CN111423305A - Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture - Google Patents
Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture Download PDFInfo
- Publication number
- CN111423305A CN111423305A CN202010301959.4A CN202010301959A CN111423305A CN 111423305 A CN111423305 A CN 111423305A CN 202010301959 A CN202010301959 A CN 202010301959A CN 111423305 A CN111423305 A CN 111423305A
- Authority
- CN
- China
- Prior art keywords
- hydrogen fluoride
- mixture
- separation
- membered cyclic
- integer
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Abstract
The invention relates to a separation method of a five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture, a five-membered cyclic fluorochloroolefin compound C as shown in a formula (1)5Cl8‑xFxSeparating the mixture from hydrogen fluoride by freezing and standing the mixture in a phase separation device, separating the mixture, wherein the upper layer is mainly hydrogen fluoride and the lower layer is mainly five-membered chlorofluoroolefin C5Cl8‑xFxWherein X is not less than 2 and not more than 6, and X is an integer. The invention separates the azeotropic mixture by a freeze separation mode, wherein the freeze separation is carried out for more than 0.5h at the temperature of 5 ℃, the recovery rate of the five-membered cyclic fluoro chloro olefin compound can reach more than 98 percent, and the equipment is simpleCompared with the traditional distillation separation method, the method saves energy consumption, and is suitable for large-scale separation of the quinary cyclic fluorine-chlorine compound (X is not less than 2 and not more than 6, and X is an integer) and the hydrogen fluoride azeotropic mixture.
Description
Technical Field
The invention relates to a five-membered cyclic chlorofluoroolefin C5Cl8-xFx(X is not less than 2 and not more than 6 and is an integer) and hydrogen fluoride, in particular to a method for separating quinary cyclofluorochloroolefin C5Cl8-xFx(X is not less than 2 and not more than 6 and is an integer) and hydrogen fluoride to separate five-membered cyclic fluorochloroolefin C5Cl8-xFx(2. ltoreq. X. ltoreq.6, wherein X is an integer).
Background
1,2,2,3,3,4, 4-heptafluorocyclopentane is considered to replace HCFC-225a/b as a cleaning agent in the precision cleaning industry, and in the process of preparing 1,2,2,3,3,4, 4-heptafluorocyclopentane, hexachlorocyclopentadiene is generally used to obtain a five-membered chlorofluoroolefin compound through multiple fluorochlorination, further fluorinated to obtain 1-chloroheptafluorocyclopentene, and then hydrogenated to obtain 1,2,2,3,3,4, 4-heptafluorocyclopentane. In the process of multi-time fluorination of the five-membered ring chloride, a compound with low fluorination degree needs to be subjected to multi-time cyclic fluorination to obtain a compound with high fluorination degree, and in the process of multi-time fluorination, the compound with high fluorination degree needs to be separated out in order to improve the reaction efficiency, so that the reaction balance is not influenced, and the production efficiency is reduced.
The separation process of organic matters and inorganic matters usually adopts extraction, distillation, rectification and other methods to process, the extraction method is used for separating the organic matters and the inorganic matters, an extracting agent needs to be strictly screened, the basic characteristics include that ① and a solvent in a raw solution are not mutually soluble, ② has higher solubility to a solute than the raw solvent, ③ is not easy to volatilize, ④ does not react with the raw solvent, and the like.
It is difficult to obtain Hydrofluorocarbons (HFC) containing no HF or chlorofluorocarbons (HCFC) containing no HF by simple distillation, for example, because some of the fluorine-containing compounds and Hydrogen Fluoride (HF) tend to form an azeotropic mixture. Patent CN101952229A discloses a process for separating HFC-245fa and HF by azeotropic distillation, which requires to recycle the removed azeotropic mixture of different compositions back to the distillation column for enrichment for separation, and which is complicated and time-consuming and not suitable for industrial production; U.S. Pat. No. 6,629,4055 discloses a process for the extractive separation of fluorine-containing compounds HFC-245fa and HF, which utilizes the property that an extracting agent has extremely high mutual solubility with HFC-245fa and extremely low mutual solubility with HF to separate HFC-245fa from HF, and then recovers HFC-245fa from the extracting agent phase by distillation separation. It was found through experiments that a pentacyclic chlorofluoroolefin compound (see formula 1, 2. ltoreq. X. ltoreq.6, wherein X is an integer) obtained by chlorofluorination of hexachlorocyclopentadiene forms an azeotropic mixture with hydrogen fluoride very easily. In the actual production process, in order to improve the reaction conversion rate, C needs to be added5Cl2F6(X-6) and C5Cl8-xFx(2. ltoreq. X. ltoreq.5, X is an integer) and C5Cl2F6Entering the next reaction, C5Cl8-xFx(X is not less than 2 and not more than 5 and is an integer) is recycled to the reaction system for further fluorination. And in separation C5Cl2F6And C5Cl8-xFx(2≤X≤5,X is an integer), C needs to be added before5Cl8-xFx(X is not less than 2 and not more than 6, and X is an integer) is separated from hydrogen fluoride, C5Cl2F6And C5Cl8-xFx(2. ltoreq. X.ltoreq.5, X.ltoreq.integer) is separated off further by distillation, however, owing to C5Cl8-xFx(2. ltoreq. X. ltoreq.6, wherein X is an integer) is also very likely to form an azeotropic mixture with hydrogen fluoride, and C is prepared by a method of distillation alone5Cl8-xFx(2. ltoreq. X.ltoreq.6, X being an integer) and hydrogen fluoride are very difficult to separate.
At present, no public report is found about a method for efficiently separating an azeotropic mixture of a five-membered cyclic fluorochloroolefin compound (X is not less than 2 and not more than 6, and X is an integer) and hydrogen fluoride, but for producing 1,2,2,3,3,4, 4-heptafluorocyclopentane, an azeotrope of the five-membered cyclic fluorochloroolefin compound and hydrogen fluoride is efficiently separated, excessive hydrogen fluoride enters a reactor again for a circulation reaction, and the process flow diagram for preparing the five-membered cyclic fluorochloroolefin compound by hexachlorocyclopentadiene is as shown in fig. 1, which is important for improving the production efficiency of the fluorination process.
Disclosure of Invention
In order to solve the above problems, the present invention provides a novel and simple separation method of a five-membered chlorofluoroolefin compound C5Cl8-xFx(X is more than or equal to 2 and less than or equal to 6 and is an integer) and hydrogen fluoride are efficiently separated, the separation step is simplified, the separation efficiency is improved, the production cost is reduced, and the five-membered cyclic chlorofluoro olefin compound C5Cl8-xFxThe recovery rate of (X is not less than 2 and not more than 6, and X is an integer) can reach more than 98 percent.
A five-membered cyclic chlorofluoro olefin compound C as shown in formula (1)5Cl8-xFx(X is more than or equal to 2 and less than or equal to 6, and X is an integer) and hydrogen fluoride mixture, placing the mixture in a phase separation device for freezing and standing, separating the mixture, wherein the upper layer is mainly hydrogen fluoride, and the lower layer is mainly five-membered cyclic chlorofluoro-olefin,wherein X is not less than 2 and not more than 6, X is an integer,
the five-membered cyclic chlorofluoroalkene compound C5Cl8-xFx(X is more than or equal to 2 and less than or equal to 6 and is an integer) and hydrogen fluoride are hexachlorocyclopentadiene, and HCl is removed through multiple times of fluorochlorination to obtain five-membered cyclic chlorofluoro-olefin compound C5Cl8-xFx(2. ltoreq. X.ltoreq.6, wherein X is an integer).
The five-membered cyclic chlorofluoroalkene compound C5Cl8-xFx(2. ltoreq. X. ltoreq.6, wherein X is an integer) and the mass ratio of the hydrogen fluoride mixture is 1: 2-3.
The freezing temperature is-20-14 ℃.
Preferably: the freezing temperature is 5-10 ℃, and the standing time is 0.5-2 hours.
The refrigerant used for freezing is cold water.
The phase separation equipment adopts pressure-resistant equipment lined with fluoroplastic, a shell pass is a refrigerant pipeline, and a mixture of five-membered cyclic chlorofluoroolefin compounds and hydrogen fluoride is introduced into a tube pass.
The invention provides a novel refrigeration separation device for efficiently separating a five-membered cyclic chlorofluoro-olefin compound C5Cl8-xFxThe separation technology and conditions of (X is not less than 2 and not more than 6, and X is an integer) and hydrogen fluoride overcome the defects of the existing distillation separation technology of fluorine-containing compounds and hydrogen fluoride. The invention utilizes the HF to be cooled into liquid under refrigeration, and unexpectedly realizes the separation with fluorine-containing compounds, adopts a simple refrigeration method to realize the separation of raw materials, improves the original separation system which mainly adopts rectification into an innovative separation system which combines a simple and efficient phase separation process, simplifies the separation process, improves the separation efficiency, reduces the energy consumption, has simpler and more stable operation, changes the traditional degassing tower combined separation technology which is unstable in operation, and utilizes the phase separation technology to realize stable, continuous and efficient separation operation. The invention can simply and efficiently separate five-membered cyclic fluorine-chlorine olefin compounds (X is more than or equal to 2 and less than or equal to 6 and X is an integer) and hydrogen fluoride。
The key separation technology utilizes a phase separation technology to replace the existing degassing tower combined separation technology with unstable operation state, and realizes stable, efficient and continuous separation operation and stable material circulation of a fluorination reaction system.
The invention has the advantages that:
(1) the invention provides a method for separating a five-membered cyclic chlorofluoroolefin compound (X is more than or equal to 2 and less than or equal to 6, and X is an integer) from a hydrogen fluoride azeotrope, which is not disclosed in other documents.
(2) The separation effect of the five-membered cyclic chlorofluoroolefin compound (X is more than or equal to 2 and less than or equal to 6, and X is an integer) and the hydrogen fluoride is realized, when the cooling temperature is 5 ℃, the mass ratio of the hydrogen fluoride to the five-membered cyclic chlorofluoroolefin compound (X is more than or equal to 2 and less than or equal to 6, and X is an integer) is 1: 2.3-2.8, the cooling time is 0.5h, and the content of the hydrogen fluoride in the five-membered cyclic chlorofluoro olefin compound (X is not less than 2 and not more than 6, and X is an integer) can be reduced to be less than 2%.
(3) The equipment used by the invention is simple and is suitable for industrial production process.
Drawings
FIG. 1 is a schematic diagram of a reaction process for preparing five-membered cyclic chlorofluoroolefins from hexachlorocyclopentadiene,
FIG. 2 shows a freeze separation apparatus used in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
The freezing separation device adopted by the invention is shown in figure 2, wherein in the aspect of equipment material selection, carbon steel pressure-resistant equipment lined with fluoroplastic has a structure that a shell layer is a refrigerant pipeline, and a medium to be separated is introduced into a coil pipe and a pipe pass.
The specific freezing separation technique is as follows: with a five-membered cyclic chlorofluoroalkene compound C5Cl8-xFxThe materials (X is not less than 2 and not more than 6, and X is an integer) and hydrogen fluoride as main materials enter a pressure-resistant separation device lined with fluoroplastic, wherein ① five-membered cyclic chlorofluoro olefin compound C5Cl8-xFx(X is not less than 2 and not more than 6 and is an integer) and hydrogen fluoride mixture enter a refrigerating device through an opening A4, and after precooling through a coil pipe, the mixture is discharged from an opening A3 to a precooling coil pipe and then enters an opening A2 of a pipe side inlet, and a refrigerantEntering a shell pass through an A1 port for circulating refrigeration, adopting cooling water as a refrigerant, being environment-friendly and clean, effectively layering the liquid-phase inorganic material hydrogen fluoride at the top of a ② separation layer and organic matters, and the liquid-phase five-membered cyclic chlorofluoro olefin compound C at the bottom of a ③ separation layer5Cl8-xFx(2. ltoreq. X.ltoreq.6, wherein X is an integer). The liquid phase hydrogen fluoride at the top of the separation layer is recycled to the reactor for re-reaction. The liquid phase organic phase at the bottom of the separation layer enters a distillation tower, and five-membered cyclic fluoro chloro olefin compounds (X is more than or equal to 2 and less than or equal to 5, and X is an integer) and C are realized by distillation5Cl2F6Separation of (4). The nozzles are shown as follows:
example 1
Introducing nitrogen into the freezing separation device shown in figure 2 for pressurizing and leakage testing (the pressure is 0.6MPa), introducing a refrigerant for cooling, reducing the temperature of a shell layer of the separation device to 5 ℃, and then filling a mixture of 20kg of anhydrous hydrogen fluoride and 50kg of five-membered cyclic fluoro chloro olefin compound (X is not less than 2 and not more than 6 and X is an integer) into the device, wherein the organic matter component is C5F2Cl6(content: 3.8%) C5F3Cl5(content: 9.7%) C5F4Cl4(content 23.4%), C5F5Cl3(content: 33.9%) with C5F6Cl2(content: 29.2%), standing until the material is cooled to 5 ℃, and then freezing and separating for 0.5h to obtain an organic phase (five-membered cyclic fluoro chloro olefin compound C)5Cl8-xFx(X is more than or equal to 2 and less than or equal to 6, X is an integer) and an inorganic phase (hydrogen fluoride) are layered, the emptying is observed through a liquid level meter, the lower organic phase is recovered, the recovered matter is sampled, deionized water is used for dissolving the hydrogen fluoride in the organic matter, the content of fluorine ions in the water solution is tested through a pH meter, so that the content of the hydrogen fluoride in the organic matter is obtained, the proportion of the hydrogen fluoride in the organic phase is obtained, meanwhile, the weight of the recovered organic matter is weighed, the weight is divided by the weight of the organic matter to be separated, the yield of the recovered organic phase is counted, and the analysis result is shown in table 1.
Example 2
The same operation as in example 1 was conducted except that the cooling temperature was changed to 6 deg.C, and the results are shown in Table 1.
Example 3
The same operation as in example 1 was carried out except that the cooling temperature was changed to 7 deg.C, and the results are shown in Table 1.
Example 4
The same operation as in example 1 was carried out except that the cooling temperature was changed to 8 deg.C, and the results are shown in Table 1.
Example 5
The same operation as in example 1 was carried out except that the cooling temperature was changed to 9 deg.C, and the results are shown in Table 1.
Example 6
The same operation as in example 1 was conducted except that the cooling temperature was changed to 10 deg.C, and the results are shown in Table 1.
Example 7
The same operation as in example 1 was conducted except that the cooling temperature was changed to 11 deg.C, and the results are shown in Table 1.
Example 8
The same operation as in example 1 was carried out except that the cooling temperature was changed to 12 deg.C, and the results are shown in Table 1.
Example 9
The same operation as in example 1 was conducted except that the cooling temperature was changed to 13 deg.C, and the results are shown in Table 1.
Example 10
The same operation as in example 1 was carried out except that the cooling temperature was changed to 14 deg.C, and the results are shown in Table 1.
Example 11
The same procedure as in example 1 was carried out, except that the cooling time was changed to 0.1h, and the results are shown in Table 1.
Example 12
The same procedure as in example 2 was carried out, except that the cooling time was changed to 0.1h, and the results are shown in Table 1.
Example 13
The same procedure as in example 2 was carried out, except that the cooling time was changed to 0.3h, and the results are shown in Table 1.
Example 14
The same procedure as in example 2 was carried out, except that the cooling time was changed to 0.7h, and the results are shown in Table 1.
Example 15
The same procedure as in example 2 was carried out, except that the cooling time was changed to 1h, and the results are shown in Table 1.
Example 16
The same procedure as in example 2 was carried out, except that the cooling time was changed to 2h, and the results are shown in Table 1.
Example 17
The same operation as in example 1 was conducted, except that 19.2kg of anhydrous hydrogen fluoride was used, and the results are shown in Table 1.
Example 18
The same operation as in example 1 was conducted, except that 18.5kg of anhydrous hydrogen fluoride was used, and the results are shown in Table 1.
Example 19
The same operation as in example 1 was conducted, except that 17.8kg of anhydrous hydrogen fluoride was used, and the results are shown in Table 1.
Example 20
The same operation as in example 1 was conducted, except that 20.8kg of anhydrous hydrogen fluoride was used, and the results are shown in Table 1.
Example 21
The same operation as in example 1 was conducted, except that the amount of anhydrous hydrogen fluoride was changed to 21.7kg, and the results are shown in Table 1.
Example 22
The same operation as in example 1 was conducted, except that 22.7kg of anhydrous hydrogen fluoride was used, and the results are shown in Table 1.
TABLE 1
Claims (7)
1. A five-membered cyclic chlorofluoro olefin compound C as shown in formula (1)5Cl8-xFxSeparating the mixture from hydrogen fluoride by freezing and standing the mixture in a phase separation device, separating the mixture to obtain an upper layer mainly comprising hydrogen fluorideHydrogen fluoride, the lower layer mainly being five-membered cyclic chlorofluoroalkene C5Cl8-xFxWherein X is not less than 2 and not more than 6, X is an integer,
2. the separation method according to claim 1, wherein the mixture of the five-membered chlorofluoroolefin compound and hydrogen fluoride is a five-membered chlorofluoroolefin compound C obtained by subjecting hexachlorocyclopentadiene to multiple fluorochlorination and HCl removal5Cl8-xFx(2. ltoreq. X.ltoreq.6, wherein X is an integer).
3. The separation process according to claim 2, the five-membered chlorofluoroolefin compound C5Cl8-xFx(2. ltoreq. X. ltoreq.6, wherein X is an integer) and the mass ratio of the hydrogen fluoride mixture is 1: 2-3.
4. The method of claim 1, wherein the freezing temperature is-20 ℃ to 15 ℃.
5. The method of claim 4, wherein the freezing temperature is 5 ℃ to 10 ℃ and the standing time is 0.5 to 2 hours.
6. The method of claim 5, wherein the refrigerant used for freezing is cold water.
7. The method according to claim 1, wherein the phase separation equipment is pressure-resistant equipment lined with fluoroplastic, a shell side is a refrigerant pipeline, and a mixture of five-membered cyclic chlorofluoroolefin compounds and hydrogen fluoride is introduced into a tube side.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010301959.4A CN111423305A (en) | 2020-04-16 | 2020-04-16 | Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010301959.4A CN111423305A (en) | 2020-04-16 | 2020-04-16 | Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111423305A true CN111423305A (en) | 2020-07-17 |
Family
ID=71554599
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010301959.4A Pending CN111423305A (en) | 2020-04-16 | 2020-04-16 | Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111423305A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08143487A (en) * | 1994-11-24 | 1996-06-04 | Agency Of Ind Science & Technol | Production of fluorinated alkene derivative and fluorinated alkane derivative |
US5847243A (en) * | 1994-06-30 | 1998-12-08 | Japan As Represented By Director General Of The Agency Of Industrial Science And Technology | Process for producing fluorinated alkene and fluorinated alkane |
CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
US6211420B1 (en) * | 1996-05-13 | 2001-04-03 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Process for the preparation of fluorinated olefin |
US6218586B1 (en) * | 1998-11-05 | 2001-04-17 | Central Glass Company, Limited | Method for preparing perhalogenated five-membered cyclic compound |
CN103570490A (en) * | 2012-07-21 | 2014-02-12 | 北京宇极神光科技有限公司 | Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene |
-
2020
- 2020-04-16 CN CN202010301959.4A patent/CN111423305A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5847243A (en) * | 1994-06-30 | 1998-12-08 | Japan As Represented By Director General Of The Agency Of Industrial Science And Technology | Process for producing fluorinated alkene and fluorinated alkane |
JPH08143487A (en) * | 1994-11-24 | 1996-06-04 | Agency Of Ind Science & Technol | Production of fluorinated alkene derivative and fluorinated alkane derivative |
US6211420B1 (en) * | 1996-05-13 | 2001-04-03 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Process for the preparation of fluorinated olefin |
CN1270575A (en) * | 1997-09-17 | 2000-10-18 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
US6218586B1 (en) * | 1998-11-05 | 2001-04-17 | Central Glass Company, Limited | Method for preparing perhalogenated five-membered cyclic compound |
CN103570490A (en) * | 2012-07-21 | 2014-02-12 | 北京宇极神光科技有限公司 | Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102101651B (en) | Method and device for refining chlorine hydride byproduct and recovering trifluoromethane in production of monochlorodifluoromethane | |
CN101298318B (en) | Method and apparatus for preparing high-pure carbon tetrafluoride gas | |
CN105347307B (en) | A kind of water-eliminating method of hydrogen chloride gas | |
CN109867262B (en) | Synthesis system and synthesis method of diborane | |
CN105481640A (en) | Low-energy consumption low-loss vinyl chloride rectifying technology | |
CN107746040A (en) | A kind of Processes and apparatus that hydrogen chloride is refined using the by-product gas for producing trichloro ethylene | |
CN111085081A (en) | Device and method for removing hydrogen fluoride in fluorine gas | |
CN111099957B (en) | Purification system and method for electronic-grade carbon tetrafluoride | |
CN111039267A (en) | Device and method for pre-purifying electrolytically prepared nitrogen trifluoride crude product | |
CN109748775A (en) | The resource utilization method of by-product fluoroform in a kind of HCFC-22 production | |
CN111423305A (en) | Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture | |
CN114314534A (en) | Natural gas helium extraction process | |
CN100513369C (en) | Method for separating and recovery difluorochloromethane azeotropic hexafluoropropene | |
CN111039749B (en) | Preparation system and method of electronic-grade carbon tetrafluoride | |
CN107648976B (en) | Method for preparing ultra-high-purity gas through low-temperature separation and low-temperature separation system | |
CN103102241A (en) | Process for producing 1, 1, 1, 2-tetrafluoroethane by gas-liquid phase method | |
CN112661115A (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF produced by fluorite method | |
CN104387300B (en) | A kind of purification process of fluoroform sulfonic acid fluoride | |
CN111185070B (en) | NF removal using low temperature HF3System and method for removing impurities from electrolysis gas | |
CN115231524A (en) | Separation and purification method and device for tail gas containing hydrogen fluoride in fluorine chemical production | |
CN115305486A (en) | Device and method for preparing high-purity fluorine gas | |
CN101070266A (en) | Freon 22/hexafluoropropylene azeotrope separating and recovering method | |
CN109534951B (en) | Separation device and separation method for 2,3,3, 3-tetrafluoropropene mixture | |
CN114572944A (en) | Preparation method of nitrogen trifluoride and nitrogen trifluoride mixed gas | |
CN104003403B (en) | The desorption method of non-condensable gas in a kind of chlorosilane |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200717 |
|
WD01 | Invention patent application deemed withdrawn after publication |