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CN-121988399-A - Fluorine ion enriched metal organic framework catalyst, preparation method and application thereof

CN121988399ACN 121988399 ACN121988399 ACN 121988399ACN-121988399-A

Abstract

The invention discloses a fluoride ion enriched metal organic framework catalyst, which comprises metal ions, an organic ligand and fluoride ions, wherein the metal ions are at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, lutetium, yttrium and zirconium, and the organic ligand is an aromatic compound containing carboxylic acid groups. The fluoride ion enriched metal organic framework catalyst is applied to the addition reaction of acyl fluoride compounds and hexafluoropropylene for preparing perfluoroketone compounds, and has the advantages of low production cost, less three wastes, capability of realizing gas phase continuous reaction and the like.

Inventors

  • MAO CHONGZHI
  • CHEN WEI
  • NI HANG
  • JIANG QIANG
  • YANG WANGSONG
  • ZHAN SHUHUI

Assignees

  • 浙江省化工研究院有限公司
  • 中化蓝天集团有限公司

Dates

Publication Date
20260508
Application Date
20241105

Claims (10)

  1. 1. A fluoride ion enriched metal organic framework catalyst is characterized in that the catalyst comprises metal ions, organic ligands and fluoride ions, The metal ion is at least one selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, lutetium, yttrium and zirconium, The organic ligand is an aromatic compound containing carboxylic acid groups.
  2. 2. The fluoride ion-enriched metal organic framework catalyst of claim 1, wherein the fluoride ion content is 1-10 mmol/gcat.
  3. 3. The fluoride ion-enriched metal organic framework catalyst of claim 2, wherein the organic ligand is at least one selected from the group consisting of trimesic acid, terephthalic acid, and 2-amino terephthalic acid.
  4. 4. The fluoride ion-enriched metal organic framework catalyst of any one of claims 1 to 3, wherein the specific surface area of the catalyst is 1000-4000 m 2 /g, the pore volume is 0.2-0.7 cm 3 /g, and the average pore diameter is 1-3 nm.
  5. 5. A process for preparing a fluoride ion-enriched metal organic framework catalyst as claimed in any one of claims 1 to 4, characterized in that the process comprises the steps of: s1, dissolving the organic ligand in a mixed solution of N, N-dimethylformamide and formic acid to obtain a solution A1 with the concentration of 0.05-0.2 mol/L; S2, dissolving the nitrate of the metal ion in water to obtain a solution A2 with the concentration of 0.5-1.0 mol/L; S3, mixing the solution A1 and the solution A2, heating to 100-150 ℃ and reacting for 12-24 hours, separating out solid after the reaction is finished, and washing with N, N-dimethylformamide to obtain solid A3; And S4, soaking the solid A3 in a fluoride salt aqueous solution for 24-48 hours, separating, drying and activating the obtained solid at 100-300 ℃ in a nitrogen atmosphere for 6-12 hours, and activating the solid in a hydrogen fluoride atmosphere for 1-6 hours.
  6. 6. The method for preparing a fluoride ion-enriched metal organic framework catalyst according to claim 5, wherein the molar ratio of the nitrate of the metal ion to the organic ligand is 1-3:1; The nitrate of the metal ion is at least one selected from lanthanum nitrate hexahydrate, cerium nitrate, praseodymium nitrate hexahydrate, neodymium nitrate pentahydrate, samarium nitrate hexahydrate, europium nitrate pentahydrate, gadolinium nitrate hexahydrate, dysprosium nitrate pentahydrate, holmium nitrate pentahydrate, erbium nitrate hexahydrate, ytterbium nitrate pentahydrate, lutetium nitrate hexahydrate, yttrium nitrate hexahydrate and zirconium nitrate pentahydrate; The fluoride salt is at least one selected from ammonium fluoride, lithium fluoride, sodium fluoride, rubidium fluoride and cesium fluoride.
  7. 7. The application of the fluoride ion-enriched metal organic framework catalyst in addition reaction is characterized in that the catalyst is used for preparing a perfluoroketone compound with a structure shown in a formula (B) by the addition reaction of acyl fluoride compounds with a structure shown in a formula (A) and hexafluoropropylene, In the formula (A) and the formula (B), R is a perfluoroalkyl group.
  8. 8. The application of the fluoride ion-enriched metal organic framework catalyst according to claim 7, wherein the molar ratio of the acyl fluoride compound to hexafluoropropylene is 0.5-2.0:1.
  9. 9. The application of the fluoride ion-enriched metal organic framework catalyst in addition reaction, which is characterized in that the reaction temperature of the addition reaction is 100-300 ℃, the reaction pressure is 0-1 bar, and the reaction space velocity is 50-500 h -1 .
  10. 10. The use of a fluoride-enriched metal organic framework catalyst of claim 7 in an addition reaction, wherein: when the acyl fluoride compound is trifluoroacetyl fluoride, the perfluoro ketone compound is 1,3, 4-heptafluoro-3- (trifluoromethyl) -2-butanone; When the acyl fluoride compound is pentafluoropropionyl fluoride, the perfluoro ketone compound is 1,2, 4, 5-nonafluoro-4- (trifluoromethyl) -3-pentanone; When the acyl fluoride compound is heptafluoro isobutyryl fluoride, the perfluoro ketone compound is 1,2,4, 5-octafluoro-2, 4-bis (trifluoromethyl) -3-pentanone; When the acyl fluoride compound is heptafluoro-n-butyryl fluoride, the perfluoro ketone compound is 1,1,1,2,4,4,5,5,6,6,6-undecane fluoro-2- (trifluoromethyl) -3-hexanone; When the acyl fluoride compound is nonafluoro-n-pentanoyl fluoride, the perfluoro ketone compound is 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecyl-fluoro-2- (trifluoromethyl) -3-heptanone; When the acyl fluoride compound is 2,3, 4-hexafluoro-3- (trifluoromethyl) butyryl fluoride, the perfluoro ketone compound is 1,1,1,2,4,4,5,6,6,6-decafluoro-2, 5-bis (trifluoromethyl) -3-hexanone; When the acyl fluoride compound is 2,3, 4-hexafluoro-2- (trifluoromethyl) butyryl fluoride, the perfluoro ketone compound is 1,1,1,2,4,5,5,6,6,6-decafluoro-2, 4-bis (trifluoromethyl) -3-hexanone; When the acyl fluoride is 3, 3-trifluoro-2-bis (trifluoromethyl) propionyl fluoride, the perfluoro ketone compound is 1,2, 5-heptafluoro-2, 4-tri (trifluoromethyl) -3-pentanone.

Description

Fluorine ion enriched metal organic framework catalyst, preparation method and application thereof Technical Field The invention relates to the field of catalysts, in particular to a fluoride ion-enriched metal organic framework catalyst, a preparation method thereof and application of the fluoride ion-enriched metal organic framework catalyst in catalytic addition reaction of acyl fluoride compounds and hexafluoropropylene for preparing perfluoroketone. Background The perfluoroketone compound is an important fluorine-containing compound, has wide application, and can be used for fire extinguishing agents, semiconductor cleaning agents, insulating gases and the like. U.S. Pat. No. 3, 6403149 discloses a process for the preparation of fluorinated ketones containing a total number of 5 to 10 carbon atoms and the application scenario. Anhydrous potassium fluoride is used as a catalyst, anhydrous diglyme is used as a solvent, and acyl fluoride and hexafluoropropylene are introduced into a high-pressure reaction kettle for reaction to prepare the perfluoroketone. In particular, the patent also discloses a treatment method of hexafluoropropylene dimer and hexafluoropropylene trimer as reaction byproducts, wherein acetic acid and potassium permanganate are added for digestion, and the final perfluoroketone reaction yield is 88.3%. Similarly, the world patent WO 2007077174 uses DMF as a solvent, and the yield of trifluoromethyl perfluoro isopropyl ketone prepared by adding trifluoro acetyl fluoride and hexafluoropropylene is 70-84%. Chinese patent CN108440261 discloses a method for preparing perfluoroketone by kettle reaction, wherein in an organic solvent, in the presence of a catalyst metal fluoride and a cosolvent, the perfluoroolefin and acyl fluoride undergo addition reaction to obtain perfluoroketone, the metal fluoride is one or more of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, chromium fluoride, nickel fluoride, zinc fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride and ferric fluoride, and the cosolvent is 15-crown ether-6 or 15-crown ether-5. The kettle type reaction method has the advantages of high reaction pressure, complex feeding operation, long reaction time and low reaction selectivity, raw material hexafluoropropylene is extremely easy to self-polymerize into hexafluoropropylene dimer or hexafluoropropylene trimer under the action of a catalyst, the catalyst and the cosolvent are difficult to separate and easy to poison, the catalytic cost is high, and the industrialized mass production is not facilitated. Chinese patent CN109336751a discloses a method for preparing perfluoroketone by gas phase addition reaction of perfluoroolefin with general formula of R 1R2C＝CR3R4 and acyl fluoride R 5 -COF in the presence of addition catalyst to obtain perfluoroketone with general formula of CFR 3R4-CR1R2-C(O)R5 or CFR 3R4-CR1R2-C(O)-CR1R2-CFR3R4, wherein general formulas of R 1、R2、R3 and R 4 are CnF 2n+1, n is a non-negative integer, general formula of R 5 is CmF2 m+ 1, m is a non-negative integer, the addition catalyst comprises active component and carrier, the active component is at least one of lithium fluoride, potassium fluoride, sodium fluoride, rubidium fluoride or cesium fluoride, the carrier is one of aluminum fluoride, magnesium fluoride, ferric fluoride, chromium fluoride, zinc fluoride, calcium fluoride, strontium fluoride and barium fluoride, and the mass percentage of the active component and the carrier is 0-20% 80-100%. The reaction conversion rate and the selectivity can reach more than 99 percent. The gas-phase catalytic addition reaction has the defects of low catalyst life, poor reproducibility of reaction results and the like, and is not suitable for industrial scale-up production although the reaction conversion rate and the selectivity are high. Disclosure of Invention In order to solve the technical problems, the invention provides a fluoride ion enriched metal organic framework catalyst which is applied to the catalytic addition reaction of acyl fluoride compounds and hexafluoropropylene for preparing perfluoroketone, has the advantages of low cost, less three wastes, high catalytic activity, good product selectivity, good reaction reproducibility and long service life, and is suitable for industrial continuous production. The invention aims at realizing the following technical scheme: The invention provides a fluoride ion enriched metal organic framework catalyst, which comprises metal ions, organic ligands and fluoride ions, The metal ion is at least one selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, lutetium, yttrium and zirconium, The organic ligand is an aromatic compound containing carboxylic acid groups. Further, the content of the fluoride ions is 1-10 mmol/gcat. Organic ligands the organic ligands useful in the art of the present