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RU-2861286-C2 - SUPPORT-FREE BIMETALLIC HYDROGENATION CATALYST, PRODUCTION AND USE THEREOF

RU2861286C2RU 2861286 C2RU2861286 C2RU 2861286C2RU-2861286-C2

Abstract

FIELD: hydrogenation catalysts. SUBSTANCE: there is provided a supported-free bimetallic hydrogenation catalyst consisting of a complex formed by bonding a central metal atom or ion with an organic ligand via a coordination bond, wherein the catalyst has a composition schematically represented by formula (I) M 1 M 2 O a [R(COO) x ] b (I), wherein M 1 and M 2 are metals, R(COO) x is an organic ligand, R is a hydrocarbyl group of the organic ligand, COO is a coordinating group of the organic ligand, x is the number of coordinating groups in the organic ligand, a is the molar ratio of the number of oxygen atoms bonded to the metal via a non-coordination bond to the total amount of metal, and b is the molar ratio of the organic ligand to the total amount of metal, wherein M 1 and M 2 , which are different from each other, are in each case independently selected from the group consisting of Group VB metals, Group VIB metals, Group VIII metals and Group IB metals that exhibit activity in a hydrogenation reaction; R is a C3-C19 hydrocarbyl group; x is 1, 2 or 3; a is 0, 1, 2, 3, 4 or 5; and b is a positive number from 1 to 6, wherein the catalyst exhibits an infrared spectrum with characteristic peaks at positions 700-1000 cm -1 , 1350-1450 cm -1 and 1500-1610 cm -1 ; a method for producing the proposed supported-free bimetallic hydrogenation catalyst; a bimetallic hydrogenation catalyst composition comprising the supported-free bimetallic hydrogenation catalyst; a method for hydroprocessing a hydrocarbon feedstock; a supported-free catalyst composition suitable for hydrogenating heavy petroleum products, the use of the proposed supported-free catalyst composition in the hydroprocessing of heavy petroleum products and a method for hydroprocessing heavy petroleum products. EFFECT: obtaining a hydrogenation catalyst having high dispersibility in the oil phase when used to catalyse the hydrogenation reaction of hydrocarbon compounds. 26 cl, 8 dwg, 9 tbl, 23 ex

Inventors

  • KHOU, Khuandi
  • VAN, Tin
  • DUN, Min
  • TAO, Menin
  • CHZHAO, I
  • LUN, Tszyun

Dates

Publication Date
20260504
Application Date
20221021
Priority Date
20211025

Claims (20)

  1. 1. A support-free bimetallic hydrogenation catalyst consisting of a complex formed by the binding of a central metal atom or central ion to an organic ligand via a coordination bond, the catalyst having a composition schematically represented by formula (I):
  2. M 1 M 2 O a [R(COO) x ] b (I),
  3. wherein M 1 and M 2 are metals, R(COO) x is an organic ligand, R is a hydrocarbyl group of the organic ligand, COO is a coordinating group of the organic ligand, x is the number of coordinating groups in the organic ligand, a is the molar ratio of the number of oxygen atoms bonded to the metal through a non-coordinating bond and the total amount of metal, and b is the molar ratio of the organic ligand and the total amount of metal, wherein:
  4. M 1 and M 2 , which differ from each other, are in each case independently selected from the group consisting of metals of group VB, metals of group VIB, metals of group VIII and metals of group IB that exhibit activity in the hydrogenation reaction;
  5. R represents a C3-C19 hydrocarbyl group;
  6. x is 1, 2, or 3;
  7. a is 0, 1, 2, 3, 4, or 5; and
  8. b is a positive number from 1 to 6,
  9. The catalyst exhibits an infrared spectrum with characteristic peaks at positions 700-1000 cm -1 , 1350-1450 cm -1 and 1500-1610 cm -1 .
  10. 2. A carrier-free bimetallic hydrogenation catalyst according to claim 1, wherein R is selected from the group consisting of normal C5-C11 alkyl, isomeric C5-C11 alkyl, C5-C12 alkyl with a cycloalkyl moiety, and aryl C6-C12;
  11. x is 1 or 2;
  12. a represents 1, 2, or 3;
  13. b is a positive number between 2 and 5.
  14. 3. A support-free bimetallic hydrogenation catalyst according to claim 1, wherein at least a portion of the complex in the catalyst has a structure represented by formula (I-1):
  15. where M 1 , M 2 , R and x are as defined above;
  16. → represents a coordination bond;
  17. x represents the number of coordinating groups in the organic ligand and is 1 or 2, preferably 1;
  18. n represents the coordination number and is a positive number from 1 to 6, preferably from 2 to 5;
  19. y represents the number of oxygen atoms simultaneously bonded to the metal M 1 and the metal M 2 through a non-coordination bond, and is 0 or 1, preferably 1; and
  20. z represents the number of oxygen atoms bonded only to the metal M2 through a non-coordinating bond and is 0, 1 or 2, preferably 0 or 1.

Description

Field of technology to which the present invention relates The present invention relates to the field of hydrogenation catalyst technology, in particular to a carrier-containing bimetallic hydrogenation catalyst, as well as to its production and use. Prior art of the present invention In 2020, China's dependence on external sources of crude oil exceeded 70%. Imported crude oil consists mainly of low-quality and heavy crude oil from the Middle East and South America, with residual oil accounting for over 50%. Therefore, efficient utilization of oil resources, particularly deep processing of residual oil, can increase the utilization rate of oil resources and alleviate China's energy security crisis. In crude oil refining, supported catalysts are the hydrogenation catalysts that have been studied for the longest period of time and are most widely used in the greatest number of industrial applications. Supported catalysts consist of three components: a catalytic active component, an auxiliary catalytic active component, and a support. The active component and auxiliary catalytic active component are primarily metals, while the support is a silicon-based or aluminum-based material or a porous material such as alumina, silica, kaolin, molecular sieve, and similar materials. To improve the properties of the metal active sites in the catalyst and increase the activity, selectivity, and stability of the catalyst, hydrogenation catalysts have been developed, which include bimetallic and polymetallic catalysts. Hydrotreating catalysts for distillate petroleum products primarily comprise Mo-Ni and W-Ni hydrotreating catalysts, with W-Mo-Ni catalysts primarily used for pretreatment by hydrogenation of vacuum distillate petroleum products. The base metals contained in the hydrogenation catalysts, such as Mo, W, and Ni, are primarily present in the sulfide form and are loaded into the pore channels of the support. Regarding the effect of auxiliary metal elements, there are theories such as the interstitial model (a structure in which Co or Ni is intercalated into MoS2 or WS2 ), the synergistic model (a structure in which Co is present in the form of Co9S8 ), the single-layer model (a structure in which MoO3 or WO3 is distributed on the support in a single-layer form) and the like models, which explain the effect of auxiliary metal elements on the structure of the host metal sulfide or the distribution of the main metal elements on the support. Since all existing bimetallic catalysts are supported catalysts, the hydrocarbon hydrogenation reaction catalyzed by such catalysts belongs to the class of heterogeneous catalytic reactions, which include the following seven steps: feedstock molecules diffuse to the outer surface of the catalyst → feedstock molecules diffuse into the pore channel of the catalyst → feedstock molecules are adsorbed on the active sites of the catalyst → feedstock molecules enter into a surface catalytic reaction with the active sites of the catalyst → reaction products are desorbed from the surface of the active sites of the catalyst → reaction products diffuse outward from the pore channel of the catalyst → reaction products diffuse into the liquid-phase system from the outer surface of the catalyst. Among these steps, the diffusion step significantly affects the probability of occurrence and the efficiency of the hydrogenation reaction catalyzed by supported bimetallic hydrogenation catalysts and limits the catalytic activity of the catalyst. In order to improve the dispersion and solubility of the catalyst in petroleum products, numerous studies have been conducted in the relevant field by Chinese and foreign researchers. Chinese Patent No. ZL201510275523.1 discloses an oil-soluble Mo-Ni-based bimetallic catalyst, its preparation and use. In the described method, nickel nitrate and ammonium molybdate are dissolved in 15-25 times the mass amount of distilled water, a small amount of glycol is added, and then an aqueous ammonia solution is added to the solution to adjust the pH value to the alkaline range; the solution is heated to a temperature of 130-160 °C under stirring and reacted for 3-5 hours, and the resulting product is filtered to obtain a solid intermediate product; This solid intermediate product is dried at 100°C and normal pressure, mixed with oleic acid, and reacted at 230-260°C for 2-4 hours to produce a petroleum-soluble Mo-Ni-containing bimetallic catalyst. This catalyst has a flexible and adjustable weight ratio of the two metals and exhibits high activity in the hydrogenation reaction and good coke inhibition. However, according to this patent, glycol and an aqueous ammonia solution are added in the first stage, the reaction product obtained in the first stage is filtered to obtain an intermediate product, and the intermediate product is dried and then sent to the second stage of the reaction. Thus, the procedures of this method are complicated, waste is generated as a result of f