US2725408A - Recovery of trichlorobenzene - Google Patents
Recovery of trichlorobenzene Download PDFInfo
- Publication number
- US2725408A US2725408A US301983A US30198352A US2725408A US 2725408 A US2725408 A US 2725408A US 301983 A US301983 A US 301983A US 30198352 A US30198352 A US 30198352A US 2725408 A US2725408 A US 2725408A
- Authority
- US
- United States
- Prior art keywords
- trichlorobenzenes
- trichlorobenzene
- mixture
- sulfuric acid
- heating
- 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 - Lifetime
Links
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 title description 21
- 238000011084 recovery Methods 0.000 title description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005869 desulfonation reaction Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000006326 desulfonation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- IGYCPGJYQTZLOJ-UHFFFAOYSA-N 1,2,3,3,4-pentachlorocyclohexene Chemical compound ClC1CCC(Cl)=C(Cl)C1(Cl)Cl IGYCPGJYQTZLOJ-UHFFFAOYSA-N 0.000 description 1
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BBVBQZMAIGLBMA-UHFFFAOYSA-N benzene;hexahydrochloride Chemical class Cl.Cl.Cl.Cl.Cl.Cl.C1=CC=CC=C1 BBVBQZMAIGLBMA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
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
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Definitions
- the present invention relates to the recovery of trichlorobenzenes, particularly from trichlorobenzenes that have been sulfonated.
- Sulfonated trichlorobenzene appears to be particularly reluctant to desulfonate under the standard desulfonating treatments, such as steam distillation or boiling with 85% sulfuric acid in water.
- Further objects of the present invention include the provision of a desulfonating technique for readily hydrolyzing sulfonated trichlorobenzenes back to trichlorobenzene.
- the desired desulfonation is readily eifected by heating the sulfonated trichlorobenzene with an aqueous sulfuric acid having an acid concentration of 75 to 90 per cent by weight, while bubbling an inert gas through the hot mixture to flush out vapors of desulfonated trichlorobenzene.
- this is followed by cooling the effluent gas to thereby cause the trichlorobenzene vapor which is carried off in this gas to be condensed from it.
- a feature of the invention is that the desulfonating acid can be the same reagent producing the original sulfonated trichlorobenzene, but with additional water added to bring down the acid concentration towithin the effective range.
- a mixture of sulfonated trichlorobenzenes was first prepared by sulfonating a commercial mixture of chlorobenzenes derived from the dehydrochlorination of insecticidal inactive benzene hexachloride isomers.
- the dehydrochlorinated mixture contained:
- the diluted layer was then reheated without transferring it from the original reaction container and nitrogen was bubbled through by means of an additional tube inserted into the flask.
- the reflux condenser was replaced by a conventional distillation condenser. A slow stream of nitrogen, barely sufficient to make itself felt, caused trichlorobenzene and water to distill over at a relatively high rate and a 56 per cent yield of desulfonated trichlorobenzene was thus recovered.
- inert gases such as helium, or other noble gases
- carbon dioxide, carbon monoxide, oxygen, or air can be used with equal effectiveness.
- Water vapor does not appear to be inert for the purposes of the desulfonation reaction which involves hydrolysis.
- the method of treating a mixture of 1,2,3- and 1,2,4- trichlorobenzenes which comprises the steps of heating the mixture with an anhydrous sulfuric acid to partially and disproportionately sulfonate the trichlorobenzenes, then removing the unsulfonated trichlorobenzenes which are now richer in the 1,2,4-isomer, diluting the remainder of the reaction mixture with water to a sulfuric acid concentration of from 75 to 90 per cent by weight, heating the thus diluted material and bubbling an inert gas through it to carry off vapors of desulfonated trichlorobenzenes and cooling the efiluent gas to condense out these trichlorobenzenes.
Description
2,725,408 RECOVERY OF TRICHLOROBENZENE Lucy Merritt, Oak Park, Mich., assignor to Ethyl Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application July 31, 1952, Serial No. 301,983
2 Claims. (Cl. 260650) The present invention relates to the recovery of trichlorobenzenes, particularly from trichlorobenzenes that have been sulfonated.
Sulfonated trichlorobenzene appears to be particularly reluctant to desulfonate under the standard desulfonating treatments, such as steam distillation or boiling with 85% sulfuric acid in water.
Among the objects of the present invention is the avoidance of the above difiiculty.
Further objects of the present invention include the provision of a desulfonating technique for readily hydrolyzing sulfonated trichlorobenzenes back to trichlorobenzene.
The above as well as still further objects of the present invention will be more clearly understood from the fol-- lowing description of several of its exemplifications.
According to the present invention, the desired desulfonation is readily eifected by heating the sulfonated trichlorobenzene with an aqueous sulfuric acid having an acid concentration of 75 to 90 per cent by weight, while bubbling an inert gas through the hot mixture to flush out vapors of desulfonated trichlorobenzene. Advantageously this is followed by cooling the effluent gas to thereby cause the trichlorobenzene vapor which is carried off in this gas to be condensed from it.
A feature of the invention is that the desulfonating acid can be the same reagent producing the original sulfonated trichlorobenzene, but with additional water added to bring down the acid concentration towithin the effective range.
Although it is not clearly understood just how the desulfonation of the present invention takes place, it has been observed that when the passage of the inert gas is interrupted, the desulfonation is markedly reduced in velocity and apparently completely stops after it progresses to a small extent, regardless of the acid strength used.
As illustrative of the present invention, a mixture of sulfonated trichlorobenzenes was first prepared by sulfonating a commercial mixture of chlorobenzenes derived from the dehydrochlorination of insecticidal inactive benzene hexachloride isomers. The dehydrochlorinated mixture contained:
68.4% of 1,2,4-trichlorobenzene 24.7% of 1,2,3-trichlorobenzene 1.0% of 1,2-dichlorobenzene 1.5% of 1,3-dichlorobenzene .6% of 1,4-dichlorobenzene 1.8% of 1,2,4,S-tetrachlorobenzene .7% of 1,2,3,4-tetrachlorobenzene .6% of l,2,3,S-tetrachlorobenzene the remainder being essentially pentachlorocyclohexene. The sulfonation was carried out in a four-necked flask 2,725,408 Patented Nov. 29, 1955 ICC? equipped with stirrer, thermometer, dropping funnel and reflux condenser. The latter was connected to a drying tube to keep out moisture present in the atmosphere. Sulfuric acid in an amount equal to the weight of the mixed chloro compounds, was utilized as the solvent. The mixed chloro compounds were added to the acid and the mixture stirred and heated until a temperature of C. was reached. Suflicient 15 per cent fuming sulfuric acid was added to react with all the l,2,3-trichloro-' benzene present. When the addition was complete, heating and stirring was continued for 4- /2 hours. The reaction mixture was allowed to cool and separated into two layers. The top layer, which consisted of unsulfonated chloro compounds was removed. As a result of this treatment, the 1,2,3-trichlor0benzene was essentially completely sulfonated, while the 1,2,4-isomer was largely unreacted. Thus a means of separation of the two isomers was provided. The lower layer, which was the acid layer, was diluted with water until an acid content of 85 per cent was reached.
The diluted layer was then reheated without transferring it from the original reaction container and nitrogen was bubbled through by means of an additional tube inserted into the flask. At the same time, the reflux condenser was replaced by a conventional distillation condenser. A slow stream of nitrogen, barely sufficient to make itself felt, caused trichlorobenzene and water to distill over at a relatively high rate and a 56 per cent yield of desulfonated trichlorobenzene was thus recovered.
The same reaction-promoting effect of the nitrogen stream is obtained when a sulfonated pure 1,2,4-trichlorobenzene, pure 1,2,3-trichlorobenzene, or pure 1,3,5-trichlorobenzene is used in place of the above mixture. Combinations of these trichlorobenzenes also respond in 'the same manner.
In place of nitrogen other inert gases such as helium, or other noble gases, carbon dioxide, carbon monoxide, oxygen, or air can be used with equal effectiveness. Water vapor does not appear to be inert for the purposes of the desulfonation reaction which involves hydrolysis.
As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope hereof, it is to be understood that the invention is not limited to the specific embodiments hereof except as defined in the appended claims.
I claim:
1. The method of treating a mixture of 1,2,3- and 1,2,4- trichlorobenzenes which comprises the steps of heating the mixture with an anhydrous sulfuric acid to partially and disproportionately sulfonate the trichlorobenzenes, then removing the unsulfonated trichlorobenzenes which are now richer in the 1,2,4-isomer, diluting the remainder of the reaction mixture with water to a sulfuric acid concentration of from 75 to 90 per cent by weight, heating the thus diluted material and bubbling an inert gas through it to carry off vapors of desulfonated trichlorobenzenes and cooling the efiluent gas to condense out these trichlorobenzenes.
2. The method of claim 1 in which the inert gas is nitrogen.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. THE METHOD OF TREATING A MIXTURE OF 1,2,30AND 1,2,4TRICHLOROBENZENES WHICH COMPRISES THE STEPS OF HEATING THE MIXTURE WITH AN ANHYDROUS SULFURIC ACID TO PARTIALLY AND DISPROPORTIONATELY SULFONATE THE TRICHLOROBENZENES, THEN REMOVING THE UNSULFONATED TRICHLOROBENZENES WHICH ARE NOW RICHER IN THE 1,2,4-ISOMER, DILUTING THE REMAINDER OF THE REACTION MIXTURE WITH WATER TO A SULFURIC ACID CONCENTRATION OF FROM 75 TO 90 PER CENT BY WEIGHT, HEATING THE THUS DILUTED MATERIAL AND BUBBLING AN INERT GAS THROUGH IT TO CARRY OFF VAPORS OF DESULFONATED TRICHLOROBENZENES AND COOLING THE EFFLUENT GAS TO CONDENSE OUT THESE TRICHLOROBENZENES.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US301983A US2725408A (en) | 1952-07-31 | 1952-07-31 | Recovery of trichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US301983A US2725408A (en) | 1952-07-31 | 1952-07-31 | Recovery of trichlorobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2725408A true US2725408A (en) | 1955-11-29 |
Family
ID=23165752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US301983A Expired - Lifetime US2725408A (en) | 1952-07-31 | 1952-07-31 | Recovery of trichlorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2725408A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1766747A (en) * | 1927-10-05 | 1930-06-24 | Gen Aniline Works Inc | Process for manufacturing vic. trihalogenbenzenes |
| US2432737A (en) * | 1945-03-19 | 1947-12-16 | Mathieson Alkali Works Inc | Production of dichlorostyrenes |
| US2511167A (en) * | 1947-06-12 | 1950-06-13 | Us Rubber Co | Recovery of chlorobenzene |
-
1952
- 1952-07-31 US US301983A patent/US2725408A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1766747A (en) * | 1927-10-05 | 1930-06-24 | Gen Aniline Works Inc | Process for manufacturing vic. trihalogenbenzenes |
| US2432737A (en) * | 1945-03-19 | 1947-12-16 | Mathieson Alkali Works Inc | Production of dichlorostyrenes |
| US2511167A (en) * | 1947-06-12 | 1950-06-13 | Us Rubber Co | Recovery of chlorobenzene |
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