Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited

Trotuş, Ioan‐Teodor; Zimmermann, T.; Schüth, Ferdi

doi:10.1021/cr400357r

Cited by 406 publications

(219 citation statements)

References 248 publications

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“…BDO, eg.,1,4-butanediol, is a bulk fine chemical raw material and feedstock used in the production of commercialized chemicals in industry, which can extend its industrial chain to produce high-value-added downstream chemicals such as tetrahydrofuran (THF), γ-butyrolactone (GBL) etc [1][2] in the fields of polyester materials, paper, medicine, automotive, pesticide, textile and household industries. [3] By far, the most important BDO production method in industry is 1,4-butynediol (BYD) hydrogenation, and based on this reaction system, noble metals (Pd, Pt etc.)…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Wang

Ya-ni

et al. 2019

ChemCatChem

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Hydrogenation of 1,4-butynediol (BYD) to 1,4-butanediol (BDO) is a two-step process, with an initial hydrogenation of BYD to 1,4-butenediol (BED) and the subsequent hydrogenation of BED to BDO. However, the BYD hydrogenation also involves many side reactions originated from the isomerization of BED. In order to inhibit the isomerization pathways, phyllosilicate-derived bimetallic NiCu@SiO 2 catalysts have been developed for efficient C�C/C=C hydrogenation in this work. Due to the formation of phyllosilicate matrix and highly dispersed metal nanoparticles, NiCu@SiO 2 showed total BYD conversion with extremely high BDO selectivity compared to a conventional impregnated Ni/SiO 2 catalyst. A remarkable result of NiCu@SiO 2 catalysts is that a new type of bimetallic catalytic sites responsible for the high hydrogenation activity can be differentiated from the Ni phyllosilicate matrix by the induction of Cu species, and these neighboring bimetallic sites with the help of weak acid phyllosilicate interface, can realize to stabilize the activated BED species (allyl alcohol form) adsorbed on the cooperative active sites, thus to avoid its isomerization to aldehyde form and unexpected C=O hydrogenolysis. Consequently, it enhanced the selectivity to the diol products BDO significantly. Owing to the benign improvement of three center synergy effect, 9Ni1Cu@SiO 2 possesses the optimum BYD direct hydrogenation ability with a rarely reported high selectivity of 90.5-94.5 % at 50°C and 1 MPa.[a] Dr.

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Section: Introductionmentioning

confidence: 99%

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Wang

Ya-ni

et al. 2019

ChemCatChem

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“…Nieuwland catalyst has recently attracted increased attention, and several reports focusing on its reaction mechanism, structure, and modification have been published [10]. For example, Fukuzumi et al demonstrated the dimerization mechanism of the catalyst by detecting copper-acetylene and copper-monovinylacetylene π-complexes using in situ NMR measurements; the results of this work indicated that eliminating MVA in the gas phase is important to avoid further reaction of the copper(I)-MVA π-complex with the acetylene π-complex, which leads to DVA formation [11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Effect of Cu+/Cu2+ Ratio on the Catalytic Behavior of Anhydrous Nieuwland Catalyst during Dimerization of Acetylene

et al. 2016

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Abstract:The relative contents of Cu + and Cu 2+ in solutions of anhydrous Nieuwland catalyst and CuCl 2 -added anhydrous Nieuwland catalyst were detected by X-ray photoelectron spectroscopy (XPS). Results indicated that Cu + could be transformed into Cu 2+ during the process of acetylene dimerization into monovinylacetylene, leading to deactivation of the catalyst. Moreover, the addition of Cu 2+ inhibited the oxidation of Cu + into Cu 2+ and enhanced the performance and lifetime of the catalyst. The optimum molar ratio of Cu + to Cu 2+ was approximately 2:1; at this ratio, up to 40% acetylene conversion may be achieved.

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“…Acetylene and other alkynes, owing to their high and diverse reactivity, are frequently used to respond to this challenge. Now this trend [1][2][3][4] gains strength due to the depletion of fossil hydrocarbons. Consequently, new methods (including those based on coal) 1,5 for acetylene production arise.…”

Section: Introductionmentioning

confidence: 99%

“…Over many years, fundamental organic synthesis has revealed a diversity of reactions of alkynes, which provide new C-C, C-N, and C-O bond formation, e.g. in important biomolecules as pyrroles, 6,7 pyridines, 2,[8][9][10] vitamins A and E, 1,11 β-carotene, 11 linalool, 11 citral, 12 steroids, 13,14 etc. In this area of organic synthesis, the application of superbasic media such as alkaline metal hydroxide or alkoxide/DMSO 15 to promote the reactions of alkynes with nucleophiles is a comparatively underestimated approach.…”

Section: Introductionmentioning

confidence: 99%

Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

Schmidt¹,

Bidusenko²,

Cherimichkina³

et al. 2015

Arkivoc

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Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited

Cited by 406 publications

References 248 publications

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Effect of Cu+/Cu2+ Ratio on the Catalytic Behavior of Anhydrous Nieuwland Catalyst during Dimerization of Acetylene

Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

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Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited

Cited by 406 publications

References 248 publications

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO2 Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO2 Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Effect of Cu+/Cu2+ Ratio on the Catalytic Behavior of Anhydrous Nieuwland Catalyst during Dimerization of Acetylene

Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

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Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO₂ Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol