skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dimethyl ether production from methanol and/or syngas

Abstract

Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

Inventors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1170379
Patent Number(s):
8,957,259
Application Number:
11/241,321
Assignee:
Battelle Memorial Institute (Richland, WA) PNNL
DOE Contract Number:
AC0576RL01830
Resource Type:
Patent
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dagle, Robert A, Wang, Yong, Baker, Eddie G, and Hu, Jianli. Dimethyl ether production from methanol and/or syngas. United States: N. p., 2015. Web.
Dagle, Robert A, Wang, Yong, Baker, Eddie G, & Hu, Jianli. Dimethyl ether production from methanol and/or syngas. United States.
Dagle, Robert A, Wang, Yong, Baker, Eddie G, and Hu, Jianli. Tue . "Dimethyl ether production from methanol and/or syngas". United States. doi:. https://www.osti.gov/servlets/purl/1170379.
@article{osti_1170379,
title = {Dimethyl ether production from methanol and/or syngas},
author = {Dagle, Robert A and Wang, Yong and Baker, Eddie G and Hu, Jianli},
abstractNote = {Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Feb 17 00:00:00 EST 2015},
month = {Tue Feb 17 00:00:00 EST 2015}
}

Patent:

Save / Share:
  • This report documents engineering, modification, and operations efforts of demonstration of dimethyl-ether/methanol coproduction in a slurry-phase reactor, carried out in a 2-ft diameter bubble column reactor. Equipment modifications made it possible to remove the product DME and by-product CO{sub 2} from the reactor effluent. Coproduction of dimethyl-ether (DME) and methanol (MeOH) was accomplished in the slurry reactor by physically mixing two different catalysts. The catalyst used to produce MeOH from syngas was manufactured by BASF (type S3-86); the catalyst used to convert MeOH to DME was Catapal {gamma}-alumina. Ratio of MeOH to DME catalysts determined the selectivity towards DME. Themore » demonstration sought to study effect of cocatalyst ratio on product selectivity. Three different proportions of DME catalyst were examined: 0, 6.6, and 19.3 wt % alumina. At each catalyst proportion, the plant was operated at two different gas space velocities. Some process variables were maintained at fixed conditions; most important variables included: reactor temperature (482F), reactor pressure (750 psig), and reactor feed gas composition (35% H{sub 2}, 51% CO,13% CO{sub 2} 1% other, nominal-molar basis).« less
  • A Pd/ZnO/Al2O3 catalyst was developed for the synthesis of methanol and dimethyl ether (DME) from syngas. Studied were temperatures of operation ranging from 250°C to 380°C. High temperatures (e.g. 380°C) are necessary when combining methanol and DME synthesis with a methanol to gasoline (MTG) process in a single reactor bed. A commercial Cu/ZnO/Al2O3 catalyst, utilized industrially for the synthesis of methanol at 220-280°C, suffers from a rapid deactivation when the reaction is conducted at high temperature (>320°C). On the contrary, a Pd/ZnO/Al2O3 catalyst was found to be highly stable for methanol and DME synthesis at 380°C. The Pd/ZnO/Al2O3 catalyst wasmore » thus further investigated for methanol and DME synthesis at P=34-69 bars, T= 250-380°C, GHSV= 5 000-18 000 h-1, and molar feeds H2/CO= 1, 2, and 3. Selectivity to DME increased with decreasing operating temperature, and increasing operating pressure. Increased GHSV’s and H2/CO syngas feed ratios also enhanced DME selectivity. Undesirable CH4 formation was observed, however, can be minimized through choice of process conditions and by catalyst design. By studying the effect of the Pd loading and the Pd:Zn molar ratio the formulation of the Pd/ZnO/Al2O3 catalyst was optimized. A catalyst with 5% Pd and a Pd:Zn molar ratio of 0.25:1 has been identified as the preferred catalyst. Results indicate that PdZn particles are more active than Pdº particles for the synthesis of methanol and less active for CH4 formation. A correlation between DME selectivity and the concentration of acid sites of the catalysts has been established. Hence, two types of sites are required for the direct conversion of syngas to DME: 1) PdZn particles are active for the synthesis of methanol from syngas, and 2) acid sites which are active for the conversion of methanol to DME. Additionally, CO2 formation was problematic as PdZn was found to be active for the water-gas-shift (WGS) reaction, under all the conditions evaluated.« less
  • CO hydrogenation has been studied over Pd/NaY and Pd/HY catalysts prepared by ion exchange, By controlling the calcination program, Pd/NaY catalysts can be tuned to selectively produce either branched C{sub 4} hydrocarbons or CH{sub 3}OH and CH{sub 3}OCH{sub 3}. On Pd/HY catalysts, C{sub 2}H{sub 6} and C{sub 3}H{sub 8} predominate. Dissociative adsorption of CO over small Pd particles leads to formation of methane and an interstitial PdC{sub 0.13} compound, detected by XRD. Reduction with H{sub 2} converts PdC{sub 0.13} to Pd and methane. During CO hydrogenation catalysis, palladium particles grow, leading to local collapse of the zeolite lattice. Pd migrationmore » is also manifest from changes in the Pd/Si ratio detected by XPS. The reaction network reveals bifunctional catalysis: formation of CH{sub 3}OH on Pd particles is followed by its conversion to CH{sub 3}OCH{sub 3} and hydrocarbons over acid sites. Readsorption of hydrocarbons on the Pd particles results in hydrogenation of unsaturated compounds and to changes in the activity, selectivity, and deactivation behavior of the catalysts.« less
  • This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalystmore » by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.« less
  • This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalystmore » by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.« less