CN105330886A - Method for reducing viscosity of residue on evaporation from distillation recovery of polymerization solvent NMP for producing PPTA - Google Patents
Method for reducing viscosity of residue on evaporation from distillation recovery of polymerization solvent NMP for producing PPTA Download PDFInfo
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Abstract
The invention discloses a method for reducing viscosity of residue on evaporation from distillation recovery of a polymerization solvent NMP for producing PPTA. The method is as below: neutralizing a mixed mother liquor containing NMP with alkali, adding composite salt, and conducting coarse steaming and concentration to dryness to obtain pie-shaped residue, wherein the composite salt comprises sulfate and calcium salt; conducting rotary drum evaporative desalination on the pie-shaped residue after coarse steaming and concentration; and isolating salt slag and NMP for refining. The method improves the viscosity of a NMP-water-CaCl2 multicomponent system, reduces the adhesiveness of CaCl2 residue on evaporation in the wall, and avoids the formation of high-viscosity NMP-water-CaCl2 ternary complex adhered to the inner surface of the evaporator and tube wall of a heat exchanger in the evaporation recovery of NMP solvent, so that the multi-effect evaporation process for distillation recovery of NMP solvent can be conducted continuously, stably and efficiently.
Description
Technical field
The invention belongs to PPTA p-aramid fiber synthesis correlative technology field, particularly PPTA polymer solvent reclaim in containing CaCl
2residue on evaporation carry out the technique of viscosity reduction modification.
Background technology
PPTA is the abbreviation of English name poly (Isosorbide-5-Nitrae-phenyleneterephthalamide), and Chinese is PPTA.PPTA is a kind of synthetic resins by p-phthaloyl chloride and Ursol D two kinds of monomer polycondensations.Utilize this resin can manufacture high performance p-aromatic polyamide fiber PPTA aramid fiber, the series product of its representative products to be du pont company's trade mark be Kevlar, be domesticly commonly called as Fanglun l414.
PPTA has lyotropic liquid crystalline, is a kind of backbone chain type organic polymer liquid crystal.The para-aramid fiber be made up of PPTA has outstanding high strength, high-modulus, high temperature resistant, corrosion resistance characteristic, good dimensional stability, suitable processing toughness, is widely used in many aspects such as space industry, steamer, cord thread, telecommunication cable and reinforced composite.
In high-performance fiber, aramid fiber occupies very consequence.In this three large high-performance fiber of aramid fiber, carbon fiber and high-strength high-modulus polyethylene fiber, the output of aramid fiber and demand are maximum.Aramid fiber is of many uses, the strategic materials that it is still unimportant and the indispensable novel material of high-tech industry, also becomes industry and civil use material gradually, in advanced composite material, life protection articles for use, communications and transportation and Superlight etc., have important application.
PPTA fiber is developed by du pont company and Dutch Aksu company the earliest, and achieves large-scale production 1970 ~ eighties.Thereafter have multiple country also to carry out the research of PPTA and other serial aramid fiber, Japanese Di Ren company, Japanese You Nijika company, Russian Te Weier company, Russian heat-resisting company, German Hirst company etc. have built up the middle-size and small-size production equipment of aramid fiber successively.
At present, PPTA aramid fiber produce market is substantially controlled by western countries manufacturers such as Duponts and monopolizes.On the one hand, they supply low and middle-end civilian aramid fiber product in a large number to market, the development of the domestic aramid fiber Development Techniques of restriction and impact China; On the other hand, they strictly control high-end aramid fiber strategic materials and enter China, forbid that its product is for key strategy fields such as China's space flight, military affairs.
The research of China's p-aramid fiber starts from 1972, and there are chemistry institute of the Chinese Academy of Sciences, Donghua University, morning twilight chemical research institute, Shanghai Institute of Synthetic Fiber and Tsing-Hua University etc. in main research unit.Between 1972 ~ 1991 years, domestic research unit successively experienced by laboratory study, lab scale and pilot scale several stage, and be listed in " six or five ", " the Seventh Five-Year Plan " and " eight or five " national key research project and national " 863 " plan, achieve a collection of scientific payoffs, but because of various reasons, unrealized industrialization eventually.
The beginning of this century, China's p-aramid fiber has welcome a new exploitation upsurge, and in engineering chemistry database, achieve many breakthroughs.The units such as Shanghai Ai Maida company, Donghua University, Yizheng Fiber Optical plant company of China Petrochemical Industry, Yantai spandex stock company have successively carried out correlation technique assessment of result and enlarged experiment test, define the Technology of independent intellectual property right, the final commercial application for PPTA aramid fiber has established engineering chemistry database basis.
The two large trunk contents that PPTA aramid fiber is produced are the production of PPTA resin and the fibrosis manufacture of PPTA resin, and the core technology of its correspondence is the continuous prodution technology of high intrinsic viscosity PPTA resin and the mass-producing fibroblast manufacturing technology of PPTA fiber.
For the production technology of PPTA resin, the key issue that current domestic development faces is:
1, high grade intermediate polymerization single polymerization monomer TPC(p-phthaloyl chloride) and PPD(Ursol D) stably manufactured and supply; 2, to control, the analysis of material purity; 3, in polymerization process, reaction with same mole control is carried out to TPC and PPD polymerization single polymerization monomer, and for the structure and material etc. of the measurement equipment of transferring polymer material; 4, in polymerization process, uniform high-efficiency mass transport limitation is carried out to polymerization single polymerization monomer, prepolymer, polymkeric substance, and for realize the twin screw reaction equipment that this homogenizes required structure, material, processing condition selected and automatic control; 5, the recycle of solvent and auxiliary agent in PPTA production of resins, and the serialization of process.
About polymer solvent NMP(N-methyl-2-pyrrolidone in PPTA production of resins) recycle utilization, the recycled solvent rate that current domestic prior art can realize is general all very low, some is not even recycled completely, and this has become, and the domestic aramid fiber device of restriction is normal, stable, one of the key factor of economical operation.Trace it to its cause and be, through the CaCl that the used polymer solvent NMP of p-aramid fiber resins synthesis generates with reaction
2by product, polymkeric substance etc. mix, separation difficulty.Realize the recycling of nmp solvent, first must complete being separated of polymkeric substance and mixed solvent, then realize NMP and CaCl
2be separated.And at NMP and CaCl
2in sepn process, NMP meeting and CaCl
2easy formation is containing the title complex of multiple water molecules.This title complex stable in properties, at NMP and CaCl
2decomposition cannot be made it under being separated working condition and discharge moisture.Further, this title complex has very high stickiness, and in the evaporation desolventizing desalination unit operation equipment of reality, title complex is assembled in a large number, be attached on the internal surface of heating installation, considerably increases the resistance of heat transfer layer, has had a strong impact on the heat transfer effect of equipment.In fact, p-aramid fiber resins synthesis field generally have employed height homogenize usefulness automatic control reaction equipment after, the one way polymerization technique technology of domestic p-aramid fiber enterprise and the distance of international most advanced level greatly reduce, but cannot the continuous and steady operation of implement device.One of its basic reason is: desalination, the recovery and utilization technology of NMP polymer solvent are not properly settled.This gordian technique bottleneck has become the principal element having a strong impact on domestic p-aramid fiber device economy and run continous-stable, the capability of sustainable development.
Polymer solvent NMP(N-methyl-2-pyrrolidone in PPTA production of resins) recycle utilization bibliographical information and patent report in, CN101457414 mentions the desalination-distillation combined method for separating of recycling NMP, salt, water mixed solvent system, salt during concrete employing electrodialysis or ion exchange resin removing are dissolved in and in Ethylene recov, is then separated water with NMP by distillation method.This method requires film of good performance or ion exchange resin, and the selection of film and ion exchange resin is the biggest problem of suitability for industrialized production, the poor stability of its life-time service, and reliability is low, and running cost is too high, does not possess industrial application feasibility.
CN1810851 proposes the circulation utilization method of polymer solvent in a kind of PPTA building-up reactions: first solvent mixture is neutralized to neutrality, then wash, filter, collect filtered liquid, washings, then carry out dewatering, desalination, slightly heat up in a steamer, rectifying, the recycle of purification recycling design.This method avoids NMP thermal degradation in acid condition, can obtain high purity (99.5%), water ratio low (< 100ppm) nmp solvent be used for recycled.But this process does not solve NMP and salt in still-process and forms the problem of the pulpous state complex compound of high viscosity, and recovery per pass is low, and process operation energy consumption is high, and continuous operation difficulty is large.
CN101289548 proposes a kind of PPTA solvent for polymerization and reclaims novel method: repeatedly wash with deionized water, and collect PPTA polymer and enter dehumidification system, washings enters solvent recovering system after then carrying out neutralizing treatment; Solvent recovering system comprises the distillation of two-stage thin-film evaporator and removes CaCl
2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, finally obtains high purity (99.5%), water ratio low (< 100ppm), meets the nmp solvent of polymerization requirement for recycled.
CN201089749 proposes a kind of PPTA solvent for polymerization retrieving arrangement: by desalination, slightly heat up in a steamer, rectifying, purifying four cell arrangements form, and can be used for reclaiming the high-quality nmp solvent obtaining and meet polymerization and require.These two patents propose the process and equipment that are applicable to continuous operation, but this process still in unresolved still-process NMP and salt form the problem of the pulpous state complex compound of high viscosity, residue on evaporation very easily sticks, blocking vaporizer, multifunctional evaporating equipment operate continuously poor feasibility, process operation efficiency is low, without economic feasibility.
CN101805456 proposes the recovery method of solvent in a kind of PPTA production of resins: comprise and adopt the washings of alkaline solution to synthesis PPTA resin to neutralize, Multi-effect concentration dewaters, Crystallization Separation, air lift and double tower rectification under vacuum obtain the solvent of purity more than 99.8%.In removal process, isolated salt is recycling through vacuum drying treatment.This processing method also will face NMP and salt and formed a difficult problem for the pulpous state complex compound of high viscosity, estimate that its actual application feasibility is poor.
CN101457414 proposes a kind of method of recycling design NMP in p-aramid fiber production process: adopt aromatic alkyl halide as the solvent NMP used in extraction agent extraction p-aramid fiber production process, NMP is arranged in extraction phase, then the NMP in Distillation recovery extraction phase.
CN101774721 proposes the treatment process containing production solvent waste liquid produced in a kind of meta-aramid fibers production process: comprise the following steps: (1) filters the waste liquid containing production solvent produced in meta-aramid fibers production process; (2) liquid of step (1) gained is sent into extraction plant and carry out extracting and separating, extraction is than being (1 ~ 3): 1, and waste water is directly discharged; (3) by the extraction phase input distillation tower in step (2) holder, extraction phase is carried out underpressure distillation separation, amount of filler accounts for 15 ~ 25% of distillation tower capacity, input speed is per hour be distillation tower capacity 8.4 ~ 16.8%, temperature 80 ~ 120 DEG C, column bottom temperature 130 ~ 150 DEG C in tower, quantity of reflux speed is per hour is 1.7 ~ 8.5% of distillation tower capacity, and discharging speed is per hour is 0.7 ~ 2.5% of distillation tower capacity; (4) the production solvent of step (3) gained is carried out rectifying again.
CN101550233 proposes the continuous recoverying and utilizing method of a kind of industrially compounding PPTA agent-solubility promoter: comprise the following steps: (1) will synthesize PPTA resin after washing, the mother liquor containing solvent NMP, salt, water and micro-oligopolymer composition obtained, through extracting and separating, is extracted phase NMP-extraction agent system and extracting phase salt, water-extraction agent system respectively; (2) by extracting phase through stripping, the water obtained after separation is for washing resin, and the extraction agent obtained recycles; (3) by extraction phase after rectifying, layering, the water that layering obtains is for washing resin; The extraction agent obtained recycles, and is separated the NMP crude product obtained and uses through purification Posterior circle.
Summary of the invention
The object of the invention is on the basis of existing technology, in conjunction with a large amount of practical studies, propose to add a small amount of stickiness properties-correcting agent in mother liquor system after polymerization, change the associated operating conditions in evaporation technology process and technical parameter, avoid the NMP-CaCl of high viscosity
2the formation condition of-water ternary complex, makes nmp solvent Distillation recovery, dehydration, CaCl
2the technological operations such as desalination can continuously, stable, carry out efficiently.
Object of the present invention can be reached by following measures:
To the method reducing residue on evaporation stickiness when producing the polymer solvent NMP Distillation recovery of PPTA, it comprises the steps:
1) will containing in NMP mixing mother liquor alkali and after, add composite salt component, slightly steam concentrate to dry, obtain pie residue; Wherein said is the mother liquor after the polyreaction of production PPTA resin, polymer water being cleaned to gained containing NMP mixing mother liquor, and described composite salt component is made up of vitriol and calcium salt;
2) described pie residue is carried out rotary drum evaporative desalination, isolate salt slag and NMP crude product.
Vitriol in the present invention can adopt vitriol of the prior art, and a kind of preferred version is one or more that vitriol is selected from copper sulfate, sodium sulfate, Tai-Ace S 150, magnesium sulfate, barium sulfate, ferric sulfate; Be preferably selected from one or more in copper sulfate, sodium sulfate, Tai-Ace S 150 further.
Calcium salt in the present invention can adopt calcium salt of the prior art, and a kind of preferred version is one or more that calcium salt is selected from calcium sulfate, calcium acetate, calcium phosphate, lime borate, calcium carbonate, is preferably selected from one or more in lime borate, calcium carbonate further.
For the consumption of composite salt component, pending the containing in NMP mixing mother liquor of every 50kg, the dosage of vitriol is 20 ~ 250g, preferably 50 ~ 200g, and the dosage of calcium salt is 30 ~ 350g, preferably 50 ~ 250g.Further, what every 50kg of vitriol or calcium salt was pending containing NMP mixing mother liquor consumption is independently of one another: copper sulfate 25 ~ 200g, sodium sulfate 50 ~ 150g, Tai-Ace S 150 50 ~ 150g, calcium carbonate 150 ~ 300g, lime borate 50 ~ 200g.Composite salt component can directly add in mother liquor, also can add in mother liquor with after a small amount of water dissolution again; Experiment finds, if only adopt a kind of salt component or a certain amounts of components to cross the character that can have a strong impact on final pie residue at least.
In step 1), in the mixing mother liquor of the described NMP of containing, contain solvent NMP, water and salt; Described alkali is calcium hydroxide, is neutralized to pH value to 6-8 with alkali, is preferably neutralized to about pH value to 7.
In step 1), by NMP-CaCl
2-H
2o sample or the NMP-CaCl containing large water gaging
2-H
2o sample makes its relative evaporate to dryness to constant weight by controlling vaporization temperature (generally below 100 DEG C), obtains pie residue, controls water ratio < 4% and the tap density < 2g/cm of residue
3.
In step 2) in, adopt evaporative desalination equipment of transferring shares to carry out rotary drum evaporative desalination, this vacuum drum drying machine of transferring shares in evaporative desalination equipment is made up of rotary drum, doctor blade system, charging tray, frame, housing and transmission system etc.Temperature in rotary drum evaporative desalination step is 100 ~ 155 DEG C, and rotary drum rotating speed is 1 ~ 20rpm.A kind of preferred working method is: first in vacuum drum drying machine, pass into 140 DEG C ~ 155 DEG C (preferably 150 DEG C) steam and heat rotary drum; Pass into 200 DEG C ~ 220 DEG C (preferably 210 DEG C) thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, pie residue is added in feeding disk continuously and carries out evaporation drying, wherein controlling rotary drum rotating speed is the preferred 6rpm of 1 ~ 10rpm(), drum surface temperature is 100 ~ 110 DEG C (preferably 106 DEG C), feed rate can regulate according to the size of equipment and treatment capacity, and bantam is generally the preferred 0.57kg/min of 0.2 ~ 1.0kg/min().
Through step 2) process, salt slag can be separated with NMP crude product, wherein NMP crude product can enter solvent recovering system, processes it by existing operational path.A kind of preferred version is: first adopt two-stage thin-film evaporator to distill in solvent recovering system and remove CaCl
2adopt topping still Separation of Water and NMP again, then adopt rectifying purification column to refine nmp solvent, obtain the nmp solvent of high purity (purity is more than 99%) water ratio low (< 100ppm), this nmp solvent meets polymerization and requires and carry out recycled.
The present invention is by moisture, the CaCl to utilization to be recycled
2add serial vitriol, calcium salt compound prescription component in nmp solvent system etc. component, change the stickiness of solvent mother liquor system, thus make the decompression Multi-effect Evaporation Processes of recovery nmp solvent can stablize, carry out continuously efficiently.
In concrete practical application of the present invention, first with water cleaning PPTA polyblend, isolating wet polymerization powder, mother liquor is with Ca (OH)
2solution is neutralized to neutrality, now add the double salt formulation system of the present invention's design, by this double salt formula system with directly joining in the mother liquor system of recovery to be evaporated after a small amount of water dissolution, mixing and stirring, then carry out the follow-up operation such as thick steaming concentrate, multiple-effect evaporation desalination.This law improves NMP-water-CaCl
2deng the stickiness of multicomponent mixture system, reduce CaCl
2the adhesion of residue on evaporation in wall, when making evaporation reclaim nmp solvent, avoids the formation of the NMP-water-CaCl of high viscosity
2ternary complex is attached in evaporator inside surface and exchanger tube wall, make the multiple-effect evaporation technological operation of Distillation recovery nmp solvent can continuously, stable, carry out efficiently.
The present invention is by loose additive formulations design and the design of succinct application art targetedly, solve NMP and salt in still-process and form the problem of the pulpous state complex compound of high viscosity, compared with the material without loose property-modifying additive, considerably reduce the stickiness of material.
Accompanying drawing explanation
Fig. 1 is the desalination recovery process schematic flow sheet of PPTA polymer solvent NMP of the present invention.
The employing of this flow process " go to glue by residue modification, multiple-effect evaporation, dehydration is refining " the nmp solvent serialization recovery process that combines, PPTA polymkeric substance isolates powder after washing, what obtain contains solvent NMP, salt, the mother liquor of water and micro-oligopolymer composition, neutrality is neutralized to through alkali lye, by adding specific component of inorganic salts, realize material adhesion properties to change, inorganic salt are directly or with joining in the mother liquor system of recovery to be evaporated after a small amount of water dissolution, mixing and stirring, through multiple-effect evaporator heating evaporation, thickening, evaporative desalination is carried out again at vacuum drum device, be separated the NMP crude product obtained and enter solvent recovering system.Solvent recovering system comprises the distillation of two-stage thin-film evaporator and removes CaCl
2, a topping still Separation of Water and NMP, a rectifying purification column refine nmp solvent and use through purification Posterior circle.
Embodiment
Come that the present invention is further illustrated below with multiple embodiment, but not because the condition of each embodiment and effect cause any restriction to the present invention.
Reference examples:
Build relevant testing apparatus according to technical process of the present invention, wash and be separated powder to PPTA polyblend, the mother liquor after separation is through Ca (OH)
2after neutralization, get the pending mother liquor of 50kg, do not add any double salt formulation system, be directly placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Solvent recovering system is entered to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, can obtain purity about 99.5%, water ratio < 100ppm nmp solvent for recycled.
Result: the upper strata adularescent crystalline particle of pie residue, as fine sand sample, can easily scrape; But bottom has the tar of middle lark and the mixture of crystal salt, become the block cake that hardens having certain degree of hardness, be difficult to pulverize, be attached on the internal surface of heating installation in block brute force, have a strong impact on subsequent heat and the heat exchange property of vaporizer.
Embodiment 1: build relevant testing apparatus according to technical process of the present invention, washes PPTA polyblend and is separated powder, and the mother liquor after separation is through Ca (OH)
2after neutralization, get the pending mother liquor of 50kg, after adding copper sulfate, each 50g of lime borate wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.5%, water ratio 95ppm.
Result: there is yellow-white powdered crystalline thing on the upper strata of pie residue, can easily scrape, and there is the pie mixture of light yellow tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 2: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding copper sulfate 50g, lime borate 100g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.2%, water ratio 90ppm.
Result: there is more yellow-white powdered crystalline thing on the upper strata of pie residue, and can easily scrape, there is the pie mixture of light yellow tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 3: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding copper sulfate, each 100g of lime borate wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.0%, water ratio 92ppm.
Result: there is more yellow-white powdered crystalline thing on the upper strata of pie residue, and can easily scrape, there is the pie mixture of light brown tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 4: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding sodium sulfate 100g, lime borate 50g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.1%, water ratio 96ppm.
Result: there is more yellow-white powdered crystalline thing on the upper strata of pie residue, and can easily scrape, there is the pie mixture of grey tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 5: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding Tai-Ace S 150, each 100g of lime borate wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.3%, water ratio 94ppm.
Result: there is more yellow-white powdered crystalline thing on the upper strata of pie residue, and can easily scrape, there is the pie mixture of light gray tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 6: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding copper sulfate 20g, calcium carbonate 150g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Solvent recovering system is entered to isolated NMP crude product, comprises the distillation of two-stage thin-film evaporator and remove CaCl
2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.5%, water ratio 97ppm.
Result: there is more yellow-white powdered crystalline thing on the upper strata of pie residue, and can easily scrape, there is the pie mixture of taupe brown tar and crystal salt in lower floor, easily breaks, and can easily pulverize.
Embodiment 7: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding copper sulfate 100g, lime borate 150g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.0%, water ratio 98ppm.
Result: have more brown color powdered crystalline thing above pie residue, have the mixture of brown tar and crystal salt to stick the end, scraped, powdering below.
Embodiment 8: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding copper sulfate 50g, calcium carbonate 250g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.3%, water ratio 95ppm.
Result: there is the light brown powdered crystalline thing of moderate on the upper strata of pie residue, and can easily scrape, there is the pie mixture of light yellow tar and crystal salt in lower floor, can easily pulverize.
Embodiment 9: build relevant testing apparatus according to technical process of the present invention, PPTA polyblend is washed and is separated powder, in mother liquor after separation and after, get the pending mother liquor of 50kg, after adding sodium sulfate 100g, calcium carbonate 150g wherein, stir, be placed in vaporizer heating evaporation, control vaporization temperature to dry, obtain pie residue.In vacuum drum drying machine, pass into 150 DEG C of steam again heat rotary drum; Pass into 210 DEG C of thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, material is added in feeding disk continuously and carries out evaporation drying.Controlling rotary drum rotating speed is 6rpm, and drum surface temperature is 106 DEG C, and feed rate is 0.57kg/min.Enter solvent recovering system to isolated NMP crude product, comprise the distillation of two-stage thin-film evaporator and remove CaCl2, a topping still Separation of Water and NMP, a rectifying purification column refines nmp solvent, nmp solvent purity 99.0%, water ratio 92ppm.
Result: there is the light grey powdered crystalline thing of moderate on the upper strata of pie residue, and can easily scrape, lower floor has the pie mixture of middle grey tar and crystal salt to stick the end, easily scrapes.
In order to the viscosity reflected reduces the real processing results such as degree and fluffy modification, experiment adopts the water ratio of residue and tap density to evaluate the treatment effect of residue.
Adopt the moisture in oven drying method mensuration pie residue and solvent.Oven drying method detection method: get quantitative instrument NMP-CaCl
2-H
2stainless steel evaporators heating evaporation put into by O sample, and control vaporization temperature to relative evaporate to dryness to constant weight, before and after weighing, the change of example weight, calculates the water ratio of residue.
The mensuration of tap density adopts YIFT-103 type natural packing method loose density meter (standard GB/T/T16913.3-1997).
Contrast test result is as following table:
| Project | Water ratio, % | Tap density, g/cm3 |
| Comparative example | 4.57 | 2.45 |
| Embodiment 1 | 3.53 | 1.72 |
| Embodiment 2 | 3.64 | 1.80 |
| Embodiment 3 | 3.73 | 1.84 |
| Embodiment 4 | 2.96 | 1.38 |
| Embodiment 5 | 3.02 | 1.42 |
| Embodiment 6 | 3.65 | 1.82 |
| Embodiment 7 | 3.35 | 1.63 |
| Embodiment 8 | 3.26 | 1.54 |
| Embodiment 9 | 3.16 | 1.74 |
Claims (10)
1., to the method reducing residue on evaporation stickiness when producing the polymer solvent NMP Distillation recovery of PPTA, it is characterized in that comprising the steps:
1) will containing in NMP mixing mother liquor alkali and after, add composite salt component, slightly steam concentrate to dry, obtain pie residue; Wherein said is the mother liquor after the polyreaction of production PPTA resin, polymer water being cleaned to gained containing NMP mixing mother liquor, and described composite salt component is made up of vitriol and calcium salt;
2) described pie residue is carried out rotary drum evaporative desalination, isolate salt slag and NMP crude product.
2. method according to claim 1, is characterized in that described containing in NMP mixing mother liquor containing solvent NMP, water and salt; Described alkali is calcium hydroxide, is neutralized to pH value to 6-8 with alkali.
3. method according to claim 1, is characterized in that one or more that described vitriol is selected from copper sulfate, sodium sulfate, Tai-Ace S 150, magnesium sulfate, barium sulfate, ferric sulfate; Described calcium salt is selected from one or more in calcium sulfate, calcium acetate, calcium phosphate, lime borate, calcium carbonate.
4. method according to claim 1, it is characterized in that pending the containing in NMP mixing mother liquor of every 50kg, the dosage of vitriol is 20 ~ 250g, and the dosage of calcium salt is 30 ~ 350g.
5. method according to claim 3, is characterized in that one or more that described vitriol is selected from copper sulfate, sodium sulfate, Tai-Ace S 150; Described calcium salt is selected from one or more in lime borate, calcium carbonate.
6. method according to claim 5, it is characterized in that every 50kg of vitriol or calcium salt pending containing NMP mixing mother liquor consumption be independently of one another: copper sulfate 25 ~ 200g, sodium sulfate 50 ~ 150g, Tai-Ace S 150 50 ~ 150g, calcium carbonate 150 ~ 300g, lime borate 50 ~ 200g.
7. method according to claim 1, is characterized in that in step 1), and thick steaming concentrate is to the water ratio < 4% of described pie residue, its tap density < 2g/cm
3.
8. method according to claim 1, is characterized in that in step 2) in, the temperature of carrying out rotary drum evaporation drying in rotary drum evaporative desalination step is 100 ~ 155 DEG C, and rotary drum rotating speed is 1 ~ 20rpm.
9. method according to claim 8, is characterized in that in step 2) in, rotary drum evaporative desalination step is: first in vacuum drum drying machine, pass into 140 DEG C ~ 155 DEG C steam and heat rotary drum; Pass into 200 DEG C ~ 220 DEG C thermal oils in charging tray chuck and cloth scraper to heat, after treating that system free-runing operation is stable, added continuously in feeding disk by pie residue and carry out evaporation drying, wherein controlling rotary drum rotating speed is 1 ~ 10rpm, and drum surface temperature is 100 ~ 110 DEG C.
10. method according to claim 1, is characterized in that step 2) in isolated NMP crude product enter solvent recovering system, first adopt the distillation of two-stage thin-film evaporator to remove CaCl within the system
2, then adopt topping still Separation of Water and NMP, then adopt rectifying purification column to refine nmp solvent, obtain purity more than 99% water ratio lower than the nmp solvent of 100ppm.
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| CN106630342A (en) * | 2016-09-26 | 2017-05-10 | 南京大学 | A decomplexing method for a N-methyl-2-pyrrolidone metal complex in salt-containing organic waste liquid |
| CN109134339A (en) * | 2018-09-13 | 2019-01-04 | 清华大学 | Method for recovering solvents is used in a kind of production of para-aramid fiber |
| CN109916824A (en) * | 2019-01-24 | 2019-06-21 | 河南神马尼龙化工有限责任公司 | A kind of screening technique of the double solvents of suitable polymerization reaction production PPTA resin |
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
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| CN101550233A (en) * | 2008-04-03 | 2009-10-07 | 中国神马集团有限责任公司 | Method for continuously recycling solvent-flux for industrially compounding PPTA |
| 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 |
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| CN101289548A (en) * | 2007-04-16 | 2008-10-22 | 常熟市贝斯特皮革有限公司 | Novel method for recovering solvent for polymerization of poly(p-phenytene terephthalamide) |
| CN101550233A (en) * | 2008-04-03 | 2009-10-07 | 中国神马集团有限责任公司 | Method for continuously recycling solvent-flux for industrially compounding PPTA |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106630342A (en) * | 2016-09-26 | 2017-05-10 | 南京大学 | A decomplexing method for a N-methyl-2-pyrrolidone metal complex in salt-containing organic waste liquid |
| CN106630342B (en) * | 2016-09-26 | 2020-02-21 | 南京大学 | Decomplexation method of N-methyl pyrrolidone metal complex in salt-containing organic waste liquid |
| CN109134339A (en) * | 2018-09-13 | 2019-01-04 | 清华大学 | Method for recovering solvents is used in a kind of production of para-aramid fiber |
| CN109916824A (en) * | 2019-01-24 | 2019-06-21 | 河南神马尼龙化工有限责任公司 | A kind of screening technique of the double solvents of suitable polymerization reaction production PPTA resin |
| CN109916824B (en) * | 2019-01-24 | 2021-09-28 | 河南神马尼龙化工有限责任公司 | Screening method of composite solvent suitable for producing PPTA resin through polymerization reaction |
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
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Effective date of registration: 20180330 Address after: 211900 Changjiang Road Jiangsu city of Yangzhou province Yizheng city Xu Town, No. 1 Co-patentee after: Sinopec Corp. Patentee after: CHINA SINOPEC YIZHENG CHEMICAL FIBER CO., LTD. Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee before: Yizheng Chemical Fiber Co., Ltd., China Petrochemical Group Corp. Patentee before: Sinopec Corp. |