CN102698779B - Catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and preparation method - Google Patents
Catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and preparation method Download PDFInfo
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- CN102698779B CN102698779B CN2012102023899A CN201210202389A CN102698779B CN 102698779 B CN102698779 B CN 102698779B CN 2012102023899 A CN2012102023899 A CN 2012102023899A CN 201210202389 A CN201210202389 A CN 201210202389A CN 102698779 B CN102698779 B CN 102698779B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 35
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 35
- 239000011701 zinc Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003682 fluorination reaction Methods 0.000 claims description 19
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 17
- 239000003595 mist Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 37
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 229910052594 sapphire Inorganic materials 0.000 abstract 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 abstract 2
- 238000004821 distillation Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- -1 hydrocarbons compound Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
The invention relates to a catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and a preparation method. The carrier of the catalyst is a mixture of beta-AlF3, alpha-AlF3 and alpha-Al2O3, the active component of the catalyst is Zn2+, and the mass percent of the active component is as follows: 1-5 percent of Zn. The preparation method of the catalyst comprises the following steps of putting gamma-Al2O3 into a muffle furnace to be roasted for 4 hours at the temperature of 1100 DEG C to obtain the carrier, namely a mixture of theta-Al2O3 and alpha-Al2O3; adding the carrier, namely the mixture of theta-Al2O3 and alpha-Al2O3 into a Zn soluble salt solution to be infused for 12 hours at the room temperature; drying liquid by distillation at the temperature of 90 DEG C, drying at the temperature of 120 DEG C to obtain a powder body; and then roasting the powder body for 4 hours in nitrogen atmosphere to be fluorated by a hydrogen fluoride gas to obtain the catalyst. The catalyst can express high activity and selectivity in a lower reaction temperature condition.
Description
Technical field
The present invention relates to a kind of chemical catalyst and preparation method thereof, especially relate to a kind of catalyst for coproduction HCFC-123, HCFC-124 and HFC-125 and preparation method.
Background technology
Pentafluoroethane (being called for short HFC-125) is a kind of fluorinated hydrocarbons compound to atmospheric ozone layer safety, and ODP value (ODP) is 0.Substitute as fluorochlorohydrocarbon (CFCs) and hydrogen fluorochlorohydrocarbon (HCFCs) is widely used as cold-producing medium, blowing agent, solvent, propellant, extinguishing chemical and dry ecthing agent.Yet commonly used to HCFC-123 (1,1-, two chloro-2,2,2-HFC-143a) and these two kinds of intermediates of HCFC-124 (1-chloro-1,2,2,2-HFC-134a) in synthetic HFC-125.What industrial preparation HCFC-123 and HCFC-124 adopted usually is that tetrachloro-ethylene (being called for short PCE) liquid-phase fluorination process prepares HCFC-123 and HCFC-124, and catalyst is antimony catalyst.In addition, also have bibliographical information to prepare HCFC-123 and HCFC-124 by gaseous fluoridizing method, catalyst is mainly chromium-based catalysts.
US Patent No. 6479718 discloses the method for Liquid preparation methods HCFC-123 a kind of, and take hydrogen fluoride (HF) and tetrachloro-ethylene as raw material, Sb (V) is catalyst (as: SbF
5, SbF
4Cl). when reaction temperature is 90 ℃, pressure is 180 pounds/square inchs, when the mol ratio of HF and tetrachloro-ethylene is 6.7:1, the conversion ratio of tetrachloro-ethylene be 90%, HCFC-123 be selectively 77%.
Chinese patent CN101157595A discloses a kind of preparation method of pentafluoroethane, take HF and tetrachloro-ethylene as raw material, adopts two step of two reactors gas phase catalytic fluorination reaction preparation HFC-125.The first reactor is fluoridized the synthetic HCFC-123 of tetrachloro-ethylene and HCFC-124, and the second reactor is fluoridized the synthetic HFC-125 of HCFC-123, HCFC-124.Catalyst is for containing the chromium oxide of various metals (as Zn, Co, Ni, Ge, In etc.) or charomic fluoride etc.
Chinese patent 200410101551.3 discloses a kind of preparation method of chromium-based fluorination catalyst, this catalyst is to add Al, Zn, Ni metal powder in chromium hydroxide, and carry out fluorination treatment with the mist of hydrogen fluoride and nitrogen, utilize metal dust and hydrofluoric effect, obtain the fluorination catalyst of high micropore ratio, high stability.
Chinese patent CN101214448A discloses a kind of preparation method of chromium-based fluorination catalyst, add the fluoride of ammonium in chromium hydroxide or chrome green, compressing, then 350 ℃ ~ 450 ℃ lower roastings, fluoridize finally by hydrogen fluoride gas and make chromium-based fluorination catalyst.
Although above-mentioned Liquid preparation methods HCFC-123 has higher conversion ratio, also has the consersion unit seriously corroded, the pressure that reaction needed is higher is difficult for the shortcomings such as large-scale production continuously; The vapor phase method reported of the document catalyst for preparing HCFC-123 is mainly chromium-based catalysts in addition, but chromium-based fluorination catalyst mainly has the following disadvantages: (1) chromium-based catalysts can produce a large amount of chromium residues in industrial a large amount of uses, be difficult to process contaminated environment; (2) chromium-based catalysts easy carbon distribution and make catalyst life not long in course of reaction.Therefore, the chromium-free fluorination catalyst that patent report arranged.Disclosing a kind of preparation method of chromium-free fluorination catalyst as Chinese patent CN1078172A, is load active component zinc on aluminium oxide, halo aluminium oxide or zirconyl oxyhalides alumina supporter, then fluoridizes through hydrogen fluoride to make ZnF
2/ AlF
3Fluorination catalyst.But this catalyst is lower to the yield that the tetrachloro-ethylene gas phase fluorination prepares HCFC-123 and HCFC-124.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of preparation technology is simple, short Catalysts and its preparation method for coproduction HCFC-123, HCFC-124 and HFC-125 of the time of fluoridizing.
For solving this technical problem, the technical solution used in the present invention is as follows:
A kind of catalyst for gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 is comprised of carrier and active component, and active constituent loading is characterized in that on carrier: described carrier is β-AlF
3, α-AlF
3, α-Al
2O
3Mixture, described active component is Zn
2+, the quality percentage composition of described active component counts 1 ~ 5% with Zn.
Be used for the preparation method of the catalyst of gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125, it is characterized in that comprising the following steps:
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, X-ray diffraction (XRD) is analyzed γ-Al
2O
3Get θ-Al after 1100 ℃ of roastings
2O
3And α-Al
2O
3Mixture; θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole, can't calculate θ-Al
2O
3And α-Al
2O
3Amount separately.
⑵ preparation catalyst:
1. calculate according to the load capacity of active component Zn and take a certain amount of θ-Al
2O
3And α-Al
2O
3Mixture carrier joins in the soluble-salt solution of Zn, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ ~ 400 ℃ nitrogen atmospheres;
2. with the gained powder through HF:N
2Mol ratio is that the mist of 4 ~ 10:1 was fluoridized 4 ~ 6 hours at 260 ℃ ~ 450 ℃,
Then pass into N
2Obtain catalyst Z nF until be cooled to room temperature
2/ α-AlF
3-β-AlF
3α-Al
2O
3
Reaction records θ-Al with X-ray diffractometer after finishing
2O
3And α-Al
2O
3Be converted into β-AlF after fluoridizing
3, α-AlF
3, α-Al
2O
3Mixture.β-AlF
3, α-AlF
3, α-Al
2O
3Integral molar quantity equal θ-Al
2O
3And α-Al
2O
3Integral molar quantity, can't calculate β-AlF
3, α-AlF
3, α-Al
2O
3Amount separately.
The soluble-salt of above-mentioned Zn is selected from a kind of in zinc chloride, zinc nitrate, zinc sulfate.
Catalyst of the present invention and the common difference that is used for the catalyst of gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 are not contain chromium, there is no some drawbacks of chromium-based catalysts.And the carrier of catalyst of the present invention is β-AlF
3, α-AlF
3, α-Al
2O
3Mixture, be converted into β-AlF after fluoridizing
3, α-AlF
3, α-Al
2O
3Mixture.Catalyst of the present invention is used for gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 has activity and selectivity preferably.
Description of drawings
Fig. 1 carrier θ-Al
2O
3And α-Al
2O
3The XRD figure of mixture
Fig. 2 ZnF
2/ α-AlF
3-β-AlF
3-α-Al
2O
3The XRD figure of catalyst
The specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.Its feature XRD figure is referring to Fig. 1, the full-automatic X-ray diffractometer of PW3040/60 type that this X-ray diffraction (XRD) analysis adopts Dutch Philips company to produce.Cu K alpha ray, tube voltage 40kV, tube current 40mA, 0.15 ° of s of sweep speed
-1, wherein 2 θ are 25.58 °, 35.15 °, 37.78 °, 43.36 °, 52.55 °, 57.50 °, 68.20 ° is typical α-Al
2O
3Characteristic diffraction peak, 2 θ are 31.35 °, 32.89 °, 36.95 °, 38.76 °, 40.05 °, 42.63 °, 67.28 °, are typical θ-Al
2O
3Characteristic diffraction peak.
⑵ preparation catalyst
1. be that 1wt% takes ZnCl according to active component Zn load capacity
2, be mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 99%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 10:1 was fluoridized 6 hours at 260 ℃, then passes into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst, its feature XRD figure be referring to Fig. 2, the full-automatic X-ray diffractometer of PW3040/60 type that this X-ray diffraction (XRD) analysis adopts Dutch Philips company to produce.Cu K alpha ray, tube voltage 40kV, tube current 40mA, 0.15 ° of s of sweep speed
-1, wherein 2 θ are 25.07 °, 42.60 °, 51.48 °, 58.07 ° is α-AlF
3Characteristic diffraction peak, 14.79 °, 29.69 ° is β-AlF
3Characteristic diffraction peak, 2 θ are 25.58 °, 35.15 °, 37.78 °, 43.36 °, 52.55 °, 57.50 °, 68.20 ° is α-Al
2O
3Characteristic diffraction peak.Due to active component Zn percentage composition cause very little, do not see ZnF in the XRD figure of catalyst
2Diffraction maximum.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 300 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. be that 3wt% takes ZnCl according to active component Zn load capacity
2, be mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 97%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 6:1 was fluoridized 5 hours at 350 ℃, then passes into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 300 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. be that 5wt% takes ZnCl according to the Zn load capacity
2, be mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 95%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 400 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 450 ℃, then passes into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 300 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
Embodiment 4
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. be that 2wt% takes Zn (NO according to the Zn load capacity
3)
26H
2O is mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 98%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4:1 was fluoridized 1 hour at 260 ℃, after be warming up to 450 ℃ and fluoridized 3 hours, then pass into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 300 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
Embodiment 5
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. the load capacity according to Zn is that 2wt% takes Zn (CH
3COO)
2, be mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 98%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 300 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4:1 was fluoridized 1 hour at 260 ℃, after be warming up to 450 ℃ and fluoridized 3 hours, then pass into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 300 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
Embodiment 6
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. be that 2wt% takes Zn (SO according to the Zn load capacity
4)
27H
2O is mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 98%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 450 ℃, then passes into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 325 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
Embodiment 7
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture, θ-Al
2O
3And α-Al
2O
3Integral molar quantity equal γ-Al
2O
3Mole.
⑵ preparation catalyst
1. be that 2wt% takes ZnCl according to the Zn load capacity
2, be mixed with solution, then according to carrier θ-Al
2O
3And α-Al
2O
3The mass percent of mixture is 98%, with carrier θ-Al
2O
3And α-Al
2O
3Mixture joins in mentioned solution, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 400 ℃, then passes into N
2Get ZnF of the present invention until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst.
Be in the stainless steel tube fixed bed reactors of 10mm at homemade internal diameter, the above-mentioned catalyst that makes of the 3ml that packs into passes into HF and tetrachloro-ethylene reacts, and the mol ratio of controlling the HF/ tetrachloro-ethylene is 10:1, air speed 240h
-1, reaction temperature is 350 ℃, and product is used gas chromatographic analysis through washing, alkali cleaning after removing HCl and HF, and the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 selectively see Table 1.
Table 1: the activity of embodiment catalyst and selective list
By data in table as seen, in the reaction of tetrachloro-ethylene gas phase fluorination coproduction HCFC-123, HCFC-124 and HFC-125, Zn content and reaction temperature are larger on the impact of catalyst, along with the increase of Zn content, the selective trend that reduces after existing increase that all presents of the activity of catalyst and HCFC-123, HCFC-124 and HFC-125; Along with the raising of reaction temperature, the conversion per pass of tetrachloro-ethylene and HFC-125 selectively increase, and selectively first increasing afterwards of HCFC-123 and HCFC-124 reduces.In the fluorination process of catalyst, first fluoridize a period of time at lower temperature, and then be warming up at a slow speed higher temperature and fluoridize, and adopt the mist of hydrogen fluoride and inert gas catalyst to be processed the activity and selectivity that more is conducive to catalyst.The Zn load capacity is the ZnF of 2wt%
2/ α-AlF
3-β-AlF
3-α-Al
2O
3Catalyst has selective preferably to HCFC-123 and HCFC-124 300 ℃ of whens reaction, what both overall selectivitys reached 78.5%, HFC-125 is selectively 5.9%.
Claims (3)
1. be used for the preparation method of the catalyst of coproduction HCFC-123, HCFC-124 and HFC-125, this catalyst is comprised of carrier and active component, and described carrier is β-AlF
3, α-AlF
3, α-Al
2O
3Mixture, described active component is Zn
2+, the quality percentage composition of described active component counts 1 ~ 5% with Zn, it is characterized in that the preparation of this catalyst comprises the following steps:
⑴ carrier θ-Al
2O
3And α-Al
2O
3The preparation of mixture:
With γ-Al
2O
3Be placed in 1100 ℃ of lower roastings of Muffle furnace 4 hours, get carrier θ-Al
2O
3And α-Al
2O
3Mixture;
⑵ preparation catalyst:
1. calculate according to the load capacity of active component Zn and take a certain amount of θ-Al
2O
3And α-Al
2O
3Mixture carrier joins in the soluble-salt solution of Zn, and after stirring, under room temperature, dipping is 12 hours;
2. after under 90 ℃ of water-baths evaporate to dryness liquid, then in 120 ℃ of baking ovens dry 12 hours, then roasting obtained powder in 4 hours under 200 ℃ ~ 400 ℃ nitrogen atmospheres;
3. with the gained powder through HF:N
2Mol ratio is that the mist of 4 ~ 10:1 was fluoridized 4 ~ 6 hours at 260 ℃ ~ 450 ℃, then passes into N
2Obtain catalyst Z nF until be cooled to room temperature
2/ α-AlF
3-β-AlF
3-α-Al
2O
3
2. preparation method according to claim 1 is characterized in that: the soluble-salt of described Zn is selected from a kind of in zinc chloride, zinc nitrate, zinc sulfate.
3. the prepared application of catalyst in gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012102023899A CN102698779B (en) | 2012-06-15 | 2012-06-15 | Catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and preparation method |
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| CN103071516B (en) * | 2012-12-28 | 2014-10-22 | 巨化集团技术中心 | Catalyst for preparing trifluoroethylene or vinyl fluoride and preparation method thereof |
| EP3015423A1 (en) * | 2014-10-31 | 2016-05-04 | Solvay SA | Catalyst comprising fluorinated metal oxide, manufacture process and hydrogenation process |
| CN107311836A (en) * | 2017-06-09 | 2017-11-03 | 浙江三美化工股份有限公司 | A kind of method that tetrachloro-ethylene prepares pentafluoroethane |
| CN112642449A (en) * | 2020-12-21 | 2021-04-13 | 江苏三美化工有限公司 | Catalyst for gas phase fluorination of 1,1,1, 2-tetrafluoroethane and preparation method thereof |
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| KR100215542B1 (en) * | 1996-04-23 | 1999-08-16 | 박원훈 | Method of producing 1,1,1,2-tetrafluoroethane and pentafluoroethane at the same time |
| CN100338001C (en) * | 2004-11-17 | 2007-09-19 | 浙江莹光化工有限公司 | Production of 1,1,1,2-tetrafluoroethykane and pentafuoethane simultaneously |
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