CN102698779A - 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 PDF

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CN102698779A
CN102698779A CN2012102023899A CN201210202389A CN102698779A CN 102698779 A CN102698779 A CN 102698779A CN 2012102023899 A CN2012102023899 A CN 2012102023899A CN 201210202389 A CN201210202389 A CN 201210202389A CN 102698779 A CN102698779 A CN 102698779A
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CN102698779B (en
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罗孟飞
程永香
谢遵运
鲁继青
王月娟
谢冠群
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Zhejiang Normal University CJNU
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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

The catalyst and the preparation method that are used for coproduction HCFC-123, HCFC-124 and HFC-125
Technical field
The present invention relates to a kind of chemical catalyst and preparation method thereof, especially relate to a kind of catalyst and preparation method who is used for coproduction HCFC-123, HCFC-124 and HFC-125.
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 it is commonly used among the synthetic HFC-125 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).What preparation HCFC-123 and HCFC-124 adopted usually in the industry is that tetrachloro-ethylene (being called for short PCE) liquid-phase fluorination process prepares HCFC-123 and HCFC-124, and catalyst is an 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.
U.S. Pat 6479718 discloses the method that a kind of liquid phase method prepares HCFC-123, is raw material with hydrogen fluoride (HF) and tetrachloro-ethylene, and Sb (V) is catalyst (as: SbF 5, SbF 4Cl). when reaction temperature is 90 ℃, pressure is 180 pounds/square inch, and when the mol ratio of HF and tetrachloro-ethylene was 6.7:1, the conversion ratio of tetrachloro-ethylene was 90%, and the selectivity of HCFC-123 is 77%.
Chinese patent CN101157595A discloses a kind of preparation method of pentafluoroethane, is raw material with HF and tetrachloro-ethylene, adopts two step of two reactors gas phase catalytic fluorination prepared in reaction HFC-125.First reactor is fluoridized synthetic HCFC-123 of tetrachloro-ethylene and HCFC-124, and second reactor is fluoridized HCFC-123, the synthetic HFC-125 of HCFC-124.Chromium oxide or the charomic fluoride etc. of catalyst for containing multiple metal (like Zn, Co, Ni, Ge, In etc.).
Chinese patent 200410101551.3 discloses a kind of preparation method of chromium-based fluorination catalyst; This catalyst is in chromium hydroxide, to add Al, Zn, Ni metal powder; 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; In chromium hydroxide or chrome green, add the fluoride of ammonium; Compression moulding 350 ℃ ~ 450 ℃ following roastings, makes chromium-based fluorination catalyst after hydrogen fluoride gas is fluoridized then.
Though above-mentioned liquid phase method prepares HCFC-123 higher conversion ratio is arranged, also have the consersion unit seriously corroded, the pressure that reaction needed is higher is difficult for shortcomings such as large-scale continuous production; The vapor phase method reported of the document catalyst for preparing HCFC-123 is mainly chromium-based catalysts in addition; But mainly there is following deficiency in chromium-based fluorination catalyst: (1) chromium-based catalysts a large amount of use in industry can produce a large amount of chromium residues; Be difficult to handle 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 like Chinese patent CN1078172A, is load active component zinc on aluminium oxide, halo aluminium oxide or zirconyl oxyhalides alumina supporter, fluoridizes through hydrogen fluoride then 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 provides that a kind of preparation technology is simple, the short Catalysts and its preparation method that is used for coproduction HCFC-123, HCFC-124 and HFC-125 of the time of fluoridizing.
For solving this technical problem, the technical scheme that the present invention adopts is following:
A kind of catalyst that is used for gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 is made up of carrier and active component, and active constituent loading is characterized in that on carrier: said carrier is β-AlF 3, α-AlF 3, α-Al 2O 3Mixture, said active component is Zn 2+, the quality percentage composition of said active component counts 1 ~ 5% with Zn.
Be used for the Preparation of catalysts method of gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125, it is characterized in that may further comprise the steps:
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following roastings of Muffle furnace 4 hours, X-ray diffraction (XRD) is analyzed γ-Al 2O 3After 1100 ℃ of roastings, get θ-Al 2O 3And α-Al 2O 3Mixture; θ-Al 2O 3And α-Al 2O 3Integral molar quantity equal γ-Al 2O 3Mole, can't calculated theta-Al 2O 3And α-Al 2O 3Amount separately.
⑵ immersion process for preparing catalyst:
1. calculate according to the load capacity of active component Zn and take by weighing a certain amount of θ-Al 2O 3And α-Al 2O 3Mixture carrier joins in the soluble-salt solution of Zn, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ ~ 400 ℃ nitrogen atmospheres then;
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 ℃,
Feed N then 2Obtain catalyst ZnF until being cooled to room temperature 2/ α-AlF 3-β-AlF 3α-Al 2O 3
Reaction finishes the back and records θ-Al with X-ray diffractometer 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, the zinc sulfate.
The difference of catalyst of the present invention and the common catalyst that is used for gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125 is not contain chromium, some drawbacks that do not have chromium-based catalysts to exist.And the carrier of catalyst of the present invention is β-AlF 3, α-AlF 3, α-Al 2O 3Mixture, after fluoridizing, be converted into β-AlF 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 concrete 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 3Place 1100 ℃ of following 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 characteristic XRD figure is referring to Fig. 1, and this X-ray diffraction (XRD) is analyzed the full-automatic X-ray diffractometer of PW3040/60 type that the Dutch Philips of employing company produces.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 immersion process for preparing catalyst
1. be that 1wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres then;
3. with the gained powder through HF:N 2Mol ratio is that the mist of 10:1 was fluoridized 6 hours at 260 ℃, feeds N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst, its characteristic XRD figure are referring to Fig. 2, and this X-ray diffraction (XRD) is analyzed the full-automatic X-ray diffractometer of PW3040/60 type that the Dutch Philips of employing company produces.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.Because active component Zn percentage composition cause is not very little seen ZnF in the XRD figure of catalyst 2Diffraction maximum.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 2
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. be that 3wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres then;
3. with the gained powder through HF:N 2Mol ratio is that the mist of 6:1 was fluoridized 5 hours at 350 ℃, feeds N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 3
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. be that 5wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 400 ℃ of nitrogen atmospheres then;
3. with the gained powder through HF:N 2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 450 ℃, feeds N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 4
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. be that 2wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres then;
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, feed N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 5
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. the load capacity according to Zn is that 2wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 300 ℃ of nitrogen atmospheres then;
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, feed N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 6
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. be that 2wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres then;
3. with the gained powder through HF:N 2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 450 ℃, feeds N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Embodiment 7
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture
With γ-Al 2O 3Place 1100 ℃ of following 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 immersion process for preparing catalyst
1. be that 2wt% takes by weighing 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 the above-mentioned solution, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ of nitrogen atmospheres then;
3. with the gained powder through HF:N 2Mol ratio is that the mist of 4:1 was fluoridized 4 hours at 400 ℃, feeds N then 2Get ZnF of the present invention until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst.
At homemade internal diameter is in the stainless steel tube fixed bed reactors of 10mm, and the above-mentioned catalyst that makes of the 3ml that packs into feeds HF and tetrachloro-ethylene and reacts, and the mol ratio of control 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 selectivity of the conversion per pass of tetrachloro-ethylene and HCFC-123, HCFC-124 and HFC-125 is seen table 1.
Table 1: embodiment activity of such catalysts and selectivity tabulation
Figure BDA00001771704100071
Visible by data in the table; In the reaction of tetrachloro-ethylene gas phase fluorination coproduction HCFC-123, HCFC-124 and HFC-125; Zn content and reaction temperature are bigger to the influence of catalyst; Along with the increase of Zn content, the selectivity of activity of such catalysts and HCFC-123, HCFC-124 and HFC-125 all presents the trend that reduces after the existing increase; Along with the raising of reaction temperature, the conversion per pass of tetrachloro-ethylene and the selectivity of HFC-125 increase, and the selectivity of HCFC-123 and HCFC-124 is to increase afterwards earlier to reduce.In the fluorination process of catalyst, earlier under lower temperature, fluoridize a period of time, and then be warming up to higher temperature at a slow speed and fluoridize, and adopt the mist of hydrogen fluoride and inert gas that catalyst is handled more to help activity of such catalysts and selectivity.The Zn load capacity is the ZnF of 2wt% 2/ α-AlF 3-β-AlF 3-α-Al 2O 3Catalyst has selectivity preferably to HCFC-123 and HCFC-124 when 300 ℃ of reactions, both reach 78.5% at overall selectivity, and the selectivity of HFC-125 is 5.9%.

Claims (4)

1. the catalyst that is used for coproduction HCFC-123, HCFC-124 and HFC-125 is made up of carrier and active component, and active constituent loading is characterized in that on carrier: said carrier is β-AlF 3, α-AlF 3, α-Al 2O 3Mixture, said active component is Zn 2+, the quality percentage composition of said active component counts 1 ~ 5% with Zn.
2. the said Preparation of catalysts method of claim 1 is characterized in that may further comprise the steps:
⑴ carrier θ-Al 2O 3And α-Al 2O 3The preparation of mixture:
With γ-Al 2O 3Place 1100 ℃ of following roastings of Muffle furnace 4 hours, get carrier θ-Al 2O 3And α-Al 2O 3Mixture;
⑵ immersion process for preparing catalyst:
1. calculate according to the load capacity of active component Zn and take by weighing a certain amount of θ-Al 2O 3And α-Al 2O 3Mixture carrier joins in the soluble-salt solution of Zn, and after stirring, dipping is 12 hours under the room temperature;
2. back evaporate to dryness liquid under 90 ℃ of water-baths, in 120 ℃ of baking ovens dry 12 hours again, roasting obtained powder in 4 hours under 200 ℃ ~ 400 ℃ nitrogen atmospheres then;
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 ℃, feeds N then 2Obtain catalyst ZnF until being cooled to room temperature 2/ α-AlF 3-β-AlF 3-α-Al 2O 3
3. preparation method according to claim 2 is characterized in that: the soluble-salt of said Zn is selected from a kind of in zinc chloride, zinc nitrate, the zinc sulfate.
4. the application of the said catalyst of claim 1 in gas phase fluorination tetrachloro-ethylene coproduction HCFC-123, HCFC-124 and HFC-125.
CN2012102023899A 2012-06-15 2012-06-15 Catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and preparation method Expired - Fee Related CN102698779B (en)

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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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