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Method of recycling butadiene by alkyne selective hydrogenation

A technology for selective hydrogenation and butadiene, applied in chemical recovery, purification/separation of hydrocarbons, chemical instruments and methods, etc., can solve problems such as easy aggregation, 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

[0014] 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 butadiene by alkyne selective hydrogenation
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  • Method of recycling butadiene 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 70v%, and the flow rate is 3Nm 3 / h, the reaction temperature is 35°C, the pH value at the end of the reaction is 9.5, 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 nickel-containing pseudo-boehmite.

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

Embodiment 1

[0083] 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 1:1. The adiabatic reactor adopts a single-stage adiabatic bubbling bed, using catalyst C1, and the catalyst is reduced at 120°C for 6h under a hydrogen atmosphere. The reaction inlet temperature is 45°C, the reaction pressure is 1.0MPa, and the liquid space velocity is 10h -1 , the molar ratio of hydrogen to alkyne is 3.0, Table 2 is the composition of materials before and after the reaction.

[0084] Material composition before and after table 2 reaction

[0085]

Embodiment 2

[0087] Dilute the alkyne-rich C4 fraction with raffinate C4 and cracked C4, and the weight ratio of the alkyne-rich C4 fraction to (raffinate + cracked C4) is 1:2. The adiabatic reactor adopts a single-stage adiabatic bubbling bed, using catalyst C2, and the catalyst is reduced at 120°C for 6 hours under a hydrogen atmosphere. The reaction inlet temperature is 30°C, the reaction pressure is 1.5MPa, and the liquid space velocity is 15h -1 , the molar ratio of hydrogen to alkyne is 3.0, Table 3 is the composition of materials before and after the reaction.

[0088] Table 3 Composition of materials before and after reaction

[0089]

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PUM

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Abstract

A method of recycling butadiene by alkyne selective hydrogenation, C-4 fraction rich in alkyne after butadiene extraction is taken as material to carry out selective hydrogenation to obtain 1,3-butadiene in an adiabatic reactor under the existence of a catalyst, with the process operation conditions: reaction inlet temperature is 20-60 DEG C, reaction pressure is 0.6-2.5 MPa, space velocity of liquid is 10-25h-1, wherein the catalyst is a palladium-molybdenum 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 butadiene by the alkyne selective hydrogenation has extremely significant good effect on effectively utilization for C-4 fraction rich in alkyne after butadiene extraction, resource waste reduction and economic benefit improvement.

Description

technical field [0001] The invention relates to a method for recovering butadiene through selective hydrogenation of alkynes, in particular to a method for recovering butadiene through selective hydrogenation of residual high-alkyne carbon four tail gas after butadiene extraction. Background technique [0002] The cracked C4 fraction usually contains 40% to 60% butadiene by mass in the pyrolysis of hydrocarbons to produce ethylene. Butadiene is an important monomer in the synthetic rubber industry. The extraction of butadiene from the cracked C4 fraction usually adopts solvent extraction methods, such as acetonitrile method, N-methylpyrrolidone method and dimethylformamide method. Due to the high concentration of alkynes in the extracted C4 fraction, and there is no industrial use value at present, it can only be used for combustion treatment. However, because of the danger of explosion of high-concentration alkynes, it is recommended for safety reasons in industrial product...

Claims

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Application Information

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IPC IPC(8): C07C5/09C07C7/167C07C11/167B01J23/89
CPCC07C5/09C07C7/167B01J23/8993C07C2523/44C07C2523/28C07C2523/89C07C2523/755B01J35/613B01J35/635B01J35/633C07C11/167Y02P20/584
Inventor 郑云弟展学成王斌马好文胡晓丽钱颖孙利民李晓军柏介军潘曦竹王书峰蒋彩兰
Owner PETROCHINA CO LTD
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