CN115779935A - Preparation method and application of fluorine-doped composite sulfate catalyst - Google Patents
Preparation method and application of fluorine-doped composite sulfate catalyst Download PDFInfo
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- CN115779935A CN115779935A CN202211504346.6A CN202211504346A CN115779935A CN 115779935 A CN115779935 A CN 115779935A CN 202211504346 A CN202211504346 A CN 202211504346A CN 115779935 A CN115779935 A CN 115779935A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 27
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- -1 polychlorotrifluoroethylene Polymers 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 10
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 abstract description 8
- 235000019404 dichlorodifluoromethane Nutrition 0.000 abstract description 8
- 238000005660 chlorination reaction Methods 0.000 abstract description 7
- 229960001701 chloroform Drugs 0.000 description 12
- 238000007323 disproportionation reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RZSJYVBYLBNFGQ-UHFFFAOYSA-N difluoromethane hydrochloride Chemical compound FCF.Cl RZSJYVBYLBNFGQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a fluorine-doped composite sulfate catalyst, wherein the preparation method comprises the following steps: A1. dissolving sulfate, nitrate and fluorine-containing polymer in a solvent, and stirring at 50-90 ℃ to form gel; A2. and drying and roasting the gel to obtain the fluorine-doped composite sulfate catalyst. The fluorine-doped composite sulfate catalyst can be used for fluorine-chlorine exchange reaction of trifluoromethane and chloroform, and has the advantages of high selectivity, good stability, strong chlorination resistance, great reduction of generation of a byproduct difluorodichloromethane and the like.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a preparation method of a fluorine-doped composite sulfate catalyst and application of the fluorine-doped composite sulfate catalyst in fluorine-chlorine exchange reaction.
Background
Trifluoromethane (CHF) 3 HFC-23) is the industrial production of difluoromethane monochloride (CHClF) 2 And HFC-22), the potential value of the greenhouse effect is about 14800 times of that of carbon dioxide, and is the gas with the second highest greenhouse effect in all greenhouse gases, and the current industry mainly adopts high-temperature incineration (over 1200 ℃) for treatment, but the incineration treatment cost is higher, and the resource waste exists. Therefore, the method has great significance for resource conversion of the trifluoromethane.
Patent CN109772377a discloses a catalyst for fluorine-chlorine exchange reaction, which is prepared by adding surfactant in the preparation process to make the prepared catalyst have polygonal prism structure, when the catalyst is used for fluorine-chlorine exchange reaction of trifluoromethane and trichloromethane, the selectivity of R22 and R21 is 49.3% and 48.2%, respectively, and the selectivity of by-product is 2.5%.
Patent CN110833837a discloses a catalyst for resource utilization of trifluoromethane, which comprises a main catalyst selected from at least one of chromium, aluminum, magnesium oxide or fluoride and a cocatalyst selected from at least one of Cr, mg, al, ni, co, zn, fe, cu, in, mn, la, ce, sm oxide or fluoride. When the catalyst is used for the fluorine-chlorine exchange reaction of trifluoromethane and chloroform, the selectivity of R22 and R21 is 42.2 percent and 56.7 percent respectively, and the selectivity of the by-product CFC-12 is about 1.1 percent.
Patent CN112979410a discloses that under the catalytic action of a main catalyst and a metal oxide, HFC-23 and halogenated hydrocarbon are subjected to a fluorine-chlorine exchange reaction, the catalyst for the fluorine-chlorine exchange reaction comprises the main catalyst and the metal oxide, the main catalyst is a chromium, aluminum and magnesium-based catalyst or a catalyst in which chromium, aluminum and magnesium are supported on activated carbon/graphite, and the metal oxide is at least one metal oxide selected from K, na, fe, co, cu, ni, zn or Ti. The catalyst is suitable for common fluorine-chlorine exchange reaction, but stable CHF (CHF) is difficult to activate 3 。
In conclusion, in the fluorine-chlorine exchange reaction of trifluoromethane and chloroform, a disproportionation by-product CFC-12 is present in addition to the products R22 and R21, and at present, the selectivity of the disproportionation by-product is not lower than 1.0%.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a fluorine-doped composite sulfate catalyst, and the fluorine-chromium-doped sulfate catalyst is used for fluorine-chlorine exchange reaction, has high selectivity of a main product, good stability and strong chlorination resistance, and effectively inhibits disproportionation side reactions of R22 and R21 and generation of a byproduct CFC-12.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a fluorine-doped composite sulfate catalyst comprises the following steps:
A1. dissolving sulfate, nitrate and fluorine-containing polymer in a solvent, and stirring at 50-90 ℃ to form gel;
A2. and drying and roasting the gel to obtain the fluorine-doped composite sulfate catalyst.
In step A1:
the sulfate is selected from at least one of chromium sulfate, aluminum sulfate, magnesium sulfate, calcium sulfate, barium sulfate, nickel sulfate or ferric sulfate, and is preferably chromium sulfate.
The nitrate is selected from at least one of magnesium nitrate, chromium nitrate, zinc nitrate, nickel nitrate, ferric nitrate, vanadium nitrate and cobalt nitrate, and is preferably nickel nitrate.
The fluorine-containing polymer is at least one selected from polyvinylidene fluoride, polytrifluoroethylene, polytrifluorochloroethylene, polyvinyl fluoride, polytetrafluoroethylene and polyvinylidene fluoride-hexafluoropropylene copolymer, and is preferably polyvinylidene fluoride.
The solvent is at least one selected from tetrahydrofuran, propylene glycol, isopropyl acetate, dimethyl sulfoxide or dimethylformamide, and is preferably tetrahydrofuran.
The mass ratio of the sulfate, the nitrate and the fluorine-containing polymer is 1 (0.01-0.2) to (0.1-2.0), and preferably 1 (0.05-0.15) to (0.5-1.5). Under the mass ratio, the prepared fluorine-doped composite sulfate catalyst has proper specific surface area and acidity, and can effectively inhibit disproportionation reaction of R22 and R21. And has good anti-chlorination capability, and can inhibit the product from further chlorination to generate the by-product CFC-12.
In the A2 step:
the drying temperature of the gel is 100-180 ℃, preferably 120-160 ℃, and the drying is carried out in an oven.
The roasting temperature rise rate of the gel is 1-5 ℃/min, the roasting temperature is 300-450 ℃, the roasting time is 5-15 h, the roasting atmosphere is at least one of air, oxygen or nitrogen, and the roasting is carried out in a muffle furnace.
The inventor of the invention finds that the fluorine-doped composite sulfate catalyst prepared by the method is particularly suitable for fluorine-chlorine exchange reaction, and is particularly suitable for reaction of trifluoromethane and chloroform for preparing difluorochloromethane and monofluorodichloromethane by fluorine-chlorine exchange.
Therefore, the invention also provides a method for resource utilization of trifluoromethane, which comprises the following steps: the preparation method comprises the steps of taking trifluoromethane and chloroform as raw materials, and preparing difluorochloromethane and monofluorodichloromethane through fluorine-chlorine exchange reaction under the action of the fluorine-doped composite sulfate catalyst prepared by any one of the preparation methods of the fluorine-doped composite sulfate catalyst.
The molar ratio of the trifluoromethane to the chloroform is 1:1-1:5, the reaction temperature is 300-400 ℃, and the reaction pressure is 0-0.50 MPa. Preferably, the molar ratio of the trifluoromethane to the chloroform is 1:2-1:3, the reaction temperature is 320-380 ℃, and the reaction pressure is 0.30-0.50 MPa.
The research shows that in the fluorine-chlorine exchange reaction of the trifluoromethane and the chloroform, the products R22 and R21 are easy to generate disproportionation reaction, and the specific reaction formula is as follows:
r22 disproportionation: 3CHClF 2 →2CHF 3 +CHCl 3
R22 disproportionation: 2CHClF 2 →CHF 3 +CHFCl 2
R21 disproportionation: 2CHCl 2 F→CHCl 3 +CHClF 2
During the reaction, the main reaction for generating R22 and R21 and the side reactions of R22 and R21 are carried out at the L acid site, so that the main reaction and the side reactions have a competitive relationship with each other, and the selectivity of the product is reduced. When the acidity is strong, the chlorine content on the catalyst surface increases, and a side reaction is likely to occur, and R22 is further bonded to chlorine on the catalyst surface to produce ODS-difluorodichloromethane (CFC-12) as a by-product. The fluorine-doped composite sulfate catalyst is obtained by adding nitrate, fluorine-containing polymer is used for fluorine doping modification, the nitrate is converted into metal oxide in the roasting process, and the metal oxide is doped into sulfate by the connection of the fluorine-containing polymer. During roasting, the fluorine-containing polymer is gradually decomposed to release HF, a fluorine ion active center is formed on the surface of the sulfate and metal oxide composite catalyst, and an acid active site of the catalyst is increased, so that the catalyst has proper acidity, and the disproportionation reaction of R22 and R21 is effectively inhibited while the intermolecular fluorine-chlorine exchange reaction of the trifluoromethane and the chloroform occurs. Meanwhile, the release of hydrogen fluoride in the roasting process can enable the catalyst to gradually form a material containing pores, so that the material becomes loose and the specific surface area of the catalyst is increased. Because the fluorine-doped composite sulfate catalyst has proper acidity and larger specific surface area, the disproportionation side reaction of products R22 and R21 is inhibited, and the activity and the stability of the catalyst are effectively improved. And the good anti-chlorination performance can inhibit R22 from further chlorination to generate ODS byproduct CFC-12, thereby greatly improving the selectivity of the main product.
Compared with the prior art, the invention has the beneficial effects that:
1. the fluorine-doped composite sulfate catalyst has proper acidic sites, can inhibit disproportionation reaction of R22 and R21 and generation of a byproduct CFC-12 when being applied to fluorine-chlorine exchange reaction of trifluoromethane and chloroform, and ensures that the selectivity of main products (R22 and R21) is more than or equal to 99.8 percent, the selectivity is high and the chlorination resistance is strong.
2. The fluorine-doped composite sulfate catalyst disclosed by the invention has the advantages of loose structure, large specific surface area and high catalytic activity, and the conversion rate of raw materials and the service life of the catalyst are improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
The embodiment provides a preparation method of a fluorine-doped composite sulfate catalyst, which comprises the following specific steps:
dissolving 40g of chromium sulfate and 3g of nickel nitrate in 40mL of tetrahydrofuran mixed solution, adding 40g of polyvinylidene fluoride (PVDF), and stirring to form gel under the condition of 80 ℃ water bath; foaming and drying at 150 ℃ for 3h, removing the organic solvent, then placing the gel in a muffle furnace, heating to 390 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 10h, and then cooling to room temperature to obtain the fluorine-doped composite chromium sulfate/nickel oxide catalyst, which is recorded as Cat1. The obtained catalyst is pressed into tablets under 15MPa for molding and then crushed into 20-40 meshes for later use.
Example 2
The operation of this example is the same as example 1 except that: and replacing nickel nitrate with ferric nitrate, and keeping the use amount of ferric nitrate unchanged to prepare the fluorine-doped composite chromium sulfate/iron oxide catalyst which is recorded as Cat2.
Example 3
The operation of this example is the same as example 1 except that: the nitrate adopts cobalt nitrate to replace nickel nitrate, and the dosage of the cobalt nitrate is unchanged, so that the fluorine-doped composite chromium sulfate/cobalt oxide catalyst is prepared and is marked as Cat3.
Example 4
The operation of this example is the same as example 1 except that: the nitrate adopts zinc nitrate to replace nickel nitrate, and the dosage of the zinc nitrate is unchanged, so that the fluorine-doped composite chromium sulfate/zinc oxide catalyst is prepared and is marked as Cat4.
Example 5
The operation of this example is the same as example 1 except that: and replacing nickel nitrate with vanadium nitrate, and keeping the use amount of the vanadium nitrate unchanged to prepare the fluorine-doped composite chromium sulfate/vanadium oxide catalyst which is marked as Cat5.
Example 6
The operation of this example is the same as example 1 except that: magnesium nitrate is used for replacing nickel nitrate in the nitrate, and the dosage of the magnesium nitrate is unchanged, so that the fluorine-doped composite chromium sulfate/magnesium oxide catalyst is prepared and is marked as Cat6.
Example 7
The operation of this example is the same as example 1 except that: and replacing nickel nitrate with aluminum nitrate in the nitrate, wherein the using amount of the aluminum nitrate is unchanged, and the fluorine-doped composite chromium sulfate/aluminum oxide catalyst is prepared and recorded as Cat7.
Example 8
The operation of this example is the same as example 1 except that: the fluorine-containing polymer adopts polyvinyl fluoride (PVF) to replace polyvinylidene fluoride, the dosage is unchanged, and the prepared fluorine-doped composite chromium sulfate/nickel oxide catalyst is marked as Cat 8.
Example 9
The operation of this example is the same as example 1 except that: the fluorine-containing polymer adopts polychlorotrifluoroethylene (ECTFE) to replace polyvinylidene fluoride, and the dosage is unchanged, and the prepared fluorine-doped composite chromium sulfate/nickel oxide catalyst is marked as Cat 9.
Comparative example 1
The operation of this example is the same as example 1 except that: without the use of fluoropolymer, a chromium sulfate/nickel oxide catalyst was prepared and is designated Cat B1.
Comparative example 2
The operation of this example is the same as example 1 except that: the fluorine-doped nickel oxide catalyst, noted Cat B2, was prepared without the use of sulfate.
Comparative example 3
The operation of this example is the same as example 1 except that: the fluorine-doped chromium sulfate catalyst was prepared without the use of nitrate and was designated Cat B3.
Example 10
The embodiment provides a method for resource utilization of trifluoromethane, which comprises the following steps:
with CHF 3 And CHCl 3 The method is characterized in that the method is used as a raw material to carry out fluorine-chlorine exchange reaction under the action of Cat 1-Cat 9 and CatB 1-B3, and comprises the following steps:
respectively taking 8mL of catalyst and loading the catalyst into a fixed bed reactor, wherein the inner diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 800 mm. In order to accelerate the catalyst evaluation efficiency, harsh reaction temperature and residence time conditions were selected, wherein the reaction temperature was 380 ℃, the residence time was 3s, the pressure was normal pressure, and the molar ratio of trifluoromethane to trichloromethane was 1.8. The reaction products were qualitatively and quantitatively analyzed, and the results are shown in table 1 below:
TABLE 1 trifluoromethane resource reaction results Table
As can be seen from the results in table 1, when the fluorine-doped composite sulfate catalyst of the present invention is used in the fluorine-chlorine exchange reaction of trifluoromethane and trichloromethane, the fluorine-doped nickel oxide catalyst and the fluorine-doped nickel sulfate catalyst both have good activity and very high selectivity (selectivity of R22+ R21 > 99.8%) compared to the chromium sulfate/nickel oxide catalyst, and the difference of the fluorine source also makes the catalysts have different catalytic activity and stability.
Claims (10)
1. A preparation method of a fluorine-doped composite sulfate catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
A1. dissolving sulfate, nitrate and fluorine-containing polymer in a solvent, and stirring at 50-90 ℃ to form gel;
A2. and drying and roasting the gel to obtain the fluorine-doped composite sulfate catalyst.
2. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the sulfate is selected from at least one of chromium sulfate, aluminum sulfate, magnesium sulfate, calcium sulfate, barium sulfate, nickel sulfate or ferric sulfate.
3. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the nitrate is selected from at least one of magnesium nitrate, chromium nitrate, zinc nitrate, nickel nitrate, ferric nitrate, vanadium nitrate and cobalt nitrate.
4. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the fluorine-containing polymer is at least one selected from polyvinylidene fluoride, polychlorotrifluoroethylene, polyvinyl fluoride, polytetrafluoroethylene and polyvinylidene fluoride-hexafluoropropylene copolymer.
5. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the solvent is at least one of tetrahydrofuran, propylene glycol, isopropyl acetate, dimethyl sulfoxide or dimethylformamide.
6. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the mass ratio of the sulfate, the nitrate and the fluorine-containing polymer is 1 (0.01-0.2) to 0.1-2.0.
7. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the drying temperature of the gel is 100 to 180 ℃, preferably 120 to 160 ℃.
8. The method for preparing a fluorine-doped complex sulfate catalyst according to claim 1, wherein: the roasting temperature rise rate of the gel is 1-5 ℃/min, the roasting temperature is 300-450 ℃, the roasting time is 5-15 h, and the roasting atmosphere is at least one of air, oxygen or nitrogen.
9. A method for resource utilization of trifluoromethane is characterized in that: using trifluoromethane and chloroform as raw materials, and under the action of the fluorine-doped composite sulfate catalyst prepared by the preparation method of the fluorine-doped composite sulfate catalyst according to any one of claims 1 to 8, performing fluorine-chlorine exchange reaction to prepare difluorochloromethane and monofluorodichloromethane.
10. The method for recycling trifluoromethane according to claim 9, wherein the method comprises the following steps: the molar ratio of the trifluoromethane to the chloroform is 1:1-1:5, the reaction temperature is 300-400 ℃, and the reaction pressure is 0-0.50 MPa.
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