst A titanium dioxide photocatalyst which can operate at wavelengths higher than 420 nm and in the visible light region has been successfully developed by EcoDevice Company, Japan.With this material, most of the available energy from the sun can be utilized (compared with only 3% available at ultra-violet bands in the <400 nm region when using older photocatalysts).The company has already signed a contract with a manufacturing company, and expects to increase the production capacity to several kilograms per month soon. It is hopeful that the price will fall in due course (presently at more than Yen 20000/g). The photocatalyst can also be applied in solar cells to decompose water to generate clean hydrogen fuel.Reagent catalysts Contract Chemicals is developing a second generation of its Envirocats supported reagent catalysts. These can replace traditional catalysts associated with unacceptable levels of waste and by-products. They can be used instead of Friedel–Crafts and Brønsted acid and oxidation catalysts. They are non-toxic, non-corrosive and inert relative to homogeneous catalysts like aluminium trichloride.Contract recently commissioned a £5 M fine chemical plant expansion at Knowsley, UK. Catalytic synthesis of tributyl citrate Tributyl citrate (TBC) is a non-toxic plasticizer, with superior compatibility and plasticization properties to impact, cold, light and water resistance.Since phthalate plasticizers are well regulated because of their undesirable environmental impact, TBC has become the material of choice. Conventionally, TBC is made with concentrated sulfuric acid as catalyst for esterification. However, due to the low yield, corrosion to equipment and environmental pollution caused by the use of sulfuric acid, newer catalysts have been developed.A homemade activated carbon-supported heteropoly acid catalyst has been prepared by a team from the Fujian Institute of Research on Structure of Matter, China. When reacting citric acid and butanol in the presence of 22.5% of the catalyst at 145°C, up to 98% pure TBC is obtainable (see article by Becky Allen on phthalates in toys in this issue of Green Chemistry).Biotechnological processes The recent patents are Merck’s for a microbial conversion of glycerol to dihydroxyacetone and Genencor’s for the microbial synthesis of quinic acid from glucose. DuPont and Genencor have jointly developed, using recombinant DNA technology, a process to create a single microbe that converts sugar from corn starch into the monomer propane-1,3-diol using a biotransformation process.The new technology will enable production of propane-1,3-diol at a cost approaching that of ethylene glycol, the monomer for production of poly- (ethylene terephthalate). The company is taking this further with the biological processing of propane-1,3-diol to the polyester poly(trimethylene terephthalate) (PTT). DuPont claims the PTT has enhanced properties compared with conventional polyester.The technology will be commercially available by 2004 and DuPont plans to build a 20000 tonnes/y plant. Recently, Shell of Holland has been developing PTT for use in the textile and carpet industries. Other research groups in various European countries and in China are also studying such production technology. DuPont builds new fluoropolymer plant for supercritical carbon dioxide process DuPont Co.(Wilmington, Delaware, USA) has begun construction of a $40 million, 2.5 million lb/year development and manufacturing facility to make meltprocessable fluoropolymers using a process based on supercritical carbon dioxide. It is planned that $275 million will be spent over the next seven years if the trials are successful.The company has already been testing the technology at a $2-million pilot plant it brought on stream in 1999 at the DuPont Experimental Station in Wilmington. It expects the new unit to open in late 2000 and produce fluorinated ethylene propylene (FEP) and perfluoroalkoxy resin (PFA). The company plans to demonstrate the technology for two to three years before building a larger plant. The technology gives DuPont the ability to make new grades of polymer which have specialized properties. It also promises to be more efficient, more flexible, and less costly than existing processes. The process came about from a partnership between DuPont and Joseph DeSimone, William R. Kenan, Jr. Distinguished Professor of Chemistry and Chemical Engineering at both the University of North Carolina at Chapel Hill and North Carolina State University in Raleigh, N.C. He is a pioneer in polymer synthesis using supercritical fluids. DuPont has supported his research since 1990. DuPont’s Teflon FEP is widely used for plenum cable insulation because of its excellent insulating properties, fire resistance, and light weight, which makes it easier to string over long distances. A new production technology based on supercritical carbon dioxide promises more specialized grades and improved process economics. DeSimone’s group reported the first successful homogeneous free radical polymerization in an inert supercritical fluid (SCF) in 1992 (S c i e n c e, 1992, 2 5 7, 945). Since then, he has expanded synthesis technology to include dispersion, cationic, ring-opening metathesis, step-growth, and additional heterogeneous p o l y m e r i z a t i o n s .