CN101507922A - Gas-phase fluorination catalyst and preparation method thereof - Google Patents
Gas-phase fluorination catalyst and preparation method thereof Download PDFInfo
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- CN101507922A CN101507922A CNA2008100613452A CN200810061345A CN101507922A CN 101507922 A CN101507922 A CN 101507922A CN A2008100613452 A CNA2008100613452 A CN A2008100613452A CN 200810061345 A CN200810061345 A CN 200810061345A CN 101507922 A CN101507922 A CN 101507922A
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- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000011651 chromium Substances 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 230000007935 neutral effect Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000013049 sediment Substances 0.000 claims description 50
- 239000012018 catalyst precursor Substances 0.000 claims description 44
- 238000000465 moulding Methods 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 description 20
- 239000012071 phase Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000008282 halocarbons Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910016569 AlF 3 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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Abstract
The invention provides a gas phase fluorination catalyst and a method for preparing the same. The aim of the invention is to provide a gas phase fluorination catalyst with high activity and stability and a method for preparing the same so as to overcome the defects of poor activity and stability existing in the prior gas phase fluorination catalyst. The catalyst of the invention comprises a carrier and active components, wherein the carrier is a compound of Y, and the active components comprise a compound of chromium and one or more of compounds of magnesium, aluminum, indium, gallium and zinc. The method for preparing the catalyst comprises: according to a certain ratio, the compounds of Y and Cr and one or more of compounds of magnesium, aluminum, indium, gallium and zinc are weighed up, added with water, evenly mixed and added with a precipitator until the precipitation is finished, and the precipitate is separated and the solution washed until the filtrate is neutral, the precipitate is dried, formed and roasted to give the a precursor of the fluorination catalyst, and the precursor of the fluorination catalyst is added with anhydrous HF and treated at a certain temperature to give the gas phase fluorination catalyst.
Description
Technical field
The present invention relates to a kind of catalyst that is used for the fluorine chlorine replacement reaction of catalysis anhydrous hydrogen fluoride and halogenated hydrocarbons, particularly be applicable to gaseous fluoridizing method production 1,1,1, a kind of catalysts for gas phase fluorination and the preparation method of 2-HFC-134a (HFC-134a).
Background technology
In recent years, because chlorofluorocarbon (chlorofluorocarbon, be abbreviated as " CFC ") contain that the chlorine atom can cause ozone degradation in the molecule under the irradiation of ultraviolet light and the problem that damages the ozone layer is serious day by day, thereby, hydrofluorocarbon not chloride in its molecule, that can not damage the ozone layer (hydrofluorocarbon is abbreviated as " HFC ") has been proposed the substitute as CFC.The method of the synthetic hydrofluorocarbon of industrialization at present has high-pressure liquid phase method and normal pressure vapor phase method, and wherein, vapor phase method is the method for these hydrofluorocarbon class methods of promising especially production.The vapor phase method of known typical is to make anhydrous hydrogen fluoride and halogenated hydrocarbons that displacement reaction take place in gas phase, and the halogen atom except that F is replaced into the F atom.But under most of situations, with the anhydrous hydrogen fluoride fluorination of halogenated hydrocarbon carry out not smooth, this and selection of catalysts are closely bound up, so far, existing a large amount of catalyst is proposed to be used in this gas phase fluorination.
As a rule, used catalysts for gas phase fluorination is with Al usually
2O
3Or AlF
3Perhaps MgF
2In Al source and Mg source or activated carbon is carrier, carrying Cr isoreactivity component.And, also advised being doped in the catalyst as cobalt, manganese, nickel, zinc etc., to improve the activity of these chromium-containing catalysts by auxiliary agent.Such catalyst is respectively about 20% and 95% the conversion ratio of HCFC-133a and the selectivity of HFC-134a under 320 ℃.At present by the disclosed fluorination catalyst One's name is legion of domestic and international patent documentation, for example:
Proposing a kind of conduct in the open No.2-95438 of Japanese unexamined patent is not the catalyst of making main composition of Cr, and it contains the In compound that is stated from as on the carrier of aluminium oxide, and handles with HF.But, to compare as the catalyst of main component with Cr, this class catalyst activity is lower.
CN 1091651C discloses a kind of being applicable in the gas phase and has carried out the catalyst that halogenated hydrocarbons is fluoridized with HF, and it specifically is that catalyst is at carrier A lF
3Or Al
2O
3Last load C r adds Mg, Ca, Sr, Ba, Sc, Ti, Zr a kind of auxiliary agent wherein.
CN 1064628A disclose a kind of be used for fluorination reaction contain the Cr catalyst, it specifically is by introducing a certain amount of active zinc or zinc compound of improving to catalyst, what be used to increase fluorination reaction contains the Cr activity of such catalysts.
CN 1145275A discloses a kind of vapor phase method by trichloro-ethylene and the synthetic HFC-134a catalyst for reaction of hydrogen fluoride reaction.It specifically is with containing SiO
2γ-Al
2O
3AlF with anhydrous HF prepared in reaction porous high-specific surface area
3Carrier, and then adopt infusion process load C r
3+, Co
2+, Mg
2+Etc. component, obtain this catalyst at last.
CN 1068244C discloses a kind of Cr of containing, Ga, O and the F chromium-based fluorination catalyst as the basic composition element, the atomic ratio of gallium and chromium is in 0.003 to 0.05 scope, this chromium-based catalysts wherein also contains at least a element that is selected from chromium, nickel, zinc, cadmium in addition, and the atomic ratio of described element and chromium is in 0.001 to 0.5 scope.
It is a kind of by Cr that CN 1099314A provides, Al, and In, the catalyst that the fluoride of Bi or oxyfluoride are formed, it is applicable to that vapor phase method catalysis synthesizes the freon substitute, as HFC-134a.
In existing catalysts for gas phase fluorination, relatively poor as not being the catalyst of making main composition of Cr with the catalyst based specific activity mutually of Cr, there is not actual application value; And based on Cr (III) compound, mainly be with Al
2O
3Or AlF
3, MgF
2Deng being carrier, however such catalyst Al at a certain temperature
2O
3Or AlF
3Be difficult to the meeting generation crystal phase transition avoided, cause catalysqt deactivation, make the service life of catalyst restricted, and more such catalyst adopts and mix to add auxiliary agent as Al, In, B, Ga, Mg, Ca, Sr, Ba, Sc, Ti, Zr wait the activity that improves fluorination catalyst.Equally based on Cr (III) compound, the promoter metal of only mixing atom and do not adopt carrier, such catalyst easily produces the unwanted difficult accessory substance that separates in the production, and the phenomenon that carbon is deposited on the catalyst is very serious, so that the activity of accelerator activator descends possibly.Such catalyst may generate Cr (VI) compound in roasting and activation process simultaneously, causes chromium species leakage serious, and this understands the inactivation of accelerator activator equally.
Summary of the invention
The objective of the invention is weak point relatively poor at the existing activity of existing catalysts for gas phase fluorination, that stability is not high, a kind of fluorine chlorine replacement reaction that is applicable to catalysis anhydrous hydrogen fluoride and halogenated hydrocarbons is provided, be particularly useful for gaseous fluoridizing method and produce 1,1,1, the catalysts for gas phase fluorination with high activity, high stability and the preparation method of 2-HFC-134a (HFC-134a).
The present invention finishes by following technical scheme, a kind of catalysts for gas phase fluorination and preparation method, its catalyst comprises carrier and active component, wherein carrier adopts the compound of Y, in the compound of active component employing chromium and the compound of A one or more, the compound of A is the compound of magnesium, aluminium, indium, gallium and zinc, and wherein the mol ratio between A, Cr and the Y is 0.01～0.5:1:0.05～20; Its preparation method is: adopt Y (NO
3)
3, YCl
3, Y
2O
3, Y (OH)
3, YF
3, Y (C
2H
3O
2)
3, Y
2(SO
4)
3In one or more as the Y presoma, adopt Cr (NO
3)
3, CrCl
3, Cr
2O
3, Cr (OH)
3, CrF
3, Cr (C
2H
3O
2)
3, Cr (OH) SO
4In one or more as the Cr presoma, the compound of A adopts one or more in halide, oxide, hydroxide, nitrate, sulfate, acetate, silicate, the acylate, precipitating reagent adopts a kind of in ammoniacal liquor, NaOH, ammonium carbonate, sodium carbonate, the potassium hydroxide, prepare sediment with coprecipitation, sediment drying, roasting obtain this catalyst precarsor, handle obtaining this catalyst again through anhydrous hydrogen fluoride.
The preparation method of catalysts for gas phase fluorination of the present invention may further comprise the steps:
1. take by weighing the compound of a certain amount of Y, the compound of Cr and the compound of A in proportion, after adding water and mixing, add precipitating reagent to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70～140 ℃ of oven dry down;
2. the sediment after will drying obtains the fluorination catalyst precursor through roasting 2～48 hours in 250～650 ℃ of temperature after the moulding, and wherein the sediment after moulding can be at air or H in roasting process
2Or N
2Carry out in the atmosphere.
3. the logical anhydrous HF of above-mentioned fluorination catalyst precursor was handled 2～48 hours under 200～600 ℃ of temperature, obtained catalysts for gas phase fluorination.
The present invention compares with existing catalysts for gas phase fluorination, has active high, stable high characteristics, and the present invention is applicable to the fluorine chlorine replacement reaction of catalysis anhydrous hydrogen fluoride and halogenated hydrocarbons, be specially adapted to gaseous fluoridizing method and produce 1,1,1,2-HFC-134a (HFC-134a).
Description of drawings
Fig. 1 is the N2 adsorption desorption thermoisopleth before and after the catalyst precarsor activation.
Fig. 2 is the preceding SEM figure of catalyst precarsor activation.
Fig. 3 is the figure of the SEM after the catalyst precarsor activation.
The specific embodiment
Further specify the new and effective fluorination catalyst of invention below by embodiment, but the present invention is not limited to following examples.
Embodiment 1
At first the load capacity according to Cr is 30wt%, and the doping of In is that 1wt% takes by weighing Cr (OH) SO
4, In (NO
3)
3And YCl
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 140 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 24 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 2
Be that the doping of 5wt%, In is that 0.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, In (NO
3)
3And Y
2O
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70 ℃ of oven dry down.Sediment after the oven dry through roasting 2 hours in 650 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 200 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 3
Be that the doping of 94wt%, In is that 1wt% takes by weighing Cr (OH) at first according to the load capacity of Cr
3, InC1
3And Y (NO
3)
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 120 ℃.With the oven dry after sediment after moulding at 500 ℃, H
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 4
Be that the doping of 20wt%, In is that 2.5wt% takes by weighing Cr (C at first according to the load capacity of Cr
2H
3O
2)
3, In
2(SO
4)
3And YF
3, mix with an amount of water, add a certain amount of urea, 70 ℃ of water-baths are heated to precipitation fully, are neutral through separating, wash to filtrate then, again with sediment oven dry under 90 ℃.With the oven dry after sediment after moulding at 450 ℃, N
2Roasting is 8 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 5
Be that the doping of 30wt%, Zn is that 1.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Zn (CH
3COO)
2And Y (NO
3)
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 90 ℃.Sediment after the oven dry through roasting 2 hours in 650 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 36 hours down at 280 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 6
Be that the doping of 20wt%, Zn is that 2wt% takes by weighing Cr (OH) SO at first according to the load capacity of Cr
4, ZnSO
4And Y
2(SO
4)
3, mix with an amount of water, add (the NH that a certain amount of concentration is 2mol/L
4)
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 70 ℃.With the oven dry after sediment after moulding at 250 ℃, H
2Roasting is 48 hours in the atmosphere, and compression molding obtains the fluorination catalyst precursor afterwards.The fluorination catalyst precursor was handled 20 hours down at 500 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 7
Be that the doping of 60wt%, Zn is that 8wt% takes by weighing CrF at first according to the load capacity of Cr
3, Zn (NO
3)
2And Y (C
2H
3O
2)
3, mix with an amount of water, add (the NH that a certain amount of concentration is 2mol/L
4)
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 140 ℃.Sediment after the oven dry through roasting 2 hours in 600 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 8
Be that the doping of 10wt%, Zn is that 3wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Zn (NO
3)
2And YF
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 12 hours in 500 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 600 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 9
Be that the doping of 10wt%, Ga is that 0.5wt% takes by weighing Cr at first according to the load capacity of Cr
2O
3, Ga (OH)
3And Y (OH)
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 110 ℃ of oven dry down.Sediment after the oven dry through roasting 24 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 10
Be that the doping of 50wt%, Ga is that 5wt% takes by weighing CrCl at first according to the load capacity of Cr
3, GaCl
3And Y
2O
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 24 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 600 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 11
Be that the doping of 70wt%, Ga is that 3wt% takes by weighing Cr (C at first according to the load capacity of Cr
2H
3O
2)
3, GaCl
3And Y (NO
3)
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70 ℃ of oven dry down.With the oven dry after sediment after moulding at 500 ℃, N
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 12
Be that the doping of 25wt%, Ga is that 1wt% takes by weighing CrCl at first according to the load capacity of Cr
3, Ga
2O
3And Y
2O
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 36 hours in 300 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 200 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 13
Be that the doping of 10wt%, Mg is that 2.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Mg (NO
3)
2And YCl
3, mix with an amount of water, the NaOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 24 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 14
Be that the doping of 70wt%, Mg is that 4.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Mg
2Si
3O
8And YCl
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 140 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 24 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 15
Be that the doping of 20wt%, Mg is that 2wt% takes by weighing Cr (OH) SO at first according to the load capacity of Cr
4, MgSO
4And Y
2(SO
4)
3, mix with an amount of water, add (the NH that a certain amount of concentration is 2mol/L
4)
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 120 ℃.With the oven dry after sediment after moulding at 600 ℃, H
2Roasting is 8 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 16
Be that the doping of 25wt%, Mg is that 1wt% takes by weighing CrCl at first according to the load capacity of Cr
3, MgCl
2And Y
2O
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 8 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 12 hours down at 500 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 17
Be that the doping of 50wt%, Al is that 1wt% takes by weighing Cr (OH) at first according to the load capacity of Cr
3, AlCl
3And Y (OH)
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 140 ℃ of oven dry down.Sediment after the oven dry through roasting 12 hours in 500 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 30 hours down at 420 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 18
Be that the doping of 10wt%, Al is that 2.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Al (NO
3)
3And YCl
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 80 ℃ of oven dry down.Sediment after the oven dry through roasting 24 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Embodiment 19
Be that the doping of 80wt%, Al is that 3.5wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, Al (NO
3)
3And YCl
3, mix with an amount of water, the NaOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 24 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Be that the doping of 20wt%, Al is that 0.5wt% takes by weighing CrCl at first according to the load capacity of Cr
3, Al
2O
3And Y (OH)
3, mix with an amount of water, the NaOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70 ℃ of oven dry down.With the oven dry after sediment after moulding at 650 ℃, N
2Roasting is 2 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity and selectivity see Table 1.
Table 1. embodiment 1-12 catalyst is to the activity of HCFC-133a and the selectivity of HFC-134a
Claims (2)
1, a kind of catalysts for gas phase fluorination and preparation method, its catalyst comprises carrier and active component, carrier adopts the compound of Y, in the compound of active component employing chromium and the compound of A one or more, wherein, the compound of A is the compound of magnesium, aluminium, indium, gallium and zinc, and the mol ratio between A, Cr and the Y is 0.01～0.5:1:0.05～20, it is characterized in that the preparation method of catalysts for gas phase fluorination is: adopt Y (NO
3)
3, YCl
3, Y
2O
3, Y (OH)
3, YF
3, Y (C
2H
3O
2)
3, Y
2(SO
4)
3In one or more as the Y presoma, adopt Cr (NO
3)
3, CrCl
3, Cr
2O
3, Cr (OH)
3, CrF
3, Cr (C
2H
3O
2)
3, Cr (OH) SO
4In one or more as the Cr presoma, the compound of A adopts one or more in halide, oxide, hydroxide, nitrate, sulfate, acetate, silicate, the acylate, precipitating reagent adopts a kind of in ammoniacal liquor, NaOH, ammonium carbonate, sodium carbonate, the potassium hydroxide, prepare sediment with coprecipitation, sediment drying, roasting obtain this catalyst precarsor, handle obtaining this catalyst again through anhydrous hydrogen fluoride.
2, catalysts for gas phase fluorination according to claim 1 and preparation method is characterized in that the concrete preparation process of this catalyst is as follows:
(1) take by weighing the compound of a certain amount of Y, the compound of Cr and the compound of A in proportion, after adding water and mixing, add precipitating reagent to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70～140 ℃ of oven dry down;
(2) sediment after will drying obtains the fluorination catalyst precursor through roasting 2～48 hours in 250～650 ℃ of temperature after the moulding, and wherein the sediment after moulding can be at air or H in roasting process
2Or N
2Carry out in the atmosphere;
(3) the logical anhydrous HF of above-mentioned fluorination catalyst precursor was handled 2～48 hours under 200～600 ℃ of temperature, obtained catalysts for gas phase fluorination.
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| CN102249846A (en) * | 2011-05-31 | 2011-11-23 | 浙江师范大学 | Co-production preparation method of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1-difluoro propylene |
| CN102267866A (en) * | 2011-05-05 | 2011-12-07 | 浙江师范大学 | Preparation method for trifluoroethylene and tetrafluoroethane |
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
| CN107721809A (en) * | 2017-10-19 | 2018-02-23 | 浙江衢化氟化学有限公司 | A kind of co-production of 2,3,3,3 tetrafluoropropene and trans 1,3,3,3 tetrafluoropropene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102267866A (en) * | 2011-05-05 | 2011-12-07 | 浙江师范大学 | Preparation method for trifluoroethylene and tetrafluoroethane |
| CN102267866B (en) * | 2011-05-05 | 2013-11-27 | 浙江师范大学 | Preparation method for trifluoroethylene and tetrafluoroethane |
| CN102249846A (en) * | 2011-05-31 | 2011-11-23 | 浙江师范大学 | Co-production preparation method of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1-difluoro propylene |
| CN102249846B (en) * | 2011-05-31 | 2013-05-08 | 浙江师范大学 | Co-production preparation method of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1-difluoro propylene |
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
| CN107721809A (en) * | 2017-10-19 | 2018-02-23 | 浙江衢化氟化学有限公司 | A kind of co-production of 2,3,3,3 tetrafluoropropene and trans 1,3,3,3 tetrafluoropropene |
| CN107721809B (en) * | 2017-10-19 | 2020-06-19 | 浙江衢化氟化学有限公司 | Co-production method of 2,3,3, 3-tetrafluoropropene and trans-1, 3,3, 3-tetrafluoropropene |
| CN114644546A (en) * | 2020-12-17 | 2022-06-21 | 陕西中蓝化工科技新材料有限公司 | Preparation method of fluoroolefin |
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