WO2004014526A1 - Verfahren zur auftrennung von gasgemischen - Google Patents
Verfahren zur auftrennung von gasgemischen Download PDFInfo
- Publication number
- WO2004014526A1 WO2004014526A1 PCT/EP2003/003753 EP0303753W WO2004014526A1 WO 2004014526 A1 WO2004014526 A1 WO 2004014526A1 EP 0303753 W EP0303753 W EP 0303753W WO 2004014526 A1 WO2004014526 A1 WO 2004014526A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- partially fluorinated
- perfluorinated
- hydrocarbons
- perfluorinated hydrocarbons
- gas
- 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.)
- Ceased
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/308—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/26—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Definitions
- the invention relates to a process for the separation of gas mixtures which contain substitutes for sulfur hexafluoride (SF 6 ).
- Gas mixtures which, for. B. SF 6 and nitrogen, are used as an insulating fill gas for underground cables or circuits, see German utility model 297 20 507.2. These mixtures usually contain 5 to 30% by volume of sulfur hexafluoride, the remainder to 100% by volume of nitrogen.
- Partially fluorinated and / or perfluorinated hydrocarbons are suitable as substitutes for SF 6 .
- the object of the present invention is to provide a process for the separation of the gas mixtures, which requires only low transport capacity when reusing the partially fluorinated and / or perfluorinated hydrocarbons from the mixtures.
- Another object is to provide a suitable device for carrying out the method according to the invention.
- the process according to the invention for the separation of partially fluorinated and / or perfluorinated hydrocarbon / inert gas mixtures provides that the mixture is mixed with hydrophobic zeolites with a Si0 2 / Al 2 0 3 ratio ("modulus") of at least 80 and a pore diameter of 4 to 20 ⁇ (0.4 to 2 nm), preferably 6 to 8.5 ⁇ (0.5 to 0.85 nm) contacted to adsorb the partially fluorinated and / or perfluorinated hydrocarbons.
- the separated inert gas z. B. nitrogen or the separated air can be released into the environment.
- Fluorinated hydrocarbons which develop a vapor pressure ⁇ 30 bar (abs.) At 50 ° C. are preferably used.
- Suitable representatives of these substance classes are e.g. B. C 3 F 8 (R218), CHF 2 CF 3 (R125), CF 3 CHFCF 3 (R227ea), CH 2 FCF 3 (Rl34a), CH 3 CH 3 (Rl43a), CHF 3 (R23), CF 4 (R14), CF 3 CF 3 (Rll ⁇ ), R404 (Rl25 / Rl43a / R134a), CF 3 OCHF 2 (E125), C 4 F 6 .
- Inert gases such as z. B. N, C0 2 , air or noble gases in question.
- Gas mixtures which also contain SF 6 in addition to the partially fluorinated and / or perfluorinated hydrocarbons can also be separated off by the process according to the invention.
- Another criterion of the compounds that can be used as SFg substitutes is their non-flammability and that they have no toxic effect. These compounds should be gaseous down to -25 ° C and a pressure of 4 to 8 bar. C 3 F 8 and / or CHF 2 CF 3 are used as particularly suitable compounds.
- the method according to the invention provides at least one adsorption stage. If necessary, the gas mixture to be separated can pass through one or more membrane separation stages before entering the adsorption stage for pre-cleaning.
- Membrane separation process and adsorption It is very well suited for mixtures of partially fluorinated and / or perfluorinated hydrocarbons (HFC) and N 2, for example from underground cables, which have a HFC content of 30 to 60% by volume.
- HFC partially fluorinated and / or perfluorinated hydrocarbons
- the membrane can be in the usual form. Membranes in the form of a bundle of hollow fibers are very suitable.
- the membrane material can, for example, be made of polysulfone, polyetherimide, polypropylene, cellulose acetate, polyimide, polyamide, polyaramide or ethyl cellulose, as described in US Pat. No. 5,730,779. Other useful membranes are described in US-A 4,838,904.
- One embodiment of the method according to the invention provides that the gas mixture is in at least one membrane separation stage into a retentate with an increased content of HFC and a permeate with a reduced content of HFC and the permeate for further separation is passed into at least one adsorption stage with the hydrophobic zeolites described above. It is preferred to provide two or more membrane separation stages and two or more adsorption stages.
- the pressure on the inlet side of the membrane or membranes is usually higher than the ambient pressure.
- the gas mixture to be separated can be applied at a pressure of up to 20 bar.
- a compressor is arranged in front of each membrane.
- the permeate When entering the adsorber stage, the permeate then usually has a pressure which corresponds approximately to the ambient pressure. If desired, the permeate can be compressed before entering the adsorber stage. But this is not necessary. It is easiest to add the permeate to the adsorber stage at the pressure resulting from the membrane.
- the pressure is then usually up to 4 bar (abs.), Preferably up to 2 bar (abs.).
- the mixture to be separated - for example a mixture of C 3 F 8 and nitrogen with 50% by volume HFC from underground cables - is applied to the first membrane. Since nitrogen preferably passes through the membrane, a permeate with a high nitrogen content and a low HFC content is obtained.
- the permeate is introduced into the adsorber or into the first adsorber; the gas mixture leaving the first adsorber is then introduced into a second, then optionally into a third, etc. adsorber.
- the retentate of the first membrane is introduced into another membrane.
- the permeate resulting from this second membrane is introduced into the first membrane.
- the retentate from the second membrane contains fluorinated hydrocarbons with small amounts of nitrogen. It can be after Liquefaction can be reused immediately with a compressor or processed with further enrichment of the partially and / or perfluorinated hydrocarbons.
- the process can be carried out very flexibly with regard to the number of membranes and adsorber stages. Depending on how far the depletion of HFCs should take place, one, two or even more adsorber stages are provided.
- the number of membranes depends on whether a gas with a high or low fluorinated hydrocarbon content should be treated. With a larger number of membranes, the HFC content in the permeate that is to be treated by adsorption is lower than when using a small number of membranes. The adsorber can then either be made smaller, or the regeneration is necessary at longer intervals. However, the expenditure on equipment can be higher (higher number of compressors).
- the pressure is reduced (pressure swing adsorption) and, if necessary, heat is applied to the occupied adsorbents.
- the released partially and / or perfluorinated
- Hydrocarbons can be liquefied under pressure or cold.
- the liquefied gases are expediently filled into steel cylinders and used for subsequent use.
- the process according to the invention is characterized by optimal splitting of the gas mixtures.
- the cleaned nitrogen or the cleaned air can be safely released into the environment.
- the method according to the invention is carried out in a mobile separation plant.
- the gas mixture which originates, for example, from underground cables or gas-insulated circuits, can be separated on the spot.
- This device for separating the gas mixtures comprises one, two or more adsorbers with a bed of zeolites with a silica / alumina ratio
- Module of at least 80 and a pore diameter of 4 to 20 ⁇ (0.4 to 2 nm), preferably 5 to 8.5 ⁇ (0.5 to 0.85 ⁇ ).
- Another embodiment has two membrane separation stages and two adsorber stages. A compressor is arranged in front of each membrane stage.
- It also includes a supply line for the gas mixture to be separated, which is connected to the entrance to the first membrane separation stage, a connecting line between the first and second membrane separation stages, which is provided for introducing the retentate from the first membrane separation stage into the second membrane separation stage, a connecting line between the second and first membrane separation stage, which is provided for introducing the permeate of the second membrane separation stage into the first membrane separation stage, a take-off line for the retentate from the second membrane separation stage, from which retentate with a high HFC content can be taken off, a feed line for the permeate of the first membrane separation stage into the first adsorber, a feed line for the gas leaving the first adsorber into the second adsorber and a take-off line from the second adsorber for the nitrogen gas
- adsorber stage Depending on the adsorber capacity and the number of membrane separation stages, only one adsorber stage can also be provided. Two adsorber stages or more are advantageous because they allow continuous operation if they are connected in parallel.
- the device is arranged in a mobile form, for example set up on the loading surface of a motor vehicle (for example a truck).
- the method according to the invention can then be carried out on the spot.
- an adsorber is a zeolite of type MFI pentasil (Wessalith DAZ ® F20) with a modulus of> 1,000, a pore size of 0.6 nm and has a particle size of 2 mm used.
- the separated nitrogen only contained traces of C 3 F 8 .
- the adsorber loaded with C 3 F 8 was desorbed in a manner known per se and the recovered C 3 F 8 liquefied under pressure and filled into steel bottles.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Separation Of Gases By Adsorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003227604A AU2003227604A1 (en) | 2002-07-25 | 2003-04-11 | Method for separating gaseous mixtures |
| JP2004526655A JP2005533647A (ja) | 2002-07-25 | 2003-04-11 | ガス混合物の分離方法 |
| EP03725006A EP1526913A1 (de) | 2002-07-25 | 2003-04-11 | Verfahren zur auftrennung von gasgemischen |
| US11/041,243 US20050183573A1 (en) | 2002-06-25 | 2005-01-25 | Method for separating gas mixtures |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10233898.1 | 2002-07-25 | ||
| DE10233898A DE10233898A1 (de) | 2002-07-25 | 2002-07-25 | Verfahren zur Auftrennung von Gasgemischen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004014526A1 true WO2004014526A1 (de) | 2004-02-19 |
Family
ID=30128386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/003753 Ceased WO2004014526A1 (de) | 2002-06-25 | 2003-04-11 | Verfahren zur auftrennung von gasgemischen |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1526913A1 (de) |
| JP (1) | JP2005533647A (de) |
| KR (1) | KR100669172B1 (de) |
| AU (1) | AU2003227604A1 (de) |
| DE (1) | DE10233898A1 (de) |
| WO (1) | WO2004014526A1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101102396B1 (ko) * | 2006-02-08 | 2012-01-05 | 엘지전자 주식회사 | 이동통신 시스템에서의 코드워드 크기 정합 방법 및 송신장치 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5181869B2 (ja) * | 2008-06-27 | 2013-04-10 | 東ソー株式会社 | Pfc吸着剤及びそれを用いたpfc除害方法 |
| WO2020225911A1 (ja) * | 2019-05-09 | 2020-11-12 | 日新電機株式会社 | 絶縁ガス用吸着剤及びガス絶縁電力機器 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417742A (en) * | 1993-12-03 | 1995-05-23 | The Boc Group, Inc. | Removal of perfluorocarbons from gas streams |
| EP0950430A1 (de) * | 1998-04-17 | 1999-10-20 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Trennung von CF4 und C2F6 von einer Perfluorverbindungen enthaltenden Mischung |
| WO2000010688A1 (de) * | 1998-08-20 | 2000-03-02 | Solvay Fluor Und Derivate Gmbh | Auftrennung von sf6 enthaltenden gasen |
| WO2001062366A1 (de) * | 2000-02-22 | 2001-08-30 | Solvay Fluor Und Derivate Gmbh | Auftrennung von sf6 enthaltenden gasen |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3908819B2 (ja) * | 1997-03-14 | 2007-04-25 | 大陽日酸株式会社 | フロンの回収方法 |
| JP2000334249A (ja) * | 1999-05-25 | 2000-12-05 | Air Prod And Chem Inc | 膜と吸着を連続して用いる半導体製造における排ガスからのフッ素化合物の分離方法 |
| JP4450944B2 (ja) * | 2000-04-19 | 2010-04-14 | 日本パイオニクス株式会社 | パーフルオロカーボンの回収方法及び分解方法 |
-
2002
- 2002-07-25 DE DE10233898A patent/DE10233898A1/de not_active Withdrawn
-
2003
- 2003-04-11 AU AU2003227604A patent/AU2003227604A1/en not_active Abandoned
- 2003-04-11 EP EP03725006A patent/EP1526913A1/de not_active Withdrawn
- 2003-04-11 WO PCT/EP2003/003753 patent/WO2004014526A1/de not_active Ceased
- 2003-04-11 JP JP2004526655A patent/JP2005533647A/ja active Pending
- 2003-04-11 KR KR1020057000825A patent/KR100669172B1/ko not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417742A (en) * | 1993-12-03 | 1995-05-23 | The Boc Group, Inc. | Removal of perfluorocarbons from gas streams |
| EP0950430A1 (de) * | 1998-04-17 | 1999-10-20 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Trennung von CF4 und C2F6 von einer Perfluorverbindungen enthaltenden Mischung |
| WO2000010688A1 (de) * | 1998-08-20 | 2000-03-02 | Solvay Fluor Und Derivate Gmbh | Auftrennung von sf6 enthaltenden gasen |
| WO2001062366A1 (de) * | 2000-02-22 | 2001-08-30 | Solvay Fluor Und Derivate Gmbh | Auftrennung von sf6 enthaltenden gasen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101102396B1 (ko) * | 2006-02-08 | 2012-01-05 | 엘지전자 주식회사 | 이동통신 시스템에서의 코드워드 크기 정합 방법 및 송신장치 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003227604A1 (en) | 2004-02-25 |
| EP1526913A1 (de) | 2005-05-04 |
| JP2005533647A (ja) | 2005-11-10 |
| DE10233898A1 (de) | 2004-02-12 |
| KR20050030951A (ko) | 2005-03-31 |
| KR100669172B1 (ko) | 2007-01-16 |
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