Liquid-phase methanol synthesis in apolar (squalane) and polar (tetraethylene glycol dimethylether) solvents

Laan, G. van der; Beenackers, A.A.C.M.; Ding, B.Z.; Strikwerda, J. C.

doi:10.1016/s0920-5861(98)00362-9

Cited by 16 publications

(4 citation statements)

References 16 publications

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“…Therefore, it is a reasonable assumption that high methanol production rates in light mineral oil are correlated with the high solubility of the reactants. Interestingly, a similar trend was reported for slurry phase CO hydrogenation with commercial Cu-based catalysts comparing the carrier liquids squalan (low polarity) and tetraethylene glycol dimethyl ether (high polarity) [25]. Hence, our data supports the statement [26] that a high methanol productivity could be achieved when choosing a carrier liquid with low polarity, providing high solubility for the reactants.…”

Section: Selection Of An Appropriate Carrier Liquidsupporting

confidence: 87%

Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Schühle

Reichenberger

Marzun

et al. 2020

Chemie Ingenieur Technik

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A promising approach for chemical energy storage from fluctuating renewable electricity is methanol synthesis from CO2 and hydrogen in a slurry reactor concept, due to efficient heat storage and easy reactor control. In combination with a promising In2O3/ZrO2 catalyst and mineral oil as carrier liquid, efficient methanol production under a wide range of changing process conditions is shown for the first time. A maximum methanol productivity of 2.1 gMeOHgIn−1h−1 and multiple recycling stability of the catalyst and the carrier liquid was achieved, showing no significant decrease in methanol yields.

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Section: Selection Of An Appropriate Carrier Liquidsupporting

confidence: 87%

Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Schühle

Reichenberger

Marzun

et al. 2020

Chemie Ingenieur Technik

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“…The synthesis and reaction tests were performed in a 300 mL continuous flow stirred-tank reactor (CSTR; Parr), with mechanical stirring at 1500 rpm and with vertical baffles to ensure the homogeneous mixing of the liquid and gas phases. Squalane (16 ppm of water, by Karl Fischer titration) was used as the solvent, as it exhibits a high boiling point and good gas solubility of the feed gases; it has already been reported to be an excellent solvent for the liquid-phase methanol synthesis and is widely used. , In a typical preparation procedure, the required amounts of Pd(OAc) 2 and Ga(OSt) 3 were suspended in 100 mL of squalane (3.18 mmol Pd+Ga L –1 ), and the mixture was degassed with N 2 (400 mL min –1 ) for 30 min. Then, the temperature was increased to 190 °C (6 °C min –1 ), and after 1 h under N 2 flow (400 mL min –1 ), the reactor was cooled to 100 °C.…”

Section: Experimental Sectionmentioning

confidence: 99%

Pd₂Ga-Based Colloids as Highly Active Catalysts for the Hydrogenation of CO₂ to Methanol

García‐Trenco

White²,

Regoutz³

et al. 2017

ACS Catal.

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Colloidal Pd2Ga-based catalysts are shown to catalyze efficiently the hydrogenation of CO2 to methanol. The catalysts are produced by the simple thermal decomposition of Pd(II) acetate in the presence of Ga(III) stearate, which leads to Pd0 nanoparticles (ca. 3 nm), and the subsequent Pd-mediated reduction of Ga(III) species at temperatures ranging from 210 to 290 °C. The resulting colloidal Pd2Ga-based catalysts are applied in the liquid-phase hydrogenation of carbon dioxide to methanol at high pressure (50 bar). The intrinsic activity is around 2-fold higher than that obtained for the commercial Cu-ZnO-Al2O3 (60.3 and 37.2 × 10–9 molMeOH m–2 s–1), respectively, and 4-fold higher on a Cu or Pd molar basis (3330 and 910 μmol mmolPd or Cu–1 h–1). Detailed characterization data (HR-TEM, STEM/EDX, XPS, and XRD) indicate that the catalyst contains Pd2Ga nanoparticles, of average diameters 5–6 nm, associated with a network of amorphous Ga2O3 species. The proportion of this Ga2O3 phase can be easily tuned by adjusting the molar ratio of the Pd:Ga precursors. A good correlation was found between the intrinsic activity and the content of Ga2O3 surrounding the Pd2Ga nanoparticles (XPS), suggesting that methanol is formed by a bifunctional mechanism involving both phases. The increase in the reaction temperature (190–240 °C) leads to a gradual decrease in methanol selectivity from 60 to 40%, while an optimum methanol production rate was found at 210 °C. Interestingly, unlike the conventional Cu-ZnO-Al2O3, which experienced approximately 50% activity loss over 25 h time on stream, the Pd2Ga-based catalysts maintain activity over this time frame. Indeed, characterization of the Pd/Ga mixture postcatalysis revealed no ripening of the nanoparticles or changes in the phases initially present

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“…Squalane was used as the reaction solvent as it exhibits a high boiling point and good gas solubility of the feed gases; it has already been reported as an excellent solvent for the liquid phase methanol synthesis process and is widely used. 39 In a typical procedure, the reactor was filled with squalane (100 mL) and then stirred at room temperature, under a flow of N 2 (400 mL min −1 ), for 30 min to de-gas the solvent. The pre-catalyst colloid (40 mL) was added, the reactor was heated to 260 °C and then pressurized to 5.0 MPa using a gas mixture comprising 95 vol% syn-gas (70% H 2 /24% CO/6% CO 2 ) and 5 vol% Ar (used as internal standard for GC analysis).…”

Section: Catalytic Experimentsmentioning

confidence: 99%

A one-step Cu/ZnO quasi-homogeneous catalyst for DME production from syn-gas

García‐Trenco

White

Shaffer

et al. 2016

Catal. Sci. Technol.

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ARTICLEThis journal is © The Royal Society of Chemistry 20xxJ. Name., 2013, 00, 1-3 | 1 Please do not adjust marginsPlease do not adjust margins a. Department of Chemistry, Imperial College London, South Kensington, London, UK, SW7 2AZ; c.k.williams@imperial.ac A simple one-pot synthetic method allows the preparation of hybrid catalysts, based on colloidal Cu/ZnO nanoparticles (NPs), used for the liquid phase synthesis of DME from syngas. The method obviates the high temperature calcinations and pre-reduction treatments typically associated with such catalysts. The hybrid catalysts are applied under typical industrially relevant conditions. The nature of the hybrid catalysts, the influence of the acid component, mass ratio between components, and Cu/Zn composition are assessed. The best catalysts comprise a colloidal mixture of Cu/ZnO NPs, as the methanol synthesis component, and -Al2O3, as the methanol dehydration component. These catalysts show high DME selectivity (65-70 %C). Interestingly, the activity (relative to Cu content) is up to three times higher than that for the reference hybrid catalyst based on the commercial Cu/ZnO/Al2O3 methanol synthesis catalyst. The hybrid catalysts are stable for at least 20 h time-on-stream, not showing any significant sintering of the Cu 0 phase. Post-catalysis,TEM/EDX shows that the hybrid catalysts consist of Cu 0 and ZnO NPs with an average size of 5-7 nm with -Al2O3 particles in close proximity.

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Liquid-phase methanol synthesis in apolar (squalane) and polar (tetraethylene glycol dimethylether) solvents

Cited by 16 publications

References 16 publications

Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Pd₂Ga-Based Colloids as Highly Active Catalysts for the Hydrogenation of CO₂ to Methanol

A one-step Cu/ZnO quasi-homogeneous catalyst for DME production from syn-gas

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Liquid-phase methanol synthesis in apolar (squalane) and polar (tetraethylene glycol dimethylether) solvents

Cited by 16 publications

References 16 publications

Slurry Phase Hydrogenation of CO2 to Methanol Using Supported In2O3 Catalysts as Promising Approach for Chemical Energy Storage

Slurry Phase Hydrogenation of CO2 to Methanol Using Supported In2O3 Catalysts as Promising Approach for Chemical Energy Storage

Pd2Ga-Based Colloids as Highly Active Catalysts for the Hydrogenation of CO2 to Methanol

A one-step Cu/ZnO quasi-homogeneous catalyst for DME production from syn-gas

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Product

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Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Slurry Phase Hydrogenation of CO₂ to Methanol Using Supported In₂O₃ Catalysts as Promising Approach for Chemical Energy Storage

Pd₂Ga-Based Colloids as Highly Active Catalysts for the Hydrogenation of CO₂ to Methanol