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CN-121988403-A - Macroporous alumina carrier, and preparation method and application thereof

CN121988403ACN 121988403 ACN121988403 ACN 121988403ACN-121988403-A

Abstract

The invention discloses a macroporous alumina carrier and a preparation method and application thereof, wherein the preparation method comprises the following steps of step 1, uniformly mixing isobutene-maleic anhydride copolymer powder, ammonium bicarbonate crystal powder, hydrated alumina, kaolin and cellulose; and 2, mixing and kneading the mixture obtained in the step 1 with water, forming, drying and roasting to obtain the large alumina carrier. The large Kong Zhayou hydrogenation protective agent carrier prepared by the method has rich large holes of hundred nanometers to micrometers, and has high mechanical strength.

Inventors

  • SONG JUNNAN
  • YANG XU
  • ZHAO YUANSHENG
  • CHENG TAO
  • CUI RUILI
  • YU SHUANGLIN
  • ZHANG CHUNGUANG
  • ZHANG ZHIGUO
  • YOU HUILING
  • ZHANG BOHAN

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241108

Claims (14)

  1. 1. The preparation method of the macroporous alumina carrier is characterized by comprising the following steps: step 1, uniformly mixing isobutene-maleic anhydride copolymer powder, ammonium bicarbonate crystal powder, hydrated alumina, kaolin and cellulose; And 2, mixing and kneading the mixture obtained in the step 1 with water, forming, drying and roasting to obtain the large alumina carrier.
  2. 2. The method for preparing a macroporous alumina carrier according to claim 1, wherein the number average molecular weight of the isobutylene-maleic anhydride copolymer is 200000 to 400000, and the powder mesh number is 800 mesh or more.
  3. 3. The method for preparing a macroporous alumina carrier according to claim 1, wherein the powder mesh number of the ammonium bicarbonate crystals is 800 mesh or more.
  4. 4. The method for preparing a macroporous alumina carrier according to claim 1, wherein the hydrated alumina is at least one selected from gibbsite, boehmite, pseudo-boehmite, amorphous aluminum hydroxide.
  5. 5. The method for preparing a macroporous alumina carrier according to claim 1, wherein the kaolin is calcined kaolin, and the powder mesh number is 800 mesh or more.
  6. 6. The method for preparing macroporous alumina carrier according to claim 1, wherein the cellulose is one or more selected from methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.
  7. 7. The preparation method of the macroporous alumina carrier according to claim 1, wherein the weight ratio of the hydrated alumina to the kaolin is 9:1-5:5, and the weight ratio of the cellulose to the total weight of the hydrated alumina and the kaolin is 5:100-15:100.
  8. 8. The method for preparing a macroporous alumina carrier according to claim 1, wherein the addition amount of the isobutylene-maleic anhydride copolymer is 5.0 to 30.0w% of the total weight of the hydrated alumina and kaolin.
  9. 9. The method for preparing macroporous alumina carrier according to claim 1, wherein the addition amount of the ammonium bicarbonate is 100-130.0 w% of the weight of the isobutylene-maleic anhydride copolymer.
  10. 10. The method for preparing a macroporous alumina carrier according to claim 1, wherein the water is added in the amount of 70.0-110.0 w% of the total weight of the hydrated alumina and kaolin in the step 2.
  11. 11. The method for preparing the macroporous alumina carrier according to claim 1, wherein the drying in the step 2 is performed at 90 ℃ to 120 ℃ for 4 to 24 hours.
  12. 12. The method for preparing a macroporous alumina carrier according to claim 1, wherein the calcination in the step 2 is performed for 4-8 hours at 900-1100 ℃.
  13. 13. The macroporous alumina carrier prepared by the preparation method of any one of claims 1 to 12, wherein the mercury intrusion pore volume is 0.4-1.0ml/g, and the pore volume with the pore diameter of >500nm accounts for 10% -45% of the total pore volume, and the intensity is >20N/mm.
  14. 14. The use of a macroporous alumina carrier prepared by the preparation method of any one of claims 1 to 12 or the macroporous alumina carrier of claim 13 in a residuum hydrogenation protecting agent or a demetallizing agent.

Description

Macroporous alumina carrier, and preparation method and application thereof Technical Field The invention belongs to the field of alumina carrier preparation, and particularly relates to a macroporous alumina carrier, and a preparation method and application thereof. Background Currently, as worldwide petroleum resources become increasingly heavier and inferior, there is an urgent need to develop clean and efficient heavy oil processing techniques. Hydrogenation is the most efficient heavy and residuum feedstock processing technique. Through hydrogenation, most of metal impurities and sulfur are removed, the carbon residue value is reduced, the quality of heavy oil is improved, and the possibility is provided for further efficient cleaning processing of the heavy oil. The combination of heavy oil and residual oil hydrotreating and heavy oil catalytic cracking technology can not only maximally convert residual oil with low utilization value and easy environmental pollution, greatly improve the light oil yield, but also obtain clean oil with high added value and superior quality. The technology combination becomes a core technology for improving economic benefit of sulfur-containing crude oil processing oil refining enterprises. The deposition of Na, ca, ni, V and other metals in heavy oil on the hydrogenation catalyst can cause permanent poisoning, and is an important factor to be considered in the heavy oil hydrogenation process. The active protecting agent and hydrodemetallization catalyst in the protecting agent are key technologies in the heavy oil hydrotreating process, and mainly serve to remove most of Ni, V and other metal impurities in the raw materials, protect downstream desulfurization (HDS) and denitrification (HDN) catalysts, and have certain desulfurization capability. The above two types of catalysts are required to have not only good metal removal ability but also high metal impurity accommodation ability. Because most of the metal impurities in the residual oil exist in colloid and asphaltene, the colloid and asphaltene are the types with the largest molecular weight, the most complex structure and the strongest polarity in petroleum components, and have larger diffusion resistance. The demetallization agent is limited by the mass transfer and diffusion efficiency of the carrier, is easy to cause orifice blockage, has serious uneven deposition distribution of the removed impurities, and has limited metal holding capacity. All of the above causes serious waste of the internal space of the catalyst, and the efficiency of the single catalyst cannot be fully exerted. Therefore, the two catalysts have larger pore volume, pore diameter and good pore channel permeability, so as to be beneficial to diffusion, reaction and deposition of macromolecular substances such as asphaltene and the like containing metal impurities in the residual oil raw materials. One of the solutions is to use macroporous alumina carrier, and in the reaction process, macropores with pore diameters above 100nm provide channels for the diffusion of macromolecular reaction substances, so as to promote the diffusion and deposition of impurities to the internal pore canal of the catalyst, thereby leading the catalyst to have high demetallization activity and high impurity capacity. In order to obtain alumina support materials having a macroporous structure, researchers have used pore-enlarging agents, hydrothermal treatments, and the like to obtain alumina having a macroporous structure. The related literature for synthesizing macroporous alumina materials by a pore-expanding agent method is more, and the method can be divided into a hard pore-expanding agent method and a soft pore-expanding agent method according to different pore-expanding agent types. The hard pore-expanding agent method represented by activated carbon can obtain better macroporous alumina, and US19820384626 discloses that carbon black is used as a pore-expanding agent, so that macroporous alumina with pore diameters distributed at 15-300 nm can be obtained, but the macroporous alumina with concentrated pore diameters is difficult to prepare due to non-uniform particle diameter distribution of the carbon black. CN201410347665.X discloses a preparation method of large pore volume and high strength alumina, wherein pore-enlarging agents such as polyacrylamide, polyvinyl alcohol, alkyl cellulose, sesbania powder, starch and the like are added to obtain an alumina carrier containing large pores, the using amount of the pore-enlarging agents accounts for 10% -30% of that of the alumina, but the specific pore diameter range is not disclosed. Although the hard pore-expanding agent method can obtain a better macroporous alumina carrier, the dosage of the pore-expanding agent is preferably more than 20 percent, so that the processing cost is greatly improved, and the decomposition of a large amount of pore-expanding agent does not meet the development requirements of