CN102675683B - Solvent and catalyst recovery technology in polyphenyl thioether production - Google Patents
Solvent and catalyst recovery technology in polyphenyl thioether production Download PDFInfo
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- CN102675683B CN102675683B CN201110066328XA CN201110066328A CN102675683B CN 102675683 B CN102675683 B CN 102675683B CN 201110066328X A CN201110066328X A CN 201110066328XA CN 201110066328 A CN201110066328 A CN 201110066328A CN 102675683 B CN102675683 B CN 102675683B
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Abstract
The invention relates to a solvent and catalyst recovery technology in polyphenyl thioether production, which comprises the steps of: after polycondensation reaction is finished, firstly adding 1-3mol/mol Na2S and fresh NMP (N-methyl pyrrolidone) solvent as a diluting agent, diluting the reaction system with NMP to obtain another mixture, and further treating the mixture by filtering, extraction, evaporation and spiral evaporator to respectively obtain a mixed solution containing NMP and water and a powder mixture containing a cosolvent and byproducts; and evaporating the mixed solution containing NMP and water to remove water to obtain NMP solvent containing certain impurities, further rectifying and purifying the NMP solvent by a rectifying tower to obtain NMP solvent with the purity of 99.98% and the recovery rate of 96-98%to be recycled for polyphenyl thioether resin synthesis, and treating the powder mixture containing the cosolvent and byproducts to obtain catalyst lithium chloride with the purity of 99.95-99.98% and the recovery rate of 98-99%.
Description
Technical field
The present invention relates to the polyphenylene sulphide production process method improvement.
Background technology
Adopting sodium sulphite and santochlor (P-DCB) is raw material, polycondensation is produced in the technological process of polyphenylene sulfide (PPS) resin under the effect of basic metal solubility promoter, needing alkali-metal NMP(N-methyl-2-pyrrolidone at polymerization stage) solution finishes catalysis, compare with the cost of other raw material, NMP and basic metal solubility promoter occupy suitable price proportion, but solvent NMP and solubility promoter are nonexpendable in theory in the production process of PPS, can can therefore, reclaim with the higher rate of recovery be the key that reduce the PPS production cost with solubility promoter still.
After polyreaction is finished, the 65-70% of NMP can be reclaimed by the method for routine, but remaining 25-30% and solubility promoter combine and have stayed in the residue, this residue is the sosoloid that is similar to complex compound, boiling point 150-160, extremely difficult the separation, even under vacuum condition, also this part NMP can't be reclaimed.
Introduced solvent and solubility promoter recovery technology in a kind of polyphenylene sulfide production at Chinese patent application number CN001161423, but pondered-over is to adopt carbonate to reclaim so-called catalyzer, yet in fact low the getting of the rate of recovery of this catalyzer dare not allow the people flatter really, its catalyst recovery is very low generally between 5-10%wt, and the solubility promoter of returning can not recycle at all.
In United States Patent (USP) number US5711873, introduce the recovery technology of the solvent of polyphenylene sulfide production, although this technology adopts low boiling point solvent as the thinner of reaction system, although in reaction system, add the filtration that low boiling point organic solvent helps reaction mixture, and low boiling point solvent also reclaims easily and purifies, but, to having relatively high expectations of the material of polymerization reaction kettle, if the later stage in reaction system adds, can increase the pressure of reactor, also take simultaneously and carve the attentive response still and surpass design and bear pressure, cause serious accident because of carelessness like this.
In United States Patent (USP) number US6437024, introduced and adopted methyl alcohol to be used as extracting the extraction agent of oligopolymer in the polyphenylene sulfide, ring compound, nmp solvent and by product alkali metal halide, this by product should be lithium chloride therein, and it is that the employing lithium sulfide is the synthetic starting material of polyphenylene sulfide.
Above shortcoming in view of prior art, the objective of the invention is to create a kind of polyphenylene sulfide produce in the novel method that reclaims of solvent and solubility promoter, make with sosoloid form residual part NMP and solubility promoter and be able to the high-recovery recovery, to reduce the production cost of PPS, the NMP that returns simultaneously and the purity of solubility promoter all are very high, meet or exceed the level of external similar retrieving arrangement, and adopt spiral evaporator to solve the dope that produces in solvent and the solubility promoter removal process, this dope is solubility promoter lithium chloride crystal in fact, the purpose that adopts spiral evaporator is the strong shearing by this equipment, reduce the viscosity of dope, reach is that NMP wherein is or/and moisture content or/and methyl alcohol easy being evaporated very, is conducive to improve the rate of recovery and the purity of nmp solvent and solubility promoter lithium chloride.
Although the present invention adopts high boiling solvent to be used as the thinner of reaction system, but, also can be than adopting low boiling point organic solvent to obtain the purity height of polyphenylene sulfide, because a lot of oligopolymer and ring compound are easy to be dissolved in the nmp solvent, for this reason, the present invention can only be with methyl alcohol for the dissolving a small amount of NMP of recovery with as the solvent that dissolves lithium chloride, be that thinner is at first removed oligopolymer and ring compound and a large amount of solubility promoter lithium chlorides in the polyphenylene sulfide and the present invention adopts NMP, therefore it is a kind of reasonable to the objective of the invention is to utilize, and simple efficiently technical process route comes nmp solvent and solubility promoter lithium chloride in the poly-p-phenylene sulfide ether resin technological process of production to reclaim.
Summary of the invention
In view of the deficiencies in the prior art, the objective of the invention is, solvent and catalyst recovery technology in a kind of polyphenylene sulfide production are provided, nmp solvent and solubility promoter lithium chloride in the simple efficiently realization poly-p-phenylene sulfide ether resin technological process of production reclaim.
Its concrete grammar is: adopting many water cure sodium and santochlor is raw material, produce polyphenylene sulfide through processing steps such as dehydration, polycondensations, it is characterized in that, take metal halide salt as catalyzer, in fact should be solubility promoter (all expressing with solubility promoter later on), relate to the solvent of polyphenylene sulfide production and the recovery of solubility promoter etc. after polycondensation is finished, its Technology comprises:
1, add fresh nmp solvent in reaction system and be used as thinner, add-on is 1-3mol/ molNa
2S, thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter lithium chloride, water and by product, the vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation, that obtain containing polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP, and the filtrate of containing NMP, water, solubility promoter lithium chloride and part by product sodium-chlor.
2,1 resulting filtrate is steamed the mixture of NMP and moisture by underpressure distillation, residuum is the dope that contains solubility promoter and by product and a small amount of NMP and moisture content bottom the decompression separation device, become the mixing liquid that contains NMP and water through overcooling, it is stand-by to mix liquid infusion fluid storage tank.
3, with 2) dope that obtains further evaporates away wherein NMP and moisture with the worm conveyor input with the spiral evaporator of star-like feeder, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.The screw diameter of the spiral evaporator of using is 75, length-to-diameter ratio is 70-80, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 250-260 ℃ 3 diameters are installed above spiral is the 85-90mm venting port, and NMP and water vapour are to adopt vacuum pump to vacuumize discharge.
4, with 1 obtain contain polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP adopt methanol extraction three times, filter, it mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrate, then its mixing solutions being inputted an other distillation tower distills, from the distillation tower top out be methanol steam, this steam is through overcooling purifying recycling, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, stand-by through input NMP and water mixed liquid body storage tank after the cooling process.
5, with 2), 3), 4) NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower, from the distillation tower overhead stream out be moisture content, this moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified, the purity that flows out from the rectifying tower top is 99.98% nmp solvent, and the rate of recovery is 96-98%.
6, with 3) solubility promoter that obtains and the meal of by product, add industrial grade benzenemethanol, making the solids concn of its pulverulent mixture in methanol solvate is 15-20%wt, its solubility promoter fully is dissolved among the methyl alcohol, then through repeatedly filtering for three times, after dissolving, the filtration, three times filtrate combines stand-by; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7, with 6) filtrate inputs another evaporator evaporation and removes methyl alcohol, the viscous mixture that contains methyl alcohol and solubility promoter from the base of evaporator remainder, this dope adopts the worm conveyor input further to evaporate away wherein remaining methyl alcohol with the spiral evaporator of star-like feeder, cool off recycling from the methanol steam process that spiral evaporator is evaporated, what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.95-99.98%, the rate of recovery is 98-99%, the screw diameter of the spiral evaporator of its application is 158, length-to-diameter ratio is 50-60, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 150-160 ℃ 3 diameters are installed above spiral is the 55-60mm venting port, and methanol gas is to adopt vacuum pump to vacuumize discharge.
The present invention is in order to reach the purpose of invention, adopt spiral evaporator to containing a small amount of NMP and moisture content or containing a small amount of methyl alcohol and the thick material of lithium chloride of moisture content and sodium-chlor further evaporates wherein NMP or moisture content or methyl alcohol, thereby make the lithium chloride of large bulk under the shearing of spiral, become fine powder, so namely solved and adopted so-called thin-film evaporator drying out to be the material of large bulk, solved again the inefficient problem of thin-film evaporator, simultaneously, the NMP that is evaporated or the recovery problem of water vapour or methanol steam have also been solved.
It is raw material that the present invention adopts many water cure sodium and p-Xylol, produces polyphenylene sulfide through processing steps such as dehydration, polycondensations.Take basic metal halide salt lithium chloride as solubility promoter, after polycondensation is finished, add first 1-3mol/ molNa
2S, fresh nmp solvent is as thinner, make reaction system under the dilution of NMP, again obtain another mixture, this mixture is through obtaining containing the wet mixture of polyphenylene sulfide and solubility promoter lithium chloride and by product sodium-chlor and a small amount of water and nmp solvent after filtering, this mixture methanol extraction is that water in the mixture and NMP and solubility promoter lithium chloride form the mixing solutions that contains water and NMP and solubility promoter lithium chloride, this solution is removed most water and NMP and methyl alcohol through evaporator evaporation, after further processing with spiral evaporator again, obtain respectively containing the mixing solutions of NMP and moisture, and the pulverulent mixture that contains solubility promoter and by product.
And filtrate being that reaction system filters out contained the mixed solution of water and NMP and solubility promoter lithium chloride and part by product sodium-chlor, this mixed solution removes most water through evaporator evaporation and NMP forms a kind of thick mixture, after further processing with spiral evaporator again, obtain respectively containing the mixing solutions of NMP and moisture, and the pulverulent mixture that contains solubility promoter and by product.
The mixing solutions that contains NMP and water is removed moisture content through pervaporation, obtain containing the nmp solvent of certain impurity, it is that 99.98% nmp solvent recycles synthetic in polyphenylene sulfide that this nmp solvent obtains purity through the further rectification and purification of rectifying tower, and the rate of recovery of nmp solvent is 96-98%.
After the pulverulent mixture that solubility promoter and by product arranged repeatedly dissolves solubility promoter through methyl alcohol again, filter, filtrate is after pervaporation is removed most methyl alcohol, obtain a kind of dope that contains methyl alcohol, dope vacuumizes through spiral evaporator and removes methyl alcohol, obtaining purity is 99.95-99.98%, and the rate of recovery is the catalyzer lithium chloride (solubility promoter) of 98-99%.
The solubility promoter and the processing method that adopt the present invention to select, can obtain respectively NMP and corresponding solubility promoter with being reclaimed by NMP and the thick Solid solution decomposition of solubility promoter when the polycondensation, wherein the rate of recovery of NMP can reach 96-98%, save raw material, reduced the production cost of PPS.
Embodiment
1) in the synthetic reaction system of polyphenylene sulfide, added a certain amount of nmp solvent as thinner before this, then the reaction system mixture is carried out filtering separation, filtrate is gone out by evaporation and is formed a kind of thick material behind most NMP and the moisture content, after thick material is removed NMP and moisture content through the further evaporation process of spiral evaporator, thereby become flour, NMP and moisture content input storage tank are pending; And the filter cake that reaction system filter to produce adds wherein residual NMP and moisture content and the completely lithium chloride that is untreated of a certain amount of methanol extraction, then its evaporation is gone out and form a kind of thick material behind most NMP and moisture content and the methanol solvate, after this thick material process spiral evaporator is processed and removed NMP and moisture content, thereby become flour; NMP and moisture content input storage tank are pending.
2) with 1) the methyl alcohol NMP that obtains and the mixing solutions of moisture content by evaporation separates remove methyl alcohol, moisture content after, it is pending that residual NMP inputs storage tank.
3) with 1) flour that obtains adds a certain amount of methyl alcohol, make wherein lithium chloride fully be dissolved among the methyl alcohol after, remove by filter undissolved by product sodium-chlor.Contain lithium chloride and methyl alcohol in the filtrate, form a kind of thick material behind the most methyl alcohol of pervaporation, this material adopts spiral evaporator further to evaporate and removes methyl alcohol, and discharging meal from the spiral evaporator head is exactly the lithium chloride of returning.
4) with 1) and 2) NMP that obtains and moisture content after pervaporation is removed moisture content, again NMP is inputted rectifying tower NMP is carried out rectification and purification, the recycling of like this solvent recuperation used in the polyphenylene sulfide production process being returned.
The embodiment that the present invention is concrete.
Embodiment 1
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 3kg (1mol/ molNa after polycondensation is finished
2S) fresh nmp solvent is used as thinner, thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product, the vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation, that obtain containing polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP, and the filtrate of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrate is steamed the mixture of NMP and moisture by underpressure distillation, residuum is the dope that contains solubility promoter and by product and a small amount of NMP and moisture content bottom the decompression separation device, become the mixing liquid that contains NMP and water through overcooling, it is stand-by to mix liquid infusion fluid storage tank.
3) with 2) dope that obtains is 75 with the worm conveyor input with the spiral evaporator screw diameter of star-like feeder, length-to-diameter ratio is 70, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 260 ℃ 3 diameters are installed above spiral is the 90mm venting port, NMP and water vapour are to adopt vacuum pump to vacuumize and discharge further to evaporate away wherein NMP and moisture, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP adopt methanol extraction three times, filter, it mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrate, then its mixing solutions being inputted an other distillation tower distills, from the distillation tower top out be methanol steam, this steam is through overcooling purifying recycling, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, stand-by through input NMP and water mixed liquid body storage tank after the cooling process.
5) with 2), 3), 4) NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower, from the distillation tower overhead stream out be moisture content, this moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified, the purity that flows out from the rectifying tower top is 99.98% nmp solvent, and the rate of recovery is 96%.
6), with 3) solubility promoter that obtains and the meal of by product, add industrial grade benzenemethanol, making the solids concn of its pulverulent mixture in methanol solvate is 15%wt, its solubility promoter fully is dissolved among the methyl alcohol, then through repeatedly filtering for three times, after dissolving, the filtration, three times filtrate combines stand-by; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) filtrate inputs another evaporator evaporation and removes methyl alcohol, the viscous mixture that contains methyl alcohol and solubility promoter from the base of evaporator remainder, this dope adopts the worm conveyor input further to evaporate away wherein remaining methyl alcohol with the spiral evaporator of star-like feeder, be 58 from the spiral evaporator screw diameter, length-to-diameter ratio is 50, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 160 ℃ 3 diameters are installed above spiral is the 55mm venting port, methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam process cooling recycling that is evaporated, what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.95%, and the rate of recovery is 98%
Embodiment 2
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 6kg (2mol/ molNa after polycondensation is finished
2S) fresh nmp solvent is used as thinner, thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product, the vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation, that obtain containing polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP, and the filtrate of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrate is steamed the mixture of NMP and moisture by underpressure distillation, residuum is the dope that contains solubility promoter and by product and a small amount of NMP and moisture content bottom the decompression separation device, become the mixing liquid that contains NMP and water through overcooling, it is stand-by to mix liquid infusion fluid storage tank.
3) with 2) dope that obtains is 75 with the worm conveyor input with the spiral evaporator screw diameter of star-like feeder, length-to-diameter ratio is 80, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 250 ℃ 3 diameters are installed above spiral is the 85mm venting port, NMP and water vapour are to adopt vacuum pump to vacuumize and discharge further to evaporate away wherein NMP and moisture, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP adopt methanol extraction three times, filter, it mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrate, then its mixing solutions being inputted an other distillation tower distills, from the distillation tower top out be methanol steam, this steam is through overcooling purifying recycling, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, stand-by through input NMP and water mixed liquid body storage tank after the cooling process.
5) with 2), 3), 4) NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower, from the distillation tower overhead stream out be moisture content, this moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified, the purity that flows out from the rectifying tower top is 99.98% nmp solvent, and the rate of recovery is 98%.
6), with 3) solubility promoter that obtains and the meal of by product, add industrial grade benzenemethanol, making the solids concn of its pulverulent mixture in methanol solvate is 20%wt, its solubility promoter fully is dissolved among the methyl alcohol, then through repeatedly filtering for three times, after dissolving, the filtration, three times filtrate combines stand-by; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) filtrate inputs another evaporator evaporation and removes methyl alcohol, the viscous mixture that contains methyl alcohol and solubility promoter from the base of evaporator remainder, this dope adopts the worm conveyor input further to evaporate away wherein remaining methyl alcohol with the spiral evaporator of star-like feeder, be 58 from the spiral evaporator screw diameter, length-to-diameter ratio is 50, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 150 ℃ 3 diameters are installed above spiral is the 60mm venting port, methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam process cooling recycling that is evaporated, what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.98%, and the rate of recovery is 99%
Embodiment 3
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 9kg (3mol/ molNa after polycondensation is finished
2S) fresh nmp solvent is used as thinner, thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product, the vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation, that obtain containing polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP, and the filtrate of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrate is steamed the mixture of NMP and moisture by underpressure distillation, residuum is the dope that contains solubility promoter and by product and a small amount of NMP and moisture content bottom the decompression separation device, become the mixing liquid that contains NMP and water through overcooling, it is stand-by to mix liquid infusion fluid storage tank.
3) with 2) dope that obtains is 75 with the worm conveyor input with the spiral evaporator screw diameter of star-like feeder, length-to-diameter ratio is 75, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 255 ℃ 3 diameters are installed above spiral is the 88mm venting port, NMP and water vapour are to adopt vacuum pump to vacuumize and discharge further to evaporate away wherein NMP and moisture, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP adopt methanol extraction three times, filter, it mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrate, then its mixing solutions being inputted an other distillation tower distills, from the distillation tower top out be methanol steam, this steam is through overcooling purifying recycling, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, stand-by through input NMP and water mixed liquid body storage tank after the cooling process.
5) with 2), 3), 4) NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower, from the distillation tower overhead stream out be moisture content, this moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified, the purity that flows out from the rectifying tower top is 99.98% nmp solvent, and the rate of recovery is 97%.
6), with 3) solubility promoter that obtains and the meal of by product, add industrial grade benzenemethanol, making the solids concn of its pulverulent mixture in methanol solvate is 18%wt, its solubility promoter fully is dissolved among the methyl alcohol, then through repeatedly filtering for three times, after dissolving, the filtration, three times filtrate combines stand-by; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) filtrate inputs another evaporator evaporation and removes methyl alcohol, the viscous mixture that contains methyl alcohol and solubility promoter from the base of evaporator remainder, this dope adopts the worm conveyor input further to evaporate away wherein remaining methyl alcohol with the spiral evaporator of star-like feeder, be 58 from the spiral evaporator screw diameter, length-to-diameter ratio is 55, adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 155 ℃ 3 diameters are installed above spiral is the 58mm venting port, methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam process cooling recycling that is evaporated, what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.97%, and the rate of recovery is 98.5%.
Claims (3)
1. solvent and catalyst recovery technology during polyphenylene sulfide is produced, adopting many water cure sodium and santochlor is raw material, produces polyphenylene sulfide through dehydration, polycondensating process step, it is characterized in that take metal halide salt as catalyzer, Technology comprises:
1) add fresh nmp solvent in reaction system and be used as thinner, add-on is 1-3molNMP/molNa
2S, thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product, mixture is inputted the vertical whizzer that vacuumizes carry out solid-liquid separation, that obtain containing polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP, and the filtrate of containing NMP, water, solubility promoter and part by product;
2) with 1) resulting filtrate steams the mixture of NMP and moisture by underpressure distillation, residuum is the dope that contains solubility promoter and by product and a small amount of NMP and moisture bottom the decompression separation device, become the mixing liquid that contains NMP and water through overcooling, it is stand-by to mix liquid infusion fluid storage tank;
3) with 2) dope that obtains further evaporates away wherein NMP and moisture with the worm conveyor input with the spiral evaporator of star-like feeder, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product;
4) with 1) obtain contain polyphenylene sulfide and part by product and the wet solid matter of a small amount of NMP adopt methanol extraction three times, filter, it mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrate, then its mixing solutions being inputted an other distillation tower distills, from the distillation tower top out be methanol steam, this steam recycles through the overcooling purifying, the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling, the NMP that flows out from the distillation tower bottom, stand-by through input NMP and water mixed liquid body storage tank after the cooling process;
5) with 2), 3), 4) NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower, from the distillation tower overhead stream out be moisture content, this moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified, the purity that flows out from the rectifying tower top is 99.98% nmp solvent, and the rate of recovery is 96-98%;
6), with 3) solubility promoter that obtains and the meal of by product, add industrial grade benzenemethanol, making the solids concn of its pulverulent mixture in methanol solvate is 15-20wt%, its solubility promoter fully is dissolved among the methyl alcohol, then through repeatedly filtering for three times, after dissolving, the filtration, three times filtrate combines stand-by; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling;
7), with 6) filtrate inputs another evaporator evaporation and removes methyl alcohol, the viscous mixture that contains methyl alcohol and solubility promoter from the base of evaporator remainder, this dope adopts the worm conveyor input further to evaporate away wherein remaining methyl alcohol with the spiral evaporator of star-like feeder, cool off recycling from the methanol steam process that spiral evaporator is evaporated, what eject from the spiral evaporator head is the solubility promoter powder, this powder is the catalyzer of returning, purity is 99.95-99.98%, and the rate of recovery is 98-99%.
2. solvent and catalyst recovery technology during described polyphenylene sulfide is produced according to claim 1 is characterized in that described solubility promoter is metal halide salt LiCl, and the screw diameter of the spiral evaporator of its application is
158, length-to-diameter ratio is 50-60, adopts the thermal oil thermostatically heating, and Heating temperature is the highest can to reach 160 ℃; It is the 55-60mm venting port that 3 diameters are installed above spiral, and methanol gas is to adopt vacuum pump to vacuumize discharge.
3. solvent and catalyst recovery technology during described polyphenylene sulfide is produced according to claim 1 is characterized in that the screw diameter of the spiral evaporator of application is
175, length-to-diameter ratio is 70-80, adopts the thermal oil thermostatically heating, and Heating temperature is the highest can be reached 260 ℃ 3 diameters are installed above spiral is the 85-90mm venting port, and NMP and water vapour are to adopt vacuum pump to vacuumize discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110066328XA CN102675683B (en) | 2011-03-18 | 2011-03-18 | Solvent and catalyst recovery technology in polyphenyl thioether production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110066328XA CN102675683B (en) | 2011-03-18 | 2011-03-18 | Solvent and catalyst recovery technology in polyphenyl thioether production |
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| Publication Number | Publication Date |
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| CN102675683A CN102675683A (en) | 2012-09-19 |
| CN102675683B true CN102675683B (en) | 2013-10-30 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104892971B (en) * | 2015-06-02 | 2017-04-26 | 敦煌西域特种新材股份有限公司 | Method for recycling solvent NMP in polyphenylene sulfide resin production process |
| CN104877167B (en) * | 2015-06-02 | 2018-02-23 | 敦煌西域特种新材股份有限公司 | The method that adjuvant used lithium chloride recycles in polyphenylene sulfide resin production process |
| CN105218816B (en) * | 2015-11-05 | 2017-10-27 | 包头市汇智工程咨询有限责任公司 | A kind of resin leaching technology produced for poly arylidene thio-ester resinoid |
| CN106395862B (en) * | 2016-08-29 | 2017-12-26 | 四川理工学院 | The recovery method of byproduct sodium chloride in a kind of polyphenylene sulfide production process |
| 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 |
| CN106366030B (en) * | 2016-10-12 | 2018-09-21 | 南京大学 | A kind of high-purity resource engineering chemistry process system of complicated chemical waste liquid |
| CN106432652B (en) * | 2016-10-20 | 2018-07-10 | 四川大学 | A kind of methods and applications that metallic catalyst is recycled from aramid fiber or polyarylether reacting slurry |
| CN106565581B (en) * | 2016-10-21 | 2019-07-12 | 天津科技大学 | The comprehensive reutilization method of mixed salt containing lithium in a kind of polyphenylene sulfide production 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 |
| CN107827128A (en) * | 2017-11-16 | 2018-03-23 | 新疆中泰新鑫化工科技股份有限公司 | The recovery method of lithium chloride in oligomer |
| CN107936288A (en) * | 2017-11-30 | 2018-04-20 | 珠海长先新材料科技股份有限公司 | A kind of method of NMP and LiCl in the recycling polyphenylene sulfide production by solvent extraction process technology |
| 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 |
| CN111004393A (en) * | 2019-12-17 | 2020-04-14 | 重庆聚狮新材料科技有限公司 | Washing water circulation process for polyphenylene sulfide production |
| CN111170511B (en) * | 2020-02-13 | 2021-11-23 | 四川明道和化学新材料有限公司 | Treatment method of sodium sulfide azeotropic dehydration liquid rectifying tower produced water |
| CN114949903B (en) * | 2022-06-14 | 2023-06-16 | 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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| US5711873A (en) * | 1993-01-15 | 1998-01-27 | Hoechst Aktiengesellschaft | Process for solvent recovery and apparatus suitable therefor |
| US6437024B1 (en) * | 1999-09-13 | 2002-08-20 | Phillips Petroleum Company | Menthanol extraction of polar organic compounds and modifier compounds from poly(arylene sulfide) polymer and oligomer streams |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5711873A (en) * | 1993-01-15 | 1998-01-27 | Hoechst Aktiengesellschaft | Process for solvent recovery and apparatus suitable therefor |
| US6437024B1 (en) * | 1999-09-13 | 2002-08-20 | Phillips Petroleum Company | Menthanol extraction of polar organic compounds and modifier compounds from poly(arylene sulfide) polymer and oligomer streams |
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