CA2077235A1 - Continuous purification of an off-gas composed of co2 + hc1 + coc12 - Google Patents
Continuous purification of an off-gas composed of co2 + hc1 + coc12Info
- Publication number
- CA2077235A1 CA2077235A1 CA002077235A CA2077235A CA2077235A1 CA 2077235 A1 CA2077235 A1 CA 2077235A1 CA 002077235 A CA002077235 A CA 002077235A CA 2077235 A CA2077235 A CA 2077235A CA 2077235 A1 CA2077235 A1 CA 2077235A1
- Authority
- CA
- Canada
- Prior art keywords
- hcl
- separator
- coc12
- dialkylformamide
- pipe
- 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
- 238000000746 purification Methods 0.000 title description 3
- 238000010924 continuous production Methods 0.000 claims abstract description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
-
- 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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0731—Purification ; Separation of hydrogen chloride by extraction
-
- 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
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
O.Z. 0050/42662 Abstract of the Disclosures A continuous process for purifying an off-gas composed of CO2 + HCl + COC12 entails using a separator filled with N,N-dialkylformamide x HCl - to react COC12 with N,N-dialkylformamide to give the Vilsmeier complex + CO2, and - to remove CO2/HCl and HCl separately from the separator.
Description
` O.Z. 0050/42662 The continuous purification of an off-qas composed of C0~ + HC1 + COCl2 The present invention relates to a continuous process for purifying an off-gas composed of C02 ~ HCl +
COC12.
This off-gas mixture is produced, for example, in the preparation of carbonyl chlorides.
Carbonyl chlorides are prepared as shown by the following equation:
o o R--C + coc12 ~ R -- C + C02 + HCl ~ COC1 OH Cl where COClz is introduced in excess in~o the reaction, and N,N-dialkylformamide is u~ed as cataly~t.
The off-gas from the reaction i5 thus composed of C02, HCl and unreacted COCla.
In the prior art, the above off-gas mixture is scrubbed with water with added ammonia in scrubbers packed with actiYe carbon. The recovery or disposal of the HCl resulting from this is complicated and therefore cost-intensiva.
It is an object of the present invention to purify above off-ga~ mixture in a straightforward, lower-cost way, which means removing the HCl from the off-ga~
misture and simultaneously utilizing the COCl2 which i~
otherwise lost.
We have found that this object is achieved by using a ~eparator filled with ~,N-dialkylformamide x HCl wherein - COCl2 is reacted with N,N-dialkylformamide to give the Vilsmeier complex + C02, and 0 - C02/HCl and HCl separately are removed from the separator.
We have also found that this ob~ect is achieved by a separator whose features according to the invention ,, , : , , - ~ : : . :
~,: . ~ :
:: ,. .. .:
. .
).~J~S
COC12.
This off-gas mixture is produced, for example, in the preparation of carbonyl chlorides.
Carbonyl chlorides are prepared as shown by the following equation:
o o R--C + coc12 ~ R -- C + C02 + HCl ~ COC1 OH Cl where COClz is introduced in excess in~o the reaction, and N,N-dialkylformamide is u~ed as cataly~t.
The off-gas from the reaction i5 thus composed of C02, HCl and unreacted COCla.
In the prior art, the above off-gas mixture is scrubbed with water with added ammonia in scrubbers packed with actiYe carbon. The recovery or disposal of the HCl resulting from this is complicated and therefore cost-intensiva.
It is an object of the present invention to purify above off-ga~ mixture in a straightforward, lower-cost way, which means removing the HCl from the off-ga~
misture and simultaneously utilizing the COCl2 which i~
otherwise lost.
We have found that this object is achieved by using a ~eparator filled with ~,N-dialkylformamide x HCl wherein - COCl2 is reacted with N,N-dialkylformamide to give the Vilsmeier complex + C02, and 0 - C02/HCl and HCl separately are removed from the separator.
We have also found that this ob~ect is achieved by a separator whose features according to the invention ,, , : , , - ~ : : . :
~,: . ~ :
:: ,. .. .:
. .
).~J~S
- 2 - o.z. 0050/42662 ' are set out in claim 2.
r~ One example of the invention with the essential inventive features is depicted in the drawing and is descri~ed in detail hereinafter. The drawing illustrates the principle of the process and ~he design of the separator.
The separator comprises two vertical pipes 1 which are connected together at the top by a U pipe 2 and at the bottom by a straight pipe 3. The two vertical pipes are each jacketed with thermostats 4, and the thermostats keep one pipe at about 20C and the other pipe at about 60C. The entire separator is filled with N,N-dialkylformamide (called DFM her~inafter) x HC1, and the DMF x HCl circulates in the two vertical pipes owing to the 20 - 60C temperature gradient.
The off-gas mixture is passed via a connector 5 into the pipe a~ 20C in countercurren~ to the circula-tion in the separator. This results in adsorption of the HCl by DFM x HCl. The resulting DFM x 2HCl flow~ into the pipe at 60C and is there thermally decomposed to DFM x HCl and HCl. The HCl escapes through the connector 6, and its purity is analyzed by FT-IR qpectroscopy.
CO2 does not form a compound with DFM x HCl and escapes through the connector 7 on the pipe at 20C. A
small amount of HCl is carried out with this. This stream is also analyzed by FT-IR spectroscopy.
By contrast, COC12 reacts with DFM x HCl as shown by the following equation .- . . .
., , .
,. .;, ~,'''` ';~
r~ One example of the invention with the essential inventive features is depicted in the drawing and is descri~ed in detail hereinafter. The drawing illustrates the principle of the process and ~he design of the separator.
The separator comprises two vertical pipes 1 which are connected together at the top by a U pipe 2 and at the bottom by a straight pipe 3. The two vertical pipes are each jacketed with thermostats 4, and the thermostats keep one pipe at about 20C and the other pipe at about 60C. The entire separator is filled with N,N-dialkylformamide (called DFM her~inafter) x HC1, and the DMF x HCl circulates in the two vertical pipes owing to the 20 - 60C temperature gradient.
The off-gas mixture is passed via a connector 5 into the pipe a~ 20C in countercurren~ to the circula-tion in the separator. This results in adsorption of the HCl by DFM x HCl. The resulting DFM x 2HCl flow~ into the pipe at 60C and is there thermally decomposed to DFM x HCl and HCl. The HCl escapes through the connector 6, and its purity is analyzed by FT-IR qpectroscopy.
CO2 does not form a compound with DFM x HCl and escapes through the connector 7 on the pipe at 20C. A
small amount of HCl is carried out with this. This stream is also analyzed by FT-IR spectroscopy.
By contrast, COC12 reacts with DFM x HCl as shown by the following equation .- . . .
., , .
,. .;, ~,'''` ';~
3 ~ ~ ,~a z ~ 0 0 5 0 / 4 2 6 6 2 C ¦ \ / ~) N + COC12 _ 2D. / ~ C19 + C02 Vilsmeier complex CO2 likewise escapeis through the connector 7 from the separator, while the Vilsmeier complex can be used, after a certain concentration in the separator, for converting carboxylic acids into carbonyl chlorides.
It is evident from what has been said that the separator according to the invention can be used to remove in a straightforward manner HCl from the off-gas mixture, and to make COC12 available for reuse.
EXAMPLE
A separator as described abova with a capacity of 1.2 1 i9 filled with 8 mol of N,N-diethylfonmamide, called DEF hereinafter. DEF x HCl is produced by metering in 8 mol of HCl. After this single preparation of the DEF x HCl and the adjustment of the separator to ~he appropriate temperatures, the purification of the off-gas mixture can start. About 100 1 of off-~as mix~ure per hour are passed through the separa~or. CO2 wi~h less than 10% of the HCl is discharged from the cooler pipe. The COCl2 content in this CO2/HC1 mixture is below the detec-tion limit of 0.01%. More than 90% of the HCl introduced - : . . ;: . :
, . :
.
,j . .
It is evident from what has been said that the separator according to the invention can be used to remove in a straightforward manner HCl from the off-gas mixture, and to make COC12 available for reuse.
EXAMPLE
A separator as described abova with a capacity of 1.2 1 i9 filled with 8 mol of N,N-diethylfonmamide, called DEF hereinafter. DEF x HCl is produced by metering in 8 mol of HCl. After this single preparation of the DEF x HCl and the adjustment of the separator to ~he appropriate temperatures, the purification of the off-gas mixture can start. About 100 1 of off-~as mix~ure per hour are passed through the separa~or. CO2 wi~h less than 10% of the HCl is discharged from the cooler pipe. The COCl2 content in this CO2/HC1 mixture is below the detec-tion limit of 0.01%. More than 90% of the HCl introduced - : . . ;: . :
, . :
.
,j . .
- 4 - o.z. 0050/42662 with the off-gas mixture is transported into the tube at 60Co After tha thermal decomposition of the DEF x 2HCl, the escaping HCl has a purity exceeding 99%.
, . ~ ! .
~ ', ' , , ' ; ~ ~' , , .',
, . ~ ! .
~ ', ' , , ' ; ~ ~' , , .',
Claims (2)
1. A continuous process for purifying an off-gas composed of CO2 + HCl + COC12, which comprises using a separator filled with N,N-dialkylformamide x HCl - to react COCl2 with N,N-dialkylformamide to give the Vilsmeier complex + CO2, and - to remove CO2/HCl and HCl separately from the separator.
2. A separator for carrying out the process as claimed in claim 1, wherein two vertical pipes 1 are connected together at the top via a U pipe 2 and at the bottom by a straight pipe 3, the two vertical pipes each have a connector 6 and 7 at the top, and one vertical pipe has a connector 5 in the lower part, and the two vertical pipes are jacketed with thermostats 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4130427A DE4130427A1 (en) | 1991-09-13 | 1991-09-13 | CONTINUOUS METHOD FOR PURIFYING AN EXHAUST GAS consisting of CO (DOWN ARROW) 2 (DOWN ARROW) + HCL + COCL (DOWN ARROW) 2 (DOWN ARROW) |
| DEP4130427.6 | 1991-09-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2077235A1 true CA2077235A1 (en) | 1993-03-14 |
Family
ID=6440489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002077235A Abandoned CA2077235A1 (en) | 1991-09-13 | 1992-08-31 | Continuous purification of an off-gas composed of co2 + hc1 + coc12 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5391363A (en) |
| EP (1) | EP0531836B1 (en) |
| JP (1) | JPH05208807A (en) |
| AT (1) | ATE132389T1 (en) |
| CA (1) | CA2077235A1 (en) |
| DE (2) | DE4130427A1 (en) |
| DK (1) | DK0531836T3 (en) |
| ES (1) | ES2081534T3 (en) |
| GR (1) | GR3018993T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693191A (en) * | 1994-11-23 | 1997-12-02 | The Dow Chemical Company | Process for recovery of anhydrous hydrogen chloride from mixtures with non-condensable gases |
| DE102004044592A1 (en) | 2004-09-13 | 2006-03-30 | Basf Ag | Process for the separation of hydrogen chloride and phosgene |
| CN108557766B (en) * | 2018-02-11 | 2019-12-27 | 浙江博瑞电子科技有限公司 | Refining method of hydrogen chloride |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798875A (en) * | 1972-02-22 | 1974-03-26 | Ici Ltd | Recovery of hydrogen fluoride |
| US4104364A (en) * | 1977-07-05 | 1978-08-01 | The United States Of America As Represented By The Secretary Of The Army | Method for hydrolyzing phosgene |
| DE2734573A1 (en) * | 1977-07-30 | 1979-02-08 | Hoechst Ag | PROCESS FOR THE DECOMPOSITION OF PHOSGENE |
| DE2805933C2 (en) * | 1978-02-13 | 1980-04-30 | Chemische Werke Huels Ag, 4370 Marl | Process for splitting off hydrogen chloride from solutions of amine hydrochlorides |
| DE3533577A1 (en) * | 1985-09-20 | 1987-03-26 | Wacker Chemitronic | METHOD FOR THE TREATMENT OF EXHAUST GASES CONTAINING CHLORSILANE AND HYDROCHLORINE |
| DE4039750A1 (en) * | 1990-12-13 | 1992-06-17 | Basf Ag | METHOD FOR REMOVING PHOSGEN FROM EXHAUST GAS |
-
1991
- 1991-09-13 DE DE4130427A patent/DE4130427A1/en not_active Withdrawn
-
1992
- 1992-08-29 AT AT92114804T patent/ATE132389T1/en active
- 1992-08-29 DK DK92114804.5T patent/DK0531836T3/en active
- 1992-08-29 ES ES92114804T patent/ES2081534T3/en not_active Expired - Lifetime
- 1992-08-29 EP EP92114804A patent/EP0531836B1/en not_active Expired - Lifetime
- 1992-08-29 DE DE59204901T patent/DE59204901D1/en not_active Expired - Fee Related
- 1992-08-31 CA CA002077235A patent/CA2077235A1/en not_active Abandoned
- 1992-09-07 JP JP4238148A patent/JPH05208807A/en not_active Withdrawn
- 1992-09-10 US US07/943,023 patent/US5391363A/en not_active Expired - Fee Related
-
1996
- 1996-02-14 GR GR960400395T patent/GR3018993T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE132389T1 (en) | 1996-01-15 |
| JPH05208807A (en) | 1993-08-20 |
| GR3018993T3 (en) | 1996-05-31 |
| ES2081534T3 (en) | 1996-03-16 |
| EP0531836B1 (en) | 1996-01-03 |
| US5391363A (en) | 1995-02-21 |
| DE4130427A1 (en) | 1993-03-18 |
| EP0531836A1 (en) | 1993-03-17 |
| DE59204901D1 (en) | 1996-02-15 |
| DK0531836T3 (en) | 1996-02-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |