CN107715897B - A kind of catalyst and preparation method thereof preparing HFO-1234ze for HFC-245fa - Google Patents

A kind of catalyst and preparation method thereof preparing HFO-1234ze for HFC-245fa Download PDF

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CN107715897B
CN107715897B CN201710947113.6A CN201710947113A CN107715897B CN 107715897 B CN107715897 B CN 107715897B CN 201710947113 A CN201710947113 A CN 201710947113A CN 107715897 B CN107715897 B CN 107715897B
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CN107715897A (en
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罗孟飞
汪云
宋建冬
王月娟
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Zhejiang Normal University CJNU
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

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Abstract

A kind of catalyst and preparation method thereof preparing HFO-1234ze for HFC-245fa, catalyst is made of carrier and active component, carrier AlF3C is prepared with sol-gal process, and wherein the mass percentage of C is AlF31.8wt.%；Active component is V2O5With the mixture of C, active component loads in two times, first time supported V2O5, V2O5Mass percentage be carrier AlF31.0~4.0wt.% of C；Second by loading citric acid, progress N2500 DEG C of roastings are converted into C in atmosphere, and the mass percentage of C is calculated as V with citric acid adding amount2O5/AlF31.0~4.0wt.% of C.Catalyst can carry out in the lower situation of reaction temperature for HFC-245fa cracking preparation HFO-1234ze, have relatively high catalytic activity and selectivity, preferable stability.

Description

A kind of catalyst and preparation method thereof preparing HFO-1234ze for HFC-245fa
Technical field
The present invention relates to catalyst of a kind of de-hydrogen halide and preparation method thereof, in particular to a kind of to be used for HFC- 245fa prepares catalyst of HFO-1234ze and preparation method thereof
Background technique
Hydrofluoroalkane (HFCs) has excellent physical and chemical performance, has extensively in industries such as refrigerant, foaming agent, industrial solvents General application.But due to the latent value GWP higher of HFCs greenhouse effects, atmospheric residence time is longer, and long-time service can cause entirely Ball climate warming is listed in one of the greenhouse gases for forbidding discharge.Fluorine containing olefine such as 1,3,3,3- tetrafluoro propylene (HFO- 1234ze) ODP value is zero, GWP value 6, high cooling efficiency, and material compatibility is good and non-ignitable not quick-fried, stable chemical performance, is recognized For the ideal substitute for being HFCs.
The synthetic method of HFO-1234ze mainly has fluorine chlorine exchange process, telomeric fluorinated method, carbene reaction and dehalogenation at present Hydrogen method etc., specific method are directed to different reaction raw materials.Patent EP486333 disclose it is a kind of using HCFC-1233zd for original Material, Cr2O3For catalyst, HFO-1234ze is produced by the fluorination reaction under the conditions of 380 DEG C.HCFC-1233zd in this method Conversion ratio is that 54.8%, HFO-1234ze is selectively 58.3%, but the temperature of this catalysis reaction is higher and catalyst is easy Inactivation.Patent US2006030744 discloses the preparation side that HFO-1234ze is generated using halide and vinyl halides as raw material Method.Reaction raw materials are first in metallic catalyst Cu or AlCl in this method3Electrophilic addition occurs under catalyst action and generates halogenated third Alkane, then high temperature sloughs HX under fluorination catalyst (Fe or Cr) effect, to obtain HFO-1234ze.The synthetic method route is multiple It is miscellaneous, expensive catalyst and easy coking and deactivation, and also by-product is more, and conversion ratio is low, is not ideal synthesis HFO-1234ze route.
Patent US20050245774 disclose it is a kind of using difluorocarbene and interpolymerized vinylidene fluoride monomer in same reactor HFO-1234ze is made in pyroreaction.The yield of this method HFO-1234ze is only 15% and reaction temperature is high, not industrial Application value.Chinese patent CN101028992A with 1,1,1,3,3- pentachloropropane (HCC-240fa) for raw material, it is anti-using 2 Device gaseous fluoridizing method is answered to prepare HFO-1234ze.The catalysts use the chromium-based catalysts of Al, Zn, Mg, Ni, this method Raw material is easy to get, yield is higher but reactor in the selectivity of HFO-1234ze there was only 50% or so.Chinese patent US5986151 One kind is disclosed in high reaction temperatures, with 1,1,1,3,3- pentafluoropropane (HFC-245fa) for raw material dehydrofluorination system The method of standby 1,3,3,3- tetrafluoropropene (HFO-1234ze).Such method reaction temperature is higher, and conversion ratio is low, and continuous production Period is short.Chinese patent CN104907063A disclose it is a kind of using 1,1,3,3,3- pentafluoropropane (HFC-245fa) at 400 DEG C Lower and chromium-based catalysts contact the method that dehydrofluorination prepares 1,3,3,3- tetrafluoropropenes (HFO-1234ze), wherein HFC- The selectivity that the conversion ratio of 245fa reaches 89.8%, HFO-1234ze is 98%.But this method reaction temperature is higher, catalyst Dosage is more and environmental pollution is larger.
In summary the preparation method in relation to 1,3,3,3- tetrafluoropropene (HFO-1234ze).For existing catalyst Speech, stability is not high, and environmental pollution is larger.Simultaneously in 1,3,3,3- tetrafluoropropene (HFO-1234ze) preparation, technique mistake Journey is relatively complicated, and by-product is more and more demanding to consersion unit, and part preparation method raw material and catalyst are expensive, and There is certain pollution to environment, is not suitable for current industrial application.
Summary of the invention
The purpose of the present invention is be directed to existing gas phase catalysis 1,1,1,3,3- pentafluoropropane (HFC-245fa) dehydrofluorination The deficiencies of preparation process present in 1,3,3,3- tetrafluoropropenes (HFO-1234ze) is complicated, stability is poor place is prepared, is provided It is a kind of simple and easy to do, there is high conversion, highly selective and stability to be preferably used for 1,1,1,3,3- pentafluoropropane cracking system The catalyst and preparation method thereof of standby 1,3,3,3- tetrafluoropropene.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
The catalyst of 1,3,3,3- tetrafluoropropenes of preparation is cracked for 1,1,1,3,3- pentafluoropropane, the catalyst is by carrier It is formed with active component, the carrier is carbon containing AlF3(with AlF3C is indicated), wherein the mass percentage of carbon (C) is AlF31.8wt.%, the active component is V2O5With the mixture of carbon.Active component loads in two times, loads for the first time V2O5, mass percentage is carrier AlF31.0~4.0wt.% of C；Second by loading citric acid, progress N2Atmosphere In 500 DEG C of roastings be converted into carbon, mass percentage (in terms of citric acid adding amount) is V2O5/AlF3The 1.0 of C~ 4.0wt.%.
The preparation method that the catalyst of 1,3,3,3- tetrafluoropropenes of preparation is cracked for 1,1,1,3,3- pentafluoropropane, uses Sol-gal process and infusion process combine, the specific steps are as follows:
(1)AlF3The preparation of C carrier
It takes a certain amount of aluminium isopropoxide and isopropanol in polytetrafluoroethylene (PTFE) cup, dissolution is sufficiently stirred under 50 DEG C of water-baths. Then HF solution (40wt.%) is taken to be slowly dropped into (Al atom and F atom stoichiometric ratio be 1:3), obtained colloidal sol, through old Change, is dry, AlF is made in roasting3C carrier, wherein the mass percentage of carbon (C) is AlF31.8wt.%.
(2)V2O5/AlF3The preparation of C catalyst
According to V2O5The mass percentage of oxide is carrier AlF31.0~4.0wt.% of C, by carrier AlF3·C It is immersed in VOC2O4·5H2It is dry by fried dry in O solution, then in N2It is roasted under atmosphere, V is made2O5/AlF3C powder.
(3)C/V2O5/AlF3The preparation of C catalyst
It is V according to citric acid mass percentage2O5/AlF31.0~4.0wt.% of C, by V2O5/AlF3C dipping Citric acid solution, it is dry by fried dry, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/V2O5/AlF3C catalyst.
1,1,1,3,3- pentafluoropropane dehydrofluorination 1,3,3,3- is cracked for gas phase catalysis through the above technical solution The catalyst of tetrafluoropropene can carry out in the lower situation of reaction temperature, at the same show relatively high catalytic activity and Selectivity, has many advantages, such as that stability is good, preparation method is simple, low in raw material price.
Detailed description of the invention
Fig. 1 is C/V in embodiment 62O5/AlF3C catalyst gas phase catalysis HFC-245fa takes off the reaction stability figure of HF.
Specific embodiment
Below for the present invention by being further described in conjunction with the embodiments, but range is embodied and is not limited to be illustrated Son.
Embodiment 1:
(1)AlF3The preparation of C carrier
According to Al ion concentration control in solution in 1mol/L, wherein Al atom and F atom stoichiometric number are 1:3.It takes 10.21g aluminium isopropoxide and 50ml isopropanol are sufficiently stirred 10 minutes in polytetrafluoroethylene (PTFE) cup under 50 DEG C of water-baths.Then it takes 7.50g HF solution (40wt.%) is slowly dropped into cup, stirring in water bath 6h at 60 DEG C, and obtained translucent colloidal sol is old at 90 DEG C Change 48h.It is most 12 hours dry through 100 DEG C afterwards, then roasted 4 hours in 500 DEG C of air atmospheres, the catalyst carrier is made AlF3C powder, wherein the mass percentage of carbon (C) is AlF31.8wt.%.
(2)V2O5/AlF3The preparation of C
According to V2O5The mass percentage of oxide is carrier AlF3The 1.0wt.% of C prepares corresponding VOC2O4· 5H2O solution.Take 0.27g VOC2O4·5H2O is dissolved in 25mL deionized water and obtains VOC2O4·5H2O solution.9.90g is carried Body AlF3C is added to VOC2O4·5H2It in O solution, is impregnated 4 hours after mixing, the lower 90 DEG C of fried drys of water bath condition, then through 120 DEG C dry 12 hours, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, V is made2O5/AlF3C powder.
(3)C/V2O5/AlF3C catalyst preparation
It is V according to citric acid mass percentage2O5/AlF3The 2.0wt.% of C prepares citric acid solution.Weigh 0.1g Citric acid is dissolved in 25ml deionized water and aqueous citric acid solution is prepared.By 4.90g V2O5/AlF3C powder is added to It in aqueous citric acid solution, is impregnated 4 hours after mixing, the lower 80 DEG C of fried drys of water bath condition, it is then 12 hours dry by 100 DEG C, then In N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/V2O5/AlF3The quality percentage of C catalyst, the C that actual loading is got on contains Amount is V2O5/AlF3The 0.38% of C.
(4) catalyst performance is tested: by prepared fine catalyst, by compression molding, 40-60 mesh is selected after crushing Particle, dosage 0.5ml is fitted into chromium nickel stainless steel reaction tube (internal diameter 1cm).React HFC- in mixed raw material gas 245fa and nitrogen volume ratio are 0.3, reaction velocity 1680h-1, measure the conversion of the HFC-245fa under 320 DEG C of reaction temperatures The selectivity of rate and HFO-1234ze.The conversion ratio of HFC-245fa and the selectivity of HFO-1234ze after catalyst reaction 1 hour It is shown in Table 1.
Embodiment 2:
(1)AlF3Preparing for C carrier is same as Example 1.
(2)V2O5/AlF3The preparation of C
According to V2O5The mass percentage of oxide is carrier AlF3The 2.0wt.% of C prepares corresponding VOC2O4· 5H2O solution.Take 0.54g VOC2O4·5H2O is dissolved in 25mL deionized water and obtains VOC2O4·5H2O solution.9.80g is carried Body AlF3C is added to VOC2O4·5H2It in O solution, is impregnated 4 hours after mixing, the lower 90 DEG C of fried drys of water bath condition, then through 120 DEG C dry 12 hours, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, V is made2O5/AlF3C powder.
(3)C/V2O5/AlF3Preparing for C catalyst is same as Example 1
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Embodiment 3:
(1)AlF3Preparing for C carrier vector is same as Example 1.
(2)V2O5/AlF3The preparation of C
According to V2O5The mass percentage of oxide is carrier AlF3The 3.0wt.% of C prepares corresponding VOC2O4· 5H2O solution.Take 0.81g VOC2O4·5H2O is dissolved in 25mL deionized water and obtains VOC2O4·5H2O solution.9.70g is carried Body AlF3C is added to VOC2O4·5H2It in O solution, is impregnated 4 hours after mixing, the lower 90 DEG C of fried drys of water bath condition, then through 120 DEG C dry 12 hours, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, V is made2O5/AlF3C powder.
(3)C/V2O5/AlF3Preparing for C catalyst is same as Example 1
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Embodiment 4:
(1)AlF3Preparing for C carrier vector is same as Example 1.
(2)V2O5/AlF3The preparation of C
According to V2O5The mass percentage of oxide is carrier AlF3The 4.0wt.% of C prepares corresponding VOC2O4· 5H2O solution.Take 1.08g VOC2O4·5H2O is dissolved in 25mL deionized water and obtains VOC2O4·5H2O solution.9.60g is carried Body AlF3C is added to VOC2O4·5H2It in O solution, is impregnated 4 hours after mixing, the lower 90 DEG C of fried drys of water bath condition, then through 120 DEG C dry 12 hours, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, V is made2O5/AlF3C powder.
(3)C/V2O5/AlF3Preparing for C catalyst is same as Example 1
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Embodiment 5:
(1)AlF3Preparing for C carrier vector is same as Example 1.
(2)V2O5/AlF3Preparing for C catalyst is same as Example 3
(3)C/V2O5/AlF3C preparation
It is V according to citric acid mass percentage2O5/AlF3The 1.0wt.% of C prepares citric acid solution.It weighs 0.05g citric acid is dissolved in 25ml deionized water and aqueous citric acid solution is prepared.By 4.95g V2O5/AlF3C powder adds Enter into aqueous citric acid solution, impregnated 4 hours after mixing, the lower 80 DEG C of fried drys of water bath condition are then small by 100 DEG C of dryings 12 When, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/V2O5/AlF3C catalyst, the quality hundred for the C that actual loading is got on Dividing content is V2O5/AlF3The 0.19% of C.
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Embodiment 6:
(1)AlF3Preparing for C carrier vector is same as Example 1.
(2)V2O5/AlF3Preparing for C catalyst is same as Example 3
(3)C/V2O5/AlF3C preparation
It is V according to citric acid mass percentage2O5/AlF3The 3.0wt.% of C prepares citric acid solution.It weighs 0.15g citric acid is dissolved in 25ml deionized water and aqueous citric acid solution is prepared.By 4.85g V2O5/AlF3C powder adds Enter into aqueous citric acid solution, impregnated 4 hours after mixing, the lower 80 DEG C of fried drys of water bath condition are then small by 100 DEG C of dryings 12 When, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/V2O5/AlF3C catalyst, the quality hundred for the C that actual loading is got on Dividing content is V2O5/AlF3The 0.58% of C.
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Embodiment 7:
(1)AlF3Preparing for C carrier vector is same as Example 1.
(2)V2O5/AlF3Preparing for C catalyst is same as Example 3
(3)C/V2O5/AlF3C preparation
It is V according to citric acid mass percentage2O5/AlF3The 4.0wt.% of C prepares citric acid solution.Weigh 0.2g Citric acid is dissolved in 25ml deionized water and aqueous citric acid solution is prepared.By 4.80g V2O5/AlF3C powder is added to It in aqueous citric acid solution, is impregnated 4 hours after mixing, the lower 80 DEG C of fried drys of water bath condition, it is then 12 hours dry by 100 DEG C, then In N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/V2O5/AlF3The quality percentage of C catalyst, the C that actual loading is got on contains Amount is V2O5/AlF3The 0.78% of C.
(4) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 1.
Comparative example 1
AlF3C carrier is as catalyst gas phase catalysis 1,1,1,3,3- pentafluoropropane cracking performance
(1)AlF3Preparing for C carrier is same as Example 1.
(2) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 2.
Comparative example 2
V2O5/AlF3C catalyst gas phase catalysis 1,1,1,3,3- pentafluoropropane cracking performance
(1)AlF3Preparing for C carrier is same as Example 1.
(2)V2O5/AlF3Preparing for C catalyst is same as Example 2.
(3) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 2.
Comparative example 3
C/AlF3C cracks 1,1,1,3,3- pentafluoropropane reactivity worth as catalyst gas phase catalysis
(1)AlF3Preparing for C carrier is same as Example 1.
(2)C/AlF3The preparation of C
It is carrier AlF according to the mass percentage of citric acid3It is water-soluble to prepare corresponding citric acid by the 2.0wt.% of C Liquid.It weighs 0.1g citric acid and is dissolved in 25ml deionized water and aqueous citric acid solution is prepared.By 4.90gAlF3C powder It is added in aqueous citric acid solution, is impregnated 4 hours after mixing, the lower 80 DEG C of fried drys of water bath condition are then small by 100 DEG C of dryings 12 When, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains C/AlF3The quality percentage of C catalyst, the C that actual loading is got on contains Amount is V2O5/AlF3The 0.45% of C.
(3) catalyst performance test is same as Example 1, and catalytic perfomance is shown in Table 2.
Table 1: embodiment catalyst cracks conversion ratio and the HFO-1234ze choosing of HFC-245fa under 320 DEG C of reaction temperatures Selecting property
Table 2: the conversion ratio and HFO-1234ze of HFC-245fa are cracked under 320 DEG C of reaction temperatures of comparative example catalyst Selectivity
By C/V in embodiment 62O5/AlF3C catalyst carries out stability test, and experimental result is shown in Fig. 1.Catalyst is initial Catalytic activity is 94.8%, and after reaction 100 hours, the conversion ratio of HFC-245fa drops to 91.4%, and conversion ratio only declines 3.4%.For HFO-1234ze selectivity close to 100%, the variation of reaction front and back is unobvious.
In conclusion 6 catalyst (C/V of embodiment2O5/AlF3C) catalytic pyrolysis HFC-245fa generates 1,3,3,3- tetra- The performance of fluoropropene is best, and the high conversion rate of HFC-245fa is and with good stability up to 94.8%.Consolidated statement 1 and table 2 as a result, it has been found that, reaction temperature be 320 DEG C when, carrier AlF3C catalytic pyrolysis HFC-245fa is converted into 1,3,3,3- tetrafluoro third The conversion ratio of alkene is 79.5%.The conversion ratio of HFC-245fa can be improved when having loaded V and citric acid to a certain extent.Institute There is catalyst in embodiment to have very high selectivity (> 99%) to 1,3,3,3- tetrafluoropropene.6 catalyst of embodiment simultaneously (C/V2O5/AlF3C) after reaction 100 hours, it is able to maintain preferable stability and highly selective.

Claims (2)

1. a kind of catalyst for preparing HFO-1234ze for HFC-245fa, it is characterised in that: catalyst is by carrier and active group It is grouped as, the carrier is AlF3C, wherein the mass percentage of C is AlF31.8wt.%, the active component is V2O5With the mixture of C, active component loads in two times, first time supported V2O5, V2O5Mass percentage be carrier AlF31.0~4.0wt.% of C；Second by loading citric acid, progress N2500 DEG C of roastings are converted into C, the matter of C in atmosphere It measures percentage composition and V is calculated as with citric acid adding amount2O5/AlF31.0~4.0wt.% of C.
2. the preparation method of catalyst described in claim 1 is held sign and is: combined using sol-gal process and infusion process, Specific step is as follows:
(1)AlF3The preparation of C carrier
It takes aluminium isopropoxide and isopropanol in polytetrafluoroethylene (PTFE) cup, dissolution is sufficiently stirred under 50 DEG C of water-baths, then takes The HF solution of 40wt.% is slowly dropped into, and Al atom and F atom stoichiometric ratio are 1:3, obtained colloidal sol, through aging, drying, AlF is made in roasting3C carrier, wherein the mass percentage of carbon is AlF31.8wt.%；
(2)V2O5/AlF3The preparation of C catalyst
According to V2O5The mass percentage of oxide is carrier AlF31.0~4.0wt.% of C, by carrier AlF3C dipping In VOC2O4·5H2It is dry by fried dry in O solution, then in N2It is roasted under atmosphere, V is made2O5/AlF3C powder；
(3)C/V2O5/AlF3The preparation of C catalyst
It is V according to citric acid mass percentage2O5/AlF31.0~4.0wt.% of C, by V2O5/AlF3C impregnates lemon Acid solution, it is dry by fried dry, then in N2It is roasted 4 hours for 500 DEG C in atmosphere, obtains finished catalyst.
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CN105935593A (en) * 2016-01-14 2016-09-14 浙江师范大学 Catalyst for converting HFC-245fa into trans 1,3,3-tetrafluoropropene and preparation method thereof
CN107042104A (en) * 2017-06-06 2017-08-15 浙江师范大学 HFO 1234ze processed catalyst and preparation method thereof is cracked for HFC 245fa

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