CA2128659A1 - Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons - Google Patents
Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbonsInfo
- Publication number
- CA2128659A1 CA2128659A1 CA 2128659 CA2128659A CA2128659A1 CA 2128659 A1 CA2128659 A1 CA 2128659A1 CA 2128659 CA2128659 CA 2128659 CA 2128659 A CA2128659 A CA 2128659A CA 2128659 A1 CA2128659 A1 CA 2128659A1
- Authority
- CA
- Canada
- Prior art keywords
- gas
- halons
- scrubber column
- gas scrubber
- stage
- 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.)
- Abandoned
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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
-
- 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]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
Abstract of the Disclosure Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons The invention relates to a process for the disposal of halons or halon-containing FCs or CFCs, wherein the latter are thermally or photochemically decomposed in the presence of a hydrogen source, the gas produced, containing HF, HBr, CO2, water and, if appropriate, HCl, is cooled, the hydrogen halides are absorbed in a scrubbing liquid in a gas scrubber column and neutralized with a base, and any elemental bromine or chlorine contained in the gas is reduced to the corresponding salts with a reducing agent.
Description
HOECHST AKTIENGESELLSCHAFT HOE 93/F 213 Dr. MA
De~cription Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons The invention relate~ to a process for the di~po~al of bromofluorocarbons or bromochlorofluorocarbons (called halons hereafter) or mixtures thereof with fluorocarbons (FCs) or chlorofluorocarbons (CFCs).
The object of the invention is to dispo~e of halons and at the ~ame time to obtain reusable products, for ~xample a concentrated brine solution containing bromine, from which elemental bromine, potassium fluoride and potassium chloride can then be recovered. Although the producer~ of halon-containing fire-extinguishing agents are faced with a dispo~al emergency, no proces~ has yet been di closed which meets these requirements and solveQ the problem of separating from one another the extremely corrosive products formed e.g. in the thermal decomposition o~
halons.
:
It has now been found, aurprisingly, that the above object is achieved by thermally decomposing halons, halon-containing FCs or halon-containing CFCs, for example by mean~ of an oxyhydrogen flame, cooling the gas stream formed, absorbing the HF and ~Br produced by the decomposition and any HCl produced (when using bromo-chlorofluorocarbon~ or halons mixed with chlorofluoro-carbona) from the gas stre~m in a gas scrubber column and neutralizing the acid~ formed with a base. If necessary, a reducing agent is also added to reduce any el~mental chlorine or bromine produced by the thermal deco~position to the corresponding salts.
The invention accordingly provide a proceas for the disposal of halons (bromofluorocarbon~ or bromochloro-fluorocarbon~) or mixtures thereof with fluorocarbon~
(FCs) or chlorofluorocarbon~ (CFCs), wherein ~ 2.8'85~
De~cription Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons The invention relate~ to a process for the di~po~al of bromofluorocarbons or bromochlorofluorocarbons (called halons hereafter) or mixtures thereof with fluorocarbons (FCs) or chlorofluorocarbons (CFCs).
The object of the invention is to dispo~e of halons and at the ~ame time to obtain reusable products, for ~xample a concentrated brine solution containing bromine, from which elemental bromine, potassium fluoride and potassium chloride can then be recovered. Although the producer~ of halon-containing fire-extinguishing agents are faced with a dispo~al emergency, no proces~ has yet been di closed which meets these requirements and solveQ the problem of separating from one another the extremely corrosive products formed e.g. in the thermal decomposition o~
halons.
:
It has now been found, aurprisingly, that the above object is achieved by thermally decomposing halons, halon-containing FCs or halon-containing CFCs, for example by mean~ of an oxyhydrogen flame, cooling the gas stream formed, absorbing the HF and ~Br produced by the decomposition and any HCl produced (when using bromo-chlorofluorocarbon~ or halons mixed with chlorofluoro-carbona) from the gas stre~m in a gas scrubber column and neutralizing the acid~ formed with a base. If necessary, a reducing agent is also added to reduce any el~mental chlorine or bromine produced by the thermal deco~position to the corresponding salts.
The invention accordingly provide a proceas for the disposal of halons (bromofluorocarbon~ or bromochloro-fluorocarbon~) or mixtures thereof with fluorocarbon~
(FCs) or chlorofluorocarbon~ (CFCs), wherein ~ 2.8'85~
a) the halonE or ~ixtures thereof with FCs or CFCB are thermally or photochamically docompo~ed ln the presence of a hydrogen cour~e, b) the ga~ produced in ~t~p a), conta~nin~ ~F, HBr, C2~ water and, 1~ approprinte, ~Cl, i8 cooled to 5 50C and c) in a gas ~crubber column, the hydrogen halides are ab~or~ed in a scrubbing liguid from the ga~ obtained in step b), and n~utralized w~th a ba~e, and any elemental bromine or chlorino contained ~n the gac is reducod to th~ correcponding ~alts with a redu-cing agent, tho scrubbing llguid and tho gao b~ing fed in ~t tho middle of the gas ~crubber column and the base and, if appropriato, the reducing agent being $ntroducod at the top of the ga~ ecrubber column, and a ga~ free of hydrogen halide~ boing withdrawn at the top of the gas ~crubber column and a brine solution being withdrawn at the bottom of the gas scrub~er ~olumn.
The halon~ (bromo~luorocarbon~ or bro~ochlorofluorocar~
bons) disposed of according to the lnvention g~nerally have 1 to 3 ~arbon atom~. They can be ~om~letely or partially halogenated.
The halons can be pre~ent individu~lly, mixed with one another or m~xed with FCe or CFC~ or both. The FCs ~d CFCs generally havo 1 to 6 carbon atom~ and can b~
completely or parti~lly halogenated.
The hydrogen source used in ~top ~ preferably hydro-gen itself or a hydroc~rbon. The thermRl decomposition i~
prefernbly carried out in a ~r~cking reactor auch a~ that described in EP-A-0 212 410.
In Btop b), the ga~ produced in ~tep a), ~ontaining ~F, HBr, C02 and w~ter (~nd also HCl when u~ing chloro$1uoro-~ ~ 2 S ~i ~
carbons or bromochlorofluorocarbons), is cooled to5 - 50C, preferably 5 - 30C.
The gas scrubber column used in ~tep c) ie preferably a two-~tage column, the scrubbing liquid and the gas produced in step a) being fed in at the top of the first stage and the base and, if appropriate, the reducing agent being introduced at the top of the second stage.
The gas scrubber column can be operated isothermally or adiabatically under normal, reduced or exces~ pre~eure.
Thepreferredoperatingprocedure i8 adiabatic, especially at normal pressure.
The gas scrubber column i~ preferably operated 50 that the brine solution leaving at the bottom has a pH of 5 - 8.4, preferably 6 - 6.5, and the ~alt content is 20 - 50% by weight, pre~erably 30 - 40% by wei~ht.
The scrubbing liquid used in step c) can be water, a dilute solution of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal hydrogencarbonate or alkaline earth metal hydrogencarbonate, or a dilute brine solution having a similar compoRition to that of the brine solution leaving at the bottom of the gas scrubber column.
Suitable reducing agenta are agueou~ solutions o~ alkali metal ~ormate, alkali metal hydrogen~ulfite, hydrazine or ~ulfur dioxide gaQ, preferably aqueou~ solution~ of sodium or potassium formate. It i8 only necessary to add a reducing agent when the gas produced in ~tep a) actually contains Br2 and/or Cl2, which can easily be e~tabli~hed by analysi~.
Ba~es which can be used are an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate or hydrogencarbonate, preferably eodium or pota~sium hydroxide or carbonate.
~, 2 ~ t~i 5 9 The invention will be illustrated in greater detail by the following Example and Figure 1.
Example 1 The decompo~it~on according to step a) wa~ carried out ~n a Diabon tube (l) (length - 800 mm, diameter = 48 mm) equipped at the upper end with an electrically ignited burner jet (2). 100 g/h of halon/CFC mixture ~40% by weight of dichlorodifluoromethane, R 12, 50% by weight of trichlorofluoromethano, R 11, 10% by weight of trifluoro-bromomethane, halon 13B1) were decompo~ed by mean~ ofoxyhydrogen (35 l/h of H2, 10.5 l/h of l). Attached to the lower end of the Diabon tube (1) was a Diabon plat~
heat exchanger (3) (length = 400 mm) in which the hot decomposition gaee~ were cooled to room temperature. The cooled ga~es were then pa~sed through the line (4) into the top of the column (5) (length = 400 mm; diameter =
100 mm; PTF~ ned steel column with lateral feed pipo and 4 mm PP Raschig rings a~ packing), which ~erved as the first stage of a two-~tage scrubber. At the beginning of the experiment, water wa~ circulated (ca. 2000 ml/h) via the line (6) with a pump (7). Attached to the column (5) was a second column (8) (length = 1000 mm: diametor - 50 mm; PTFE- lined ~teel coll~n with lateral feed pipe and 4 mm PP Raschig rings as packing) as the ~econd stage. 30% by weight agu~ous ROH (ca. 300 ml/h) was metered into the top of the column (8) from the storage ve~sel (9) via the line (10) and 10% by weight aqueous potassium formate ~olution (ca. 30 ml/h) was metered in from the storage ve~sel (11) via the lines (12) and (10).
The metering process was controlled by the pH and the electrical potential (measurement at the outlet of the colum~ (8)). When 100 g of halon/CFC mixture had been pa~sed through, the oontinuous discharge of part (ca.
330 ml/h) of the bottom of the column (5) into th~
~torage vessel (1~) via the line (13) was started. The e$fluent brine ~olution had a salt content of ca.
~ 3 30 - 35% by weight. Elemental bromine and chlorine and hypobromit e, hypochlorite, bromate and chlorate were undetectable by analysi~. The proportion of carbonate and hydrogen-carbonate wa~ b610w 0.1% by weight at a pH of the brine solution of 6.5. C02 escaped at the top of the column (8) via the line (15).
The halon~ (bromo~luorocarbon~ or bro~ochlorofluorocar~
bons) disposed of according to the lnvention g~nerally have 1 to 3 ~arbon atom~. They can be ~om~letely or partially halogenated.
The halons can be pre~ent individu~lly, mixed with one another or m~xed with FCe or CFC~ or both. The FCs ~d CFCs generally havo 1 to 6 carbon atom~ and can b~
completely or parti~lly halogenated.
The hydrogen source used in ~top ~ preferably hydro-gen itself or a hydroc~rbon. The thermRl decomposition i~
prefernbly carried out in a ~r~cking reactor auch a~ that described in EP-A-0 212 410.
In Btop b), the ga~ produced in ~tep a), ~ontaining ~F, HBr, C02 and w~ter (~nd also HCl when u~ing chloro$1uoro-~ ~ 2 S ~i ~
carbons or bromochlorofluorocarbons), is cooled to5 - 50C, preferably 5 - 30C.
The gas scrubber column used in ~tep c) ie preferably a two-~tage column, the scrubbing liquid and the gas produced in step a) being fed in at the top of the first stage and the base and, if appropriate, the reducing agent being introduced at the top of the second stage.
The gas scrubber column can be operated isothermally or adiabatically under normal, reduced or exces~ pre~eure.
Thepreferredoperatingprocedure i8 adiabatic, especially at normal pressure.
The gas scrubber column i~ preferably operated 50 that the brine solution leaving at the bottom has a pH of 5 - 8.4, preferably 6 - 6.5, and the ~alt content is 20 - 50% by weight, pre~erably 30 - 40% by wei~ht.
The scrubbing liquid used in step c) can be water, a dilute solution of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal hydrogencarbonate or alkaline earth metal hydrogencarbonate, or a dilute brine solution having a similar compoRition to that of the brine solution leaving at the bottom of the gas scrubber column.
Suitable reducing agenta are agueou~ solutions o~ alkali metal ~ormate, alkali metal hydrogen~ulfite, hydrazine or ~ulfur dioxide gaQ, preferably aqueou~ solution~ of sodium or potassium formate. It i8 only necessary to add a reducing agent when the gas produced in ~tep a) actually contains Br2 and/or Cl2, which can easily be e~tabli~hed by analysi~.
Ba~es which can be used are an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate or hydrogencarbonate, preferably eodium or pota~sium hydroxide or carbonate.
~, 2 ~ t~i 5 9 The invention will be illustrated in greater detail by the following Example and Figure 1.
Example 1 The decompo~it~on according to step a) wa~ carried out ~n a Diabon tube (l) (length - 800 mm, diameter = 48 mm) equipped at the upper end with an electrically ignited burner jet (2). 100 g/h of halon/CFC mixture ~40% by weight of dichlorodifluoromethane, R 12, 50% by weight of trichlorofluoromethano, R 11, 10% by weight of trifluoro-bromomethane, halon 13B1) were decompo~ed by mean~ ofoxyhydrogen (35 l/h of H2, 10.5 l/h of l). Attached to the lower end of the Diabon tube (1) was a Diabon plat~
heat exchanger (3) (length = 400 mm) in which the hot decomposition gaee~ were cooled to room temperature. The cooled ga~es were then pa~sed through the line (4) into the top of the column (5) (length = 400 mm; diameter =
100 mm; PTF~ ned steel column with lateral feed pipo and 4 mm PP Raschig rings a~ packing), which ~erved as the first stage of a two-~tage scrubber. At the beginning of the experiment, water wa~ circulated (ca. 2000 ml/h) via the line (6) with a pump (7). Attached to the column (5) was a second column (8) (length = 1000 mm: diametor - 50 mm; PTFE- lined ~teel coll~n with lateral feed pipe and 4 mm PP Raschig rings as packing) as the ~econd stage. 30% by weight agu~ous ROH (ca. 300 ml/h) was metered into the top of the column (8) from the storage ve~sel (9) via the line (10) and 10% by weight aqueous potassium formate ~olution (ca. 30 ml/h) was metered in from the storage ve~sel (11) via the lines (12) and (10).
The metering process was controlled by the pH and the electrical potential (measurement at the outlet of the colum~ (8)). When 100 g of halon/CFC mixture had been pa~sed through, the oontinuous discharge of part (ca.
330 ml/h) of the bottom of the column (5) into th~
~torage vessel (1~) via the line (13) was started. The e$fluent brine ~olution had a salt content of ca.
~ 3 30 - 35% by weight. Elemental bromine and chlorine and hypobromit e, hypochlorite, bromate and chlorate were undetectable by analysi~. The proportion of carbonate and hydrogen-carbonate wa~ b610w 0.1% by weight at a pH of the brine solution of 6.5. C02 escaped at the top of the column (8) via the line (15).
Claims (7)
1. A process for the disposal of halons (bromo-fluorocarbons or bromochlorofluorocarbons) or mixtures thereof with fluorocarbons (FCB) or chlorofluorocarbons (CFCs), wherein a) the halons or mixtures thereof with FCs or CFCs are thermally or photochemically decomposed in the presence of a hydrogen source, b) the gas produced in step a), containing HF, HBr, CO2, water and, if appropriate, HCl, is cooled to 5 - 50°C, and c) in a gas scrubber column, the hydrogen halides are absorbed in a scrubbing liquid from the gas obtained in step b), and neutralized with a base, and any elemental bromine or chlorine contained in the gas is reduced to the corresponding salts with a redu-cing agent, the scrubbing liquid and the gas being fed in at the middle of the gas scrubber column and the base and, if appropriate, the reducing agent being introduced at the top of the gas scrubber column, and a gas free of hydrogen halides being withdrawn at the top of the gas scrubber column and a brine solution being withdrawn at the bottom of the gas scrubber column.
2. The process as claimed in claim 1, wherein the halons have 1 to 3 carbon atoms.
3. The process as claimed in claim 1 or 2, wherein the FCs or CFCs have 1 to 6 carbon atoms.
4. The process as claimed in one of claims 1 to 3, wherein the gas scrubber column used in step c) is operated adiabatically.
5. The process as claimed in one of claims 1 to 4, wherein the gas scrubber column used in step c) is operated so that the brine solution leaving at the bottom of the first stage has a pH of 5 - 8.4.
6. The process as claimed in one of claims 1 to 4, wherein the gas scrubber column used in step c) is operated so that the bring solution leaving at the bottom of the first stage has a salt content of 30 - 40% by weight.
7. The process as claimed in one of claims 1 to 6, wherein the gas scrubber column used in step c) is a two-stage column and the scrubbing liquid and the gas produced in step a) are fed in at the top of the first stage and the base and, if appropriate, the reducing agent are introduced at the top of the second stage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934324908 DE4324908A1 (en) | 1993-07-24 | 1993-07-24 | Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons |
| DEP4324908.6 | 1993-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2128659A1 true CA2128659A1 (en) | 1995-01-25 |
Family
ID=6493637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2128659 Abandoned CA2128659A1 (en) | 1993-07-24 | 1994-07-22 | Process for the disposal of halons or halon-containing fluorocarbons or chlorofluorocarbons |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0636388A1 (en) |
| JP (1) | JPH07178313A (en) |
| CA (1) | CA2128659A1 (en) |
| DE (1) | DE4324908A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI776610B (en) * | 2020-08-24 | 2022-09-01 | 日商昭和電工股份有限公司 | Refining method of sea dragon |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705140A (en) * | 1995-07-18 | 1998-01-06 | Transformation Technologies, Ltd. | Process for the transformation of halogenated refrigerant gases |
| US20010009652A1 (en) * | 1998-05-28 | 2001-07-26 | Jose I. Arno | Apparatus and method for point-of-use abatement of fluorocompounds |
| CN100551467C (en) | 2002-03-28 | 2009-10-21 | 兴研株式会社 | The decomposer of organic compound |
| EP2686610B1 (en) * | 2011-03-14 | 2015-09-30 | URT Umwelt- und Recyclingtechnik GmbH | Method and system for treating fluids containing refrigerant and/or propellant |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982039A (en) * | 1987-09-03 | 1991-01-01 | University Of Southern California | Conversion of halogenated toxic substances |
| US5457267A (en) * | 1992-03-28 | 1995-10-10 | Hoechst Aktiengesellschaft | Process for disposing of halons or halon-containing fluorocarbons or chlorofluorocarbons |
-
1993
- 1993-07-24 DE DE19934324908 patent/DE4324908A1/en not_active Withdrawn
-
1994
- 1994-07-11 EP EP94110731A patent/EP0636388A1/en not_active Withdrawn
- 1994-07-22 JP JP17128994A patent/JPH07178313A/en active Pending
- 1994-07-22 CA CA 2128659 patent/CA2128659A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI776610B (en) * | 2020-08-24 | 2022-09-01 | 日商昭和電工股份有限公司 | Refining method of sea dragon |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07178313A (en) | 1995-07-18 |
| EP0636388A1 (en) | 1995-02-01 |
| DE4324908A1 (en) | 1995-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |