CN102101823B - Gas phase purification method for 1,1-difluoroethane - Google Patents
Gas phase purification method for 1,1-difluoroethane Download PDFInfo
- Publication number
- CN102101823B CN102101823B CN 200910155070 CN200910155070A CN102101823B CN 102101823 B CN102101823 B CN 102101823B CN 200910155070 CN200910155070 CN 200910155070 CN 200910155070 A CN200910155070 A CN 200910155070A CN 102101823 B CN102101823 B CN 102101823B
- Authority
- CN
- China
- Prior art keywords
- c2h4f2
- gas phase
- reaction tubes
- sorbent material
- purification
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention relates to a method for purifying 1,1-difluoroethane by gas phase absorption separation. In the method, by using one or more of silica gel, activated aluminum oxide, activated magnesia and aluminosilicate absorbents and carbon absorbents, preferably an absorbent with a Brunauer-Emmett-Teller (BET) specific surface area more than or equal to 400m<2>/g and a single-point average aperture of 5 to 30 angstroms, the 1,1-difluoroethane content in a 1,1-difluoroethane coarse product containing vinyl chloride can be improved to over 99.99 percent, the total olefin content is reduced to below tens of ppm or even below 10ppm, and the vinyl chloride content is reduced to below several ppm or even below 1ppm. The 1,1-difluoroethane can be used alone or in combination with other materials as a low-temperature refrigerator, a foaming agent, a propellant, an etching gas, a cleaning agent or an intermediate of other fluorocarbons.
Description
Technical field
The present invention relates to a kind of 1, the method that the method for purification of 1-C2H4F2 C2H4F2, especially Gas Phase Adsorption are separated.
Background technology
1,1-C2H4F2 C2H4F2 (HFC-152a), atmospheric boiling point-24.023 ℃, ODP value (consuming the ozone latent energy value) is 0, GWP value (chamber effect potential value) is 0.03, be a kind of good Ozone Depleting Substances (ODS) substitute, can use separately also can mix with other materials and use as low-temperature refrigerant, whipping agent, propelling agent, etching gas, clean-out system or as the intermediate of other charcoal fluorine cpd.
1, the production method of 1-C2H4F2 C2H4F2 (HFC-152a) mainly contains two kinds of acetylene method and vinylchlorid methods, when adopting vinylchlorid to be raw material, remove 1 in its reaction process, outside 1-C2H4F2 C2H4F2 (HFC-152a) product, also has unreacted vinylchlorid, hydrogen fluoride, vinyl fluoride and other organic by-products such as 1-fluoro-1-monochloroethane).Means by rectifying can be removed most by product, but vinylchlorid can form azeotrope with HFC-152a, has increased the difficulty of purifying, and common rectificating method is difficult to both are separated.
Method of purification for HFC-152a has had a lot of people that it is studied, and mentions among the Canadian Patent CA832502 and uses hydrogen fluoride to react to separate HFC-152a with chlorinated hydrocarbon (chloride alkene); US Patent No. 3995010 discloses to use and has contained hypochlorous solution medium deviate from vinylchlorid from steam, and this method can not remove the very low vinylchlorid of content (ppm level), and can produce undesirable by product, and actual application value is not high; Chinese patent CN1074434 discloses the use light chlorination process and has removed vinylchlorid from 1, the 1-C2H4F2 C2H4F2, generates trichloroethane and other halogenated alkanes, and the recycling distillation method is separated it with the 1.1-C2H4F2 C2H4F2.
Chinese patent CN1878738 discloses and has used zeolite or carbon absorbent and contain thick 1 of at least a compound that is selected from the saturated chlorine-containing compound that unsaturated compound that each comfortable intramolecularly has two carbon atoms and each comfortable intramolecularly have two carbon atoms, 1-C2H4F2 C2H4F2 contact,, 1-C2H4F2 C2H4F2 highly purified 1 in order to obtain.Though this method can purify to 1,1-C2H4F2 C2H4F2 more than 99.9% basically, total olefin content more than dozens or even hundreds of ppm, the content of vinylchlorid more than 5ppm, still can not satisfy high-purity 1, the requirement of 1-C2H4F2 C2H4F2.
US Patent No. 5396001 discloses with gac and thick 1, and vinylchlorid is removed in the contact of 1-C2H4F2 C2H4F2, and this method can not be removed to the content of vinylchlorid the ppm level, and the content of vinylchlorid is more than 3% in the product.
Summary of the invention
The invention provides a kind ofly 1, the gas phase method of purification of 1-C2H4F2 C2H4F2 can be with 1, the content of 1-C2H4F2 C2H4F2 purifies to more than 99.99%, total olefin content is removed to tens ppm even below the 10ppm, and wherein content of vinylchloride is removed to several ppm even below the 1ppm, and technological operation is simple.
For achieving the above object, the invention provides following technical scheme:
Make and contain 1 of vinylchlorid, 1-C2H4F2 C2H4F2 crude product contacts with the sorbent material gas phase, and described sorbent material is handled by chlorine and/or hydrogen chloride gas in advance.The present invention does not have particular requirement for chlorine and hydrogen chloride gas, and general commercial gas drying is handled and can be used.
The sorbent material that the present invention uses is one or more the combination that is selected from silica gel, activated alumina, activated magnesia, sial salt sorbent material and the carbon absorbent.Sial salt sorbent material is preferably zeolite and/or molecular sieve, special preferred molecular sieve.Carbon absorbent is preferably gac.Further the BET specific surface area of preferred adsorbent is more than or equal to 400m
2/ g, single-point mean pore size (calculating with the BET specific surface area) 5～
Especially the BET specific surface area of preferred adsorbent is more than or equal to 700m
2/ g, single-point mean pore size (with the BET specific surface area) is 8～
The present invention is carrying out chlorine and/or hydrogen chloride gas when handling, the preferred 0.05～1L/min of the gas flow of chlorine and/or hydrogenchloride, further preferred 0.05～0.5L/min to sorbent material; Treatment time is preferably 1～15h, more preferably 1～10h.
It is a kind of 1 that the present invention also provides, and the method for purification of 1-C2H4F2 C2H4F2 comprises the steps:
(1) feeds chlorine and/or hydrogen chloride gas to the reaction tubes that sorbent material is housed, with the airtight 0.5～5h of reaction tubes, vacuumize processing then;
What (2) feed gas phase in the reaction tubes contains 1 of vinylchlorid, 1-C2H4F2 C2H4F2 crude product, and contact stops;
(3) collect 1,1-C2H4F2 C2H4F2.
The present invention is when feeding chlorine and/or hydrogen chloride gas to the reaction tubes that sorbent material is housed, temperature in the reaction tubes there are not special requirement, general temperature all can be operated, suitably improve temperature and be conducive to the carrying out of handling, can heat reaction tubes earlier, also can the limit heating edge feed chlorine and/or hydrogen chloride gas to reaction tubes, general preferred limit heating edge feeds chlorine and/or hydrogen chloride gas to reaction tubes, Heating temperature is preferably 25～450 ℃, more preferably 25～350 ℃, be preferably 1～3h heat-up time.After feeding chlorine and/or hydrogen chloride gas, preferably reaction tubes is carried out airtight for some time, about 0.5～5h, and then generally use the nitrogen purging reaction tubes with rare gas element, and vacuumize processing, make reaction tubes naturally cool to normal temperature at last.
What feed gas phase in the reaction tubes contains 1 of vinylchlorid, behind the 1-C2H4F2 C2H4F2 crude product, and valve-off, contact stops the regular hour, and gas chromatographic analysis is carried out in sampling at regular intervals.It is 5～3600s that the contact residence time is preferably, further preferred 5～1800s.Pressure when contact stops in the reaction tubes preferably remains on 2-10 normal atmosphere.
When handling, preferably in advance total olefin content in 1, the 1-C2H4F2 C2H4F2 crude product is handled to 200ppm, especially below the 100ppm.
Contain 1 of vinylchlorid, the feeding amount of 1-C2H4F2 C2H4F2 crude product is decided on the adsorptive power of sorbent material, general feeding amount should be make sorbent material reach absorption saturated till.
The present invention also provides a kind of renovation process of sorbent material, may further comprise the steps:
(1) make described sorbent material add thermal desorption, Heating temperature is 30～450 ℃, and be 0.5～20h heat-up time;
(2) feed chlorine and/or hydrogen chloride gas to the described sorbent material of handling through desorption of step (1), with the airtight 0.5～5h of reaction tubes, regenerate.
Heating temperature is preferably 50～350 ℃ in the above-mentioned steps (1), and being preferably heat-up time is 2～10h.
Above-mentioned steps (2) is after feeding chlorine or hydrogen chloride gas to the sorbent material of handling through desorption, best airtight for some time, about 0.5～5h, and then generally use the nitrogen purging reaction tubes with rare gas element, vacuumize processing, make reaction tubes naturally cool to normal temperature at last.
By method of purification of the present invention, can will contain 1 of vinylchlorid, in the 1-C2H4F2 C2H4F2 crude product 1, the content of 1-C2H4F2 C2H4F2 purifies to more than 99.99%, total olefin content is removed to tens ppm even below the 10ppm, and wherein content of vinylchloride is removed to several ppm even below the 1ppm.
Embodiment
Specifically describe below by the present invention of embodiment.Following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
The silica gel that adds 17.5g (33ml) in the reaction cartridge pipe, specific surface area: 750-850m
2/ g, mean pore size: 22-
Heating remains on about 50 ℃ the temperature in the reaction tubes, and pressure remains on about 2 normal atmosphere, feeds chlorine in reaction tubes, and flow is 0.0) L/min, time 2h, off-response tube valve, airtight 2 hours.Stop heating, open valve, use the nitrogen purging reaction tubes, vacuumize processing, make reaction tubes naturally cool to normal temperature.Contain 1 of vinylchlorid with what the speed of 0.1L/min fed gas phase in the reaction tubes, 1-C2H4F2 C2H4F2 crude product, 1,1-C2H4F2 C2H4F2 content is 99.992%, content of vinylchloride is 0.00201%, and total olefin content is 0.00219%, and adsorption process pressure remains on about 5 normal atmosphere, gas chromatographic analysis, result such as table 1 are carried out in sampling after the 20th, 40 and 60 minute respectively.
Embodiment 2
In the reaction cartridge pipe, add 140g (265ml) molecular sieve, specific surface area 830-860m
2/ g, mean pore size: 14-
Heating remains on about 350 ℃ the temperature in the reaction tubes, and pressure remains on about 5 normal atmosphere, feeds chlorine in reaction tubes, and flow is 0.05L/min, time 3h, off-response tube valve, airtight 2 hours.Stop heating, open valve, use the nitrogen purging reaction tubes, vacuumize processing, make reaction tubes naturally cool to normal temperature.Contain 1 of vinylchlorid with what the speed of 0.1L/min fed gas phase in the reaction tubes, 1-C2H4F2 C2H4F2 crude product, 1,1-C2H4F2 C2H4F2 content 99.992%, content of vinylchloride is 0.00201%, and total olefin content is 0.00219%, and adsorption process pressure remains on about 3 normal atmosphere, gas chromatographic analysis, result such as table 1 are carried out in sampling after the 20th, 40 and 60 minute respectively.
Embodiment 3
In reaction tubes, add 17.5g (33ml) zeolite, specific surface area 620-750m
2/ g, mean pore size 22-
Heating remains on about 350 ℃ the temperature in the reaction tubes, and pressure remains on about 8 normal atmosphere, feeds chlorine gas in reaction tubes, and flow is 0.05L/min, time 10h, off-response tube valve, airtight 2 hours.Stop heating, open valve, use the nitrogen purging reaction tubes, vacuumize processing, make reaction tubes naturally cool to normal temperature.Contain 1 of vinylchlorid with what the speed of 0.1L/min fed gas phase in the reaction tubes, 1-C2H4F2 C2H4F2 crude product, 1,1-C2H4F2 C2H4F2 content is 99.992%, content of vinylchloride is 0.00201%, and total olefin content is 0.00219%, and adsorption process pressure remains on about 8 normal atmosphere, gas chromatographic analysis, result such as table 1 are carried out in sampling after the 20th, 40 and 60 minute respectively.
Embodiment 4
In reaction tubes, add 17.5g (33ml) gac, specific surface area: 880-930m
2/ g, mean pore size: 11-
Heating remains on about 60 ℃ the temperature in the reaction tubes, and pressure remains on about 2 normal atmosphere, feeds hydrogen chloride gas in reaction tubes, and flow is 0.05L/min, time 5h, off-response tube valve, airtight 2 hours.Stop heating, open valve, use the nitrogen purging reaction tubes, vacuumize processing, make reaction tubes naturally cool to normal temperature.Contain 1 of vinylchlorid with what the speed of 0.1L/min fed gas phase in the reaction tubes, 1-C2H4F2 C2H4F2 crude product, 1, the 1-C2H4F2 C2H4F2 is 99.992%, content of vinylchloride is 0.00201%, and total olefin content is 0.00219%, and reaction process pressure remains on about 1 normal atmosphere, gas chromatographic analysis, result such as table 1 are carried out in sampling after the 20th, 40 and 60 minute respectively.
Embodiment 5
The saturated sorbent material of absorption among the embodiment 2 is packed in the heating jacket, use earlier nitrogen purging, under 450 ℃ of conditions, heated 4 hours then.Vacuum in the holding tube in the whole desorption process.After treating that desorption is finished, the temperature of heating jacket is remained on about 50 ℃, pressure remains on about 5 normal atmosphere, feeds hydrogen chloride gas in reaction tubes, and flow is 0.05L/min, time 3h, off-response tube valve, airtight 2 hours.Stop heating, open valve, use the nitrogen purging reaction tubes, vacuumize processing, make reaction tubes naturally cool to normal temperature.Contain 1 of vinylchlorid with what the speed of (0.1) L/min fed gas phase in the reaction tubes, 1-C2H4F2 C2H4F2 crude product, 1,1-C2H4F2 C2H4F2 content is 99.992%, content of vinylchloride is 0.00201%, and total olefin content is 0.00219%, and reaction process pressure remains on about 3 normal atmosphere, gas chromatographic analysis, result such as table 1 are carried out in sampling after the 20th, 40 and 60 minute respectively.
Table 1 embodiment result data table
Claims (10)
1. the gas phase method of purification of a 1-C2H4F2 C2H4F2, it is characterized in that making and contain 1 of vinylchlorid, 1-C2H4F2 C2H4F2 crude product contacts with the sorbent material gas phase, described sorbent material is one or more the combination that is selected from silica gel, activated alumina, activated magnesia, sial salt sorbent material and the carbon absorbent, described sorbent material is handled by chlorine and/or hydrogen chloride gas, and the BET specific surface area of described sorbent material is more than or equal to 700m
2/ g, the single-point mean pore size is
2. described 1 according to claim 1, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that described sial salt sorbent material is zeolite and/or molecular sieve, and described carbon absorbent is gac.
3. described 1 according to claim 1, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that described sorbent material is molecular sieve and/or gac.
4. described 1 according to claim 1, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that described chlorine and/or hydrogen chloride gas flow are 0.05～1L/min, and the treatment time is 1～15h.
5. described 1 according to claim 4, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that described chlorine and/or hydrogen chloride gas flow are 0.05～0.5L/min, and the treatment time is 1～10h.
6. one kind 1, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that, comprises the steps:
(1) feeds chlorine and/or hydrogen chloride gas to the reaction tubes that the described sorbent material of claim 1 is housed, with the airtight 0.5～5h of reaction tubes, vacuumize processing then;
What (2) feed gas phase in the reaction tubes contains 1 of vinylchlorid, 1-C2H4F2 C2H4F2 crude product, and contact stops;
(3) collect 1,1-C2H4F2 C2H4F2.
7. according to claim 6 described 1, the gas phase method of purification of 1-C2H4F2 C2H4F2, it is characterized in that in the described step (1) reaction tubes being heated, Heating temperature is 25～450 ℃, be 1～3h heat-up time, the contact residence time is 5～3600s in the described step (2), and the pressure when contact stops in the reaction tubes remains on 2-10 normal atmosphere.
8. described 1 according to claim 7, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that described Heating temperature is 25～350 ℃, and the contact residence time is 5～1800s.
9. described 1 according to claim 6, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that in the saturated back of adsorbents adsorb it being carried out manipulation of regeneration, may further comprise the steps:
(1) make described sorbent material add thermal desorption, Heating temperature is 30～450 ℃, and be 0.5～20h heat-up time;
(2) feed chlorine and/or hydrogen chloride gas to the described sorbent material of handling through desorption of step (1), with the airtight 0.5～5h of reaction tubes, regenerate.
10. described 1 according to claim 9, the gas phase method of purification of 1-C2H4F2 C2H4F2 is characterized in that the described Heating temperature of step (1) is 50～350 ℃, and be 2～10h heat-up time, the airtight 1～3h of reaction tubes in the described step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910155070 CN102101823B (en) | 2009-12-16 | 2009-12-16 | Gas phase purification method for 1,1-difluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910155070 CN102101823B (en) | 2009-12-16 | 2009-12-16 | Gas phase purification method for 1,1-difluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102101823A CN102101823A (en) | 2011-06-22 |
| CN102101823B true CN102101823B (en) | 2013-08-28 |
Family
ID=44154913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910155070 Expired - Fee Related CN102101823B (en) | 2009-12-16 | 2009-12-16 | Gas phase purification method for 1,1-difluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102101823B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201307327D0 (en) | 2013-04-23 | 2013-05-29 | Mexichem Amanco Holding Sa | Process |
| GB201410174D0 (en) | 2014-06-09 | 2014-07-23 | Mexichem Amanco Holding Sa | Process |
| CN111250038B (en) * | 2020-03-09 | 2023-01-13 | 临海市利民化工有限公司 | Method for separating and purifying hexafluoropropylene dimer and adsorbent used by same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874657A (en) * | 1996-11-01 | 1999-02-23 | E. I. Du Pont De Nemours And Company | Process for the purification of 1,1-difluoroethane |
| CN1223993A (en) * | 1997-12-01 | 1999-07-28 | 索尔维公司 | Processes for producing and purifying 1,1-difluoroethane, and product thus obtained |
| CN1556083A (en) * | 2004-01-09 | 2004-12-22 | 浙江埃克盛化工有限公司 | Preparation method of difluoro chloroethane and its production equipment |
| CN1878738A (en) * | 2003-11-10 | 2006-12-13 | 昭和电工株式会社 | Purification method of, 1, 1-difluoroethane |
-
2009
- 2009-12-16 CN CN 200910155070 patent/CN102101823B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874657A (en) * | 1996-11-01 | 1999-02-23 | E. I. Du Pont De Nemours And Company | Process for the purification of 1,1-difluoroethane |
| CN1223993A (en) * | 1997-12-01 | 1999-07-28 | 索尔维公司 | Processes for producing and purifying 1,1-difluoroethane, and product thus obtained |
| CN1878738A (en) * | 2003-11-10 | 2006-12-13 | 昭和电工株式会社 | Purification method of, 1, 1-difluoroethane |
| CN1556083A (en) * | 2004-01-09 | 2004-12-22 | 浙江埃克盛化工有限公司 | Preparation method of difluoro chloroethane and its production equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102101823A (en) | 2011-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102076645B (en) | Process for the purification of 2, 3, 3, 3-tetrafluoro-1-propene (hfo-1234yf) | |
| WO2014185499A1 (en) | Method for purifying hydrogen chloride | |
| JPH0761964B2 (en) | Method for purifying 1,1,1,2-tetrafluoroethane | |
| US5233107A (en) | Process for the purification of chlorofluorohydrocarbons | |
| JP2012001495A (en) | Method for purifying 2,3,3,3-tetrafluoropropene | |
| AU755192B2 (en) | Purification of 1,1,1,3,3-pentafluorobutane | |
| CN108026003B (en) | Process for purifying and drying hydrofluoroolefin streams | |
| JP2008537720A (en) | Purification of nitrogen trifluoride | |
| JP2003261480A (en) | Method for purifying hexafluoro-1,3-butadiene | |
| CN102101823B (en) | Gas phase purification method for 1,1-difluoroethane | |
| US7084316B2 (en) | Process for purifying pentafluoroethane, process for producing the same, and use thereof | |
| US5261948A (en) | Carbon molecular sieve for the kinetic separation of acid gases and fluorocarbons | |
| JP2003286013A (en) | Method of purifying gaseous nitrogen trifluoride | |
| CN104496746B (en) | Method that is a kind of while preparing 1,1,1,2,2- pentachloropropanes and 2,3,3,3- tetrachloropropylenes | |
| CN102101822B (en) | Liquid phase purification method for 1,1- difluoroethane | |
| US10047026B2 (en) | Process for reducing 1233xf concentration in 244bb | |
| JPH0578266A (en) | Process for purifying 1,1,1,2-tetrafluoroethane | |
| CN103449959B (en) | Preparation method of ultra-pure 1,1,1,2,3,3,3-heptafluoropropane | |
| JP4552246B2 (en) | Method for producing purified fluorocarbon or chlorofluorocarbon | |
| EP3371107A1 (en) | Method for removal of fluorinated organics from byproduct anhydrous or aqueous hydrochloric acid in the 1234yf via 1230xa process | |
| JP2924660B2 (en) | Purification method of tetrafluoromethane | |
| JPH0692879A (en) | Method for purifying pentafluoroethane | |
| JP3908819B2 (en) | CFC recovery method | |
| KR102612966B1 (en) | Process for purifying octafluorocyclobutane | |
| WO2022069434A1 (en) | A process for the purification of fluorinated olefins in gas phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130828 Termination date: 20151216 |
|
| EXPY | Termination of patent right or utility model |