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CN-117943033-B - Unsupported catalyst, preparation method and application thereof, and hydrogenation and dehydrogenation methods for nitrogen-containing heterocyclic organic matters

CN117943033BCN 117943033 BCN117943033 BCN 117943033BCN-117943033-B

Abstract

The invention relates to the field of organic liquid hydrogen storage, and discloses a non-supported catalyst, a preparation method and application thereof, and a hydrogenation and dehydrogenation method of nitrogen-containing heterocyclic organic matters, wherein the catalyst comprises Ni and Mo, the molar ratio of the Mo to the Ni is 0.2-5:1 based on elements, the Ni is positioned on the surface of a Mo enrichment micro-area, and the average grain size of the Ni is 1-200nm. The non-supported catalyst provided by the invention has a hydrogenation/dehydrogenation bidirectional catalytic function, has higher hydrogenation activity and higher dehydrogenation activity, and the hydrogenation and dehydrogenation activities are close to those of noble metals and far higher than those of conventional non-noble metal catalysts.

Inventors

  • PENG BO
  • LIN WEI
  • YANG XUE
  • SONG YE
  • SHEN NINGYUAN
  • WANG RUOYU

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260508
Application Date
20221026

Claims (20)

  1. 1. The unsupported catalyst is characterized by comprising Ni and Mo, wherein the molar ratio of Mo to Ni is 0.2-2:1 in terms of elements, the Ni is positioned on the surface of a Mo enrichment micro-area, the average grain size of the Ni is 20-100nm, the catalyst is rod-shaped, the length-diameter ratio is 1-100:1, the length of the catalyst is 1-10 mu m, the diameter of the catalyst is 0.1-1 mu m, mo in the catalyst is at least partially in the form of oxide, the Ni in the catalyst is at least partially in the form of simple substance Ni, and the specific surface area of the catalyst is 100-300cm 2 /g.
  2. 2. The catalyst of claim 1, wherein the molar ratio of Mo to Ni on an elemental basis is 0.8-2:1.
  3. 3. The catalyst of claim 2, wherein the molar ratio of Mo to Ni on an elemental basis is 0.8-1.2:1.
  4. 4. The catalyst of claim 1, wherein the catalyst aspect ratio is 4-10:1.
  5. 5. The catalyst of claim 1, wherein the catalyst has a length of 2-5 μm.
  6. 6. The catalyst of claim 1, wherein the catalyst has a diameter of 0.2-0.5 μm.
  7. 7. A process for the preparation of the unsupported catalyst of any one of claims 1 to 6 comprising the steps of: (1) Firstly mixing a nickel source, a molybdenum source and a solvent to obtain a first mixed solution; wherein the mole ratio of the molybdenum source calculated by Mo to the nickel source calculated by Ni is 0.2-5:1; (2) Performing second mixing on the first mixed solution and the alkali liquor to obtain a second mixed solution; (3) Thirdly mixing the second mixed solution with alcohol to obtain a third mixed solution; (4) Heating the third mixed solution to react to obtain catalyst precursor powder; (5) And (3) contacting the catalyst precursor powder with a hydrogen-containing atmosphere to obtain the unsupported catalyst.
  8. 8. The process according to claim 7, wherein the molar ratio of the molybdenum source calculated as Mo to the nickel source calculated as Ni is 0.8-2:1.
  9. 9. The process according to claim 8, wherein the molar ratio of the molybdenum source calculated as Mo to the nickel source calculated as Ni is 0.8-1.2:1.
  10. 10. The production method according to claim 7, wherein a total mass concentration of the nickel source and the molybdenum source in the first mixed solution is 0.005 to 5 g/mL.
  11. 11. The production method according to claim 10, wherein a total mass concentration of the nickel source and the molybdenum source in the first mixed solution is 0.01 to 1 g/mL.
  12. 12. The production method according to claim 7, wherein the nickel source is at least one selected from the group consisting of nickel chloride, nickel nitrate, nickel sulfate, nickel phosphate, nickel fluoroborate, nickel acetate, nickel acetylacetonate, nickel sulfamate and nickel citrate.
  13. 13. The production method according to claim 7, wherein the molybdenum source is at least one selected from the group consisting of molybdic acid, phosphomolybdic acid, ammonium molybdate, and molybdenum chloride.
  14. 14. The preparation method according to claim 7, wherein the solvent is water.
  15. 15. The method of claim 7, wherein the first mixing is at a temperature of 10-50 ℃.
  16. 16. The method of claim 15, wherein the first mixing is at a temperature of 15-40 ℃.
  17. 17. The process according to claim 7, wherein the alkaline solution is an aqueous solution containing an alkaline compound.
  18. 18. The method according to claim 17, wherein the basic compound is an organic base and/or an inorganic base.
  19. 19. The production method according to claim 18, wherein the basic compound is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, ethylenediamine and isopropylamine.
  20. 20. The process according to claim 17, wherein the alkali liquor has a concentration of the basic compound of 0.2 to 5mol/L.

Description

Unsupported catalyst, preparation method and application thereof, and hydrogenation and dehydrogenation methods for nitrogen-containing heterocyclic organic matters Technical Field The invention relates to the field of organic liquid hydrogen storage, in particular to an unsupported catalyst, a preparation method and application thereof, and hydrogenation and dehydrogenation methods of nitrogen-containing heterocyclic organic matters. Background Hydrogen is used as renewable energy, so that the energy efficiency is high, and almost no waste is generated. The development of hydrogen energy is expected to become an important way for improving energy efficiency, reducing petroleum consumption, improving ecological environment and guaranteeing energy safety, and the development of sustainable and high-efficiency large-scale hydrogen production technology is urgent need of hydrogen energy era. Hydrogen exists in a gaseous form under normal conditions, is inflammable, explosive and diffusive, so that people are required to give priority to the problems of safety, high efficiency and no leakage loss in the storage and transportation of hydrogen in practical application, which brings great difficulty to the storage and transportation. Therefore, hydrogen utilization is required to solve the problem of hydrogen storage and transportation. The realization of large-scale efficient hydrogen storage and transportation is the key for realizing hydrogen multi-scene application, and the current main storage and transportation modes are three modes of gas storage and transportation, liquid storage and transportation and chemical hydrogen storage. The gas storage and transportation and the liquid hydrogen storage and transportation are based on physical mode, the requirements of the former on the tightness and pressure resistance of the tank material are high, the problem of low hydrogen transportation efficiency exists, the conventional 20MPa long-tube trailer has the hydrogen transportation density of only about 1%, the long-distance hydrogen transportation cost is high, the requirement of the latter on the heat preservation of the material is high, the manufacturing cost of equipment is high, the liquid hydrogen volatilization loss is high in the long-distance hydrogen transportation scene, and the hydrogen liquefaction cost is high. Gaseous hydrogen storage tanks have been widely used on vehicles and low temperature liquid hydrogen is widely used in the aerospace field, but the technology of civil chemical hydrogen storage is still in the research and development stage. The chemical hydrogen storage is a technology for generating stable compounds by utilizing the hydrogen storage medium to react with hydrogen under certain conditions and then realizing hydrogen release by changing the conditions, and mainly comprises organic liquid hydrogen storage, liquid ammonia hydrogen storage, coordination hydride hydrogen storage, inorganic hydrogen storage and methanol hydrogen storage. The organic liquid hydrogen storage technology has the advantages of easily available raw materials, good compatibility between hydrogen absorption and hydrogen release product transportation equipment and a traditional oil gas transportation system, low transportation cost, no need of large-scale investment and the like, does not cause the resource waste of the traditional oil gas system in the future energy conversion development, and is considered as a chemical hydrogen storage technology with the most application prospect. The hydrogen carrier for organic liquid storage and transportation is mainly aromatic hydrocarbon compound, wherein the aromatic hydrocarbon compound ring containing heterocycle is widely researched due to the reaction temperature of hydrogen absorption, hydrogen desorption, easy separation of product hydrogen and organic matters and the like. CN111569901a discloses a preparation method and application of a bimetallic catalyst for hydrogenation and dehydrogenation of non-noble metal and noble metal of organic hydrogen storage material, which comprises mixing metal oxide (alumina, silica, tin oxide, molybdenum oxide, cerium oxide), graphene and molecular sieve carrier (MCM-41, HY) with non-noble metal precursor (Ni, cu, mg, fe) or noble metal (Pt, pd, rh, ru, au) precursor mixture solution by adopting an impregnation method, and obtaining the catalyst for hydrogen storage and dehydrogenation of organic carrier through sufficient stirring, drying, roasting and reduction. Hydrogenation is carried out on the liquid organic hydrogen storage carrier under the action of a catalyst to obtain hydrogenated organic liquid, and then dehydrogenation is carried out on the hydrogenated organic liquid to obtain the liquid organic hydrogen storage carrier. The catalyst has the advantages of high catalyst activity, good stability and low price in the hydrogen storage reaction of the organic hydrogen storage material. CN110841630A provides a hy