CN102391159B - Process and system for recovering sulfonic acid mother liquor by dewatering - Google Patents
Process and system for recovering sulfonic acid mother liquor by dewatering Download PDFInfo
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- CN102391159B CN102391159B CN 201110316313 CN201110316313A CN102391159B CN 102391159 B CN102391159 B CN 102391159B CN 201110316313 CN201110316313 CN 201110316313 CN 201110316313 A CN201110316313 A CN 201110316313A CN 102391159 B CN102391159 B CN 102391159B
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- mother liquor
- toluene
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Abstract
The invention discloses a process and system for recovering sulfonic acid mother liquor by dewatering, relating to the field of chemical engineering. In the invention, through dewatering and concentrating the sulfonic acid mother liquor, a mixed acid of a high-concentration sulfuric acid and a sulfonic acid is obtained, and then toluene in the mother liquor is separated for recovery; the obtained sulfonic acid mother liquor subjected to dewatering and the toluene can be reused in sulfonation reactions; and the sulfonic acid part in the sulfonic acid mother liquor subjected to dewatering can be recycled through sulfonation and crystallization processes, thereby achieving the purpose of carrying out various multi-item recycling on the sulfonic acid mother liquor. By using the process and system disclosed by the invention, the recovery rates of toluene, a sulfuric acid and a sulfonic acid are effectively improved, and the toluene, the sulfuric acid and the sulfonic acid can be reused in sulfonation reactions, so that the consumption of main materials in the process of production is significantly reduced, and the consumption of the toluene is reduced by more than 10%; and the process is good in continuity and strong in controllability, and because of recycling the mother liquor, the emission of the 'three wastes' is reduced, thereby saving the production cost and reducing the pollution to the environment.
Description
Technical field
The present invention relates to chemical field, is a kind of sulfonic acid mother liquor dewatering and recovery technology and the system that is applied to produce in the p-methyl benzenesulfonic acid process specifically.
Background technology
In the process of Chemical Manufacture p-methyl benzenesulfonic acid, be sulphonating agent sulfonation toluene with the vitriol oil, use partial crystallization selectivity principle to produce p-methyl benzenesulfonic acid then, isolate sulfonic acid crystal and mother liquor through decrease temperature crystalline after the sulfonation reaction.This handicraft product purity is higher, uses extensively, but inevitably produces excessive sulfonic acid mother liquor in producing.Analyze by the p-sulfonic acid mother liquor composition, contain sulfuric acid (H
2SO
4) 25～40%, sulfonic acid 35～45%, H
2O15～25%.The sulfonic acid mother liquor of this surplus is used for industries such as casting usually as the low value spent acid, wasted organism part wherein.
Summary of the invention
For solving the technical problem of above-mentioned existence, the invention provides a kind of sulfonic acid mother liquor dewatering and recovery technology, with the dehydration of sulfonic acid mother liquor, the concentrated nitration mixture that obtains high-concentration sulfuric acid, sulfonic acid, and the toluene in the mother liquor separated recovery, with sulfonic acid mother liquor after the dehydration that obtains and toluene recycling in sulfonation reaction, sulfonic acid part in the sulfonic acid mother liquor of dehydration back can obtain recycling after oversulfonate, Crystallization Procedure, reaches the classify purpose of multinomial recycling of sulfonic acid mother liquor.
For achieving the above object, the technical solution used in the present invention is as follows: a kind of sulfonic acid mother liquor dewatering and recovery technology, realized by the following step:
1) the sulfonic acid mother liquor is carried out underpressure distillation dehydration, toluene vapor and the water vapor of generation cool off, the cooling of lowering the temperature of the sulfonic acid mother liquor part after the dehydration, and another part is directly used in complex acid;
2) toluene vapor and water vapor obtain liquid and toluene non-condensable gas after overcooling, liquid carries out the toluene water sepn, the toluene non-condensable gas forms the toluene water mixed liquid through the washing cooling, carries out the toluene water sepn again, and the toluene recycling that said two devices obtains after separating is in sulfonation reaction;
3) the sulfonic acid mother liquor after the dehydration is through the part of cooling cooling, by absorbing SO
3Gas forms oleum, mixes with another part dehydration back sulfonic acid mother liquor that cools off, and recycling is in sulfonation reaction.
The mass concentration of sulfuric acid is 45-60% in the sulfonic acid mother liquor in the step 1) after the dehydration, and the mass concentration of sulfonic acid is 40-60%.
Described volume ratio of mixing with the oleum of generation without a part of sulfonic acid mother liquor of cooling is 1:1～1.4:1.
A kind of sulfonic acid mother liquor dewatering and recovery system, include dehydration still, water cooler I, absorption tower, water cooler II, surge tank, water-jet pump, toluene water separator, toluene accumulator tank and complex acid groove, described dehydration still is connected with water cooler I, water cooler II, complex acid groove respectively; Described water cooler I is connected in turn with absorption tower, complex acid groove; Described water cooler II is connected in turn with surge tank, toluene water separator, toluene accumulator tank; Described surge tank is connected in turn with water-jet pump, toluene water separator.
The invention has the beneficial effects as follows: the present invention adopts multistage temperature controlled vacuum system, assurance low-pressure distillation sulfonic acid mother liquor dehydration production process is separated with the automatic of toluene water, effectively improved the rate of recovery of toluene, sulfuric acid, sulfonic acid, and with its recycle in sulfonation reaction, make that main raw material(s) consumption obviously reduces in the production process, toluene consumption reduces more than 10%; The continuity of this technology is good, and controllability is strong, because it is recycled mother liquor, has reduced the discharging of " three wastes ", has reduced the pollution to environment when saving production cost.
Description of drawings
Accompanying drawing 1 is system architecture synoptic diagram of the present invention.
Embodiment
Describe the present invention below in conjunction with accompanying drawing 1 and specific embodiment:
According to shown in Figure 1, analysis by p-sulfonic acid mother liquor and dehydration back sulfonic acid mother liquor composition as can be known, can concentrate described sulfonic acid mother liquor by the mode of underpressure distillation dehydration, improve in the mother liquor after the vitriol oil concentration, it is the sulfonation reaction that reusable edible carries out next step, simultaneously can separate out sulfonic acid xln recycling, and the toluene vapor that distills out and water vapor can be through repeatedly cooling, toluene water sepn and obtain toluene, recycling is in sulfonation reaction, thereby reaches the purpose of the multinomial recycling of classification.
Concrete sulfonic acid mother liquor dewatering and recovery technology, realized by the following step:
1) the sulfonic acid mother liquor is carried out the underpressure distillation dehydration, toluene vapor and the water vapor of generation cool off, sulfonic acid mother liquor after the dehydration that contains 45-60% sulfuric acid, 40-60% sulfonic acid that obtains, a part
(accounting for the 30%-60% of dehydration back sulfonic acid mother liquor total amount)The cooling of lowering the temperature, another part
(accounting for the 40%-70% of dehydration back sulfonic acid mother liquor total amount)Be directly used in complex acid;
2) toluene vapor and water vapor obtain liquid and toluene non-condensable gas after overcooling, liquid carries out the toluene water sepn, the toluene non-condensable gas forms the toluene water mixed liquid through the washing cooling, carries out the toluene water sepn again, and the toluene recycling that said two devices obtains after separating is in sulfonation reaction;
3) the sulfonic acid mother liquor after the dehydration is through the part of cooling cooling, by absorbing SO
3Gas forms oleum, dewaters back sulfonic acid mother liquor according to volume ratio with the another part that cools off
1:1-1:1.4 ratioMix, recycling is in sulfonation reaction.
Under the prerequisite that adopts multistage temperature controlled vacuum system, sulfonic acid mother liquor dewatering and recovery system, include dehydration still 1, water cooler I 2, absorption tower 3, water cooler II 4, surge tank 5, water-jet pump 6, toluene water separator 7, toluene accumulator tank 8 and complex acid groove 9, described dehydration still 1 is connected with water cooler I 2, water cooler II 4, complex acid groove 9 respectively; Described water cooler I 2 is connected in turn with absorption tower 3, complex acid groove 9; Described water cooler II 4 is connected in turn with surge tank 5, toluene water separator 7, toluene accumulator tank 8; Described surge tank 5 is connected in turn with water-jet pump 6, toluene water separator 7.
Described dehydration still 1 is used for the p-sulfonic acid mother liquor and carries out the underpressure distillation dehydration; Described water cooler I 2 is used for a part of sulfonic acid mother liquor after the distillation is lowered the temperature, and cooling back mother liquor enters absorption tower 3; Described absorption tower 3 is used for absorbing SO
3Gas and form oleum; Described water cooler II 4 can adopt the glass cools device, is used for cooling from toluene vapor and water vapor that dehydration still 1 distills out, obtains cooling off back toluene water mixed liquid and toluene non-condensable gas; Described surge tank 5 is used for receiving the toluene water mixed liquid and the toluene non-condensable gas carries out gas-water separation; Described water spraying vacuum pump 6 forms the toluene water mixed liquid for washing that the toluene non-condensable gas is lowered the temperature; Described toluene water separator 7 is for separating of the toluene water mixed liquid; Described toluene accumulator tank 8 is used for collecting the toluene of separating; Described complex acid groove 9 is used for mixing the oleum without sulfonic acid mother liquor and formation after the dehydration of cooling.
In the production process, the sulfonic acid mother liquor that produces in the sulfonation reaction process joined in the dehydration still 1 that uses the heating of 0.4 ~ 0.6Mpa low-pressure steam heat up, guarantee between temperature of charge≤150 ℃, vacuum-0.08 ~-0.99 Mpa.
The toluene vapor that produces, water vapor enters glass condenser 4, the non-condensable gas of the liquid that cooling back produces and temperature≤35 ℃ through surge tank 5 gas-water separation after liquid enter toluene separator 7, non-condensable gas enters water-jetting type vacuum pump 6 and washs and cool to temperature≤30 ℃, the toluene water mixed liquid that forms in water-jetting type vacuum pump 6 water tanks overflow to toluene water separator 7, be used further to sulfonation reaction after isolated toluene enters toluene accumulator tank 8 in the toluene water separator 7, isolated water recycling is in cooling in the toluene water separator 7, posies such as crystallization, guarantee that water temperature is lower than 40 ℃, reach the optimum recovery effect of toluene.
A dehydration back sulfonic acid mother liquor part is cooled to temperature≤40 ℃ through dehydration stepmother liquid water cooler I 2, enters absorption tower 3 again and is used for absorbing gas SO
3Form oleum, reach acid temperature≤80 ℃; Another part is directly used in complex acid groove 9 and this oleum by the 7.5:5.5 mixed, supplies with the sulfonation post and carries out sulfonation reaction.
Classification is recycled after the separating for several times of final realization sulfonic acid mother liquor.
Claims (1)
1. a sulfonic acid mother liquor dewatering and recovery technology is characterized in that, is realized by the following step:
1) the sulfonic acid mother liquor is carried out underpressure distillation dehydration, toluene vapor and the water vapor of generation cool off, the cooling of lowering the temperature of the sulfonic acid mother liquor part after the dehydration, and another part is directly used in complex acid;
2) toluene vapor and water vapor obtain liquid and toluene non-condensable gas after overcooling, liquid carries out the toluene water sepn, the toluene non-condensable gas forms the toluene water mixed liquid through the washing cooling, carries out the toluene water sepn again, and the toluene recycling that said two devices obtains after separating is in sulfonation reaction;
3) the sulfonic acid mother liquor after the dehydration is through the part of cooling cooling, by absorbing SO
3Gas forms oleum, mixes with another part dehydration back sulfonic acid mother liquor that cools off, and recycling is in sulfonation reaction.
2. a kind of sulfonic acid mother liquor dewatering and recovery technology according to claim 1 is characterized in that, the mass concentration of sulfuric acid is 45-60% in the sulfonic acid mother liquor in the step 1) after the dehydration, and the mass concentration of sulfonic acid is 40-60%.
3. a kind of sulfonic acid mother liquor dewatering and recovery technology according to claim 1 is characterized in that, described volume ratio of mixing with the oleum of generation without the part dehydration back sulfonic acid mother liquor of cooling is 1:1～1.4:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110316313 CN102391159B (en) | 2011-10-18 | 2011-10-18 | Process and system for recovering sulfonic acid mother liquor by dewatering |
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|---|---|---|---|
| CN 201110316313 CN102391159B (en) | 2011-10-18 | 2011-10-18 | Process and system for recovering sulfonic acid mother liquor by dewatering |
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| CN102391159B true CN102391159B (en) | 2013-07-17 |
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| CN103524384B (en) * | 2013-10-21 | 2016-04-20 | 金能科技股份有限公司 | In a kind of sulfonate solution, inorganic salt sodium sulfate carries salt processing method |
| CN114516822B (en) * | 2022-03-07 | 2023-06-02 | 运城学院 | Refining and recycling method for waste sulfonic acid generated by sulfonation of alkylbenzene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1820862A (en) * | 2005-12-07 | 2006-08-23 | 锦州石化精细化工有限公司 | Process for treating alkyl benzene sulfonate filter slag |
| CN202297427U (en) * | 2011-10-18 | 2012-07-04 | 金能科技股份有限公司 | Sulfoacid mother liquor dewatering and recovery system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930702B2 (en) * | 1982-03-26 | 1984-07-28 | 三菱瓦斯化学株式会社 | Crystallization separation method of "A"-xylene-4-sulfonic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1820862A (en) * | 2005-12-07 | 2006-08-23 | 锦州石化精细化工有限公司 | Process for treating alkyl benzene sulfonate filter slag |
| CN202297427U (en) * | 2011-10-18 | 2012-07-04 | 金能科技股份有限公司 | Sulfoacid mother liquor dewatering and recovery system |
Non-Patent Citations (1)
| Title |
|---|
| JP昭58-167559A 1983.10.03 |
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