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Pd/Au-series supported hydrogenation catalyst

A hydrogenation catalyst, supported technology, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, hydrogenation to hydrocarbons, etc., can solve the problem of increased catalyst cost, strong randomness and complexation. Not strong and other problems, to achieve the effect of excellent activity and selectivity, good anti-coking performance, and lower production costs

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

This method has the following disadvantages: (1) affected by the pore structure of the carrier, the dispersion of active components cannot be precisely controlled, and the randomness is strong
(2) Affected by the surface tension of the immersion liquid and the solvation effect, the precursor of the metal active component is deposited on the surface of the carrier in the form of aggregates, which cannot form a uniform distribution
(3) Carbon dihydrogenation requires high catalyst selectivity. The interaction between the additive Ag and the active component Pd is the key factor to improve the catalyst selectivity. The catalyst prepared by the traditional method, due to the different surface tension of the Pd and Ag solutions , Pd and Ag cannot be distributed in the same layer, and the additive effect of Ag is not obvious. It is necessary to increase the amount of Ag to promote the role of the additive, which will hinder the transfer of hydrogen and cause the oligomerization reaction to occur. The possibility increases, the amount of green oil generation increases, and the life of the catalyst is affected
Using this patented method, the carrier adsorbs a specific polymer compound, and chemically adsorbs the polymer through the hydroxyl group of alumina. The amount of polymer compound adsorbed by the carrier will be limited by the number of hydroxyl groups of alumina; The complexation effect of the catalyst is not strong, and sometimes the loading capacity of the active components does not meet the requirements, and some active components remain in the impregnating 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 complex process flow

Method used

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  • Pd/Au-series supported hydrogenation catalyst
  • Pd/Au-series supported hydrogenation catalyst
  • Pd/Au-series supported hydrogenation catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Weigh Φ4.5mm, length 4.5mm, specific surface 2.0m 2 / g, columnar α-Al with a pore volume of 0.20mL / g 2 o 3 Carrier 500g.

[0041] Dissolve 15.77g of 4,4-dihydroxy-2,2-bipyridine in 600mL of ethanol solution, impregnate the above-mentioned carrier in the above-mentioned solution, and let it stand for 2 hours to fully load 4,4-dihydroxy-2,2-bipyridine After being placed on the alumina support, it was dried at 80°C for 10 hours to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0042] Weigh an appropriate amount of palladium chloride, chloroauric acid dissolved in 600mL deionized water containing an appropriate amount of hydrochloric acid, adjust the pH to 2.0. The above-mentioned hydroxyl-bipyridine / Al 2 o 3 Add the precursor to the prepared solution, stir for 10 minutes, let it stand for 2 hours, and pour off the residual liquid to obtain PdAu-hydroxy-bipyridine / Al 2 o 3 Precursor (number of moles of hydroxyl-bipyridine: (Pd+Au)=30). After drying at 120°C for 4h,...

Embodiment 2

[0055] Weigh Φ2.5mm, the specific surface area is 50m 2 / g, 500g of spherical carrier with a pore volume of 0.75ml / g, which contains θ-Al 2 o 3 Carrier 440g, titanium oxide 60g.

[0056] Dissolve 6.82g of 4,4-dihydroxy-2,2-bipyridine in 600mL ethanol solution, impregnate the above carrier in the above solution, and let the dihydroxy-2,2-bipyridine be completely loaded on the alumina carrier after standing for 8 hours After drying, dry at 110°C for 6 hours to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0057] Weigh an appropriate amount of palladium chloride and chloroauric acid dissolved in 600mL deionized water containing an appropriate amount of hydrochloric acid, adjust the pH to 2.5, and form 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, and pour out the residual liquid to obtain PdAu-hydroxy-bipyridine / Al 2 o 3 Prebody.

[0058] The precursor prepare...

Embodiment 3

[0076] Weigh 4.5*4.5mm, length is 4.5mm, specific surface area is 15m 2 / g, 500g of cylindrical carrier with a pore volume of 0.30ml / g, in which Al 2 o 3 400g, magnesium oxide 100g, Al 2 o 3 α-Al 2 o 3 .

[0077] Dissolve 19.28g 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'- After the bipyridine was completely loaded on the alumina carrier, it was dried at 120°C for 4 h to obtain the hydroxyl-bipyridine / Al 2 o 3 Prebody.

[0078] Weigh an appropriate amount of palladium chloride, and chloroauric acid is dissolved in 650mL deionized water containing an appropriate amount of hydrochloric acid, and the pH value is adjusted to 3.0, and the above-mentioned hydroxyl-bipyridine / Al 2 o 3 Add the precursor to the prepared solution, stir for 60min, let it stand for 12h, pour out the residual liquid, and obtain PdAu-hydroxyl-bipyridine / Al 2 o 3 Precursor (number of moles of hydroxyl...

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Abstract

The invention relates to a Pd / Au-series supported hydrogenation catalyst which contains palladium and gold, and a carrier mainly contains Al2O3. On the basis that the mass of the catalyst is 100%, the catalyst includes 0.01-0.55% of the palladium and 0.02-0.25% of the gold. The catalyst is an alloy-type bimetal catalyst. Because adverse effects due to surface tension and solvation effect of an impregnation liquid on dispersion of the palladium and gold, the palladium-gold alloy can be formed more easily in the catalyst. The catalyst has excellent selectivity, can be used for selective hydrogenation of C2, C3 and the like fractions, has excellent hydrogenation activity, selectivity and anti-coking performance, and also has high yield increase of ethylene and propylene.

Description

technical field [0001] The invention relates to a hydrogenation catalyst, in particular to a palladium-gold series supported hydrogenation catalyst. Background technique [0002] Ethylene is one of the most important basic raw materials in the petrochemical industry. As a monomer for the synthesis of various polymers - ethylene, most of it is produced from petroleum hydrocarbons (such as ethane, propane, butane, naphtha and light diesel oil, etc.) Cracked in the system. The ethylene-based C2 fraction obtained by this method also contains 0.5% to 2.5% (mole fraction) of acetylene. The presence of acetylene will complicate the polymerization process of ethylene and deteriorate the polymer properties. When polyethylene is produced by high-pressure method, there is a danger of explosion due to the accumulation of acetylene; in addition, when polyethylene is produced, the presence of acetylene will also reduce the activity of the polymerization catalyst and increase the consump...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/52B01J35/10C07C11/04C07C5/09
CPCY02P20/52
Inventor 车春霞颉伟路明梁玉龙钱颖韩伟谭都平郭珺高源张忠东张小奇常晓昕景喜林任世宏蔡小霞
Owner PETROCHINA CO LTD
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