CN-121972208-A - Cobalt-indium-carbon catalyst suitable for methanol liquid phase reforming hydrogen production and aromatic hydrocarbon hydrogenation, and preparation method and application thereof

CN121972208ACN 121972208 ACN121972208 ACN 121972208ACN-121972208-A

Abstract

The invention provides a cobalt-indium-carbon catalyst suitable for methanol liquid phase reforming hydrogen production and aromatic hydrocarbon hydrogenation, and a preparation method and application thereof, and belongs to the technical field of metal carbide catalyst preparation. The preparation method of the cobalt-indium-carbon catalyst comprises the steps of adding a cobalt source, an indium source, an amino acid coordination additive and a nitrogen-rich carrier into a solvent containing organic amine, placing the obtained mixed solution into a reaction kettle, performing hydrothermal reaction at a solvent filling rate of 20-40%, filtering, washing and drying after the reaction is finished to obtain a nitrogen-anchored metal precursor/carrier intermediate, and performing high-temperature carbonization on the obtained nitrogen-anchored metal precursor/carrier intermediate to obtain the cobalt-indium-carbon catalyst. According to the invention, an amino acid coordination additive is introduced by a nitrogen anchored pre-carbonization-synthesis gas controlled carbonization two-step sequential method to construct a coordination complex-nitrogen anchored dual-anchor system, and the prepared cobalt-indium-carbon bimetallic carbide catalyst can be simultaneously used for hydrogen production by methanol liquid phase reforming and ethylene tar naphthalene hydrogenation reaction.

Inventors

Jia Ankang
CHEN KUN
HOU YUNHUI
FENG LIXIN
LIU HAIBO
XIA WEI

Assignees

中国石油大学(华东)

Dates

Publication Date: 20260505
Application Date: 20260409

Claims (10)

1. The preparation method of the cobalt-indium-carbon catalyst suitable for the hydrogen production by methanol liquid phase reforming and the aromatic hydrocarbon hydrogenation is characterized by comprising the following steps: (1) Adding a cobalt source, an indium source, an amino acid coordination additive and a nitrogen-rich carrier into a solvent containing organic amine, placing the obtained mixed solution into a reaction kettle, carrying out hydrothermal reaction under the solvent filling rate of 20-40%, filtering, washing and drying after the reaction is finished to obtain a nitrogen-anchored metal precursor/carrier intermediate, wherein the molar ratio of cobalt element in the cobalt source to indium element in the indium source is 3:1, the amino acid coordination additive is glycine or histidine, the ratio of the total molar number of cobalt element in the cobalt source to indium element in the indium source to the molar number of the amino acid coordination additive is 1:0.5-2, the nitrogen-rich carrier is g-C 3 N 4 , the mass of cobalt element in the cobalt source is 0.1-2.5% of the mass of the nitrogen-rich carrier, the organic amine is urea or ethylenediamine, the solvent is N, N-dimethylformamide, methanol or acetone, and the concentration of the organic amine in the solvent containing organic amine is 0.01-0.01 mol/L; (2) And (2) carbonizing the nitrogen anchored metal precursor/carrier intermediate obtained in the step (1) at a high temperature to obtain a cobalt-indium-carbon catalyst suitable for hydrogen production by methanol liquid phase reforming and aromatic hydrocarbon hydrogenation, wherein the high temperature carbonization is carried out in a CO/H 2 /Ar mixed gas, the volume percentage of CO in the CO/H 2 /Ar mixed gas is 3-10%, the volume percentage of H 2 is 10-30%, the high temperature carbonization temperature is 380-420 ℃, and the high temperature carbonization time is 30-90min.
2. The method for preparing the cobalt-indium-carbon catalyst suitable for the hydrogen production and the aromatic hydrocarbon hydrogenation by the methanol liquid phase reforming according to claim 1, wherein in the step (1), the cobalt source is cobalt octacarbonyl or cobalt nitrate, and the indium source is InCl 3 or indium nitrate.
3. The method for preparing the cobalt-indium-carbon catalyst suitable for the hydrogen production and the aromatic hydrocarbon hydrogenation by the methanol liquid phase reforming according to claim 1, wherein the preparation method is characterized in that the g-C 3 N 4 in the step (1) is prepared by weighing melamine, placing the melamine in a crucible with a cover, placing the crucible in a muffle furnace, raising the temperature to 140-160 ℃ at a temperature raising rate of 1-5 ℃ per minute, preserving heat for 20-40 minutes, raising the temperature to 500-600 ℃ at a temperature raising rate of 0.5-2 ℃ per minute, preserving heat for 100-150 minutes, naturally cooling to room temperature, and grinding the crucible through a 200-mesh screen to obtain the g-C 3 N 4 carrier.
4. The method for preparing cobalt indium carbon catalyst for use in liquid phase reforming of methanol to produce hydrogen and aromatic hydrocarbon according to claim 1, wherein the ratio of the total mass of cobalt source, indium source, amino acid coordination additive and nitrogen-rich carrier to the volume of organic amine-containing solvent in step (1) is 1mg:0.2-0.5mL.
5. The method for preparing cobalt indium carbon catalyst for hydrogen production and aromatic hydrocarbon hydrogenation by methanol liquid phase reforming according to claim 1, wherein the temperature of the hydrothermal reaction in step (1) is 210-240 ℃, and the time of the hydrothermal reaction is 4-12h.
6. The method for preparing cobalt indium carbon catalyst suitable for hydrogen production and aromatic hydrocarbon hydrogenation by methanol liquid phase reforming according to claim 1, wherein the washing in step (1) is carried out 2-4 times by using absolute ethanol, and the drying is carried out at 50-60 ℃ to constant weight.
7. The method for preparing cobalt indium carbon catalyst for hydrogen production and aromatic hydrocarbon hydrogenation by methanol liquid phase reforming according to claim 1, wherein the flow rate of the CO/H 2 /Ar mixed gas in step (2) is 20-40mL/min.
8. The method for preparing cobalt indium carbon catalyst for hydrogen production and aromatic hydrocarbon hydrogenation by methanol liquid phase reforming according to claim 1, wherein the heating rate in step (2) is 2-6 ℃ per min.
9. A cobalt indium carbon catalyst suitable for methanol liquid phase reforming hydrogen production and aromatic hydrocarbon hydrogenation, which is characterized in that the cobalt indium carbon catalyst is prepared by the preparation method of any one of claims 1-8.
10. The use of cobalt indium carbon catalyst for the liquid phase reforming of methanol to produce hydrogen and aromatics hydrogenation according to claim 9, for catalyzing the liquid phase reforming of methanol to produce hydrogen or ethylene tar naphthalene hydrogenation.

Description

Cobalt-indium-carbon catalyst suitable for methanol liquid phase reforming hydrogen production and aromatic hydrocarbon hydrogenation, and preparation method and application thereof Technical Field The invention relates to a cobalt-indium-carbon catalyst suitable for methanol liquid phase reforming hydrogen production and aromatic hydrocarbon hydrogenation, and a preparation method and application thereof, and belongs to the technical field of metal carbide catalyst preparation. Background The petrochemical industry faces the dual requirements of energy supply optimization and heavy oil resource utilization, and the two key directions of ethylene tar naphthalene hydrofining and methanol liquid phase reforming on-site hydrogen production are strict industrial requirements on the high efficiency and stability of the catalyst. The traditional intermetallic carbide catalyst is limited by the difficult precise regulation and control of the structure and the insufficient industrial circulation stability, and the preparation methods such as a one-step method, an impregnation method and the like can not control the microscopic crystal form and the metal dispersity, so that the catalyst has low activity in methanol hydrogen production, fast attenuation of the circulation performance, low conversion rate in naphthalene hydrogenation, weak applicability of aromatic hydrocarbon substrates and difficulty in meeting the petrochemical large-scale production requirement. Meanwhile, the existing preparation process realizes the anchoring of the metal precursor by only relying on carrier nitrogen sites or solvents, is easy to cause the problems of agglomeration and uneven dispersion in the hydrothermal nucleation process of metal ions, and is difficult to realize the molecular dispersion of the metal precursor even through the regulation and control of the filling rate of the low solvents, thereby limiting the exposure quantity and the structural stability of the active sites of the catalyst. For example, chinese patent document CN111545199a provides a supported platinum-tin bimetallic catalyst, first, pt 3 Sn nanoparticles are prepared by a solvothermal synthesis method, naOH is added for corrosion, then PtSn-c nanoparticles are supported on a CeO 2 carrier by an adsorption method, and then, the PtSn-c/CeO 2 catalyst is formed by calcination. However, this method of synthesizing a mediated macromolecular polymer (e.g., PVP) with a strongly basic reagent has significant drawbacks, not only in that it can easily lead to interfacial impurity residues and complicated purification procedures, but also in that its stepwise asynchronous strategy of "pre-nucleation followed by interfacial immobilization" greatly increases the thermodynamic propensity of nanocrystals to undergo secondary agglomeration, leading to limited dispersion of the active phase and weak metal-carrier interactions (MSI). More serious, the harsh strong alkaline medium is extremely liable to cause excessive stripping and erosion of the preset bimetallic lattice, thereby weakening or even thoroughly destroying the precise sequence of the core catalytic sites. Therefore, the research and development of the catalyst which has high activity, high stability and wide substrate applicability and can be simultaneously adapted to the hydrogenation reaction of the methanol liquid phase reforming hydrogen production and the ethylene tar naphthalene has important significance. Disclosure of Invention Aiming at the defects of the prior art, in particular to the problems of uneven dispersion of a metal precursor, insufficient exposure of an active site and to-be-improved catalyst stability in the traditional process, the invention provides a cobalt-indium-carbon catalyst suitable for hydrogen production by methanol liquid phase reforming and arene hydrogenation, and a preparation method and application thereof. According to the invention, through a two-step sequential method of nitrogen anchoring pre-carbonization-synthesis gas controllable carbonization, an amino acid coordination additive is innovatively introduced to construct a coordination complex-nitrogen anchoring double-anchoring system, and the prepared cobalt indium carbon bimetallic carbide catalyst can be simultaneously used for the hydrogen production by methanol liquid phase reforming and the hydrogenation reaction of ethylene tar naphthalene, has high activity, high stability and wide substrate applicability, and has high metal resource utilization rate and obvious economic and industrial application values. The technical scheme of the invention is as follows: the preparation method of the cobalt-indium-carbon catalyst suitable for the hydrogen production by methanol liquid phase reforming and the aromatic hydrocarbon hydrogenation comprises the following steps: (1) Adding a cobalt source, an indium source, an amino acid coordination additive and a nitrogen-rich carrier into a solvent containing organic amine,