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CN-121991311-A - Noble metal-COF composite material, and preparation method and application thereof

CN121991311ACN 121991311 ACN121991311 ACN 121991311ACN-121991311-A

Abstract

The invention relates to a noble metal-COF composite material, a preparation method and application thereof, wherein the composite material comprises a COF-1 carrier and noble metal, the noble metal is coordinately connected with carboxyl in the COF-1 carrier to form a structure with a structural formula shown as a formula (I), the noble metal is used as a connecting node to bridge the COF-1 carrier, R 1 and R 2 are respectively alkane chains, and M is noble metal. The noble metal-COF composite material prepared by the invention has the dual functions of low-temperature efficient adsorption and high-temperature catalytic oxidation, can be used for selectively capturing the organic amine at a low-temperature stage and efficiently and highly selectively catalyzing and oxidizing the organic amine into harmless products such as nitrogen at a high-temperature stage, thereby realizing the harmless and recycling of the organic amine.

Inventors

  • MAO JIANYONG
  • WANG DAN
  • Geng Yousheng
  • LI CONG
  • HU PENGXIANG
  • LI LING
  • WANG HUI

Assignees

  • 浙江新和成股份有限公司
  • 山东新和成精化科技有限公司

Dates

Publication Date
20260508
Application Date
20260129

Claims (10)

  1. 1. The precious metal-COF composite material is characterized by comprising a COF-1 carrier and precious metal, wherein the precious metal is coordinately connected with carboxyl in the COF-1 carrier to form a structure with a structural formula shown in a formula (I), and the precious metal is used as a connecting node to bridge the COF-1 carrier; , Wherein R 1 and R 2 are respectively alkane chains, and M is noble metal.
  2. 2. The precious metal-COF composite according to claim 1, wherein the precious metal is present in the composite in a mass fraction of 0.8wt.% to 1.1wt.%.
  3. 3. The noble metal-COF composite of claim 1, wherein R 1 =(CH 2 ) n , n = 2-5; And/or R 2 =(CH 2 ) m , m=1 to 10; and/or M is at least one of Pd, pt or Ru.
  4. 4. A method for preparing the noble metal-COF composite material according to any one of claims 1 to 3, comprising the steps of: The structure is that The first compound with the structural formula of X-R 2 -COOH is subjected to substitution reaction with a second compound with the structural formula of X being halogen to generate a third compound shown as a formula (II), Wherein, R 1 and R 2 are both alkane chains; the third compound and noble metal salt undergo coordination reaction to obtain a metal complex shown in a formula (III), Wherein x is an integer; the metal complex and 1,3, 5-tri (4-cyano-methyl benzene) benzene are subjected to synthesis reaction to generate the noble metal-COF composite material.
  5. 5. The method for preparing a noble metal-COF composite according to claim 4, wherein the molar ratio of the first compound to the second compound is 1:3.05 to 1:4.40; and/or the molar ratio of the third compound to the 1,3, 5-tri (4-cyanomethylphenyl) benzene is 2.5:2-3.6:2.
  6. 6. The method of preparing a noble metal-COF composite according to claim 4, wherein the first compound is selected from the group consisting of 、 Or (b) At least one of (a) and (b); And/or the second compound is at least one selected from chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid, 5-chlorovaleric acid or 8-chlorooctanoic acid; And/or the noble metal salt is selected from at least one of palladium salt, platinum salt or ruthenium salt; And/or, a catalyst is also added when the first compound and the second compound are subjected to substitution reaction, and the catalyst is at least one of triethylamine, pyridine or cyclohexylamine; And/or the temperature of the substitution reaction of the first compound and the second compound is 70-110 ℃ and the time is 12-24 hours; and/or the temperature of the coordination reaction between the third compound and the noble metal salt is 20-150 ℃ and the time is 24-72 h; and/or the temperature of the synthesis reaction of the metal complex and the 1,3, 5-tri (4-cyanomethyl benzene) is 50-180 ℃ and the time is 24-48 h.
  7. 7. Use of the noble metal-COF composite material according to any one of claims 1 to 3 for catalytic oxidation of organic amines.
  8. 8. A method for purifying a gas stream containing an organic amine, comprising the steps of: Feeding a gas stream containing an organic amine into a device filled with the noble metal-COF composite material according to any one of claims 1 to 3 for adsorption operation; And after the adsorption operation is finished, introducing oxygen-containing gas into the device to perform catalytic oxidation reaction.
  9. 9. The method of purifying an organic amine-containing gas stream according to claim 8, wherein the organic amine-containing gas stream is selected from the group consisting of an organic amine-containing hydrogen chloride gas stream; and/or the temperature of the adsorption operation is 10-40 ℃ and the pressure is 0.3-0.5 MPa; and/or the temperature of the catalytic oxidation reaction is 100-200 ℃ and the pressure is 1.0-2.0 MPa; And/or, the purification treatment method adopts at least two devices to operate in parallel, in the operation process, the gas flow containing the organic amine is controlled to enter the device in adsorption operation, meanwhile, the gas containing oxygen is controlled to enter the device in catalytic oxidation reaction, and the continuous purification of the gas flow containing the organic amine is realized by periodically switching the operation states of the devices.
  10. 10. A process for producing isocyanates by the phosgene method, characterized in that the process further comprises a purification treatment of the gas stream containing organic amines according to claim 8 or 9.

Description

Noble metal-COF composite material, and preparation method and application thereof Technical Field The invention relates to the technical field of organic amine treatment, in particular to a precious metal-COF composite material, a preparation method and application thereof. Background Chlorine is an important raw material for chloridizing industry and is widely applied to the industries of chemical industry, electronic industry, medical industry, textile, petrochemical industry, environmental protection and the like. However, in industrial processes for producing various chlorine products, the chlorine utilization is generally lower than 50%, and hydrogen chloride as a byproduct is generated, which has strong corrosiveness, high transportation cost, strong market regionality, low price and small demand, and causes long-term supply and demand, and if the excessive hydrogen chloride is treated by adopting an alkali neutralization mode, not only resources are wasted, but also environmental pollution is caused. Therefore, technologies such as a direct oxidation method, an electrolytic method, a catalytic oxidation method and the like are gradually developed in industry to convert hydrogen chloride into chlorine so as to realize the recycling of byproduct hydrogen chloride. In the hydrogen chloride catalytic oxidation process, raw hydrogen chloride is usually derived from byproduct gas of an upstream chemical process, and various impurities are often included in the raw hydrogen chloride. For example, the isocyanate is produced by a phosgene method, and the byproduct hydrogen chloride gas often contains organic amine impurities. On the one hand, the organic amine is easy to combine with hydrogen chloride to form organic amine hydrochloride, and after entering a catalytic oxidation system, the organic amine can further react under the chlorine-rich condition to generate nitrogen trichloride with explosion hazard, so that serious potential safety hazard is brought to the production process. On the other hand, during catalytic oxidation, organic amines may be converted to carbon dioxide, water and nitrogen oxides (NO x) by the action of a catalyst. However, NO x is an important atmospheric contaminant itself, which promotes photochemical smog formation, exacerbates global climate warming, affects secondary aerosol generation, and creates multiple hazards to human health. Therefore, development of a high-efficiency catalyst is urgently needed, not only excellent catalytic oxidation activity is needed, organic amine can be thoroughly degraded, but also directional conversion of nitrogen element in amine molecules to environment-friendly nitrogen (N 2) is needed, and harmful NO x is not generated, so that recycling of hydrogen chloride resources is achieved, and meanwhile negative influences on environment and health are reduced to the greatest extent. From literature reports, the supported noble metal catalyst has better catalytic activity, but in the traditional supported noble metal catalyst, the noble metal loading is higher, usually more than 3% is needed, and the reaction condition is more severe. For example, the RuPd/CeO 2 catalyst prepared by the impregnation method has good catalytic performance only under the reaction conditions of 200 ℃ and 2.0MPa, and the total load of Ru and Pd is up to 5% (Topics in catalysis 2005.33:77-96), and the Pd/C catalyst can remove 80% of ammonia nitrogen at 150 ℃ and 2.0MPa, but the noble metal Pd content of the catalyst also reaches 3% (APPLIED CATALYSIS benvironmental,1998,16 (3): 261-268). In addition, patent CN106669668A discloses a catalyst for catalyzing combustion to remove amine organic matters, which has low ignition temperature and high activity, can catalyze the amine organic matters to generate N 2、CO2 and H 2 O with high selectivity, remarkably inhibit NO x from generating, avoid secondary pollution, but can not directionally adsorb the organic amine gas, has low treatment efficiency, and patent CN111604058A discloses a dual-functional catalyst which comprises an oxidation catalyst and a nitrogen oxide reduction catalyst, can realize efficient catalytic oxidation of volatile organic amine, and simultaneously effectively avoid the formation of NO x, but the reaction temperature is more than 240 ℃, and has high energy consumption. Patent CN114682296a discloses a catalyst synthesized by adopting a honeycomb matrix and a ZSM-5 multistage molecular sieve to load active components, which can selectively decompose organic amine into CO 2、H2 O and NH 3, avoid generating NO x, and realize ammonia recovery at the same time, but the purity of NH 3 generated by catalysis is lower, further purification treatment is required, and the process complexity and treatment cost are increased. Patent CN118440266a provides a heterogeneous catalyst formed by complexing a chiral covalent organic framework compound and Pd metal, which can show high catalytic efficiency in Aldol condensati