CN103920484A - Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof - Google Patents
Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof Download PDFInfo
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- CN103920484A CN103920484A CN201310012803.4A CN201310012803A CN103920484A CN 103920484 A CN103920484 A CN 103920484A CN 201310012803 A CN201310012803 A CN 201310012803A CN 103920484 A CN103920484 A CN 103920484A
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Abstract
The invention discloses a catalyst for a hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane. A catalyst precursor is formed by an aluminum-containing compound, a modified component A and a modified component B, and then the catalyst is obtained by baking and carrying out fluorination treatment of the catalyst precursor, wherein the modified component A is a combination of one, two, three or more selected from compounds of lanthanide metals, group IIIA metals, group IVB metals and group VA metals, and the modified component B is a combination of one, two, three or more selected from compounds of bentonite, graphite, silicon carbide, pseudo-boehmite and a sesbania powder. The catalyst provided by the invention is low in cost, high in activity, long in service life, and simple in preparation process, and can overcome the defects that a commonly used aluminum-based catalyst is severe in carbon deposition, short in service life, complicated in preparation process and the like.
Description
Technical field
The present invention relates to a kind of fluorination catalyst, particularly relate to a kind of Catalysts and its preparation method for acetylene hydrofluorination reaction.
Background technology
PVF (VF) is a kind of important fluorochemical monomer, can be used for preparing polyvinyl fluoride (PVF) and fluorine-containing fine chemicals.Wherein PVF is the one that in fluororesin, fluorinated volume is minimum, density is minimum; there is the characteristics such as good chemical resistance, hydrophobicity, wearability, resistance to ag(e)ing and non-viscosity, be widely used in inside coating, oil field oil pipeline anticorrosion etc. of encapsulation, the packing container of protective layer, aircraft industry and the solar cell of construction material.
1,1-Difluoroethane (HFC-152a) is a kind of good ozone consuming substances substitute, is again the intermediate of producing polyvinylidene fluoride resin.Du Pont adopts HFC-152a cracking process to prepare the monomer of polyfluoroethylene resin; Synthetic fluororesin is had many uses, and the market demand is vigorous.
In prior art, mainly contain with the synthetic VF of acetylene method and HFC-152a catalyst used: compound containing mercury, containing cadmium compound, containing composite catalyst, zinc compound and the aluminum contained compound of chromium compound, fluosulfonic acid and metal chloride.Although zinc-base catalyst is selectively high, its poor stability, service life are not long.Containing not only price but also difficult preparation of mercury catalyst, also unstable, strong toxicity.Toxicity containing cadmium catalyst and fluosulfonic acid/metal chloride composite catalyst is also very strong.Aluminium-based catalyst has raw material cheaply to be produced easily, and after reaction, waste residue is processed the advantages such as easy, is the catalyst that has research and application prospect most.
US Patent No. 2471525 discloses name and has been called: the patented technology of Reaction of an acetylene with HF to produce vinyl fluoride and/or difluoroethane and homologues thereof, use Al
2o
3, AlF
3, load has metal fluoride (as SbF
3, ZnF
2, CdF
2, CoF
2) Al
2o
3catalyst, carries out hydrofluorination reaction to alkynes.Result shows, as independent use Al
2o
3while making catalyst, the conversion ratio of acetylene is 70～80%, and load the Al of metal fluoride
2o
3while making catalyst, C
2h
2conversion ratio can bring up to more than 95%.But this catalytic reaction process initial stage can generate water, tar and gaseous by-products, cause the selective decline of VF and HFC-152a, and water is combined rear generation macro-corrosion liquid corrosion equipment with unreacted hydrogen fluoride, tar can result in blockage to reaction unit.
US Patent No. 2716142 discloses name and has been called: Preparation of vinyl fluoride and1, the patented technology of 1-difluoroethane and catalyst therefore, uses Al
2(SO
4)
3as catalyst, after 100～200 DEG C are fluoridized pretreatment, prepare VF for acetylene hydrofluorination.At 320 DEG C, HF and C
2h
2mol ratio be 3: 1, C
2h
2volume space velocity is 28h
-1time, C
2h
2conversion ratio be 95.1%, now HFC-152a is primary product, is selectively 86.6%; Improve reaction temperature to 400 DEG C, C
2h
2volume space velocity to 205h
-1, C
2h
2conversion ratio drop to 81.0%, and VF selectively up to 93.8%.
US Patent No. 3187060 discloses name and has been called: the patented technology of Process for hydrofluorination of acetylenic hydrocarbons, and by anhydrous AlCl
3with porous α-Al
2o
3after mixing by the volume ratios of 2: 5, fluoridize pretreatment, at 280 DEG C, HF and C
2h
2mol ratio be 1: 1, C
2h
2volume space velocity be 110h
-1condition under carry out acetylene hydrofluorination reaction, reaction 200h after, C
2h
2conversion ratio be 80%, VF be selectively 78%.
Chinese patent CN101367037A discloses name and has been called: a kind of acetylene in gas phase is fluoridized the patented technology of the method for preparing PVF, adopt prepared by the precipitation method taking Al, Zn as main body, add the catalyst containing one or more compounds in Mg, Y, Sm, La, produce VF and R152a for acetylene hydrofluorination reaction.At 300 DEG C, HF and C
2h
2mol ratio be 2.5: l, air speed 900h
-1condition under, it is selectively 73.0% that conversion ratio reaches as high as 96.0%, VF.But the preparation of this catalyst is had relatively high expectations to precipitating reagent and deposition condition, is not suitable for industrial amplification production.
Therefore needing to find a kind of catalyst that can better solve acidity of catalyst, coke content and reactivity fluoridizes and prepares PVF and 1,1-Difluoroethane for acetylene in gas phase.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, activity is high, the life-span is long, the simple Catalysts and its preparation method of preparation technology, for the synthetic PVF and 1 of acetylene in gas phase method, 1-Difluoroethane, solves at present the problems such as, service life short, complicated process of preparation serious for the existing carbon distribution of aluminium-based catalyst of acetylene hydrofluorination reaction.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of acetylene hydrofluorination reaction that is used for is prepared PVF and 1, the catalyst of 1-Difluoroethane, first by aluminum contained compound, modified component A and modified component B composition catalyst precursor, after roasting and fluorination treatment, obtain again catalyst, described modified component A is selected from lanthanide series metal, IIIA is metal, IVB is that metal and VA are the one in the compound of metal, more than two or three combination, described modified component B is selected from bentonite, graphite, carborundum, boehmite, one in sesbania powder, more than two or three combination, described aluminum contained compound, the quality proportioning of modified component A and modified component B is 65%～98.5%: 1%～25%: 0.05%～10%.
The present invention is by adding acidity and the pore passage structure of modified component A modulation aluminium-based catalyst, thereby raising catalytic performance weakens the generation of knot carbon reaction.It is that metal, IVB are that metal and VA are one, more than two or three combination in the compound of metal that available modified component A is selected from lanthanide series metal, IIIA, be preferably one in the compound that is selected from lanthanum, cerium, zirconium, boron, gallium, indium and bismuth, more than two or three combination, be more preferably selected from one in the compound of lanthanum, zirconium, boron, gallium and bismuth, more than two or three combine.Modified component A is preferably from corresponding oxide, hydroxide or the nitrate of lanthanum, cerium, zirconium, boron, gallium, indium and bismuth.
The present invention, by adding modified component B, obviously declines the hot(test)-spot temperature of beds, is conducive to industrial applications.Suitable modified component B is selected from one, more than two or three combination in bentonite, graphite, carborundum, boehmite, sesbania powder, is preferably the one, two or three being selected from bentonite, graphite and carborundum.
In catalyst precursor of the present invention, the quality proportioning that aluminum contained compound, modified component A and modified component B are suitable is 65%～98.5%: 1%～25%: 0.05%～10%, more preferably 85%～97%: 2%～10%: 1%～5%.Described aluminum contained compound is preferably aluminium oxide, aluminium hydroxide, aluminum fluoride, hydration aluminum fluoride or fluorine alumina.
The present invention also provides the preparation method of described catalyst, in accordance with the following methods preparation:
(1) preparation of catalyst precursor:
A, by modified component A at N
2under atmosphere, air atmosphere or vacuum condition, heat-treat, heat treatment temperature is 100～800 DEG C;
B, by aluminum contained compound, modified component A and modified component B by 65%～98.5%: 1%～25%: 0.05%～10% quality proportioning is carried out mechanical mixture;
C, by the catalyst powder extrusion modling mixing, 105～150 DEG C dry 6～24h, make catalyst precursor;
(2) catalyst precursor step (1) being made is roasting 2～12h at 200～500 DEG C of temperature, in inert gas atmosphere;
(3) mixture or the anhydrous hydrogen fluoride that in the catalyst precursor after the roasting making toward step (2), pass into anhydrous hydrogen fluoride and nitrogen carry out fluorination treatment 2～12h, and 150～400 DEG C for the treatment of temperatures, obtain catalyst.
The present invention also provides described catalyst to prepare the application in PVF and 1,1-Difluoroethane at acetylene hydrofluorination reaction, under catalyst action, PVF and 1 are prepared in HF and acetylene in gas phase reaction, 1-Difluoroethane, reaction temperature is preferably 220～320 DEG C, more preferably 240～320 DEG C; HF and C
2h
2mole proportion optimization be 1～3: l, more preferably 1.3～1.8: l; Raw material air speed is preferably 250～2500h
-1, more preferably 250～500h
-1.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these detailed description of the invention.One skilled in the art would recognize that the present invention contained all alternatives, improvement project and the equivalents that within the scope of claims, may comprise.
Embodiment 1
By La
2o
3, B
2o
3100 DEG C of processing 6h under air atmosphere, mix in mass ratio at 1: 1 respectively, obtain modified component A.By AlF
3, modified component A, bentonite mix by quality percentage composition 95%, 4%, 1%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 18h at 105 DEG C, makes catalyst precursor.Get in the carbon steel reaction tube that 300g catalyst precursor packs φ 30*1200 into, at N
2protect lower 200 DEG C of roasting 6h, then pass into HF: N
2=1: 12 mixture is fluoridized 2h at 150 DEG C, is warming up to 400 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 4h to pure HF, obtains catalyst of the present invention, is labeled as Cat.1-1.
Comparative example 1
With AlF
3as a comparison case, investigate and add modified component to the catalyst impact in service life.By AlF
3with the extrusion modling of wet mixing extrusion, dry 18h at 105 DEG C, make catalyst precursor.Get 300g catalyst precursor and pack diameter 30mm into, in the carbon steel reaction tube of length 1200mm, at N
2protect lower 200 DEG C of roasting 6h, then pass into HF: N
2=1: 12 mixture is fluoridized 2h at 150 DEG C, is warming up to 400 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 4h to pure HF, obtains catalyst of the present invention, is labeled as Cat.1-0.
The catalyst Cat.1-1, the Cat.1-0 that make are applied in acetylene hydrofluorination reaction, investigate activity and the service life of catalyst.250 DEG C of reaction temperatures, HF/C
2h
2mol ratio 1.3～1.5: 1, air speed 240～260h
-1.Catalyst Cat.1-1, Cat.1-0 are to C
2h
2reactivity and VF and HFC-152a selectively in table 1.As can be seen from Table 1, add modified component and not only make C
2h
2conversion ratio improves, and has extended the service life of catalyst, and successive reaction 330h, still has fine activity, is conducive to industrialized application.
Table 1. catalyst life
Embodiment 2
By La (NO
3)
3under nitrogen atmosphere, 400 DEG C of roasting 16h, obtain modified component A.By AlF
3, modified component A, graphite mix by quality percentage composition 85%, 10%, 5%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 24h at 105 DEG C, makes catalyst precursor.Get in the carbon steel reaction tube that 300g catalyst precursor packs ф 30*1200 into, at N
2protect lower 200 DEG C of roasting 16h, then pass into HF: N
2=1: 1 mixture is fluoridized 2h at 200 DEG C, is warming up to 320 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 4h to pure HF, obtains catalyst of the present invention, is labeled as Cat.2-1.
Comparative example 2
According to the method for embodiment 2, difference is not add graphite, obtains catalyst of the present invention, is labeled as Cat.2-0.By measuring beds hot(test)-spot temperature, investigate the diluting effect of modified component B to catalyst heat.
The catalyst Cat.2-1, the Cat.2-0 that make are applied in acetylene hydrofluorination reaction, investigate activity and the beds hot(test)-spot temperature of catalyst.250 DEG C of reaction temperatures, HF/C
2h
2mol ratio 1.3～1.5: 1, air speed 500～520h
-1.Catalyst Cat.2-1, Cat.2-0 are to C
2h
2the selective and beds hot(test)-spot temperature of reactivity, VF and HFC-152a in table 2.As can be seen from Table 2, add modified component B and not only can not make C
2h
2conversion ratio declines, and also makes the hot(test)-spot temperature of beds obviously decline, and is conducive to industrialized application.In table 2, data are mean value in reaction 90h.
The test of table 2. catalyst performance
Embodiment 3
By La (OH)
3under air atmosphere, 400 DEG C of roasting 6h, obtain modified component A.By AlF
3, modified component A, carborundum mix by quality percentage composition 85%, 10%, 5%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 24h at 120 DEG C, makes catalyst precursor.Get 10g catalyst precursor and pack diameter 14mm into, in the carbon steel reaction tube of length 600mm, at N
2protect lower 200 DEG C of roasting 6h, then pass into HF: N
2=1: 12 mixture is fluoridized 2h at 150 DEG C, is warming up to 350 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 4h to pure HF, obtains catalyst of the present invention, is labeled as Cat.3.
The catalyst Cat.3 that this embodiment is made is applied in acetylene hydrofluorination reaction, HF/C
2h
2mol ratio be 1.4: 1, it is to C
2h
2reactivity and VF and HFC-152a selectively in table 3.
Table 3. temperature and air speed are on reaction impact
Embodiment 4
By Ga (NO
3)
3under nitrogen atmosphere, 300 DEG C of roasting 12h, obtain modified component A.By AlF
3, modified component A, graphite mix by quality percentage composition 97%, 2%, 1%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 24h at 150 DEG C, makes catalyst precursor.Get 10g catalyst precursor and pack diameter 14mm into, in the carbon steel reaction tube of length 600mm, 300 DEG C of roasting 12h under He protection, then pass into HF: N
2=1: 4 mixture is fluoridized 2h at 200 DEG C, is warming up to 350 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 6h to pure HF, obtains catalyst of the present invention, is labeled as Cat.4.
The catalyst Cat.4 that this embodiment is made is applied in acetylene hydrofluorination reaction, and air speed is 500h
-1, it is to C
2h
2reactivity and VF and HFC-152a selectively in table 4.
Table 4. temperature and mol ratio are on reaction impact
Embodiment 5
By Bi
2o
3under air atmosphere, process 6h for 200 DEG C, obtain modified component A.By Al
2o
3, modified component A, graphite mix by quality percentage composition 94%, 5%, 1%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 24h at 150 DEG C, makes catalyst precursor.Get 10g catalyst precursor and pack diameter 14mm into, in the carbon steel reaction tube of length 600mm, 400 DEG C of roasting 12h under Ar protection, then pass into HF: N
2=1: 12 mixture is fluoridized 2h at 150 DEG C, is warming up to 370 DEG C and fluoridizes 2h, then increases gradually HF concentration and fluoridizes 6h to pure HF, obtains catalyst of the present invention, is labeled as Cat.5.
The catalyst Cat.5 that this embodiment is made is applied in acetylene hydrofluorination reaction, HF/C
2h
2mol ratio is 1.4: 1, and air speed is 500h
-1, it is to C
2h
2reactivity and VF and HFC-152a selectively in table 5.
Table 5. catalyst and temperature are on reaction impact
Embodiment 6
By ZrO
2vacuumizing 500 DEG C of roasting 4h under condition, obtain modified component A.By AlF
3, modified component A, bentonite mix by quality percentage composition 90%, 9%, 1%, through ball milling blend, with the extrusion modling of wet mixing extrusion, dries 18h at 150 DEG C, makes catalyst precursor.Get 10g catalyst precursor and pack diameter 14mm into, in the carbon steel reaction tube of length 600mm, 300 DEG C of roasting 12h under He protection, then pass into HF: N
2=1: 4 mixture is fluoridized 2h at 150 DEG C, is warming up to 400 DEG C and fluoridizes 1h, then increases gradually HF concentration and fluoridizes 4h to pure HF, obtains catalyst of the present invention, is labeled as Cat.6.
The catalyst Cat.6 that this embodiment is made is applied in acetylene hydrofluorination reaction, at 250 DEG C of reaction temperatures, HF and C
2h
2mol ratio be 1.8: 1, air speed 250h
-1condition under, C
2h
2conversion ratio is that 86.4%, VF is selectively that 47.6%, HFC-152a is selectively 51.9%.
Claims (8)
1. prepare PVF and 1 for acetylene hydrofluorination reaction for one kind, the catalyst of 1-Difluoroethane, it is characterized in that first by aluminum contained compound, modified component A and modified component B composition catalyst precursor, after roasting and fluorination treatment, obtain again catalyst, described modified component A is selected from lanthanide series metal, IIIA is metal, IVB is that metal and VA are the one in the compound of metal, more than two or three combination, described modified component B is selected from bentonite, graphite, carborundum, boehmite, one in sesbania powder, more than two or three combination, described aluminum contained compound, the quality proportioning of modified component A and modified component B is 65%～98.5%: 1%～25%: 0.05%～10%.
2. prepare PVF and 1 according to claimed in claim 1 for acetylene hydrofluorination reaction, the catalyst of 1-Difluoroethane, it is characterized in that described modified component A is selected from one, more than two or three combination in the compound of lanthanum, cerium, zirconium, boron, gallium, indium and bismuth, modified component B is selected from the one, two or three in bentonite, graphite and carborundum, and the quality proportioning of described aluminum contained compound, modified component A and modified component B is 85%～97%: 2%～10%: 1%～5%.
3. according to the catalyst of preparing PVF and 1,1-Difluoroethane for acetylene hydrofluorination reaction claimed in claim 2, described in it is characterized in that, urge modified component A to be selected from one, more than two or three combination in the compound of lanthanum, zirconium, boron, gallium and bismuth.
4. prepare PVF and 1 according to claimed in claim 1 for acetylene hydrofluorination reaction, the catalyst of 1-Difluoroethane, it is characterized in that in described catalyst precursor, aluminum contained compound is aluminium oxide, aluminium hydroxide, aluminum fluoride, hydration aluminum fluoride or fluorine alumina.
5. prepare PVF and 1 according to claimed in claim 2 for acetylene hydrofluorination reaction, the catalyst of 1-Difluoroethane, is characterized in that the modified component A in described catalyst is selected from the corresponding oxide of lanthanum, cerium, zirconium, boron, gallium, indium and bismuth, hydroxide or nitrate.
6. according to the catalyst of preparing PVF and 1,1-Difluoroethane for acetylene hydrofluorination reaction claimed in claim 1, it is characterized in that preparing in accordance with the following methods:
(1) preparation of catalyst precursor:
A, by modified component A at N
2under atmosphere, air atmosphere or vacuum condition, heat-treat, heat treatment temperature is 100～800 DEG C;
B, by aluminum contained compound, modified component A and modified component B by 65%～98.5%: 1%～25%: 0.05%～10% quality proportioning is carried out mechanical mixture;
C, by the catalyst powder extrusion modling mixing, 105～150 DEG C dry 6～24h, make catalyst precursor;
(2) catalyst precursor step (1) being made is roasting 2～12h at 200～500 DEG C of temperature, in inert gas atmosphere;
(3) mixture or the anhydrous hydrogen fluoride that in the catalyst precursor after the roasting making toward step (2), pass into anhydrous hydrogen fluoride and nitrogen carry out fluorination treatment 2～12h, and 150～400 DEG C for the treatment of temperatures, obtain catalyst.
7. according to the application of preparing the catalyst of PVF and 1,1-Difluoroethane for acetylene hydrofluorination reaction claimed in claim 1, it is characterized in that under catalyst action, PVF and 1 are prepared in HF and acetylene in gas phase reaction, 1-Difluoroethane, reaction temperature is 220～320 DEG C, HF and C
2h
2mole proportioning be 1～3: l, air speed is 250～2500h
-1.
8. according to the application of preparing the catalyst of PVF and 1,1-Difluoroethane for acetylene hydrofluorination reaction claimed in claim 7, it is characterized in that 240～320 DEG C of described reaction temperatures, HF and C
2h
2mole proportioning be 1.3～1.8: l, air speed is 250～500h
-1.
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|---|---|---|---|
| CN201310012803.4A CN103920484A (en) | 2013-01-14 | 2013-01-14 | Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof |
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|---|---|---|---|
| CN201310012803.4A CN103920484A (en) | 2013-01-14 | 2013-01-14 | Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866359A (en) * | 2015-12-14 | 2017-06-20 | 浙江省化工研究院有限公司 | A kind of method that PVF is prepared by 1,1- Difluoroethane cracking |
| CN110586200A (en) * | 2019-10-08 | 2019-12-20 | 西安凯立新材料股份有限公司 | Regeneration method of gold-carbon catalyst for acetylene hydrochlorination |
| CN111229274A (en) * | 2020-03-13 | 2020-06-05 | 浙江工业大学 | High-energy mechanical ball-milling SiC Lewis acid catalyst, and preparation method, preparation method and application thereof |
| CN112608213A (en) * | 2020-11-23 | 2021-04-06 | 浙江衢化氟化学有限公司 | Method for preparing 1, 1-difluoroethane in gas phase |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866359A (en) * | 2015-12-14 | 2017-06-20 | 浙江省化工研究院有限公司 | A kind of method that PVF is prepared by 1,1- Difluoroethane cracking |
| CN110586200A (en) * | 2019-10-08 | 2019-12-20 | 西安凯立新材料股份有限公司 | Regeneration method of gold-carbon catalyst for acetylene hydrochlorination |
| CN110586200B (en) * | 2019-10-08 | 2022-08-12 | 西安凯立新材料股份有限公司 | Regeneration method of gold-carbon catalyst for acetylene hydrochlorination |
| CN111229274A (en) * | 2020-03-13 | 2020-06-05 | 浙江工业大学 | High-energy mechanical ball-milling SiC Lewis acid catalyst, and preparation method, preparation method and application thereof |
| CN111229274B (en) * | 2020-03-13 | 2022-08-19 | 浙江工业大学 | High-energy mechanical ball-milling SiC Lewis acid catalyst and preparation method and application thereof |
| CN112608213A (en) * | 2020-11-23 | 2021-04-06 | 浙江衢化氟化学有限公司 | Method for preparing 1, 1-difluoroethane in gas phase |
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