Role of in-Situ Produced Methanol on the Catalyst Deactivation in the Liquid Phase Methanol Synthesis Process

Tartamella, Timothy; Lee, Sung‐Gyu

doi:10.1080/08843759608947607

Cited by 5 publications

(4 citation statements)

References 5 publications

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“…The deactivation of Cu/ZnO/Al 2 O 3 catalyst during methanol synthesis [17,23,40] as well as the regeneration of deactivated catalyst [18,23,25,26,28,41] has been investigated in great detail. Long-term (120 h) methanol synthesis experiments were conducted to observe the progress of catalyst deactivation in the following environments: typical CO-rich syngas (CO, H 2 , CO 2 , CH 4 ), feed gas mixture without CO, and feed gas mixture without CO 2 .…”

Section: Catalyst Deactivationmentioning

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: Catalyst Deactivationmentioning

confidence: 99%

Liquid phase methanol and dimethyl ether synthesis from syngas

2005

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“…enhances the stability of Cu-Zn-based catalysts in low concentrations [33], assists Cu sintering [33][34][35][36][37] and disruption of the Cu-Zn synergy [16] at high partial pressures, hinders coke formation [20], deactivates γ-Al 2 O 3 by strong adsorption [17][18][19], and reduces formation of deactivating carbonaceous compounds on H-ZSM-5 [18]. High partial pressure of methanol is also suggested to intensify Cu sintering [38]. Moreover, certain dehydration byproducts such as toluene, if present in large concentrations (500 ppm), can permanently deactivate the Cu-based catalyst through wax formation and pore filling [39].…”

Section: Introductionmentioning

confidence: 99%

Catalyst Deactivation During One-Step Dimethyl Ether Synthesis from Synthesis Gas

et al. 2017

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Catalysts for direct synthesis of dimethyl ether (DME) from synthesis gas should essentially contain two functions, i.e. methanol synthesis and methanol dehydration. In the present work, the deactivation of both functions of hybrid catalysts during direct DME synthesis under industrially relevant conditions has been investigated with special focus on the influence of each reaction step on the deactivation of the catalyst function corresponding to the other step. A physical mixture of a Cu-Zn-based methanol synthesis catalyst and a ZSM-5 methanol dehydration catalyst was used. The metallic catalyst appears to deactivate due to Cu sintering, with no apparent effect from the methanol dehydration step under the conditions applied. The acid catalyst deactivates due to accumulation of hydrocarbon species formed in its pores.Synthesis gas composition, i.e. H 2 /CO ratio and CO 2 -content (which directly affects partial pressure of water), seems to influence the zeolite deactivation.

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“…This phenomenon may be explained by the fact that the aforementioned increase of copper crystallite size implies a more difficult reduction of Cu/Zn catalysts. The catalytic activity might be mainly affected by the size of reducible crystal; as the solubility of water in substrate is low, the catalytic surface would be rendered inactive by the accumulation of water, and the presence of water can also cause damage to the Cu/Zn catalyst by promotion of the crystal growth [30,31]. TEM images of the Cu/Zn catalyst samples are shown in Fig.…”

Section: Characterization Of Catalystsmentioning

confidence: 99%

Effect of water on Cu/Zn catalyst for hydrogenation of fatty methyl ester to fatty alcohol

Cao

Fan

et al. 2009

Korean J. Chem. Eng.

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The effect of water on Cu/Zn catalyst prepared by co-precipitation for hydrogenation of methyl laurate in a slurry phase was studied using a stirred autoclave reactor system. The catalysts were characterized by means of XRD, BET, H 2 -TPR, SEM and TEM. The results indicate that catalytic activity decreases with increased amount of water in methyl laurate. Correlating with the results from the above characterization, it is found that the main causes for the water deactivation of the Cu/Zn catalyst were the water occlusion of active catalyst sites by the low solubility of water in the substrate and the promotion of crystal growth, as well as the Cu/Zn catalyst agglomeration in the presence of water.

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Role of in-Situ Produced Methanol on the Catalyst Deactivation in the Liquid Phase Methanol Synthesis Process

Cited by 5 publications

References 5 publications

Liquid phase methanol and dimethyl ether synthesis from syngas

Liquid phase methanol and dimethyl ether synthesis from syngas

Catalyst Deactivation During One-Step Dimethyl Ether Synthesis from Synthesis Gas

Effect of water on Cu/Zn catalyst for hydrogenation of fatty methyl ester to fatty alcohol

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