CN104671219A - Sulfuric chloride separation and purification technique - Google Patents
Sulfuric chloride separation and purification technique Download PDFInfo
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- CN104671219A CN104671219A CN201310636403.0A CN201310636403A CN104671219A CN 104671219 A CN104671219 A CN 104671219A CN 201310636403 A CN201310636403 A CN 201310636403A CN 104671219 A CN104671219 A CN 104671219A
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- chloride
- sulfuryl chloride
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- purifying
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4561—Compounds containing sulfur, halogen and oxygen only
- C01B17/4592—Sulfuryl chloride (SO2Cl2)
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a technique for separating and purifying sulfuric chloride from a trifluoro-acetyl chloride production reaction waste liquid by a double-tower rectification process. The technique can obtain the high-purity sulfuric chloride product, and has the advantage of low production cost. The prepared sulfuric chloride can be used for chlorination of aromatic compounds and the like.
Description
Technical field
The present invention relates to a kind of sulfuryl chloride purification technique, especially relate to the purification technique of sulfuryl chloride in a kind of trifluoroacetyl chloride production process waste reaction solution.
Background technology
Sulfuryl chloride is a kind of important Chemicals, can be used for the chlorination of the chlorination of aromatics, the chlorination of carboxylic acid and other various organic and mineral compound, also for the manufacture of pharmaceuticals, dyestuff, tensio-active agent etc.Its preparation method mainly comprises three kinds: (1) chlorination process, the sulfurous gas of drying and chlorine is reacted under activated-carbon catalyst exists, and the sulfuryl chloride of generation, through condensation, obtains sulfuryl chloride finished product; (2) be that catalyzer makes sulfurous gas and chlorine direct reaction obtain sulfuryl chloride with gac or camphor; (3) fixed bed catalyst is passed through by Freon 113 (CFC-113a or R113a) and sulphur trioxide.
For the third production method, in reaction product except trifluoroacetyl chloride and sulfuryl chloride, also comprise unreacted Freon 113, sulphur trioxide (SO
3) and the impurity such as pyrosulfuryl chloride that produces of side reaction.Reaction product obtains trifluoroacetyl chloride gas products through condensation separation, remaining phlegma is by the recyclable part Freon 113 of air distillation and sulphur trioxide, but the purity of sulfuryl chloride is only about 70% in still liquid, do not reach first grade requirement (>95%), can not effectively utilize.
Existing technique adopts simple rectifying to extract R113a and SO
3after, by raffinate in hydrolysis kettle to reclaim the R113a remained, meanwhile, sulfuryl chloride then creates the strong acid waste liquids such as a large amount of sulfuric acid and hydrochloric acid because of hydrolysis, cause the significant wastage of sulfuryl chloride important by-products resource.If purified to sulfuryl chloride product and utilize, not only can effectively reduce trifluoroacetyl chloride production cost, and the large shortcoming of existing technique spent acid quantity discharged can be overcome.
Summary of the invention
The invention provides a kind of technique of separating-purifying sulfuryl chloride from trifluoroacetyl chloride production process waste reaction solution, trifluoroacetyl chloride production cost can be reduced, overcome the large shortcoming of existing technique spent acid quantity discharged.
Sulfuryl chloride of the present invention is obtained by fixed bed catalyst by Freon 113 (CFC-113a) and sulphur trioxide, and reaction equation is as follows:
SO
3+CF
3CCl
3→SO
2Cl
2+CF
3COCl↑
In sulfuryl chloride building-up process, usually containing sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride etc. in its product mixture, count in mass ratio: sulfuryl chloride 70% ~ 85%, Freon 113 1% ~ 10%, sulphur trioxide 10% ~ 20%, pyrosulfuryl chloride 2% ~ 5%.At ambient pressure (101.325kPa), the boiling point of sulfuryl chloride is 69.1 DEG C, Freon 113 boiling point is 46.0 DEG C, sulphur trioxide boiling point is 44.8 DEG C, three's boiling point is comparatively close, common distillation operation is difficult to three to be separated, and the present invention obtains highly purified sulfuryl chloride by the means of two stage rectification, specific as follows:
Produce a technique for separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride, adopt double columns rectification process, comprise the following steps:
(1) one-level rectifying tower (3) is sent in the logistics (2) containing sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride and carry out rectifying, control rectification temperature 90 ~ 110 DEG C, reflux ratio is 3 ~ 7, the logistics (5) that tower top obtains being essentially Freon 113 and sulphur trioxide is circulated to trifluoroacetyl chloride reactor (1), and tower bottom obtains the logistics (4) being mainly sulfuryl chloride and pyrosulfuryl chloride;
(2) two-stage rectification tower (8) is sent in logistics (4) and carry out rectifying, controlling rectification temperature is 120 ~ 140 DEG C, and reflux ratio is 1 ~ 7, and tower top obtains high purity sulfuryl chloride finished product (9), and tower bottom obtains the high boiling material (10) containing pyrosulfuryl chloride.
As preferred mode, in above-mentioned steps (1), one-level rectifying tower (3) is preferably packing tower, and theoretical plate number is preferably 5 ~ 12, and the temperature that overhead distillate is essentially the logistics (5) of Freon 113 and sulphur trioxide is 50 ~ 70 DEG C; In above-mentioned steps (2), two-stage rectification tower (8) is preferably packing tower, and theoretical plate number is preferably 7 ~ 10; Filler in described one-level rectifying tower (3) and two-stage rectification tower (8) is preferably glass filler or ceramic packing.
After above-mentioned steps (1) first step rectifying, tower top place obtains being essentially in the logistics (5) of Freon 113 and sulphur trioxide, and pyrosulfuryl chloride content is less than 0.1%, and sulfuryl chloride mass content is less than 1%.
The purity of the sulfuryl chloride finished product prepared through the present invention is more than 98%, and as preferred mode, the purity of sulfuryl chloride finished product is more than 99%.
Compared with prior art, the present invention has following beneficial effect:
(1) two stage rectification technique, can sulfuryl chloride in efficient recovery trifluoroacetyl chloride production process waste reaction solution, and sulfuryl chloride product purity reaches more than 98%, the rate of recovery reaches 60% ~ 80%;
(2) recycling is carried out to trifluoroacetyl chloride production process waste reaction solution, not only environmental protection, and effectively can reduce the production cost of trifluoroacetyl chlorine products.
Accompanying drawing explanation
Fig. 1 is sulfuryl chloride separating-purifying double columns rectification process flow process, wherein:
1-trifluoroacetyl chloride reactor, 2-contains the production waste reaction solution of sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride, 3-one-level rectifying tower, 4-will be the logistics of sulfuryl chloride and pyrosulfuryl chloride, and 5-is essentially the logistics of Freon 113 and sulphur trioxide, 6-low-boiling-point substance products pot, 7-is essentially the logistics of Freon 113 and sulphur trioxide, 8-two-stage rectification tower, 9-sulfuryl chloride finished product, 10-is containing the high boiling material of pyrosulfuryl chloride
Embodiment
Below in conjunction with concrete real examination example, the present invention is further described, but these embodiments can not be limit the invention to.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in right.
Embodiment 1
Accompanying drawing Fig. 1 adopts double tower continuous atmospheric distillation separating-purifying sulfuryl chloride to specifications, produce waste reaction solution (2) from trifluoroacetyl chloride production line, wherein the mass content of sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride is respectively 80%, 5%, 12% and 3%.One-level rectifying tower (3) and two-stage rectification tower (8) all load glass spring filler.Waste reaction solution (2) will be produced pass into one-level rectifying tower (3) and carry out rectifying, control tower top and bottom temperature are respectively 48 ~ 56 DEG C and 100 ~ 105 DEG C, the reflux ratio of one-level rectifying tower (3) is 5, theoretical plate number 10 pieces, the logistics (5) being essentially Freon 113 and sulphur trioxide is obtained from tower top, be circulated to reactor (1) and proceed reaction, tower bottom obtains the logistics (4) being mainly sulfuryl chloride, and wherein the mass content of sulfuryl chloride is about 95%.Continue that the logistics (4) being mainly sulfuryl chloride is passed into two-stage rectification tower (8) and carry out rectifying, control tower top and bottom temperature are respectively 68 ~ 69.5 DEG C and about 130 DEG C, rectifier column reflux ratio is 3, theoretical plate number 8 pieces, collect from tower top and obtain high purity sulfuryl chloride finished product (9), purity is 98.6%, and the rate of recovery is 65.2%, and tower bottom obtains the high boiling material (10) containing pyrosulfuryl chloride.
Embodiment 2
Other conditions are with embodiment 1, change and produce waste reaction solution (2), wherein the mass content of sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride is respectively 85%, 7%, 4% and 4%, collects obtain from two-stage rectification tower (8) tower top, purity is 98.2%, and the rate of recovery is 80.3%.
Embodiment 3
Other conditions are with embodiment 1, and the reflux ratio changing one-level rectifying tower (3) is 5, and the purity of the high purity sulfuryl chloride finished product (9) obtained after two-stage rectification is 99.1%, and the rate of recovery is 75.4%.
Embodiment 4
Other conditions are with embodiment 1, and the reflux ratio changing two-stage rectification tower (8) is 7, and the purity of the high purity sulfuryl chloride finished product (9) obtained after two-stage rectification is 99.5%, and the rate of recovery is 68.7%.
Claims (8)
1. produce a technique for separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride, it is characterized in that adopting double columns rectification process, comprise the following steps:
(1) one-level rectifying tower (3) is sent in the logistics (2) containing sulfuryl chloride, Freon 113, sulphur trioxide and pyrosulfuryl chloride and carry out rectifying, control rectification temperature 90 ~ 110 DEG C, reflux ratio is 3 ~ 7, the logistics (5) that tower top obtains being essentially Freon 113 and sulphur trioxide is circulated to trifluoroacetyl chloride reactor (1), and tower bottom obtains the logistics (4) being mainly sulfuryl chloride and pyrosulfuryl chloride;
(2) two-stage rectification tower (8) is sent in logistics (4) and carry out rectifying, controlling rectification temperature is 120 ~ 140 DEG C, and reflux ratio is 1 ~ 7, and tower top obtains high purity sulfuryl chloride finished product (9), and tower bottom obtains the high boiling material (10) containing pyrosulfuryl chloride.
2., according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that in described step (1), one-level rectifying tower (3) is packing tower, theoretical plate number is 5 ~ 12.
3., according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that in described step (2), two-stage rectification tower (8) is packing tower, theoretical plate number is 7 ~ 10.
4., according to the technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride described in Claims 2 or 3, it is characterized in that in described rectifying tower, filler is glass filler or ceramic packing.
5. according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that in described logistics (2), each main component is counted in mass ratio: sulfuryl chloride 70% ~ 85%, Freon 113 1% ~ 10%, sulphur trioxide 10% ~ 20%, pyrosulfuryl chloride 2% ~ 5%.
6., according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that the purity of described sulfuryl chloride finished product (9) is more than 98%.
7. according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that described step (1) tower top place obtains being essentially in the logistics (5) of Freon 113 and sulphur trioxide, pyrosulfuryl chloride content is less than 0.1%, and sulfuryl chloride mass content is less than 1%.
8., according to technique of producing separating-purifying sulfuryl chloride waste reaction solution from trifluoroacetyl chloride according to claim 1, it is characterized in that the temperature that the middle overhead distillate of described step (1) is essentially the logistics (5) of Freon 113 and sulphur trioxide is 50 ~ 70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310636403.0A CN104671219A (en) | 2013-12-02 | 2013-12-02 | Sulfuric chloride separation and purification technique |
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|---|---|---|---|
| CN201310636403.0A CN104671219A (en) | 2013-12-02 | 2013-12-02 | Sulfuric chloride separation and purification technique |
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| CN104671219A true CN104671219A (en) | 2015-06-03 |
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|---|---|---|---|
| CN201310636403.0A Pending CN104671219A (en) | 2013-12-02 | 2013-12-02 | Sulfuric chloride separation and purification technique |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540219A (en) * | 2018-09-30 | 2019-12-06 | 山东潍坊润丰化工股份有限公司 | Resource utilization method of industrial byproduct sodium chloride |
| CN115285942A (en) * | 2022-07-04 | 2022-11-04 | 山东奥友化学有限责任公司 | Sulfuryl chloride environment-friendly closed cycle rectification process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725475A (en) * | 1969-04-05 | 1973-04-03 | Kali Chemie Ag | Process of preparing fluorine containing perhalogencarboxylic acid fluorides or chlorides |
| US5296640A (en) * | 1992-09-15 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Process for preparing perhaloacyl chlorides |
| CN102351681A (en) * | 2011-08-16 | 2012-02-15 | 浙江大学 | Method for continuously synthesizing trifluoroacetyl chloride and sulfuryl fluoride |
-
2013
- 2013-12-02 CN CN201310636403.0A patent/CN104671219A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725475A (en) * | 1969-04-05 | 1973-04-03 | Kali Chemie Ag | Process of preparing fluorine containing perhalogencarboxylic acid fluorides or chlorides |
| US5296640A (en) * | 1992-09-15 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Process for preparing perhaloacyl chlorides |
| CN102351681A (en) * | 2011-08-16 | 2012-02-15 | 浙江大学 | Method for continuously synthesizing trifluoroacetyl chloride and sulfuryl fluoride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540219A (en) * | 2018-09-30 | 2019-12-06 | 山东潍坊润丰化工股份有限公司 | Resource utilization method of industrial byproduct sodium chloride |
| CN115285942A (en) * | 2022-07-04 | 2022-11-04 | 山东奥友化学有限责任公司 | Sulfuryl chloride environment-friendly closed cycle rectification process |
| CN115285942B (en) * | 2022-07-04 | 2023-12-22 | 山东奥友化学有限责任公司 | Environment-friendly closed circulation rectification process for sulfuryl chloride |
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Application publication date: 20150603 |