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Method for selective hydrogenation of acetylene to ethylene

A selective, acetylene hydrogenation technology, applied in chemical instruments and methods, hydrogenation to hydrocarbons, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of low selectivity of Pd catalysts

Active Publication Date: 2018-06-12
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Pd has been successfully applied in industry due to its good activity and selectivity in the selective hydrogenation of acetylene, but the Pd catalyst has the problem of low selectivity and a large amount of ethylene being excessively reduced to ethane

Method used

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  • Method for selective hydrogenation of acetylene to ethylene
  • Method for selective hydrogenation of acetylene to ethylene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Will H 2 PdCl 4 0.01mol·L -1 And Ni(C 2 H 3 O 2 ) 2 0.01mol·L -1 Dissolve in tetrahydrofuran, add 1 times equivalent of PPh to the system 3 Ligand. After stirring for 0.5h, add a certain amount of sodium borohydride to make the concentration of sodium borohydride 0.1mol·L -1 . After stirring for 2h, the solvent was evaporated, the product was washed with n-hexane, and finally extracted with dichloromethane. Dissolve the metal cluster protected by the ligand in methanol, add a certain amount of tetramethylorthosilicate to make the final mass ratio of total metal to silica 0.01%, and add concentrated ammonia (mass Concentration 28%), until all silicone ester is hydrolyzed. After washing and drying, it is calcined under oxygen at 200℃ for 1h. Take H 2 1%, ethylene 50%, acetylene 0.1%, the rest is helium, normal pressure, reaction temperature is 50℃, space velocity is 10000h -1 , Carry out selective hydrogenation reaction. The conversion rate is 90%, and the ethylene sel...

Embodiment 2

[0015] Put Ni(C 2 H 3 O 2 ) 2 0.01mol·L -1 Dissolve in tetrahydrofuran, add 1 equivalent of PPh to the system 3 Ligand. After stirring for 0.5h, add a certain amount of sodium borohydride to make the concentration of sodium borohydride 0.1mol·L -1 . After stirring for 2h, the solvent was evaporated, the product was washed with n-hexane, and finally extracted with dichloromethane. Dissolve the metal cluster protected by the ligand in methanol, add a certain amount of tetramethylorthosilicate to make the final mass ratio of total metal to silica 0.01%, and add concentrated ammonia (mass Concentration 28%), until all silicone ester is hydrolyzed. After washing and drying, it is calcined in oxygen at 200℃ for 1h. Take H 2 1%, ethylene 50%, acetylene 0.1%, the rest is helium, normal pressure, reaction temperature is 50℃, space velocity is 10000h -1 , Carry out selective hydrogenation reaction. The conversion rate is 85%, and the ethylene selectivity is 95%.

Embodiment 3

[0017] Will H 2 PdCl 4 0.01mol·L -1 With Cu(C 2 H 3 O 2 ) 2 0.01mol·L -1 Dissolve in tetrahydrofuran, add 1 equivalent of PPh to the system 3 Ligand. After stirring for 5h, add a certain amount of sodium borohydride to make the concentration of sodium borohydride 0.1mol·L -1 . After stirring for 2h, the solvent was evaporated, the product was washed with n-hexane, and finally extracted with dichloromethane. The metal cluster protected by the ligand is dissolved in methanol, and a certain amount of tetramethyl orthosilicate is added to make the final mass ratio of total metal to silicon dioxide 0.01%. Add ammonia (mass concentration) dropwise to the system. 28%), until the silicone ester is completely hydrolyzed. After washing and drying, it is calcined at 200℃ for 1h under a condition of oxygen. Take H 2 1%, ethylene 50%, acetylene 0.1%, the rest is helium, normal pressure, reaction temperature is 50℃, space velocity is 10000h -1 , Carry out selective hydrogenation reaction....

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Abstract

The invention relates to a method for selective hydrogenation of acetylene to ethylene at normal pressure. A catalyst PdxM / SiO2 (0<=x<=0.05) is obtained by taking a metal cluster PdxMy as a precursorand silicon dioxide as a carrier and carrying out high-temperature roasting. Gas-phase hydrogenation is carried out on acetylene-containing ethylene mixed gas under a normal pressure condition, and the acetylene is subjected to selective hydrogenation to be reduced to ethylene. The catalyst is the PdxM / SiO2 type catalyst, wherein the M is selected from Ag, Au, Cu and Ni, and the molar ratio of thePd to the M is 0-20; and a metal cluster with ligand protection is protected by silicon dioxide and then subjected to high-temperature roasting to remove the ligand so as to prepare the catalyst. ThePdxM / SiO2 catalyst is used for the selective hydrogenation of acetylene at normal pressure, and acetylene reduction can be carried out under a relatively mild condition, so that a hydrocarbon with ethylene as the main product is obtained, and the selectivity of the catalyst is 85-99%. The method provided by the invention has technical feasibility, the catalyst material has a long service life, the effect is notable when the catalyst is used in the selective hydrogenation treatment of the acetylene to the ethylene, and the method has good economic and environmental benefits.

Description

Technical field [0001] The invention relates to a petrochemical catalyst preparation technology, in particular to a catalyst for selective hydrogenation of acetylene to produce ethylene, and a preparation method and application thereof. Background technique [0002] Ethylene is a basic chemical raw material and an intermediate for the synthesis of many organic substances. It is often used in the industry to prepare plastics, synthetic fibers, organic solvents, etc. Its output has become a measure of a country's petrochemical development level. In the industrial production process of petroleum cracking to prepare ethylene, a small amount of acetylene is generated. The presence of acetylene seriously affects the performance of the ethylene polymerization catalyst and reduces the quality of the product. Therefore, reducing the content of acetylene in an ethylene-rich environment is a very important part of the ethylene polymerization process. Common methods for removing acetylene ...

Claims

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Application Information

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IPC IPC(8): C07C5/09C07C11/04B01J23/89B01J23/66
CPCB01J23/66B01J23/892B01J23/8926C07C5/09C07C2521/08C07C2523/66C07C2523/89C07C11/04Y02P20/52
Inventor 王峰陈海军李杲张超峰王敏王业红
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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