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Alkyne-containing C4 fraction selective hydrogenation method

A technology for selective hydrogenation and carbon four fractions, applied in the fields of hydrocarbons, 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

[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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  • Alkyne-containing C4 fraction selective hydrogenation method
  • Alkyne-containing C4 fraction selective hydrogenation method
  • Alkyne-containing C4 fraction selective hydrogenation method

Examples

Experimental program
Comparison scheme
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 4Nm 3 / h, the reaction temperature is 40°C, the pH value at the end of the reaction is 10, 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 1...

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 1:1. The isothermal reactor adopts single-stage isothermal bubbling bed, adopts catalyst C1, and the catalyst is reduced under hydrogen atmosphere at 120°C for 6h. The reaction inlet temperature is 50°C, the reaction pressure is 1.5MPa, and the liquid space velocity is 7h -1 , the molar ratio of hydrogen to alkyne is 3.5, Table 2 is the composition of materials before and after the reaction.

[0085] Material composition before and after table 2 reaction

[0086]

Embodiment 2

[0088] Dilute the alkyne-rich C4 fraction with raffinate C4 and cracked C4, the weight ratio of the alkyne-rich C4 fraction to (raffinate + cracked C4) is 1:6. The isothermal reactor adopts single-stage isothermal bubbling bed, adopts catalyst C2, and the catalyst is reduced at 120°C for 6 hours under hydrogen atmosphere. The reaction inlet temperature is 60°C, the reaction pressure is 2.0MPa, and the liquid space velocity is 12h -1 , the molar ratio of hydrogen to alkyne is 2.5, Table 3 is the composition of materials before and after the reaction.

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

[0090]

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Abstract

The invention relates to an alkyne-containing C4 fraction selective hydrogenation method. According to the method, rich-alkyne C4 fractions after butadiene extraction are used as raw materials; underthe existence of catalysts, an isothermal reactor is used; selective hydrogenation is performed to obtain 1,3-butadiene; the used process operation conditions are as followings: the reaction temperature is 30 to 75 DEG C, the reaction pressure is 1.0 to 3.0 MPa, and the liquid space velocity is 7 to 18h<-1>. The catalyst is a palladium-molybdenum series catalyst which is prepared from nickel-containing alumina carriers and has a specific crystal form; the dispersity and the utilization rate of active metal can be greatly improved; the hydrogenation performance of the catalyst is improved. Whenbeing used, the method has good effects that the rich-alkyne C4 fractions after butadiene extraction are effectively utilized; the resource waste is reduced; the economic benefits are greatly improved.

Description

technical field [0001] The invention relates to a method for selective hydrogenation of alkyne-containing carbon four fractions, in particular to a method for selectively hydrogenating butadiene-rich alkyne carbon four fractions 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 production. Considering that wh...

Claims

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Application Information

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IPC IPC(8): C07C7/167C07C5/09C07C11/167B01J23/89
CPCB01J23/002B01J23/8993B01J2523/00C07C5/09C07C7/167C07C2523/89C07C11/167B01J2523/11B01J2523/31B01J2523/68B01J2523/824B01J2523/847B01J2523/22B01J2523/13B01J2523/3706B01J2523/3712
Inventor 郑云弟马好文王斌胡晓丽孙利民展学成钱颖王书峰潘曦竹蒋彩兰尹玲玲李燕
Owner PETROCHINA CO LTD
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