CN1050829A - Parametric pump fractional crystallization method and pfc crystallizer - Google Patents
Parametric pump fractional crystallization method and pfc crystallizer Download PDFInfo
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- CN1050829A CN1050829A CN90109470A CN90109470A CN1050829A CN 1050829 A CN1050829 A CN 1050829A CN 90109470 A CN90109470 A CN 90109470A CN 90109470 A CN90109470 A CN 90109470A CN 1050829 A CN1050829 A CN 1050829A
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Abstract
A kind of equipment and method that is used for organic melt liquid mixing system separation purification.PFC crystallizer of the present invention is vertical pipe type structure, heat-transfer medium is by the film applicator in the crystallizer, forms the liquid film of even decline at the crystallizer outer wall, strengthen with crystallizer in the heat transfer of fused solution, eliminate the hysteresis phenomenon when medium temperature changes, saved a large amount of heat energy.Nitrogen passes through pulser, nitrogen distributor and nozzle, bubbling in crystallizer, the heat and mass transfer of reinforcement crystallisation process.The accurate temperature of control heat-transfer medium, partly crystallization, sweating and melt purified crystalline material in the crystallizer of fused solution.Method of the present invention and crystallizer crystallization yields height, purity height, yield height, reduced investment.
Description
The invention belongs to the separation of organic compound.
Industrial sectors such as modern Speciality Petrochemicals, medicine, agricultural chemicals, food often adopt the rectifying separation liquid mixture.The rectifying energy consumption is big, and facility investment is big, and temperature-sensitive that has or difficult separation mixture should not be used rectifying.Another kind of separation method is a crystallization process.The crystallization operation energy consumption is low, and is little for boiling-point difference, the mixing system that the fusing point difference is big, and crystallization method is particularly suitable.Industrial crystallization has two classes, i.e. suspension crystallization and fusion-crystallization.The xln that suspension crystallization generates is in suspended state, must often need operations such as filter cake washing, squeezing or recrystallizations by filtering or centrifugation realization solid-liquid separation, could obtain product, Production Flow Chart is long, and the many investments of equipment are big, the operation complexity, the production cost height.The fusion-crystallization method is with the solid material fusing, by heating surface liquation is cooled off, and at the cooling surface continuous crystallisation, crystallization ends remaining mother liquor discharging, realize solid-liquid separation, do not need specific equipments such as solid-liquid separation, Production Flow Chart is short, and equipment is few, invest for a short time, energy consumption is low, and refining effect is good.Existing intermittent type fusion Steppecd crystallization has three kinds.(1) directional crystallization method (" fuel and chemical industry ", the 20th volume, the 6th phase, P28-30).The crystallizer of this method is box crystallizer, and molten materials relies on xln sweating purifying crystal material in the whole crystallizations of crystallizer outside surface, does not have the measure of enhancement of heat transfer, mass transfer, and equipment volume is huge, and the operational cycle is long, and spatiotemporal efficiency is low.(2) MWB method (CEP, 76, April, 65(1980)).The crystallizer of this method is a vertical type pipe type crystallizer, heat-transfer medium flows at shell side, with pump melt is sent into crystallizer, be sprayed onto the inner-wall surface of every crystallizer, at the middle continuous crystallisation that flows downward, uncrystallized mother liquor is drawn from the crystallizer bottom, through the heat fused crystallization, again spray reciprocation cycle.The power consumption of this method pumping mother liquor is big.Must improve the temperature of circulating mother liquor in order to melt thin crystalline substance, and need this heat is removed when crystallization, energy consumption is big.Crystallize into bottleneck easily in flushing liquor ingress, stop up crystallizer.(3) Rutgers method (United States Patent 4,552,575, (1985)).The crystallizer of this method also is the vertical type pipe type, and melt is in the crystallization of crystallizer inwall, and heat-transfer medium flows through outside pipe, inserts an airway by top in every crystallizer, feeds nitrogen bubble liquid layer, enhancement of heat transfer and mass transfer.Rutgers method production efficiency of equipment height, floor space is few, good product quality, energy consumption is low.The a part of space of melt but airway accounts for, when crystallizer is higher, airway and the concentric difficulty of crystallizer, produce the dispersive bubble, bubbling efficient is poor, the mold structure complexity, crystallizer airway more for a long time is also many, the fluid resistance of every airway is difficult to evenly, is easy to generate " the dead pipe " of not air guide, and separation efficiency descends.The stagnant storage of crystallizer shell side heat-transfer medium is big, and the basin volume of outfit is big, and for example reduces or elevated temperature when changing the heat-transfer medium temperature, and the heat that need remove or import into is big, and heat-energy losses is big.In the process that changes the heat-transfer medium temperature, hysteresis phenomenon is serious, temperature variation that can not the timely adjustment heat-transfer medium.
The purpose of this invention is to provide a kind of parametric pump fractional crystallization method and parameter pump (PFC) crystallizer that is used to separate organic melt liquid mixing system, overcome the shortcoming of existing fractional crystallization method and crystallizer, the production efficiency height, good product quality, energy consumption is low, and reduced investment is easy to operate.
The PFC crystallizer is a vertical type pipe type structure, loads fused solution in the every crystallizer, and heat-transfer medium flows at the crystallizer outer wall.The fractional crystallization of parameter pump is made up of part crystallization, crystallizing layer sweating, three processes of crystallizing layer fusing of fused solution, accurately controls the temperature of heat-transfer medium, makes partly crystallization and sweating process carry out good separating effect, product yield height in the best condition.The working method of three processes is as follows.
1. fused solution partial crystallization.The melting material temperature that enters crystallizer is higher than by the fusing point of purification thing more than 5 ℃, the temperature of heat-eliminating medium is hanged down 4-8 ℃ than the fusing point of crystallisate, melts is carried out crystallisation by cooling, and the rate of temperature fall of heat-eliminating medium is 0.5-4 ℃/min, and crystallization time is 20-70 minute.Heat-eliminating medium becomes liquid film to descend by the outer wall that film applicator is distributed to every crystallizer, and the heat of melt liquid makes its temperature be reduced to fusing point in the absorption tube, and the guiding crystalline material grows into crystallizing layer to crystallizer inner-wall surface continuous crystallisation.Total liquid measure of liquid film only is full of the 1/40-1/20 of liquid measure for the crystallizer shell side, the minimizing of heat-transfer medium amount had both reduced the volume of heat-transfer medium basin, had saved energy, and has eliminated the hysteresis phenomenon that occurs when changing the heat-transfer medium temperature.Uncrystallized mother liquor is discharged crystallizer, finishes solid-liquid separation, and the crystallizing layer material has obtained enrichment.In order to improve heat transfer, the rate of mass transfer between fused solution and the crystallizing layer, be provided with the nitrogen uniform device in the bottom of crystallizer, send the pulse nitrogen gas stream to stir toward fusion liquid layer drum, weaken the resistance of heat and mass, make fusion liquid layer axial and radial temperature and concentration homogenizing simultaneously.The nitrogen flow of every crystallizer is 10-140l/h, pulse-repetition 10-70I/min, pulse width 0.1-1.0s.
2. crystallizing layer sweating.Owing to reasons such as peritectoid, surface adsorption, lattice dislocation, make crystallizing layer carry impurity secretly in the crystallisation process.Be removal of contamination, with the heating medium that hangs down 4-8 ℃ than the melting temperature of crystallizing layer, temperature rise rate with 0.5-2 ℃/min heats up, crystallizing layer is added thermal sweating, be higher or lower than 1-2 ℃ of this crystalline melting point substance up to the heating medium temperature, constant temperature 20-70min under this temperature discharges crystallizer at any time with the sweat of impurity, and crystallizing layer is further purified.Stop drum during the sweating and send nitrogen.
3. crystallizing layer fusing.With being higher than the heating medium of crystallizing layer fusing point more than 5 ℃, add the crystallizing layer behind the thermal sweating, the melts after all fusing obtains to purify with it are discharged crystallizer.
More than three processes form a crystallization stage.The mother liquor of different concns, sweating, melt separated deposit, the concentration ratio stock liquid enrichment 1-5% of melt.If will obtain more highly purified product, the melt of crystallizing layer can be used as raw material, repeat above three process one or many, can get the high purity product more than 99.85%.Mother liquor, sweating are done with quadrat method processing repeatedly, discharge residue up to the last level.In order to improve the rate of recovery of crystalline material, the available cryogenic media crystallization of the last grade, yield can reach more than 96%.
Fig. 1 is the PFC crystallizer, 1 is nitrogen outlet among the figure, and 2 is the molten materials import, and 3 is the heat-transfer medium import, 4 is heat transfer medium outlet, 5 is mother liquor, the outlet of sweating melt, and 6 is nitrogen inlet, and 7 is heat-transfer medium card formula film applicator, 8 is the crystallizer housing, 9 is crystallizer, and 10 is the nitrogen uniform device, and 11 is the pulse of nitrogen device.
Fig. 2 is the part sectioned view of heat-transfer medium card formula film applicator, and 1 is crystallizer among the figure, and 2 is the cloth fenestra, and 3 is card formula film applicator, and the diameter of cloth fenestra is than the big 0.3-5mm of crystallizer external diameter, and film applicator is made by stainless steel, copper or other anticorrosive materials.
Fig. 3 is the nitrogen uniform device, and wherein 1 is the nitrogen nozzle, and 2 is sealed steel ball, and 3 is short tube, and 4 is the nitrogen surge chamber, and the structure of nozzle has trumpet type, tubular type, ball-shaped, cylinder shape, and the nozzle diameter is than the little 2-20mm of crystallizer internal diameter.Nozzle, sealed steel ball, short tube are made with stainless steel, copper or other anticorrosive wear-resistant material.
Fig. 4 is the pulse of nitrogen device.1 is nitrogen outlet among the figure, and 2 is valve, and 3 is pull bar, and 4 is nitrogen inlet, and 5 is cam, and 6 is spring.By the rotation of motor drives cam, frequency is on demand answered back to pull bar, and compression spring produces the pulse nitrogen gas stream with the nitrogen outlet valve open.
Example one, NAPTHALENE FLAKES. (INDUSTRIAL GRADE purified is refined naphthalene.Application drawing 5 parameter pump step crystallizers and crystallization technique flow process purification refined naphthalene.1 is the circulating nitrogen gas compressor among Fig. 5, and 2 is solid industrial naphthalene, and 3 are molten naphthalene jar, and 4 is the naphthalene pump, and 5 is the pulse of nitrogen device, and 6 is tundish, and 7 is the PFC crystallizer, and 8 is heat-transfer medium, and 9 is the naphthalene slag, and 10 is the product refined naphthalene, and 11 is the heat-transfer medium interchanger, and 12 is water circulating pump.At first be that 95% solid industrial naphthalene is molten into the liquid naphthalene, be pumped into the PFC crystallizer with naphthalene with purity.Heat-transfer medium water is supplied with by water circulation system, back and forth uses the temperature of leaning on water cooler and well heater accurately to regulate water.Fusion naphthalene partly Tc is 79 °-32 ℃, and crystallization time 20-60 minute, sweating temperature was 75-82 ℃, and 20-80 minute sweating time, melting crystal layer temperature is 90-99 ℃, and fusing time is 5-30 minute.Nitrogen produces air pulse through pulser, to liquid naphthalene layer bubbling, and the nitrogen flow 10-140l/h of every crystallizer, pulse-repetition 10-70l/min, nitrogen circulation is used.The fusion naphthalene is handled through three crystallization stage, can get the refined naphthalene of purity＞99.5%.Mother liquor and sweating are discharged the naphthalene slag after reclaiming the level processing through three, cool off last crystallization stage with normal-temperature water, naphthalene yield 〉=95%.The speed of the percent crystallization in massecuite of strict crystallization control level, sweating rate, temperature variation can obtain the refined naphthalene of purity＞99.8%.
The separation of example two, neighbour, santochlor
Boiling point adjacent, santochlor is respectively 180.5 ℃ 174.12 ℃, and fusing point is-17 ℃ and 54.2 ℃, adopts method and apparatus of the present invention to separate, and energy consumption only is the 10-30% of rectificating method.
At first will mix the dichlorobenzene melt and send into the PFC crystallizer, the red-tape operati condition is as follows:
Tc crystallization time sweating temperature sweating time nitrogen flow crystallizer pulse-repetition
℃ min ℃ min l/h L/min
20-54 20-70 40-57 20-80 10-120 10-70
Through the two-stage crystallization treatment, obtaining purity is the santochlor product of 99.8-99.9%.
Example three, adjacent, the p-Nitrophenyl chloride of separation.
Separate adjacent, p-Nitrophenyl chloride with distillating method, obtaining GB first grade p-Nitrophenyl chloride needs 170 of theoretical plate numbers, reflux this 30, tower still temperature＞200 ℃, still carbonization, polymerization are serious.Use method and apparatus of the present invention and separate, can avoid above-mentioned shortcoming, good product quality, energy consumption is low, production cost is low.
To mix the nitro-chlorobenzene raw material molten solution and send into the PFC crystallizer, through the two-stage crystallization, acquisition purity is 99.2% product p-Nitrophenyl chloride.The range of temperature of heat-transfer medium and drum send the condition of nitrogen as follows:
Tc crystallization time sweating temperature sweating time nitrogen flow pulse-repetition
℃ min ℃ of min l/h crystallizer l/min
40-82 20-60 78-85 20-70 10-80 10-60
Claims (6)
1, a kind of be used to separate purify the vertical pipe type crystallizer and the method for molten liquid machine mixture system are arranged, melt-blended liquid carries out the part crystallization in crystallizer, sweating and fusing, heat-transfer medium flows at shell side, feed nitrogen in the crystallizer and stir melt liquid, cause turbulence, the invention is characterized in and be provided with heat-transfer medium card formula film applicator in the crystallizer, the nitrogen uniform device, be connected with a pulse of nitrogen device with this uniform device, heat-transfer medium and nitrogen all link with external system, closed cycle is back and forth used, crystallization technique of the present invention be with the melting mixing material in crystallizer of the present invention through partly crystallization of one or many, sweating and fusing reach the purpose of purification.
2, heat-transfer medium card formula film applicator according to claim 1 is characterized in that this card formula film applicator made by corrosion resistant materials such as stainless steel or copper, and wherein the cloth film hole diameter is than the big 0.3-5mm of crystallizer external diameter.
3, nitrogen uniform device according to claim 1 is characterized in that this uniform device by nitrogen inlet, the nitrogen surge chamber, short tube, sealed steel ball nitrogen nozzle constitutes, and all is inserted with the nitrogen nozzle every crystallizer bottom, and nitrogen is through nozzle air-blowing in each crystallizer, nozzle has tubaeform, sphere, taper shape, cylindrical, the diameter of nozzle is than the little 2-20mm of crystallizer diameter, and sealed steel ball and nozzle are made by anticorrosive wear-resistant materials such as stainless steel or copper.
4, pulse of nitrogen device according to claim 1 is characterized in that, by valve, nitrogen outlet, pull bar, spring, cam, nitrogen inlet constitutes, the timing ratio of the open and close of valve is (1: 2)-(1: 12), and the stroke of valve rod is 3-12mm, and the sectional area ratio of nitrogen inlet and outlet is 1: (0.4-0.9).
5, part crystallization technique according to claim 1, the temperature that it is characterized in that heat-eliminating medium is than low 4 ℃-6 ℃ of the fusing point of crystalline material, fused solution is cooled off, rate of cooling is 0.5-4 ℃/min, carries out partial crystallization at the crystallizer inwall, and crystallization time is 20-70min, in crystallisation process nitrogen by pulser to nitrogen uniform device input pulse nitrogen, blast crystallizer through nozzle, it is every crystallizer 20-20l/h that nitrogen feeds speed, and pulse-repetition is 20-70I/min.
6, sweating according to claim 1, it is characterized in that through part crystalline crystal, heat with the heating medium that is lower than 4-8 ℃ of this crystalline melting point, the temperature of this heating medium heats up with the temperature rise rate of 0.5-2 ℃/min, make crystal constantly be heated sweating, up to the heat-transfer medium temperature be elevated in the crystalline material fusing point ± 1-2 ℃ scope in, carry out constant temperature 20-70min sweating, sweat is discharged crystallizer at any time, stops drum during the sweating and send nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109470A CN1027963C (en) | 1990-11-29 | 1990-11-29 | Parametric pump fractional crystallization method and PFC crystallizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109470A CN1027963C (en) | 1990-11-29 | 1990-11-29 | Parametric pump fractional crystallization method and PFC crystallizer |
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| CN1050829A true CN1050829A (en) | 1991-04-24 |
| CN1027963C CN1027963C (en) | 1995-03-22 |
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| CN90109470A Expired - Fee Related CN1027963C (en) | 1990-11-29 | 1990-11-29 | Parametric pump fractional crystallization method and PFC crystallizer |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041408C (en) * | 1994-01-19 | 1998-12-30 | 扬州大学师范学院 | Di-substituted benzene position isomer continuous solidifying and separating method |
| CN101475436B (en) * | 2009-02-02 | 2012-06-06 | 济宁碳素工业总公司 | Method for producing refined naphthalene by riser type crystallization process |
| CN103694210A (en) * | 2014-01-13 | 2014-04-02 | 南通奥凯生物技术开发有限公司 | Method for purifying dehydroacetic acid |
| CN103801106A (en) * | 2012-11-02 | 2014-05-21 | 中国石油化工集团公司 | Sleeve type crystallizer |
| CN104208900A (en) * | 2014-09-11 | 2014-12-17 | 江苏华伦化工有限公司 | Crystal catcher applied to acid anhydrides |
| CN105031966A (en) * | 2015-08-17 | 2015-11-11 | 天津市鹏翔科技有限公司 | Multi-tube falling-film crystallizer and method |
| CN106890475A (en) * | 2017-02-08 | 2017-06-27 | 兖矿科蓝凯美特化工有限公司 | A kind of dynamic crystallisers and the processing technology using its production high-purity refined naphthalene |
| CN107648880A (en) * | 2017-11-06 | 2018-02-02 | 天津理工大学 | A kind of melt crystallization separating device and method |
| CN107750181A (en) * | 2015-06-24 | 2018-03-02 | 苏舍化学技术有限公司 | Semicontinuous method for crystallising and device |
| WO2020029114A1 (en) * | 2018-08-08 | 2020-02-13 | 南通奥凯生物技术开发有限公司 | Method for purifying dehydroacetic acid |
| CN112675568A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Separation and purification device and separation and purification method |
-
1990
- 1990-11-29 CN CN90109470A patent/CN1027963C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041408C (en) * | 1994-01-19 | 1998-12-30 | 扬州大学师范学院 | Di-substituted benzene position isomer continuous solidifying and separating method |
| CN101475436B (en) * | 2009-02-02 | 2012-06-06 | 济宁碳素工业总公司 | Method for producing refined naphthalene by riser type crystallization process |
| CN103801106A (en) * | 2012-11-02 | 2014-05-21 | 中国石油化工集团公司 | Sleeve type crystallizer |
| CN103801106B (en) * | 2012-11-02 | 2015-11-25 | 中国石油化工集团公司 | A kind of extension type crystallizer |
| CN103694210A (en) * | 2014-01-13 | 2014-04-02 | 南通奥凯生物技术开发有限公司 | Method for purifying dehydroacetic acid |
| CN103694210B (en) * | 2014-01-13 | 2015-11-25 | 南通奥凯生物技术开发有限公司 | A kind of method of dehydroacetic acid (DHA) of purifying |
| CN104208900A (en) * | 2014-09-11 | 2014-12-17 | 江苏华伦化工有限公司 | Crystal catcher applied to acid anhydrides |
| CN107750181A (en) * | 2015-06-24 | 2018-03-02 | 苏舍化学技术有限公司 | Semicontinuous method for crystallising and device |
| US10981844B2 (en) | 2015-06-24 | 2021-04-20 | Sulzer Management Ag | Semi-continuous crystallization method and apparatus |
| CN107750181B (en) * | 2015-06-24 | 2021-04-06 | 苏尔寿管理有限公司 | Semi-continuous crystallization method and apparatus |
| CN105031966B (en) * | 2015-08-17 | 2017-02-01 | 天津市鹏翔科技有限公司 | Multi-tube falling-film crystallizer and method |
| CN105031966A (en) * | 2015-08-17 | 2015-11-11 | 天津市鹏翔科技有限公司 | Multi-tube falling-film crystallizer and method |
| CN106890475A (en) * | 2017-02-08 | 2017-06-27 | 兖矿科蓝凯美特化工有限公司 | A kind of dynamic crystallisers and the processing technology using its production high-purity refined naphthalene |
| CN107648880A (en) * | 2017-11-06 | 2018-02-02 | 天津理工大学 | A kind of melt crystallization separating device and method |
| WO2020029114A1 (en) * | 2018-08-08 | 2020-02-13 | 南通奥凯生物技术开发有限公司 | Method for purifying dehydroacetic acid |
| CN112675568A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Separation and purification device and separation and purification method |
| CN112675568B (en) * | 2019-10-18 | 2022-04-05 | 中国石油化工股份有限公司 | Separation and purification device and separation and purification method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1027963C (en) | 1995-03-22 |
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