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A modified alumina carrier and its preparation method and hydrorefining catalyst

An alumina carrier and alumina technology, which is applied in the field of oil hydrogenation, can solve problems such as high price, and achieve the effects of improving reaction activity, improving catalytic activity, and pore structure not easily damaged.

Active Publication Date: 2022-03-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This catalyst has excellent hydrodesulfurization catalytic effect, but the carrier of the catalyst is all made of graphene oxide, which is expensive

Method used

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  • A modified alumina carrier and its preparation method and hydrorefining catalyst
  • A modified alumina carrier and its preparation method and hydrorefining catalyst
  • A modified alumina carrier and its preparation method and hydrorefining catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Put 1 L of aluminum sulfate solution (concentration of 0.2 mol / L) and 1 L of sodium metaaluminate solution (concentration of 0.3 mol / L) in the raw material tank respectively, and place 1 L of pure water in the reaction tank as the bottom liquid, pass The temperature of the reaction tank is controlled to 60° C. by water circulation, and a small amount of sodium hydroxide is added to make the pH value of the solution 8.5. Inject the aluminum sulfate solution into the reaction tank at a rate of 10 mL / min, and at the same time inject the sodium metaaluminate solution and adjust the rate so that the pH value of the reaction tank solution is constant at 8.8. After 60 min, the neutralization is completed, and the Na is fully washed to remove + ions and SO 4 2- After ionization, a certain amount of deionized water was added to obtain pseudo-boehmite slurry A with a solid-to-liquid ratio of 8% (calculated as alumina).

[0039] Take 300g of graphene oxide, add it to 1.5L of dei...

Embodiment 2

[0041] 13g graphene and 13g ZSM-5 molecular sieve (SiO 2 / Al 2 o 3 The molar ratio is 30.0, the unit cell constant is 20 Å, and the relative crystallinity is 85%), and put it into the 625g pseudoboehmite slurry A obtained in Example 1, stir well and then add 200g ethanol, continue stirring evenly, then add 50g of tetraethoxysilane, after continuous stirring, a small amount of tetramethylammonium hydroxide was added to adjust the pH value of the slurry to 8.5. Put it in a closed autoclave, age at 185°C for 24 hours, take it out and filter until the water content of the filter cake is 39%, add 8g of ethylenediamine and 6g of tetraethoxysilane and knead it into a plastic body, then extrude into a strip, and dry at 100°C After 3 hours, it was calcined at 500° C. for 4 hours under the protection of nitrogen to obtain the final modified alumina carrier S-1.

[0042] 93.1g of Co(NO 3 ) 2 .6H 2 O is dissolved in 200mL of deionized water, after dissolving, add ammonium citrate wh...

Embodiment 3

[0045] 10g graphene and 10g ZSM-5 molecular sieve (SiO 2 / Al 2 o 3 The molar ratio is 30.0, the unit cell constant is 20 Å, and the relative crystallinity is 85%), put it into the 180g pseudoboehmite slurry A obtained in Example 1, stir evenly, then add 200g ethanol, continue stirring evenly, then add 50g of tetraethoxysilane, after continuous stirring, a small amount of tetramethylammonium hydroxide was added to adjust the pH value of the slurry to 8.5. Put it in a closed autoclave, age at 185°C for 24 hours, take it out and filter until the water content of the filter cake is 39%, add 8g of ethylenediamine and 6g of tetraethoxysilane and knead it into a plastic body, then extrude into a strip, and dry at 100°C After 3 hours, it was calcined at 500° C. for 4 hours under the protection of nitrogen to obtain the final modified alumina carrier S-2.

[0046] 93.1g of Co(NO 3 ) 2 .6H 2 O is dissolved in 200mL of deionized water, after dissolving, add ammonium citrate which i...

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Abstract

The invention discloses a modified alumina carrier, its preparation method and a hydrofining catalyst. Based on the weight of the modified alumina carrier, it includes molecular sieve, graphene and alumina, and has a specific surface area of ​​300-400m 2 / g, the pore volume is 0.5‑0.8cm 3 / g, the average pore size is 7‑9nm. The preparation method of the carrier is as follows: (1) Mix pseudo-boehmite precursor slurry, mesoporous molecular sieve, graphene and organic alcohol to obtain slurry A; (2) Add silane coupling agent to slurry A and mix evenly, Then adjust the pH value to obtain the slurry B; (3) Aging the slurry B. After the aging is over, the material is filtered to remove a certain amount of water, and then an organic amine and a silane coupling agent are added to knead into a plastic body. After molding, drying and roasting , to obtain a modified alumina carrier. The modified alumina carrier of the present invention has better adsorption capacity of hydrogen molecules and hydrogen overflow properties, and the hydrogenation refining catalyst prepared by the carrier is suitable for a liquid phase circulation hydrogenation process and has good hydrogenation activity.

Description

technical field [0001] The invention relates to the technical field of hydrogenation of oil products, in particular to a modified alumina carrier, a preparation method thereof and a hydrogenation refining catalyst. Background technique [0002] With the increasingly stringent environmental protection regulations, the development and use of ultra-low sulfur or even sulfur-free diesel is the trend of clean fuel development worldwide. Hydrogenation of diesel raw materials in a conventional trickle bed to produce qualified diesel products is currently the most commonly used method. In the conventional trickle bed hydrogenation process, in order to control the reaction temperature of the catalyst bed and allow the hydrogen to fully contact with the oil, a relatively large volume ratio of hydrogen to oil is usually used, and there must be a large amount of hydrogen surplus after the hydrogenation reaction is completed . The excess hydrogen is usually pressurized by the circulatin...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40B01J29/48B01J29/03B01J29/70B01J29/78B01J35/10B01J32/00C10G45/12
CPCB01J29/40B01J29/48B01J29/0308B01J29/0341B01J29/7007B01J29/7815C10G45/12C10G2400/04C10G2300/202B01J2229/18B01J35/635B01J35/647B01J35/615
Inventor 刘丽郭蓉孙进杨涛姚运海
Owner CHINA PETROLEUM & CHEM CORP
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