4.0 Article

Stability improvement of the Nieuwland catalyst in the dimerization of acetylene to monovinylacetylene

Journal

JOURNAL OF NATURAL GAS CHEMISTRY
Volume 21, Issue 5, Pages 495-500

Publisher

ELSEVIER SCIENCE BV
DOI: 10.1016/S1003-9953(11)60396-4

Keywords

monovinylacetylene; dimerization reaction; Nieuwland catalyst; acetylene; stability

Funding

  1. National Basic Research Program of China [2009CB219901]

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In the process of dimerization of acetylene to produce monovinylacetylene (MVA), the loss of active component CuCl in the Nieuwland catalyst due to the formation of a dark red precipitate was investigated. The formula of the precipitate was CuCl center dot 2C(2)H(2)center dot I/5NH(3), and it was presumed to be formed by the combination of NH3, C2H2 and [Cu]-acetylene pi-complex, which was an intermediate in the dimerization reaction. The addition of hydrochloric acid into the catalyst can reduce the formation of precipitate, whereas excessive H+ is unfavorable to the dimerization reaction of acetylene. To balance between high acetylene conversion and low loss rate of CuCl, the optimum mass percentage of HCl in the added hydrochloric acid was determined. The result showed the optimum mass percentage of HCl decreased from 5.0% to 3.2% when the space velocity of acetylene was from 140 h(-1) to 360 h(-1). The result in this work also indicated the pH of the Nieuwland catalyst should be kept in the range of 5.80-5.97 during the reaction process, which was good for both catalyst life and acetylene conversion.

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