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№ 5

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В научном совете по катализу

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Фонд им. К.И. Замараева




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CFC's destroyed in cement manufacture

Now for the good news for cement manufacturers: Chlorofluorocarbons (CFCs) can be destroyed with over 99.9999% efficiency in a cement kiln without adverse effects for the process or product, in a development announced by Chichibu-Onoda Cement Corp. (Tokyo).

CFCs are injected at 2-4 kg/h into the center of the flame of a rotary kiln, (1500АC). The CFCs are converted to CO2, water, HF and HCL. Lime already present during cement production, absorbs and reacts with the acid gases to form harmless calcium salts. The Cl concentration in the clinker, remains below industrial specifications. When tests were performed in a commercial kiln of 210 m.t./h clinker capacity, CFCs, such as CFC-11, -12 and -113, could not be detected in the exhaust from the kiln, and dioxin levels were below 0.02 ng/m3. Chichibu-Onoda expects that 25 m.t. CFCs/yr can be destroyed in a kiln with clinker capacity of 5000 m.t./d and plans to offer the service for a disposal charge of $10/kg.

Source: Chemical Engineering/ July 1997

Business News from Focus on Catalysts

Missing link in catalyst development

Interdisciplinarity is a requirement nowadays for much research funding. Yet, curiously, the disciplines of catalyst development (practised by chemists) and process development (practised by chemical engineers) are seldom linked.

If process developers are the first customers for catalysts, one would expect there to be good co-operation between catalyst producers and process developers, so that the catalyst and the process could together best be optimised. Yet this interdisciplinary link seems generally to be missing. The large companies which are both catalyst producers and process developers з e.g. UOP, IFP з have internal structures which address the problem. But the middle-ranking catalyst producers and their academic collaborators, need good links to the world of process engineering. The LINK programme on Applied Catalysis and Catalytic Processes, launched in London last year, addressed this problem, but I have not yet seen the outcom. The latest EPSRC Managed Programme in Catalysis and Catalytic Processes specifically calls for joint proposals between chemists and process engineers. Let us hope that these initiatives are successful, and that the new Institute of Applied Catalysis applies some of its funds in this direction also.

Alan E. Comyns

Air Products, DoE, to colaborate on new syngas process

Air Products and Chemicals and the Department of Energy have established an $84 M collaboration to develop and scale up Air Products membrane-based technolodgy for converting natural gas into synthesis gas. The process could reduce the cost of syngas production by 25% relative to conventional methane technology. The first two years of an 8-year development plan will be used to develop membranes and catalysts. This will be followed by an experimental unit and then a 500,000 cu ft/day prototype. In the final stage there will be scale-up to 15M cu ft/day at La Porte TX.

Source: Chemical Week, 159 (21) (28 May 1997) 13

Acrylonitrile from propane to be demonstrated

BP has commissioned a demonstration plant for making acrylonitrile from propane by its new process (see Focus on Catalysts, Nov. 1996, 5). BP expects the production cost to be 20% less than that of the usual route from propylene, and aims to base future acrylonitrile investments on this process.

Zeolite-type crystals incorporate cobalt

Using a design technique known as charge-matching, chemists at the University of California, Santa Barbara, have synthesized dozens of cobalt-rich zeolite-type crystals. The new materials have the potential to expand the already rich range of zeolites' uses in catalysis and gas separation.

The experiments were conducted by Galen D. Stucky, professor in the departments of chemistry and materials, and graduate student Pingyun Feng and X-ray crystallographer Xianhui Bu [Nature. 388, 735 (1997)].

The cagelike frames of zeolites enclose molecular-sized cavities. The porous materials belong to the aluminosilicate family and are known in both natural and synthetic forms. Researchers have long tried to prepare zeolite-type materials in which aluminum atoms are replaced with transition-metal atoms. The wide variety of oxidation states and other chemical properties available to transition metals ж relative to aluminum ж is expected to result in new materials with a number of useful characteristics, such as a broader range of reactions that can be catalyzed.

Transition metals have previously been incorporated into some zeolite analogs, particularly in the aluminophosphate series. But the number of aluminum sites replaced with transition-metal atoms in that family of compounds has not exceeded 38%, according to the UC Santa Barbara chemists. Stucky's group, however, now reports preparing many cobalt phosphate-based zeolite counterparts ж some with cobalt concentrations near 90%.
tural information that's proving very useful in understanding the fundamentals of zeolite synthesis," Stucky says. "The significance of this work is not just that we've made a collection of new zeolite analogs. Rather it's a general synthesis procedure that can lead to the preparation of untold numbers of useful materials."
In an accompanying commentary in Nature, Robert L. Bedard of the UOP Research Center, Des Plains, III., describes Stucky's new procedure as "clever". But, he adds, whether the "route is more generally applicable to other divalent transition metals is not yet clear."

The strategy for synthesizing crystals with zeolite structure, Feng explains, is to match the charge and shape of the framework cavity ж the host ж with an appropriate filler material ж the guest. The host's features are varied by adjusting the ratio of divalent cobalt ions to trivalent aluminum ions. The charge-to-volume ratio of the guests - which in the present study are alkyl ammonium ions ж is controlled by the size and shape of the alkyl groups and the number of charged nitrogen atoms.

Through a series of modifications to host and guest ж while ensuring that both are appropriately charge- and shape-matched ж the Santa Barbara researchers synthesized a large group of cobalt phosphate-bazed zeolite analogs. Some of the new crystals possess structures previously seen only in nature. Some of the products even have structures that were proposed theoretically but never observed ж from natural or synthetic sources.

By uncovering the details of the interaction between organic guests and an inorganic framework, Stucky aims to prepare zeolite analogs in which pore size, framework charge, and magnetic and redox properties are tightly controlled. Such materials, he says, will lead to very efficient separations and high catalytic selectivity.

Mitch Jacoby

Phillips develops LLDPE metallocene catalyst System

Phillips Petroleum has joined the linear low-density polyethylene (LLDPE) market with a new metallocene catalyst system that can be dropped into the company's high-density polyethylene (HDPE) slurry loop production units. The system yields clear, strong plastic films.

The company held a test run producing "several million pounds" of LLDPE at its Houston Chemical Complex in December 1996, according to Don G. Brady, polyethylene manager for Phillips Chemical Co., a division of Phillips Petroleum. He expects to produce 20 million lb in four runs in 1997.

Speaking at a press conference, Brady claimed Phillips' slurry-made LLDPE is similar to ж but easier to process than ж competitors' gas-phase metallocene LLDPE. And an HDPL slurry loop unit can be switched to LLDPE production in a matter of hours, then back to HDPE when needed. "This is a significant breakthrough", says Patrick W. Duke, vice president for polymers at Houston-based petrochemical consulting firm DeWitt. "It would give some flexibility for producers to move back and forth depending on market conditions".

LLDPE offers big opportunities, explained Jack L. Howe, president of Phillips Chemical. It now accounts for 30% of the polyethylene market and "is growing faster that any other segment". Metallocene LLDPE could invade the large markets of LDPE (low-density polyethylene) and traditional LLDP 7 LLDPE demand is expected to see annual growth of 14% or more worldwide through 2000, predicts Duke, while HDPE is expected to grow 5% and LDPE less than 2%. Using, metallocene-catalyzed LLDPE technology to create stronger, clearer films has been a recent focus of plastics producers. Dow Chemical just said it will build annual capacity for 1.2 million metric tons of LLDPE (see page 31). In August 1996, Dow and BP Chemicals announced a joint venture to license metallocene-catalyzed LLDPE technology the same week that Exxon Chemical and Union Carbide made a similar announcement (C@EN, Aug. 12, 1996, page 9).

Phillips' technology is responsible for 30% of worldwide HDPE production. The company has six 300 million-lb-per-year HDPE units in Houston and is expanding them to total 2.2 billion lb per year by 1999. A 400 million-lb-per-year joint-venture plant in Singapore with Sumitomo Chemical is planned to add 450 million lb per year by 1998. In addition, the slurry loop technology is licensed to 81 plants in 14 countries. The LLDPE innovation "redefines our value package for licensees". says Howe.

However, some challenges remain in the path of metallocene catalyst LLDPE market expansion ж catalyst cost is still high, catalyst productivity is low, and processibility is not as good as standard LLDPE.

NICE (A Network for Industrial Catalysis in Europe) seeks support as a Thematic Network

A proposal was submitted to the European Commission's Industrial @ Materials Technologies Programme (Brite-Euram) at the end of October to establish NICE as a Thematic Network. The three objectives of the Thematic Network are:
1) to provide a European forum for the dissemination and exchange of scientific and technological knowledge and ideas relating to all aspects of industrial catalysis;
2) to define research gaps, needs and opportunities in industrial catalysis in order that EU and Member State RTD Programme planners and the catalysis community in general may have improved understanding of needs and priorities;
3) to promote co-ordinated, multi-disciplinary, collaborative research that will enable European industry to gain advantage through the development of new or improved catalytic processes.

The proposal was submitted by ICI (as coordinator) together with DECHEMA, BP, Degussa, DSM, Hoechst, Johnson Matthey, Neste, Norsk Hydro, Rhone-Poulenc, Snamprogetti, Solvay, Centre National de la Recherche Scientifique and Universite Catholique de Louvain who together make up the Steering Group of the network.

Six initial Focus Groups have been proposed in the general areas of:

  • New Catalysis
  • Fine Chemical Production
  • Reaction Engineering and Multiphase Systems
  • Kinetics and Modelling
  • Characterisation and Testing
  • New Feedstocks

The Focus Groups will operate via a series of structured workshops and the network will provide training opportunites for researchers as well as create an Internet site and a newsletter. The Steering Group will also produce an annual Survey of Research Gaps, Needs and Opportunities in Industrial Catalysis.

Membership of the network will be open to all European companies with interests in catalysis, academic researchers, and to representatives of relevant EU and Member State research programmes. The Thematic Network aims to have an active membership of companies from diverse industrial sectors and representation of all the leading catalysis research groups within Europe. The interests of the European Federation of Catalysis Societies (EFCATS) and the Catalysis Working Party of the European Federation of Chemical Engineering (EFCE) will be represented in the Steering Group.

The Thematic Network (if supported) will be dual funded. The requested EU funding will be complemented by financial contributions of companies who will pay up to 10 kECU for three years' membership of the network.

The outcome of the evaluation of the Thematic Network is expected to be known early in the New Year. If it is successful, it is expected that the Thematic Network wouid be launched in the summer of 1998.
Dale Laidler, ICI
For further details of the Thematic Network proposal please contact either: Dale Laidler at ICI (dale_ laidler@ici.corn), or Kurt Wagemann at DECHEMA (e-mail: fopla @dechema.de).


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