Synthesis of Hydrocarbons From Dimethyl Ether: Selectivtties Towards Light Hydrocarbons

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

doi:10.1080/08843759608947606

Cited by 11 publications

(4 citation statements)

References 2 publications

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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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“…In addition, the experimental conditions were chosen such that a maximization of the C 5 + fraction could be reached. At higher temperatures, undesired increased formation of C 2 = -C 4 = olefins was observed by other authors. − …”

Section: Resultsmentioning

confidence: 54%

DME-to-Hydrocarbon over an MFI Zeolite: Product Selectivity Controlled by Oxygenates under the Kinetic Regime

Ortega

Kolb

2019

Ind. Eng. Chem. Res.

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The influence of process variables on the DME-to-hydrocarbon (DtH) conversion has been assessed. The reaction was studied at atmospheric pressure, over an MFI zeolite (H-ZSM-5, SiO2/Al2O3 = 58), in a gradientless recycle reactor, under the kinetic regime, and process variables in the range of 598–648 K and space time in the range of 0.008–0.040 h kgcat kgDME –1. The results showed that DME and methanol are not in equilibrium, that the cis-/trans-C4 olefins are in equilibrium with each other but not with the 1-butene, while C5 + hydrocarbons are favored at high oxygenates conversion. Finally, it was observed for the first time, to best of the knowledge of the current authors, that under kinetically controlled conditions, the selectivity to main groups of products can be described by the oxygenates conversion (x oxy), independently of the process conditions, which means that the x oxy controls the process selectivity independently of reaction temperature and space time.

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“…The UA researchers, since 1985, carried out process development studies in various fundamental and applied aspects, i.e., demonstration of process feasibility, intrinsic kinetics, process chemistry, thermodynamic analysis and development of a software package for combined phase and chemical reaction equilibria for this multiphase and multicomponent system (which enables one to compute the concentrations of dissolved syngas components in the liquid solvent phase, at given reaction conditions), external mass transfer analysis, thermal stability, and scale-up [4][5][6][7][8]. The UA researchers' also first conceived the direct one-step DME synthesis process, termed as LPDME tm process [9][10][11][12] and later, the DME-to-olefins and DME-to-hydrocarbons processes [13][14][15][16], both enhancements over Mobil Oil's original methanolto-gasoline and methanol-to-olefins process [17][18][19][20]. The APCI component has been more focused on catalyst deactivation studies and feasibility/demonstration studies on the pilot scale (5 TPD & 10 TPD scale), of the LPMeOH tm and LPDME tm processes, at its Alternative Fuels Development Unit (AFDU) in LaPorte, Texas [21][22][23][24].…”

Section: Review Articlementioning

confidence: 99%

The Direct Dimethyl Ether (DME) Synthesis Process from Syngas: Current Status and Future prospects I. Process Feasibility and Chemical Synergy in LPDMEtm Process

Gogate

2018

PPS

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A novel one-step process for co-production of dimethyl ether (DME) and methanol, in the liquid phase was first conceived by the UA researchers, as an advance over the liquid phase methanol synthesis process (LPMeOH tm ). The one-step, direct DME process (LPDME tm ) is based on the application of "dual catalysis", where 2 functionally different yet compatible catalysts are used as a physical mixture, well-dispersed in the inert liquid phase. Three different reactions, methanol synthesis (via CO and CO 2 ), water-gas shift, and methanol dehydration (to form DME) take place over the 2 catalysts, Cu/ZnO/Al 2 O 3 and typically γ-Al 2 O 3 . The favorable thermodynamic and kinetic coupling of methanol dehydration reaction (very rapid and at/near thermodynamic equilibrium) with the methanol synthesis reaction (slower kinetics and highly thermodynamic) leads the beneficial "chemical synergy". This synergy helps to overcome the limitation on thermodynamic equilibrium conversion, and increases the per-pass syngas conversionand reactor productivity. The catalyst deactivation phenomena in LPDME tm processes also greatly alleviated compared to methanol alone; the increase in syngas conversion and methyl equivalent productivity (MEP) are sustained over a longer on-stream time.Here, we review the salient developments in the LPDME tm process since its inception, first at UA research laboratories and elsewhere including Air Products and Chemicals, Inc. First, we demonstrate the rationale of the LPDME tm process, and outline briefly the research studies in the two processes, that illustrate the chemical synergy in the LPDME tm process. This successful example of "cooperative catalysis" can be adapted in principle to many other organic reactions. We then briefly discern the intrinsic kinetics of the LPMeOH tm and LPDME tm systems, and also shed light of the catalyst deactivation phenomena in these processes. In closing, we outline the reactor design/scale-up and plant operational experience of the 3 commercial technologies, as currently practiced by JFE holdings, BP-AMOCO, and Halder-Topsoe.

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Synthesis of Hydrocarbons From Dimethyl Ether: Selectivtties Towards Light Hydrocarbons

Cited by 11 publications

References 2 publications

Liquid phase methanol and dimethyl ether synthesis from syngas

Liquid phase methanol and dimethyl ether synthesis from syngas

DME-to-Hydrocarbon over an MFI Zeolite: Product Selectivity Controlled by Oxygenates under the Kinetic Regime

The Direct Dimethyl Ether (DME) Synthesis Process from Syngas: Current Status and Future prospects I. Process Feasibility and Chemical Synergy in LPDMEtm Process

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