Synthesis of Methyl Acetate from Dimethyl Ether Using Group VIII Metal Salts of Phosphotungstic Acid

Sardesai, Abhay; Lee, Sung‐Gyu; Tartamella, Timothy

doi:10.1080/00908310252888682

Cited by 17 publications

(17 citation statements)

References 7 publications

(9 reference statements)

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“…This process has been studied in great detail [45][46][47][48][49][50][51][52][53][54]. Research studies have also been conducted to examine the conversion of dimethyl ether into gasolinerange hydrocarbons [55][56][57], lower olefins [58][59][60][61], and methyl acetate [62]. Research efforts by Air Products and Chemicals in this area have been mentioned [63].…”

Section: Introductionmentioning

confidence: 99%

Liquid phase methanol and dimethyl ether synthesis from syngas

2005

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The Liquid Phase Methanol Synthesis (LPMeOH TM ) process has been investigated in our laboratories since 1982. The reaction chemistry of liquid phase methanol synthesis over commercial Cu/ZnO/Al 2 O 3 catalysts, established for diverse feed gas conditions including H 2 -rich, CO-rich, CO 2 -rich, and CO-free environments, is predominantly based on the CO 2 hydrogenation reaction and the forward water-gas shift reaction. Important aspects of the liquid phase methanol synthesis investigated in this in-depth study include global kinetic rate expressions, external mass transfer mechanisms and rates, correlation for the overall gas-to-liquid mass transfer rate coefficient, computation of the multicomponent phase equilibrium and prediction of the ultimate and isolated chemical equilibrium compositions, thermal stability analysis of the liquid phase methanol synthesis reactor, investigation of pore diffusion in the methanol catalyst, and elucidation of catalyst deactivation/regeneration. These studies were conducted in a mechanically agitated slurry reactor as well as in a liquid entrained reactor. A novel liquid phase process for co-production of dimethyl ether (DME) and methanol has also been developed. The process is based on dual-catalytic synthesis in a single reactor stage, where the methanol synthesis and water gas shift reactions takes place over Cu/ZnO/Al 2 O 3 catalysts and the in-situ methanol dehydration reaction takes place over c-Al 2 O 3 catalyst. Co-production of DME and methanol can increase the single-stage reactor productivity by as much as 80%. By varying the mass ratios of methanol synthesis catalyst to methanol dehydration catalyst, it is possible to co-produce DME and methanol in any fixed proportion, from 5% DME to 95% DME. Also, dual catalysts exhibit higher activity, and more importantly these activities are sustained for a longer catalyst on-stream life by alleviating catalyst deactivation.

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Section: Introductionmentioning

confidence: 99%

Liquid phase methanol and dimethyl ether synthesis from syngas

2005

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“…Cs 2 HPW 12 O 40 was a good catalyst and introducing Rh in Cs 2 HPW 12 O 40 improved the catalytic activity for the DME carbonylation [22,23]. However, only tungstophosphoric acid have been reported for the DME carbonylation in literature till now [22][23][24][25][26]. In the present study, we investigated the catalytic performance of tungstosilicic acid for the heterogeneous carbonylation of DME to methyl acetate.…”

Section: Introductionmentioning

confidence: 89%

“…7 shows the effect of CO/DME flow rate ratio in the DME carbonylation over Rh/Cs 3 On the other hand, with increasing CO/DME flow rate ratio from 1.8 to 45, the DME conversion greatly increased from 0.9 to 99.4 % over Rh/Cs 3 HSiW 12 O 40 . A high CO/DME flow rate ratio is usually to be used for improving the DME conversion in the heterogeneous DME carbonylation with CO [24][25][26][27]. However, the CO conversion becomes low at a high CO/DME flow rate ratio according to the reaction equation of DME carbonylation with CO (Eq.…”

Section: Rhmentioning

confidence: 98%

“…The decrease of the DME conversion after reaction for 5 h was 7.5 and 10.5 % over Rh/Cs 3 HSiW 12 O 40 and Rh/Cs 2 HPW 12 O 40 , respectively. The deactivation of heteropoly acid catalysts in the DME carbonylation has been reported in literature [26]. The carbonaceous deposits on the catalyst surface are usually the main reason for the catalyst deactivation during the reaction [38][39][40].…”

Section: Rhmentioning

confidence: 99%

“…Furthermore, DME can be used as a starting material for producing dimethoxymethane [15,16], light olefins [21], methyl acetate [22][23][24][25][26][27][28][29][30], and so on. Methyl acetate is an important chemical in industry.…”

Section: Introductionmentioning

confidence: 99%

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Heterogeneous carbonylation of dimethyl ether to methyl acetate over bifunctional catalysts containing Rh and heteropoly acids

Liu

Murata

Inaba

2015

Reac Kinet Mech Cat

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The carbonylation of dimethyl ether to methyl acetate was carried out in a high-pressure flowed fix-bed reaction system over heterogeneous halide-free catalysts. The TG curves indicated that solid 12-tungstosilicic acid had a crystal structure (with six crystallization waters) identical to that of solid 12-tungstophosphoric acid, although they had different number of protons in molecules. The BET surface areas greatly increased by Cs substitution in H 4 SiW 12 O 40 , and Cs 3 HSiW 12 O 40 showed a BET surface area of 206 m 2 g -1 . For the DME carbonylation at 473 K on 1 MPa under a CO/DME flow rate ratio of 18, Cs 3 HSiW 12 O 40 showed a DME conversion (6.7 %) higher than that over Cs 2 HPW 12 O 40 (4.6 %) because Cs 3 HSiW 12 O 40 had a larger surface area. Cs 3 HSiW 12 O 40 and Cs 2 HPW 12 O 40 showed high selectivity for methyl acetate of (98.0 and 97.5 %). By adding 1.0 wt% Rh in Cs 3 HSiW 12 O 40 , the DME conversion greatly increased from 6.7 to 30.8 % because a multiplier effect occurred between Rh and heteropoly acid. Rh/Cs 3 HSiW 12 O 40 showed a higher catalytic performance than those over the reported Rh/Cs 2 HPW 12 O 40 and Rh/H-MOR for the carbonylation. The DME conversion increased with increasing Rh loading from 0 to 1.0 wt% but became almost constant when Rh loading ranged from 1.5 to 3.0 wt% over Rh/Cs 3 HSiW 12 O 40 . With increasing the CO/DME ratio from 1.8 to 45, the DME conversion increased from 0.9 to 99.4 % over Rh/Cs 3 HSiW 12 O 40 at 473 K under 1 MPa. The 1 wt% Rh/Cs 3 HSiW 12 O 40 catalyst showed an initial DME conversion of 30.8 % (after 5 min on stream) but the DME conversion decreased to 23.3 % after 5 h on stream at 473 K on 1 MPa under a CO/DME flow rate ratio of 18.

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