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A kind of selective hydrogenation catalyst and its preparation

A catalyst and composite oxide technology, which is applied in the fields of hydrogenation to hydrocarbons, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of uneven particle size and particle size distribution of amorphous alloys , The metal reactor has problems such as corrosion and difficulty in mass synthesis, so as to avoid agglomeration or crystallization, increase mechanical strength, and increase sol capacity.

Active Publication Date: 2015-09-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The disadvantage of this method is that the reaction temperature is high and the pressure is high, ammonia gas corrodes the metal reactor under high temperature and high pressure, and it is difficult to synthesize in large quantities
U.S. Patents US4695560, US4523048, US4761509 and Chinese Patent CN1032157 disclose a method for the selective hydrogenation of diolefins in alkane dehydrogenation products. The catalyst used in this method is characterized by Al 2 o 3 It is a supported nickel catalyst, which must be sulfurized before use, and in order to achieve a certain reactivity, the selective hydrogenation reaction must be carried out at a temperature greater than 200 ° C. Under this condition, there will be some cracking side effects. The reaction occurs, increasing the consumption of materials
Chinese patent CN1268549A introduces a method for removing C 10 ~C 16 The selective hydrogenation method of medium straight-chain diene, the catalyst used in this method is characterized by Al 2 o 3 Supported palladium catalyst, in order to improve the catalyst's diene hydrogenation conversion rate and generate monoene selectivity, the method adopts a multi-stage hydrogenation process, thereby increasing equipment investment
Since the reaction between metal ions and borohydride compounds is exothermic, and the preparation reaction of the above-mentioned catalysts is carried out at room temperature or higher, local overheating may be caused, resulting in the agglomeration or crystallization of the generated alloy particles, and the obtained amorphous The size and particle size distribution of the state alloy particles are not uniform
[0006] Currently, there is little literature on amorphous catalysts for the selective hydrogenation of long-chain n-diolefins to long-chain n-monoolefins

Method used

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  • A kind of selective hydrogenation catalyst and its preparation
  • A kind of selective hydrogenation catalyst and its preparation
  • A kind of selective hydrogenation catalyst and its preparation

Examples

Experimental program
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Effect test

Embodiment 1

[0028] The carrier adopts Al in the patent CN1184289C of Yanshan Branch of Beijing Research Institute of Chemical Industry 2 o 3 -TiO 2 Composite oxide carrier, weigh 5g Al 2 o 3 -TiO 2 Titanium oxide is 5% of the quality of alumina, slowly added to 20ml of nickel sulfate aqueous solution under stirring, the concentration of nickel sulfate is 5% based on the theoretical loading of Ni, impregnated and stirred for 4 hours, filtered, and 12ml of distilled water was added to the filter cake, Add a certain amount of 1mol / L KBH at 0°C under nitrogen protection 4 The solution had a molar ratio of Ni:B of 1:1, and the solution was dropped within 15 minutes. Stir vigorously until no gas is produced. Catalyst 1 was prepared, and the data are shown in Table 1.

Embodiment 2

[0030] The carrier adopts Al in the patent CN1184289C of Yanshan Branch of Beijing Research Institute of Chemical Industry 2 o 3 -TiO 2 Composite oxide carrier, weigh 5g Al 2 o 3 -TiO 2 , titanium oxide is 5% of the quality of alumina, slowly added to 20ml of nickel nitrate aqueous solution under stirring, the concentration of nickel nitrate is based on the theoretical loading of Ni as 10%, impregnated and stirred for 4 hours, filtered, and 12ml of distilled water was added to the filter cake, Add a certain amount of 1mol / L KBH at 0°C under nitrogen protection 4 The solution has a molar ratio of Ni:B of 1:2, and the solution is dropped within 15 minutes. Stir vigorously until no gas is produced. Catalyst 2 was prepared, and the data are shown in Table 1.

Embodiment 3

[0032] The carrier adopts Al in the patent CN1184289C of Yanshan Branch of Beijing Research Institute of Chemical Industry 2 o 3 -TiO 2 Composite oxide carrier, weigh 5g Al 2 o 3 -TiO 2 , titanium oxide is 10% of the mass of alumina, slowly added to 20ml of nickel chloride aqueous solution under stirring, the concentration of nickel chloride is based on the theoretical loading of Ni as 15%, impregnated and stirred for 4 hours, filtered, and 12ml of filter cake was added Distilled water, add a certain amount of 1mol / L KBH at 0°C under nitrogen protection 4 The solution had a molar ratio of Ni:B of 1:2.5, and the solution was dropped within 15 minutes. Stir vigorously until no gas is produced. Catalyst 3 was prepared, and the data are shown in Table 1.

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Abstract

The invention relates to a selective hydrogenation catalyst which comprises an Ni-B amorphous alloy and an Al2O3-TiO2 composite oxide supporter material, wherein the content of the Ni-B amorphous alloy is 4-40 wt%, preferably 4-20 wt%; and the Ni / B mol ratio is 3:1-1:3, preferably 1:1-1:3. The invention also relates to a preparation method of the catalyst. The catalyst provided by the invention can be used for selective hydrogenation of diolefins, and is especially suitable for selective hydrogenation of C10-C16 long-chain normal diolefins. The catalyst has the characteristics of high catalytic activity, high selectivity and favorable low-temperature activity.

Description

technical field [0001] The invention relates to a hydrogenation catalyst for petroleum hydrocarbons, in particular to a catalyst for selective hydrogenation of long-chain normal diolefins. The present invention also relates to the preparation of the aforementioned catalysts. Background technique [0002] long chain (C 10 ~C 16 ) normal monoolefins are one of the important raw materials of higher fatty alcohols and synthetic detergents. Currently, the production of long chain normal monoolefins in the world mainly adopts the long chain normal paraffin dehydrogenation Palcol process of UOP Company in the United States. C in this process 10 ~C 16 The long-chain alkanes produced by the dehydrogenation unit contain 1-3wt% diolefins. The presence of these diolefins will cause a large number of side reactions in the subsequent alkylation process, reducing the production of alkylbenzenes. The rate and quality will affect the color of sulfonic acid after sulfonation of alkylbenz...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/755C07C5/05
Inventor 杜周柴忠义纪玉国任玉梅季静
Owner CHINA PETROLEUM & CHEM CORP