CN102675682A - Recovery and utilization method of highly toxic medium hydrothion waste gas generated in polyphenylene sulfide production - Google Patents
Recovery and utilization method of highly toxic medium hydrothion waste gas generated in polyphenylene sulfide production Download PDFInfo
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- CN102675682A CN102675682A CN2011100663275A CN201110066327A CN102675682A CN 102675682 A CN102675682 A CN 102675682A CN 2011100663275 A CN2011100663275 A CN 2011100663275A CN 201110066327 A CN201110066327 A CN 201110066327A CN 102675682 A CN102675682 A CN 102675682A
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Abstract
The invention discloses a recovery and utilization method of highly toxic medium hydrothion waste gas generated in polyphenylene sulfide production. The method includes: adopting waterish sodium sulphide and p-dichlorobenzene as raw materials to be subjected to process steps such as sodium sulphide dehydration and polycondensation to produce polyphenylene sulfide monomers, leading waste gas rich in hydrogen sulfide to be reacted with ammonia water in an alkali liquor absorption tank, leading the reaction product ammonium sulfide to be concentrated to serve as component conditioning agents for polyphenylene sulfide production to be conveyed to a reaction kettle so as to effectively regulate polymerized polyphenylene sulfide resin molecules, wherein the molecular weight distribution coefficient after regulation can keep between 1.91-1.93. After being subjected to ammonium sulfide processing and regulating, content of various metal chloride ions and non-metal chloride ions in the polyphenylene sulfide resin is small, and the total amount of metal ions is 200-300 ppm. By adopting the method, highly toxic medium hydrothion waste gas is treated and good environment protection effect is achieved; and a virtuous closed circle is formed due to the fact that the orginal water gas is converted into production raw materials capable of being reused.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material.
Background technology
Adopting alkali metalsulphide and santochlor is that raw material is produced in the technological process of polyphenylene sulfide monomer (PPS) through polycondensating process, can produce the waste gas that is rich in the hydrogen sulfide poisonous medium, and it is unfavorable that environmental protection is caused.And prior art adopts the physical absorption method, has secondary pollution.
In one Chinese patent application number CN03117750.6, introduce the absorption treatment process of hydrogen sulfide in the polyphenylene sulfide synthesis technique flow process; Pondered-over is the absorption processing of hydrogen sulfide; Really be peace often only; Though utilize the alkali lye absorbing hydrogen sulphide, the sodium sulphite that reaction generates utilizes synthetic with polyphenylene sulfide again, is not difficult to find very mediocrity of this invention.
Above shortcoming in view of prior art; The objective of the invention is to study that hypertoxic medium hydrogen sulfide waste gas reclaims and utilize method in a kind of polyphenylene sulfide production; Make it to overcome the above shortcoming of prior art, simultaneously the hydrogen sulfide good use of returning is used as the molecular weight regulator of synthetic polyphenylene sulfide, also fully utilize the synthetic heat that discharges of polyphenylene sulfide simultaneously; And will synthesize in the polyphenylene sulfide technical process sodium sulphite and deviate from water and recycle; Adopt method of the present invention, make hypertoxic medium hydrogen sulfide waste gas obtain administering on the one hand, reach good environment protecting; Constitute optimum closed cycle owing to converting original waste gas to can return use raw materials for production on the other hand.
The objective of the invention is because in the technical process of synthetic polyphenylene sulfide; At first the sodium sulphite that contains mass crystallization water is dewatered; Again because of sodium sulphite in dehydration process, handle though sodium sulphite is added basic metal highly basic, hydrolysis can take place having under the situation of water in sodium sulphite; Emit a large amount of hydrogen sulfide, the hypertoxicity of hydrogen sulfide forces it is absorbed processing.
Summary of the invention
The present invention realizes through following means
Hypertoxic medium hydrogen sulfide waste gas reclaims and utilizes method in the polyphenylene sulfide production; Adopting many water cure sodium and santochlor is that raw material is produced the polyphenylene sulfide monomer through process steps such as sodium sulphite dehydration, polycondensations; It is characterized in that; The waste gas that is rich in hydrogen sulfide is reacted with ammoniacal liquor in the alkali lye tourie; The polyphenylene sulfide molecule that again the reaction product ammonium sulfide is concentrated after accomplish polymerization as the component regulator conveying meeting reaction kettle of polyphenylene sulfide production the back is regulated effectively, and the MWD coefficient after overregulating can remain between the 1.91-1.93, and its concrete treatment process comprises:
1, the hydrogen sulfide that hydrolysis in the dehydration is produced feeds in the strong aqua of 14-18% and absorbs processing hydrogen sulfide, in tourie, is reacted into the ammonium sulfide dilute solution.
2, with 1) ammonium sulfide solution that obtains, under protection of nitrogen gas, the heat that discharges with the polyphenylene sulfide polyreaction is condensed into the 16-20%wt ammonium sulfide solution.The moisture content that is evaporated turns back to storage tank through condensing surface cooling recovery and is used for polyphenylene sulfide polyphenylene sulfide washing subsequently.
3, with 2) ammonium sulfide solution that obtains under protection of nitrogen gas, further use underpressure distillation, it is for use to make the concentration of ammonium sulfide solution become 70-80%wt.
4, with 3) to be configured to concentration be that (N-Methyl pyrrolidone) nmp solution of 1M ammonium sulfide is for use for the 70-80%wt ammonium sulfide solution that obtains.
5, with 4) (N-Methyl pyrrolidone) nmp solution of the 1M ammonium sulfide that obtains calculate good with 0.1-0.5mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is that insulation 1h gets final product under 260-280 ℃ the condition in temperature.Various metals and nonmetal cl ions are low in the polyphenylene sulfide after processing is regulated through ammonium sulfide, and the metals ion total amount is at 200-300ppm, and nonmetal cl ions total amount is at 300-500ppm, and the melt flow index of polyphenylene sulfide is at 220-240g/10min.Weight-average molecular weight is between 46000-48000.
In the ammoniacal liquor tourie that hydrogen sulfide that the present invention deviates from the water smoking in the polyphenylene sulfide synthesis technique flow process and water vapour feed 14-18%wt in the lump, through the absorption of ammoniacal liquor, ammonia react generation ammonium sulfide in hydrogen sulfide and the ammoniacal liquor; Under protection of nitrogen gas; Thereby obtain the rarer ammonium sulfide solution of concentration, with in synthetic heat (100-150 ℃ water vapour) the input ammonium sulfide solution jar that discharges of polyphenylene sulfide, this storage tank has stirring and chuck then; Be through the synthetic heat that discharges of the polyphenylene sulfide of control input; Make and ammonium sulfide dilute solution temperature is housed rises to 100 ℃ gradually, and evaporate certain water vapour, water vapour is cooled off for use; Ammonium sulfide solution is condensed into the solution that concentration is 16-20%wt simultaneously; And then, reclaim the moisture content that distills out with the underpressure distillation of ammonium sulfide solution process, obtain the solution that the Containing Sulfur ammonium is 70-80%wt; Ammonium sulfide solution with this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is the 1M ammonium sulfide at last, through calculating with 0.1-0.5mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is under 260-280 ℃ the condition in temperature, insulation 1h.
Description of drawings:
Fig. 1 reclaims and utilizes the process flow sheet of method for hypertoxic medium hydrogen sulfide waste gas in the polyphenylene sulfide production of the present invention.
The hydrolysis in the process of sodium sulphite dehydration of polyphenylene sulfide synthetic dehydration still goes out hydrogen sulfide and discharges water vapour; After hydrogen sulfide absorbs through ammoniacal liquor; Utilize the synthetic heat that discharges of polyphenylene sulfide to concentrate, again ammonium sulfide solution is carried out underpressure distillation and further dewater, then the nmp solution of formulating vulcanization ammonium; Through calculating the molal quantity that in reaction system, adds with the ammonium sulfide of certain molar ratio; Reaction system is incubated processing, and it is narrow so just to have obtained molecular weight ranges, and the MWD coefficient is narrow, the polyphenylene sulfide of melting index narrow range.
Embodiment
Embodiment 1
To contain H
2S feeds the ammoniacal liquor tourie reaction at 500 liters, and waste gas is imported by the lower end, adopts Bubbling method, H
2S converts (NH into
4)
2S under protection of nitrogen gas, thereby obtains the rarer ammonium sulfide solution of concentration; With in synthetic heat (100-150 ℃ water vapour) the input ammonium sulfide solution jar that discharges of polyphenylene sulfide, this storage tank has stirring and chuck, is through the synthetic heat that discharges of the polyphenylene sulfide of control input then; Make and ammonium sulfide dilute solution temperature is housed rises to 100 ℃ gradually, and evaporate certain water vapour, water vapour is cooled off for use; Ammonium sulfide solution is condensed into the solution that concentration is 16%wt simultaneously; And then, reclaim the moisture content that distills out with the underpressure distillation of ammonium sulfide solution process, obtain the solution that the Containing Sulfur ammonium is 70%wt; Ammonium sulfide solution with this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is the 1M ammonium sulfide at last, through calculating with 0.1mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is that insulation 1h gets final product under 260 ℃ the condition in temperature.
Embodiment 2
To contain H
2S feeds the ammoniacal liquor tourie reaction at 500 liters, and waste gas is imported by the lower end, adopts Bubbling method, H
2S converts (NH into
4)
2S under protection of nitrogen gas, thereby obtains the rarer ammonium sulfide solution of concentration; With in synthetic heat (100-150 ℃ water vapour) the input ammonium sulfide solution jar that discharges of polyphenylene sulfide, this storage tank has stirring and chuck, is through the synthetic heat that discharges of the polyphenylene sulfide of control input then; Make and ammonium sulfide dilute solution temperature is housed rises to 100 ℃ gradually, and evaporate certain water vapour, water vapour is cooled off for use; Ammonium sulfide solution is condensed into the solution that concentration is 20%wt simultaneously; And then, reclaim the moisture content that distills out with the underpressure distillation of ammonium sulfide solution process, obtain the solution that the Containing Sulfur ammonium is 80%wt; Ammonium sulfide solution with this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is the 1M ammonium sulfide at last, through calculating with 0.5mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is that insulation 1h gets final product under 260 ℃ the condition in temperature.
Embodiment 3
To contain H
2S feeds the ammoniacal liquor tourie reaction at 500 liters, and waste gas is imported by the lower end, adopts Bubbling method, H
2S converts (NH into
4)
2S under protection of nitrogen gas, thereby obtains the rarer ammonium sulfide solution of concentration; With in synthetic heat (100-150 ℃ water vapour) the input ammonium sulfide solution jar that discharges of polyphenylene sulfide, this storage tank has stirring and chuck, is through the synthetic heat that discharges of the polyphenylene sulfide of control input then; Make and ammonium sulfide dilute solution temperature is housed rises to 100 ℃ gradually, and evaporate certain water vapour, water vapour is cooled off for use; Ammonium sulfide solution is condensed into the solution that concentration is 18%wt simultaneously; And then, reclaim the moisture content that distills out with the underpressure distillation of ammonium sulfide solution process, obtain the solution that the Containing Sulfur ammonium is 75%wt; Ammonium sulfide solution with this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is the 1M ammonium sulfide at last, through calculating with 0.3mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is that insulation 1h gets final product under 260 ℃ the condition in temperature.
Claims (1)
1. hypertoxic medium hydrogen sulfide waste gas reclaims and utilizes method in the polyphenylene sulfide production; Adopting many water cure sodium and santochlor is that raw material is produced the polyphenylene sulfide monomer through process steps such as sodium sulphite dehydration, polycondensations; It is characterized in that; The waste gas that is rich in hydrogen sulfide is reacted with ammoniacal liquor in the alkali lye tourie; The polyphenylene sulfide molecule that again the reaction product ammonium sulfide is concentrated after accomplish polymerization as the component regulator conveying meeting reaction kettle of polyphenylene sulfide production the back is regulated effectively, regulates the MWD coefficient and can remain between the 1.91-1.93, and its concrete treatment process comprises:
1), hydrogen sulfide that hydrolysis in the dehydration is produced feeds in the strong aqua of 14-18% and absorbs processing hydrogen sulfide, in tourie, is reacted into the ammonium sulfide dilute solution;
2) with 1) ammonium sulfide solution that obtains, under protection of nitrogen gas, the heat that discharges with the polyphenylene sulfide polyreaction is condensed into the 16-20%wt ammonium sulfide solution;
The moisture content that is evaporated turns back to storage tank through condensing surface cooling recovery and is used for polyphenylene sulfide polyphenylene sulfide washing subsequently;
3) with 2) ammonium sulfide solution that obtains under protection of nitrogen gas, further use underpressure distillation, it is for use to make the concentration of ammonium sulfide solution become 70-80%wt;
4) the 3 70-80%wt ammonium sulfide solutions that obtain being configured to concentration is that (N-Methyl pyrrolidone) nmp solution of 1M ammonium sulfide is for use;
5) with 4) (N-Methyl pyrrolidone) nmp solution of the 1M ammonium sulfide that obtains calculate good with 0.1-0.5mol/molNa
2The mol ratio of S adds in the reaction kettle that polyphenylene sulfide polyreaction accomplished, and is under 260-280 ℃ the condition in temperature, insulation 1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110066327.5A CN102675682B (en) | 2011-03-18 | 2011-03-18 | Recovery and utilization method of highly toxic medium hydrothion waste gas generated in polyphenylene sulfide production |
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| CN201110066327.5A CN102675682B (en) | 2011-03-18 | 2011-03-18 | Recovery and utilization method of highly toxic medium hydrothion waste gas generated in polyphenylene sulfide production |
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| CN102675682A true CN102675682A (en) | 2012-09-19 |
| CN102675682B CN102675682B (en) | 2014-01-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114008111A (en) * | 2019-07-09 | 2022-02-01 | 株式会社吴羽 | Method for producing polyarylene sulfide, method for dehydration treatment, and apparatus for producing polyarylene sulfide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265524A1 (en) * | 1986-03-24 | 1988-05-04 | Tohpren Co., Ltd. | Process for removing impurities from polyphenylene sulfide resin |
| CN1539863A (en) * | 2003-04-25 | 2004-10-27 | 四川省华拓科技有限责任公司 | Method for recycling and using virulent exhaust gas of sulfureted hydrogen generated in production of polyphenylene sulfide |
-
2011
- 2011-03-18 CN CN201110066327.5A patent/CN102675682B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265524A1 (en) * | 1986-03-24 | 1988-05-04 | Tohpren Co., Ltd. | Process for removing impurities from polyphenylene sulfide resin |
| CN1539863A (en) * | 2003-04-25 | 2004-10-27 | 四川省华拓科技有限责任公司 | Method for recycling and using virulent exhaust gas of sulfureted hydrogen generated in production of polyphenylene sulfide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114008111A (en) * | 2019-07-09 | 2022-02-01 | 株式会社吴羽 | Method for producing polyarylene sulfide, method for dehydration treatment, and apparatus for producing polyarylene sulfide |
| CN114008111B (en) * | 2019-07-09 | 2022-07-26 | 株式会社吴羽 | Method for producing polyarylene sulfide, method for dehydration treatment, and apparatus for producing polyarylene sulfide |
| US11453752B2 (en) | 2019-07-09 | 2022-09-27 | Kureha Corporation | Method for producing polyarylene sulfide, dehydration method, and device for producing polyarylene sulfide |
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Granted publication date: 20140122 Termination date: 20180318 |