CN105218817A - A kind of residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation - Google Patents
A kind of residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation Download PDFInfo
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- CN105218817A CN105218817A CN201510743879.3A CN201510743879A CN105218817A CN 105218817 A CN105218817 A CN 105218817A CN 201510743879 A CN201510743879 A CN 201510743879A CN 105218817 A CN105218817 A CN 105218817A
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Abstract
The present invention relates to a kind of residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation, water is utilized to carry out elutriation to finished product tower reactor is residual, NMP is wherein made to be dissolved in water, and oligopolymer is owing to adding water in solvent solubleness reduces and then separate out, filter after washing, oligopolymer and fine-grained resin reclaim as low-molecular-weight resin, filtrate is for containing NMP, part salt, the aqueous solution of polycondensation auxiliary agent, precipitate under the effect of another kind of auxiliary agent, filtered and recycled is precipitated as polycondensation auxiliary agent, filtrate contains NMP and water and a small amount of salt, anti-mixed solvent groove of sending back to carries out being separated of water and NMP again, reach the object reclaiming the residual middle NMP of still and polycondensation auxiliary agent.Its advantage is: can ensure that system is driven continuously, without the need to high temperature carbonization, effective reclaim finished product still residual in contained NMP and polycondensation auxiliary agent, reduce production cost, improve the utilization ratio of NMP and reaction promoter, improve production environment, decrease the pollution to environment.
Description
Technical field
The invention belongs to organic polymer material field, be related specifically to distillation tower bottom product process in the middle production of resins solvent recovering system of poly arylidene thio-ester (PAS) resinoid (organic polymer material, as poly arylidene thio-ester, polyaryl thioether sulfone, polyarylene sulfide ketone etc.) and reclaim a kind of technical process of wherein residual solvent.
Background technology
In the resinoid production of poly arylidene thio-ester, polycondensation will use polar organic solvent N-Methyl pyrrolidone (being called for short NMP) as solvent, and can go out be mainly the salt of sodium-chlor by by-product in process of production, and various additives in production process, auxiliary agent, catalyzer are also salt, also will use water in production process, these salts are just dissolved in the mixed solvent of NMP-water; Can generate in reaction process by product, molecular weight deficiency oligopolymer (also known as oligopolymer), also have unreacted raw material, solvent NMP to decompose after product, filtration unit fail the fine-grained resin etc. collected, these materials are dissolved or suspended in mixed solvent too.
Polycondensation uses solvent NMP, recycles, and needs to carry out recovery and uses, namely NMP is separated from the mixed solvent dissolving all kinds of salt, oligopolymer, unreacting material, resin, degradation production, side reaction product etc.; This separation system is called solvent recovering system.
In the latter stage of rectifying, the NMP major part in tower bottom of rectifying tower is recovered, and thus the concentration of above-mentioned various impurity just raises, and owing to there being the existence of oligopolymer, forms a kind of paste of very thickness, is called that tower reactor still is residual, wherein containing a large amount of NMP and oligopolymer.
The main technique of domestic and international solvent recuperation is all adopt distillation technology, adopts rectifying tower to be separated mixed solvent.To the salt taked, tower reactor still, the processing mode of residual and by product, degradation production to some extent need not.Because of the salt taked with tower reactor still is residual interiorly again must reclaim use all containing a large amount of NMP, to reduce production cost.
Method domestic is at present, to the salt taked out with tower reactor still is residual carries out high-temperature vacuum destructive distillation, make NMP formed steam again condensation get off to reclaim.Problems existing: (1) adopts salt and tower reactor still is residual because adopting high-temperature vacuum destructive distillation, material the least possible (namely utilizing rectifying tower to reclaim NMP as far as possible), thus the operation of rectifying tower is discontinuous, and the quality of NMP product is also unstable; (2) owing to being high temperature carbonization, need to set up heat-conducting oil system; (3) because pyrolysis temperature is very high, exceeded the decomposition calibration (164 DEG C) of NMP, caused a lot of NMP to decompose, and degradation production fails to be separated from solvent, cause the accumulation in the recycling of solvent of this product, cause the quality of solvent NMP to decline, even scrap and can not use; (4) due to the existence of oligopolymer, paste thickness very, during destructive distillation, the NMP of internal batch can not be distilled out of completely, adopt salt and still residual in the NMP rate of recovery not high; (5) because finishing column tower reactor needs to distill 90% of the NMP in mixed solvent, system becomes very thickness, frequent blocking tower reactor, interchanger, recycle pump and pipeline, thus within every 48 hours, the work of boiling tower reactor, reboiler and pipeline is carried out with regard to needing, cause the actual driving rate of total system to decline, throughput reduces.
The present invention is studied the residual processing mode of poly arylidene thio-ester resinoid production system solvent recuperation distillation system finished product tower reactor.
Summary of the invention
The object of this invention is to provide a kind ofly can ensure that system is driven continuously, residual without the need to high temperature carbonization, efficient recovery still in the residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation of contained NMP and polycondensation auxiliary agent.
Inventive principle: the present invention utilizes water to carry out elutriation to finished product tower reactor is residual, NMP is wherein made to be dissolved in water, and oligopolymer is owing to adding water in solvent solubleness reduces and then separate out, filter after washing, oligopolymer and fine-grained resin reclaim as low-molecular-weight resin, filtrate is for containing NMP, part salt, the aqueous solution of polycondensation auxiliary agent, precipitate under the effect of another kind of auxiliary agent, filtered and recycled is precipitated as polycondensation auxiliary agent, filtrate contains NMP and water and a small amount of salt, anti-mixed solvent groove of sending back to carries out being separated of water and NMP again, reach the object reclaiming the residual middle NMP of still and polycondensation auxiliary agent.
Technical scheme of the present invention is as follows:
(1) still raffinate leaching groove A and still raffinate leaching groove B two still raffinates leaching grooves are set, to still raffinate leaching groove B nitrogen replacement and the water being filled with 40 ~ 50% of leaching groove volume as the residual leaching liquid of still, start stirring;
(2) in still raffinate leaching groove B, still raffinate is carried; After the conveying of still raffinate, open steaming out, by clean for residual for still in line of pipes purging (because still raffinate can very thickness when temperature reduces, meeting blocking pipe, must blow clean);
(3) stir leaching after 0.5 hour, stop stirring, natural subsidence;
Now, the NMP during still is residual and auxiliary agent are dissolved in water, and the oligopolymer be originally dissolved in NMP is then separated out due to adding of water, form throw out;
(4), after natural subsidence, open still raffinate leaching groove B side bleeder valve, residual for the still containing water, NMP, auxiliary agent leaching liquid is pumped in auxiliary agent withdrawing can; After having sent, still raffinate leaching groove B bottom valve is opened, throw out mud is put in still raffinate leaching groove A, containing oligopolymer, water, NMP, auxiliary agent in this throw out mud;
(5) auxiliary agent reclaims: the stirring starting auxiliary agent withdrawing can; In auxiliary agent withdrawing can, add precipitation agent, auxiliary agent and precipitation agent generation chemical reaction, continue stirring until and react completely, and generates solid precipitation;
(6) material in auxiliary agent withdrawing can is put into auxiliary agent and reclaim filter inner filtration; Filtrate is containing NMP, water and the auxiliary agent precipitation of wearing filter on a small quantity, flows automatically to the interior also natural subsidence of filtrate accepting groove; Filter cake is the reaction promoter of returning, after drying reprocessing, reuses;
(7) filter pump sends in mixed solvent storage tank the NMP reclaimed wherein; After wherein contained auxiliary agent precipitation accumulation, counter sending back in auxiliary agent withdrawing can together processes when the residual leaching of next batch still;
(8) secondary leaching: the one-level spiral desalinization of soil by flooding or leaching washing lotion sent here by washing step is delivered in still raffinate leaching groove A, starts and stirs; This washing lotion main component is water, the sodium-chlor containing trace;
(9) after in still raffinate leaching groove B, throw out mud all puts into still raffinate leaching groove A, wait-receiving mode next batch still raffinate;
(10) start the residual leaching liquid filter of still, still raffinate leaching liquid pump, throw out mud in still raffinate leaching groove A is filtered, filter cake is collected; Filtrate is containing water, on a small quantity NMP, on a small quantity polycondensation auxiliary agent, the liquid wearing the oligopolymer of filter, flows automatically to the residual leaching liquid of still as next batch in still raffinate leaching groove B;
(11) repeating step 1 ~ 10, processes next batch still raffinate, and during repeating step 1, the residual leaching liquid of still be filled with in still raffinate leaching groove B is that the filtrate gravity flow leached in groove A by the still raffinate of last batch comes.
Described natural subsidence is settled down to throw out and liquid layered, visually sees less than having material in liquid still till precipitation.
Precipitation agent described in step 5 is water soluble carbonate.
The add-on of the precipitation agent described in step 5 is according to detecting material in auxiliary agent withdrawing can, calculates the content of wherein auxiliary agent, determines by the proportioning of reacting with auxiliary agent.
Advantage of the present invention is: can ensure that system is driven continuously, without the need to high temperature carbonization, effective reclaim finished product still residual in contained NMP and polycondensation auxiliary agent, reduce production cost, improve the utilization ratio of NMP and reaction promoter, improve production environment, decrease the pollution to environment.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the residual leaching of solvent recuperation finished product tower reactor;
Fig. 2 be in the process flow of the residual leaching of solvent recuperation finished product tower reactor NMP flow to schematic diagram;
Fig. 3 be in the process flow of the residual leaching of solvent recuperation finished product tower reactor water flow to schematic diagram;
Fig. 4 be in the process flow of the residual leaching of solvent recuperation finished product tower reactor auxiliary agent flow to schematic diagram;
Fig. 5 be in the process flow of the residual leaching of solvent recuperation finished product tower reactor low-molecular-weight resin (oligopolymer) flow to schematic diagram.
Embodiment
Embodiment 1
The residual leaching of finished product tower reactor applying the present invention to 3000 tons/year of polyphenylene sulfide production equipment solvent recovering systems is reclaimed:
Note: polyphenylene sulfide is the resinoid one of poly arylidene thio-ester.
Along with the NMP rectifying in finishing column is distilled away, constantly there is the new thick NMP containing impurity to supplement into simultaneously, oligopolymer (the low molecular weight polyphenylene sulfide resin contained in tower bottoms, dissolve in NMP), auxiliary agent equal size increases gradually, form finished product bottom product, the NMP that this still is residual to be contained, oligopolymer, auxiliary agent need to recycle; When oligopolymer in finished product tower reactor is accumulated to need degree to be processed, stop to finishing column charging, process finished product bottom product, treatment step is as follows:
(1) still raffinate leaching groove A and still raffinate leaching groove B two still raffinates leaching grooves are set, to still raffinate leaching groove B nitrogen replacement and the water being filled with 40 ~ 50% of leaching groove volume as the residual leaching liquid of still, start stirring;
(2) in still raffinate leaching groove B, still raffinate is carried; After the conveying of still raffinate, open steaming out, by clean for residual for still in line of pipes purging (because still raffinate can very thickness when temperature reduces, meeting blocking pipe, must blow clean);
(3) stir leaching after 0.5 hour, stop stirring, natural subsidence 3 hours;
Now, the NMP during still is residual and auxiliary agent are dissolved in water, and the oligopolymer be originally dissolved in NMP is then separated out due to adding of water, form throw out;
(4), after natural subsidence, open still raffinate leaching groove B side bleeder valve, residual for the still containing water, NMP, auxiliary agent leaching liquid is pumped in auxiliary agent withdrawing can; After having sent, still raffinate leaching groove B bottom valve is opened, throw out mud is put in still raffinate leaching groove A, containing oligopolymer, water, NMP, auxiliary agent in this throw out mud;
(5) auxiliary agent reclaims: the stirring starting auxiliary agent withdrawing can; In auxiliary agent withdrawing can, add water soluble carbonate as precipitation agent, auxiliary agent and precipitation agent generation chemical reaction, Keep agitation 20min, to reacting completely, generates solid precipitation;
(6) material in auxiliary agent withdrawing can is put into auxiliary agent and reclaim filter inner filtration; Filtrate is containing NMP, water and the auxiliary agent precipitation of wearing filter on a small quantity, flows automatically to the interior also natural subsidence of filtrate accepting groove 4 hours; Filter cake is the reaction promoter of returning, after drying reprocessing, reuses;
(7) filter pump sends in mixed solvent storage tank the NMP reclaimed wherein; After wherein contained auxiliary agent precipitation accumulation, counter sending back in auxiliary agent withdrawing can together processes when the residual leaching of next batch still;
(8) secondary leaching: the one-level spiral desalinization of soil by flooding or leaching washing lotion sent here by washing step is delivered in still raffinate leaching groove A, starts and stirs; This washing lotion main component is water, the sodium-chlor containing trace;
(9) after in still raffinate leaching groove B, throw out mud all puts into still raffinate leaching groove A, wait-receiving mode next batch still raffinate;
(10) start the residual leaching liquid filter of still, still raffinate leaching liquid pump, throw out mud in still raffinate leaching groove A is filtered, filter cake is collected; Filtrate is containing water, on a small quantity NMP, on a small quantity polycondensation auxiliary agent, the liquid wearing the oligopolymer of filter, flows automatically to the residual leaching liquid of still as next batch in still raffinate leaching groove B;
(11) repeating step 1 ~ 10, processes next batch still raffinate, and during repeating step 1, the residual leaching liquid of still be filled with in still raffinate leaching groove B is that the filtrate gravity flow leached in groove A by the still raffinate of last batch comes.
The filter cake collected in step 10 is low-molecular-weight resin (oligopolymer) and fine-grained resin, concentrates and send washing step washing, drying, sell as defective resin when being accumulated to some amount.
The residual leaching technology Con trolling index of finished product tower reactor:
In process of production, each equipment normal operation always, reaches the object reclaiming the residual middle NMP of finished product tower reactor, oligopolymer and polycondensation auxiliary agent.
Claims (3)
1., for the residual leaching technology of still of poly arylidene thio-ester resinoid production solvent recuperation, it is characterized in that: processing step is as follows:
(1) still raffinate leaching groove A and still raffinate leaching groove B two still raffinates leaching grooves are set, to still raffinate leaching groove B nitrogen replacement and the water being filled with 40 ~ 50% of leaching groove volume as the residual leaching liquid of still, start stirring;
(2) in still raffinate leaching groove B, still raffinate is carried; After the conveying of still raffinate, open steaming out, by clean for residual for still in line of pipes purging;
(3) stir leaching after 0.5 hour, stop stirring, natural subsidence;
Now, the NMP during still is residual and auxiliary agent are dissolved in water, and the oligopolymer be originally dissolved in NMP is then separated out due to adding of water, form throw out;
(4), after natural subsidence, open still raffinate leaching groove B side bleeder valve, residual for the still containing water, NMP, auxiliary agent leaching liquid is pumped in auxiliary agent withdrawing can; After having sent, still raffinate leaching groove B bottom valve is opened, throw out mud is put in still raffinate leaching groove A;
(5) auxiliary agent reclaims: the stirring starting auxiliary agent withdrawing can; In auxiliary agent withdrawing can, add precipitation agent, auxiliary agent and precipitation agent generation chemical reaction, continue stirring until and react completely, and generates solid precipitation;
(6) material in auxiliary agent withdrawing can is put into auxiliary agent and reclaim filter inner filtration; Filtrate is containing NMP, water and the auxiliary agent precipitation of wearing filter on a small quantity, flows automatically to the interior also natural subsidence of filtrate accepting groove; Filter cake is the reaction promoter of returning, after drying reprocessing, reuses;
(7) filter pump sends in mixed solvent storage tank the NMP reclaimed wherein; After wherein contained auxiliary agent precipitation accumulation, counter sending back in auxiliary agent withdrawing can together processes when the residual leaching of next batch still;
(8) secondary leaching: the one-level spiral desalinization of soil by flooding or leaching washing lotion sent here by washing step is delivered in still raffinate leaching groove A, starts and stirs;
(9) after in still raffinate leaching groove B, throw out mud all puts into still raffinate leaching groove A, wait-receiving mode next batch still raffinate;
(10) start the residual leaching liquid filter of still, still raffinate leaching liquid pump, throw out mud in still raffinate leaching groove A is filtered, filter cake is collected; Filtrate flows automatically to the residual leaching liquid of still as next batch in still raffinate leaching groove B;
(11) repeating step 1 ~ 10, processes next batch still raffinate, and during repeating step 1, the residual leaching liquid of still be filled with in still raffinate leaching groove B is that the filtrate gravity flow leached in groove A by the still raffinate of last batch comes.
2. the residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation according to claim 1, is characterized in that: described natural subsidence is settled down to throw out and liquid layered, visually sees less than having material in liquid still till precipitation.
3. the residual leaching technology of still for poly arylidene thio-ester resinoid production solvent recuperation according to claim 1, is characterized in that: the precipitation agent described in step 5 is water soluble carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
| CN114949903A (en) * | 2022-06-14 | 2022-08-30 | 山东明化新材料有限公司 | Parallel polyarylene sulfide resin production solvent and catalyst separation and recovery system and method |
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| JP2000256010A (en) * | 1999-03-11 | 2000-09-19 | Idemitsu Petrochem Co Ltd | Recovering method of lithium |
| CN101205298A (en) * | 2006-12-20 | 2008-06-25 | 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 |
| CN102276838A (en) * | 2011-06-15 | 2011-12-14 | 南京大学 | Separation and recovery method for n-methylpyrrolidone (NMP) and lithium chloride catalyst during polyphenylene sulfide producing |
-
2015
- 2015-11-05 CN CN201510743879.3A patent/CN105218817A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256010A (en) * | 1999-03-11 | 2000-09-19 | Idemitsu Petrochem Co Ltd | Recovering method of lithium |
| CN101205298A (en) * | 2006-12-20 | 2008-06-25 | 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 |
| CN102276838A (en) * | 2011-06-15 | 2011-12-14 | 南京大学 | Separation and recovery method for n-methylpyrrolidone (NMP) and lithium chloride catalyst during polyphenylene sulfide producing |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
| CN114949903A (en) * | 2022-06-14 | 2022-08-30 | 山东明化新材料有限公司 | Parallel polyarylene sulfide resin production solvent and catalyst separation and recovery system and method |
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