CN102527414B - 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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- CN102527414B CN102527414B CN2011104464849A CN201110446484A CN102527414B CN 102527414 B CN102527414 B CN 102527414B CN 2011104464849 A CN2011104464849 A CN 2011104464849A CN 201110446484 A CN201110446484 A CN 201110446484A CN 102527414 B CN102527414 B CN 102527414B
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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 for the preparation of difluoromethane or monochlorodifluoromethane and preparation method and application.
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 simultaneously good serviceability.The compounding substances of the compositions such as difluoromethane and other ODS substitute such as pentafluoroethane (common name HFC-125) substitutes HCFC-22 as cold-producing medium and also has energy-saving effect concurrently.Purposes is wide, and development prospect is boundless, occupies critical role in the ODS substitute, 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 front two process routes all have distinct disadvantage.First method, reducing process prepare difluoromethane reaction difficulty, low conversion rate, and the product impurity of producing is many, and the rectifying separation difficulty now is eliminated substantially; 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 occur to fluoridize in fluorination reaction process, makes the antimony pentafluoride increased content, 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 a small amount of moisture content, corrosion can be stronger, causes the equipment frequent, and the normal operation of producing has been caused impact; The third method, liquid phase method flaorination process are the important technologies in the preparation difluoromethane technique, and the advantage of technique is significantly to have improved utilization rate and the product yield of raw material, has reduced simultaneously three wastes treating capacity.The method hydrogen fluoride and carrene quality proportioning are generally about 1.0～3.0, conversion ratio is very high, unreacted reactant, intermediate product use by the recirculation of condensing reflux tower in course of reaction, the growing amount of accessory substance is very low, if raw material contains a small amount of moisture content, 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.The method hydrogen fluoride and monochlorodifluoromethane quality proportioning are generally about 2.0～4.0, conversion ratio is very high, unreacted reactant, intermediate product use by the recirculation of condensing reflux tower in course of reaction, the growing amount of accessory substance is very low, if raw material contains a small amount of moisture content, corrosion can be very strong, causes device damage, impacts producing normal operation.
Because catalyst S bCl
xF
yDegree of fluorination little, less to the corrosion of equipment about y≤1～3, very high catalytic activity is arranged.Therefore, the technology of the fluorination catalyst of exploitation preparation difluoromethane or monochlorodifluoromethane and reduction equipment corrosion is a current important research direction.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the invention is to prepare a kind of fluorination catalyst for the preparation of 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 comprised of 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, after carrier vacuumized 6 hours and carry out preliminary treatment, join mixing and stirring in the saturated solution of metal sulfate, in 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 for 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 by weight percentage with the chloride of antimony, 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, the 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, the method is under the condition that any one fluorination catalyst exists in claim 1-8, with raw material carrene or chloroform and respectively preheating in preheater of hydrogen fluoride, enter together reactor after mixing by blender again, 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 again is circulated to the reactor cycles use, isolate difluoromethane or monochlorodifluoromethane and hydrogen chloride from the top and remove the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtain difluoromethane or monochlorodifluoromethane crude product, through redrying dewater to get product difluoromethane or monochlorodifluoromethane.
By above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) the used catalytic component of the present invention is cheap and easy to get, low cost of manufacture, and operating process is simple, mild condition, and the three wastes are few, and convenient post-treatment is little to the corrosion of equipment, catalyst active high, long service life;
2) by catalyst of the present invention for the preparation of difluoromethane or monochlorodifluoromethane, technique is simple, the difluoromethane that obtains or monochlorodifluoromethane purity are up to more than 99%, conversion ratio is up to more than 0.94;
3) catalyst of the present invention is little to the corrosion of 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
The present invention is described further below in conjunction with specific embodiment, 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 active carbon and the NaAl (SO of above-mentioned processing
4)
2The abundant mixing and stirring of saturated solution, vacuumize dewater under the condition after, with deionized water this mixture is vacuumized while washing again, at last, leave standstill and dry, mixture is put in thorough drying and dewatering in 250 ℃ of dryers, is ground into powder through grinder, obtain co-catalyst behind 200 orders that sieve.
Above-mentioned carrier replaces active carbon with one or more mixtures in active carbon, aluminium oxide, magnesia, diatomite or the silica, metal sulfate class 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
The mixture that at first with the 150kg weight ratio is diatomite, silica and the aluminium oxide of 1:2:1 vacuumizes under the vavuum pump of-80kPa, carries out preliminary treatment, in addition with 16kg metal sulfate KAl (SO
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, vacuumize dewater under the condition after, with deionized water this mixture is vacuumized while washing again, at 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
At first being the diatomite of 1:1 and active carbon with the 150kg weight ratio vacuumizes under the vavuum pump of-70kp, carries out preliminary treatment, in addition with 26kg metal sulfate KCr (SO
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, vacuumize dewater under the condition after, with deionized water this mixture is vacuumized while washing again, at last, leave standstill and dry, mixture is put in thorough drying and dewatering in 250 ℃ of dryers, is ground into powder through grinder, must go up co-catalyst behind 250 orders that sieve.
The preparation of the co-catalyst of embodiment 4 MgO activity charcoal loads
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, vacuumize dewater under the condition after, with deionized water this mixture is vacuumized while washing again, at 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 SbCl of above-mentioned antimony
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 MgO-Supported
With active carbon and MgO-Supported co-catalyst powder 80kg and the SbClF for preparing
480kg is pressed into reactor and makes fluorination catalyst.
The preparation of embodiment 7 diatomite and silicon dioxide carried fluorination catalyst
With diatomite and silicon dioxide carried co-catalyst powder 80kg and the SbCl for preparing
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 again is circulated to the reactor cycles use.The top is isolated difluoromethane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the difluoromethane crude product, through the redrying product 85kg/h that dewaters to get, and 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 again is circulated to the reactor cycles use.The top is isolated monochlorodifluoromethane methane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the monochlorodifluoromethane crude product, through the redrying product 137kg/h that dewaters to get, and 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 again is circulated to the reactor cycles use.The top is isolated difluoromethane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the difluoromethane crude product, and through the redrying product 76kg/h that dewaters to get, conversion ratio is 0.962, and 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 again is circulated to the reactor cycles use.The top is isolated monochlorodifluoromethane methane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the monochlorodifluoromethane crude product, through the redrying product 150kg/h that dewaters to get, and conversion ratio 0.94, purity is 99%.
The application of fluorination catalyst in fluorination reaction of embodiment 12 active carbons and MgO-Supported
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 again is circulated to the reactor cycles use.The top is isolated difluoromethane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the difluoromethane crude product, and through the redrying product 73kg/h that dewaters to get, conversion ratio is 0.96, and purity is 99%.
The application of fluorination catalyst in fluorination reaction of embodiment 13 active carbons and MgO-Supported
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 again is circulated to the reactor cycles use.The top is isolated monochlorodifluoromethane methane and hydrogen chloride and is removed the sour gas such as de-chlorine hydride through washing and alkali cleaning, obtains the monochlorodifluoromethane crude product, through the redrying product 126kg/h that dewaters to get, and 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 comprised of 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
3Or SbClF
4In 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, after carrier vacuumized 6 hours and carry out preliminary treatment, join mixing and stirring in the saturated solution of metal sulfate, in 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 for 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 by weight percentage with the chloride of antimony, 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 a difluoromethane or monochlorodifluoromethane, the 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 a difluoromethane or monochlorodifluoromethane, the method is under the condition that any one fluorination catalyst exists in claim 1-8, with raw material carrene or chloroform and respectively preheating in preheater of hydrogen fluoride, enter together reactor after mixing by blender again, 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 again is circulated to the reactor cycles use, isolate difluoromethane or monochlorodifluoromethane and hydrogen chloride from the top and remove de-chlorine hydride through washing and alkali cleaning, obtain difluoromethane or monochlorodifluoromethane crude product, through redrying dewater to get product difluoromethane or monochlorodifluoromethane.
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| 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 |
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| US6407296B1 (en) * | 1994-07-01 | 2002-06-18 | Daikin Industries Ltd. | Process for producing difluoromethane |
| FR2736050B1 (en) * | 1995-06-29 | 1997-08-01 | Atochem Elf Sa | PROCESS FOR PRODUCING DIFLUOROMETHANE |
| AU2002317470A1 (en) * | 2002-07-10 | 2004-02-02 | Srf Limited | A process for the production of difluoromethane |
| CN1313423C (en) * | 2005-01-27 | 2007-05-02 | 鹰鹏化工有限公司 | Method for preparing difluoromethane by stage continuous fluorination |
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|---|---|---|---|---|
| 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 |
| CN109939734B (en) * | 2019-04-19 | 2021-10-29 | 临海市利民化工有限公司 | Perfluorosulfonic acid resin catalyst, preparation method and application in preparation of dichlorofluoromethane |
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