Mechanistic study of a new low-temperature methanol synthesis on Cu/MgO catalysts

Yang, Renqiang; Zhang, Yi; Iwama, Yuki; Tsubaki, Noritatsu

doi:10.1016/j.apcata.2005.04.051

Cited by 57 publications

(29 citation statements)

References 32 publications

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“…12 Proposed mechanism for the synthesis reaction of a low temperature methanol from syngas (CO/CO 2 /H 2 ) using 2-propanol promoter, b classical high-temperature methanol from syngas (CO/H 2 ) [56][57][58]. The reaction mechanism of the new low temperature methanol synthesis is expressed as follows [52][53][54][55] The formation of alkyl formate was a key step in the low temperature methanol synthesis reaction. It changed the normal reaction path of classical, high-temperature methanol synthesis, which was from formate via methoxy to methanol.…”

Section: Kinetics Analysismentioning

confidence: 99%

“…The mechanism of low temperature methanol synthesis on Cu/MgO catalyst with ethanol solvent was also investigated [54]. According to the observations above, a possible mechanism is offered as scheme in Fig.…”

Section: Reaction Mechanism In Ethanol Mediamentioning

confidence: 99%

“…The reaction mechanism of low temperature methanol synthesis above is investigated by in situ DRIFTS [52][53][54][55][56][57][58].…”

Section: Reaction Mechanism and Kinetics Of Low Temperature Methanol mentioning

confidence: 99%

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A New Method of Low Temperature Methanol Synthesis

Yang

Meng

et al. 2009

Catal Surv Asia

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Low temperature methanol synthesis is a promising technique for the practical methanol industry. New developments of a new kind of low temperature methanol synthesis were reviewed, including the effects of feed gas, reaction solvent, supercritical media and catalyst modification. The reaction mechanism and kinetics were also summarized primarily. Carbon dioxide played an important role in this new kind of low temperature methanol synthesis. It reacted with hydrogen adsorbed on catalyst surface to form HCOOM, an important reaction intermediate. Alcohol solvent in the low temperature methanol synthesis performed not only a media, but also a homogeneous catalyst. The reaction of the adsorbed formate species with alcohol on Cu/ZnO catalyst surface proceeded according to the Rideal mechanism rather than Langmuir-Hinshelwood mechanism to form alkyl formate. The formation of alkyl formate from alcohol solvent and hydrogenation of such an alkyl formate were the key steps in low temperature methanol synthesis reaction. These results provided new insights into low temperature methanol synthesis.

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Section: Kinetics Analysismentioning

confidence: 99%

Section: Reaction Mechanism In Ethanol Mediamentioning

confidence: 99%

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A New Method of Low Temperature Methanol Synthesis

Yang

Meng

et al. 2009

Catal Surv Asia

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“…Recent decades, a low temperature methanol synthesis process in liquid phase was developed in order to enhance the CO conversion and methanol selectivity of the thermodynamic merits for the conversion of syngas to methanol in conventional process . For the low temperature methanol synthesis in liquid phase process, the Cu based catalyst with alcohol as solvent has been widely studied . Generally, the reaction pathway is consisted of two main steps of the carbonylation of alcohol and the hydrogenolysis of the ester intermediate as shown in following, while few literatures reported the active center of the Cu based catalyst for the low temperature methanol synthesis from syngas in the liquid phase.

true \begin{matrix} First step & CO + ROH \to HCOOR \\ Second step & HCOOR + {2 H}_{2} \to {CH}_{3} OH + ROH \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

Investigation of Active Center of Cu‐Based Catalyst for Low Temperature Methanol Synthesis from Syngas in Liquid Phase: The Contribution of Cu⁺ and Cu⁰

et al. 2017

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LaCuMn catalyst was prepared under different reduction temperature and passivation time, and used to catalyze CO hydrogenation to methanol in liquid phase. The effect of reductive copper species on the catalytic activity and the product distribution was studied. The results showed that the surface content of reductive copper species greatly affect the catalytic activity and the approximate molar ratio of Cu+ to Cu0 was important. The mixture of CuZn/AC‐N2 with only Cu+ and CuZn/AC‐H2 with only Cu0 was utilized for the low temperature methanol synthesis from syngas in liquid phase. It was confirmed that both of the reductive copper species of Cu+ and Cu0 were active species and Cu+ was superior to Cu0. Moreover, the synergic function of Cu+ and Cu0 led to the enhancement of the catalytic activity of Cu based catalyst, and the optimum molar ratio of surface Cu+ to Cu0 was in the range of 3.5 to 4.0.

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“…Cu-MgO catalysts are commercially used for cyclohexanol conversion to cyclohexanone, and also proposed for other alcohol dehydrogenation processes [4,5] as well as to C=O bond hydrogenation [6,7], including a new route of methanol synthesis through ethyl formate [8,9]. For the last 20 years, it was carefully studied by many researchers in order to uncover the peculiarities of structural properties and make links between preparation procedure and catalytic properties of mixed oxide.…”

Section: Introductionmentioning

confidence: 99%

Effect of anionic admixtures on the copper–magnesium mixed oxide reduction

Khassin

Filonenko

Minyukova

et al. 2010

Reac Kinet Mech Cat

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The anionic composition, structural parameters, optical properties and reduction behavior of Cu-MgO solid solution in hydrogen dramatically change after exposure to air. The air-exposed Cu-Mg oxide contains a lot of CO 3 2-and OHanions. Its reduction proceeds via two stages: (1) diffusion of Cu 2? to the surface and (2) chemical interaction of Cu 2? with hydrogen. The effective activation energy gradually increases from that of the chemical step (65 kJ/mol) to that of the transport step of Cu 2? diffusion (130 kJ/mol). This behavior follows the ''compensation effect'', which is close to those reported earlier for CuO reduction. On the contrary, reduction of Cu 2? from the Cu-Mg oxide sample, which was not exposed to air after thermal pretreatment in the inert gas, proceeds in one step at 120-160°C with the effective activation energy of 19 kJ/mol, which is manifold less than the reported effective activation energies for various Cu-oxide systems. Water molecules eliminate from the sample slowly along with further heating up to 450°C.

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Mechanistic study of a new low-temperature methanol synthesis on Cu/MgO catalysts

Cited by 57 publications

References 32 publications

A New Method of Low Temperature Methanol Synthesis

A New Method of Low Temperature Methanol Synthesis

Investigation of Active Center of Cu‐Based Catalyst for Low Temperature Methanol Synthesis from Syngas in Liquid Phase: The Contribution of Cu⁺ and Cu⁰

Effect of anionic admixtures on the copper–magnesium mixed oxide reduction

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Mechanistic study of a new low-temperature methanol synthesis on Cu/MgO catalysts

Cited by 57 publications

References 32 publications

A New Method of Low Temperature Methanol Synthesis

A New Method of Low Temperature Methanol Synthesis

Investigation of Active Center of Cu‐Based Catalyst for Low Temperature Methanol Synthesis from Syngas in Liquid Phase: The Contribution of Cu+ and Cu0

Effect of anionic admixtures on the copper–magnesium mixed oxide reduction

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Investigation of Active Center of Cu‐Based Catalyst for Low Temperature Methanol Synthesis from Syngas in Liquid Phase: The Contribution of Cu⁺ and Cu⁰