Disproportionation catalysts

In 1971, a short communication was published [54] by Kumada and co-workers reporting the formation of di- and polysilanes from dihydrosilanes by the action of a platinum complex. Also the Wilkinson catalyst (Ph3P)3RhCl promotes hydrosilation. If no alkenes are present, formation of chain silanes occurs. A thorough analysis of the product distribution shows a high preference for polymers (without a catalyst, disproportionation reactions of the silanes prevail). Cross experiments indicate the formation of a silylene complex as intermediate and in solution, free silylenes could also be trapped by Et3SiH [55, 56],... 

This side reaction leads to undesirable losses of xylenes. With REHY zeolite as catalyst, disproportionation occurs at a rate comparable to that of isomerization of m-xylene (8), e.g., 14% disproportionation at 16% isomerization. In fact, the product, trimethylbenzene, is postulated as an important intermediate in isomerization (8). 

Neither isomerization initiators nor cracking inhibitors need to be present when isomerization occurs in the presence of these acidic catalysts. Disproportionation does not accompany the isomerization. 

Xylene inter-isomerization is a well-known acid catalyzed reaction. Over acid catalysts disproportionation is generally observed as a side reaction. Over the bifunctional catalysts used in the commercial processes xylenes can also undergo two other primary reactions ... 

The role of VO(acac) is presumably identical with that of the oxidative polymerization of diphenyl disulfide. The V(IV) catalysts disproportionate to give a V(ll) and V(III) species. The V(V) species oxidizes monomer 311 producing cation-radical 328 and V(1V). V(III) is readily oxidized in triflic acid by oxygen to regenerate the V(IV) catalyst [211]. 

Several of the side reactions encountered in ATRP, such as catalyst dissociation and competitive monomer complexation, become more pronounced when the catalyst is used at very low concentration. These and other undesirable reactions, such as catalyst disproportionation or radical coordination to the metal center, can often be avoided with the appropriate choice of transition metal and complexing ligands. Still other side reactions, such as electron transfer between alkyl radicals and the metal catalysts, can actually be minimized by using low catalyst concentrations. This work aimed to demonstrate that with a thorough knowledge of the components of the ATRP equilibrium and a general awareness of potential side reactions under certain conditions, ATRP catalysts can be rationally selected and conditions optimized for very diverse polymerization systems. 

Figure 12 illustrates that while the Cu7N,N,N, N", N"-pentamethyldiethylenetriamine (PMDETA) complex is active, it disproportionates in aqueous ATRP. On the other hand, ligands such as bpy, HMTETA, and TPMA can be used in aqueous media, although with rather different activities. If necessary, catalyst disproportionation in water can be suppressed by using an appropriate cosolvent or by addition of a pseudoligand that will stabilize Cu versus Cu , such as pyridine, which allows... 

The catalyst disproportionation in water can be suppressed by using an appropriate cosolvent that stabilizes Cu vx. Cu (such as pyridine). It has been demonstrated that the use of pyridine as a cosolvent for aqueous ATRP of ionic monomers such as sodium 4-styrenesulfonate and 2-(A,A,A-trialkyl-ammonio)ethyl methacrylate salts completely suppressed the catalyst disproportionation and well-defined polyelectolytes were obtained. 

A second Mobil process is the Mobil s Vapor Phase Isomerization Process (MVPI) (125,126). This process was introduced in 1973. Based on information in the patent Hterature (125), the catalyst used in this process is beHeved to be composed of NiHZSM-5 with an alumina binder. The primary mechanism of EB conversion is the disproportionation of two molecules of EB to one molecule of benzene and one molecule of diethylbenzene. EB conversion is about 25—40%, with xylene losses of 2.5—4%. PX is produced at concentration levels of 102—104% of equiHbrium. Temperatures are in the range of 315—370°C, pressure is generally 1480 kPa, the H2/hydrocatbon molar ratio is about 6 1, and WHSV is dependent on temperature, but is in the range of 2—50, although normally it is 5—10. 

Amorphous Silica—Alumina Based Processes. Amorphous siHca—alumina catalysts had been used for many years for xylene isomerization. Examples ate the Chevron (130), Mamzen (131), and ICI (132—135). The primary advantage of these processes was their simpHcity. No hydrogen was requited and the only side reaction of significance was disproportionation. However, in the absence of H2, catalyst deactivation via coking... 

The Chevron process was used in two U.S. plants, although it is no longer used. Cycle lengths tanged from 6—30 d, depending on catalyst age and OX content of the feed. Operating conditions were temperature of 370—470°C and space velocity of about 0.5/h. Addition of 5 wt % steam reduced disproportionation losses. 

Shell Higher Olefin Process) plant (16,17). C -C alcohols are also produced by this process. Ethylene is first oligomerized to linear, even carbon—number alpha olefins using a nickel complex catalyst. After separation of portions of the a-olefins for sale, others, particularly C g and higher, are catalyticaHy isomerized to internal olefins, which are then disproportionated over a catalyst to a broad mixture of linear internal olefins. The desired fraction is... 

The purple permanganate ion [14333-13-2], MnOu can be obtained from lower valent manganese compounds by a wide variety of reactions, eg, from manganese metal by anodic oxidation from Mn(II) solution by oxidants such as o2one, periodate, bismuthate, and persulfate (using Ag" as catalyst), lead peroxide in acid, or chlorine in base or from MnO by disproportionation, or chemical or electrochemical oxidation. 

Catalysis. As of mid-1995, zeoHte-based catalysts are employed in catalytic cracking, hydrocracking, isomerization of paraffins and substituted aromatics, disproportionation and alkylation of aromatics, dewaxing of distillate fuels and lube basestocks, and in a process for converting methanol to hydrocarbons (54). 

Selective Toluene Disproportionation. Toluene disproportionates over ZSM-5 to benzene and a mixture of xylenes. Unlike this reaction over amorphous sihca—alumina catalyst, ZSM-5 produces a xylene mixture with increased -isomer content compared with the thermodynamic equihbtium. Chemical modification of the zeohte causing the pore diameter to be reduced produces catalysts that achieve almost 100% selectivity to -xylene. This favorable result is explained by the greatly reduced diffusivity of 0- and / -xylene compared with that of the less bulky -isomer. For the same reason, large crystals (3 llm) of ZSM-5 produce a higher ratio of -xyleneitotal xylenes than smaller crystahites (28,57). 

Koch Chemical Company is the only U.S. suppHer of all PMBs (except hexamethylbenzene). Its process has the flexibility of producing isodurene, prehnitene, and pentamethylbenzene, should a market develop. Koch s primary process (20) is based on isomerization, alkylation, and disproportionation conducted in the presence of a Friedel-Crafts catalyst. For the synthesis of mesitylene and hemimellitene, pseudocumene is isomerized. If durene, isodurene, or prehnitene and pentamethylbenzene are desired, pseudocumene is alkylated with methyl chloride (see Alkylation Friedel-CRAFTSreactions). 

The thermodynamic equilibria are illustrated in Figures 1 and 2. Figure 1 shows the resulting composition after pure pseudocumene or a recycle mixture of C PMBs is disproportionated with a strong Friedel-Crafts catalyst. At 127°C (400 K), the reactor effluent contains approximately 3% toluene, 21% xylenes, 44% C PMBs, 29% C q PMBs, and 3% pentamethylbenzene. The equihbrium composition of the 44% C PMB isomers is shown in Figure 2. Based on the values at 127°C, the distribution is 29.5% mesitylene, 66.0% pseudocumene, and 4.5% hemimellitene (Fig. 2). After separating mesitylene and hemimellitene by fractionation, toluene, xylenes, pseudocumene (recycle plus fresh), C q PMBs, and pentamethylbenzene are recycled to extinction. 

The Tatoray process, which was developed by Toray Industries, Inc., and is available for Hcense through UOP, can be appHed to the production of xylenes and benzene from feedstock that consists typically of toluene [108-88-3] either alone or blended with aromatics (particularly trimethylbenzenes and ethyl-toluenes). The main reactions are transalkylation (or disproportionation) of toluene to xylene and benzene or of toluene and trimethylbenzenes to xylenes in the vapor phase over a highly selective fixed-bed catalyst in a hydrogen atmosphere at 350—500°C and 1—5 MPa (10—50 atm). Ethyl groups are... 

The Xylene Plus process of ARGO Technology, Inc. (95,96) and the FINA T2BX process (97) also use a fixed-bed catalyst in the vapor phase for transalkylation of toluene to produce xylenes and benzene. The Mobil low temperature disproportionation (LTD) process employs a zeoHte catalyst for transalkylation of toluene in the Hquid phase at 260—315°C in the absence of hydrogen (98). 

Thermal cracking tends to deposit carbon on the catalyst surface which can be removed by steaming. Carbon deposition by this mechanism tends to occur near the entrance of the catalyst tubes before sufficient hydrogen has been produced by the reforming reactions to suppress the right hand side of the reaction. Promoters, such as potash, are used to help suppress cracking in natural gas feedstocks containing heavier hydrocarbons. Carbon may also be formed by both the disproportionation and the reduction of carbon monoxide... 

In disproportionation, rosin is heated over a catalyst to transfer hydrogen, yielding dehydro (5) and dihydro (8) resin acids. The dehydro acids are stabilized by the aromatic ring the dihydro acids contain only an isolated double bond in place of the less stable conjugated double bonds. 

Disproportionation reactions of siUcon hydrides occur readily in the presence of a variety of catalysts. For example ... 

The most common catalysts in order of decreasing reactivity are haUdes of aluminum, boron, zinc, and kon (76). Alkali metals and thek alcoholates, amines, nitriles, and tetraalkylureas have been used (77—80). The largest commercial processes use a resin—catalyst system (81). Trichlorosilane refluxes in a bed of anion-exchange resin containing tertiary amino or quaternary ammonium groups. Contact time can be used to control disproportionation to dichlorosilane, monochlorosilane, or silane. 

Similar disproportionation reactions are catalyzed by organic catalysts, eg, adiponittile, pyridine, and dimethyl acetamide. Methods for the redistribution of methyUiydridosilane mixtures from the direct process have been developed to enhance the yield of dimethylchlorosilane (158). 

Dehydrogenation ofy -menthadienes and a-piuene ia the vapor phase over catalysts such as chromia—alumina produces y -cymene (70). / -Menthadienes can be disproportionated over a Cu—Ni catalyst to give a mixture of yvmenthane andy -cymene (71). 

Disproportionation to Benzene and Xylenes. With acidic catalysts, toluene can transfer a methyl group to a second molecule of toluene to yield one molecule of benzene and one molecule of mixed isomers of xylene. 

Lyondell and Sun Oil Co. are the main producers of benzene by disproportionation. Eiaa Oil Co. of Texas has developed the Eiaa T2BX process for toluene disproportionation usiag a proprietary catalyst. The new catalyst is claimed to reduce hydrogen consumption and is suitable for feeds containing small amounts of moisture (53). A commercial production unit was started up ia the fall of 1985. 

Disproportionation. Carbon monoxide readily disproportionates into elemental carbon and carbon dioxide [124-38-9] on a catalyst surface... 

This decomposition is thermodynamically favored by decreasing temperature and increasing pressure (28). Decomposition is extremely slow below 673 K in the absence of a catalyst however, between 673—873 K many surfaces, particularly iron (29), cobalt, and nickel (30), promote the disproportionation reaction. 

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