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Hydrofining catalyst and preparation method thereof

A hydrogenation refining and catalyst technology, applied in the field of oil hydrogenation, can solve the problems of cracking reaction, easy nitrogen poisoning deactivation, high catalyst cost, etc.

Active Publication Date: 2021-04-09
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN104368376A adopts multi-level pore zeolite to support nickel-tungsten hydrodesulfurization catalyst, which shows good catalytic activity in the process of hydrodesulfurization, but the small pore diameter and pore volume of the catalyst are not conducive to the diffusion of polycyclic aromatic hydrocarbons, and the acidity of the zeolite carrier If it is too strong, it will cause supersaturation or cracking reaction of polycyclic aromatic hydrocarbons, resulting in a decrease in diesel yield
CN106582707A discloses a supported alloy type aromatic hydrocarbon saturation catalyst and its preparation method, by using the catalyst to be selected from at least one of alumina, silicon oxide, titanium oxide or amorphous silicon aluminum as a carrier, with noble metal Ir, metal Ni and The technical scheme that the alloy formed by at least one metal selected from Sn or Bi is the active component solves the problem of uncontrollable or low saturation degree of polycyclic aromatic hydrocarbons, but the noble metal Ir is expensive, and the catalyst high cost
[0005] In summary, although the above-mentioned method can improve the PAH hydrogenation saturation activity of the catalyst, the acid content on the catalyst is too high, which will easily cause the reduction of diesel yield, and the cost of the noble metal catalyst is too high. susceptible to nitrogen poisoning inactivation

Method used

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  • Hydrofining catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Add 20g of tributyl phosphate into a 3L reaction tank, place 1L of deionized water as the bottom liquid, and mix 1L of aluminum sulfate solution (concentration of 1mol / L) and 1L of sodium metaaluminate solution (concentration of 2.4mol / L) L) were placed in the raw material tanks respectively, and the temperature of the reaction tanks was controlled to 60°C through water circulation. The aluminum sulfate solution was injected into the reaction tank at a rate of 10 mL / min, while the sodium metaaluminate solution was injected and the rate was adjusted to keep the pH value of the reaction tank solution constant at 8.8, and the neutralization was completed after 90 min. Keep 60°C and pH 8.8 in the reaction tank, aging for 3 hours, and remove Na after full washing + ions and SO 4 2- After ionization, after filtration, the filter cake was dried at 150°C for 3 hours to obtain pseudo-boehmite powder.

[0027] Take 200g of pseudo-boehmite powder, mix with 6g of nitric acid, 6g...

Embodiment 2

[0031] Add 32g of tributyl phosphate into a 3L reaction tank, place 1L of deionized water as the bottom liquid, and mix 1L of aluminum sulfate solution (concentration of 1 mol / L) and 1 L of sodium metaaluminate solution (concentration of 2.4 mol / L) were respectively placed in the raw material tank, and the temperature of the reaction tank was controlled to 60°C through water circulation. The aluminum sulfate solution was injected into the reaction tank at a rate of 10 mL / min, while the sodium metaaluminate solution was injected and the rate was adjusted to keep the pH value of the reaction tank solution constant at 8.8, and the neutralization was completed after 90 min. Keep 60°C and pH 8.8 in the reaction tank, aging for 3 hours, and remove Na after full washing + ions and SO 4 2- After ionization, after filtration, the filter cake was dried at 150°C for 3 hours to obtain pseudo-boehmite powder.

[0032] Take 200g of pseudo-boehmite powder, mix with 6g of nitric acid, 6g ...

Embodiment 3

[0036] Add 48g of tributyl phosphate into a 3L reaction tank, place 1 L of deionized water as the bottom liquid, and mix 1 L of aluminum sulfate solution (concentration of 1 mol / L) and 1 L of sodium metaaluminate solution (concentration of 2.4 mol / L) were respectively placed in the raw material tank, and the temperature of the reaction tank was controlled to 60°C through water circulation. The aluminum sulfate solution was injected into the reaction tank at a rate of 10 mL / min, while the sodium metaaluminate solution was injected and the rate was adjusted to keep the pH value of the reaction tank solution constant at 8.8, and the neutralization was completed after 90 min. Keep 60°C and pH 8.8 in the reaction tank, aging for 3 hours, and remove Na after full washing + ions and SO 4 2- After ionization, after filtration, the filter cake was dried at 150°C for 3 hours to obtain pseudo-boehmite powder.

[0037] Take 200g of pseudo-boehmite powder, mix with 6g of nitric acid, 6...

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Abstract

The invention discloses a hydrofining catalyst and a preparation method thereof, the hydrofining catalyst comprises a modified alumina carrier and a hydrogenation active component, the modified alumina carrier comprises phosphorus and a modifier A, the modifier A is magnesium oxide, calcium oxide or zirconium oxide, the phosphorus accounts for 0.1wt%-5wt% of the elements, and the modifier A accounts for 3wt%-15wt% of the elements; based on the total weight of the catalyst, a VIB group metal accounts for 2.0%-30% of the total weight of the catalyst in terms of oxide, and a VIII group metal accounts for 0.1%-10% of the total weight of the catalyst in terms of oxide. The preparation method comprises the following steps: (1) adding an aluminum source and a precipitant into an aqueous solution containing a phosphate type anionic surfactant for precipitation reaction to obtain pseudo-boehmite powder, and molding the powder to obtain a carrier; and (2) impregnating the carrier with a modifier A precursor aqueous solution, mixing the impregnated carrier with a urea solution, carrying out hydrothermal treatment to obtain a modified alumina carrier, and loading an active component to obtain the catalyst. The catalyst provided by the invention has the characteristics of appropriate acid amount and mesoporous aperture, uniform active metal dispersion, low price and the like, and has good hydrodesulfurization and polycyclic aromatic hydrocarbon hydrogenation saturation activity.

Description

technical field [0001] The invention relates to the technical field of hydrogenation of oil products, in particular to a hydrogenation refining catalyst and a preparation method thereof. Background technique [0002] As my country's environmental requirements become more and more stringent, the requirements for the content of sulfur, nitrogen and polycyclic aromatic hydrocarbons in diesel oil are also becoming more and more stringent. It took my country less than 10 years to complete the quality upgrade of vehicle diesel. The diesel standard was upgraded from the National III standard implemented in 2010 to the National VI standard implemented in 2019. The sulfur content in diesel was reduced from 350ppm to 10ppm. The national V standard of diesel is that the sulfur content is less than 10ppm, and the content of polycyclic aromatic hydrocarbons is not more than 11%. The national VI standard of diesel is that the sulfur content is less than 10ppm, and the content of polycycli...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/19C10G45/08
CPCB01J27/19C10G45/08C10G2300/1055C10G2300/202C10G2300/70B01J35/635B01J35/633B01J35/647B01J35/615Y02P30/20
Inventor 刘丽李扬杨成敏姚运海段为宇孙进郭蓉周勇郑步梅丁莉
Owner CHINA PETROLEUM & CHEM CORP
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