CN102527414A - Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application - Google Patents
Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application Download PDFInfo
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- CN102527414A CN102527414A CN2011104464849A CN201110446484A CN102527414A CN 102527414 A CN102527414 A CN 102527414A CN 2011104464849 A CN2011104464849 A CN 2011104464849A CN 201110446484 A CN201110446484 A CN 201110446484A CN 102527414 A CN102527414 A CN 102527414A
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- monochlorodifluoromethane
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Abstract
The invention relates to a fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, a preparation method and an application and belongs to the catalyst preparation technology. An antimonial chloride and a promoter are mixed to be the fluorination catalyst, wherein the promoter comprises metal sulfates and a carrier; the weight percentage of the antimonial chloride to the promoter is (50-70):(30-50); the weight percentage of the carrier to the metal sulfates is (80-90):(10-20); and the obtained fluorination catalyst is used for preparing the difluoromethane or monochlorodifluoromethane. The fluorination catalyst provided by the invention is low in preparation cost and is used for preparing the difluoromethane or monochlorodifluoromethane; the operation process is simple and the condition is mild; the purity of the difluoromethane or monochlorodifluoromethane reaches up to 99%; the corrosion to equipment is small; the service life is long; the service life of the reaction equipment of the difluoromethane is increased from 2-6 months to more than 6-18 months; and the service life of the reaction equipment of the monochlorodifluoromethane is increased from 12-18 months to more than 24-36 months.
Description
Technical field
The invention belongs to catalyst preparation technology, be specifically related to a kind of fluorination catalyst and preparation method and application that is used to prepare difluoromethane or monochlorodifluoromethane.
Background technology
Difluoromethane, chemical formula are CH
2F
2, common name HFC-32 has outstanding environmental performance, and consuming atmospheric ozone layer latent energy value (ODP) is 0, and global warming potential (GWP) is 0.12, also has good serviceability simultaneously.The compounding substances of difluoromethane and other ODS substitute such as pentafluoroethane compositions such as (common name HFC-125) substitutes HCFC-22 as cold-producing medium and also has energy-conservation effect concurrently.Purposes is wide, and development prospect is boundless, in the ODS substitute, occupies critical role, is main kind.The annual requirement of estimating global difluoromethane will be above 100,000 t.And monochlorodifluoromethane, chemical formula is CHClF
2, common name HCFC-22 is as the main production raw material of pentafluoroethane.Therefore countries in the world are paid special attention to the technology of preparing of difluoromethane or monochlorodifluoromethane.
The process route of difluoromethane preparation mainly contains 3: 1, CFC-12 or HCFC-22 reduction preparation difluoromethane; 2, the carrene gas phase fluorination prepares difluoromethane; 3, the carrene liquid-phase fluorination prepares difluoromethane.Du pont company has successively carried out the test of above-mentioned 3 process routes, finds that preceding two process routes all have distinct disadvantage.First method, reducing process prepare difluoromethane reaction difficulty, and conversion ratio is low, and the product impurity of producing is many, and the rectifying separation difficulty is eliminated at present basically; Second method is because the molar ratio of vapor phase method reaction hydrogen fluoride and carrene is wanted 100:1 (referenced patent CN94191526 " production of difluoromethane ", Daikin ZL patent No. 95193919.x) at least.The excessive meeting of AHF causes catalyst to take place to fluoridize in fluorination reaction process, and antimony pentafluoride content is increased, and causes the corrosion of reactor to be accelerated.Generally speaking, in course of reaction to iron and steel year corrosion rate can be up to 45～60mm.If raw material contains small amount of moisture, corrosion can be stronger, causes the equipment frequent change, and the normal operation of producing has been caused influence; The third method, liquid phase method flaorination process are the important technologies in the preparation difluoromethane technology, and the advantage of technology is significantly to have improved utilization ratio of raw materials and product yield, has reduced three wastes treating capacity simultaneously.This method hydrogen fluoride and carrene quality proportioning are generally about 1.0～3.0; Conversion ratio is very high, and unreacted reactant, intermediate product use through the recirculation of condensing reflux tower in course of reaction, and the growing amount of accessory substance is very low; If raw material contains small amount of moisture; Corrosion can be very strong, causes device damage, impacts producing normal operation.
The process route of monochlorodifluoromethane mainly is that the chloroform liquid-phase fluorination process prepares monochlorodifluoromethane.This method hydrogen fluoride and monochlorodifluoromethane quality proportioning are generally about 2.0～4.0; Conversion ratio is very high, and unreacted reactant, intermediate product use through the recirculation of condensing reflux tower in course of reaction, and the growing amount of accessory substance is very low; If raw material contains small amount of moisture; Corrosion can be very strong, causes device damage, impacts producing normal operation.
Because catalyst S bCl
xF
yDegree of fluorination little, less about y≤1～3 to corrosion on Equipment, very high catalytic activity is arranged.Therefore, the fluorination catalyst of development and preparation difluoromethane or monochlorodifluoromethane is a current research direction with the technology that reduces equipment corrosion.
Summary of the invention
To the problems referred to above that exist in the prior art, the objective of the invention is to prepare a kind of fluorination catalyst that is used to prepare difluoromethane or monochlorodifluoromethane, and the application of this catalyst in difluoromethane and monochlorodifluoromethane production.
Described a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane; It is characterized in that described fluorination catalyst is made up of the chloride and the co-catalyst of antimony; Described co-catalyst comprises metal sulfate class and carrier; The chloride of described antimony and the percentage by weight of co-catalyst are 50-70:30-50, and the percentage by weight of described carrier and metal sulfate class is 80-90:10-20.
Described a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, the chloride that it is characterized in that described antimony is SbCl
5, SbCl
4F, SbCl
3F
2, SbCl
2F
3, SbClF
4Or SbF
5In one or more mixtures.
Described a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane is characterized in that described metal sulfate class is NaAl (SO
4)
2, KAl (SO
4)
2, RbAl (SO
4)
2, CsAl (SO
4)
2, NH
4Al (SO
4)
2, TlAl (SO
4)
2, NaCr (SO
4)
2, KCr (SO
4)
2, RbCr (SO
4)
2, CsCr (SO
4)
2, NH
4Cr (SO
4)
2, TlCr (SO
4)
2, NaFe (SO
4)
2, KFe (SO
4)
2, RbFe (SO
4)
2, CsFe (SO
4)
2, NH
4Fe (SO
4)
2, TlFe (SO
4)
2In one or more mixtures.
Described a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane is characterized in that described carrier is one or more mixtures in active carbon, aluminium oxide, magnesia, diatomite or the silica.
Described a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane is characterized in that the chloride of described antimony and the percentage by weight of co-catalyst are 60-70:30-40.
Described a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane is characterized in that comprising the steps:
1) preparation of co-catalyst: feed intake by weight percentage, with carrier vacuumize carried out preliminary treatment in 6 hours after, join mixing and stirring in the saturated solution of metal sulfate; Under situation about vacuumizing, remove surface solution; With deionized water this mixture is vacuumized while washing again, leave standstill dry after, thorough drying and dewatering in 250 ℃ of dryers; Be ground into powder through grinder, sieving, it is subsequent use to obtain the co-catalyst powder;
2) the co-catalyst powder that step 1) is obtained mixes for the inventory of 30-50:50-70 with the chloride of antimony by weight percentage, obtains fluorination catalyst.
Described a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane, it is characterized in that the described carrier evacuated pressure of step 1) be-60～-80kPa.
Described a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane is characterized in that the described co-catalyst powder of step 1) 200～300 orders that sieve.
The preparation method of described a kind of difluoromethane or monochlorodifluoromethane, this method are under the condition that any one catalyst exists in claim 1-8, and carrene or chloroform and hydrogen fluoride reaction are obtained.
The preparation method of described a kind of difluoromethane or monochlorodifluoromethane; This method is under the condition that any one fluorination catalyst exists in claim 1-8; With raw material carrene or chloroform and hydrogen fluoride preheating in preheater respectively; Again through getting into reactor after the mixer mixing together, at 50～150 ℃, reaction pressure 1～18kg/cm
2Carry out fluorination reaction under the absolute pressure; Material heats up in a steamer into the condensation separation tower and separates; The knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again; Isolate from the top difluoromethane or monochlorodifluoromethane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydride, obtain difluoromethane or monochlorodifluoromethane bullion, through redrying dewater product difluoromethane or monochlorodifluoromethane.
Through above-mentioned technology, compared with prior art, beneficial effect of the present invention is following:
1) the used catalytic component of the present invention is cheap and easy to get, low cost of manufacture, and also operating process is simple, mild condition, and the three wastes are few, and convenient post-treatment is little to corrosion on Equipment, and activity of such catalysts is high, long service life;
2) be used to prepare difluoromethane or monochlorodifluoromethane by catalyst of the present invention, technology is simple, and difluoromethane that obtains or monochlorodifluoromethane purity are up to more than 99%, and conversion ratio is up to more than 0.94;
3) catalyst of the present invention is little to corrosion on Equipment, and after use, the consersion unit of difluoromethane extended to more than 6-18 month from 2-6 month service life; The consersion unit of monochlorodifluoromethane extended to more than 24-36 month from 12-18 month service life.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
The preparation of the co-catalyst that embodiment 1 is activated carbon supported
At first the 150kg active carbon is vacuumized under the vavuum pump of-60kPa, carry out preliminary treatment, in addition with 37.5kg metal sulfate NaAl (SO
4)
2Be dissolved at normal temperatures and pressures and reach hypersaturated state in the deionized water, saturated solution is taken out, then, with above-mentioned active carbon processed and NaAl (SO
4)
2The abundant mixing and stirring of saturated solution; After under the condition of vacuumizing, dewatering, with deionized water this mixture is vacuumized while washing again, last; Leave standstill and dry; Mixture is put in thorough drying and dewatering in 250 ℃ of dryers, is ground into powder, obtain co-catalyst behind 200 orders that sieve through grinder.
Above-mentioned carrier replaces active carbon with one or more mixtures in active carbon, aluminium oxide, magnesia, diatomite or the silica, and the metal sulfate class is with NaAl (SO
4)
2, KAl (SO
4)
2, RbAl (SO
4)
2, CsAl (SO
4)
2, NH
4Al (SO
4)
2, TlAl (SO
4)
2, NaCr (SO
4)
2, KCr (SO
4)
2, RbCr (SO
4)
2, CsCr (SO
4)
2, NH
4Cr (SO
4)
2, TlCr (SO
4)
2, NaFe (SO
4)
2, KFe (SO
4)
2, RbFe (SO
4)
2, CsFe (SO
4)
2, NH
4Fe (SO
4)
2, TlFe (SO
4)
2In one or more mixtures replace NaAl (SO
4)
2, also can obtain same effect.
The preparation of the co-catalyst of embodiment 2 tripolite loadings
Be that the mixture of diatomite, silica and the aluminium oxide of 1:2:1 vacuumizes under the vavuum pump of-80kPa at first, carry out preliminary treatment, in addition with 16kg metal sulfate KAl (SO with the 150kg weight ratio
4)
2Be dissolved at normal temperatures and pressures and reach hypersaturated state in the deionized water, then, with above-mentioned active carbon and KAl (SO
4)
2The abundant mixing and stirring of saturated solution; After under the condition of vacuumizing, dewatering, with deionized water this mixture is vacuumized while washing again, last; Leave standstill and dry; Mixture is put in thorough drying and dewatering in 250 ℃ of dryers, is ground into powder through grinder, 300 orders that sieve obtain fluorination catalyst.
The preparation of embodiment 3 diatomite and activated carbon supported co-catalyst
Be that diatomite and the active carbon of 1:1 vacuumizes under the vavuum pump of-70kp at first, carry out preliminary treatment, in addition with 26kg metal sulfate KCr (SO with the 150kg weight ratio
4)
2Be dissolved at normal temperatures and pressures and reach hypersaturated state in the deionized water, then, with above-mentioned active carbon and KCr (SO
4)
2The abundant mixing and stirring of saturated solution; After under the condition of vacuumizing, dewatering, with deionized water this mixture is vacuumized while washing again, last; Leave standstill and dry; Mixture is put in thorough drying and dewatering in 250 ℃ of dryers, is ground into powder, must go up co-catalyst behind 250 orders that sieve through grinder.
The preparation of the co-catalyst that embodiment 4 magnesia are activated carbon supported
At first 150kg magnesia and active carbon being vacuumized under the vavuum pump of-60kp, carry out preliminary treatment, is the metal sulfate NaFe (SO of 1:1 in addition with the 35kg weight ratio
4)
2And NaFe (SO
4)
2Mixture be dissolved at normal temperatures and pressures and reach hypersaturated state in the deionized water, then, with above-mentioned active carbon and NaFe (SO
4)
2The abundant mixing and stirring of saturated solution; After under the condition of vacuumizing, dewatering, with deionized water this mixture is vacuumized while washing again, last; Leave standstill and dry; Mixture is put in 250 ℃ of dryers thoroughly drying and dewatering, is ground into powder through grinder, sieving 200 obtains co-catalyst.
The preparation of the fluorination catalyst that embodiment 5 is activated carbon supported
Activated carbon supported co-catalyst powder 90kg and SbCl that embodiment 1 is prepared
5And SbF
5Mass ratio is the 200kg fluorination catalyst of 5:1.
The chloride of above-mentioned antimony is used SbCl
4F, SbCl
3F
2, SbCl
2F
3, SbClF
4Or SbF
5In any one or a few mixture replace SbCl
5, all same effect can be arranged.
The preparation of the fluorination catalyst of embodiment 6 active carbons and magnesia load
With the active carbon for preparing and magnesia load cocatalyst powder 80kg and SbClF
480kg is pressed into reactor and makes fluorination catalyst.
The preparation of embodiment 7 diatomite and silicon dioxide carried fluorination catalyst
With the diatomite for preparing and silicon dioxide carried co-catalyst powder 80kg and SbCl
3F
2And SbClF
4Mass ratio is that the 120kg of 1:1 is pressed into reactor and makes fluorination catalyst.
The application of fluorination catalyst in fluorination reaction that embodiment 8 is activated carbon supported
In the reactor of the 1.41kg fluorination catalyst that the step 5 of packing into prepares, the inventory of carrene by 141kg/h and ammonium acid fluoride 67kg/h is preheating in preheater about 60 ℃ respectively, be pressed into reactor.50 ℃ of temperature, reaction pressure is at 1kg/cm in reaction temperature
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate difluoromethane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the difluoromethane bullion, through redrying dewater product 85kg/h, conversion ratio 0.985, purity is 99%.
The application of fluorination catalyst in fluorination reaction that embodiment 9 is activated carbon supported
In the reactor of the 10kg fluorination catalyst for preparing of packing into, the inventory of chloroform by 200kg/h and ammonium acid fluoride 71kg/h is preheating in preheater about 60 ℃ respectively, be pressed into reactor.150 ℃ of temperature, reaction pressure is at 18 kg/cm in reaction temperature
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate monochlorodifluoromethane methane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the monochlorodifluoromethane bullion, through redrying dewater product 137kg/h, conversion ratio 0.95, purity is 99%.
Embodiment 10 diatomite and the silicon dioxide carried application of fluorination catalyst in fluorination reaction
In the reactor of the 2.6kg fluorination catalyst for preparing of packing into, the inventory of carrene by 130kg/h and ammonium acid fluoride 61kg/h is preheating in preheater about 60 ℃ respectively, be pressed into reactor.100 ℃ of temperature, reaction pressure is at 10kg/cm in reaction temperature
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate difluoromethane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the difluoromethane bullion, through redrying dewater product 76kg/h, conversion ratio is 0.962, purity is 99%.
Embodiment 11 diatomite and the silicon dioxide carried application of fluorination catalyst in fluorination reaction
In the reactor of the 3kg fluorination catalyst for preparing of packing into, the inventory of chloroform by 221kg/h and ammonium acid fluoride 79kg/h is preheating in preheater about 60 ℃ respectively, be pressed into reactor.120 ℃ of temperature, reaction pressure is at 12 kg/cm in reaction temperature
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate monochlorodifluoromethane methane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the monochlorodifluoromethane bullion, through redrying dewater product 150kg/h, conversion ratio 0.94, purity is 99%.
The application of fluorination catalyst in fluorination reaction of embodiment 12 active carbons and magnesia load
In the reactor of the fluorination catalyst for preparing of packing into, with carrene by the inventory of 125kg/h and ammonium acid fluoride 59kg/h respectively in preheater preheating be pressed into reactor.At 100 ℃ of temperature, reaction pressure 10kg/cm
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate difluoromethane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the difluoromethane bullion, through redrying dewater product 73kg/h, conversion ratio is 0.96, purity is 99%.
The application of fluorination catalyst in fluorination reaction of embodiment 13 active carbons and magnesia load
In the reactor of the fluorination catalyst for preparing of packing into, the inventory of chloroform by 187kg/h and ammonium acid fluoride 67kg/h is preheating in preheater about 60 ℃ respectively, be pressed into reactor.80 ℃ of temperature, reaction pressure is at 6 kg/cm in reaction temperature
2React under the absolute pressure, after reaction finished, material heated up in a steamer into the condensation separation tower and separates, and the knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again.The top isolate monochlorodifluoromethane methane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydrides, obtain the monochlorodifluoromethane bullion, through redrying dewater product 126kg/h, conversion ratio 0.934, purity is 99%.
Claims (10)
1. fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane; It is characterized in that described fluorination catalyst is made up of the chloride and the co-catalyst of antimony; Described co-catalyst comprises metal sulfate class and carrier; The chloride of described antimony and the percentage by weight of co-catalyst are 50-70:30-50, and the percentage by weight of described carrier and metal sulfate class is 80-90:10-20.
2. a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane according to claim 1, the chloride that it is characterized in that described antimony is SbCl
5, SbCl
4F, SbCl
3F
2, SbCl
2F
3, SbClF
4Or SbF
5In one or more mixtures.
3. a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane according to claim 1 is characterized in that described metal sulfate class is NaAl (SO
4)
2, KAl (SO
4)
2, RbAl (SO
4)
2, CsAl (SO
4)
2, NH
4Al (SO
4)
2, TlAl (SO
4)
2, NaCr (SO
4)
2, KCr (SO
4)
2, RbCr (SO
4)
2, CsCr (SO
4)
2, NH
4Cr (SO
4)
2, TlCr (SO
4)
2, NaFe (SO
4)
2, KFe (SO
4)
2, RbFe (SO
4)
2, CsFe (SO
4)
2, NH
4Fe (SO
4)
2, TlFe (SO
4)
2In one or more mixtures.
4. a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane according to claim 1 is characterized in that described carrier is one or more mixtures in active carbon, aluminium oxide, magnesia, diatomite or the silica.
5. a kind of fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane according to claim 1 is characterized in that the chloride of described antimony and the percentage by weight of co-catalyst are 60-70:30-40.
6. a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane according to claim 1 is characterized in that comprising the steps:
1) preparation of co-catalyst: feed intake by weight percentage, with carrier vacuumize carried out preliminary treatment in 6 hours after, join mixing and stirring in the saturated solution of metal sulfate; Under situation about vacuumizing, remove surface solution; With deionized water this mixture is vacuumized while washing again, leave standstill dry after, thorough drying and dewatering in 250 ℃ of dryers; Be ground into powder through grinder, sieving, it is subsequent use to obtain the co-catalyst powder;
2) the co-catalyst powder that step 1) is obtained mixes for the inventory of 30-50:50-70 with the chloride of antimony by weight percentage, obtains fluorination catalyst.
7. a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane according to claim 6, it is characterized in that the described carrier evacuated pressure of step 1) be-60～-80kPa.
8. a kind of preparation method who prepares the fluorination catalyst of difluoromethane or monochlorodifluoromethane according to claim 6 is characterized in that the described co-catalyst powder of step 1) 200～300 orders that sieve.
9. the preparation method of difluoromethane or monochlorodifluoromethane, this method is under the condition that any one catalyst exists in claim 1-8, and carrene or chloroform and hydrogen fluoride reaction are obtained.
10. the preparation method of difluoromethane or monochlorodifluoromethane; This method is under the condition that any one fluorination catalyst exists in claim 1-8; With raw material carrene or chloroform and hydrogen fluoride preheating in preheater respectively; Again through getting into reactor after the mixer mixing together, at 50～150 ℃, reaction pressure 1～18kg/cm
2Carry out fluorination reaction under the absolute pressure; Material heats up in a steamer into the condensation separation tower and separates; The knockout tower bottom is isolated accessory substance and is circulated to the reactor cycles use again; Isolate from the top difluoromethane or monochlorodifluoromethane and hydrogen chloride through washing and alkali cleaning except that sour gas such as de-chlorine hydride, obtain difluoromethane or monochlorodifluoromethane bullion, through redrying dewater product difluoromethane or monochlorodifluoromethane.
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| WO2015085781A1 (en) * | 2013-12-12 | 2015-06-18 | 西安近代化学研究所 | Chromium-free gas phase fluorination catalyst and application thereof |
| CN105001039A (en) * | 2015-06-02 | 2015-10-28 | 江苏三美化工有限公司 | Method for improving service life of R32 reaction kettle |
| CN106966874A (en) * | 2017-05-15 | 2017-07-21 | 临海市利民化工有限公司 | A kind of synthetic method of Sevoflurane |
| CN107308799A (en) * | 2017-06-16 | 2017-11-03 | 浙江金氟隆化工装备有限公司 | A kind of gas purifying device of chlorodifluoromethane |
| CN109939734A (en) * | 2019-04-19 | 2019-06-28 | 临海市利民化工有限公司 | A kind of perfluorinated sulfonic resin catalyst, preparation method and preparing the application in Dichloromonofluoromethane |
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