Hydrogenation method of C4 fraction containing rich alkynes and dialkenes

A technology for carbon four fractions and diolefins, which is applied in the field of selective hydrogenation of alkyne-rich residual materials, can solve the problems of harsh operating conditions, high catalyst selectivity requirements, losses, etc., and achieves improved operating time and long cycle The effect of stable operation and increased effective contact area

Inactive Publication Date: 2013-04-17
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this method is still aimed at recovering 1,3-butadiene, the operating conditions are relatively harsh, and the selectivity of the catalyst is required to be high, and the loss of 1,3-butadiene will inevitably be caused in the hydrogenation process

Method used

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  • Hydrogenation method of C4 fraction containing rich alkynes and dialkenes
  • Hydrogenation method of C4 fraction containing rich alkynes and dialkenes
  • Hydrogenation method of C4 fraction containing rich alkynes and dialkenes

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Experimental program
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Effect test

Embodiment 1

[0019] The raw material is the residual C4 material of butadiene extraction rich in alkyne and diene and the remaining C4 material of MTBE plant, the weight ratio of the remaining C4 material and the residual C4 material rich in alkyne and diene is 2: 1. The hydrogenation reactor adopts α-Al catalyst 2 o 3 Loading 0.2% palladium-based catalyst, and adding additives X1 (0.05% Au, 0.1% Ag and 1% Cu) and X2 (0.1% lanthanum); the reactor is a two-stage isothermal type in series Fixed bed, reactor inlet temperature is 30°C, reaction pressure is 1.5MPa, liquid hourly space velocity is 2.0h -1 The molar ratio of hydrogen to the total amount of alkynes and dienes in the first reactor is 1, and the molar ratio of hydrogen to the total amount of alkynes and dienes in the second reactor is 3. Table 1 is the composition of materials before and after the reaction .

[0020] Material composition before and after table 1 reaction

[0021]

Embodiment 2

[0023] The raw material is the residual C4 material of butadiene extraction rich in alkyne and diene and the remaining C4 material of MTBE plant, the weight ratio of the remaining C4 material and the residual C4 material rich in alkyne and diene is 2: 1. The hydrogenation reactor adopts α-Al catalyst 2 o 3 Loaded with 0.2% palladium-based catalyst, and added promoters X1 (0.05% Au, 0.1% Ag and 1% Cu), X2 (0.1% Lanthanum) and X3 (0.2% Li and 0.1% K ); the reactor is two series-connected two-stage isothermal fixed beds, the reactor inlet temperature is 30°C, the reaction pressure is 1.5MPa, and the liquid hourly space velocity is 2.0h -1 The molar ratio of hydrogen to the total amount of alkynes and dienes in the first reactor is 1, and the molar ratio of hydrogen to the total amount of alkynes and dienes in the second reactor is 3. Table 2 is the composition of materials before and after the reaction .

[0024] Material composition before and after table 2 reaction

[0025...

Embodiment 3

[0028] The raw material is the residual C4 material of butadiene extraction rich in alkyne and diene and the remaining C4 material of MTBE plant, the weight ratio of the remaining C4 material and the residual C4 material rich in alkyne and diene is 2: 1. The hydrogenation reactor adopts α-Al catalyst 2 o 3 A 15% copper-based catalyst was loaded with additives X1 (0.1% Au, 0.2% Ag), X2 (0.1% Lanthanum and 0.1% Ce) and X3 (0.2% Li, 0.2% K ); the reactor is two serially connected two-stage isothermal fixed beds, the inlet temperature of the reactor is 30°C, the reaction pressure is 1.5MPa, and the liquid hourly space velocity is 1.5h -1 The molar ratio of hydrogen to the total amount of alkynes and dienes in the first reactor is 1.5, and the molar ratio of hydrogen to the total amount of alkynes and dienes in the second reactor is 3. Table 3 is the composition of materials before and after the reaction .

[0029] Table 3 Composition of materials before and after reaction

[...

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Abstract

The invention relates to a hydrogenation method of C4 fraction containing rich alkynes and dialkenes. A raw material containing C4 fraction and H2 enter two hydrogenation reactor which are connected in series; each reactor is telescopic, wherein the inner tube is filled with a catalyst, and the outer tube is filled with a heat removal medium which is 8-18 DEG C new water; the mol ratio of the hydrogen to the inlet total alkyne and dialkene content of the first reactor is 1.0-6.0, the mol ratio of the hydrogen to the inlet total alkyne and dialkene content of the second reactor is 1.0-6.0, the reaction temperature of the reactor inlet is 20-60 DEG C, the reaction pressure is 0.5-4.0 MPa, and the liquid hourly space velocity is 1.0-30 h<-1>; the reaction product is cooled and enters a gas-liquid separation tank to be separated; and the catalyst in the reactor is an aluminum-oxide-supported palladium-base catalyst or copper-base catalyst. The alkyne content in the material hydrogenated by the method is less than 100 mu g/g, and the dialkene content is less than 1000 mug/g. The material hydrogenated by the method can be used as domestic liquefied gas or methylethylketone raw material.

Description

technical field [0001] The invention relates to a method for selective hydrogenation of C4 fractions rich in alkynes and dienes, in particular to a method for selective hydrogenation of residual materials rich in alkynes obtained after butadiene extraction. Background technique [0002] During the high-temperature pyrolysis of hydrocarbon steam to produce ethylene, a certain amount of C4 fractions will be produced by-product. These C4 fractions contain about 40-65% of 1,3-butadiene, and about 0.5-2.0% of alkyne impurities, mainly including methylacetylene (MA), ethylacetylene (EA ) and vinyl acetylene (VAC), etc. In the industry, this part of the carbon four fraction is often treated to remove alkyne, and the high-purity 1,3-butadiene component is recovered as a raw material for synthetic rubber and resin. Polymer grade butadiene requires a purity of greater than 99.7 wt%, and an alkyne content of less than 25 ppm. The 1,3-butadiene in cracking C4 hydrocarbons is generall...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G70/02
Inventor 晁会霞谭振明曾佑富邹士应廖斌闫桂玲朱凌辉
Owner PETROCHINA CO LTD
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