CN109289885B - Catalyst for gas-phase catalytic synthesis of perfluoroiodocarbon compound and preparation and application thereof - Google Patents
Catalyst for gas-phase catalytic synthesis of perfluoroiodocarbon compound and preparation and application thereof Download PDFInfo
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- CN109289885B CN109289885B CN201810976624.5A CN201810976624A CN109289885B CN 109289885 B CN109289885 B CN 109289885B CN 201810976624 A CN201810976624 A CN 201810976624A CN 109289885 B CN109289885 B CN 109289885B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 33
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 33
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 alkali metal salts Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RRNXYHYDSDAOFW-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C(F)(F)F RRNXYHYDSDAOFW-UHFFFAOYSA-N 0.000 description 2
- 229920004449 Halon® Polymers 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000483002 Euproctis similis Species 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SOEBNUZZZSSRNB-UHFFFAOYSA-N difluoro(diiodo)methane Chemical compound FC(F)(I)I SOEBNUZZZSSRNB-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a gas-phase photo-thermal catalytic synthesis perfluoroiodomethane catalyst, and a preparation method and application thereof. The catalyst consists of a carrier and an active component, wherein the carrier is one or a combination of more of tin oxide, titanium dioxide, zirconium dioxide or cadmium sulfide, and the active component comprises C coated on the surface of the carrier3N4And metal elements loaded on the surface of the carrier, wherein the metal elements consist of lanthanide and at least one alkali metal element, the mass ratio of the lanthanide to the alkali metal element is 1.0 (0.1-30), and C is the weight of the carrier in the catalyst3N4The loading is 0.5-30%, and the loading of lanthanide is 0.1-8.0%. The invention provides application of the catalyst in gas-phase photo-thermal catalytic synthesis of a perfluoroiodocarbon compound. The catalyst provided by the invention has good photocatalytic performance, can reduce reaction temperature, improve selectivity and inhibit carbon deposition generation so as to prolong the service life of the catalyst.
Description
Technical Field
The invention relates to a catalyst for synthesizing perfluoroiodocarbon compounds by gas-phase catalysis, and a preparation method and application thereof.
Background
CF3I is a high value-added halogenated alkane. In the field of fire extinguishing agents, the Halons fire extinguishing agent has the characteristics of good safety performance, high fire extinguishing efficiency, high economic effect and the like, and is one of ideal substitutes of Halons fire extinguishing agents; in the field of refrigerants, CF3The I molecule does not contain chlorine atoms and bromine atoms which consume ozone, ODP is 0, GWP is low, the I molecule is not easy to burn, and oil solubility and material compatibility are good. The C-I bond has low energy and is easy to decompose under the irradiation of heat or ultraviolet rays, thus being one of ideal substitutes of the traditional Freon refrigerant; in the field of organic synthesis, CF3The compound I contains CF 3. the compound is an important trifluoride reagent and is widely applied to the fields of pesticides, medicines, surfactants, dyes and the like. In addition, CF3The I has good application prospect in the fields of semiconductor etching agents, foaming agents and the like.
The synthesis method which has been proposed as the first time as having industrial prospect is the thermal decomposition method of perfluorocarboxylic acid salt [ ALBERT L H, WILLIAM G F].Journal of American Chemical Society,1950,72:3806–3807.]The starting material is CF3COOM (M ═ Ag, Na, K, Hg, Pb, Ba) and I2Wherein the thermal decomposition effect of the silver salt is optimal, and the thermal decomposition yield can reach more than 80%. Although the method has high yield, the cost is high, open fire heating is needed in the reaction process, solid reactants are easy to flush, and the production is unsafe. Later researchers replaced the silver salt with a relatively inexpensive potassium or sodium salt, but the results were not ideal and the yield was low, about 40%. 1967, Paskovich [ DONALD P, PETER G, GEORGE S H. Simplified method for the preparation of fluoroalkyldiols [ J].Journal ofOrganic Chemistry,1967,32(5):833–834.]Put forward in twoRefluxing methyl formamide (DMF) with potassium or sodium salt as reactant, CF3The yield of I can also reach 70 percent. Then some researchers at home and abroad grope solvents and reaction conditions, and find that the reaction route has poor repeatability and the reaction time is as long as 10 hours. Improvement of preparation method of trifluoroiodomethane [ J ] of Huantang et al (Schwan, Dial tsunami, national institute of pharmaceutical chemistry of liberty army)]Chemical reagent, 1989,11(2):123.]Some improvements are made to this by using sulfolane as solvent, at 170-180 ℃ and when the reaction time reaches 4h, CF3The yield of I reaches about 80 percent. Sulfolane has a higher boiling point than DMF, and can increase reaction rate by increasing reaction temperature, which is favorable for intermediate decomposition and CF3And I is generated, so that the reaction time is shortened. Although the method has the advantages of safe operation, short reaction time, high yield, recyclable solvent and the like, the cost is too high, and the method has no industrial significance.
In 1990, D.Naumann and W.Tyrra [ Naumann D, Tyrra W.polar trifluoromethyl reactions: the formation of bis- (trifluoromethyl) pyridine (III) complexes and trifluoromethyl cations and relations [ J.].Canadian Journal of Chemistry-Revue Canadienne de Chimie,1991,69(2):327-333.]Et al found to be CF3IX2(X：F，Cl，OCOCF3) And Cd (CF)3)2·D(D：CH3CN or diglyme) as raw material, acetonitrile and pyridine as solvent to synthesize I (CF)3)3And I (CF)3)2X, further decomposition of these two intermediates to CF3I。
Su[Su De Bao,Duan Jian Xing,Chen Qing Yun.A simple，novel method for the preparation of trifluoromethyliodide and diiododifluoromethane[J].Journal ofthe Chemical Society,Chemical Communications,1992,(11):807-808.]Iodine, KF and ClCF with the same molar ratio of 1:1:12CO2CH3Adding into a solution containing DMF and CuI, and reacting at 100-120 ℃ for about 3 hours to finally obtain CF3The yield of I reaches about 80 percent.
Albert et al [ Albert L H, William G F. the classification of silver trifluoroacetata to trifluoroiodomethane[J].Journal of America Chemical Societies,1950,72(8):3806-3807.]Using the Hunsdiecker (Hengsidick) reaction method to react CF3COOAg powder and excessive iodine simple substance are mixed together and heated to be decomposed, and finally CF is obtained3The yield of the crude product of I is more than 80 percent.
The above-mentioned methods for synthesizing trifluoroiodomethane are all batch reactions, and have the problems of expensive raw materials and difficult treatment of by-products, so that they are not an ideal process suitable for industrial scale-up.
Luchunshan recently disclosed a method for synthesizing perfluoroiodomethane [ CN105396604A ], using a supported catalyst consisting of a carrier and an active component supported on the carrier, wherein the carrier is a porous material, the active component comprises a phosphorus element and a metal element, and the metal element consists of a lanthanide element and at least one alkali metal element. The catalyst is applied to the reaction of synthesizing the perfluoroiodocarbon compound by gas-phase catalysis of the perfluoroalkane compound, and has higher catalytic activity. However, the gas phase catalysis process still has the defects of high temperature, serious carbon deposition, theoretical upper limit of yield and the like.
Aiming at the carbene formation mechanism and the disproportionation characteristic thereof in the gas phase catalysis process, the invention changes the carbene disproportionation process by adjusting the reaction environment, inhibits the generation of carbon deposition and breaks the upper limit of the yield in the prior art.
Disclosure of Invention
The invention aims to provide a supported catalyst for gas-phase catalytic synthesis of a perfluoroiodocarbon compound from a perfluoroalkane compound, which has good photocatalytic performance, can reduce reaction temperature, improve selectivity and inhibit carbon deposition so as to prolong the service life of the catalyst.
The second purpose of the invention is to provide a preparation method of the catalyst.
The third purpose of the invention is to provide the application of the catalyst in the catalytic synthesis of the perfluoroiodocarbon compound from the perfluoroalkane compound, so as to reduce the reaction temperature, improve the selectivity, inhibit the generation of carbon deposit and prolong the service life of the catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a catalyst for synthesizing perfluoroiodocarbon compounds by gas phase catalysis, which consists of a carrier and an active component, wherein the carrier is one or a combination of more of tin oxide, titanium dioxide, zirconium dioxide or cadmium sulfide, and the active component comprises C coated on the surface of the carrier3N4And metal elements loaded on the surface of the carrier, wherein the metal elements consist of lanthanide and at least one alkali metal element, the mass ratio of the lanthanide to the alkali metal element is 1.0 (0.1-30), and C is the weight of the carrier in the catalyst3N4Amount of load (i.e. C)3N4The mass percent of the lanthanide element and the carrier) is 0.5-30%, and the lanthanide element loading (i.e. the mass percent of the lanthanide element and the carrier) is 0.1-8.0%.
The lanthanide is one of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, preferably La, Ce and Sm.
Further, the alkali metal element is K, Rb or Cs.
Furthermore, the metal element is composed of a lanthanide element and an alkali metal element, and the mass ratio of the lanthanide element to the alkali metal element is preferably 1.0 (1.0-20.0).
Further, the metal element is composed of one lanthanide element and two alkali metal elements, and the mass ratio of the lanthanide element to the two alkali metal elements is preferably 1.0 (1.0-20.0) (the sum of the two alkali metal elements).
Further, in the catalyst, the lanthanide loading is preferably 0.1 to 6.5%, more preferably 0.5 to 6.5%, still more preferably 0.5 to 1%.
Further, in the catalyst, C3N4The loading is preferably 1.0 to 20%.
In another aspect, the present invention provides a preparation method of the catalyst, where the preparation method is:
(1) c is to be3N4Dissolved in sulfuric acid solutionCoating the obtained solution on the surface of a carrier, and then drying;
(2) loading soluble compounds containing metal elements on the carrier treated in the step (1) by adopting an impregnation method, taking the carrier to stand and dry after the impregnation is finished, and then roasting the carrier for 0.5 to 10 hours at the temperature of 200-750 ℃ in the inert or hydrogen atmosphere without oxygen and water to prepare the catalyst.
In the present invention, C3N4Can be prepared by a method reported in the literature, such as direct pyrolysis of precursors like dicyandiamide or urea in air [ Dong, f.; wu, l.; sun, y.; fu, m.; wu, z.; lee, s.c., effective synthesis of polymeric g-C3N4layered materials as novel effective light drive photosystems. journal of materials Chemistry 2011,21(39),15171.]。
Further, in the step (1), the concentration of the sulfuric acid solution is preferably 0.5 to 0.7M, preferably 0.5M. Invention for C3N4The feeding ratio of the sulfuric acid to the sulfuric acid is not particularly required, and the C/g is general3N435-75mL (preferably 50mL) of sulfuric acid solution is added. C3N4Dissolution in the sulfuric acid solution may be by means of heating, stirring, and the like. The drying condition after coating is vacuum state (-0.08 to-0.0 MPa), drying at 60-120 deg.C for 0.5-10 hr, preferably drying at 80-110 deg.C for 2-8 hr.
Further, the soluble compound containing a metal element refers to a nitrate, a halide, a carbonate, or an oxalate of the metal element.
Furthermore, the impregnation method can adopt co-impregnation or step impregnation, wherein in the co-impregnation method, a plurality of soluble compounds containing metal elements are dissolved to prepare a mixed solution, and then the soluble compounds containing the metal elements are loaded on the carrier together. When the stepwise impregnation is adopted, a plurality of soluble compounds containing metal elements are respectively prepared into solution and then are loaded on the carrier step by step. In the impregnation method of the present invention, equal volume impregnation is preferably adopted. The impregnation temperature is 15 to 80 ℃, preferably 20 to 80 ℃, more preferably 20 to 70 ℃.
Further, the standing time after completion of the impregnation is 0.5 to 12 hours, preferably 2 to 8 hours.
Furthermore, in the preparation method of the catalyst, the drying condition is that the catalyst is dried for 0.5 to 10 hours at the temperature of between 60 and 120 ℃ under the vacuum state (-0.08 to-0.0 MPa), and is preferably dried for 2 to 8 hours at the temperature of between 80 and 110 ℃.
Further, in the preparation method of the catalyst, the calcination process must be carried out in an inert or hydrogen atmosphere free of oxygen and water, and the calcination conditions are preferably as follows: roasting at 250-650 deg.c for 0.5-8 hr.
Further, the preparation method of the catalyst is specifically carried out according to the following steps:
(1) c is to be3N4Dissolving in sulfuric acid solution, coating the obtained solution on the surface of a carrier, and then drying;
(2) a lanthanide metal salt and one or two alkali metal salts are mixed according to the lanthanide series: the mass ratio of alkali metal elements is 1.0, (1.0-20.0) feeding and dissolving to prepare mixed aqueous solution, and soaking the mixed aqueous solution and a carrier in an equal volume at the temperature of 20-70 ℃, wherein the mass ratio of lanthanide to the carrier is 0.5-1.0: 100, then standing for 2-8 hours at the temperature, then drying in vacuum at 80-110 ℃ for 2-8 hours, and finally roasting at 250-650 ℃ for 0.5-8 hours in an inert or hydrogen atmosphere without oxygen and water to prepare the catalyst.
In a third aspect, the invention provides an application of the catalyst in gas-phase catalytic synthesis of a perfluoroiodocarbon compound, wherein the application process comprises the following steps:
controlling the temperature of a photocatalytic reactor loaded with a catalyst to be between 50 and 450 ℃, simultaneously introducing a perfluoroalkane compound and iodine vapor into the reactor under the irradiation of a light source with the wavelength range of 200-460nm, fully contacting and reacting with the catalyst under 1.0 to 1.5 atmospheric pressures, and absorbing, drying and separating the obtained tail gas by alkali liquor to obtain a corresponding perfluoroiodocarbon compound; the perfluoroalkane compound is selected from the group consisting of compounds of the formula CxF2x+1One or mixture of any several of H compounds, wherein the chemical formula of the perfluoroiodocarbon compound is CxF2x+1I, wherein x is 1-6.
Further, the wavelength range of the light source is preferably 250-350 nm.
Further, in the catalyst application, the perfluoroalkane compound is preferably CF3H or CF3CF2H or a mixture of both. The space velocity is not higher than 800h-1。
Furthermore, in the application of the catalyst, the mass ratio of the perfluoroalkane compound to the iodine vapor is 1.0 (0.5-2.0).
Further, the reactor may be a gas-solid phase reactor such as a fixed bed, a fluidized bed, etc.
Further, the perfluoroalkane compound and iodine vapor are irradiated through the photoreactor for not less than 5 seconds before being brought into contact with the catalyst.
Compared with the prior art, the invention has the following advantages:
1) c adopted in the invention3N4And various oxides such as tin oxide, titanium dioxide, zirconium dioxide or cadmium sulfide as carriers or mixtures thereof are good photocatalyst carriers, and can improve the photocatalytic efficiency. More importantly C3N4Can interact with the carrier to modulate the further photocatalysis performance.
2) The photocatalysis is introduced into the reaction of synthesizing the perfluoroiodocarbon compound by the perfluoroalkane compound, so that the perfluoroalkane compound is promoted to be excited to generate free radicals, the carbene disproportionation process is effectively inhibited, the upper limit of the prior art of the conversion rate is broken, the selectivity is improved, the carbon deposition is reduced, and the reaction temperature is reduced.
3) The catalyst of the invention has the advantages of convenient preparation, easy control of the conditions of the preparation process and good repeatability. And the photocatalysis is adopted, so that the method is green and environment-friendly, and meanwhile, no oxygen is added, so that the stability and the service life of the catalyst are improved.
4) The reaction selectivity of synthesizing the perfluoroiodocarbon compound by the perfluoroalkane compound under the catalysis of the catalyst can reach 77.2 percent at most, and the yield can reach 70.83 percent at most.
Detailed Description
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
Example 1-example 11
Weighing dicyandiamide or urea according to literature [ Dong, f.; wu, l.; sun, y.; fu, m.; wu, z.; lee, s.c., effective synthesis of polymeric g-C3N4layered materials as novel effective light drive photosystems. journal of materials Chemistry 2011,21(39),15171.]Reported methods Synthesis of C3N4Mixing C with3N4Adding the mixture into a 0.5M sulfuric acid solution, wherein the feeding ratio of the mixture to the sulfuric acid solution is 1 g: 50mL, heating in water bath at 80 ℃, stirring for dissolving, coating the obtained solution on the surface of the carrier, and drying at 85 ℃ for 12 hours under vacuum condition (-0.08 to-0.0 MPa). Then weighing one lanthanide metal salt and one/two soluble alkali metal salts, and dissolving to prepare the dipping water solution. After the catalyst is fully dissolved, the catalyst and the treated carrier are dipped in the same volume, then the catalyst is kept stand for a certain time at the temperature, and then the catalyst is dried in vacuum (-0.08 to-0.0 MPa), and finally the catalyst is roasted in inert atmosphere or hydrogen atmosphere to prepare the catalyst. The mass ratio of each element in the catalyst was measured by ICP. Specifically, the results are shown in Table 1.
Comparative example 1
Weighing and dissolving two alkali metal salts and a rare earth additive according to the mass ratio (15-20) of 1 to prepare a mixed aqueous solution, impregnating the mixed aqueous solution with a mixture of titanium dioxide and cadmium sulfide at a temperature of 20-70 ℃ in an equal volume, wherein the loading capacity of the rare earth element (namely the mass percentage of the rare earth element to a carrier) is 0.1-2.0 wt%, standing the mixture at the temperature for 12-24 hours, drying the mixture at a temperature of 80-110 ℃ in vacuum for 2-8 hours, and finally roasting the dried mixture at a temperature of 600 ℃ in an inert atmosphere without oxygen and water for 0.5-8 hours to prepare the supported catalyst. The mass ratio of each element in the catalyst was measured by ICP. Specifically, as shown in table 1:
example 12 example 18
In a gas-solid reactor such as a fixed bed reactor or a fluidized bed reactor, a perfluoroalkane compound or a mixture of several perfluoroalkane compounds,The iodine vapor is introduced into the reactor according to the mass ratio of 1.0:1.0, and the perfluoroalkane compound and the iodine vapor are irradiated by the photoreactor for not less than 5s before entering the catalyst bed layer. Setting the light wavelength at 250-350nm and the space velocity at not higher than 200-800h-1And fully contact-reacting with catalyst at 50-450 deg.C and 1.0-1.5 atmospheric pressure. Absorbing the tail gas by alkali liquor, drying and separating to obtain the perfluoroiodocarbon compound. The product was analyzed by agilent 7890A gas chromatography. Specifically, as shown in table 2.
Comparative example 2
In a gas-solid reactor such as a fixed bed reactor or a fluidized bed reactor and the like, a perfluoroalkane compound or a mixture of several perfluoroalkane compounds and iodine vapor are simultaneously introduced into the reactor according to the mass ratio of 1:0.75, and the space velocity is 200--1And fully contact-reacting with catalyst at 50-450 deg.C and 1.0-1.5 atmospheric pressure. Absorbing the tail gas by alkali liquor, drying and separating to obtain the perfluoroiodocarbon compound. The product was analyzed by agilent 7890A gas chromatography. Specifically, as shown in table 2:
Claims (12)
1. a catalyst for synthesizing perfluoroiodocarbon compound by gas-phase photo-thermal catalysis is composed of a carrier and an active component, wherein the carrier is one or more of tin oxide, titanium dioxide, zirconium dioxide or cadmium sulfide, and the active component is C coated on the surface of the carrier3N4And metal elements loaded on the surface of the carrier, wherein the metal elements comprise lanthanide and at least one alkali metal element, the mass ratio of the lanthanide to the alkali metal element is 1.0 (0.1-30), and in the catalyst, based on the mass of the carrier, C3N4The loading is 0.5-30%, and the loading of lanthanide is0.1-8.0%.
2. The catalyst for gas-phase photo-thermal catalytic synthesis of perfluoroiodocarbon compounds according to claim 1, wherein: the metal element consists of a lanthanide element and an alkali metal element, and the mass ratio of the lanthanide element to the alkali metal element is 1.0 (1.0-20.0).
3. The catalyst for gas-phase photo-thermal catalytic synthesis of perfluoroiodocarbon compounds according to claim 1, wherein: the metal element consists of one lanthanide element and two alkali metal elements, and the mass ratio of the lanthanide element to the two alkali metal elements is 1.0 (1.0-20.0).
4. The catalyst for gas-phase photothermal catalytic synthesis of a perfluoroiodocarbon compound according to any one of claims 1 to 3, wherein: the lanthanide is one of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; the alkali metal element is K, Rb or Cs.
5. The catalyst for gas-phase photothermal catalytic synthesis of a perfluoroiodocarbon compound according to any one of claims 1 to 3, wherein: in the catalyst, the load of lanthanide is 0.1-6.5%; c3N4The loading amount is 1.0-20%.
6. The catalyst for gas-phase photo-thermal catalytic synthesis of perfluoroiodocarbon compounds according to claim 5, wherein: in the catalyst, the load of lanthanide is 0.5-6.5%.
7. The catalyst for gas-phase photo-thermal catalytic synthesis of perfluoroiodocarbon compounds according to claim 5, wherein: in the catalyst, the load of lanthanide is 0.5-1%.
8. The preparation method of the catalyst for gas-phase photo-thermal catalytic synthesis of the perfluoroiodocarbon compound according to claim 1, which comprises the following steps:
(1) c is to be3N4Dissolving in sulfuric acid solution, coating the obtained solution on the surface of a carrier, and then drying;
(2) loading a soluble compound containing metal elements on the carrier treated in the step (1) by adopting an impregnation method, standing and drying the carrier after the impregnation is finished, and then roasting the carrier for 0.5 to 10 hours at the temperature of 200-750 ℃ in an inert or hydrogen atmosphere without oxygen and water to prepare the gas-phase photo-thermal catalytic synthesis perfluoroiodocarbon compound catalyst.
9. The method of claim 8, wherein: the preparation method specifically comprises the following steps:
(1) c is to be3N4Dissolving in sulfuric acid solution, coating the obtained solution on the surface of a carrier, and then drying;
(2) a lanthanide metal salt and one or two alkali metal salts are mixed according to the lanthanide series: the mass ratio of alkali metal elements is 1.0, (1.0-20.0) feeding and dissolving to prepare mixed aqueous solution, and soaking the mixed aqueous solution and a carrier at the temperature of 20-70 ℃ in an equal volume, wherein the mass ratio of lanthanide to the carrier is 0.5-6.5: 100, standing for 2-8 hours at the temperature, then drying for 2-8 hours at 80-110 ℃ in vacuum, and finally roasting for 0.5-8 hours at 250-650 ℃ in the inert or hydrogen atmosphere without oxygen and water to prepare the catalyst for synthesizing the perfluoroiodocarbon compound by gas-phase photo-thermal catalysis.
10. The use of the catalyst for gas-phase photothermal catalytic synthesis of perfluoroiodocarbon compound according to claim 1 in gas-phase photothermal catalytic synthesis of perfluoroiodocarbon compound, wherein the process comprises:
controlling the temperature of a photocatalytic reactor loaded with a catalyst to be between 50 and 450 ℃, simultaneously introducing a perfluoroalkane compound and iodine vapor into the reactor under the irradiation of a light source with the wavelength range of 200-460nm, fully contacting and reacting with the catalyst under 1.0 to 1.5 atmospheric pressures, and absorbing, drying and separating the obtained tail gas by alkali liquor to obtain a corresponding perfluoroiodocarbon compound; the perfluoroalkane compound is selected fromHas the self-chemical formula of CxF2x+1One or mixture of any several of H compounds, wherein the chemical formula of the perfluoroiodocarbon compound is CxF2x+1I, wherein x is 1-6.
11. The use of claim 10, wherein: the wavelength range of the light source is 250-350 nm.
12. The use of claim 10, wherein: the perfluoroalkane compound and iodine vapor are irradiated by a photoreactor for not less than 5s before contacting with the catalyst.
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| US4794200A (en) * | 1986-10-10 | 1988-12-27 | Rhone-Poulenc Chimie | Process for the preparation of trifluoromethyl iodide |
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