CN102675682B - 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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- CN102675682B CN102675682B CN201110066327.5A CN201110066327A CN102675682B CN 102675682 B CN102675682 B CN 102675682B CN 201110066327 A CN201110066327 A CN 201110066327A CN 102675682 B CN102675682 B CN 102675682B
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- polyphenylene sulfide
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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 synthesis of polymer material field.
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 hydrogen sulfide poisonous medium, and it is unfavorable that environmental protection is caused.And prior art adopts physical absorption method, there is secondary pollution.
In Chinese Patent Application No. code CN03117750.6, introduce the absorption treatment process of hydrogen sulfide in polyphenylene sulfide synthesis technique flow process, puzzling is the absorption processing of hydrogen sulfide, really be peace often only, although utilize alkali liquor absorption hydrogen sulfide, the sodium sulphite recycling that reaction generates is synthetic with polyphenylene sulfide, but is not difficult to find that this invention is very mediocre.
Above shortcoming in view of prior art, the object of the invention is to study a kind of hypertoxic medium hydrogen sulfide waste gas recycle method in polyphenylene sulfide production, make it to overcome the above shortcoming of prior art, the hydrogen sulfide of returning is well used to as the molecular weight regulator of synthetic polyphenylene sulfide simultaneously, also fully utilize the synthetic heat discharging of polyphenylene sulfide simultaneously, and will synthesize in polyphenylene sulfide technical process sodium sulphite and deviate from water and recycle, adopt method of the present invention, on the one hand hypertoxic medium hydrogen sulfide waste gas is governed, reach good environment protecting, owing to original waste gas being converted to the raw materials for production that can return to use, form optimum closed cycle on the other hand.
The object of the invention is in the technical process due to synthetic polyphenylene sulfide, first the sodium sulphite that contains mass crystallization water is dewatered, again because sodium sulphite is in dehydration process, although add basic metal highly basic to process to sodium sulphite, but sodium sulphite can be hydrolyzed in the situation that having water, emit a large amount of hydrogen sulfide, the hypertoxicity of hydrogen sulfide forces it is absorbed and is processed.
Summary of the invention
The present invention realizes by following means
Hypertoxic medium hydrogen sulfide waste gas recycle method in polyphenylene sulfide production, adopting many water cure sodium and santochlor is that raw material dewaters through sodium sulphite, the processing steps such as polycondensation are produced polyphenylene sulfide monomer, it is characterized in that, the hydrogen sulfide containing waste gas of richness is reacted with ammoniacal liquor in alkali liquor absorption tank, polyphenylene sulfide molecule after the component conditioning agent conveying meeting reactor of producing as polyphenylene sulfide after reaction product ammonium sulfide is concentrated again completes polymerization regulates effectively, molecular weight distribution coefficient after overregulating can remain between 1.91-1.93, its concrete treatment process comprises:
1, hydrogen sulfide hydrolysis in dehydration being produced passes in the strong aqua of 14-18% and absorbs processing hydrogen sulfide, is reacted into ammonium sulfide dilute solution in tourie.
2, by 1) ammonium sulfide solution that obtains, under the protection of nitrogen, with the heat that polyphenylene sulfide polyreaction discharges, be condensed into 16-20%wt ammonium sulfide solution.Through condenser, cooling recovery turns back to storage tank for polyphenylene sulfide polyphenylene sulfide washing subsequently to the moisture content being evaporated.
3, by 2) ammonium sulfide solution that obtains under the protection of nitrogen, further use underpressure distillation, make the concentration of ammonium sulfide solution become 70-80%wt stand-by.
4, by 3) to be configured to concentration be that (N-Methyl pyrrolidone) nmp solution of 1M ammonium sulfide is stand-by for the 70-80%wt ammonium sulfide solution that obtains.
5, by 4) (N-Methyl pyrrolidone) nmp solution of the 1M ammonium sulfide that obtains calculates with 0.1-0.5mol/molNa
2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260-280 ℃, insulation 1h.In polyphenylene sulfide after ammonium sulfide is processed adjusting, various metals and nonmetal chlorion are low, and metal ion total amount is at 200-300ppm, and nonmetal chlorion 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 ammonia absorption tank that the hydrogen sulfide that the present invention deviates from the water smoking in polyphenylene sulfide synthesis technique flow process and water vapour pass into 14-18%wt in the lump, absorption through ammoniacal liquor, in hydrogen sulfide and ammoniacal liquor, ammonia react generates ammonium sulfide, under the protection of nitrogen, thereby obtain the rarer ammonium sulfide solution of concentration, then by synthetic heat (water vapour of 100-150 ℃) the input ammonium sulfide solution tank discharging of polyphenylene sulfide, this storage tank is with stirring and chuck, it is the synthetic releases heat of polyphenylene sulfide by control inputs, make to be equipped with ammonium sulfide dilute solution temperature and rise to gradually 100 ℃, and evaporate certain water vapour, water vapour is cooling stand-by, ammonium sulfide solution is condensed into the solution that concentration is 16-20%wt simultaneously, and then by the underpressure distillation of ammonium sulfide solution process, the moisture content that recovery distills out, obtain the solution that Containing Sulfur ammonium is 70-80%wt, finally the ammonium sulfide solution of this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is 1M ammonium sulfide, through calculating with 0.1-0.5mol/molNa
2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260-280 ℃, insulation 1h.
accompanying drawing explanation:
Fig. 1 is the process flow sheet of hypertoxic medium hydrogen sulfide waste gas recycle method during polyphenylene sulfide of the present invention is produced.
The synthetic dehydrating kettle of polyphenylene sulfide hydrolysis hydrogen sulfide and discharge water vapour in the process of sodium sulphite dehydration, hydrogen sulfide is after ammonia absorption, utilize the synthetic heat heating discharging of polyphenylene sulfide concentrated, again ammonium sulfide solution being carried out to underpressure distillation further dewaters, then the nmp solution of formulating vulcanization ammonium, through calculating, in reaction system, add the molal quantity with the ammonium sulfide of certain mol ratio, reaction system is incubated to processing, so just obtained molecular weight ranges narrow, molecular weight distribution coefficient is narrow, the polyphenylene sulfide of melting index narrow range.
Embodiment
Embodiment 1
Will be containing H
2s passes into the ammonia absorption tank reaction at 500 liters, and waste gas is inputted by lower end, adopts Bubbling method, H
2s is converted to (NH
4)
2s, under the protection of nitrogen, thereby obtain the rarer ammonium sulfide solution of concentration, then by synthetic heat (water vapour of 100-150 ℃) the input ammonium sulfide solution tank discharging of polyphenylene sulfide, this storage tank is with stirring and chuck, it is the synthetic releases heat of polyphenylene sulfide by control inputs, make to be equipped with ammonium sulfide dilute solution temperature and rise to gradually 100 ℃, and evaporate certain water vapour, water vapour is cooling stand-by, ammonium sulfide solution is condensed into the solution that concentration is 16%wt simultaneously, and then by the underpressure distillation of ammonium sulfide solution process, the moisture content that recovery distills out, obtain the solution that Containing Sulfur ammonium is 70%wt, finally the ammonium sulfide solution of this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is 1M ammonium sulfide, through calculating with 0.1mol/molNa
2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260 ℃, insulation 1h.
Embodiment 2
Will be containing H
2s passes into the ammonia absorption tank reaction at 500 liters, and waste gas is inputted by lower end, adopts Bubbling method, H
2s is converted to (NH
4)
2s, under the protection of nitrogen, thereby obtain the rarer ammonium sulfide solution of concentration, then by synthetic heat (water vapour of 100-150 ℃) the input ammonium sulfide solution tank discharging of polyphenylene sulfide, this storage tank is with stirring and chuck, it is the synthetic releases heat of polyphenylene sulfide by control inputs, make to be equipped with ammonium sulfide dilute solution temperature and rise to gradually 100 ℃, and evaporate certain water vapour, water vapour is cooling stand-by, ammonium sulfide solution is condensed into the solution that concentration is 20%wt simultaneously, and then by the underpressure distillation of ammonium sulfide solution process, the moisture content that recovery distills out, obtain the solution that Containing Sulfur ammonium is 80%wt, finally the ammonium sulfide solution of this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is 1M ammonium sulfide, through calculating with 0.5mol/molNa
2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260 ℃, insulation 1h.
Embodiment 3
Will be containing H
2s passes into the ammonia absorption tank reaction at 500 liters, and waste gas is inputted by lower end, adopts Bubbling method, H
2s is converted to (NH
4)
2s, under the protection of nitrogen, thereby obtain the rarer ammonium sulfide solution of concentration, then by synthetic heat (water vapour of 100-150 ℃) the input ammonium sulfide solution tank discharging of polyphenylene sulfide, this storage tank is with stirring and chuck, it is the synthetic releases heat of polyphenylene sulfide by control inputs, make to be equipped with ammonium sulfide dilute solution temperature and rise to gradually 100 ℃, and evaporate certain water vapour, water vapour is cooling stand-by, ammonium sulfide solution is condensed into the solution that concentration is 18%wt simultaneously, and then by the underpressure distillation of ammonium sulfide solution process, the moisture content that recovery distills out, obtain the solution that Containing Sulfur ammonium is 75%wt, finally the ammonium sulfide solution of this concentration is mixed with into (N-Methyl pyrrolidone) nmp solution that concentration is 1M ammonium sulfide, through calculating with 0.3mol/molNa
2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260 ℃, insulation 1h.
Claims (1)
- Polyphenylene sulfide produce in hypertoxic medium hydrogen sulfide waste gas recycle method, adopting many water cure sodium and santochlor is that raw material is produced polyphenylene sulfide monomer through sodium sulphite dehydration, polycondensating process step, it is characterized in that, the hydrogen sulfide containing waste gas of richness is reacted with ammoniacal liquor in alkali liquor absorption tank, the polyphenylene sulfide molecule that the component conditioning agent of producing as polyphenylene sulfide after reaction product ammonium sulfide is concentrated is again transmitted back to after reactor completes polymerization regulates effectively, Molecular regulator amount distribution coefficient remains between 1.91-1.93, and its concrete treatment process comprises:1), hydrogen sulfide that hydrolysis in dehydration is produced passes in the strong aqua of 14-18% and absorbs processing hydrogen sulfide, is reacted into ammonium sulfide dilute solution in tourie;2) by 1) the ammonium sulfide dilute solution that obtains, under the protection of nitrogen, with the heat that polyphenylene sulfide polyreaction discharges, be condensed into 16-20%wt ammonium sulfide solution;Through condenser, cooling recovery turns back to storage tank for polyphenylene sulfide polyphenylene sulfide washing subsequently to the moisture content being evaporated;3) by 2) ammonium sulfide solution that obtains under the protection of nitrogen, further use underpressure distillation, make the concentration of ammonium sulfide solution become 70-80%wt stand-by;4) by 3) to be configured to concentration be that the N-Methyl pyrrolidone nmp solution of 1M ammonium sulfide is stand-by for the 70-80%wt ammonium sulfide solution that obtains;5) by 4) the N-Methyl pyrrolidone nmp solution of the 1M ammonium sulfide that obtains calculates with 0.1-0.5mol/molNa 2the mol ratio of S adds in the reactor that polyphenylene sulfide polyreaction completed, and in temperature, is under the condition of 260-280 ℃, insulation 1h.
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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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| 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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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 |
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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 |
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