Catalyst development

The Reaction. Acrolein has been produced commercially since 1938. The first commercial processes were based on the vapor-phase condensation of acetaldehyde and formaldehyde (1). In the 1940s a series of catalyst developments based on cuprous oxide and cupric selenites led to a vapor-phase propylene oxidation route to acrolein (7,8). In 1959 Shell was the first to commercialize this propylene oxidation to acrolein process. These early propylene oxidation catalysts were capable of only low per pass propylene conversions (ca 15%) and therefore required significant recycle of unreacted propylene (9—11). 

Two catalysts have emerged as commercially viable. The Mobil—Badger ethylbenzene process, which has been in commercial use since 1980, employs a ZeoHte catalyst and operates in the gas phase. A Hquid-phase ethylbenzene process joindy Hcensed by Lummus and UOP uses a Y-type ZeoHte catalyst developed by Unocal. This Hquid-phase process was commercialized in 1990. The same Y-type ZeoHte catalyst used for the production of ethylbenzene is being offered for the production of cumene but has not yet been commercialized. 

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. 

The strategy of the catalyst development was to use a rhodium complex similar to those of the Wilkinson hydrogenation but containing bulky chiral ligands in an attempt to direct the stereochemistry of the catalytic reaction to favor the desired L isomer of the product (17). Active and stereoselective catalysts have been found and used in commercial practice, although there is now a more economical route to L-dopa than through hydrogenation of the prochiral precursor. 

A thorough list of references is given in J. T. Richardson, Principles of Catalyst Development, Plenum Press, New York, 1989. 

Performance Evaluation. Successful catalyst development requires a satisfactory means to determine the performance of the catalyst. The only significant proof of improvement in catalyst performance Hes in evaluation in a reactor under the proper conditions. 

Ethylene oxide is produced in large, multitubular reactors cooled by pressurized boiling Hquids, eg, kerosene and water. Up to 100 metric tons of catalyst may be used in a plant. Typical feed stream contains about 30% ethylene, 7—9% oxygen, 5—7% carbon dioxide the balance is diluent plus 2—5 ppmw of a halogenated moderator. Typical reactor temperatures are in the range 230—300°C. Most producers use newer versions of the Shell cesium-promoted silver on alumina catalyst developed in the mid-1970s. 

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. 

Catalytic Pyrolysis. This should not be confused with fluid catalytic cracking, which is used in petroleum refining (see Catalysts, regeneration). Catalytic pyrolysis is aimed at producing primarily ethylene. There are many patents and research articles covering the last 20 years (84—89). Catalytic research until 1988 has been summarized (86). Almost all catalysts produce higher amounts of CO and CO2 than normally obtained with conventional pyrolysis. This indicates that the water gas reaction is also very active with these catalysts, and usually this leads to some deterioration of the olefin yield. Significant amounts of coke have been found in these catalysts, and thus there is a further reduction in olefin yield with on-stream time. Most of these catalysts are based on low surface area alumina catalysts (86). A notable exception is the catalyst developed in the former USSR (89). This catalyst primarily contains vanadium as the active material on pumice (89), and is claimed to produce low levels of carbon oxides. 

A major step in catalyst development was the introduction of crystalline zeolitic, or molecular sieve catalysts. Their activity is very high, some of the active sites being estimated at 10,000 times the effectiveness of amorphous silica-... 

For the synthesis of ammonia, Nj -i- 3H2 —> 2NH3, over an iron catalyst, develop the rate expression for the following mechanism... 

Stereoregular polymerization of ethene and propene by catalysts developed by K. Ziegler and by G. Natta (shared Nobel Prize 1963). 

From a historical perspective it is interesting to note that the Nozaki experiment was, in fact, a mechanistic probe to establish the intermediacy of a copper carbe-noid complex rather than an attempt to make enantiopure compounds for synthetic purposes. To achieve synthetically useful selectivities would require an extensive exploration of metals, ligands and reaction conditions along with a deeper understanding of the reaction mechanism. Modern methods for asymmetric cyclopropanation now encompass the use of countless metal complexes [2], but for the most part, the importance of diazoacetates as the carbenoid precursors still dominates the design of new catalytic systems. Highly effective catalysts developed in... 

Eor most gas process environments-refineries, catalyst development sites, research and development and plant laboratories-a knowledge of the exact composition of the... 

In the preceding section, it has been shown that considerable attention has been devoted to palladium as a heterogeneous catalyst. The present section describes the homogeneous palladium catalysts developed for hydrogenation of NBR. The main drive behind the development of various catalyst systems is to find suitable substituents of the Rh catalyst. Palladium complexes are much cheaper as compared with Rh and exhibit comparable activity and selectivity to Rh and Ru complexes. 

FROM TANKS TO AUTOMOBILE RACING TO CATALYTIC CRACKING AND CATALYST DEVELOPMENT... 

Deep catalytic cracking (DCC) is a catalytic cracking process which selectively cracks a wide variety of feedstocks into light olefins. The reactor and the regenerator systems are similar to FCC. However, innovation in the catalyst development, severity, and process variable selection enables DCC to produce more olefins than FCC. In this mode of operation, propylene plus ethylene yields could reach over 25%. In addition, a high yield of amylenes (C5 olefins) is possible. Figure 3-7 shows the DCC process and Table 3-10 compares olefins produced from DCC and FCC processes. ... 

Catalysts developed in the titanium-aluminum alkyl family are highly reactive and stereoselective. Very small amounts of the catalyst are needed to achieve polymerization (one gram catalyst/300,000 grams polymer). Consequently, the catalyst entrained in the polymer is very small, and the catalyst removal step is eliminated in many new processes. Amoco has introduced a new gas-phase process called absolute gas-phase in which polymerization of olefins (ethylene, propylene) occurs in the total absence of inert solvents such as liquefied propylene in the reactor. Titanium residues resulting from the catalyst are less than 1 ppm, and aluminum residues are less than those from previous catalysts used in this application. 

Before discussing mechanisms of the reactions, it is appropriate to review FCC catalyst development and examine its cracking properties. An in-depth discussion of FCC catalyst was presented in Chapter... 

The chapter by Hausberger et al. deals with catalyst development, and the performance of several new high-nickel catalysts in bench-scale and large pilot tests with high carbon oxide concentrations. Kinetics of the reaction over these catalysts are developed. 

All tests reported here were performed with a special methanation catalyst developed by BASF, Ludwigshafen, for the process. The catalyst had a relatively high nickel content on a carrier. It was charged to reactors D2 and D3 in unreduced form and had to be activated by reduction with hydrogen. 

P. Shimizu (LaPorte-Davison, Inc.) What are the important and likely areas of future R D work on methanation vis a vis catalyst development, process development, or whatever ... 

Dr. Woodward I tried to indicate in my paper that in ammonia-hydrogen plant operation, in comparison with several other catalysts in such plants, the methanation catalyst situation is really well under control. Speaking for our company, and I would guess others, it s not a particularly active research area because we have higher priorities in catalyst development. As regards methanation catalysts for SNG, I did not discuss that today and perhaps I should let some other fellows answer first. Sulfur tolerance is one area for future development. 

Serious research in catalytic reduction of automotive exhaust was begun in 1949 by Eugene Houdry, who developed mufflers for fork lift trucks used in confined spaces such as mines and warehouses (18). One of the supports used was the monolith—porcelain rods covered with films of alumina, on which platinum was deposited. California enacted laws in 1959 and 1960 on air quality and motor vehicle emission standards, which would be operative when at least two devices were developed that could meet the requirements. This gave the impetus for a greater effort in automotive catalysis research (19). Catalyst developments and fleet tests involved the partnership of catalyst manufacturers and muffler manufacturers. Three of these teams were certified by the California Motor Vehicle Pollution Control Board in 1964-65 American Cyanamid and Walker, W. R. Grace and Norris-Thermador, and Universal Oil Products and Arvin. At the same time, Detroit announced that engine modifications by lean carburation and secondary air injection enabled them to meet the California standard without the use of catalysts. This then delayed the use of catalysts in automobiles. 

There has been substantial work on catalyst development with the aim of finding more active catalysts and catalysts appropriate for different monomers and reaction media.270,271 48 The complexes 149-151 (Table 9.6) appear to be some of the more active catalysts. 

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