CN102888000A - 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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- CN102888000A CN102888000A CN2011101997574A CN201110199757A CN102888000A CN 102888000 A CN102888000 A CN 102888000A CN 2011101997574 A CN2011101997574 A CN 2011101997574A CN 201110199757 A CN201110199757 A CN 201110199757A CN 102888000 A CN102888000 A CN 102888000A
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- Prior art keywords
- water
- sodium
- dehydration
- sulfide
- sodium sulfide
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 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 18
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 230000019086 sulfide ion homeostasis Effects 0.000 title abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 title abstract 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 title abstract 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 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 5
- 239000011734 sodium Substances 0.000 claims description 30
- 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 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 238000009156 water cure Methods 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- 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
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 9
- 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
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 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
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyphenylene Polymers 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 polyphenylene sulphide production process method improvement.
Background technology
Adopting alkali metalsulphide and santochlor is that raw material is in the technological process of the explained hereafter polyphenylene sulfide monomers (PPS) such as sodium sulphite dehydration, polycondensation, because the crystal water that alkali metalsulphide is often removed with needs need to carry out dewatering before the polycondensation at the adding santochlor for this reason.And conventional method is to set up special dehydration facility to dewater, and this has increased construction investment and operation site space on the one hand, needs on the other hand extra energy expenditure.
In Chinese patent application CN00116141.5, introduce the many water cure sodium dewatering in a kind of polyphenylene sulfide production, this is indispensable processing step in the polyphenylene sulfide synthesis technique flow process, but, because it is a lot of not enough that technology controlling and process index and concrete treatment process exist, in addition, this patent does not point out people's polyphenylene sulfide to synthesize real dewatering process.
Above shortcoming in view of prior art, the objective of the invention is to create the many water cure sodium dewatering in a kind of polyphenylene sulfide production, dehydration operation and subsequent production are not carried out in same reaction vessel, make it to have construction investment province, the space, place is relatively little, comprehensive utilization of energy is reasonable, the advantage of the little and production operation aspect of energy consumption.
The objective of the invention is to introduce the reasonable dewatering process step of many water cure sodium in a kind of polyphenylene sulfide resin production process flow process, and adopt reasonable distillation technology with the water vapour and NMP and the complete Separation and Recovery recycling of hydrogen sulfide that remove, such purpose reaches the reasonable comprehensive utilization of the energy on the one hand, reduce production costs on the other hand, also have and protected on the one hand the retaining ring border, reduce the quantity discharged of waste water.
Summary of the invention:
Many water cure sodium dehydration technique during polyphenylene sulfide is produced, adopting many water cure sodium and santochlor is that raw material is produced polyphenylene sulfide through processing steps such as sodium sulphite dehydration, polycondensations, it is characterized in that, adopt infrared on-line detecting system control to remove the amount of water in many water cure of raw material sodium water smoking, make the moisture content in the system remain on 1.1-1.2mol/molNa
2Between the S, with many water cure sodium and the nmp solution azeotropic of in reactor, heating, temperature 180-204 ℃; The crystal water of many water cure sodium is deviate from the water vapor form, then separated the water vapour and N-Methyl pyrrolidone and the hydrogen sulfide that produce in the dehydration through the atmospheric distillation tower, its concrete technology technological step comprises:
1, under the control of online infrared detection system, in the reaction system that contains sodium sulphite, N-Methyl pyrrolidone (NMP), solubility promoter sodium-acetate, adopt electrically heated slowly reaction system to be heated, the molal quantity by the residue water in the online infrared detection system hierarchy of control remains on 1.1-1.2mol/molNa
2Between the S.
2, with 1) water vapour that removes and NMP and hydrogen sulfide pass into the atmospheric distillation tower, and the vapor phase rectifying separation is gone out NMP, water vapour, hydrogen sulfide body respectively from bottom, top and the middle and upper part of rectifying tower through overcooling, absorb recycling.
3, for three-five water cure sodium, the azeotropic time of heating is 2-3 hour, and hydrogen sulfide is passing through processing and utilizing by ammonia absorption.
Adopt method of the present invention, simplified on the one hand processing unit, save site space; The intensification system that the temperature elevation system of temperature elevation system and polycondensation of dewatering on the other hand keeps relative stability has been avoided extra energy expenditure and raw-material waste.
Description of drawings:
The process flow diagram of the many water cure sodium dehydration technique during Fig. 1, polyphenylene sulfide of the present invention are produced.
It is raw material that the present invention adopts many water cure sodium and santochlor (P-DCB), through the sodium sulphite molecule oligomerisation-explained hereafter polyphenylene sulfide monomers (PPS) such as polymer polycondensation that dewater-hang down.In many water cure of raw material sodium water smoking, adopt the control of infrared on-line detecting system to remove the amount of water, with many water cure sodium and NMP (N-Methyl pyrrolidone) azeotropic of in reactor, heating, temperature 180-220 ℃; The crystal water of many water cure sodium is overflowed with water vapor, also have simultaneously part NMP and hydrogen sulfide, the mixed gas that contains water vapour, NMP and hydrogen sulfide from formation, and mixed gas is inputted the atmospheric distillation tower separate, what flow out from the rectifying tower top is water vapour, the polyphenylene sulfide washing of workshop section after this water vapour is used for through the cooling recovery; What flowed out the middle and upper part is that hydrogen sulfide is by alkali lye or ammonia absorption recycling; The N-Methyl pyrrolidone solvent that flow out the bottom is through the purifying recycling.
Embodiment:
Embodiment 1
In 25 liters of reactors, add Na
2S.3H
2Each 4 kilograms of O and NMP, catalyzer LiCl1.2 kilogram is heated to 180 ℃, keeps this temperature, and the system azeotropic removed the amount of water about 3 hours in infrared on-line detecting system control, make the moisture content in the system remain on 1.1mol/molNa
2Between the S, the crystal water of many water cure sodium is overflowed with water vapor, also have simultaneously part NMP and hydrogen sulfide, the mixed gas that contains water vapour, NMP and hydrogen sulfide from formation, and mixed gas is inputted the atmospheric distillation tower separate, what flow out from the rectifying tower top is water vapour, the polyphenylene sulfide washing of workshop section after this water vapour is used for through the cooling recovery; What flowed out the middle and upper part is that hydrogen sulfide is by alkali lye or ammonia absorption recycling; The N-Methyl pyrrolidone solvent that flow out the bottom is through the purifying recycling.
Embodiment 2
In 25 liters of reactors, add Na
2S.9H
24 kilograms of 4.7 kilograms of O and NMP, 1.2 kilograms of catalyzer LiCl are heated to 204 ℃ and keep this temperature, and the system azeotropic removes the amount of water in infrared on-line detecting system control about 2 hours, make the moisture content in the system remain on 1.2mol/molNa
2Between the S, the crystal water of many water cure sodium is overflowed with water vapor, also have simultaneously part NMP and hydrogen sulfide, the mixed gas that contains water vapour, NMP and hydrogen sulfide from formation, and mixed gas is inputted the atmospheric distillation tower separate, what flow out from the rectifying tower top is water vapour, the polyphenylene sulfide washing of workshop section after this water vapour is used for through the cooling recovery; What flowed out the middle and upper part is that hydrogen sulfide is by alkali lye or ammonia absorption recycling; The N-Methyl pyrrolidone solvent that flow out the bottom is through the purifying recycling.
Embodiment 3
In 25 liters of reactors, add Na
2S.9H
24 kilograms of 4.7 kilograms of O and NMP, 1.2 kilograms of catalyzer LiCl, pressure heating to 200 ℃ keeps this temperature, and the system azeotropic removes the amount of water in infrared on-line detecting system control about 2.5 hours, make the moisture content in the system remain on 1.15mol/molNa
2Between the S, the crystal water of many water cure sodium is overflowed with water vapor, also have simultaneously part NMP and hydrogen sulfide, the mixed gas that contains water vapour, NMP and hydrogen sulfide from formation, and mixed gas is inputted the atmospheric distillation tower separate, what flow out from the rectifying tower top is water vapour, the polyphenylene sulfide washing of workshop section after this water vapour is used for through the cooling recovery; What flowed out the middle and upper part is that hydrogen sulfide is by alkali lye or ammonia absorption recycling; The N-Methyl pyrrolidone solvent that flow out the bottom is through the purifying recycling.
The experiment proved that, adopt dewatering of the present invention, many advantages are also arranged on the accessibility of production operation, material repeatedly need not be carried, simplified operation, made things convenient for production.
In addition, because NMP toxicity is minimum, also be feasible aspect environmental protection so dewatering of the present invention is recycled.
In actual production, the time of heating azeotropic decides on the crystal water number of concrete used sodium sulphite, in general, for three water cure sodium, when the azeotropic time of heating is 2-3 for well; For nine water cure sodium, the azeotropic time of heating is to be advisable in 3-4 hour.
Claims (2)
1. the many water cure sodium dehydration technique during polyphenylene sulfide is produced, adopting many water cure sodium and santochlor is that raw material is produced polyphenylene sulfide through processing steps such as sodium sulphite dehydration, polycondensations, it is characterized in that, adopt infrared on-line detecting system control to remove the amount of water in many water cure of raw material sodium water smoking, make the moisture content in the system remain on 1.1-1.2mol/molNa
2Between the S, with many water cure sodium and the nmp solution azeotropic of in reactor, heating, temperature 180-204 ℃; The crystal water of many water cure sodium is deviate from the water vapor form, then separated the water vapour and N-Methyl pyrrolidone and the hydrogen sulfide that produce in the dehydration through the atmospheric distillation tower, its concrete technology technology comprises:
1) under the control of online infrared detection system, in the reaction system that contains sodium sulphite, N-Methyl pyrrolidone, solubility promoter sodium-acetate, adopt electrically heated slowly reaction system to be heated, the molal quantity by the residue water in the online infrared detection system hierarchy of control remains on 1.1-1.2mol/molNa
2Between the S;
2) with 1) water vapour that removes and NMP and hydrogen sulfide pass into the atmospheric distillation tower, and the vapor phase rectifying separation is gone out NMP, water vapour, hydrogen sulfide body respectively from bottom, top and the middle and upper part of rectifying tower through overcooling, absorb recycling.
2. the many water cure sodium dehydration technique during described polyphenylene sulfide is produced according to claim 1 is characterized in that described sodium sulphite is three-five water cure sodium, and the azeotropic time of heating is 2-3 hour, hydrogen sulfide by ammonia absorption through processing and utilizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN102888000A true CN102888000A (en) | 2013-01-23 |
| CN102888000B CN102888000B (en) | 2014-05-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103788373A (en) * | 2014-02-21 | 2014-05-14 | 珠海长先化学科技有限公司 | Dehydration process of multi-water sodium sulfide during polyphenyl thioether resin synthesis |
| CN111286027A (en) * | 2020-02-13 | 2020-06-16 | 四川明道和化学新材料有限公司 | Production method of polyphenylene sulfide with low covalent bonding chlorine |
| CN114621441A (en) * | 2022-04-27 | 2022-06-14 | 浙江新和成特种材料有限公司 | Polyphenylene sulfide preparation process capable of recovering and recycling hydrogen sulfide waste gas |
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| 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 |
| US20040249118A1 (en) * | 2001-09-27 | 2004-12-09 | Masaru Kagoshima | Process for production of polyarylene 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 |
-
2011
- 2011-07-18 CN CN201110199757.4A patent/CN102888000B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040249118A1 (en) * | 2001-09-27 | 2004-12-09 | Masaru Kagoshima | Process for production of polyarylene sulfide |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103788373A (en) * | 2014-02-21 | 2014-05-14 | 珠海长先化学科技有限公司 | Dehydration process of multi-water sodium sulfide during polyphenyl thioether resin synthesis |
| 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 |
| CN111286027A (en) * | 2020-02-13 | 2020-06-16 | 四川明道和化学新材料有限公司 | Production method of polyphenylene sulfide with low covalent bonding chlorine |
| 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 |
| CN114621441A (en) * | 2022-04-27 | 2022-06-14 | 浙江新和成特种材料有限公司 | Polyphenylene sulfide preparation process capable of recovering and recycling hydrogen sulfide waste gas |
| 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 |
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