Method of recycling butene by alkyne selective hydrogenation

A technology for selective hydrogenation and alkyne, applied in chemical recovery, chemical instruments and methods, hydrogenation to hydrocarbons, etc., which can solve the problems of easy agglomeration, poisoning and deactivation of active components

Active Publication Date: 2018-11-23
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] The active components of conventional noble metal catalysts are prone to agglomeration and poisoning and deactivation during the reaction process, and the dispersion of palladium metal is a problem that many researchers are trying to solve

Method used

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  • Method of recycling butene by alkyne selective hydrogenation
  • Method of recycling butene by alkyne selective hydrogenation
  • Method of recycling butene by alkyne selective hydrogenation

Examples

Experimental program
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Effect test

preparation example Construction

[0054] Embodiment uses the preparation of catalyst 1~6

[0055] Preparation of Catalyst C1:

[0056] Concentrate 4L to 50g Al 2 o 3 / L of sodium metaaluminate solution is placed in a stainless steel container with a stirrer and gas can be introduced into the bottom of the tank, the nickel nitrate solution is prepared and placed in a high-position container, a mixed gas of carbon dioxide and air is introduced, and the peristaltic pump is started at the same time Control the flow rate and drop the prepared nickel nitrate solution, the carbon dioxide concentration in the mixed gas is 60v%, and the flow rate is 3Nm 3 / h, the reaction temperature is 30°C, the pH value at the end of the reaction is 10.0, stop feeding carbon dioxide, age for 30 minutes, filter and separate the mother liquor, wash, and dry at 120°C for 5 hours to obtain pseudo-boehmite containing nickel.

[0057] Mix and knead nickel-containing pseudo-boehmite with nitric acid and water, extrude into strips, dry at...

Embodiment 1

[0084] The C4 fraction rich in alkynes is diluted with the C4 raffinate, and the weight ratio of the C4 fraction rich in alkynes to the C4 raffinate is 1:20. The adiabatic reactor adopts a single-stage adiabatic fixed bed, using catalyst C1, and the catalyst is reduced at 120°C for 6 hours under a hydrogen atmosphere. The reaction inlet temperature is 40°C, the reaction pressure is 2.0MPa, and the liquid space velocity is 15h -1 , the molar ratio of hydrogen to alkynes+dienes is 5.0, Table 2 is the composition of the materials before and after the reaction.

[0085] Table 2 Composition of materials before and after reaction

[0086]

Embodiment 2

[0088] The C4 fraction rich in alkynes is diluted with C4 after ether, and the weight ratio of the C4 fraction rich in alkynes to C4 after ether is 1:18. The adiabatic reactor adopts a single-stage adiabatic fixed bed, adopts catalyst C2, and the catalyst is reduced at 120°C for 6 hours under a hydrogen atmosphere. The reaction inlet temperature is 38°C, the reaction pressure is 1.5MPa, and the liquid space velocity is 17h -1 , the molar ratio of hydrogen to alkynes+dienes is 4.0, Table 3 is the composition of the materials before and after the reaction.

[0089] Table 3 Composition of materials before and after reaction

[0090]

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Abstract

The invention discloses a method of recycling butene by alkyne selective hydrogenation, wherein the method takes C-4 fraction rich in alkynes after butadiene extraction as raw material to carry out alkynes and akadiene selective hydrogenation to obtain butene an adiabatic reactor under the action of catalyst, with the process operation conditions: reactor inlet temperature is 25-100 DEG C, reaction pressure is 0.6-2.5 MPa, space velocity of liquid to be 15-25h<-1>, wherein the catalyst is palladium-molybdenum-silver selective hydrogenation catalyst prepared with alumina supporter containing nickel and with specific crystal form that can greatly improve the dispersion and utilization of reactive metal and the hydrogenation performance of the catalyst. The method of recycling butene by the alkyne selective hydrogenation has extremely significant good effect on effectively utilization for C-4 fraction with rich alkynes after butadiene extraction, resource waste reduction and economic benefit improvement.

Description

technical field [0001] The invention relates to a method for selectively hydrogenating highly unsaturated hydrocarbons in C4 fractions to recover butenes, in particular to a method for selectively hydrogenating alkynes to recover butenes. Background technique [0002] 1,3-butadiene is an important monomer of synthetic rubber. In industry, it mainly uses cracked C4, a by-product of hydrocarbon cracking to produce ethylene, as raw material, and is produced by solvent extraction. Except containing 40~60wt% of 1,3-butadiene in cracking C4, usually also contain 1~2wt% alkyne (mainly vinyl acetylene), in order to obtain polymerization grade 1,3-butadiene ( Butadiene purity ≥ 99.5%, alkyne content < 100ppm), butadiene is usually extracted by two-stage extractive rectification plus two-stage ordinary rectification. C-tetraynes as impurities are mainly discharged in the second extractive distillation tower. Taking a set of 800,000 tons / year ethylene plant as an example, the annua...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C5/05C07C5/08C07C11/08B01J35/10B01J23/89
CPCB01J23/002B01J23/8993B01J35/1014B01J35/1019B01J35/1038B01J35/1042B01J2523/00C07C5/05C07C5/08B01J2523/11B01J2523/18B01J2523/68B01J2523/824B01J2523/847B01J2523/22B01J2523/3712B01J2523/13B01J2523/3706C07C11/08Y02P20/584
Inventor 郑云弟钱颖胡晓丽马好文展学成王斌孙利民王书峰蒋彩兰潘曦竹谢培思蔡小霞李平智
Owner PETROCHINA CO LTD
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