CN1317353A - Differential crystallization method able to control gradient field and its equipment and application - Google Patents
Differential crystallization method able to control gradient field and its equipment and application Download PDFInfo
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Abstract
A differential crystallization method with controllable gradient field, its differential crystallizer, and its application are disclosed. It features that a centrally symmetrical spiral flow generated on the surface of horizontally rotating disk is used to ensure the same gradient and crystallizing condition on said surface. In the crystal deposition state, the unsaturated mother liquid on the surface of crystals is displaced continuously and uniformly by the saturated mother liquid. By regulating the primary and secondary nucleation, uniform crystal particles are obtained. Its advantages include high purity, low power and high operation stability.
Description
The present invention relates to a kind of controlled gradient fields the differential crystallisation, be applicable to and the crystallization apparatus and the application of the rotational circle disc type of this method belong to separation field.
At present, the most general solution crystallization method of industrial employing is a stirred crystallization.The stirring-type crystallization apparatus is widely used in crystallisation by cooling, adds thermal crystalline, evaporative crystallization, reactive crystallization and vacuum evaporating crystalization process.Yet, because the stirred crystallization method and be provided with intrinsic, the repeatedly cooling of mother liquor between cooler and agitator (or heating), stirring, mixing, crystalline growth.The secondary nucleation that mechanical collision that the degree of supersaturation of mother liquor part and stirring cause and shearing cause is the uneven main cause of distribution of particles.Thereby because the excessive cladding of impurity and the purity that absorption influences product of easily causing of cocrystallization that degree of supersaturation causes and fine particle surface area.Often need to reduce yield in order to improve purity.The inhomogeneous use that also can influence product of crystal grain size.Therefore improve the main target that crystalline particle distribution (CSD) becomes the new crystallization operation of research and development.
Heating or cooling to mother liquor in the stirred crystallization method have two characteristics: the first, in batches, discontinuous method; The second, heat when all mother liquors and crystal grain are mixed or cool off.So just require big hot cross surface long-pending, bigger mother liquor degree of supersaturation.
Because the ungood mixed function of present agitator itself must improve by increasing rotating speed and increasing number of blade.The agitating function of Xiao Haoing is very big like this, but still is difficult to the supersaturation mother liquor is carried out desirable mixing with crystal, and the degree of supersaturation field that stirring produces is difficult to control.
Since the degree of supersaturation in the stirred crystallization is cooled off or the influence of heat medium temperature and flow outside, also be subjected to crystallization process to influence (dynamic changes of nucleus number, crystal grain distribution, crystal yardstick etc.), therefore, poor repeatability when batch crystallization is operated, operational stability is poor, influences product quality.
Chinese scholars to stirring-type crystallization study from many aspects, comprise the optimization that changes structure of mould and physical dimension, the shape of paddle and for the cooling layout and the control of temperature decline curve, and the water conservancy diversion skeleton symbol stirs the agitated crystallizer of guide cylinder both sides cooling at the bottom of developing the most rational current W, but all fail fundamentally to solve crystalline particle distributing homogeneity problem.People such as Xu Zuoqing have designed the agitated crystallizer that a kind of lower end is installed the guide shell of helical stir oar, are used for the production of heavy soda ash and monohydrated sodium carbonate.Though obviously increased the crystal yardstick, particle size distribution (20 orders and be 58.5% more than 40 orders) has only improved 19.9%.(Chinese patent CN 87217100)
People such as the M Si Tepansiji of Switzerland Sulzer Chemtech Ag have proposed a kind of method of fractional crystallization material and have been applicable to the crystallizer of this method, only make the material that when by crystallization, is easy to break away from crystal surface carry out classification and the situation of uncontrollable crystallization landing can not occur, but not mentioned this sensitivity of crystalline particle distributing homogeneity and important problem (CN 1209348A).
The object of the present invention is to provide a kind of new controlled gradient fields differential solution crystallization method and the rotating circular disk crystallization apparatus of realizing the differential method for crystallising of controlled gradient fields.Can replace at the saturated mother liquor of the trace the unsaturated mother liquor that makes plane of crystal under the crystal crystallization state is fallen (liter) temperature constantly, everywhere equably by micro component after by method and apparatus provided by the invention.Method of the present invention obtained more even than former various solution crystallization methods, even the crystalline particle of same size, can finish crystallization and configuration of littler power of agitator and film-cooled heat setting under bigger operating flexibility.
Controlled gradient fields differential method for crystallising of the present invention can utilize to horizontally rotate disk and realize.Specific implementation method is that the center symmetry helical constant speed that produces on the rotating circular disk surface flows, axially can both obtain even temperature, concentration everywhere on each horizontal plane, having guaranteed has identical gradient on the disc surfaces, thereby just can obtain identical crystallization condition on disk.Yet concentration on the axial direction and thermograde can be controlled by disk temperature and mother liquor temperature and disc rotation speed.Do not produce secondary nucleation thereby can control, guarantee that all seeded growth conditions are identical, can obtain crystal fully uniformly.
The prerequisite that realizes the differential crystallization is a crystal and constantly the separating and upgrade of mother liquor, and the controlling of temperature and concentration field in the mother liquor.Screw type flow process owing to symmetry on the disk has guaranteed axially evenly to flow as shown in Figure 1, and has caused height level's direction concentration and uniform distribution of temperature vertically.For a saturated solution, its temperature only changes with height, so its saturated concentration also only becomes with height, the disk top just has a continuous thermograde, concentration gradient (temperature difference on the unit length and concentration difference) to distribute.Allow rotating circular disk be cooled off, just can obtain maximum degree of supercooling, and on each horizontal level above the upper surface, will reach certain corresponding temperature at disk upper surface.Thereby on disk, just can set up an orderly controlled gradient fields.So just can guarantee with the crystallization control process in the temperature lowering curve along continuous straight runs identical everywhere, identical everywhere crystallization condition is arranged on disc surfaces, thereby reaches the conception that the crystallization control crystallite size is evenly distributed.
The crystallization apparatus that is applicable to the rotational circle disc type of the differential method for crystallising of controlling gradient recited above is made of saturated crystallization liquid (mother liquor) groove, rotating circular disk assembly, cooling liquid bath, adjustable speed magnetic stirring apparatus, cooling fluid low level water inlet, the high-order delivery port of cooling fluid and peristaltic pump or head tank circulating pump.And the rotating circular disk assembly places the stainless steel ball of disk below to form by stainless steel rotating circular disk, aluminium matter cooling cylinder, steel cooling annulus, rareearth magnetic material and one group.Driving, cooling and sealing three big problems have mainly been solved.
What at first solve is the disk driving problems.This device adopts magnetically-actuated with several rareearth magnetic materials (Fig. 6) along placement of disk diameter direction and the collocation method realization down of different magnetic.
This crystallization apparatus requires rotating circular disk should drive liquid flow for realizing cooling continuously, again liquid is constantly cooled off simultaneously, for reaching favorable cooling effect, has taked the measure of 3 aspects.The first, the cooling liquid bath that is complementary with the mother liquor tank volume is set, guarantee the cooling liquid measure of certain volume; The second, increase aluminium matter cooling cylinder, strengthen convection heat transfer' heat-transfer by convection and conduction heat transfer; The 3rd, adopt comparatively reasonably inlet and outlet system: directly flow to rotating circular disk lower surface (minimum temperature cooling disk) again by the cooling system of the high-order delivery port water outlet of cooling fluid through the center water pipe by the water inlet of cooling fluid low level water inlet.
In this device, rotating circular disk need solve sealing problem.Because driving force is not enough, can't adopt the axle envelope.So designed a cover hydrolock sealing system.Through multiple test, finally adopt peristaltic pump (available cooling fluid head tank) that enough hydraulic pressure is provided, select ethylene glycol (or high concentration NaCl, the CaCl of density for use greater than mother liquor
2Mixed solution) makes two kinds of liquid stabilising layerings, can reach the effect of sealing.For the reliability that improves sealing with solve mother liquor and the cooling fluid problem of dissolving each other, also adopted the special seal material and as the seal of types such as O type circle, backbone sealing ring, but need provide bigger quiet moment of torsion to export.
Device provided by the invention is 0.5～100 liter of a mother liquor tank volume, 0.2～100 liter of cooling bath volume, and disk diameter 65～300mm, rotating speed can be regulated in 0.05 revolutions per second～2.5 revolutions per seconds scopes.
Rotating circular disk of the present invention can also be realized cooling with method for air-cooling and heat pipe method.
The device that is applicable to controlled gradient fields differential method for crystallising provided by the invention is provided with annular space, not only for the backflow mother liquor provides passage, to avoid mobile being interfered on the rotating circular disk around rotating circular disk; And the follow-up cold excessively saturated mother liquor contact after can allowing crystal deposition make crystal and undersaturated mother liquor separates effectively, realize continuous differential crystallization; Also can set out materials device and system in the annulus.
The device that is applicable to controlled gradient fields differential crystallisation provided by the invention, mother liquor is flowed, and crystal crystallization particle deposition is in the annular space of disc surfaces and disk perimeter, in order to prevent that the granule grain of crystallization from moving with mother liquor, screen cloth can be set above disk, guarantee separating of mother liquor and grain of crystallization, bigger relative velocity is arranged between mother liquor and plane of crystal, the mother liquor at easier renewal plane of crystal place, thus guarantee that the plane of crystal place keeps certain degree of supersaturation.This crystallization process only needs to upgrade very a spot of mother liquor, so required power of agitator is also low.And this liquid, brilliant separate, make crystal growing process to control; And can be anti-interference.This method for crystallising is good reproducibility not only, and has good operational stability.
Controlled gradient fields differential method for crystallising of the present invention and device thereof, only the mother liquor to the trace on the disc surfaces cools off (or heating) continuously, only need replace a small amount of unsaturated mother liquor at plane of crystal place.So heat exchange area than in the stirred crystallization owing to intermittently heat or to cool off required heat exchange area much smaller in batches.
Controlled gradient fields differential method for crystallising of the present invention and device thereof, owing to will avoid mechanical shearing and the too fast secondary nucleation that flow velocity caused, disk need be controlled at work under the very low rotating speed, makes the mobile maintenance laminar condition on the disk, and this just can significantly reduce power of agitator.
Controlled gradient fields differential method for crystallising of the present invention and device thereof, at the liquid level place insulation cover and thermostat are set, can be suppressed at effectively and produce secondary nucleation on the liquid level, can also suppress the secondary nucleation of liquid level in addition with the method for horizontal baffle controls recirculating zone size.And the method for the accurate feed supplement in disc surfaces center can local ground control saturated concentration.
The solution crystallization process that the method according to this invention is particularly suitable for antibiotic, biochemical product, medicine and has other materials of same purity requirement.Or the repeatedly operation of the primary crystallization in the recrystallization process.The recrystallization process that comprises the feedstock purification preparation of growing single-crystal material.
Further specify substantive distinguishing features of the present invention and marked improvement below by accompanying drawing and preferred embodiment.
Fig. 1 is a controlled gradient fields rotating circular disk near surface liquid fluid distribution map provided by the invention.
Fig. 2 is the cooling chart of differential crystallization.
Fig. 3 is the schematic longitudinal elevation view of controlled gradient fields rotating disk crystallization apparatus provided by the invention.
Fig. 4 is the horizontal baffle schematic diagram that band differential micrometer is regulated among Fig. 3.
Fig. 5 is the accurate flow-control feed supplement in a center device schematic diagram among Fig. 3.
Fig. 6 is the cooling system and the disk drive unit schematic diagram of crystallization apparatus shown in Figure 3.
Fig. 7 is a magnetic material configuration schematic diagram in Fig. 6 disk drive unit.
Fig. 8 is the controlled gradient fields rotating circular disk differential crystallization apparatus of another kind of band thermostat (heating).
To evenly flowing, its temperature only becomes with height controlled gradient fields differential crystallisation provided by the invention as can be seen from Figure 1 in rotating circular disk near surface flow axis, that is concentration also only becomes with height.Form controlled temperature and concentration gradient field.
Fig. 2 is the cooling curve of differential crystallization, abscissa is cool time, ordinate is a temperature, as seen from the figure, in the method for crystallising of controlled gradient fields provided by the invention, its cooldown rate obviously is different from the cooling curve in the stirred crystallization, it is that a kind of continuous cooling cooling is promptly along the slope direction decline temperature of cooling curve, in fact utilize temperature controller to divide 30 time periods in range of temperature Δ T=6～200 ℃, every section temperature drop can be as small as temperature element precision (every period is adjustable in 10 seconds to 30 minutes).So the control decrease of temperature reaches the purpose of diagram differential cooling substantially, thereby can avoid secondary nucleation fully; Because only a spot of solution is cooled off, so as long as control disk temperature, rely on the temperature difference (thermograde) of continuous distributed in the solution, flow through motionless substantially plane of crystal in an orderly manner, just the crystal that can guarantee to separate out is by the smooth reposefully decline of cooling curve, each as long as upgrade a spot of mother liquor, that is new supersaturation mother liquor replaces unsaturated mother liquor on a small quantity, reaches the purpose of differential crystallization.Thereby can obtain suitable homogeneous granules Size Distribution, and can guarantee result's repeatability.
Rounding dish crystallizer shown in Fig. 3 mainly is made up of crystallization tank 10, cooling liquid bath 4, demarcation strip 1 and rotating circular disk 11, and rotating circular disk 11 is placed on the interior ball 3 of the raceway of the demarcation strip 1 under the crystallization tank 10; Mother liquor cell wall 19 is installed in the groove of demarcation strip 1, is bonded and sealed with encapsulant 12, and insulation cover 17 is equipped with at mother liquor tank 10 tops, plays and keeps the liquid level temperature, reduces secondary nucleation.An accurate flow-control feed supplement device 30 can be installed in the center of lid.The differential chi 21 of mobile and horizontal baffle plate 20 must pass insulation cover 17 and be installed on the support 22.Mother liquor is contained in crystallization tank 10, and the diameter of crystallization tank 10 forms an annular space 18 greater than the diameter of rotating circular disk 11 around rotating circular disk.Annular space 18 is not only the passage that mother liquor upwards refluxes, and also is the space of crystal deposition, growth.When rotating circular disk is constantly cooled off, when mother liquor reaches certain degree of supercooling, can produce nucleation one time; Control thermograde and rotating speed well, can suppress secondary nucleation effectively.Crystal deposition more helps cooling homogeneously crystallized and by rotating circular disk in annular space 18.Crystallization tank bottom or on the cell wall discharging opening 2 is set on every side can be with gap or discharge crystal grain continuously.Ring-type screen cloth 90 is set above rotating circular disk, can plays making the mother liquor that the granule seed crystal is big with viscosity, flow velocity is higher separate purpose, realize the differential crystallization process.
The horizontal baffle 20 of the band differential chi that is provided with in the crystallization tank 10 plays control recirculation zone size and control liquid level temperature, avoids being back to liquid level the secondary nucleation of cold generation and the effect of the thermograde in the recirculating zone took place.Differential chi 21 passes insulation cover 17 and is fixed on the support 22, and support is fixed on the mother liquor cell wall 19.Magnetic material or sunk lock nut 25 are corresponding with differential chi 21 on horizontal baffle 20 downsides, clamp horizontal baffle 20 (Fig. 4).Because need accurately control the boundary layer on the rotating circular disk, so the necessary strict level of the installation of horizontal fishplate bar, and parallel with disk 11; Horizontal baffle must be smooth smooth, do not go out protrusion and groove and seam.The precision that differential chi 21 moves can be determined according to boundary layer thickness and mother liquor thickness of feed layer.
A mother liquor thermostat 70 can be set on crystalline mother solution groove 10, is heating tank evaporating, add in the thermal crystalline.The bottom contacts (see figure 8) with the mother liquor liquid level, the groove planted agent thermostat 71 is arranged, and can be the logical coil pipe that adds hot water or cooling water, also can be the device that directly freezes or heat, as semiconductor refrigerating or electric calorifie installation.Control thermostat 71 again after the temperature of thermostatic medium is exported to temperature control instrument by temperature element in the groove.Flowing of thermostatic medium can be organized (not drawing among the figure) by the jet of agitator or pump.Thermostat can suppress the secondary nucleation at liquid level place, is doing the heating evaporation time spent, can improve liquid level place mother liquid concentration.
The accurate flow-control feed supplement in center device 30 (referring to Fig. 5) can be set on rotating circular disk 11 centers.The device 31 of this device outlet should be regulated.Feed supplement tube 33 belows connect feed supplement needle tubing 34.Plunger 32 is arranged in the feed supplement tube 33, and moving of plunger 32 can drive (not shown) by precision control ground straight-line displacement device.Feed supplement speed also can be controlled with the accurate constant displacement pump of different accuracy as required.Can utilize the saturated concentration of this system's control mother liquor local.Feed supplement pipe size is little, can not surpass 1/10th of disk diameter.
Screw thread under the rotating circular disk 11 joins with the aluminum cooling cylinder 8 that passes the demarcation strip intermediate throughholes; Be placed in the cooling bath 4, the O type circle 13 on the cooling cylinder 8 constitutes axial seal with demarcation strip 1 intermediate throughholes.The lower end screw thread of cooling cylinder 8 is connected with the steel annulus 7 of placing rareearth magnetic material 6; Through hole 91 and fin on the cooling cylinder can strengthen heat loss through convection.Cooling fluid flows through passage 22 on the chamber wall of cooling bath 4 from cooling inlet 5 and flows into and pass steel annulus 7 in the cooling tube 23 that cooling bath 4 centers are provided with, flow out from outlet 24, can impact cooling rotating circular disk near the cooling tube 23 of rotating disc downside.Cooling fluid flows downward along the inboard of cooling cylinder 8, and the through hole 91 and the steel annulus 7 that pass on the cylinder flow out cooling cylinder 8, can effectively utilize the heat loss through convection cooling.Leakage fluid dram 9 drains into cooling fluid storage tank 80 on the cooling fluid from the cooling bath 4 at last; Send refrigeration plant 50 cooling reuses back to by peristaltic pump 40.By coolant temperature and coolant rate crystallization control groove lower bottom part temperature effectively, measure back input temperature controller 52 by sensor 51, control signal input switch voltage-stabilized power supply 53, refrigeration plant 50 is controlled, the cooling liquid outlet temperature is reduced by the crystallization cooling curve, can realize the optimization differential crystallization of controlled gradient fields.
Utilize a pair of N-S pole pair of arranging on the rareearth magnetic material driving-disc 60 on the motor output shaft 65 (seeing among the figure) that is no less than, pole pair 65 promotes 7 rotations of the rareearth magnetic material on the steel annulus 6 in the cooling bath 4 when rotating, thereby the crystallization task is finished in 11 rotations of driven rotary disk.Connected mode between the heat radiation aluminium matter cooling cylinder 5 under motor output shaft and the rotating circular disk 11 can adopt and directly be connected transmission, and should increase the hermetically-sealed construction of corresponding rotating shaft.Rotating speed can be with various mechanical speed changes or electrically-actuated throttle device, adaptive various motor.Figure 4 shows that a kind of stepper motor 61, by manual control 64 control step machine governors 63, the pulse signal of output input dynamo-electric machine driving machine 62 rear drive stepper motors 61 of step.
Rotating circular disk 11 can directly cool off heat radiation cooling cylinder 8 with method for air-cooling, and motor 61 can directly drag cylinder 8 and rotating circular disk.Cooling cylinder under the rotating circular disk 11 also can be made up of the heat pipe tube bank, and motor 61 can directly drive the heat pipe tube bank, and the tube bank cold junction can cool off with liquid cools or air.
As everyone knows, the condition for fear of the secondary nucleation crystallization is: (1) avoids excessive degree of supercooling; (2) avoid undue mechanical shock; (3) guarantee that the crystal and the mother liquor of separating out constantly are separated into prerequisite.By the above-mentioned and described controlled gradient fields (temperature provided by the invention of accompanying drawing, concentration) differential method for crystallising, and be applicable to the method and custom-designed disc rotary type crystallization apparatus can reach this three conditions fully, can clearly be seen that from top statement simultaneously, method basic point of departure provided by the invention is to utilize to horizontally rotate identical gradient and crystallization condition on the mobile assurance of the center symmetry screw disc surfaces that produces on the disc surfaces, the surperficial unsaturated mother liquor that makes crystal under the crystal deposition state constantly, everywhere equably by the saturated mother liquor displacement of the trace after the cooling, mother liquid concentration, the temperature of rotating circular disk and degree of supercooling, rotary speed are to determine according to object fully.
The average dimension of disk crystalline particle provided by the invention increases significantly, the crystal decentralization reduces, and the uniformity of particle is bright for improving, and corresponding confidential interval shows the credibility height of test data.
The natural cooling crystallization time is long, and in the probability minimizing of crystal growth later-stage secondary nucleation, the large scale particle is on the contrary more than stirred crystallization, but a crystal body yardstick decentralization is big.And stirred crystallization is favourable (comparing with spontaneous nucleation) to reducing the particle decentralization with increasing the particle average dimension.The disk crystallization is owing to realized the differential crystallization, and mother liquor is only cold all the time in the crystallization process after elementary nucleation, so can secondary nucleation.Long because of the elementary nucleating growth time of disk crystallization again, initial number of crystals particle average dimension more at least is big more.From the crystal distribution graph, fully consistent with theoretical analysis, so rotating circular disk differential crystallization is better than stirred crystallization aspect crystalline particle uniformity and the average dimension and natural cooling crystallization is convictive improving.
Stir natural cooling crystallization with stirred crystallization and nothing and compare, the superiority of disk crystallization is significant.
Described by accompanying drawing, the crystallization apparatus of rotational circle disc type of the present invention as can be seen has following feature:
(1) crystallization apparatus of rotational circle disc type of the present invention, be by the rate of temperature fall of rotating speed control and control disk below cooling bath and the gradient fields and the degree of supersaturation of liquid level thermostat control mother liquor, reach the inhibition secondary nucleation, the purpose of the homogeneously crystallized process of control bulky grain;
(2) crystallization apparatus of rotational circle disc type of the present invention, the rotation disk perimeter is provided with annular space in mother liquor tank, guarantee that the mother liquor return flow line makes the mobile minimum interference on rotating circular disk surface, and precipitable crystal flows the static mother liquor of crystal, make supersaturation mother liquor amount minimum, thereby make the film-cooled heat minimum;
(3) crystallization apparatus of rotational circle disc type of the present invention, under rotating circular disk, be provided with cooling bath, cooling water pipe outlet in the groove forms plane jet on the lower surface of rotating circular disk, rotating circular disk is formed the even cooling of symmetry, rotating circular disk is down with heat-conducting cylinder of spiral marking connection, perforate and fin is set on the tube, plane jet flows down along this inner tube wall, discharge outlet is discharged from the cooling bath, heat radiation and cooling (freezing) back are with being pumped back to water inlet, and rotating circular disk also can be directly with air-cooled or heat pipe mode cooling;
(4) crystallization apparatus of rotational circle disc type of the present invention is by dense mother liquor feeding-system control concentration field and mother liquor degree of supersaturation under the mother liquor thermostat, thereby reaches the purpose of crystallization control process;
(5) crystallization apparatus of rotational circle disc type of the present invention is by the setting of horizontal baffle in the mother liquor tank and the control of position.Control the size of mother liquor recirculating zone, thereby reach the control of gradient;
(6) crystallization apparatus of rotational circle disc type of the present invention is the adjustment by the radial and axial position of crystallization control body drawing mechanism baffle plate, the size of control discharging crystal grain;
(7) crystallization apparatus of rotational circle disc type of the present invention be with cut apart on the plate axis hole with the axle on flexible sealing material separate mother liquor and cooling fluid;
(8) rotating circular disk crystallization of the present invention is provided with motor-driven structure below cooling bath, drives cooling heat conduction cylinder and disk rotation in the cooling bath;
(9) rotating circular disk crystallization apparatus of the present invention utilizes temperature control system that refrigeration system is regulated and control, the temperature lowering curve of strict control cooling water and to the control of disc rotation speed; To thermostat internal heater and cooling (freezing) water regulation and control thermostat temperature, control mother liquor layer liquid level temperature;
(10) rotating circular disk crystallization of the present invention also can utilize the liquid level thermostat to keep the proper temperature at liquid level place, reaches the purpose of interior mother solution gradient of crystallization control groove and concentration gradient;
(11) rotating circular disk crystallization apparatus of the present invention, when being used for its sky evaporative crystallization, as long as mother liquor tank is connected when being used to add thermal crystalline and evaporative crystallization with vacuum system, liquid level mother liquor heating tank is set in mother liquor tank, improve the mother liquor temperature by heating to medium in the groove, vaporization is evaporated until the liquid level place, and thermograde between maintenance and rotating circular disk and concentration gradient.
(12) crystallization apparatus of rotational circle disc type of the present invention also can utilize screen cloth that mother liquor is separated with the little grain of crystallization that moves with liquid, thereby can realize the differential method for crystallising.
The crystallization of table 1 disk
| Numbering | Solute KNO 3(g) | Solvent H 2O(ml) | Rotating speed (revolutions per second) | The mother liquor initial temperature (℃) | The whole temperature of mother liquor (℃) | Coolant temperature (℃) surveyed in 5 | ||||||
| ????1 | ????80 | ????100 | ????1.43 | ????69.6 | ????29.8 | ?10.1 | ??8.7 | ??8.6 | ??8.6 | ??8.5 | ||
| ????2 | ????80 | ????100 | ????1.88 | ????77.7 | ????32.9 | ?17.8 | ?15.2 | ?14.9 | ?14.2 | ?13.7 | ||
| ????3 | ????60 | ????100 | ????2.31 | ????74.1 | ????31.6 | ?17.5 | ?14.5 | ?13.8 | ?13.3 | ?12.9 | ||
| ????4 | ????60 | ????90 | ????1.30 | ????80.2 | ????29.8 | ?19.0 | ?18.5 | ?18.2 | ?17.6 | ?16.4 | ?15.8 | ?15.0 |
| ????5 | ????60 | ????90 | ????1.36 | ????68.2 | ????29.4 | ?20.7 | ?18.3 | ?17.4 | ?16.5 | ?15.9 | ||
| ????6 | ????70 | ????100 | ????1.36 | ????69.2 | ????37.3 | ?20.6 | ?19.4 | ?18.0 | ?16.3 | ?15.4 | ||
| ????7 | ????60 | ????90 | ????1.25 | ????65.5 | ????30.2 | ?17.4 | ?16.7 | ?15.4 | ?15.0 | ?14.8 | ||
| ????8 | ????80 | ????100 | ????0.857 | ????76.3 | ????29.5 | ?17.4 | ?15.6 | ?13.9 | ?13.3 | ?12.7 | ?12.2 | ?11.7 |
| ????9 | ????70 | ????100 | ????0.857 | ????81.0 | ????28.4 | ?15.5 | ?14.7 | ?13.9 | ?13.7 | ?12.6 | ?12.1 | ?11.5 |
| ????10 | ????70 | ????100 | ????1.07 | ????82.5 | ????30.2 | ?15.6 | ?14.8 | ?13.5 | ?13.2 | ?12.7 | ?12.0 | ?11.6 |
| ????11 | ????60 | ????100 | ????1.03 | ????59.4 | ????28.6 | ?16.1 | ?16.1 | ?16.1 | ?16.1 | ?16.1 | ||
Table 2 stirred crystallization
| Numbering | Solute KNO 3(g) | Solvent H 2O(ml) | Rotating speed (revolutions per second) | The mother liquor initial temperature (℃) | The whole temperature of mother liquor (℃) |
| ?1 | ????70 | ????100 | ????/ | ????/ | ?29.8 |
| ?2 | ????80 | ????100 | ????/ | ????/ | ?29.3 |
| ?3 | ????70 | ????100 | ????/ | ????/ | ?30.6 |
| ?4 | ????70 | ????100 | ????/ | ????/ | ?26.2 |
| ?5 | ????70 | ????100 | ????/ | ????/ | ?21.6 |
Table 3 spontaneous nucleation
| Numbering | Solute KNO 3(g) | Solvent H 2O(ml) | Rotating speed (revolutions per second) | The mother liquor initial temperature (℃) | The whole temperature of mother liquor (℃) |
| ?1 | ????70 | ????100 | ????/ | ????/ | ?34.1 |
| ?2 | ????60 | ????100 | ????/ | ????/ | ?34.6 |
| ?3 | ????70 | ????100 | ????/ | ????/ | ?20.4 |
| ?4 | ????70 | ????100 | ????/ | ????/ | ?14.5 |
| ?5 | ????70 | ????100 | ????/ | ????/ | ?19.1 |
The crystallization-stable of three kinds of crystallization modes of table 4 relatively
The disk crystallization
Spontaneous nucleation
Stirred crystallization
| Unit: order | ????＞20(g) | ????％ | 20～40 | ????％ | ????40～60 | ????％ | 60～80 | ????％ | 80～100 | ％ | ＜100 | ％ | 20～60 |
| ????1 | ????0.350 | ????0.80 | ????27.935 | ????70.60 | ??10.958 | ????27.71 | ????0.266 | ????0.67 | ????0.053 | ????0.13 | ????0.007 | ????0.10 | ?98.31 |
| ????2 | ????0.367 | ????1.20 | ????28.462 | ????95.93 | ???0.788 | ?????2.67 | ????0.047 | ????0.16 | ????0.014 | ????0.05 | ????0.012 | ????0.02 | ?98.60 |
| ????3 | ????0.064 | ????0.31 | ????15.730 | ????77.21 | ???4.099 | ????20.12 | ????0.408 | ????2.00 | ????0.054 | ????0.27 | ????0.017 | ????0.08 | ?97.33 |
| ????4 | ????0.551 | ????2.14 | ????24.787 | ????96.52 | ???0.289 | ?????1.13 | ????0.023 | ????0.09 | ????0.016 | ????0.06 | ????0.014 | ????0.05 | ?97.65 |
| ????5 | ????0.131 | ????0.49 | ????21.505 | ????80.55 | ???4.782 | ????17.91 | ????0.170 | ????0.64 | ????0.056 | ????0.21 | ????0.055 | ????0.21 | ?98.46 |
| ????6 | ????0.237 | ????0.85 | ????22.385 | ????80.13 | ???4.977 | ????17.82 | ????0.244 | ????0.87 | ????0.052 | ????0.19 | ????0.041 | ????0.15 | ?97.95 |
| ????7 | ????0.263 | ????0.90 | ????25.772 | ????88.17 | ???3.048 | ????10.43 | ????0.106 | ????0.36 | ????0.022 | ????0.08 | ????0.020 | ????0.07 | ?98.60 |
| ????8 | ????0.065 | ????0.19 | ????20.942 | ????60.16 | ???10.935 | ????31.41 | ????2.366 | ????6.71 | ????0.303 | ????0.86 | ????0.200 | ????0.57 | ?91.57 |
| ????9 | ????0.033 | ????0.13 | ????19.628 | ????78.05 | ???4.319 | ????17.17 | ????0.529 | ????2.10 | ????0.436 | ????1.73 | ????0.204 | ????0.81 | ?95.22 |
| ????10 | ????0.037 | ????0.24 | ????12.581 | ????83.25 | ???1.554 | ????10.28 | ????0.646 | ????4.27 | ????0.201 | ????1.33 | ????0.094 | ????0.62 | ?93.53 |
| ????11 | ????0.145 | ????0.73 | ????13.851 | ????69.93 | ???5.215 | ????26.33 | ????0.497 | ????2.51 | ????0.069 | ????0.35 | ????0.030 | ????0.15 | ?96.26 |
| ????12 | ????0.080 | ????0.22 | ????20.991 | ????58.82 | ??11.167 | ????30.96 | ????2.899 | ????8.03 | ????0.561 | ????1.56 | ????0.373 | ????1.03 | ?89.78 |
| ????1 | ????11.12 | ???36.27 | ???12.988 | ????42.28 | ????4.164 | ????13.46 | ????1.108 | ????3.61 | ????0.404 | ?1.32 | ????0.940 | ????3.06 | ?78.55 |
| ????2 | ?????0.208 | ?????3.09 | ?????2.488 | ????36.93 | ????2.410 | ????35.77 | ????1.120 | ???16.62 | ????0.130 | ?1.93 | ????0.381 | ????5.66 | ?40.02 |
| ????3 | ????12.543 | ????32.17 | ????18.230 | ????46.75 | ????6.655 | ????17.07 | ????0.757 | ????1.94 | ????0.421 | ?1.08 | ????0.386 | ????0.99 | ?78.12 |
| ????4 | ????12.132 | ????31.66 | ????19.643 | ????51.26 | ????5.615 | ????14.65 | ????0.555 | ????1.45 | ????0.237 | ?0.62 | ????0.140 | ????0.37 | ?82.92 |
| ????5 | ????15.945 | ????39.71 | ????17.019 | ????42.38 | ????5.344 | ????13.31 | ????1.392 | ????3.47 | ????0.209 | ?0.52 | ????0.245 | ????0.61 | ?82.09 |
| ????1 | ????0.944 | ????2.76 | ????12.930 | ????37.86 | ????13.727 | ????40.20 | ????4.415 | ????12.14 | ????0.877 | ????2.57 | ????1.526 | ????4.47 | ?78.06 |
| ????2 | ????1.150 | ????2.29 | ????25.015 | ????49.72 | ????13.568 | ????26.97 | ????5.987 | ????11.90 | ????3.010 | ????5.98 | ????1.577 | ????3.15 | ?76.69 |
| ????3 | ????0.913 | ????2.24 | ????21.113 | ????51.77 | ????11.357 | ????27.85 | ????4.705 | ????11.54 | ????1.573 | ????3.86 | ????1.119 | ????2.74 | ?79.62 |
| ????4 | ????0.188 | ????0.58 | ????14.540 | ????44.83 | ????12.486 | ????38.50 | ????3.521 | ????10.86 | ????1.643 | ????5.07 | ????0.057 | ????0.18 | ?83.33 |
| ????5 | ????9.597 | ????20.78 | ?????5.097 | ????11.04 | ????30.560 | ????66.18 | ????0.528 | ????1.144 | ????0.268 | ???0.58 | ????0.123 | ????0.27 | ?77.22 |
Table 5
| The disk crystallization | Stirred crystallization | Spontaneous nucleation | |
| Crystal grain distribution concentration degree | 96.68% (20～60 order) | 78.98% (20～60 order) | 72.50% (＞40 order) |
| Arithmetic average deviation | ????1.84％ | ?????1.99％ | ??12.99％ |
| Standard deviation | ????0.84％ | ?????1.19％ | ??8.16％ |
| 90% confidential interval | ???96.68％±0.199％ | ????78.98％±0.438％ | ??72.50％±3％ |
| 98% confidential interval | ???96.68％±0.282％ | ????78.98％±0.619％ | ??72.50％±4.24％ |
Claims (15)
1. the differential solution crystallization method of a controlled gradient fields comprises saturated solution and separate out the crystal process from supersaturated solution, it is characterized in that:
(1) utilizes the center symmetry helical movement at the uniform velocity that on the rotating circular disk surface, produces, axially can both obtain even temperature and concentration everywhere on each horizontal plane, and concentration in the axial direction and temperature, gradient can be controlled by disk temperature and disc rotation speed;
(2) separate out crystal under sedimentation state, the unsaturated mother liquor that makes plane of crystal is constantly replaced by the saturated mother liquor of the trace after the micro component cooling everywhere equably.
2. press the differential solution crystallization method of the described controlled gradient fields of claim 1, it is characterized in that around described rotating circular disk, being provided with an annular space, the crystal grain of separating out is deposited in the annular space of disc surfaces and disk perimeter, and can allow the crystal of separating out and undersaturated mother liquor effectively separate the back and contact, realize continuous differential crystallization with follow-up filtrated stock; Also can circular screen be set above rotating circular disk simultaneously, the granule seed crystal of separating out mother liquor big with viscosity, that flow velocity is higher is separated.
3. press the differential solution crystallization method of the described controlled gradient fields of claim 1, it is characterized in that controlling the thermograde that the disk temperature obtains continuous distributed in the solution, flow through the plane of crystal of separating out in an orderly manner, the crystal that assurance is separated out only needs to upgrade a spot of mother liquor by the smooth reposefully decline of cooling curve.
4, by the differential solution crystallization method of the described controlled gradient fields of claim 3, it is characterized in that utilizing temperature controller in temperature range Δ T=6～200 ℃, to divide 30 time period differential coolings, every section temperature drop can be as small as the temperature element precision.Every period is adjustable in 10 seconds to 30 minutes.
5. the crystallization apparatus of the rotational circle disc type of a differential method for crystallising that is applicable to controlled gradient fields is characterized in that mainly by crystalline mother solution groove, rotating circular disk assembly, cooling system, adjustable speed magnetically-actuated system.
6. by the described rotational circle disc type of claim 5 crystallization apparatus, it is characterized in that described rotating circular disk assembly places the stainless steel ball of disk below to form by stainless steel rotating circular disk, aluminium matter cooling cylinder, steel cooling annulus, horse tellurium shape rareearth magnetic material and one group.
7. by claim 5 or 6 described rotational circle disc type crystallization apparatus, it is characterized in that magnetically-actuated is adopted in the driving of rotating circular disk, several rareearth magnetic materials are placed along the disk circumference direction, and the collocation method realization down of different magnetic.
8. by the described rotational circle disc type of claim 5 crystallization apparatus, it is characterized in that around the rotating circular disk in the mother liquor tank annular space being set; Rotating circular disk is placed on the ball in the raceway of the demarcation strip under the crystalline mother solution groove; The mother liquor cell wall is installed in the groove of demarcation strip, is bonded and sealed with encapsulant; Also circular screen can be set in the annular space.
9. by the described rotational circle disc type of claim 5 crystallization apparatus, it is characterized in that being provided with the cooling liquid bath under rotating circular disk, the cooling water pipe outlet in the groove forms plane jet on the lower surface of rotating circular disk, rotating disc is formed the even cooling of symmetry; Connect a cooling cylinder with screw under the rotating circular disk, perforate and heat radiation vapour is set on the post, plane jet is along under this inner wall, and discharge outlet is discharged from the cooling bath, and heat radiation and cooling back send back to the cooling fluid water inlet with peristaltic pump, or directly cool off cylinder with air; Or the heat pipe bundle is set under the rotating circular disk disk is directly cooled off.
10. by the rotational circle disc type device of arbitrary claim among the claim 5-9, it is characterized in that rotating circular disk by speed governing, driver regulated and control the rotating speed of drive system; By regulation and control to refrigeration system, the rate of temperature fall of control disk below cooling liquid bath; By thermograde and the degree of supersaturation of mother liquor tank thermostat with the control mother liquor is set.
11. rotational circle disc type device by arbitrary claim among the claim 5-10, it is characterized in that the mother liquor tank top is equipped with insulation cover, the center of insulation cover is equipped with an accurate flow-control feed supplement, and it exports near disc surfaces, and feed supplement pipe diameter is 1/10 of disk diameter to the maximum; Horizontal baffle with little micrometer roll adjustment is set, with the size of control mother liquor recirculating zone in mother liquor tank.
12. by the described rotational circle disc type of claim 5 device, it is characterized in that 0.2～200 liter of 0.5～500 liter of cooling bath solvent of mother liquor tank volume, disk diameter 65～300mm, rotating speed can be regulated in 0.03 revolutions per second～2.5 revolutions per seconds scope.
13., it is characterized in that described rotating circular disk adopts hydrolock sealing system and seals such as O type circle, outside framework oil seal by the described rotational circle disc type of claim 5 device; Pass through the setting of the flat baffle plate of trough inner water and the control of position, control the size of mother liquor recirculating zone, thereby reach the control of gradient fields; Horizontal baffle has the differential chi, and the differential chi passes insulation cover and is fixed on the support, and support then is fixed on the wall of female chute; Magnetic material or sunk lock nut are corresponding with the differential chi on the horizontal baffle downside, clamp horizontal baffle, and parallel with disk.Differential chi mobile accuracy can be determined according to the boundary layer thickness and the feed liquid layer thickness of rotating circular disk.
14. by the rotational circle disc type crystallization apparatus of arbitrary claim among the claim 5-11, when it is characterized in that being used for vacuum evaporating crystalization, mother liquor tank and vacuum system connect; When being used to add thermal crystalline and evaporative crystallization, liquid level mother liquor heating tank is set in mother liquor tank, improves the mother liquor temperature, thermograde and concentration gradient until between the vaporization evaporation of liquid level place and maintenance and rotating circular disk by heating to medium in the groove.
15. by the differential crystallisation of the described controlled gradient fields of claim 1, particularly suitable and antibiotic, biological products, medicine and solution crystallization with other materials of same purity requirement; To using in arbitrary crystallization and purification in any recrystallization process.
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| CNB011054921A CN1143716C (en) | 2001-02-28 | 2001-02-28 | Differential crystallization method able to control gradient field and its equipment and application |
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