Industrial catalysts development

The need for high-throughput preparation in industrial catalyst development... 

The production of ammonia during the early 1900s stimulated the increasing use of industrial catalysts. Development of the synthesis catalyst set a pattern for all other catalysts subsequently used in chemical and refining processes. 

These developments worrld rmdoubtedly have taken place in the fullness of time without the need for wartime gas masks, but this is just another good example of how general theories and improved industrial catalysts develop from... 

Catalyst Development. Traditional slurry polypropylene homopolymer processes suffered from formation of excessive amounts of low grade amorphous polymer and catalyst residues. Introduction of catalysts with up to 30-fold higher activity together with better temperature control have almost eliminated these problems (7). Although low reactor volume and available heat-transfer surfaces ultimately limit further productivity increases, these limitations are less restrictive with the introduction of more finely suspended metallocene catalysts and the emergence of industrial gas-phase fluid-bed polymerization processes. 

Almost all industrial catalysts are developed by researchers who are motivated to improve processes or create new ones. Thus the organization that first uses a new catalyst is usually the one that has discovered it. This organization, however, only rarely becomes the manufacturer of the catalyst used on a large scale. Catalysts are for the most part highly complex specialty chemicals, and catalyst manufacturers tend to be more efficient than others in producing them. Catalyst manufacturing is a competitive industry. Catalyst users often develop close relations with catalyst manufacturers, and the two may work together to develop and improve proprietary catalysts. 

Oxychlorination of methane can yield significant amounts of methylene chloride. A number of patents were obtained by Lummus in the mid-1970s on a high temperature, molten salt oxychlorination process (22,23). Catalyst development work has continued and generally consists of mixtures of Cu, Ni, Cr, or Fe promoted with an alkah metal (24—27). There are no industrial examples of this process at the present time. 

Whether butadiene reacts with itself to give linear polymers or 8- or 12-carbon rings is a function of the catalyst and conditions used. Development of catalysts needed to give the desired products is the job of catalyst research chemists. Although catalysis is critically important in the chemical industry and much work has been done on it in research laboratories for many years, catalyst development remains more of an art than a predictable science, and the chemists involved in this type of research use methods they have learned experimentally, not from books or in classrooms. 

Firstly, there are technical reasons concerning catalyst and reactor requirements. In the chemical industry, catalyst performance is critical. Compared to conventional catalysts, they are relatively expensive and catalyst production and standardization lag behind. In practice, a robust, proven catalyst is needed. For a specific application, an extended catalyst and washcoat development program is unavoidable, and in particular, for the fine chemistry in-house development is a burden. For coated systems, catalyst loading is low, making them unsuited for reactions occurring in the kinetic regime, which is particularly important for bulk chemistry and refineries. In that case, incorporated monolithic catalysts are the logical choice. Catalyst stability is crucial. It determines the amount of catalyst required for a batch process, the number of times the catalyst can be reused, and for a continuous process, the run time. 

Since the first synthesis of ammonia, catalyst development and chemical reaction engineering have been instrumental in the creation of the chemical process industry. As a result, catalytic processes have contributed much to the realization of prosperous civilizaticm. In the future, catalytic processes are expected to fulfill important roles in petroleum refining, diemical processing and environmental preservation. However, at present, many catalytic processes discharge large amounts of byproducts and consume large amounts of auxiliary raw materials. 

In industry, the emphasis is mainly on developing an active, selective, stable and mechanically robust catalyst. To accomplish this, tools are needed which identify those structural properties that discriminate efficient from less efficient catalysts. All information that helps to achieve this is welcome. Empirical relationships between those factors that govern catalyst composition (e.g. particle size and shape, and pore dimensions) and those that determine catalytic performance are extremely useful in catalyst development, although they do not always give fundamental insights into how the catalyst operates on the molecular level. 

The BET area of a catalyst or a catalyst support is one of the first properties one wants to know in catalyst development. All industrial laboratories and many academic laboratories possess equipment for measuring this property. 

The Raney nickel is a very efficient catalyst for the dehydrogenation of 2-butanol into butanone (Scheme 45) with a good selectivity (90%). But, for industrial applications selectivities as high as 99% are required. This can be achieved by poisoning some sites by reaction with Bu4Sn (the best results are obtained with a Sn/Ni ratio of 0.02), which probably occurs first on the sites responsible for the side reactions. The consequence is a slight decrease of the catalytic activity and an increase of the selectivity in 2-butanone which can reach 99%. This catalyst, developed by IFF, has been used commercially in Japan for several years [180]. 

Gezdhmte Chemie im Mikroreaktor, VDI Nachrichten, June 2000 Micro-reactor enterprises shape and material variety of micro reactors selectivity gains and new project regimes direct fluorination faster process development BASF investigations safety increase speed-up of catalyst development production for fine chemistry and pharmacy numbering-up first industrial examples for micro-reactor production [215]. 

The catalytic performance of metal depends on the kinds of metal and supports, size and structure, and addition of other element(s). Thus, many trial and errors have been carried out in order to develop industrial catalysts. Even now, this is true for the research and development of practical catalysts. 

The industrial catalyst for n-butane oxidation to maleic anhydride (MA) is a vanadium/phosphoras mixed oxide, in which bulk vanadyl pyrophosphate (VPP) (VO)2P207 is the main component. The nature of the active surface in VPP has been studied by several authors, often with the use of in situ techniques (1-3). While in all cases bulk VPP is assumed to constitute the core of the active phase, the different hypotheses concern the nature of the first atomic layers that are in direct contact with the gas phase. Either the development of surface amorphous layers, which play a direct role in the reaction, is invoked (4), or the participation of specific planes contributing to the reaction pattern is assumed (2,5), the redox process occurring reversibly between VPP and VOPO4. 

The task of developing a suitable catalyst for commercial applications involves many considerations, ranging from obvious factors like catalyst activity and selectivity to variables like the catalyst shape and the composition of the binder used in a pelletizing process. This section is devoted to a discussion of these considerations and of the techniques involved in manufacturing industrial catalysts. 

Particular attention is now given to the characterization of the supported species, and to the control of stability and recycling of the catalyst. The behavior of the supported catalyst under the reaction conditions (temperature, pressure, and nature of reactants and products) is certainly a less well-developed area, even though these data are valuable for the conception and development of a fully recyclable catalyst. Very few chemical engineering studies have been so far reported they will become crucial if the objective is the synthesis of an industrial catalyst. 

MPC [Mitsui Petrochemical] A continuous process for polymerizing propylene, based on the Ziegler-Natta process, but using a much more active catalyst so that de-ashing (catalyst removal) is not required. The catalyst contains magnesium in addition to titanium successive versions of it have been known as HY-HS (high yield, high stereospecifity), HY-HS II, and T-catalyst. Developed jointly by Mitsui Petrochemical Industries, Japan, and Montedison SpA, Italy, in 1975, and now licensed in 56 plants worldwide. 

Nedol [New Energy Development Organization liquifaction] A coal liquifaction process in development in Japan by the New Energy and Industrial Technology Development Organization (NEDO), Tokyo. Crushed coal is mixed with a pyrite catalyst and slurried in a hydrogenated heavy oil. Liquifaction takes place at 450°C, 170 bar. The overall oil yield is 59 percent. 

Tatoray [Transalkylation aromatics Toray] A process for transalkylating toluene, and/or trimethylbenzenes, into a mixture of benzene and xylenes. Operated in the vapor phase, with hydrogen, in a fixed bed containing a zeolite catalyst. Developed jointly by Toray Industries and UOP and now licensed by UOP. First operated commercially in Japan in 1969 as of 1992, 23 units were operating and 6 more were in design and construction. 

In the last 3 years, this concept has been successful and several catalysts developed at the Leibniz-Institut fur Katalyse have been transferred to industry. Among these, a palladium catalyst is nowadays used for the synthesis of pharmaintermediates on the several-thousand kilogram scale. 

Most of the work on ethanol reforming to date focused mainly on catalyst development, optimization of reaction operations and thermodynamic analyses. However, detailed kinetic studies, which are very useful to understand the activity at the molecular level and to build a suitable catalytic reactor on an industrial scale for the reforming of ethanol need to be pursued. 

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