CN105327695A - Chromium based catalyst for dehydrofluorination, and preparation method and application thereof - Google Patents
Chromium based catalyst for dehydrofluorination, and preparation method and application thereof Download PDFInfo
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- CN105327695A CN105327695A CN201410383447.1A CN201410383447A CN105327695A CN 105327695 A CN105327695 A CN 105327695A CN 201410383447 A CN201410383447 A CN 201410383447A CN 105327695 A CN105327695 A CN 105327695A
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Abstract
The invention discloses a chromium based catalyst ford ehydrofluorination. The catalyst contains 15mol%-95mol% of chromium and 5mol%-85mol% of an active metal, and the active metal is a combination of one, two or three selected from the group consisting of aluminum, zinc, magnesium, cobalt, nickel, iron and copper. The catalyst provided by the invention can be used for vinyl fluoride preparation through 1,1-difluoroethane cracking; and the catalyst has the advantages of simple preparation process, low cost of raw materials and high reaction activity and stability.
Description
Technical field
The present invention relates to a kind of chromium-based catalysts, particularly relate to a kind of for dehydrofluorination chromium-based catalysts and preparation method thereof.
Background technology
PVF (VF) is a kind of important fluorochemical monomer, mainly for the preparation of polyvinyl fluoride (PVF).PVF is the one that in fluororesin, fluorinated volume is minimum, density is minimum; there is the characteristics such as excellent chemical resistance, hydrophobicity, wearability, resistance to ag(e)ing and non-viscosity, be widely used in the encapsulation of the protective layer of construction material, aircraft industry and solar cell, the inside coating of packing container, the anticorrosion of oil field oil pipeline etc.
Prior art discloses the syntheti c route of multiple VF monomer, being wherein raw material with acetylene and HF, production Technology is comparatively ripe, but have that catalyst life is short, selective on the low side, the problem such as quantity of three wastes large and raw material acetylene is inflammable and explosive of VF.Such as US Patent No. 2892000 report uses chrome green or chromic salts to prepare the method for VF with acetylene hydrofluorination for catalyst.
The another kind of method preparing VF is with 1,1-Difluoroethane (HFC-152a) prepares VF for raw material gas phase dehydrofluorination, both avoided and used inflammable and explosive acetylene, also have that preparation technology is simple simultaneously, the selective height of VF and the advantage such as impurity is few, be conducive to improving VF quality, and then promote the quality of PVF film, prior art report is as follows:
(1) US Patent No. 2599631 reports in catalyst-free situation, and HFC-152a pyrolysis under 562 ~ 797 DEG C of high temperature generates VF, and reaction conversion ratio is only 40%.And under the effect of catalyst, as with CaF
2for catalyst, when 500 DEG C, conversion ratio is 66%; Take activated carbon as catalyst, at 600 DEG C of temperature, conversion ratio can rise to 78%.The method reaction temperature is high, and HFC-152a low conversion rate.
(2) US Patent No. 5880315 reports the method being prepared VF by thermal cracking HFC-152a, by MAlF
5(H
2o)
2or NH
4mAlF
6(H
2o) (M=Zn, Mg) pyrolysis under the high temperature conditions, obtains MgF
2/ AlF
3, ZnF
2/ AlF
3, MgF
2-ZnF
2/ AlF
3catalyst, wherein Mg: Al, Zn: Al and Mg+Zn: Al mol ratio is 1: 1.At 300 DEG C and air speed 600h
-11h and 48h is reacted, ZnF under condition
2/ β-AlF
3catalyst is 44.8% and 43.5%, MgF to the conversion ratio of HFC-152a
2/ β-AlF
3catalyst is 42.8% and 43.4% to the conversion ratio of HFC-152a.
(3) US Patent No. 6262321B1 reports at MgF
2/ AlF
3, ZnF
2/ AlF
3, MgF
2-ZnF
2/ AlF
3catalyst series (wherein Mg: Al, Zn: Al, Mg+Zn: Al mol ratio>=4: 1) under effect, prepared the method for VF by HFC-152a.As concrete embodiment, with MgF
2/ AlF
3(Mg: Al=9: 1) is example, at 275 DEG C, air speed 514h
-1react under condition, the conversion ratio of HFC-152a be 40%, VF selective be 99.9%.The method is reacted at a lower temperature, HFC-152a low conversion rate, cause catalyst space-time yield and production efficiency low.
(4) Chinese patent CN103071516A is reported in Ni-Co-Ag-TbF
3/ AlF
3-Al
2o
3(Ni:Co:Ag:Tb=1:1:1:1) under catalyst action, the method for VF is prepared by HFC-152a, at 420 DEG C, air speed 700h
-1condition under, reaction conversion ratio be 82.5%, VF selective be 99.3%.Point out simultaneously the adding of Ni/Co content ratio, reaction temperature, Tb and Ag, Ni/Co/Ag/Tb content comparison catalyst impact comparatively large, and reaction temperature is optimum temperature at 420 DEG C.This method for preparing catalyst is complicated, expensive, is unfavorable for that industry is amplified.
(5) US Patent No. 6034289A reports the method that HFC-152a prepares VF under catalyst action, and described catalyst is main active with chrome green and uses B
2o
3modification is carried out to it.For guignet green chromium oxide catalyst: at 250 DEG C, air speed 300h
-1under condition, reaction conversion ratio is only 19.7%.
Above-mentionedly prepare in the catalyst of VF for HFC-152a dehydrofluorination, aluminium-based catalyst needs to react at a lower temperature, cause to avoid high temperature AlF
3crystal transfer, thus the inactivation causing catalyst, but lower temperature can make the conversion ratio of HFC-152a on the low side, causes production efficiency to decline; Although chromium-based catalysts can use in high reaction temperatures, can not occur to cause catalysqt deactivation because of crystal transfer, there is active lower problem.
Summary of the invention
The object of the present invention is to provide a kind of chromium-based catalysts of dehydrofluorination, can be used in 1,1-Difluoroethane cracking for PVF, not only preparation technology is simple, low raw-material cost, and there is higher reactivity and stability.
The technical solution used in the present invention is as follows:
A kind of chromium-based catalysts of dehydrofluorination, for 1,1-Difluoroethane cracking is for PVF, described catalyst contains chromium and active metal, the one, more than two or three that described active metal is selected from aluminium, zinc, magnesium, cobalt, nickel, iron and copper combines, and the molar percentage of described chromium and active metal is 15mol% ~ 95mol%, 5mol% ~ 85mol%.
As preferred mode, the molar percentage of above-mentioned chromium and active metal is preferably 25mol% ~ 90mol%, 10mol% ~ 75mol%; The one of above-mentioned active metal preferably in aluminium, zinc, magnesium and cobalt, more than two or three combination.
Present invention also offers the preparation method of the chromium-based catalysts of above-mentioned dehydrofluorination, comprise blending method and the precipitation method.When preparing with blending method, comprise the following steps:
(1) amount being 15mol% ~ 95mol% and 5mol% ~ 85mol% according to the molar percentage of chromium and active metal takes trivalent chromium compound and metallic compound, and ball milling is blended, compressing, obtains the presoma of described catalyst;
(2) by the presoma N of catalyst obtained for step (1)
2, H
2or Ar roasting 2 ~ 12h at 300 ~ 800 DEG C, then pass into HF and the N that volume ratio is 1:2 ~ 4
2mist or HF gas at 200 ~ 450 DEG C of activation process 12 ~ 36h, obtain described Dehydrofluorination catalyst.
As preferred mode, the preferred autoxidation chromium of the trivalent chromium compound in above-mentioned steps (1), chromium hydroxide, charomic fluoride or fluorine chromium oxide, and more preferably chromium hydroxide; The one of above-mentioned active metallic compound preferably in the oxide of aluminium, zinc, magnesium, cobalt, nickel, iron and copper, hydroxide, fluoride and oxyfluoride, more than two or three combination, and be more preferably selected from one in the oxide of aluminium, zinc, magnesium and cobalt, hydroxide, fluoride and oxyfluoride, more than two or three combination; Preferably by the presoma N of catalyst obtained for step (1) in above-mentioned steps (2)
2, H
2or Ar roasting 2 ~ 12h at 350 ~ 450 DEG C, then pass into hydrogen fluoride gas at 250 ~ 360 DEG C of activation process 12 ~ 36h, obtain described Dehydrofluorination catalyst.
When preparing with the precipitation method, comprise the following steps:
(1) amount being 15mol% ~ 95mol% and 5mol% ~ 85mol% according to the molar percentage of chromium and active metal takes trivalent chromium compound and metallic compound, add water after mixing, add precipitating reagent to precipitate, pH to 7.5 ~ 10.5 of adjustment solution, are precipitated thing;
(2) by sediment dry 10 ~ 24h at 100 ~ 150 DEG C, then roasting 2 ~ 6h at 350 ~ 800 DEG C, obtains the presoma of described catalyst, and by the presoma compression molding of catalyst;
(3) catalyst precursor of compression molding is first used N at ambient pressure
2, H
2or Ar dry 2 ~ 12h at 200 ~ 400 DEG C, then pass into HF and the N that volume ratio is 1:2 ~ 4
2mist or HF gas fluoridize 12 ~ 36h at 200 ~ 450 DEG C, then pass into N
2be cooled to room temperature, obtain described chromium-based catalysts.
In the above-mentioned precipitation method, the precipitating reagent of use comprises ammoniacal liquor.
As preferred mode, the trivalent chromium compound in above-mentioned steps (1) is preferably chromic nitrate, chromium chloride, chromium sulfate or potassium chromium sulfate; The one of above-mentioned active metallic compound preferably in the nitrate of aluminium, zinc, magnesium, cobalt, nickel, iron and copper, halide and sulfate, more than two or three combines; Preferably by sediment dry 10 ~ 24h, then roasting 2 ~ 6h at 350 ~ 450 DEG C at 100 ~ 150 DEG C in above-mentioned steps (2); Preferably the catalyst precursor of compression molding is first used N at ambient pressure in above-mentioned steps (3)
2, H
2or Ar dry 2 ~ 12h at 200 ~ 400 DEG C, then pass into HF and the N that volume ratio is 1:2 ~ 4
2mist or HF gas fluoridize 12 ~ 36h at 250 ~ 360 DEG C, then pass into N
2be cooled to room temperature, obtain described chromium-based catalysts.
The chromium-based catalysts of dehydrofluorination of the present invention is when preparing PVF for 1,1-Difluoroethane gas phase dehydrofluorination, and reaction temperature is preferably 200 ~ 400 DEG C, more preferably 320 ~ 400 DEG C, is particularly preferably 320 ~ 370 DEG C; Air speed is preferably 100 ~ 2000h
-1, more preferably 100 ~ 1000h
-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 all alternatives, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
Embodiment 1
By Cr (NO
3)
39H
2o is dissolved in a certain amount of water, adds ammoniacal liquor as precipitating reagent under stirring, and the pH of adjustment solution, to 9.0, makes the Cr of dissolving
3+fully can precipitate, by the slurry by filtration of formation, washing, at 110 DEG C of dry 24h, obtain Cr (OH)
3.By gained Cr (OH)
3consist of 50mol%, 50mol% with MgO by the Mole percent of Cr, Mg to carry out ball milling and mix, compression molding, obtained catalyst precursor.
Catalyst precursor is loaded in the carbon steel reaction tube of ф 14*1000, at H
2the lower 300 DEG C of roasting 6h of atmosphere, pass into volume ratio HF:N
2for the mist of 1:4 fluoridizes 2h at 250 DEG C, then with the ramp to 360 DEG C of 1 DEG C/min, continue to fluoridize 12h, then pass into pure HF and fluoridize 4h, obtained chromium-based catalysts.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 320 ~ 400 DEG C, air speed 100 ~ 1000h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 1 of PVF.
Table 1
Embodiment 2
Chromium-based catalysts is prepared according to method described in embodiment 1, but by Cr (OH)
3form with the Mole percent of MgO and be adjusted to 30mol% and 70mol%, obtain chromium-based catalysts of the present invention.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 350 DEG C, air speed 500h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 2 of PVF.
Table 2
| Reaction time | Conversion ratio | PVF is selective |
| (h) | (％) | (％) |
| 1 | 65.0 | 99.5 |
| 24 | 65.8 | 99.6 |
| 100 | 65.9 | 99.6 |
| 500 | 60.2 | 99.8 |
| 1000 | 50.4 | 99.9 |
Embodiment 3
By KCr (SO
4)
212H
2o is dissolved in a certain amount of water, adds ammoniacal liquor as precipitating reagent under stirring, and the pH of adjustment solution, to 8.5, makes the Cr of dissolving
3+fully can precipitate, by the slurry by filtration of formation, washing, at 150 DEG C of dry 24h, obtain Cr (OH)
3.By gained Cr (OH)
3with AlF
3consist of 75mol%, 25mol% by the Mole percent of Cr, Al and carry out ball milling mixing, compression molding, obtained catalyst precursor.
Catalyst precursor is loaded in the carbon steel reaction tube of ф 14*1000, at N
2the lower 400 DEG C of roasting 6h of atmosphere, pass into volume ratio HF: N
2be 1: 2 mist fluoridize 2h at 250 DEG C, then with the ramp to 360 DEG C of 1 DEG C/min, continue to fluoridize 12h, then pass into pure HF and fluoridize 4h, obtained chromium-based catalysts of the present invention.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 320 ~ 350 DEG C, air speed 300h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 3 of PVF.
Table 3
Embodiment 4
According to mole percent 95mol%, the 5mol% of Cr, Co, take a certain amount of CrF
3, Co
2o
3, ball milling mixes, compression molding, obtained catalyst precursor.Catalyst precursor is loaded in the carbon steel reaction tube of ф 14*1000, at N
2the lower 350 DEG C of roasting 2h of atmosphere, pass into volume ratio HF: N
2be 1: 1 mist fluoridize 2h at 250 DEG C, then with the ramp to 360 DEG C of 1 DEG C/min, continue to fluoridize 12h, then pass into pure HF and fluoridize 4h, obtained chromium-based catalysts of the present invention.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 320 ~ 350 DEG C, air speed 300h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 4 of PVF.
Table 4
Embodiment 5
According to mole percent 90mol%, the 10mol% of Cr, Zn, take a certain amount of Cr
2o
3, ZnO, ball milling mixes, compression molding, obtained catalyst precursor.Loaded by catalyst precursor in the carbon steel reaction tube of ф 14*1000,450 DEG C of roasting 2h, pass into volume ratio HF: N under an ar atmosphere
2be 1: 8 mist fluoridize 2h at 250 DEG C, then with the ramp to 360 DEG C of 1 DEG C/min, continue to fluoridize 12h, then pass into pure HF and fluoridize 12h, obtained chromium-based catalysts of the present invention.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 320 ~ 350 DEG C, air speed 500h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 5 of PVF.
Table 5
Comparative example 1
By KCr (SO
4)
2be dissolved in a certain amount of water, add ammoniacal liquor as precipitating reagent under stirring, the pH of adjustment solution, to 8.5, makes the Cr of dissolving
3+abundant precipitation, by the slurry by filtration of formation, washing, at 150 DEG C of dry 24h, obtains Cr (OH)
3.By gained Cr (OH)
3compression molding, loads in the carbon steel reaction tube of ф 14*1000, at N
2the lower 400 DEG C of roasting 6h of atmosphere, pass into volume ratio HF: N
2be 1: 4 mist fluoridize 2h at 250 DEG C, then fluoridize 24h with the ramp to 360 of 1 DEG C/min DEG C, then pass into pure HF and fluoridize 4h, obtain chromium-based catalysts of the present invention.
Obtained chromium-based catalysts is used for 1,1-Difluoroethane dehydrofluorination, controlling reaction temperature is 320 ~ 400 DEG C, air speed 500h
-1, the conversion ratio of 1,1-Difluoroethane and the selective as table 6 of PVF.Controlling reaction temperature is 350 DEG C, air speed 500h
-1, under the differential responses time, the conversion ratio of 1,1-Difluoroethane and the selective as table 7 of PVF.
Table 6
Table 7
From above-described embodiment data, the reaction conversion ratio of pure chrome catalysts lower and less stable, easy in inactivation.Chromium-based catalysts containing other metallic element prepared by the present invention, compared with pure chromium-based catalysts, has higher dehydrofluorination Activity and stabill, at temperature 350 DEG C, air speed 500h
-1condition under react 1000h, the conversion ratio of 1,1-Difluoroethane remains on more than 50%, PVF selective more than 98%.
Claims (10)
1. the chromium-based catalysts of a dehydrofluorination, for 1,1-Difluoroethane cracking is for PVF, it is characterized in that described catalyst contains chromium and active metal, the one, more than two or three that described active metal is selected from aluminium, zinc, magnesium, cobalt, nickel, iron and copper combines, and the molar percentage of described chromium and active metal is 15mol% ~ 95mol%, 5mol% ~ 85mol%.
2. according to the chromium-based catalysts of dehydrofluorination according to claim 1, it is characterized in that the molar percentage of described chromium and active metal is 25mol% ~ 90mol%, 10mol% ~ 75mol%, the one, more than two or three that described active metal is selected from aluminium, zinc, magnesium and cobalt combines.
3., according to the chromium-based catalysts of dehydrofluorination according to claim 1, it is characterized in that described catalyst is prepared according to blending method, comprise the following steps:
(1) amount being 15mol% ~ 95mol% and 5mol% ~ 85mol% according to the molar percentage of chromium and active metal takes trivalent chromium compound and active metallic compound, and ball milling is blended, compressing, obtains the presoma of described catalyst;
(2) by the presoma N of catalyst obtained for step (1)
2, H
2or Ar roasting 2 ~ 12h at 300 ~ 800 DEG C, then pass into hydrogen fluoride gas at 200 ~ 450 DEG C of activation process 12 ~ 36h, obtain described Dehydrofluorination catalyst.
4. according to the chromium-based catalysts of dehydrofluorination according to claim 3, it is characterized in that the trivalent chromium compound in described step (1) is selected from chromium oxide, chromium hydroxide, charomic fluoride or fluorine chromium oxide, active metallic compound is selected from one in the oxide of aluminium, zinc, magnesium, cobalt, nickel, iron and copper, hydroxide, fluoride and oxyfluoride, more than two or three combination.
5. according to the chromium-based catalysts of dehydrofluorination according to claim 4, it is characterized in that the trivalent chromium compound in described step (1) is chromium hydroxide, active metallic compound is selected from one in the oxide of aluminium, zinc, magnesium and cobalt, hydroxide, fluoride and oxyfluoride, more than two or three combination.
6., according to the chromium-based catalysts of dehydrofluorination according to claim 3, it is characterized in that the presoma N of catalyst obtained for step (1) in described step (2)
2, H
2or Ar roasting 2 ~ 12h at 350 ~ 450 DEG C, then pass into hydrogen fluoride gas at 250 ~ 360 DEG C of activation process 12 ~ 36h.
7., according to the chromium-based catalysts of dehydrofluorination according to claim 1, it is characterized in that described catalyst is prepared according to the precipitation method, comprise the following steps:
(1) amount being 15mol% ~ 95mol% and 5mol% ~ 85mol% according to the molar percentage of chromium and active metal takes trivalent chromium compound and active metallic compound, add water after mixing, add precipitating reagent to precipitate, pH to 7.5 ~ 10.5 of adjustment solution, are precipitated thing;
(2) by sediment dry 10 ~ 24h at 100 ~ 150 DEG C, compressing, obtain the presoma of described catalyst;
(3) by the presoma N of catalyst obtained for step (2)
2, H
2or Ar roasting 2 ~ 12h at 300 ~ 800 DEG C, then pass into hydrogen fluoride gas at 200 ~ 450 DEG C of activation process 12 ~ 36h, obtain described Dehydrofluorination catalyst.
8. according to the chromium-based catalysts of dehydrofluorination according to claim 7, it is characterized in that the trivalent chromium compound in described step (1) is chromic nitrate, chromium chloride, chromium sulfate or potassium chromium sulfate, active metallic compound is selected from one in the nitrate of aluminium, zinc, magnesium, cobalt, nickel, iron and copper, halide and sulfate, more than two or three combination; In described step (3), the catalyst precursor of compression molding is first used N at ambient pressure
2, H
2or Ar dry 2 ~ 12h at 200 ~ 400 DEG C, then pass into hydrogen fluoride gas at 250 ~ 360 DEG C of activation process 12 ~ 36h.
9., according to the chromium-based catalysts of the dehydrofluorination one of claim 1 to 8 Suo Shu, it is characterized in that 1,1-Difluoroethane cracking is 200 ~ 400 DEG C for the reaction temperature of PVF, air speed is 100 ~ 2000h
-1.
10., according to the chromium-based catalysts of dehydrofluorination according to claim 9, it is characterized in that 1,1-Difluoroethane cracking is 320 ~ 400 DEG C for the reaction temperature of PVF, air speed is 100 ~ 1000h
-1.
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| CN105664983A (en) * | 2016-02-23 | 2016-06-15 | 常熟三爱富中昊化工新材料有限公司 | Catalyst for preparing fluorinated alkene |
| CN109174139A (en) * | 2018-08-16 | 2019-01-11 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof for 1,1- Difluoroethane gas phase removal HF preparation vinyl fluoride |
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| CN111375398A (en) * | 2018-12-29 | 2020-07-07 | 浙江省化工研究院有限公司 | Isomerization catalyst and application thereof |
| CN112264035A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Catalyst for preparing vinyl fluoride by gas phase removing hydrogen fluoride from 1, 1-difluoroethane |
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| CN109174139A (en) * | 2018-08-16 | 2019-01-11 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof for 1,1- Difluoroethane gas phase removal HF preparation vinyl fluoride |
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