CN102513136B - Fluorinated chrome base fluorination catalyst and application thereof - Google Patents
Fluorinated chrome base fluorination catalyst and application thereof Download PDFInfo
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- CN102513136B CN102513136B CN201110379806.2A CN201110379806A CN102513136B CN 102513136 B CN102513136 B CN 102513136B CN 201110379806 A CN201110379806 A CN 201110379806A CN 102513136 B CN102513136 B CN 102513136B
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Abstract
The invention discloses a fluorinated chrome base fluorination catalyst and application thereof. The weight percentage composition of a precursor of the catalyst is that chromic oxide 80.0%-99.0% and rare-earth metal oxide 1.0%-20.0%, wherein the rare-earth metal oxide is selected from one or more of CeO2, La2O3, Nd2O3, Y2O3, ZrO2 and Yb2O3. The precursor of the catalyst is roasted at 300 DEG C-400 DEG C, and the fluorinated chrome base fluorination catalyst is obtained by fluorating the precursor of the catalyst by utilizing hydrogen fluoride gas at 350-450 centidegree. The obtained fluorination catalyst has the advantages of being good in carbon deposit resistance performance and activation and the like. The catalyst is mainly used for preparation of hydrofluoroolefin and hydrogen fluorine chlorine olefins.
Description
Technical field
The present invention relates to a kind of fluorinated chrome base fluorination catalyst synthesizing HF hydrocarbon and uses thereof.Especially the fluorination catalyst preparing HF hydrocarbon (HFOs) or hydrogen perhaloalkenes (HCFOs) for gas phase fluorination halogenated hydrocarbons is related to.
Background technology
In recent years, due to global warming, HF hydrocarbon (HFOs) and hydrogen perhaloalkenes (HCFOs) are used for alternative hot room effect in a large number and are dived the hydrogen fluorohydrocarbon (HFCs) of value (GWPs).
In fluorine chemical, often adopt the method for gas phase fluorination halogenated hydrocarbons to prepare HFOs and HCFOs, it is simple that this method has equipment, is easy to the advantages such as continuous large-scale production, safety.What play the role of a nucleus in gas phase fluorination halohydrocarbons reaction is fluorination catalyst.At present, industrial catalysts for gas phase fluorination is for containing chromium fluorination catalyst.
Such as Chinese patent 200410101551.3 discloses a kind of chromium-based fluorination catalyst, this catalyst mixes 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 high micropore ratio, the chromium-based fluorination catalyst of high stability.
Current chromium-based fluorination catalyst, mainly be used in synthesis hydrogen fluorohydrocarbon (HFCs), also may be used for the fluorination reaction of serial HF hydrocarbon (HFOs) and hydrogen perhaloalkenes (HCFOs), but in the fluorination reaction of HF hydrocarbon (HFOs) and hydrogen perhaloalkenes (HCFOs), the catalytic activity of above-mentioned chromium-based fluorination catalyst is lower, and the easy carbon distribution of such fluorination catalyst, catalytic life is shorter.
Summary of the invention
Technical problem to be solved by this invention is the deficiency overcoming technical background, provides the fluorinated chrome base fluorination catalyst that a kind of catalytic life is longer and catalytic activity is high.
Another technical problem to be solved by this invention is the purposes of above-mentioned fluorinated chrome base fluorination catalyst at preparation HFOs or HCFOs.
In order to solve the problems of the technologies described above, the presoma mass percent of fluorinated chrome base fluorination catalyst of the present invention consists of: chromium oxide 80.0% ~ 99.0%; Rare-earth oxide 1.0% ~ 20.0%; Wherein rare-earth oxide is selected from CeO
2, La
2o
3, Nd
2o
3, Y
2o
3, ZrO
2and Yb
2o
3in one or more.This fluorinated chrome base fluorination catalyst obtains by the following method:
1) aqueous solution of the soluble-salt of chromium and the soluble-salt of rare-earth oxide is contained by the preparation of presoma mass percent, ammoniacal liquor regulates the pH value of the soluble-salt aqueous solution to be 7.5 ~ 8.0, through precipitation, aging, filter, washing, drying, 300 ~ 400 DEG C of roasting roastings 8 hours, granulation, shaping, obtain catalyst precursor; Wherein said soluble-salt is nitrate, sulfate, chlorate or oxalates;
2) catalyst precursor is fluoridized 12 hours at 350 DEG C ~ 450 DEG C with hydrogen fluoride gas, obtain fluorinated chrome base fluorination catalyst.
The preparation of fluorinated chrome base fluorination catalyst of the present invention, the preferred chlorate of soluble-salt of chromium, the soluble-salt preferably nitrate of rare earth metal.
Preferred fluorinated chromium-based fluorination catalyst of the present invention, the mass percent of its precursor consists of: chromium oxide: 80%; Rare-earth oxide CeO
2: 7.0%, La
2o
3: 5.0%, Nd
2o
3: 2.0%, Y
2o
3: 2.0%, ZrO
2: 2.0%, Yb
2o
3: 2.0%;
The sintering temperature of catalyst precursor is 300 ~ 400 DEG C, preferably 350 DEG C.
The temperature of the catalyst precursor hydrogen fluoride fluorination treatment after high-temperature roasting is 350 ~ 450 DEG C, preferably 400 DEG C, and more preferably initially fluoridizing temperature is 300 DEG C, is warming up to 400 DEG C gradually and continues to fluoridize.
Fluorinated chrome base fluorination catalyst of the present invention is used for the purposes that halogenated hydrocarbons prepares HF hydrocarbon or hydrogen perhaloalkenes.
Fluorinated chrome base fluorination catalyst of the present invention is applicable to gas phase fluorination halohydrocarbons reaction preparation series preparation HFOs or HCFOs.Halogenated hydrocarbons can be 1, 1, 1, 3-tetra-chloropropane (TCP), 1, 1, 1, 3, 3-pentachloropropane (HCC-240fa), 1, 1, 1, 2, 2-pentachloropropane (HCC-240ab), 1, 1, 1, 2, 3-pentachloropropane (HCC-240db), 1-chloro-3, 3, 3-trifluoro propene (HCFO-1233zd), 1-chloro-1, 3, 3, 3-tetrafluoeopropene (HCFC-244fa), 1, 1, 2, 3-tetrachloropropylene (HCC-1230xf), 2, 3, 3, 3-tetrachloropropylene (HCFO-1233xf), 2-chloro-1, 1, 1, 2-tetrafluoropropane (HCFC-244bb), 1, 1, 1, 2, 3-pentafluoropropane (HFC-245eb), 1, 1, 1, 2, 2-pentafluoropropane (HFC-245cb), 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa), 1, 1, 1, 2, 3, 3-HFC-236fa (HFC-236ea) etc., HFOs or HCFOs is trifluoro propene (HFO-1243zf), HCFO-1233zd, 1,3,3,3-tetrafluoeopropene (HFO-1234ze), HCFO-1233xf, 2,3,3,3-tetrafluoeopropene (HFO-1234yf), 1,1,1,2,3-five fluorine propylene (HFO-1225ye) etc.
Advantage of the present invention:
The service life of fluorinated chrome base fluorination catalyst of the present invention is longer, such as gas phase fluorination HCFO-1233zd synthesize HFO-1234ze, HCFC-244fa take off HCl Reactive Synthesis HFO-1234ze, HCFC-244bb take off HCl Reactive Synthesis HFO-1234yf and HFC-236ea take off HF Reactive Synthesis HFO-1225ye react in, the service life of this fluorinated chrome base fluorination catalyst is all not less than 200 hours; Synthesize HCFO-1233xf, gas phase fluorination HCC-1230xf at gas phase fluorination HCC-240ab to synthesize in HCFO-1233xf, gas phase fluorination TCP synthesis HFO-1243zf, gas phase fluorination HCC-240db synthesis HCFO-1233xf and gas phase fluorination HCC-240fa synthesis HCFO-1233zd reaction, the service life of this fluorinated chrome base fluorination catalyst is not less than 500 hours.
The better catalytic activity of fluorinated chrome base fluorination catalyst of the present invention, its yield synthesizing HFO-1234ze at HCFO-1233zd can reach 82.8%, the yield synthesizing HCFO-1233zd at HCC-240fa can reach 94.0%, the yield synthesizing HFO-1243zf at TCP can reach 98.0%, the yield synthesizing HCFO-1233xf at HCC-240ab or HCC-240db or HCC-1230xf can reach 94.0%, HCFC-244fa synthesizes the yield of HFO-1234ze and can reach the yield that 85.5%, HCFC-244bb synthesizes HFO-1234yf and can reach 82.8%.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide CeO
2: 7.0%, La
2o
3: 5.0%, Nd
2o
3: 2.0%, Y
2o
3: 2.0%, ZrO
2: 2.0%, Yb
2o
3: 2.0%.
The preparation of catalyst:
In tank reactor, chromium chloride, Ce (NO is prepared by the mass percent of above-mentioned chromium-based fluorination catalyst presoma
3)
4, La (NO
3)
3, Nd (NO
3)
3, Y (NO
3)
3, Zr (NO
3)
4with Yb (NO
3)
3the aqueous solution, temperature 20 DEG C ~ 90 DEG C stir under add ammoniacal liquor, regulate the pH value of the above-mentioned aqueous solution to be 7.5 ~ 8.5, static, filter, wash obtained filter cake with water, and after the filter cake obtained in temperature 100 DEG C ~ 200 DEG C dryings, by its compression molding, 300 DEG C ~ 400 DEG C roastings 8 hours, obtain catalyst precursor, the presoma of this gained is through granulation, shaping, and fluoridize 12 hours at 350 DEG C ~ 450 DEG C hydrogen fluoride gas, obtain fluorinated chrome base fluorination catalyst.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorinated chrome base fluorination catalyst of 60ml, pass into HF and HCFO-1233zd and react, the mol ratio of control HF/HCFO-1233zd is 10: 1, time of contact is 10.9 seconds, reaction temperature 380 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 90.0%, HFO-1234ze is 92.0% with the conversion ratio of gas chromatographic analysis HCFO-1233zd; Reacting 200 hours, be the selective of 80.0%, HFO-1234ze is 90.0% with the conversion ratio of gas chromatographic analysis HCFO-1233zd.
Embodiment 2
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide CeO
2: 20.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and HCC-240fa to react, the mol ratio of control HF/HCC-240fa is 10: 1, and time of contact is 5.5 seconds, reaction temperature 200 DEG C, product is after washing, alkali cleaning removing HCl and HF, reacting 20 hours, be the selective of 100%, HCFO-1233zd is 94.0% with the conversion ratio of gas chromatographic analysis HCC-240fa; Reacting 200 hours, be the selective of 100%, HCFO-1233zd is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240fa.
Embodiment 3
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 99.0%; Rare-earth oxide La
2o
3: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,1,2,2-pentachloropropane (HCC-240ab) is reacted, the mol ratio of control HF/HCC-240ab is 15: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 94.0% with the conversion ratio of gas chromatographic analysis HCC-240ab; Reacting 500 hours, be the selective of 90.0%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240ab.
Embodiment 4
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide Nd
2o
3: 10.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
HF and 1,1,2,3-tetrachloropropylene react, and the mol ratio of control HF/1,1,2,3-tetrachloropropylene is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 93.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene; Reacting 500 hours, be the selective of 92.0%, HCFO-1233xf is 93.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene.Embodiment 5
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide Y
2o
3: 10.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,1,2,2-pentachloropropane (HCC-240ab) is reacted, the mol ratio of control HF/HCC-240ab is 15: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240ab; Reacting 500 hours, be the selective of 90.0%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240ab.
Embodiment 6
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 99.0%; Rare-earth oxide Yb
2o
3: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
HF and TCP reacts, and the mol ratio of control HF/TCP is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HFO-1243zf is 98.0% with the conversion ratio of gas chromatographic analysis TCP; Reacting 500 hours, be the selective of 92.0%, HFO-1243zf is 95.0% with the conversion ratio of gas chromatographic analysis TCP.
Embodiment 7
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide CeO
2: 14.0%, La
2o
3: 6.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,1,2,3-pentachloropropane (HCC-240db) is reacted, the mol ratio of control HF/CC-240db is 15: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240db; Reacting 500 hours, be the selective of 91.0%, HCFO-1233xf is 91.0% with the conversion ratio of gas chromatographic analysis HCC-240db
Embodiment 8
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide: CeO
2: 5.0%, Nd
2o
3: 5.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HFC-236ea and react, time of contact is 30 seconds, reaction temperature 380 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 70%, HFO-1225ye is 90.0% with the conversion ratio of gas chromatographic analysis HFC-236ea; Reacting 200 hours, be the selective of 50.0%, HFO-1225ye is 90.0% with the conversion ratio of gas chromatographic analysis HFC-236ea.
Embodiment 9
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide Y
2o
3: 14.0%, La
2o
3: 6.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,1,2,3-pentachloropropane (HCC-240db) is reacted, the mol ratio of control HF/HCC-240db is 15: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis HCC-240db; Reacting 500 hours, be the selective of 90.0%, HCFO-1233xf is 91.0% with the conversion ratio of gas chromatographic analysis HCC-240db.
Embodiment 10
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 95.0%; Rare-earth oxide La
2o
3: 5.0%, Yb
2o
3: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
HF and TCP reacts, and the mol ratio of control HF/TCP is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HFO-1243zf is 97.0% with the conversion ratio of gas chromatographic analysis TCP; Reacting 500 hours, be the selective of 90.0%, HFO-1243zf is 92.0% with the conversion ratio of gas chromatographic analysis TCP.
Embodiment 11
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide CeO
2: 10.0%, La
2o
3: 9.0%, Y
2o
3: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,2,3-tetrachloropropylene reacts, control HF/1,1, the mol ratio of 2,3-tetrachloropropylene is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene; Reacting 500 hours, be the selective of 90.0%, HCFO-1233xf is 90.5% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene.
Embodiment 12
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide CeO
2: 1.0%, Nd
2o
3: 9.0%, Y
2o
3: 10.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,2,3-tetrachloropropylene reacts, control HF/1,1, the mol ratio of 2,3-tetrachloropropylene is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene; Reacting 500 hours, be the selective of 91.0%, HCFO-1233xf is 90.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene.
Embodiment 13
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide La
2o
3: 10.0%, Y
2o
3: 9.0%, ZrO
2: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HF and 1,1,2,3-tetrachloropropylene reacts, control HF/1,1, the mol ratio of 2,3-tetrachloropropylene is 10: 1, and time of contact is 10.9 seconds, reaction temperature 260 DEG C.Product is after washing, alkali cleaning removing HCl and HF, and reacting 20 hours, be the selective of 100%, HCFO-1233xf is 92.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene; Reacting 500 hours, be the selective of 90.0%, HCFO-1233xf is 90.0% with the conversion ratio of gas chromatographic analysis 1,1,2,3-tetrachloropropylene.
Embodiment 14
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide CeO
2: 4.0%, Nd
2o
3: 3.0%, Y
2o
3: 2.0%, ZrO
2: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244fa and react, time of contact is 10.9 seconds, reaction temperature 400 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234ze is 95.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa; Reacting 200 hours, be the selective of 72.0%, HFO-1234ze is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa.
Embodiment 15
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide CeO
2: 3.0%, Nd
2o
3: 2.0%, Y
2o
3: 3.0%, ZrO
2: 2.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244fa and react, time of contact is 10.9 seconds, reaction temperature 400 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234ze is 93.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa; Reacting 200 hours, be the selective of 74.0%, HFO-1234ze is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa.
Embodiment 16
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide CeO
2: 4.0%, La
2o
3: 4.0%, Y
2o
3: 1.0%, ZrO
2: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244fa and react, time of contact is 10.9 seconds, reaction temperature 400 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234ze is 93.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa; Reacting 200 hours, be the selective of 71.0%, HFO-1234ze is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa.
Embodiment 17
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide CeO
2: 1.0%, La
2o
3: 4.0%, Y
2o
3: 3.0%, Nd
2o
3: 2.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244fa and react, time of contact is 10.9 seconds, reaction temperature 400 DEG C.React after 20 hours, product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234ze is 92.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa; Reacting 200 hours, be the selective of 74.0%, HFO-1234ze is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244fa.
Embodiment 18
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide: CeO
2: 6.0%, La
2o
3: 5.0%, Nd
2o
3: 3.0%, Y
2o
3: 3.0%, Yb
2o
3: 3.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244bb and react, time of contact is 10.9 seconds, reaction temperature 350 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234yf is 92.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb; Reacting 200 hours, be the selective of 70.0%, HFO-1234yf is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb.
Embodiment 19
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 90.0%; Rare-earth oxide: CeO
2: 5.0%, La
2o
3: 2.0%, ZrO
2: 1.0%, Y
2o
3: 1.0%, Yb
2o
3: 1.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244bb and react, time of contact is 10.9 seconds, reaction temperature 350 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234yf is 91.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb; Reacting 200 hours, be the selective of 72.0%, HFO-1234yf is 89.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb.
Embodiment 20
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide: CeO
2: 6.0%, La
2o
3: 5.0%, Nd
2o
3: 3.0%, ZrO
2: 3.0%, Yb
2o
3: 3.0%.
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244bb and react, time of contact is 10.9 seconds, reaction temperature 350 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234yf is 92.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb; Reacting 200 hours, be the selective of 72.0%, HFO-1234yf is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb.
Embodiment 21
Mass percent composition with reference to following chromium-based fluorination catalyst presoma is implemented:
Chromium oxide: 80.0%; Rare-earth oxide: CeO
2: 6.0%, Y
2o
3: 5.0%, Nd
2o
3: 3.0%, La
2o
3: 3.0%, ZrO
2: 3.0%
The preparation of catalyst:
Catalyst preparation step is substantially the same manner as Example 1, is not both chromium-based fluorination catalyst presoma mass percent different.
The application of catalyst:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the above-mentioned obtained fluorination catalyst of 60ml, pass into HCFC-244bb and react, time of contact is 10.9 seconds, reaction temperature 350 DEG C.Product through washing, after alkali cleaning, react 20 hours, be the selective of 90.0%, HFO-1234yf is 91.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb; Reacting 200 hours, be the selective of 70.0%, HFO-1234yf is 90.0% with the conversion ratio of gas chromatographic analysis HCFC-244bb.
Claims (2)
1. a fluorinated chrome base fluorination catalyst, is characterized in that: the presoma mass percent of this catalyst consists of chromium oxide 80.0% ~ 99.0%; Rare-earth oxide 1.0% ~ 20.0%; Wherein rare-earth oxide is selected from La
2o
3, Nd
2o
3, Y
2o
3and Yb
2o
3in one or more, this catalyst obtains by the following method:
1) aqueous solution of the soluble-salt of chromium and the soluble-salt of rare-earth oxide is contained by the preparation of presoma mass percent, ammoniacal liquor regulates the pH value of the soluble-salt aqueous solution to be 7.5 ~ 8.0, through precipitation, aging, filter, washing, drying, 300 ~ 350 DEG C of roastings 8 hours, granulation, shaping, obtain catalyst precursor; Wherein above-mentioned soluble-salt is nitrate, sulfate, chlorate or oxalates;
2) catalyst precursor is fluoridized 12 hours at 350 ~ 450 DEG C with hydrogen fluoride gas, obtain fluorinated chrome base fluorination catalyst.
2. a fluorinated chrome base fluorination catalyst as claimed in claim 1 is used for the purposes that gas phase fluorination halohydrocarbons reaction prepares HFOs or HCFOs.
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| CN102989489B (en) * | 2011-09-14 | 2015-04-22 | 中化蓝天集团有限公司 | 2,3,3,3-tetrafluoropropylene preparation method |
| CN103055843B (en) * | 2012-12-31 | 2015-06-24 | 浙江衢化氟化学有限公司 | Catalyst for synthesizing 2,3,3,3-tetrafluoropropene and preparation method and application thereof |
| WO2016025288A1 (en) | 2014-08-14 | 2016-02-18 | The Chemours Company Fc, Llc | Process for the production of e-1,3,3,3-tetrafluoropropene (hfc-1234ze) by dehydrofluorinatiokl |
| CN107552064B (en) * | 2017-08-11 | 2018-12-04 | 乳源东阳光氟有限公司 | A kind of fluorination catalyst and preparation method thereof |
| CN107519901A (en) * | 2017-08-25 | 2017-12-29 | 乳源东阳光氟有限公司 | A kind of method that chromate waste water recovery prepares fluorination catalyst |
| 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 |
| CN108440261A (en) * | 2018-04-20 | 2018-08-24 | 北京宇极科技发展有限公司 | The preparation method of perfluor ketone |
| CN109569674B (en) * | 2018-11-06 | 2019-10-18 | 东莞东阳光科研发有限公司 | A kind of fluorination catalyst and its preparation method and application |
| CN113527049A (en) * | 2020-04-22 | 2021-10-22 | 陕西中蓝化工科技新材料有限公司 | Process for coproducing trans/cis-HFO-1234 ze and HFO-1234yf |
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| CN1099375A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Method of producing fluoro halohydrocarbon and fluorohydrocarbon by gas-phase catalysis |
| CN1099314A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Preparation of catalysts fluoride and its application |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
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| WO2008030440A2 (en) * | 2006-09-05 | 2008-03-13 | E. I. Du Pont De Nemours And Company | Process to manufacture 2,3,3,3-tetrafluoropropene |
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| CN1099375A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Method of producing fluoro halohydrocarbon and fluorohydrocarbon by gas-phase catalysis |
| CN1099314A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Preparation of catalysts fluoride and its application |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
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