Methyl acetate catalyst

Another specific and important aspect to consider is the possibility that an environmentally heterogeneous photocatalyst can lead to the undesirable formation of reaction intermediates which are more toxic than the starting reagents. For instance, the Ti02-based photodegradation of ethanol, a relatively innocuous air pollutant, occurs through its transformation into the more toxic acetaldehyde. Condensation reactions can also lead to the formation of traces of methyl formate, ethyl formate, or methyl acetate. Catalyst design is therefore important to increase the overall oxidation rate to ensure complete mineralization (formation of C02 and H20). 

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. 

Acetylation of acetaldehyde to ethyUdene diacetate [542-10-9], a precursor of vinyl acetate, has long been known (7), but the condensation of formaldehyde [50-00-0] and acetic acid vapors to furnish acryflc acid [97-10-7] is more recent (30). These reactions consume relatively more energy than other routes for manufacturing vinyl acetate or acryflc acid, and thus are not likely to be further developed. Vapor-phase methanol—methyl acetate oxidation using simultaneous condensation to yield methyl acrylate is still being developed (28). A vanadium—titania phosphate catalyst is employed in that process. 

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. 

The chemical complex includes the methanol plant, methyl acetate plant, and acetic anhydride plant. The methanol plant uses the Lurgi process for hydrogenation of CO over a copper-based catalyst. The plant is capable of producing 165,000 t/yr of methanol. The methyl acetate plant converts this methanol, purchased methanol, and recovered acetic acid from other Eastman processes into approximately 440,000 t/yr of methyl acetate. 

The acetic anhydride process employs a homogeneous rhodium catalyst system for reaction of carbon monoxide with methyl acetate (36). The plant has capacity to coproduce approximately 545,000 t/yr of acetic anhydride, and 150,000 t/yr of acetic acid. One of the many challenges faced in operation of this plant is recovery of the expensive rhodium metal catalyst. Without a high recovery of the catalyst metal, the process would be uneconomical to operate. 

This process is one of the three commercially practiced processes for the production of acetic anhydride. The other two are the oxidation of acetaldehyde [75-07-0] and the carbonylation of methyl acetate [79-20-9] in the presence of a rhodium catalyst (coal gasification technology, Halcon process) (77). The latter process was put into operation by Tennessee Eastman in 1983. In the United States the total acetic anhydride production has been reported to be in the order of 1000 metric tons. 

A related but distinct rhodium-catalyzed methyl acetate carbonylation to acetic anhydride (134) was commercialized by Eastman in 1983. Anhydrous conditions necessary to the Eastman acetic anhydride process require important modifications (24) to the process, including introduction of hydrogen to maintain the active [Rhl2(CO)2] catalyst and addition of lithium cation to activate the alkyl methyl group of methyl acetate toward nucleophilic attack by iodide. 

Bisamides. Methylenebisamides are prepared by the reaction of the primary fatty amide and formaldehyde in the presence of an acid catalyst. AijAT-Methylenebisoleamide has been made via this route without the use of refluxing solvent (55). Polymethylenebisamides can be made from fatty acid, esters, or acid haUdes with diamines while producing water, alcohol, or mineral acid by-products. Eatty acids and diamines, typically ethylenediamine, have been condensed in the presence of NaBH and NaH2P02 to yield bisamides (56). When stearic acid, ethylenediamine, and methyl acetate react for 6 h at... 

A Belgian patent (178) claims improved ethanol selectivity of over 62%, starting with methanol and synthesis gas and using a cobalt catalyst with a hahde promoter and a tertiary phosphine. At 195°C, and initial carbon monoxide pressure of 7.1 MPa (70 atm) and hydrogen pressure of 7.1 MPa, methanol conversions of 30% were indicated, but the selectivity for acetic acid and methyl acetate, usehil by-products from this reaction, was only 7%. Ruthenium and osmium catalysts (179,180) have also been employed for this reaction. The addition of a bicycHc trialkyl phosphine is claimed to increase methanol conversion from 24% to 89% (181). 

Slotted plate for catalyst support designed with openings for vapor flow Ion exchanger fibers (reinforced ion exchange polymer) used as solid-acid catalyst None specified Hydrolysis of methyl acetate Evans and Stark, Eiir. Pat. Appl. EP 571,163 (1993) Hirata et al., Jap. Patent 05,212,290 (1993)... 

A methyl group can be introduced into an aromatic ring by treatment of diazonium salts with tetramethyltin and a palladium acetate catalyst." The reaction has been performed with Me, Cl, Br, and NO2 groups on the ring. A vinylic group can be introduced with CH2=CHSnBu3. 

The final step in the process involves reacting purified carbon monoxide from the gas separation plant with methyl acetate to form acetic anhydride, using a proprietary catalyst system and process. Part of the acetic anhydride is reacted with methanol to produce acetic acid and methyl acetate, and the latter is recirculated to the carbonylation step. 

Reactive distillation is one of the classic techniques of process intensification. This combination of reaction and distillation was first developed by Eastman Kodak under the 1984 patent in which methyl acetate was produced from methanol and acetic acid. One of the key elements of the design is to use the acetic acid as both a reactant and an extraction solvent within the system, thereby breaking the azeotrope that exists within the system. Likewise, the addition of the catalyst to the system allowed sufficient residence time such that high yields could be obtained, making the process commercially viable. Other examples in which reactive distillation may enhance selectivity include those of serial reactions, in which the intermediate is the desired product, and the reaction and separation rates can be systematically controlled to optimize the yield of the desired intermediate. ... 

Fig. 5.5.3 ]H NMR spectrum obtained from a sample containing catalyst and reaction mixture (i.e., methanol, acetic acid, methyl acetate and water). Peaks A and B are the intra- and inter-particle ]H resonances, respectively, associated with the OH group. Peak C is the ]H resonance of the CH30 group associated with...

Other companies (e.g., Hoechst) have developed a slightly different process in which the water content is low in order to save CO feedstock. In the absence of water it turned out that the catalyst precipitates. Clearly, at low water concentrations the reduction of rhodium(III) back to rhodium(I) is much slower, but the formation of the trivalent rhodium species is reduced in the first place, because the HI content decreases with the water concentration. The water content is kept low by adding part of the methanol in the form of methyl acetate. Indeed, the shift reaction is now suppressed. Stabilization of the rhodium species and lowering of the HI content can be achieved by the addition of iodide salts. High reaction rates and low catalyst usage can be achieved at low reactor water concentration by the introduction of tertiary phosphine oxide additives.8 The kinetics of the title reaction with respect to [MeOH] change if H20 is used as a solvent instead of AcOH.9 Kinetic data for the Rh-catalyzed carbonylation of methanol have been critically analyzed. The discrepancy between the reaction rate constants is due to ignoring the effect of vapor-liquid equilibrium of the iodide promoter.10... 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

An aqueous solution of methyl acetate (A) enters a CSTR at a rate of 0.5 L s 1 and a concentration (cAo) of 0.2 mol L-1. The tank is initially filled with 2000 L of water so that material flows out at a rate of 0.5 L s 1. A negligibly small stream of HCI (catalyst) is added to the entering solution of acetate so that the concentration of acid in the tank is maintained at 0.1 mol L-1, in which case the hydrolysis of acetate occurs at a rate characterized by kA = 1.1 I 10-4 s-1. What is the concentration of acetate in the outlet stream at the end of 30 min, and what is the eventual steady-state concentration ... 

Figure 6-3. Mechanism for the hydrogenation of a prochiral substrate methyl acet-amidocinnamate (MAC) with a catalyst containing a chiral chelating diphosphine ligand...

Initial theoretical studies focused on steps (1) and (2). Several model systems were examined with ab initio calculations.1191 For the reaction of methyl amine with methyl acetate, it was shown that the addition/elimi-nation (through a neutral tetrahedral intermediate) and the direct displacement (through a transition state similar to that shown in Figure 5a) mechanisms for aminolysis had comparable activation barriers. However, in the case of methyl amine addition to phenyl acetate, it was shown that the direct displacement pathway is favored by approximately 5 kcal/mol.1201 Noncovalent stabilization of the direct displacement transition state was therefore the focus of the subsequent catalyst design process. 

In these studies, chemical conversion was determined in situ by measuring the lH resonance associated with OH groups present. In practice two such resonances exist associated with chemical species inside and outside the catalyst particles, respectively. The difference in chemical shift between these intra- and inter-particle species arises because of the different electronic environment of the molecules inside the catalyst particles compared to their environment in the bulk fluid in the inter-particle space. In this work, chemical conversion was determined from the MR signal acquired from species in the inter-particle space of the bed because the signal from inside the catalyst particles is also going to be influenced, to an unknown extent, by relaxation time contrast. In addition to possible relaxation contrast effects, there will also be modifications to the chemical shifts of individual species resulting from adsorption onto the catalyst this may cause peak broadening and reduces the accuracy with which we can determine the chemical shift of the species of interest. As follows from eqn (11) which describes the esterification reaction of methanol and acetic acid to form methyl acetate and water ... 

Furthermore, even the ligand, necessary to stabilize the catalyst, can reduce Pd(II) to Pd(0) complexes and formation of phosphine oxides [62-64], In the preparation of [Pd(AcO)2(dppp)], from Pd(AcO)2 and dppp in MeOH, phosphine oxides have been found to form together with methyl acetate and palladium metal [65]. The reaction can be schematized as follows ... 

In a working catalytic system, however, the principal solvent component is acetic acid, so esterification (Eq. 2) leads to substantial conversion of the substrate into methyl acetate. Methyl acetate is activated by reaction with the iodide co-catalyst (Eq. 3) ... 

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