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Hydrogenation method before deethanization before carbon distillate

A pre-hydrogenation and pre-removal technology, which is applied in the direction of hydrocarbons, chemical instruments and methods, hydrogenation and hydrocarbon production, etc., can solve the problems of affecting the activity of the catalyst, the loading of active components not meeting the requirements, and the increase of the cost of the catalyst. Achieve good anti-CO fluctuation ability, excellent hydrogenation activity and stability, and improve the effect of device operation stability

Active Publication Date: 2017-12-19
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 cooperation 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
[0021] In recent years, due to the inferior quality of raw materials in some ethylene plants, their carbon dioxide hydrogenation plants contain certain impurities such as As and S, and bimetallic supported catalysts with Pd as the active component and Ag as the promoter are used in this type of plant. Impurities such as As and S affect the activity of the catalyst, and in severe cases, the catalyst may be deactivated, thereby bringing the risk of alkyne leakage in the device

Method used

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  • Hydrogenation method before deethanization before carbon distillate
  • Hydrogenation method before deethanization before carbon distillate
  • Hydrogenation method before deethanization before carbon distillate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] Weigh Φ4.3mm, length is 4.3mm, specific surface area is 19m 2 / g, columnar α-Al with a pore volume of 0.22ml / g 2 o 3 Carrier 500g.

[0065] Dissolve 68.72g of 4,4-dihydroxy-2,2-bipyridine in 700mL ethanol solution, impregnate the above-mentioned carrier in the above-mentioned solution, and let the dihydroxy-2,2-bipyridine completely load on the alumina after standing for 2 hours After being mounted on the carrier, dry at 60°C for 10 hours to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0066] Weigh 0.256g Pd(NO 3 ) 2 , 1.04g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 600mL deionized water containing an appropriate amount of nitric acid, and the pH was adjusted to 2.0 to prepare a mixed solution. The above-mentioned hydroxyl-bipyridine / Al 2 o 3 The precursor was added to the prepared solution, stirred for 10 minutes, left to stand for 2 hours, and the residue was poured out to obtain PdCu-hydroxy-bipyridine / Al 2 o 3 Precursor (number of moles of hydroxyl-bipyrid...

Embodiment 2

[0077] Weigh Φ3.5×3.5mm, specific surface area is 35m 2 / g, 500g of cylindrical carrier with a pore volume of 0.38ml / g, containing Al 2 o 3 400g,TiO 2 100g, Al 2 o 3 It is a mixed crystal form of θ and α.

[0078] Dissolve 231.71g of 4,4-dihydroxy-2,2-bipyridine in 750mL ethanol solution, impregnate the above-mentioned carrier in the above-mentioned solution, and let the dihydroxy-2,2-bipyridine be completely loaded on the alumina after standing for 8 hours After being mounted on the carrier, dry at 90°C for 8 hours to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0079] Weigh 0.683g Pd(NO 3 ) 2 , 5.2g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 600mL deionized water containing an appropriate amount of nitric acid, and the pH value was adjusted to 2.5 to prepare a mixed solution. The above-mentioned hydroxyl-bipyridine / Al 2 o 3 Add the precursor to the prepared solution, stir for 60 minutes, let it stand for 8 hours, pour out the residual liquid, and dry the remaining s...

Embodiment 3

[0098] Weigh Φ3.5mm, the specific surface area is 5.0m 2 / g, the pore volume is 0.25ml / g, the heap ratio is 0.95g / ml toothed spherical carrier 500g, in which α-Al 2 o 3 460g, 40g of titanium oxide.

[0099] Dissolve 25.54g of 6,6'-dihydroxy-3,3'-bipyridine in 650mL ethanol solution, impregnate the above carrier in the above solution, and let 6,6'-dihydroxy-3,3' -Bipyridine was completely loaded on the alumina support, and dried at 120°C for 4h to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0100] Weigh 0.854gPd(NO 3 ) 2 , 6.94g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 600mL deionized water containing an appropriate amount of nitric acid, and the pH was adjusted to 3.0 to prepare a mixed solution. The above-mentioned hydroxyl-bipyridine / Al 2 o 3 Add the precursor to the prepared solution, stir for 60 minutes, let stand for 12 hours, pour out the residual liquid, and dry the remaining solid at 110°C for 8 hours to obtain PdNi-hydroxy-bipyridine / Al 2 o 3 Precursor (num...

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Abstract

The invention relates to a method for selective hydrogenation of carbon distillates, which adopts a pre-deethanizer pre-hydrogenation process, enters the top effluent from the pre-deethanizer tower in an ethylene plant into a fixed-bed reactor for selective hydrogenation, It is characterized in that the adiabatic bed reactor is equipped with a Pd-Ni catalyst, and the catalyst is combined with a bipyridyl derivative with a hydroxyl group through an alumina carrier during the preparation process, and the hydroxyl bipyridine derivative combined with the active The components form metal complexes; the method of the invention can greatly improve the activity and selectivity of the hydrogenation reaction, reduce the amount of green oil generated, prolong the service life of the catalyst, and at the same time ensure that the hydrogenation of acetylene is qualified, achieving the goal of improving the efficiency of the device. operational stability. The catalyst used in the present invention has excellent anti-impurity interference ability and excellent anti-CO fluctuation ability, and is especially suitable for use in carbon dioxide pre-hydrogenation devices with high S and As impurities, which can reduce the impact of runaway temperature on the device.

Description

technical field [0001] The invention relates to a method for selective hydrogenation, in particular to a method for selective hydrogenation of carbon distillates to remove acetylene. Background technique [0002] The production of polymer grade ethylene 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 reaches the standard, the selectivity of the catalyst is excellent, which can make ethylene generate as little ethane as possible, which is beneficial to improving the entire process. It is of great significance to improve the ethylene yield of the process and improve the economic benefits of the device. [0003] The cracked carbon distillate contains acetyl...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C11/04C07C7/167C07C5/09C07C7/163B01J23/89
CPCY02P20/52
Inventor 钱颖车春霞韩伟邱皖龙景喜林巩红光张忠东常晓昕付含琦任世宏黄德华王书峰蔡小霞张峰王涛
Owner PETROCHINA CO LTD