CN102888000B - Dehydration technology of multi-water sodium sulfide in polyphenylene sulfide production - Google Patents
Dehydration technology of multi-water sodium sulfide in polyphenylene sulfide production Download PDFInfo
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- CN102888000B CN102888000B CN201110199757.4A CN201110199757A CN102888000B CN 102888000 B CN102888000 B CN 102888000B CN 201110199757 A CN201110199757 A CN 201110199757A CN 102888000 B CN102888000 B CN 102888000B
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- sulfide
- water
- sodium
- sodium sulfide
- wateriness
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052979 sodium sulfide Inorganic materials 0.000 title claims abstract description 31
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 23
- 230000018044 dehydration Effects 0.000 title claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 13
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 230000019086 sulfide ion homeostasis Effects 0.000 title claims abstract description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000000391 smoking effect Effects 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- -1 and vapor Chemical compound 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 238000004781 supercooling Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 208000005156 Dehydration Diseases 0.000 abstract 5
- 239000013078 crystal Substances 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a dehydration technology of multi-water sodium sulfide in a polyphenylene sulfide production. The technology uses the multi-water sodium sulfide and p-dichlorobenzene as raw materials to produce the polyphenylene sulfide through sodium sulfide dehydration, polycondensation and other steps. During the dehydration stage of the multi-water sodium sulfide, an infrared on-line detection system is used to control removed amount of the water, so that the moisture in the system is kept between 1.1-1.2 mol/mol Na2S. The multi-water sodium sulfide and an NMP solution are heated to boil in a reactor under a temperature of 180 to 240 DEG C, so that crystal water of the sodium sulfide is removed in a form of water vapor. The water vapor, N-methylpyrrolidone and hydrogen sulfide gas generated during the dehydration process are separated through a normal-pressure rectifying tower. The technology provided by the invention, for one hand, simplifies technology equipment and saves on-site space, and for the other hand, maintains relatively stable heating systems for dehydration and condensation polymerization, thereby preventing additional energy consumption and waste of raw materials.
Description
Technical field
The present invention relates to the improvement of polyphenylene sulphide production process method.
Background technology
Alkali metal sulphide and paracide is used to be dehydrated for raw material through vulcanized sodium, in the technical process of technique productions polyphenylene sulfide monomer (PPS) such as polycondensation, because alkali metal sulphide is often with the crystallization water for needing to remove, need to be dehydrated before paracide progress polycondensation reaction is added for this.And conventional method is to set up special dehydration facility to be dehydrated, this aspect increases construction investment and operation site space, on the other hand needs extra energy ezpenditure.
The wateriness sodium sulfide dewatering in a kind of polyphenylene sulfide production is introduced in Chinese Patent Application No. CN00116141.5, this is indispensable processing step in polyphenylene sulfide synthesis technique flow, but, because there are many deficiencies in technology controlling and process index and specific processing method, in addition, the patent does not point out people's polyphenylene sulfide to synthesize real dewatering process.
In view of the disadvantage mentioned above of prior art, the purpose of the present invention is to create the wateriness sodium sulfide dewatering in a kind of polyphenylene sulfide production, dehydrating operations are made to be carried out with subsequent production not in same reaction vessel, with construction investment province, place space be relatively small, comprehensive utilization of energy rationally, energy consumption is small and production operation in terms of advantage.
The purpose of the present invention is to introduce a kind of reasonable dewatering process step of wateriness sodium sulfide in polyphenylene sulfide resin production process flow, and the vapor and NMP and hydrogen sulfide gas of removing are kept completely separate by recycling using reasonable distillation technology, on the one hand such purpose reaches that the right combination of the energy is utilized, on the other hand production cost is reduced, also has and has on the one hand protected retaining ring border, the discharge capacity of waste water is reduced.
The content of the invention：
Wateriness sodium sulfide dehydration technique in polyphenylene sulfide production, use wateriness sodium sulfide and paracide to be dehydrated for raw material through vulcanized sodium, the processing step such as polycondensation production polyphenylene sulfide, it is characterized in that, the amount of removing water is controlled using infrared on-line detecting system in the raw material wateriness sodium sulfide water smoking, the moisture content in system is maintained at 1.1-1.2mol/molNa2Between S, wateriness sodium sulfide and nmp solution are heated into azeotropic, 180-204 DEG C of temperature in a kettle.；The crystallization water of wateriness sodium sulfide is deviate from water vapour form, then separate the vapor and 1-METHYLPYRROLIDONE and hydrogen sulfide gas that will be produced in dehydration by atmospheric distillation tower, its concrete technology technical step includes：
1st, under the control of online infrared detection system, in containing vulcanized sodium, 1-METHYLPYRROLIDONE (NMP), the reaction system of cosolvent sodium acetate, slowly reaction system is heated using electrical heating, 1.1-1.2mol/molNa is maintained at by the molal quantity of the remaining water in online infrared detection system control system2Between S.
2nd, the vapor and NMP and hydrogen sulfide gas of 1) removing are passed through atmospheric distillation tower, NMP is isolated into steam phase rectifying, vapor, hydrogen sulfide body are recycled from the bottom, top and middle and upper part of rectifying column through supercooling, absorption respectively.
3rd, for three-five water vulcanized sodium, the heating azeotropic time is 2-3 hours, and hydrogen sulfide gas is utilized by ammonia absorption by processing.
Using the method for the present invention, process equipment is on the one hand simplified, site space is saved；On the other hand dehydration temperature elevation system and the heating system that keeps relative stability of temperature elevation system of polycondensation reaction, it is to avoid the waste of extra energy ezpenditure and raw material.
Brief description of the drawings：
Fig. 1, the present invention polyphenylene sulfide production in wateriness sodium sulfide dehydration technique process flow diagram.
The present invention uses wateriness sodium sulfide and paracide (P-DCB) for raw material, and-technique productions polyphenylene sulfide the monomer (PPS) such as low molecule oligomerisation-macromolecule polycondensation is dehydrated through vulcanized sodium.In the raw material wateriness sodium sulfide water smoking, control to remove the amount of water using infrared on-line detecting system, wateriness sodium sulfide and NMP (1-METHYLPYRROLIDONE) are heated into azeotropic, 180-220 DEG C of temperature in a kettle.；The crystallization water of wateriness sodium sulfide is set to be escaped with water vapour, also part NMP and hydrogen sulfide gas simultaneously, from mixed gas of the formation containing vapor, NMP and hydrogen sulfide gas, and separated mixed gas input atmospheric distillation tower, outflow is vapor at the top of from rectifying column, the polyphenylene sulfide washing of vapor workshop section after cooling recovery is used for；Middle and upper part outflow is that hydrogen sulfide gas is recycled by alkali lye or ammonia absorption；The 1-METHYLPYRROLIDONE solvent of bottom outflow is recycled by purifying.
Embodiment：
Embodiment 1
In 25 liters of reactors, Na is added2S.3H2Each 4 kilograms of O and NMP, LiCl1.2 kilograms of catalyst is heated to 180 DEG C, keeps the temperature, and system azeotropic 3 hours or so controls the amount of removing water in infrared on-line detecting system, the moisture content in system is maintained at 1.1mol/molNa2Between S, the crystallization water of wateriness sodium sulfide is set to be escaped with water vapour, also part NMP and hydrogen sulfide gas simultaneously, from mixed gas of the formation containing vapor, NMP and hydrogen sulfide gas, and separated mixed gas input atmospheric distillation tower, outflow is vapor at the top of from rectifying column, the polyphenylene sulfide washing of vapor workshop section after cooling recovery is used for；Middle and upper part outflow is that hydrogen sulfide gas is recycled by alkali lye or ammonia absorption；The 1-METHYLPYRROLIDONE solvent of bottom outflow is recycled by purifying.
Embodiment 2
In 25 liters of reactors, Na is added2S.9H24.7 kilograms of O and 4 kilograms of NMP, 1.2 kilograms of catalyst LiCl, are heated to 204 DEG C and keep the temperature, system azeotropic controls the amount of removing water for 2 hours or so in infrared on-line detecting system, the moisture content in system is maintained at 1.2mol/molNa2Between S, the crystallization water of wateriness sodium sulfide is set to be escaped with water vapour, also part NMP and hydrogen sulfide gas simultaneously, from mixed gas of the formation containing vapor, NMP and hydrogen sulfide gas, and separated mixed gas input atmospheric distillation tower, outflow is vapor at the top of from rectifying column, the polyphenylene sulfide washing of vapor workshop section after cooling recovery is used for；Middle and upper part outflow is that hydrogen sulfide gas is recycled by alkali lye or ammonia absorption；The 1-METHYLPYRROLIDONE solvent of bottom outflow is recycled by purifying.
Embodiment 3
In 25 liters of reactors, Na is added2S.9H24.7 kilograms of O and 4 kilograms of NMP, 1.2 kilograms of catalyst LiCl, pressure heating keep the temperature to 200 DEG C, and system azeotropic controls the amount of removing water for 2.5 hours or so in infrared on-line detecting system, the moisture content in system is maintained at 1.15mol/molNa2Between S, the crystallization water of wateriness sodium sulfide is set to be escaped with water vapour, also part NMP and hydrogen sulfide gas simultaneously, from mixed gas of the formation containing vapor, NMP and hydrogen sulfide gas, and separated mixed gas input atmospheric distillation tower, outflow is vapor at the top of from rectifying column, the polyphenylene sulfide washing of vapor workshop section after cooling recovery is used for；Middle and upper part outflow is that hydrogen sulfide gas is recycled by alkali lye or ammonia absorption；The 1-METHYLPYRROLIDONE solvent of bottom outflow is recycled by purifying.
It the experiment proved that, using the dewatering of the present invention, also have many advantages in the convenience of production operation, repeatedly conveyed without by material, simplify operation, facilitate production.
Further, since NMP toxicity is minimum, so it is also feasible that the dewatering of the present invention, which is recycled in terms of environmental protection,.
In actual production, the time of azeotropic is heated depending on the crystallization water number of specific vulcanized sodium used, generally, for three water vulcanized sodium, when heating the azeotropic time for 2-3 preferably；For nine water vulcanized sodium, the heating azeotropic time was advisable for 3-4 hours.
Claims (2)
1. the wateriness sodium sulfide dewatering in polyphenylene sulfide production, wateriness sodium sulfide and paracide is used to be dehydrated for raw material through vulcanized sodium, polycondensating process step produces polyphenylene sulfide, it is characterized in that, the amount of removing water is controlled using online infrared detection system in the raw material wateriness sodium sulfide water smoking, the moisture content in system is maintained at 1.1-1.2mol/molNa2Between S, wateriness sodium sulfide and nmp solution are heated into azeotropic, 180-204 DEG C of temperature in a kettle.；The crystallization water of wateriness sodium sulfide is deviate from water vapour form, then separate the vapor and 1-METHYLPYRROLIDONE and hydrogen sulfide gas that will be produced in dehydration by atmospheric distillation tower, its concrete technology technology includes：
1）Under the control of online infrared detection system, in containing vulcanized sodium, 1-METHYLPYRROLIDONE, the reaction system of cosolvent sodium acetate, slowly reaction system is heated using electrical heating, 1.1-1.2mol/molNa is maintained at by the molal quantity of the remaining water in online infrared detection system control system2Between S；
2）By 1）The vapor and NMP and hydrogen sulfide gas of removing are passed through atmospheric distillation tower, and steam phase rectifying is isolated into NMP, and vapor, hydrogen sulfide body are recycled from the bottom, top and middle and upper part of rectifying column through supercooling, absorption respectively.
2. the wateriness sodium sulfide dewatering in polyphenylene sulfide production according to claim 1, it is characterised in that the vulcanized sodium is three-five water vulcanized sodium, the heating azeotropic time is 2-3 hours, and hydrogen sulfide gas is utilized by ammonia absorption by processing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110199757.4A CN102888000B (en) | 2011-07-18 | 2011-07-18 | Dehydration technology of multi-water sodium sulfide in polyphenylene sulfide production |
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| CN201110199757.4A CN102888000B (en) | 2011-07-18 | 2011-07-18 | Dehydration technology of multi-water sodium sulfide in polyphenylene sulfide production |
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| CN102888000B true CN102888000B (en) | 2014-05-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103241716A (en) * | 2013-04-22 | 2013-08-14 | 中国石油化工股份有限公司 | Heating control method for dehydrating crystallized sodium sulfide for synthesizing polyphenylene sulfide |
| CN103788373B (en) * | 2014-02-21 | 2016-08-24 | 珠海长先新材料科技股份有限公司 | The dewatering process of many water cures sodium in the synthesis of a kind of polyphenylene sulfide |
| CN111286027B (en) * | 2020-02-13 | 2022-06-10 | 四川明道和化学新材料有限公司 | Production method of polyphenylene sulfide with low covalent bonding chlorine |
| CN114621441B (en) * | 2022-04-27 | 2024-01-30 | 浙江新和成特种材料有限公司 | Recyclable hydrogen sulfide waste gas Process for preparing recycled polyphenylene sulfide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454918A (en) * | 2002-04-29 | 2003-11-12 | 自贡鸿鹤化工股份有限公司 | Method of dehydration in reaction kettle for production of polyphenylene sulfide |
| CN1732210A (en) * | 2002-12-27 | 2006-02-08 | 吴羽化学工业株式会社 | Process for producing polyarylene sulfide |
| CN101429288A (en) * | 2008-12-09 | 2009-05-13 | 江苏新中投资有限公司 | Method for treating process liquid generated in production process of polyphenylene sulfide |
| CN101935397A (en) * | 2010-09-17 | 2011-01-05 | 四川得阳化学有限公司 | Process for synthesizing low-chlorine polyphenylene sulfide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1440996B1 (en) * | 2001-09-27 | 2010-05-26 | Kureha Corporation | Process for production of polyarylene sulfide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454918A (en) * | 2002-04-29 | 2003-11-12 | 自贡鸿鹤化工股份有限公司 | Method of dehydration in reaction kettle for production of polyphenylene sulfide |
| CN1732210A (en) * | 2002-12-27 | 2006-02-08 | 吴羽化学工业株式会社 | Process for producing polyarylene sulfide |
| CN101429288A (en) * | 2008-12-09 | 2009-05-13 | 江苏新中投资有限公司 | Method for treating process liquid generated in production process of polyphenylene sulfide |
| CN101935397A (en) * | 2010-09-17 | 2011-01-05 | 四川得阳化学有限公司 | Process for synthesizing low-chlorine polyphenylene sulfide resin |
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