A kind of preparation method of palladium-gold series supported hydrogenation catalyst

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

Active Publication Date: 2018-07-13
PETROCHINA CO LTD
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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 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

Method used

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  • A kind of preparation method of palladium-gold series supported hydrogenation catalyst
  • A kind of preparation method of palladium-gold series supported hydrogenation catalyst
  • A kind of preparation method of palladium-gold series supported hydrogenation catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0050] 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.

[0051] Dissolve 2.80g of 4,4-dihydroxy-2,2-bipyridine in 600mL ethanol solution, impregnate the above carrier in the above solution, and let it stand for 2 hours to make 4,4'-dihydroxy-2,2'-bipyridine After pyridine was completely loaded on the alumina support, it was dried at 60°C for 10 h to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0052] 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, and make a mixed solution, 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 The precursor, the molar ratio of hydroxyl-bipyridine to (Pd+Au) is 15. After dryi...

Embodiment 2

[0063] 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.

[0064] Dissolve 2.19g 4,4'-dihydroxy-2,2'-bipyridine in 600mL ethanol solution, impregnate the above carrier in the above solution, and let 4,4'-dihydroxy-2,2' -bipyridine was completely loaded on the alumina carrier, and dried at 90°C for 8h to obtain hydroxy-bipyridine / Al 2 o 3 Prebody.

[0065] 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 2.5, and make 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 solid at 110°C for 6 hours to obtain PdAu-hydroxy-bipyridine / Al 2 o 3 Precursor (hydroxy-bipyridine moles...

Embodiment 3

[0083] 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 α-Al 2 o 3 400g, magnesium oxide 100g.

[0084] Dissolve 39.4g 6,6'-dihydroxy-3,3'-bipyridine in 600mL 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.

[0085] 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 3.2, and make 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 solid at 100 °C for 8 hours to obtain PdAu-hydroxy-bipyridine / Al 2 o 3 Precursor (number of moles ...

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Abstract

The invention relates to a preparation method of a palladium-gold-based supported hydrogenation catalyst. The catalyst contains palladium and gold, and the carrier contains Al2O3. After drying, it is impregnated with a mixed solution of Pd and Au, dried and calcined to obtain a Pd-Au catalyst. Since the adverse effects of the surface tension of the immersion liquid and the solvation effect on the dispersion of palladium-gold are overcome in the preparation method, the prepared catalyst is more conducive to the formation of palladium-gold alloy, and the catalyst has excellent activity, selectivity and anti-coking performance. The catalyst of the invention can be used in the selective hydrogenation process of fractions such as C2 and C3, and has good hydrogenation activity, excellent selectivity and good anti-coking performance; meanwhile, it brings relatively high increment of ethylene and propylene.

Description

technical field [0001] The invention relates to a preparation method of a catalyst, in particular to a preparation method of 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...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/52C07C11/04C07C7/167
CPCY02P20/52
Inventor 车春霞常晓昕颉伟谭都平袁华斌景喜林路明张小奇韩伟钱颖梁玉龙程琳王玲玲杨珊珊景丽郭珺
Owner PETROCHINA CO LTD
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