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Method of purifying ethylene through selective hydrogenation

A technology of selective hydrogenation and ethylene rectification tower, which is applied in the field of selective hydrogenation of ethylene, can solve the problems of high reaction temperature, complicated process flow, increased catalyst cost, etc., and achieves the effect of good hydrogenation activity and low reaction temperature

Active Publication Date: 2016-07-06
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Using this patented method, the carrier adsorbs a specific polymer compound through the chemical adsorption of the hydroxyl group of alumina and the polymer, and the amount of the polymer compound adsorbed by the carrier will be limited by the number of hydroxyl groups of alumina; the functionalized polymer and Pd The complexation effect is not strong, and sometimes the loading capacity of the active components does not meet the requirements, and some active components remain in the impregnation solution, resulting in an increase in the cost of the catalyst; the preparation of carbon dioxide hydrogenation catalysts by this method also has the disadvantage of complicated process flow
[0012] In the selective hydrogenation refining process of ethylene with high space velocity, the hydrogenation condition requires high catalyst activity, and the bimetallic supported catalyst with Pd as the active component and Ag as the promoter is used in this type of device. The reaction temperature is high, the activity cannot meet the requirements of the device well, and the disadvantage of leaking alkyne is prone to occur. It is necessary to choose a more suitable auxiliary agent to prepare the catalyst to meet the hydrogenation requirements of the device.

Method used

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  • Method of purifying ethylene through selective hydrogenation
  • Method of purifying ethylene through selective hydrogenation
  • Method of purifying ethylene through selective hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Weigh Φ4.2mm, the specific surface area is 23.0m 2 / g, pore volume 0.35mL / g, bulk density 0.88g / mL spherical α-Al 2 O 3 Carrier 500g.

[0048] Dissolve 198.89g of 4,4-dihydroxy-2,2-bipyridine in 700 mL of ethanol solution, immerse the above-mentioned carrier in the above-mentioned solution, and let it stand for 2h so that the dihydroxy-2,2-bipyridine is completely loaded on the alumina carrier After loading, dry at 60°C for 10 hours to obtain hydroxy-bipyridine / Al 2 O 3 Forebody.

[0049] Weigh 0.39gPd(NO 3 ) 2 , 2.36gCu(NO 3 ) 2 Dissolve it in 600mL deionized water containing nitric acid, adjust the pH to 1.5, and prepare a mixed solution. The above hydroxy-bipyridine / Al 2 O 3 Add the precursor to the prepared solution, stir for 10 minutes, let stand for 2 hours, pour out the remaining liquid to obtain PdACu-hydroxy-bipyridine / Al 2 O 3 Precursor (moles of hydroxyl-bipyridine: (Pd+Cu)=75). After drying at 120℃ for 4h, calcining in air atmosphere at 550℃ for 2h to obtain (Pd...

Embodiment 2

[0065] Weigh Φ3.5mm, height 3.5mm, specific surface area is 60.0m 2 / g, cylindrical δ-Al with pore volume of 0.66mL / g and bulk density of 0.67g / mL 2 O 3 Carrier 500g.

[0066] Dissolve 7.87g of 4,4-dihydroxy-2,2-bipyridine in 650mL ethanol solution, immerse the above-mentioned carrier in the above-mentioned solution, and let it stand for 8h so that the dihydroxy-2,2-bipyridine is completely loaded on the alumina carrier After loading, dry at 90°C for 8 hours to obtain hydroxy-bipyridine / Al 2 O 3 Forebody.

[0067] Weigh 0.54gPd(NO 3 ) 2 , 1.18gCu(NO 3 ) 2 Dissolve it in 600mL deionized water containing appropriate amount of nitric acid, adjust the pH to 2.0, prepare a mixed solution, and combine the above-mentioned hydroxy-bipyridine / Al 2 O 3 Add the precursor to the prepared solution, stir for 60 minutes, let stand for 8 hours, pour out the remaining liquid, and obtain PdCu-hydroxy-bipyridine / Al 2 O 3 Precursor (moles of hydroxy-bipyridine: (Pd+Cu)=5).

[0068] The precursor prepare...

Embodiment 3

[0080] Weigh Φ4.3mm, the specific surface area is 47.0m 2 / g, 500g tooth spherical carrier with pore volume of 0.19mL / g and bulk ratio of 0.79g / mL, of which θ-Al 2 O 3 460g, 40g titanium oxide.

[0081] Dissolve 21.88g 6,6'-dihydroxy-3,3'-bipyridine in 700mL ethanol solution, immerse the above carrier in the above solution, and let it stand for 12h to make 6,6'-dihydroxy-3,3'- After the bipyridine is completely loaded on the alumina carrier, it is dried at 120°C for 4 hours to obtain hydroxy-bipyridine / Al 2 O 3 Forebody.

[0082] Weigh 0.39gPd(NO 3 ) 2 , 0.59gCu(NO 3 ) 2 Dissolve in 600mL deionized water containing appropriate amount of nitric acid, adjust the pH to 3.2, prepare a mixed solution, and combine the above hydroxy-bipyridine / Al 2 O 3 The precursor was added to the prepared solution, stirred for 60 minutes, allowed to stand for 8 hours, and the remaining liquid was poured out. The remaining solid was dried at 100°C for 8 hours to obtain PdCu-hydroxy-bipyridine / Al 2 O 3 Pr...

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Abstract

The invention relates to a method of purifying ethylene through selective hydrogenation. An adiabatic bed reactor for hydrogenation is arranged after an ethylene rectification column and before an ethylene polymerization reactor. A Pd-Cu-series catalyst is arranged in a fixed bed reactor and is prepared with an alumina-series carrier. During preparation of the catalyst, the alumina-series carrier is combined with a bipyridine derivative having a hydroxyl group, wherein a metal complex is formed from the hydroxyl bipyridine derivative combined on the carrier and an active component. Selectivity of the hydrogenation method is greatly better than that in a conventional hydrogenation method, ethylene loss is reduced, activity of the hydrogenation is excellent, the outlet content of acetylene is significantly lower than that with catalysts prepared through other two methods, and purity of ethylene is increased so that performance of a polymerization-grade ethylene product is improved well. Through reduction on green oil, active center of the catalyst is not covered by side product, so that the activity and the selectivity of the catalyst are maintained well, thereby prolonging the service life of the catalyst.

Description

Technical field [0001] The invention relates to a selective hydrogenation method, in particular to a selective hydrogenation refining method of ethylene. Background technique [0002] Polymer grade ethylene production is the leader of the petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials for downstream polymerization units. Among them, the selective hydrogenation of acetylene has an extremely important impact on the ethylene processing industry. In addition to ensuring that the acetylene content at the outlet of the hydrogenation reactor meets the standard, the selectivity of the catalyst is excellent, which can make ethylene generate as little ethane as possible, which is helpful for improving the entire process. The ethylene yield of the process is of great significance to improve the economic efficiency of the device. [0003] The pyrolysis C2 fraction contains 0.5%-2.5% mole fraction of acetylene. When producing polyethylene, a s...

Claims

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Application Information

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IPC IPC(8): C07C11/04C07C7/167B01J23/89
CPCY02P20/52
Inventor 韩伟车春霞常晓昕梁玉龙钱颖谭都平张忠东付含琦丛日新黄德华任世宏景喜林胡晓丽蔡小霞袁华斌
Owner PETROCHINA CO LTD
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