Dimethyl ether catalysts

Key Words methanol, dimethyl ether, catalyst, blast furnace, energy, industrial waste gas, CO-CO2-H2, Cu-Zn0-Al203, Y-A1203. 

Similar activation takes place in the carbonylation of dimethyl ether to methyl acetate in superacidic solution. Whereas acetic acid and acetates are made nearly exclusively using Wilkinson s rhodium catalyst, a sensitive system necessitating carefully controlled conditions and use of large amounts of the expensive rhodium triphenylphosphine complex, ready superacidic carbonylation of dimethyl ether has significant advantages. 

The unit has virtually the same flow sheet (see Fig. 2) as that of methanol carbonylation to acetic acid (qv). Any water present in the methyl acetate feed is destroyed by recycle anhydride. Water impairs the catalyst. Carbonylation occurs in a sparged reactor, fitted with baffles to diminish entrainment of the catalyst-rich Hquid. Carbon monoxide is introduced at about 15—18 MPa from centrifugal, multistage compressors. Gaseous dimethyl ether from the reactor is recycled with the CO and occasional injections of methyl iodide and methyl acetate may be introduced. Near the end of the life of a catalyst charge, additional rhodium chloride, with or without a ligand, can be put into the system to increase anhydride production based on net noble metal introduced. The reaction is exothermic, thus no heat need be added and surplus heat can be recovered as low pressure steam. 

Dimethyl Ether. Synthesis gas conversion to methanol is limited by equiUbrium. One way to increase conversion of synthesis gas is to remove product methanol from the equiUbrium as it is formed. Air Products and others have developed a process that accomplishes this objective by dehydration of methanol to dimethyl ether [115-10-6]. Testing by Air Products at the pilot faciUty in LaPorte has demonstrated a 40% improvement in conversion. The reaction is similar to the Hquid-phase methanol process except that a soHd acid dehydration catalyst is added to the copper-based methanol catalyst slurried in an inert hydrocarbon Hquid (26). 

Mobil MTG and MTO Process. Methanol from any source can be converted to gasoline range hydrocarbons using the Mobil MTG process. This process takes advantage of the shape selective activity of ZSM-5 zeoHte catalyst to limit the size of hydrocarbons in the product. The pore size and cavity dimensions favor the production of C-5—C-10 hydrocarbons. The first step in the conversion is the acid-catalyzed dehydration of methanol to form dimethyl ether. The ether subsequendy is converted to light olefins, then heavier olefins, paraffins, and aromatics. In practice the ether formation and hydrocarbon formation reactions may be performed in separate stages to faciHtate heat removal. 

Methanol can be dehydrated over an acidic catalyst to give dimethyl ether and water ... 

Bisphenol A diglycidyl ether [1675-54-3] reacts readily with methacrylic acid [71-49-4] in the presence of benzyl dimethyl amine catalyst to produce bisphenol epoxy dimethacrylate resins known commercially as vinyl esters. The resins display beneficial tensile properties that provide enhanced stmctural performance, especially in filament-wound glass-reinforced composites. The resins can be modified extensively to alter properties by extending the diepoxide with bisphenol A, phenol novolak, or carboxyl-terrninated mbbers. 

Liquid mixtures of methanol and hydrochloric acid slowly yield methyl chloride even at 0°C (20,21), The typical process is carried out by contacting the alcohol with hydrochloric acid at 70 to 160°C and 0.1—1 MPa (15—150 psig) in the presence of a catalyst such as zinc chloride, quaternary amines (18,19,22), or with no catalyst at aH (23,24). TypicaHy 0.5 to 3% of the methanol is converted to dimethyl ether. Product methyl chloride is taken out of the reactor as a vapor and is cooled to condense as much of the water vapor and HCl as possible. Dimethyl ether and the residual water is then removed and the finished methyl chloride is condensed. 

Methanol to Ethylene. Methanol to ethylene economics track the economics of methane to ethylene. Methanol to gasoline has been flilly developed and, during this development, specific catalysts to produce ethylene were discovered. The economics of this process have been discussed, and a catalyst (Ni/SAPO 34) with almost 95% selectivity to ethylene has been claimed (99). Methanol is converted to dimethyl ether, which decomposes to ethylene and water the method of preparation of the catalyst rather than the active ingredient of the catalyst has made the significant improvement in yield (100). By optimizing the catalyst and process conditions, it is claimed that yields of ethylene, propylene, or both are maximized. This is still in the bench-scale stage. 

With the discovery of the crowns and related species, it was inevitable that a search would begin for simpler and simpler relatives which might be useful in similar applications. Perhaps these compounds would be easier and more economical to prepare and ultimately, of course, better in one respect or another than the molecules which inspired the research. In particular, the collateral developments of crown ether chemistry and phase transfer catalysis fostered an interest in utilizing the readily available polyethylene glycol mono- or dimethyl ethers as catalysts for such reactions. Although there is considerable literature in this area, much of it relates to the use of simple polyethylene glycols in phase transfer processes. Since our main concern in this monograph is with novel structures, we will discuss these simple examples further only briefly, below. 

The reaction occurs in the liquid phase at relatively low temperatures (about 50°C) in the presence of a solid acid catalyst. Few side reactions occur such as the hydration of isohutene to tertiary hutyl alcohol, and methanol dehydration and formation of dimethyl ether and water. However, only small amounts of these compounds are produced. Figure 5-8 is a simplified flow diagram of the BP Etherol process. 

Dimethyl carbonate (DMC) is a colorless liquid with a pleasant odor. It is soluble in most organic solvents but insoluble in water. The classical synthesis of DMC is the reaction of methanol with phosgene. Because phosgene is toxic, a non-phosgene-route may be preferred. The new route reacts methanol with urea over a tin catalyst. However, the yield is low. Using electron donor solvents such as trimethylene glycol dimethyl ether and continually distilling off the product increases the yield. ... 

Aprotic solvents may also dissolve a phase-transfer catalyst to realize higher rate.sAselectivities. Thus, in a claim, dichloronitrobenzene was reacted with KF in an aprotic solvent like 2-chlorotoluene, in the presence of hexadecyltributyl phoshonium bromide /crown ether/ PEG-dimethyl ether, to give chlorofluoronitrobenzene. 

H(hydrogen)-mordenite catalyst The crystallites were approximate parallelepipeds, the long dimension of which was assumed to be the pore length. Their analysis was based on straight, parallel pores in an isothermal crystallite (2 faces permeable). They measured (initial) rates of dehydration of methanol (A) to dimethyl ether in a differential reactor at 101 kPa using catalyst fractions of different sizes. Results (for two sizes) are given in the table below, together with... 

Reflux 6.9 g triphenylphosphine and 6.6 g lauryl bromide (or equimolar amount of homolog) in 40 ml xylene for 60 hours. Remove solvent and wash residue with 5X20 ml ether (by decanting) to get 11 g lauryl triphenylphosphonium bromide (I). To a stirred suspension of 5.6 g (0.011M)(I) in 50 ml ether add 0.01M butyllithium solution (see Organic Reactions 8,258(1954) for preparation). Stir Vz hour at room temperature and slowly add 1.66 g 3,5-dimethoxybenzaldehyde (preparation given elsewhere here) in 10 ml ether over Vi hour. After 15 hours, filter, wash filtrate with water and dry, evaporate in vacuum. Dilute residue with pentane, filter and remove solvent. Dissolve the residual oil in 25 ml ethyl acetate and hydrogenate over O.lg Adams catalyst at one atmosphere and room temperature for 2 hours. Filter and evaporate in vacuum to get the 5-alkylresorcinol dimethyl ether which can be reciystallized from pentane and demethylated as described elsewhere here. 

Figure 1.8 TPSR spectra obtained after saturation of a Mo03/AI203 catalyst with methanol at room temperature [61], Seen here are mass spectrometry traces corresponding to methanol (mle = 28 and 32), formaldehyde (mle = 28 and 30), water (mle = 18), and dimethyl ether (mle = 45). These data were used to propose a mechanism for the selective oxidation of methanol on Mo03-based catalysts. (Reproduced with permission from Elsevier.)...

One of the major advantages of the metal oxide catalyst over that of the straight metal catalyst is the elimination of the need for a methanol recovery tower. The metal oxide catalysts result in not only high yields, but also very high conversion rates. Consequently, there is no need to recover the small amounts of methanol that remain unreacted. It becomes part of the aqueous formaldehyde solution and serves as a stabilizer for the system. By-products are CO, CO2, dimethyl ether, and formic acid. The process yields (the percent of the methanol that ends up in formaldehyde) are 95-98%. 

Chen, Y., Zhou, H., Zhu, J., Zhang, Q., Wang, Y., Wang, D., and Wei, F. (2008) Direct synthesis of a fluidizable SAPO-34 catalyst for a fluidized dimethyl ether to olefins process. 

Methanol or dimethyl ether feeds were fed from an ISCO positive-displacement pump. Liquid products were collected in a room-temperature trap and gaseous products were analyzed by on-line gas chromatography and volumes measured by a wet-test meter. The catalyst could be regenerated in-situ by switching to a nitrogen/air mixture. 

In addition to the successful reductive carbonylation systems utilizing the rhodium or palladium catalysts described above, a nonnoble metal system has been developed (27). When methyl acetate or dimethyl ether was treated with carbon monoxide and hydrogen in the presence of an iodide compound, a trivalent phosphorous or nitrogen promoter, and a nickel-molybdenum or nickel-tungsten catalyst, EDA was formed. The catalytst is generated in the reaction mixture by addition of appropriate metallic complexes, such as 5 1 combination of bis(triphenylphosphine)-nickel dicarbonyl to molybdenum carbonyl. These same catalyst systems have proven effective as a rhodium replacement in methyl acetate carbonylations (28). Though the rates of EDA formation are slower than with the noble metals, the major advantage is the relative inexpense of catalytic materials. Chemistry virtually identical to noble-metal catalysis probably occurs since reaction profiles are very similar by products include acetic anhydride, acetaldehyde, and methane, with ethanol in trace quantities. 

Vapor-Phase Carbonylation of Dimethyl Ether and Methyl Acetate with Supported Transition Metal Catalysts... 

It was found that a nickel-activated carbon catalyst was effective for vapor phase carbonylation of dimethyl ether and methyl acetate under pressurized conditions in the presence of an iodide promoter. Methyl acetate was formed from dimethyl ether with a yield of 34% and a selectivity of 80% at 250 C and 40 atm, while acetic anhydride was synthesized from methyl acetate with a yield of 12% and a selectivity of 64% at 250 C and 51 atm. In both reactions, high pressure and high CO partial pressure favored the formation of the desired product. In spite of the reaction occurring under water-free conditions, a fairly large amount of acetic acid was formed in the carbonylation of methyl acetate. The route of acetic acid formation is discussed. A molybdenum-activated carbon catalyst was found to catalyze the carbonylation of dimethyl ether and methyl acetate. 

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