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Selective hydrogenation method of alkyne and alkadiene in C4 hydrocarbon material flow

A technology for selective hydrogenation and diolefins, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, hydrogenation to hydrocarbons, etc., can solve the problems of cumbersome preparation process and complex catalyst composition, and achieve high Response performance, energy saving effect

Active Publication Date: 2014-02-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the need to include specific Pd precursors or crystal form control agents in the preparation process, the composition of the catalyst becomes complicated and the preparation process is more cumbersome
In addition, the adsorption capacity of the reactants on the surface of the catalyst noble metal is an important factor affecting its activity and selectivity, which has not been reflected in the existing literature.

Method used

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  • Selective hydrogenation method of alkyne and alkadiene in C4 hydrocarbon material flow
  • Selective hydrogenation method of alkyne and alkadiene in C4 hydrocarbon material flow
  • Selective hydrogenation method of alkyne and alkadiene in C4 hydrocarbon material flow

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Take 13.5ml 10mg / ml PdCl 2 Solution, add 1mol / L NaOH solution dropwise to adjust the pH to 5.6, then spray to 100.0g Al 2 o 3 Spherical carrier surface, use 20ml of 50% v / v isopropanol aqueous solution to wet the carrier, and use it under vacuum 60 The Coγ radiation source was irradiated at room temperature for 15 hours, and the absorbed dose rate was 35Gy / min. After irradiation, the sample was placed in an oven, and dried at 80° C. and 120° C. for 12 hours in turn to obtain the catalyst A, which had a gray-black appearance and a Pd content of 0.135 wt%.

Embodiment 2

[0042] Take 30ml 10mg / ml PdCl 2 solution, sprayed to 100.0g of La and K modified Al 2 o 3 Spray 5ml of 1mol / L NaOH solution on the surface of the toothed spherical carrier, use 20ml of 50% v / v isopropanol aqueous solution to wet the carrier, and use it under vacuum 60 The Coγ radiation source was irradiated at room temperature for 15 hours, and the absorbed dose rate was 70Gy / min. After irradiation, the sample was placed in an oven, and dried at 80° C. and 120° C. for 12 hours in turn to obtain the catalyst B, which had a gray appearance and a Pd content of 0.300 wt%.

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Abstract

The invention provides a selective hydrogenation method of alkyne and alkadiene in a C4 hydrocarbon material flow. The method provided by the invention comprises the following steps of: adding the C4 hydrocarbon material flow containing alkyne and / or alkadiene and hydrogen gas into a hydrogenation reactor which is filled with a load type palladium catalyst; carrying out the selective hydrogenation on the alkyne and / or alkadiene in the C4 hydrocarbon material flow to form olefin when an inlet temperature is in a range of 10-80 DEG C, a mol ratio of the hydrogen gas to the sum of the alkyne and the alkadiene is 1-10 and a reaction pressure is in a range of 0.1-4 Mpa, and removing the olefin, wherein the load type palladium catalyst comprises a carrier, palladium and selective modified components; testing the load type palladium catalyst by utilizing a carbon monoxide adsorption in-situ infrared spectroscopy at the temperature of 40 DEG C to obtain an area ratio of a bridge type absorption peak at the 1930-1990cm<-1> to a bridge type absorption peak at the 1870-1930cm<-1> in an obtained infrared spectrogram is less than 0.2, more preferably less than 0.15. The method provided by the invention has a high selectivity to the selective hydrogenation of the alkyne and the alkadiene in the C4 hydrocarbon material flow and can be operated for a long period.

Description

technical field [0001] The present invention relates to a method for selective hydrogenation, more specifically, the present invention relates to a method for selective hydrogenation of alkynes and dienes in C4 hydrocarbon streams. Background technique [0002] The mixed carbon four fraction is a mixture of various alkanes, olefins, dienes, and alkynes containing 4 carbon atoms, mainly derived from the refinery gas produced in the petroleum refining process and the by-product of the cracking of petroleum hydrocarbons to produce ethylene. Cracking C4 contains n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene, isobutene, 1,2-butadiene, 1,3-butadiene, Methylacetylene, ethylacetylene, vinylacetylene and other saturated and unsaturated hydrocarbons are mainly used in industrial production to produce 1,3-butadiene, isobutene and butene. In the method of producing butene by cracking carbon four, one is to directly carry out selective hydrogenation of cracked carbon four,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C5/09C07C5/05C07C9/10C07C11/08B01J23/44B01J23/63
Inventor 杨栋彭晖乐毅戴伟于海波张齐毛祖旺穆玮朱云仙高树升
Owner CHINA PETROLEUM & CHEM CORP
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