CN105107533B - A kind of preparation method of vapor phase dehydrofluorination catalysts - Google Patents
A kind of preparation method of vapor phase dehydrofluorination catalysts Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of vapor phase dehydrofluorination catalysts, preparation method is the following steps are included: (1) under nitrogen protection, magnesium ethylate is reacted with hydrofluoric acid and flowed back at 80 DEG C, and roasting obtains high-specific surface area fluorination magnesium matrix at 300~400 DEG C；(2) the aqueous solution for loading component is impregnated on fluorination magnesium matrix, and the fluorination Mg catalyst that 300~400 DEG C of roastings are loaded under nitrogen protection；(3) activated catalyst is handled with perfluoro caprylic acid.The present invention is made using anhydrous sol-gel fluoride process has high-specific surface area, cellular structure fluorination magnesium matrix abundant, then catalyst is made using infusion process carrying transition metal, catalyst is modified through perfluoro caprylic acid surface, the good catalyst activity because prepared by, gas phase dehydrofluorination selectivity is high, since reaction condition can mildly make to react operation steady in a long-term.
Description
Technical field
The present invention relates to a kind of preparation method of vapor phase dehydrofluorination catalysts and purposes, specifically a kind of to be used for gas
Fluorine-containing alkane prepares the preparation method of the Dehydrofluorination catalyst of Fluorine containing olefine under the conditions of phase.
Background technique
Hydrofluoroalkane (HFCs) has excellent physical and chemical performance, and ozone-depleting value (ODP) of diving is zero, is widely used in freezing
The industries such as agent, cleaning agent, foaming agent, extinguishing chemical, medicine and pesticide are very important basic chemical industry products in national economy.
But the latent value (GWP) of HFCs greenhouse effects is higher, a large amount of uses can cause global warming.Hydrofluoroolefin compounds (HFOs)
Such as 2,3,3,3- tetrafluoropropenes (HFO-1234yf) have physical and chemical performance similar with HFCs, have zero odp value and GWP value
Low advantage is the ideal substitute for being used for automotive air-conditioning system refrigerant HFA 134a on a large scale at present.Meanwhile
HF hydrocarbon has certain chemical activity, can derive many organic fluorocompounds, is production high added value fluoride-containing PMMA
With the base stock of high molecular material, it is able to satisfy the irreplaceable special use of the general organic matter such as special purpose and sophisticated industry
On the way, development prospect is very wide.
There are three ways to fluorine-containing alkane dehydrofluorination prepares Fluorine containing olefine: high-temperature cracking method, liquid alkaline method and gas phase catalysis
Method.High-temperature cracking method energy consumption is high, and consersion unit requires harshness, and by-product is more；Liquid alkaline method is needed using highly basic, a large amount of salt of by-product,
Large-scale use can bring environmental problem；Gas-phase catalysis reaction temperature is lower, and target product selectivity is high, becomes fluorine-containing at present
Alkane dehydrofluorination prepares the research emphasis of Fluorine containing olefine.Dehydrofluorination catalyst then occupy core in the exploitation of gas-phase catalysis
Cardiac status.
Known several methods for preparing fluorinated olefins.For example, US5679875 discloses 1,1,1,2,3- pentafluoropropene of preparation
With the method for 1,1,1,2,3- pentafluoropropane；US6031141, which is disclosed, obtains fluorohydrocarbon dehydrofluorination using chromium-containing catalyst
The catalysis process of fluorinated olefins；US5396000 discloses the preparation method of 1,1,1,2,3- pentafluoropropene, utilizes gas phase catalysis
Dehydrohalogenation prepares 1,1,1,2,3- pentafluoropropene and hydrogen fluoride, then in the presence of hf to progress gas-phase catalytic hydrogenation；
US6548719 is disclosed by making the fluorohydrocarbon method that dehydrohalogenation prepares fluorinated olefins in the presence of a phase transfer catalyst；
US2006/0106263 discloses the preparation and purification of fluoroolefin compounds；WO98/33755 discloses hexafluoropropane defluorinate
Change the catalysis process of hydrogen preparation pentafluoropropene.
US20060787840 uses HFC-236ea and HFC-245cb for raw material, raw in catalyst self-operating dehydrofluorination
Produce HFC-1225ye and HFO-1234yf, then from reaction product, unreacted hydrofluorocarbon and HF separate HFC-1225ye and
HFO-1234yf.Dehydrofluorination temperature controls 200~500 DEG C, catalyst choice aluminum fluoride, fluorided alumina and oxyfluoride
Change aluminium carried metal.Reaction is preferably reacted in the presence of an inert gas.
US20060816650 disclose HFC-245cb generated in the presence of Dehydrofluorination catalyst HFO-1234yf and
HFO-1234ze, dehydrogenation fluoric acid catalyst choice fluorided alumina and/or aluminum fluoride, and proposed simultaneously with reaction product and HF shape
At mode the separating-purifying HFO-1234yf and HFO-1234ze of azeotropic mixture.
That there are specific surface areas is small for the catalyst of dehydrofluorination in the prior art, and catalyst service life is short, conversion ratio
Low disadvantage, it is difficult to prepare Fluorine containing olefine requirement suitable for serialization gas phase reaction.
Summary of the invention
In order to overcome the defects of reaction selectivity of the existing technology is not high, stability is poor and insufficient, of the invention mesh
Be to provide a kind of preparation method for vapor phase dehydrofluorination catalysts, improve the selectivity and stability of catalyst, especially
It is the preparation method that the catalyst of Fluorine containing olefine is prepared for alkane fluorine-containing under gas phase condition.This method simple process, it is at low cost,
High income has good prospects for commercial application, is particularly suitable for large-scale industrial production.
In order to solve the above-mentioned technical problem, it adopts the following technical scheme that
A kind of preparation method of vapor phase dehydrofluorination catalysts, it is characterised in that the following steps are included:
(1) it weighs a certain amount of fresh magnesium rod under room temperature under nitrogen protection first and is added in dehydrated alcohol, control reaction
Temperature is 80 DEG C, and reaction time 1h obtains the alcohol suspension of magnesium ethylate；Then under nitrogen protection, by ethyl alcohol obtained
The alcohol suspension of magnesium is slowly dropped in the ethanol solution of hydrogen fluoride, and control dropping temperature is 60 DEG C, after being added dropwise, control
Reaction temperature processed is 80 DEG C, and the reaction time is 10~20h；Then after the completion of reaction, handled by being filtered, washed and dried
To reaction product；Reaction product is finally subjected to calcination process under nitrogen protection, control maturing temperature is 300~400 DEG C, is obtained
Magnesium matrix is fluorinated to high-specific surface area；
(2) aqueous solution for first preparing the corresponding soluble-salt of load component, with the aqueous solution of the soluble-salt of load component
The time of dipping fluorination magnesium matrix, dipping fluorination magnesium matrix is at least 5h；Then the solid after dipping is dried, is controlled
Drying temperature processed is 80~100 DEG C, and drying time is at least 8h, obtains solid dried object；Finally under nitrogen protection, by solid
Dried object carries out calcination process, and control maturing temperature is 300~400 DEG C, and calcining time is at least 10h, and the fluorination of load is made
Mg catalyst；
(3) the fluorination Mg catalyst of load obtained is first subjected in alcohol solvent immersion treatment, controls soaking time
At least 5h；Then it is added perfluoro caprylic acid into alcohol solvent, control reaction temperature is 40~70 DEG C, the reaction time is 10~
20h；Finally after the completion of reaction, by filtering, drying and processing, after the activation that can carry out gas phase dehydrofluorination catalysis reaction is made
Fluorination Mg catalyst.
Further, in step (1), the mass ratio of hydrogen fluoride and magnesium rod is controlled 1.6~2.0.
Further, in step (2), component is loaded by one of transition metal ions or more than one solubility
Salt composition.
Further, transition metal ions Zn2+、Ni2+、Cu2+、Cr3+、Al3+、Fe3+、La3+And Zr4+。
Further, soluble-salt is nitrate or chlorate.
Further, in step (2), the dosage for loading component is the 3%~20% of magnesium fluoride catalyst matrix quality.
Further, in step (3), the fluorination Mg catalyst of load and the mass ratio of alcohol solvent are 1: (3~10).
Further, in step (3), the additional amount of perfluoro caprylic acid is the 0.2% of the magnesium fluoride catalyst matrix quality of load
~2%.
Further, in step (1), fluorination magnesium matrix is still able to maintain preferable heat at 300~400 DEG C after calcination process
Stability.
Further, the specific surface area for being fluorinated magnesium matrix is greater than 200m2/ g, the pore-size distribution for being fluorinated magnesium matrix concentrates on 2~
5nm。
As a result of the above technical solution, the following beneficial effects are obtained:
The present invention be a kind of preparation method for vapor phase dehydrofluorination catalysts, this method simple process, it is at low cost,
High income, good catalyst activity, gas phase dehydrofluorination selectivity is high, reaction condition can mildly make to react operation steady in a long-term,
With good prospects for commercial application, it is particularly suitable for large-scale industrial production.The present invention is using anhydrous sol-gel fluorination
Method is that magnesium ethylate and anhydrous hydrogen fluoride is used to pass through fluorination reaction in ethanol, hydrolysis, roast the magnesium fluoride for obtaining high-specific surface area
Matrix, and obtained fluorination magnesium matrix is immersed in transition metal ions, Dehydrofluorination catalyst is obtained by high-temperature roasting,
Perfluoro caprylic acid activated catalyst is finally used, obtains finally carrying out the magnesium fluoride after the activation of gas phase dehydrofluorination catalysis reaction and urges
Agent.The fluorination Mg catalyst of load can keep relatively mild condition in dehydrofluorination process, can prevent from reacting
The carbon deposition phenomenon caused by acutely.The dip loading transition metal ions Zn on fluorination magnesium matrix2+、Cr3+、Al3+、Fe3+、La3+,
They have the acid-base property on regulating catalyst surface, inhibit the effect grown up under magnesium fluoride crystal grain high temperature；On fluorination magnesium matrix
Dip loading transition metal ions Ni2+、Cu2+、Zr4+The heating conduction of catalyst can be provided.
The present invention can be made using anhydrous sol-gel fluoride process with high-specific surface area, cellular structure fluorine abundant
Change magnesium matrix.After metal alkoxide and anhydrous hydrogen fluoride react, metal ion polymerize to form M-F-M key with fluorine ion, and
The stable colloidal sol being made of nano metal fluoride particle is formd under operating condition, with the extension of time, these nanometers
Particle will be connected in series to the gel for being formed together three-D space structure, remove the solvent inside gel, and in calcination process
After porous metal in height ratio surface area fluoride can be obtained.Anhydrous sol-gel fluoride process prepares magnesium fluoride, adjusts in operation
The mass ratio of suitable fluorine and magnesium metal, generates fluorination reaction with Mg (OCH2CH3)2-xFxFor the magnesium fluorine containing alkoxide of general formula
Compound, and corresponding hydrogen-oxygen fluoride or oxygen fluoride are generated after hydrolyzing respectively, generating after fully fluorinated has Gao Bibiao
The fluorination magnesium matrix of area.Fluorination magnesium matrix still keeps preferable thermal stability, specific surface after roasting at 300~400 DEG C
Product is greater than 200m2/g, and pore-size distribution concentrates on 2~5nm.
Catalyst produced by the present invention has the characteristics that high-specific surface area, cellular structure are abundant, thus good catalyst activity,
Gas phase dehydrofluorination selectivity is high, since reaction condition can mildly make to react operation steady in a long-term.The catalyst is containing fluothane
Vapor phase dehydrofluorination reaction is prepared in Fluorine containing olefine, and for catalyst continuous operation after 500h, conversion ratio remains within 60%
More than, selectively maintain 98.5% or more.Such as catalyst is in the preparation HFO-1234yf reaction of HFC-245eb dehydrofluorination
In, the selectivity that the conversion ratio of catalyst continuous operation 500h, HFC-245eb maintain 60% or more, HFO-1234yf maintains
98.5% or more.
Specific embodiment
A kind of preparation method of vapor phase dehydrofluorination catalysts, catalyst prepared by the present invention are suitable for containing under gas phase condition
Fluothane hydrocarbon dehydrofluorination prepares Fluorine containing olefine, comprising the following steps:
(1) it weighs a certain amount of fresh magnesium rod under room temperature under nitrogen protection first and is added in dehydrated alcohol, control reaction
Temperature is 80 DEG C, and reaction time 1h obtains the alcohol suspension of magnesium ethylate.Then under nitrogen protection, by ethyl alcohol obtained
The alcohol suspension of magnesium is slowly dropped in the ethanol solution of hydrogen fluoride, the control of the mass ratio of hydrogen fluoride and magnesium rod 1.6~
2.0, control dropping temperature is 60 DEG C, and after being added dropwise, control reaction temperature is 80 DEG C, and the reaction time is 10~20h.Then
After the completion of reaction, reaction product is obtained by being filtered, washed and dried processing.Finally under nitrogen protection by reaction product into
Row calcination process, control maturing temperature are 300~400 DEG C, obtain high-specific surface area fluorination magnesium matrix.
(2) aqueous solution for first preparing the corresponding soluble-salt of load component loads component by one in transition metal ions
Kind or more than one soluble-salt composition, transition metal ions Zn2+、Ni2+、Cu2+、Cr3+、Al3+、Fe3+、La3+And Zr4 +, soluble-salt is nitrate or chlorate, with the aqueous solution dipping fluorination magnesium matrix of the soluble-salt of load component, load
The dosage of component is the 3%~20% of magnesium fluoride catalyst matrix quality, and the time of dipping fluorination magnesium matrix is at least 5h.Then
Solid after dipping is dried, control drying temperature is 80~100 DEG C, and drying time is at least 8h, obtains solid
Dried object.Finally under nitrogen protection, solid dried object is subjected to calcination process, control maturing temperature is 300~400 DEG C, roasting
The burning time is at least 10h, and the fluorination Mg catalyst of load is made.
(3) the fluorination Mg catalyst of load obtained is first subjected to immersion treatment, the magnesium fluoride of load in alcohol solvent
The mass ratio of catalyst and alcohol solvent is 1: (3~10), control soaking time are at least 5h；Then it is added into alcohol solvent
Perfluoro caprylic acid, the additional amount of perfluoro caprylic acid are the 0.2%~2% of the magnesium fluoride catalyst matrix quality of load, control reaction temperature
Degree is 40~70 DEG C, and the reaction time is 10~20h；Finally after the completion of reaction, by filtering, drying and processing, being made can be carried out
Fluorination Mg catalyst after the activation of gas phase dehydrofluorination catalysis reaction.
The present invention is to use magnesium ethylate and anhydrous hydrogen fluoride in ethanol by being fluorinated using anhydrous sol-gel fluoride process
Reaction, hydrolysis, roasting obtain high-specific surface area fluorination magnesium matrix, and by obtained fluorination magnesium matrix be immersed in transition metal from
In son, Dehydrofluorination catalyst is obtained by high-temperature roasting, perfluoro caprylic acid activated catalyst is finally used, obtains finally carrying out
Fluorination Mg catalyst after the activation of gas phase dehydrofluorination catalysis reaction.The fluorination Mg catalyst of load is in dehydrofluorination process
Can keep relatively mild condition, can prevent reaction excessively acutely caused by carbon deposition phenomenon.It is impregnated on fluorination magnesium matrix
Carrying transition metal ion Zn2+、Cr3+、Al3+、Fe3+、La3+, they have the acid-base property on regulating catalyst surface, inhibit fluorination
The effect grown up under magnesium crystal grain high temperature；The dip loading transition metal ions Ni on fluorination magnesium matrix2+、Cu2+、Zr4+It can provide
The heating conduction of catalyst.
The present invention can be made using anhydrous sol-gel fluoride process with high-specific surface area, cellular structure fluorine abundant
Change magnesium matrix.After metal alkoxide and anhydrous hydrogen fluoride react, metal ion polymerize to form M-F-M key with fluorine ion, and
The stable colloidal sol being made of nano metal fluoride particle is formd under operating condition, with the extension of time, these nanometers
Particle will be connected in series to the gel for being formed together three-D space structure, remove the solvent inside gel, and in calcination process
After porous metal in height ratio surface area fluoride can be obtained.Anhydrous sol-gel fluoride process prepares magnesium fluoride, adjusts in operation
The mass ratio of suitable fluorine and magnesium metal, generates fluorination reaction with Mg (OCH2CH3)2-xFxFor the magnesium fluorine containing alkoxide of general formula
Compound, and corresponding hydrogen-oxygen fluoride or oxygen fluoride are generated after hydrolyzing respectively, generating after fully fluorinated has Gao Bibiao
The fluorination magnesium matrix of area.Fluorination magnesium matrix still keeps preferable thermal stability, specific surface after roasting at 300~400 DEG C
Product is greater than 200m2/g, and pore-size distribution concentrates on 2~5nm.
Catalyst produced by the present invention has the characteristics that high-specific surface area, cellular structure are abundant, thus good catalyst activity,
Gas phase dehydrofluorination selectivity is high, since reaction condition can mildly make to react operation steady in a long-term.The catalyst is containing fluothane
Vapor phase dehydrofluorination reaction is prepared in Fluorine containing olefine, and for catalyst continuous operation after 500h, conversion ratio remains within 60%
More than, selectively maintain 98.5% or more.Such as catalyst is in the preparation HFO-1234yf reaction of HFC-245eb dehydrofluorination
In, the selectivity that the conversion ratio of catalyst continuous operation 500h, HFC-245eb maintain 60% or more, HFO-1234yf maintains
98.5% or more.
Below with reference to embodiment, invention is further described in detail:
Embodiment 1
Step 1: under nitrogen protection, first weigh 195 grams of fresh magnesium rod and be added portionwise in 600ml dehydrated alcohol, magnesium rod
It is controlled after adding at 80 DEG C of temperature and reacts 1h, obtain the alcohol suspension of magnesium ethylate；It then under nitrogen protection will be configured
The alcohol suspension of magnesium ethylate is slowly dropped in the ethanol solution of 825 gram of 40% hydrogen fluoride, controls dropping temperature at 60 DEG C
Under, it is added dropwise in 80 DEG C of reaction 10h；It is finally filtered, washed and dried drying, and roasts at 300 DEG C obtain under nitrogen protection
High-specific surface area is fluorinated magnesium matrix.
Step 2: the chloride containing 15 grams of Fe, Zr, Cr is first dissolved in wiring solution-forming in 200ml distilled water respectively；Then plus
Enter in above-mentioned fluorination magnesium matrix and impregnate 5h, under nitrogen protection, the solid after dipping is dried into 8h at 80 DEG C；Finally 300
10h is roasted at DEG C, and the fluorination Mg catalyst of load is made.
Step 3: the fluorination Mg catalyst of load obtained is impregnated 5h in 1500 grams of alcohol solvents, 1 gram is added entirely
Fluorine octanoic acid, reacts 10h at 40 DEG C, and vapor phase dehydrofluorination catalysts product is made in filtering, drying.
Test is using the continuous micro- trans- chromatogram arrangement of CDS2804 type.HFC-236ea is passed through to 200 DEG C of preheater preheating,
It is anti-that progress gas phase in the fixed-bed tube reactor of 3 grades of series connection DN40*1500mm equipped with 100ml catalyst is passed through after preheating
It answers, reaction temperature is 220 DEG C, and reaction pressure is normal pressure, reaction product gas chromatographic analysis after water washing removes hydrogen fluoride.
Embodiment 2
Step 1: under nitrogen protection, weighing 200 grams of fresh magnesium rod and being added portionwise in 800ml dehydrated alcohol, magnesium rod adds
1h is reacted under control temperature 70 C after complete, obtains the alcohol suspension of magnesium ethylate；Then under nitrogen protection by configured second
The alcohol suspension of magnesium alkoxide is slowly dropped in the ethanol solution of 900 gram of 40% hydrogen fluoride, controls dropping temperature at 60 DEG C, drop
It adds and finishes in 80 DEG C of reaction 12h；It is finally filtered, washed and dried drying, and roasting obtains Gao Bibiao at 340 DEG C under nitrogen protection
Area is fluorinated magnesium matrix.
Step 2: the nitrate containing 45 grams of La, Cu, Cr is first dissolved in wiring solution-forming in 300ml distilled water respectively；Then plus
Enter in above-mentioned fluorination magnesium matrix and impregnate 5h, under nitrogen protection, the solid after dipping is dried into 9h at 90 DEG C；Finally 340
14h is roasted at DEG C, and the fluorination Mg catalyst of load is made.
Step 3: the fluorination Mg catalyst of load obtained is impregnated 5h in 3000 grams of alcohol solvents, 6 grams are added entirely
Fluorine octanoic acid, reacts 15h at 60 DEG C, and vapor phase dehydrofluorination catalysts product is made in filtering, drying.
Test is using the continuous micro- trans- chromatogram arrangement of CDS2804 type.HFC-236ea is passed through to 200 DEG C of preheater preheating,
It is anti-that progress gas phase in the fixed-bed tube reactor of 3 grades of series connection DN40*1500mm equipped with 100ml catalyst is passed through after preheating
It answers, reaction temperature is 230 DEG C, and reaction pressure is normal pressure, reaction product gas chromatographic analysis after water washing removes hydrogen fluoride.
Embodiment 3
Step 1: under nitrogen protection, weighing 200 grams of fresh magnesium rod and being added portionwise in 800ml dehydrated alcohol, magnesium rod adds
1h is reacted at 80 DEG C of temperature of control after complete, obtains the alcohol suspension of magnesium ethylate；Then under nitrogen protection by configured second
The alcohol suspension of magnesium alkoxide is slowly dropped in the ethanol solution of 1000 gram of 40% hydrogen fluoride, controls dropping temperature at 60 DEG C,
It is added dropwise in 80 DEG C of reaction 16h；It is finally filtered, washed and dried drying, and roasting obtains high ratio at 380 DEG C under nitrogen protection
Surface area is fluorinated magnesium matrix.
Step 2: the nitrate containing 80 grams of Ni, Cr, Al, Zr is first dissolved in wiring solution-forming in 200ml distilled water respectively；So
After be added in above-mentioned fluorination magnesium matrix and impregnate 5h, under nitrogen protection, by the solid after dipping at 90 DEG C dry 10h；Finally
18h is roasted at 40 DEG C, the fluorination Mg catalyst of load is made.
Step 3: the fluorination Mg catalyst of load obtained is impregnated 5h in 2000 grams of alcohol solvents, 5 grams are added entirely
Fluorine octanoic acid, reacts 16h at 50 DEG C, and vapor phase dehydrofluorination catalysts product is made in filtering, drying.
Test is using the continuous micro- trans- chromatogram arrangement of CDS2804 type.HFC-245fa is passed through to 200 DEG C of preheater preheating,
It is anti-that progress gas phase in the fixed-bed tube reactor of 3 grades of series connection DN40*1500mm equipped with 100ml catalyst is passed through after preheating
It answers, reaction temperature is 240 DEG C, and reaction pressure is normal pressure, reaction product gas chromatographic analysis after water washing removes hydrogen fluoride.
Embodiment 4
Step 1: under nitrogen protection, weighing 195 grams of fresh magnesium rod and being added portionwise in 800ml dehydrated alcohol, magnesium rod adds
1h is reacted at 80 DEG C of temperature of control after complete, obtains the alcohol suspension of magnesium ethylate；Then under nitrogen protection by configured second
The alcohol suspension of magnesium alkoxide is slowly dropped in the ethanol solution of 1025 gram of 40% hydrogen fluoride, controls dropping temperature at 60 DEG C,
It is added dropwise in 80 DEG C of reaction 20h；It is finally filtered, washed and dried drying, and roasting obtains high ratio at 400 DEG C under nitrogen protection
Surface area is fluorinated magnesium matrix.
Step 2: first by containing 100 grams of Ni, Cu, Al, La, Zn chloride be dissolved in 200ml distilled water respectively be made into it is molten
Liquid；Then it is added in above-mentioned fluorination magnesium matrix and impregnates 5h, under nitrogen protection, the solid after dipping is dried into 8h at 100 DEG C；
20h is roasted at last 400 DEG C, the fluorination Mg catalyst of load is made.
Step 3: the fluorination Mg catalyst of load obtained is impregnated 5h in 5000 grams of alcohol solvents, 10 grams are added
Perfluoro caprylic acid, reacts 20h at 70 DEG C, and vapor phase dehydrofluorination catalysts product is made in filtering, drying.
Test is using the continuous micro- trans- chromatogram arrangement of CDS2804 type.HFC-236ea is passed through to 200 DEG C of preheater preheating,
It is anti-that progress gas phase in the fixed-bed tube reactor of 3 grades of series connection DN40*1500mm equipped with 100ml catalyst is passed through after preheating
It answers, reaction temperature is 241 DEG C, and reaction pressure is normal pressure, reaction product gas chromatographic analysis after water washing removes hydrogen fluoride.
Comparative example 1
Mg catalyst is fluorinated using support type, is activated without perfluoro caprylic acid, other are the same as embodiment 1.
Test is using the continuous micro- trans- chromatogram arrangement of CDS2804 type.HFC-245eb is passed through to 200 DEG C of preheater preheating,
It is anti-that progress gas phase in the fixed-bed tube reactor of 3 grades of series connection DN40*1500mm equipped with 100ml catalyst is passed through after preheating
Answer, reaction pressure is normal pressure, reaction product after water washing removes hydrogen fluoride gas chromatographic analysis HFC-245eb conversion ratio and
HFO-1234yf selectivity.The HFC-245eb of above embodiments and comparative example at differential responses temperature and space velocities turns
Rate and the results are shown in Table 1 with HFO-1225ye, above embodiments and comparative example are in differential responses temperature and space velocities
Under HFC-236ea conversion ratio and the results are shown in Table 2 with HFO-1225ye.
Table 1
| Catalyst | Reaction temperature/DEG C | Air speed/h-1 | HFC-245eb conversion ratio/% | HFO-1234yf selectivity/% |
| Embodiment 1 | 218~221 | 200 | 64 | 99.0 |
| Embodiment 2 | 229~231 | 150 | 65 | 99.2 |
| Embodiment 3 | 240~242 | 300 | 68 | 98.7 |
| Embodiment 4 | 239~241 | 500 | 66 | 98.5 |
| Comparative example 1 | 240~242 | 200 | 50 | 75.5 |
Table 2
| Catalyst | Reaction temperature/DEG C | Air speed/h-1 | HFC-236ea conversion ratio/% | HFO-1225ye selectivity/% |
| Embodiment 1 | 228~230 | 190 | 70 | 98.8 |
| Embodiment 2 | 209~210 | 250 | 71 | 99.3 |
| Embodiment 3 | 220~222 | 400 | 69 | 99.1 |
| Embodiment 4 | 229~231 | 400 | 70 | 98.7 |
| Comparative example 1 | 230~232 | 200 | 56 | 80.6 |
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (8)
1. a kind of preparation method of vapor phase dehydrofluorination catalysts, it is characterised in that the following steps are included:
(1) it weighs a certain amount of fresh magnesium rod under room temperature under nitrogen protection first and is added in dehydrated alcohol, control reaction temperature
It is 80 DEG C, reaction time 1h obtains the alcohol suspension of magnesium ethylate；Then under nitrogen protection, by the ethyl alcohol obtained
The alcohol suspension of magnesium is slowly dropped in the ethanol solution of hydrogen fluoride, and control dropping temperature is 60 DEG C, after being added dropwise, control
Reaction temperature processed is 80 DEG C, and the reaction time is 10~20h；Then after the completion of reaction, handled by being filtered, washed and dried
To reaction product；The reaction product is finally subjected to calcination process under nitrogen protection, control maturing temperature is 300~400
DEG C, obtain high-specific surface area fluorination magnesium matrix；
(2) aqueous solution for first preparing the corresponding soluble-salt of load component, with the soluble-salt of the load component
Aqueous solution impregnates the fluorination magnesium matrix, and the time for impregnating the fluorination magnesium matrix is at least 5h；Then by the solid after dipping
It is dried, control drying temperature is 80~100 DEG C, and drying time is at least 8h, obtains solid dried object；Finally in nitrogen
Under gas shielded, the solid dried object is subjected to calcination process, control maturing temperature is 300~400 DEG C, and calcining time is at least
The fluorination Mg catalyst of load is made in 10h；
(3) the fluorination Mg catalyst of the load obtained is first subjected to immersion treatment in alcohol solvent, the load
The mass ratio for being fluorinated Mg catalyst and the alcohol solvent is 1: (3~10), control soaking time are at least 5h；Then to institute
It states and perfluoro caprylic acid is added in alcohol solvent, the additional amount of the perfluoro caprylic acid is the magnesium fluoride catalyst matrix of the load
The 0.2%~2% of quality, control reaction temperature are 40~70 DEG C, and the reaction time is 10~20h；Finally after the completion of reaction, warp
Filtering, drying and processing, the fluorination Mg catalyst after the activation that can carry out gas phase dehydrofluorination catalysis reaction is made.
2. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 1, it is characterised in that: in the step
(1) in, the mass ratio of the hydrogen fluoride and the magnesium rod is controlled 1.6~2.0.
3. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 1, it is characterised in that: in the step
(2) in, the load component is made of one of transition metal ions or more than one soluble-salt.
4. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 3, it is characterised in that: the transition gold
Category ion is Zn2+、Ni2+、Cu2+、Cr3+、Fe3+、La3+And Zr4+。
5. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 3, it is characterised in that: the solubility
Salt is nitrate or chlorate.
6. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 1, it is characterised in that: in the step
(2) in, the dosage of the load component is the 3%~20% of magnesium fluoride catalyst matrix quality.
7. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 1, it is characterised in that: in the step
(1) in, the fluorination magnesium matrix is still able to maintain preferable thermal stability at 300~400 DEG C after calcination process.
8. a kind of preparation method of vapor phase dehydrofluorination catalysts according to claim 7, it is characterised in that: the magnesium fluoride
The specific surface area of matrix is greater than 200m2The pore-size distribution of/g, the fluorination magnesium matrix concentrate on 2~5nm.
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