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Volkova, G. G.; Plyasova, L. M.; Саланов, А. Н.; Kustova, G. N.; Yurieva, T. M.; Likholobov, V. A.

doi:10.1023/a:1015420828251

Cited by 54 publications

(29 citation statements)

References 22 publications

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“…In this context, DME carbonylation to methyl acetate (MA) over heteropolyacids seems to be a quite promising route. For example, a RhPW 12 O 40 /SiO 2 catalyst was reported to give 16% yield of MA at 498 K [4], and a Rh/Cs x H 3-x PW 12 O 40 solid acid showed 33% conversion of DME with 94% selectivity of MA at 473 K [5,6]. However, these catalysts also favored the formation of hydrocarbons, leading to a severe deactivation by deposition of carbonaceous residues.…”

Section: Introductionmentioning

confidence: 99%

Dimethyl Ether Carbonylation to Methyl Acetate over HZSM-35

et al. 2010

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Dimethyl ether (DME) carbonylation to methyl acetate (MA) was comparatively investigated over HZSM-35 and mordenite (HMOR) zeolites. The HZSM-35 catalyst showed rather high selectivity and stability without obvious deactivation for 32 h on-stream at 473 K with a MA yield of *11%. On the other hand, the HMOR catalyst showed similar initial activity, but the yield of MA rapidly decreased to only 5% after 20 h on-stream. It was further revealed that the deposition rate of coke over the HZSM-35 catalyst was much lower than that on the HMOR zeolite, indicating that the formation rate of coke was strongly dependent on the pore sizes of the zeolites. The pore structure of HZSM-35 having a one-dimensional channel 10 member-ring (10-MR) and a perpendicularly intersected one-dimensional 8 member-ring (8-MR) channel effectively limited the formation of aromatic compounds which act as the precursors of coke.

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Section: Introductionmentioning

confidence: 99%

Dimethyl Ether Carbonylation to Methyl Acetate over HZSM-35

et al. 2010

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“…[1][2][3] Zeolites [4][5][6][7][8][9] and Keggin polyoxometallate clusters [10][11][12][13] also catalyze the carbonylation of alcohols and ethers (Koch reaction) to form carboxylic acids and esters. Surface alkyl groups, formed by alcohol dissociation, alkene protonation, or alkane deprotonation at acidic sites react with CO to form acylium ions, which then form carboxylic acids and esters, as in the reactions of isobutane on sulfated zirconia [14] and tert-butyl alcohol [5,7,8] on acidic ZSM5, MOR, BEA, and Y-zeolites to form pivalic acid.…”

mentioning

confidence: 99%

Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites

Cheung

Bhan

Sunley³

et al. 2006

Angew Chem Int Ed

368

261

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Methanol carbonylation is currently used to produce acetic acid with Rh and Ir organometallic complexes and iodide cocatalysts. [1][2][3] Zeolites [4][5][6][7][8][9] and Keggin polyoxometallate clusters [10][11][12][13] also catalyze the carbonylation of alcohols and ethers (Koch reaction) to form carboxylic acids and esters. Surface alkyl groups, formed by alcohol dissociation, alkene protonation, or alkane deprotonation at acidic sites react with CO to form acylium ions, which then form carboxylic acids and esters, as in the reactions of isobutane on sulfated zirconia [14] and tert-butyl alcohol [5,7,8] on acidic ZSM5, MOR, BEA, and Y-zeolites to form pivalic acid. Carbonylation of methanol and dimethyl ether (DME) on acidic zeolites and polyoxometallate clusters occurs concurrently with side reactions (Scheme 1) and significant catalyst deactivation. [4,6,[9][10][11][12][13] We report herein stable and highly selective (> 99 %) halide-free catalysts based on zeolites for DME carbonylation to methyl acetate at low temperatures (423-463 K). The reaction rates are much higher than for methanol carbonylation because water may adsorb competitively at CO binding sites and/or cause parallel methanol dehydration Scheme 1. Network of carbonylation, hydration, dehydration, and methanol-to-hydrocarbon chemistries.

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“…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%

“…Acidic zeolites H-mordenite [27][28][29][30] and heteropoly acids Cs 3-x H x PW 12 O 40 [22][23][24][25] have been reported as effective catalysts for the heterogeneous carbonylation of DME. 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].…”

Section: Introductionmentioning

confidence: 99%

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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Cited by 54 publications

References 22 publications

Dimethyl Ether Carbonylation to Methyl Acetate over HZSM-35

Dimethyl Ether Carbonylation to Methyl Acetate over HZSM-35

Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites

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

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