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CN-121988347-A - Composite solid acid catalyst and preparation method and application thereof

CN121988347ACN 121988347 ACN121988347 ACN 121988347ACN-121988347-A

Abstract

The invention relates to the technical field of carbon capture and discloses a composite solid acid catalyst and a preparation method and application thereof, wherein the composite solid acid catalyst comprises, by weight, 5-20 parts of CeO 2 -SiO 2 composite oxide, 20-40 parts of functionalized metal-organic framework material and 0.5-2 parts of rare earth metal oxide auxiliary agent. The composite solid acid catalyst organically combines the advantages of the three through specific material combination and structural design, so that the composite solid acid catalyst is adapted to a composite amine carbon capture system, the analysis energy consumption of a composite amine absorbent in the carbon capture process is obviously reduced, the desorption energy consumption is greatly reduced, the stability and the service life of the catalyst are improved, and meanwhile, the preparation method is simple and easy to operate in flow and is suitable for industrial production.

Inventors

  • SHEN RUIXU
  • WANG ZHENGRONG
  • WANG KAILIANG
  • WANG YANG
  • SU JUNHUA
  • HE JIA
  • WU CHONG
  • SUN LUCHANG

Assignees

  • 中国华电科工集团有限公司
  • 华电环保系统工程有限公司

Dates

Publication Date
20260508
Application Date
20251219

Claims (10)

  1. 1. The composite solid acid catalyst is characterized by comprising the following raw materials in parts by weight: 5-20 parts of CeO 2 -SiO 2 composite oxide, 20-40 parts of functionalized metal-organic frame material and 0.5-2 parts of rare earth metal oxide auxiliary agent.
  2. 2. The composite solid acid catalyst according to claim 1, comprising the following raw materials in parts by weight: 10 parts of CeO 2 -SiO 2 composite oxide, 30 parts of functionalized metal-organic framework material and 1 part of rare earth metal oxide auxiliary agent.
  3. 3. The composite solid acid catalyst according to claim 1 or 2, wherein the mass ratio of CeO 2 to SiO 2 in the CeO 2 -SiO 2 composite oxide is 1:1-2; And/or the functionalized metal-organic framework material is a sulfonic acid group modified metal-organic framework material; and/or the rare earth metal oxide auxiliary agent is selected from La 2 O 3 ; And/or the metal-organic framework material is selected from at least one of UiO-66, MIL-101 and MIL-53.
  4. 4. A method for preparing a composite solid acid catalyst according to any one of claims 1 to 3, comprising the steps of: mixing CeO 2 -SiO 2 composite oxide, functionalized metal-organic frame material and rare earth metal oxide auxiliary agent, pressing, forming and roasting to obtain the composite solid acid catalyst.
  5. 5. The method for preparing a composite solid acid catalyst according to claim 4, wherein the method for preparing the CeO 2 -SiO 2 composite oxide comprises the steps of: dissolving soluble salts of Ce and Si in water, regulating pH to be alkaline to obtain precipitate, and washing, drying and roasting to obtain CeO 2 -SiO 2 composite oxide; Optionally, the soluble salt of Ce is selected from at least one of Ce (NO 3 ) 3 ·6H 2 O、CeCl 3 ·7H 2 O、Ce 2 (SO 4 ) 3 , cerium acetate hydrate, (NH 4 ) 2 Ce(NO 3 ) 6 ); Optionally, the soluble salt of Si is selected from at least one of Na 2 SiO 3 ·9H 2 O、Na 2 SiO 3 、K 2 SiO 3 、(C 2 H 5 O) 4 Si; optionally, the mass ratio of the soluble salt of Ce to the soluble salt of Si is 1:1-2.
  6. 6. The method for preparing a composite solid acid catalyst according to claim 5, wherein in the method for preparing the CeO 2 -SiO 2 composite oxide, at least one of water, alcohol-water mixed solution and dilute ammonia water solution is used for washing, the drying temperature is 60-120 ℃, the drying time is 6-24 hours, the roasting temperature is 300-800 ℃, and the roasting time is 2-6 hours; And/or, said adjusting the pH to 9-10.
  7. 7. The method for preparing a composite solid acid catalyst according to claim 4, wherein the method for preparing the functionalized metal-organic framework material comprises the steps of: Mixing and stirring the metal-organic framework material and the organic ligand containing sulfonic acid groups in an organic solvent, filtering and drying to obtain a functionalized metal-organic framework material; optionally, the mass ratio of the sulfonic acid group-containing organic ligand to the metal-organic framework material is 1-5:1-20; optionally, the mixing and stirring temperature is 25-80 ℃, and the mixing and stirring time is 12-60 hours; optionally, the drying temperature is 60-120 ℃ and the drying time is 6-24 hours; Optionally, the organic ligand containing sulfonic acid group is selected from at least one of 2-sulfonic terephthalic acid, sulfosalicylic acid, aminobenzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonyl chloride and sulfobenzoic acid; Optionally, the organic solvent is N, N-dimethylformamide.
  8. 8. The method for preparing a composite solid acid catalyst according to claim 4, wherein in the method for preparing a composite solid acid catalyst, the mixing is performed by ball milling; Optionally, the ball milling rotating speed is 200-500 rpm, and the ball milling time is 2-6 hours; and/or in the preparation method of the composite solid acid catalyst, the roasting temperature is 300-800 ℃ and the roasting time is 1-3h.
  9. 9. Use of a composite solid acid catalyst according to any one of claims 1 to 3 or a composite solid acid catalyst prepared by the preparation method according to any one of claims 4 to 8 for desorbing carbon dioxide in an amine absorbent.
  10. 10. A method for regenerating an organic amine solution, which comprises the steps of adding a catalyst to an amine solution adsorbed with carbon dioxide for desorption and collecting the carbon dioxide, wherein the catalyst is the composite solid acid catalyst according to any one of claims 1 to 3 or the composite solid acid catalyst prepared by the preparation method according to any one of claims 4 to 8.

Description

Composite solid acid catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of carbon capture, in particular to a composite solid acid catalyst, and a preparation method and application thereof. Background With the increasing global interest in climate change, carbon capture, utilization and sequestration (CCUS) technologies have become a key strategy to achieve carbon emission reduction goals. Chemical absorption processes are dominant in the field of industrial carbon capture by virtue of their high absorptivity, with organic amine absorbents being most commonly used. However, the energy consumption of the desorption regeneration loop after the organic amine absorbs the carbon dioxide is extremely high, which greatly limits the large-scale popularization and application of the technology. To reduce desorption energy consumption, the prior art has attempted a number of approaches, including developing new absorber formulations, optimizing regeneration processes, introducing catalysts, and the like. In the aspect of catalysts, when the traditional composite amine absorbent desorbs carbon dioxide, high-temperature heating is needed, a large amount of heat energy is consumed, the operation cost is increased, oxidation and decomposition of the amine absorbent are easily caused, the service life of the catalyst is shortened, the absorbent is frequently replaced to further increase the cost burden, while the traditional solid acid catalyst such as zeolite molecular sieve has certain catalytic activity, but has the problems of limited specific surface area, uneven acid site distribution, easy poisoning and inactivation and the like, the requirements of high activity, high stability and good suitability for a composite amine absorbent system cannot be met, meanwhile, the catalytic efficiency of the traditional solid acid catalyst is low, the energy absorption consumption is difficult to effectively reduce, while some metal oxide catalysts such as CeO 2、SiO2 and CeO have certain oxidation and reduction performance, but the acid site is insufficient, the SiO 2 has high chemical stability, but the catalytic activity is insufficient when the catalyst is singly used, and the requirement of high-efficiency carbon capture is difficult to be met. Metal-organic frameworks (MOFs) materials have recently shown potential catalytic advantages in the field of gas adsorption separations due to their ultra-high specific surface area, regular pore structure and designable functionalized sites. However, MOFs materials have poor mechanical strength and poor hydrothermal stability, and cannot adapt to industrial complex working conditions when being independently used as carbon capture desorption catalysts, and are easy to damage and inactivate in actual industrial processes. Therefore, there is a need for a catalyst that can meet the requirements of low desorption energy consumption, high stability and high carbon capture efficiency at the same time. Disclosure of Invention The invention provides a composite solid acid catalyst and a preparation method and application thereof, and aims to solve the problem that the catalyst in the prior art cannot meet the requirements of low desorption energy consumption, high stability and high carbon capture efficiency. In a first aspect, the invention provides a composite solid acid catalyst, which comprises, by weight, 5-20 parts of CeO 2-SiO2 composite oxide, 20-40 parts of functionalized metal-organic framework material and 0.5-2 parts of rare earth metal oxide auxiliary agent. Further, the composite oxide comprises, by weight, 10 parts of CeO 2-SiO2 composite oxide, 30 parts of functionalized metal-organic framework material and 1 part of rare earth metal oxide auxiliary agent. Further, the mass ratio of CeO 2 to SiO 2 in the CeO 2-SiO2 composite oxide is 1:1-2. Further, the functionalized metal-organic framework material is a sulfonic acid group modified metal-organic framework material. Further, the rare earth metal oxide auxiliary agent is selected from La 2O3. Further, the metal-organic framework material is selected from at least one of UiO-66, MIL-101 and MIL-53. In a second aspect, the present invention provides a method for preparing the above composite solid acid catalyst, comprising the steps of: mixing CeO 2-SiO2 composite oxide, functionalized metal-organic frame material and rare earth metal oxide auxiliary agent, pressing, forming and roasting to obtain the composite solid acid catalyst. Further, the preparation method of the CeO 2-SiO2 composite oxide comprises the following steps: Dissolving soluble salts of Ce and Si in water, regulating pH to be alkaline to obtain precipitate, washing, drying and roasting to obtain CeO 2-SiO2 composite oxide. In some alternative embodiments, the soluble salt of Ce is selected from Ce (at least one of NO 3)3·6H2O、CeCl3·7H2O、Ce2(SO4)3, cerium acetate hydrate, (NH 4)2Ce(NO3)6). In s