CN109748775B - Resource utilization method of by-product trifluoromethane in HCFC-22 production - Google Patents
Resource utilization method of by-product trifluoromethane in HCFC-22 production Download PDFInfo
- Publication number
- CN109748775B CN109748775B CN201711088468.0A CN201711088468A CN109748775B CN 109748775 B CN109748775 B CN 109748775B CN 201711088468 A CN201711088468 A CN 201711088468A CN 109748775 B CN109748775 B CN 109748775B
- Authority
- CN
- China
- Prior art keywords
- trifluoromethane
- reaction
- difluoromethane
- recycling
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for resource utilization of trifluoromethane, which is firstly selected from MgF2、Al2O3Partially fluorinated alumina and AlF3Reacting trifluoromethane with dichloromethane under the action of at least one catalyst to obtain a reaction product containing difluoromethane and difluoromethane chloride, and rectifying to obtain difluoromethane. The method provided by the invention not only can realize the resource utilization of the trifluoromethane, but also can convert the trifluoromethane into the high-value difluoromethane, and has good economic benefits.
Description
Technical Field
The invention relates to a resource utilization method of by-product trifluoromethane in HCFC-22 production, in particular to a resource utilization method for converting the by-product trifluoromethane into difluoromethane.
Background
Difluoromethane monochloride (HCFC-22, R22 or CHClF)2) Have been the most widely used refrigerants and blowing agents, and are being gradually banned because they are ozone depleting substances. However, HCFC-22 is also a main raw material for producing plastic monomers such as Tetrafluoroethylene (TFE) and Hexafluoropropylene (HFP), and it accounts for 40% or more of the consumption of HCFC-22 as a raw material for producing fluorocarbons such as TFE, and therefore, its mass production is inevitable, in which the capacity of HCFC-22 in our country exceeds half of the total amount (about 70 ten thousand tons). CHF3Is an inevitable by-product generated in the process of producing R22, and CHF is a common technical scheme3The amount of the compound produced is about 2-5% of R22 [ Journal of Fluorine Chemistry,2012,140:7-16]。
CHF3Has strong greenhouse effect, and the Global Warming Potential (GWP) of the compound is CO214800 times higher. Fluorocarbon emissions (CO) in 2050, based on statistical data and estimates from the united nations environmental planning agency (UNEP)2Equivalent) will account for 9-19% of global greenhouse gas emissions [ Proc. Natl. Acad. Sci. USA,2009.106(27): p.10949-10954]Wherein in 2013, CHF in China3The emission amount of the fertilizer accounts for 68 percent of the emission amount of the whole worldThe amount of the raw trifluoromethane can reach more than 2 ten thousand tons, which is converted into CO2The annual emission reaches 2.96 hundred million tons. Therefore, CHF3The resource utilization of strong greenhouse gases becomes an important subject in realizing energy conservation and emission reduction.
Currently, industrially, the by-product trifluoromethane generated in the production process of HCFC-22 is generally treated by direct discharge or high-temperature incineration at 1200 ℃, wherein: the direct discharge can bring environmental pollution, the high-temperature incineration treatment operation at 1200 ℃ and the equipment cost are higher, and the production cost of HCFC-22 is increased. If the by-product trifluoromethane can be converted into useful compounds, not only the problem of disposal of the by-product trifluoromethane can be solved, but also new economic effects can be added.
US patent 3009966 discloses that pyrolysis of trifluoromethane at 700-. PFIB has extremely high toxicity and is complicated to process.
WO96/29296 discloses a process for the co-cleavage of HCFC-22 with a fluoroalkane to form predominantly macromolecular fluoroalkanes. In the route, the conversion rate of HCFC-22 can reach 100%, but the yield of pentafluoroethane is only 60%, and 40% of byproducts are products with low additional value. Thus, additional by-products are produced during the handling of HFC-23 that require further processing.
U.S. patent No. 2003/0166981 also uses pyrolysis of trifluoromethane and HCFC-22 to produce pentafluoroethane (HFC-125), heptafluoropropane (HFC-227ea), a mixture of TFE and HFP at 690-775 ℃ in the presence of gold as a catalyst. However, like the above method, the pyrolysis temperature is high and the reaction conditions are severe.
Chinese patent CN104628514A reports that methane and trifluoromethane are introduced into a reactor filled with a catalyst in a certain proportion, and O is added in a certain proportion2The reaction is carried out under the condition of higher temperature, and the vinylidene fluoride is generated under the action of a catalyst.
Chinese patent CN104628513A discloses a method for converting trifluoromethane and chloroform into HCFC-22 under the action of a catalyst. The main products obtained by the method are difluorochloromethane and monofluoromethane, which are all freon controlled substances and have low additional value.
In the prior art, when the trifluoromethane is treated by a gas phase cracking reaction, a certain conversion rate can be reached only by very high reaction temperature, and a large amount of byproducts and serious carbon deposition are generated; when the halogenated hydrocarbon is added to convert the trifluoromethane into HCFC-22, the trifluoromethane is only converted into HCFC-22, and the trifluoromethane cannot be converted into a compound with higher value.
Therefore, further technical studies are required to utilize trifluoromethane as a resource and convert it into a more valuable compound.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a resource utilization method of by-product trifluoromethane in HCFC-22 production, which converts the by-product trifluoromethane into difluoromethane with higher value.
The chemical equation that the invention may relate to is as follows:
CH2Cl2+CHF3→CH2ClF+CHClF2；
CH2ClF+CHF3→CH2F2+CHClF2；
2CH2ClF→CH2F2+CHCl2；
2CHClF2→CHCl2F+CHF3；
CH2Cl2+HF→CH2ClF+HCl；
CH2ClF+HF→CH2F2+HCl；
CHClF2+HF→CHF3+HCl。
the invention provides the following technical scheme:
a method for resource utilization of trifluoromethane, the method comprising:
(1) reacting trifluoromethane with dichloromethane under the action of a catalyst to obtain a reaction product containing difluoromethane and difluoromethane chloride,
the catalyst is selected from MgF2、Al2O3Partially fluorinated alumina and AlF3At least one of;
(2) and (3) rectifying and separating a reaction product containing difluoromethane and difluorochloromethane, and circulating the obtained difluorochloromethane to a difluorochloromethane production device to obtain the difluoromethane, namely the product difluoromethane.
In the method provided by the invention, the raw materials of the trifluoromethane and the dichloromethane can be the trifluoromethane and the dichloromethane obtained in the production of HCFC-22.
The ratio of the raw materials of the trifluoromethane and the dichloromethane meets the requirement of smoothly carrying out the reaction.
Preferably, the molar ratio of the trifluoromethane to the dichloromethane is 1: 1-1: 5.
More preferably, the molar ratio of the trifluoromethane to the dichloromethane is 1: 1-1: 2
The method provided by the invention improves the catalytic efficiency and stability of the catalyst by adding the promoting gas in the reaction stage. The promoting gas may be selected from Cl2、CCl4、H2、O2、CO2、O3And nitrogen oxides.
The addition amount of the promoting gas may be determined according to the catalytic efficiency and stability of the catalyst.
Preferably, the molar ratio of the promoting gas to the trifluoromethane is 1: 0.01-0.5.
More preferably, the molar ratio of the promoting gas to the trifluoromethane is 1: 0.01-0.1.
The method provided by the invention can further add HF gas in the reaction stage to improve the selectivity of difluoromethane and difluoromethane chloride.
The amount of the HF gas to be added may be determined according to the desired selectivity for difluoromethane and difluoromethane monochloride.
Preferably, the amount of the HF gas added is 0.5-40% of the total volume of the feed of trifluoromethane and dichloromethane.
It is further preferred that the amount of the HF gas added is 1.0% to 20% of the total volume of the feed of trifluoromethane and dichloromethane.
In the method provided by the invention, in the reaction stage, the reaction temperature is satisfied, so that the reaction can be smoothly carried out.
Preferably, the reaction temperature is 200 to 500 ℃.
Further preferably, the reaction temperature is 350-450 ℃.
In the method provided by the invention, in the reaction stage, the reaction pressure is satisfied, so that the reaction can be smoothly carried out.
Preferably, the reaction pressure is 1 to 10 bar.
Further preferably, the reaction pressure is 1 to 3 bar.
In the method provided by the invention, in the reaction stage, the space velocity of the raw materials is satisfied, so that the reaction is smoothly carried out.
Preferably, the space velocity of the raw material is 50-10000 h-1。
Further preferably, the space velocity of the raw materials is 100-1000 h-1。
The method provided by the invention uses a catalyst selected from MgF2、Al2O3Partially fluorinated alumina and AlF3At least one of (1).
Namely: either MgF selected from the group consisting of2、Al2O3Partially fluorinated alumina and AlF3One kind selected from MgF may be used2、Al2O3Partially fluorinated alumina and AlF3Two of (1), it is also possible to use a compound selected from MgF2、Al2O3Partially fluorinated alumina and AlF3Three of (1), MgF selected from the group consisting of2、Al2O3Partially fluorinated alumina and AlF3Four of them.
The catalyst used in the invention is preferably pretreated before use, and the preferred pretreatment method is as follows:
firstly using N2Treating at 200-250 deg.C for 3-5 hr, and treating with HF or HCFC-22 at 200-400 deg.C for 3-5 hr.
In the method provided by the invention, in the rectification separation step, the rectification temperature meets the requirement of separating reaction products.
Preferably, the rectification temperature is-50 to-10 ℃.
More preferably, the rectification temperature is-40 to-30 ℃.
According to the method provided by the invention, in the rectification separation step, the rectification pressure meets the requirement of separating reaction products.
Preferably, the rectification pressure is 0.1-1.0 MPa.
More preferably, the rectification pressure is 0.1 to 0.5 MPa.
Compared with the prior art, the method provided by the invention has the following advantages: (1) realizing resource utilization of the by-product trifluoromethane in HCFC-22 production and converting the by-product trifluoromethane into high-value difluoromethane;
(2) the reaction temperature is low and is far lower than the cracking temperature of 700-800 ℃, so that the energy consumption is low, the equipment investment is low, the catalyst selectivity is high, and the service life is long;
(3) the difluorochloromethane generated by the reaction is recycled to the HCFC-22 production system, no tail gas is discharged, and the method is safe and environment-friendly.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
Pretreatment of a catalyst: adding gamma-aluminum oxide to N2The mixture is treated at 250 ℃ for 5h, fluorinated at 250 ℃ for 2 h under a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treated at 300 ℃ for 5 h.
Reaction: trifluoromethane and dichloromethane were passed in a 1:1 molar ratio into a reactor containing 20ml of the pretreatedThe reactor of the gamma-aluminum oxide catalyst has the temperature of 350 ℃, the pressure of 1bar and the space velocity of 1000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 32.3%, 26.2% and 41.1%, respectively, and with conversions of trifluoromethane and dichloromethane of 18.4% and 17.7%, respectively. The catalyst activity is kept stable after reaction for 150 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-40 ℃ and the rectifying pressure is controlled to be about 0.3 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 2
Pretreatment of a catalyst: adding magnesium fluoride to N2At 200℃The treatment is carried out for 5h, the fluorination treatment is carried out for 2 h at 350 ℃ in a mixed atmosphere of 10 percent hydrogen fluoride and 90 percent nitrogen, and finally the treatment is carried out for 5h at 350 ℃ in the presence of hydrogen fluoride.
Reaction: introducing trifluoromethane and dichloromethane into a reactor filled with 20ml of pretreated magnesium fluoride catalyst at a molar ratio of 1:1, at a temperature of 450 ℃, a pressure of 2bar and a space velocity of 2000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 21.5%, 26.2% and 40.4%, respectively, in which the conversions of trifluoromethane and dichloromethane were 13.6% and 12.1%, respectively. The activity of the catalyst is kept stable after reaction for 200 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-50 ℃ and the rectifying pressure is controlled to be about 0.1 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 3
Preparing a catalyst: 260.4g of Al (NO) were weighed out3)3·9H2Dissolving O in 500ml water, adding 25% ammonia water solution dropwise into the above solution, controlling pH to 7, starting magnetic stirring, centrifuging, drying, collecting the lower layer precipitate, drying at 100 deg.C, and adding N2Roasting at 500 deg.C for 3h in atmosphere to obtain Al2O3A catalyst.
Reaction: loading the catalyst into a reactor, introducing trifluoromethane and dichloromethane into the reactor containing 20ml of pretreated gamma-alumina catalyst at a molar ratio of 1:1, at 350 deg.C and 1bar, and at a space velocity of 1000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 24.8%, 21.7% and 43.4%, respectively, and with conversions of trifluoromethane and dichloromethane of 33.1% and 29.5%, respectively. The activity of the catalyst is kept stable after reaction for 200 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-30 ℃ and the rectifying pressure is controlled to be about 0.5 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 4
Preparing a catalyst: 130.2g of Al (NO) are weighed out3)3·9H2Dissolving O and 51.4g of magnesium nitrate in 500ml of water, dropwise adding 25% ammonia water solution into the solution, controlling the pH value to 7, starting magnetic stirring, centrifugally drying, taking the lower layer precipitate, drying at 100 ℃ and then adding N2Roasting for 3h at 500 ℃ in the atmosphere to obtain the magnesium-aluminum composite catalyst.
Pretreatment of a catalyst: adding magnesium-aluminum composite catalyst into N2The treatment is carried out for 4h at 240 ℃, the fluorination treatment is carried out for 3h at 350 ℃ under a mixed atmosphere of 10 percent hydrogen fluoride and 90 percent nitrogen, and finally the treatment is carried out for 3h at 350 ℃ under hydrogen fluoride.
Reaction: loading the pretreated catalyst into a reactor, and adding trifluoromethane and bis (tert-butyl ether)Methyl chloride is introduced into a reactor filled with 20ml of pretreated catalyst at a molar ratio of 1:2, the temperature is 350 ℃, the pressure is 1bar, and the space velocity is 1000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 27.2%, 28.1% and 44.4%, respectively, in which the conversions of trifluoromethane and dichloromethane were 31.0% and 21%, respectively. The catalyst activity is kept stable after 250 hours of reaction.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-40 ℃ and the rectifying pressure is controlled to be about 0.1 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 5
Preparing a catalyst: weighing 20g of commercial alpha-AlF with the purity of more than 99 percent3Powder and 30g of commercial MgF of the same purity2Placing in a ball milling tank, ball milling and mixing at 200 r/min for 30min, tabletting at 15MPa, crushing into 0.8-1.4mm granules, drying at 100 deg.C, and adding N2Roasting for 3h at 500 ℃ in the atmosphere to obtain the magnesium-aluminum composite catalyst.
Pretreatment of a catalyst: adding magnesium-aluminum composite catalyst into N2The treatment is carried out for 4h at 240 ℃, the fluorination treatment is carried out for 3h at 350 ℃ under a mixed atmosphere of 10 percent hydrogen fluoride and 90 percent nitrogen, and finally the treatment is carried out for 3h at 350 ℃ under hydrogen fluoride.
Reaction: introducing trifluoromethane and dichloromethane into a reactor filled with 20ml of pretreated gamma-aluminum oxide catalyst at a molar ratio of 1:1, at a temperature of 350 ℃, a pressure of 1bar and a space velocity of 1000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 32.6%, 33.4% and 33.1%, respectively, in which the conversions of trifluoromethane and dichloromethane were 36.1% and 35.5%, respectively. The catalyst activity is kept stable after reaction for 150 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-40 ℃ and the rectifying pressure is controlled to be about 0.1 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 6
Pretreatment of a catalyst: adding gamma-alumina catalyst into N2The mixture is treated at 250 ℃ for 5h, fluorinated at 400 ℃ for 2 h under a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treated at 400 ℃ for 5 h.
Reaction: reacting trifluoromethane, dichloromethane and O2Introducing into a reactor filled with 20ml of pretreated catalyst at a molar ratio of 1:1:0.02 at 350 deg.C and 3bar pressure at space velocity of 500h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 27.3%, 26.8% and 45.8%, respectively, and with conversions of trifluoromethane and dichloromethane of 28.6% and 27.1%, respectively. The catalyst activity is kept stable after reaction for 300 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-40 ℃ and the rectifying pressure is controlled to be about 0.3 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 7
Pretreatment of a catalyst: alpha-AlF3Catalysts in N2The mixture is treated at 250 ℃ for 5h, fluorinated at 400 ℃ for 2 h under a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treated at 400 ℃ for 5 h.
Reaction: reacting trifluoromethane, dichloromethane and CCl4The mixture containing 20ml of pretreated alpha-AlF is introduced at a molar ratio of 1:1:0.043Reactor of catalyst at 350 deg.C, pressure 2bar, space velocity 2000h-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 28.6%, 29.1% and 41.0%, respectively, and with conversions of trifluoromethane and dichloromethane of 32.9% and 35.6%, respectively. The activity of the catalyst is kept stable after reaction for 200 h.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-30 ℃ and the rectifying pressure is controlled to be about 0.4 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Example 8
Pretreatment of a catalyst: adding gamma-alumina catalyst into N2The mixture is treated at 250 ℃ for 5h, fluorinated at 400 ℃ for 2 h under a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treated at 400 ℃ for 5 h.
Reaction: introducing trifluoromethane, dichloromethane and HF at a molar ratio of 1:1:0.4 into a reactor containing 20ml of pretreated chromium oxide catalyst at 350 deg.C, 2bar and 2000 hr-1To obtain a reaction product. During the reaction, all lines were kept at 60 ℃ using a heating tape. Of the reaction products, the main products included difluoromethane, monofluoromethane chloride and difluoromonochloromethane with selectivities of 48.2%, 11.3% and 40.1%, respectively, and with conversions of trifluoromethane and dichloromethane of 28.1% and 45.6%, respectively. The catalyst activity is kept stable after 250 hours of reaction.
And (3) rectification: and (3) rectifying the reaction product by a rectifying tower, wherein the rectifying temperature is controlled to be about-30 ℃ and the rectifying pressure is controlled to be about 0.4 MPa. And obtaining a difluoromethane product at the top of the rectifying tower. And a material flow containing the chlorodifluoromethane and the monochlorfluoromethane is obtained at the bottom of the rectifying tower and recycled to the HCFC-22 reaction system to continuously participate in the reaction.
Claims (12)
1. A method for resource utilization of trifluoromethane is characterized by comprising the following steps:
(1) reacting trifluoromethane and dichloromethane under the action of a catalyst to obtain a reaction product containing difluoromethane and difluoromethane monochloride, wherein the reaction temperature is 350-450 ℃;
the catalyst is selected from MgF2、Al2O3Partially fluorinated alumina and AlF3At least one of;
(2) and (3) rectifying and separating a reaction product containing difluoromethane and difluorochloromethane, and circulating the obtained difluorochloromethane to a difluorochloromethane production device to obtain the difluoromethane, namely the product difluoromethane.
2. The method for recycling trifluoromethane according to claim 1, wherein the molar ratio of trifluoromethane to dichloromethane is 1: 1-1: 5.
3. The method for recycling trifluoromethane according to claim 2, wherein the molar ratio of trifluoromethane to dichloromethane is 1: 1-1: 2.
4. The method for recycling trifluoromethane according to claim 1, wherein in the step (1), the reaction pressure is 1-10 bar, and the space velocity of the raw material is 50-10000 h-1。
5. The method for recycling trifluoromethane according to claim 4, wherein in the step (1), the reaction pressure is 1-3 bar, and the space velocity of the raw material is 100-1000 h-1。
6. The method for recycling trifluoromethane according to claim 1, wherein the catalyst is N-substituted prior to the reaction2Treating at 200-250 deg.C for 3-5 hr, and treating with HF or HCFC-22 at 200-400 deg.C for 3-5 hr.
7. The method for recycling trifluoromethane according to claim 1, wherein in the step (2), the rectification temperature is-50 to-10 ℃, and the rectification pressure is 0.1 to 1.0 MPa.
8. The method for recycling trifluoromethane according to claim 7, wherein in the step (2), the rectification temperature is-45 to-30 ℃, and the rectification pressure is 0.1 to 0.5 MPa.
9. The method for recycling trifluoromethane according to claim 1, wherein in the step (1), trifluoromethane and dichloromethane are reacted in the presence of a promoting gas under the action of a catalyst to obtain a reaction product containing difluoromethane and difluoromethane monochloromethane, and the promoting gas is selected from Cl2、CCl4、H2、O2、CO2、O3And at least one of nitrogen oxides, wherein the molar ratio of the promoting gas to the trifluoromethane is 1: 0.01-0.5.
10. The method for recycling trifluoromethane according to claim 9, wherein the molar ratio of the promoter gas to trifluoromethane is 1: 0.01-0.1.
11. The method for recycling trifluoromethane according to claim 1, wherein in step (1), HF gas is added in an amount of 0.5-40% of the total volume of the feed materials of trifluoromethane and dichloromethane.
12. The method for recycling trifluoromethane according to claim 11, wherein in the step (1), the amount of the HF gas added is 1.0-20% of the total volume of the feed materials of trifluoromethane and dichloromethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711088468.0A CN109748775B (en) | 2017-11-08 | 2017-11-08 | Resource utilization method of by-product trifluoromethane in HCFC-22 production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711088468.0A CN109748775B (en) | 2017-11-08 | 2017-11-08 | Resource utilization method of by-product trifluoromethane in HCFC-22 production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109748775A CN109748775A (en) | 2019-05-14 |
| CN109748775B true CN109748775B (en) | 2021-08-17 |
Family
ID=66400265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711088468.0A Active CN109748775B (en) | 2017-11-08 | 2017-11-08 | Resource utilization method of by-product trifluoromethane in HCFC-22 production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109748775B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973685B (en) * | 2019-12-13 | 2022-06-28 | 浙江省化工研究院有限公司 | Method for reducing carbon deposition of catalyst in HFC-23 resource utilization |
| CN112979410B (en) | 2019-12-13 | 2022-06-28 | 浙江省化工研究院有限公司 | Method for improving catalyst stability in HFC-23 resource utilization |
| CN111875473B (en) * | 2020-06-09 | 2022-08-02 | 浙江省化工研究院有限公司 | Preparation method of HFC-365mfc and HFC-245fa |
| CN111960916B (en) * | 2020-06-09 | 2022-07-05 | 浙江省化工研究院有限公司 | Resource utilization method of R23 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144605A (en) * | 1976-05-25 | 1977-12-02 | Central Glass Co Ltd | Preparation of trifluoromethane |
| CN1263795A (en) * | 2000-03-18 | 2000-08-23 | 浙江莹光化工有限公司 | Fluorinating catalyst for preparing fluoroparaffin |
| CN1701056A (en) * | 2003-09-10 | 2005-11-23 | 昭和电工株式会社 | Process for production of hydrofluorocarbons, products thereof and use of the products |
| CN103467239A (en) * | 2013-09-13 | 2013-12-25 | 常熟三爱富中昊化工新材料有限公司 | Technique for preparing monochlorodifluoromethane by decomposing trifluoromethane |
| CN104628513A (en) * | 2015-02-11 | 2015-05-20 | 浙江工业大学 | Method for resource utilization of fluoroform |
| JP2015120668A (en) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | Method for manufacturing fluoromethanes |
-
2017
- 2017-11-08 CN CN201711088468.0A patent/CN109748775B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144605A (en) * | 1976-05-25 | 1977-12-02 | Central Glass Co Ltd | Preparation of trifluoromethane |
| CN1263795A (en) * | 2000-03-18 | 2000-08-23 | 浙江莹光化工有限公司 | Fluorinating catalyst for preparing fluoroparaffin |
| CN1701056A (en) * | 2003-09-10 | 2005-11-23 | 昭和电工株式会社 | Process for production of hydrofluorocarbons, products thereof and use of the products |
| CN103467239A (en) * | 2013-09-13 | 2013-12-25 | 常熟三爱富中昊化工新材料有限公司 | Technique for preparing monochlorodifluoromethane by decomposing trifluoromethane |
| JP2015120668A (en) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | Method for manufacturing fluoromethanes |
| CN104628513A (en) * | 2015-02-11 | 2015-05-20 | 浙江工业大学 | Method for resource utilization of fluoroform |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109748775A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109748775B (en) | Resource utilization method of by-product trifluoromethane in HCFC-22 production | |
| EP1943203B1 (en) | Method for producing fluorinated organic compounds | |
| EP2326612B1 (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| CN110833837B (en) | Catalyst for resource utilization of trifluoromethane | |
| EP2632882A1 (en) | Process for producing 2,3,3,3-tetrafluoropropene | |
| KR102000371B1 (en) | Method for producing dry etching gas | |
| CN107522592B (en) | Method for coproducing various halogenated olefins and fluorinated alkanes | |
| US20190169099A1 (en) | Process for the preparation of fluoroolefin compounds | |
| WO2014094587A1 (en) | 1, 3, 3, 3-tetrafluoropropene preparation process | |
| CN103467239A (en) | Technique for preparing monochlorodifluoromethane by decomposing trifluoromethane | |
| JP6082820B2 (en) | Method for jointly manufacturing HFO-1234ze and HFC-245fa | |
| WO2017028442A1 (en) | Method for preparing 2,3,3,3-tetrafluoropropene using methyl magnesium chloride | |
| CN109748776B (en) | Method for preparing difluoromethane by resource utilization of by-product trifluoromethane in HCFC-22 production | |
| CN106946647B (en) | A kind of method that the isomerization of mixture room temperature prepares trans-1,3,3,3-tetrafluoropropene | |
| JP5246327B2 (en) | Method for producing fluorine-containing propene by gas phase fluorination | |
| CN116037120B (en) | Preparation method of positive and negative isomer of 1, 4-hexafluoro-2-butene | |
| CN116037117B (en) | Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene | |
| CN109809959A (en) | A kind of preparation method of 1,1,1,2,3- pentachloropropane | |
| CN109772377B (en) | Catalyst for fluorine-chlorine exchange reaction | |
| CN102120714B (en) | Method for preparing pentafluoroethane | |
| CN108610233B (en) | Preparation method of 3, 3, 3-trifluoropropene | |
| CN106380370B (en) | A kind of short-cut method of chlorofluorocarbons resource utilization | |
| CN102070395B (en) | Method for preparing pentafluoroethane | |
| CN109939702B (en) | Catalyst and method for preparing pentafluoroethane by using CDM application technology | |
| CN115403443A (en) | Preparation method of fluorine-containing olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |