CN1345892A - Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether - Google Patents
Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether Download PDFInfo
- Publication number
- CN1345892A CN1345892A CN00116142A CN00116142A CN1345892A CN 1345892 A CN1345892 A CN 1345892A CN 00116142 A CN00116142 A CN 00116142A CN 00116142 A CN00116142 A CN 00116142A CN 1345892 A CN1345892 A CN 1345892A
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- CN
- China
- Prior art keywords
- catalyst
- nmp
- metal halide
- recovering
- carbonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 230000018044 dehydration Effects 0.000 claims abstract 2
- 238000006297 dehydration reaction Methods 0.000 claims abstract 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 13
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 8
- 230000019086 sulfide ion homeostasis Effects 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- WZPDTOPYCQOUJT-UHFFFAOYSA-N disodium;sulfide;dihydrate Chemical compound O.O.[Na+].[Na+].[S-2] WZPDTOPYCQOUJT-UHFFFAOYSA-N 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006389 polyphenyl polymer Polymers 0.000 abstract description 4
- 150000003568 thioethers Chemical class 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 150000005309 metal halides Chemical class 0.000 abstract description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to a technique for recovering solent and catalyst in the course of production of polyphenyl thioether and is characterized by that said invention includes the following steps: using polyhydrate sodium sulfide and p-xylene as raw material, through the processes of dehydration and polycondensation, to produce polyphenyl thioether monomer, metal halide is used as catalyst, after polycondensation reaction is completed, firstly, using carbonate to soake the filtered-out reaction residuum to make the reaction residuum undergo the process of double decomposition to obtain carbonate deposit matter and soluble salt solution, then filtering, making the filtrating richly containing NMP return to raw material treatment, and recovering the filter cake, and under the acid condition obtaining original metal halide catalyst. The recovery rate of NMP can be up to 93%, and recovery rate of the catalyst and be up to 95%.
Description
The invention relates to an improvement of a production process of polyphenylene sulfide.
In the process of Producing Polyphenylene Sulfide (PPS) monomer by polycondensation under the action of alkali metal catalyst by using sodium sulfide and P-dichlorobenzene (P-DCB) as raw materials, NMP (N-methyl pyrrolidone) solution of alkali metal is needed to complete catalysis in the polymerization stage, compared with the cost of other raw materials, NMP and the alkali metal catalyst occupy equivalent price proportion, but NMP and the catalyst are not consumed theoretically in the production process of PPS, so that the key of reducing the production cost of PPS is whether the catalyst can be recovered at a higher recovery rate or not.
After the polymerization is completed, 65-70% of NMP can be recovered by a conventional method, but the remaining 25-30% combined with the catalyst remains in a residue which is a solid solution like a complex, has a boiling point of 150-160, is extremely difficult to separate, and even under vacuum conditions, this portion of NMP cannot be recovered.
In view of the above disadvantages of the prior art, the present invention is directed to a new method for recovering solvent and catalyst in the production of polyphenylene sulfide, so as to recover the portion of NMP and catalyst remaining in solid solution, thereby reducing the production cost of PPS.
The object of the present invention is achieved by the following method.
The solvent and catalyst recovering technology for producing polyphenyl thioether adopts sodium sulfide and p-xylene as material and produces polyphenyl thioether monomer through dewatering, polycondensation and other technological steps. Using metal halide salt as catalyst, after finishing polycondensation reaction: firstly, soaking the filtered reaction residue by carbonate to ensure that the residue is subjected to double decomposition to form carbonate precipitate and soluble salt solution; then filtering, and returning the filter liquor rich in NMP to the raw material for treatment; and recovering the filtered filter cake under an acidic condition to obtain the original metal halide salt catalyst.
The catalyst and the process method selected by the invention can decompose and recover the NMP and the catalyst viscous solid solution during polycondensation to respectively obtain the NMP and the corresponding catalyst, wherein the recovery rate of the NMP can reach 93 percent, the raw material is saved, and the production cost of the PPS is reduced.
In practice, LiCl and CaCl are used as metal halides as catalyst2、MgCl2(ii) a The carbonate is Na2CO3、K2CO3、MgCO3Soaking the residue in an aqueous solution of the compound, and carrying out double decomposition on the catalyst LiCl combined with the NMP and NaCl to generate LiCO which is insoluble in both water and NMP3Precipitation, the reaction equation of which is as follows (to use LiCl and Na)2CO3The reaction system is as an example):
the filtrate obtained after filtration mainly contains NMP and NACL, and the filtrate is recovered by rectification under vacuum condition like NMP of other discharged liquid in the process.
The filter cake obtained after filtration, namely LI2CO3, is reacted with HCL
And recovering to obtain LiCl.
Example 1
600g LiCl and 12Kg NMP solution were added in the polymerization reaction, and after the polycondensation reaction was completed, the solvent and catalyst were recovered to obtain 11.16Kg NMP and 570g LiCl, with recovery rates of 93% and 95%, respectively.
Example 2 polymerization with 700g CaCl2And NMP solution 14Kg, after the polycondensation reaction is completed, the solvent and catalyst are recovered, and NMP 12.95Kg and CaCl are recovered2672g, and the recovery rates are respectively 92.5 percent and 96 percent.
Claims (4)
1. The solvent and catalyst recovery technology in polyphenylene sulfide production adopts sodium sulfide dihydrate and p-dichlorobenzene as raw materials, and produces polyphenylene sulfide monomer through the process steps of dehydration, polycondensation and the like, and is characterized in that metal halide salt is used as a catalyst, and after the polycondensation reaction is finished:
1) soaking the filtered reaction residue in carbonate to double decompose the residue into carbonate precipitate
Starch and soluble salt solution.
2) Filtering on the basis of 1), and returning the filtrate rich in NMP to raw material treatment; filtered filter
Recovering the cake under acidic condition to obtain the original metal halide salt catalyst.
2. The solvent and catalyst recovery technique in polyphenylene sulfide production as claimed in claim 1, wherein said metal halide salt as catalyst is LiCl, CaCl2、MgCl2Any one of the above.
3. The method as claimed in claim 2, wherein the carbonate is Na2CO3K2CO3、MgCO3Any one of the above.
4. The solvent and catalyst recovery technique in polyphenylene sulfide production as claimed in claim 1 or 2, wherein the acidic substance added to the filter cake is HCl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00116142A CN1345892A (en) | 2000-09-30 | 2000-09-30 | Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00116142A CN1345892A (en) | 2000-09-30 | 2000-09-30 | Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1345892A true CN1345892A (en) | 2002-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00116142A Pending CN1345892A (en) | 2000-09-30 | 2000-09-30 | Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1345892A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805456A (en) * | 2010-03-16 | 2010-08-18 | 苏州兆达特纤科技有限公司 | Method for reclaiming solvent in poly(p-phenytene terephthalamide)resin production |
| CN101205298B (en) * | 2006-12-20 | 2011-05-11 | 自贡鸿鹤化工股份有限公司 | Method for recovering distillation residual liquid of polyphenylene sulfide resin synthesis by compression process |
| CN102698498A (en) * | 2012-05-28 | 2012-10-03 | 自贡鸿鹤化工股份有限公司 | Solid-liquid separation method for salted mixed liquid in production of polyphenylene sulfide |
| CN104447480A (en) * | 2014-11-06 | 2015-03-25 | 中国科学院过程工程研究所 | Continuous recycling method of NMP (N-methyl pyrrolidone) solvent for polyphenylene sulfide production device |
| CN106366030A (en) * | 2016-10-12 | 2017-02-01 | 南京大学 | High-purity recycling process system of complex chemical waste liquid |
| CN106478481A (en) * | 2016-10-08 | 2017-03-08 | 南京大学 | Waste water ultra-pure separation and purification technique of methyl pyrrolidone containing N and paracide |
| CN106565956A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process |
| CN106832284A (en) * | 2017-03-23 | 2017-06-13 | 四川纽湃斯新材料有限公司 | The production method of polyphenylene sulfide and its recovery method of distillation residual liquid |
| CN107892314A (en) * | 2017-11-16 | 2018-04-10 | 新疆中泰新鑫化工科技股份有限公司 | The method that lithium chloride is reclaimed from the residual slurries of kettle of the lithium chloride containing catalyst |
| CN107983393A (en) * | 2017-12-29 | 2018-05-04 | 内蒙古聚贤化工材料科技有限公司 | A kind of method that lithium chloride is recycled in the production for polyphenylene sulfide |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN110204723A (en) * | 2019-07-02 | 2019-09-06 | 西北师范大学 | A kind of preparation method of heat resistant poly diphenyl sulfide |
| CN112940244A (en) * | 2019-12-11 | 2021-06-11 | 南通星辰合成材料有限公司 | Pretreatment method for polyphenylene oxide solvent recovery |
| CN115746302A (en) * | 2022-11-28 | 2023-03-07 | 宜宾学院 | Recovery process of materials in polyphenylene sulfide production process |
-
2000
- 2000-09-30 CN CN00116142A patent/CN1345892A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205298B (en) * | 2006-12-20 | 2011-05-11 | 自贡鸿鹤化工股份有限公司 | Method for recovering distillation residual liquid of polyphenylene sulfide resin synthesis by compression process |
| CN101805456A (en) * | 2010-03-16 | 2010-08-18 | 苏州兆达特纤科技有限公司 | Method for reclaiming solvent in poly(p-phenytene terephthalamide)resin production |
| CN102698498A (en) * | 2012-05-28 | 2012-10-03 | 自贡鸿鹤化工股份有限公司 | Solid-liquid separation method for salted mixed liquid in production of polyphenylene sulfide |
| CN104447480B (en) * | 2014-11-06 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of nmp solvent continuous recovery method of polyphenylene sulfide process units |
| CN104447480A (en) * | 2014-11-06 | 2015-03-25 | 中国科学院过程工程研究所 | Continuous recycling method of NMP (N-methyl pyrrolidone) solvent for polyphenylene sulfide production device |
| CN106478481A (en) * | 2016-10-08 | 2017-03-08 | 南京大学 | Waste water ultra-pure separation and purification technique of methyl pyrrolidone containing N and paracide |
| CN106478481B (en) * | 2016-10-08 | 2018-07-06 | 南京大学 | The ultra-pure separation and purification technique of waste water containing N-Methyl pyrrolidone and paracide |
| CN106366030A (en) * | 2016-10-12 | 2017-02-01 | 南京大学 | High-purity recycling process system of complex chemical waste liquid |
| WO2018072739A1 (en) * | 2016-10-21 | 2018-04-26 | 天津科技大学 | Method for comprehensive recycling of by-product slurry during polyphenylene sulfide production |
| CN106565956A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process |
| CN106565956B (en) * | 2016-10-21 | 2018-09-28 | 天津科技大学 | By-product slurry comprehensive reutilization method in a kind of polyphenylene sulfide production process |
| CN106832284A (en) * | 2017-03-23 | 2017-06-13 | 四川纽湃斯新材料有限公司 | The production method of polyphenylene sulfide and its recovery method of distillation residual liquid |
| CN106832284B (en) * | 2017-03-23 | 2019-03-29 | 四川纽湃斯新材料有限公司 | The production method of polyphenylene sulfide and its recovery method of distillation residual liquid |
| CN107892314A (en) * | 2017-11-16 | 2018-04-10 | 新疆中泰新鑫化工科技股份有限公司 | The method that lithium chloride is reclaimed from the residual slurries of kettle of the lithium chloride containing catalyst |
| CN107983393A (en) * | 2017-12-29 | 2018-05-04 | 内蒙古聚贤化工材料科技有限公司 | A kind of method that lithium chloride is recycled in the production for polyphenylene sulfide |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN110204723A (en) * | 2019-07-02 | 2019-09-06 | 西北师范大学 | A kind of preparation method of heat resistant poly diphenyl sulfide |
| CN112940244A (en) * | 2019-12-11 | 2021-06-11 | 南通星辰合成材料有限公司 | Pretreatment method for polyphenylene oxide solvent recovery |
| CN112940244B (en) * | 2019-12-11 | 2022-10-11 | 南通星辰合成材料有限公司 | Pretreatment method for polyphenylene oxide solvent recovery |
| CN115746302A (en) * | 2022-11-28 | 2023-03-07 | 宜宾学院 | Recovery process of materials in polyphenylene sulfide production process |
| CN115746302B (en) * | 2022-11-28 | 2024-07-26 | 宜宾学院 | Material recycling process in polyphenylene sulfide production process |
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