CN107233744B - A kind of cooling crystallization method of film auxiliary nucleation - Google Patents
A kind of cooling crystallization method of film auxiliary nucleation Download PDFInfo
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- CN107233744B CN107233744B CN201710435278.5A CN201710435278A CN107233744B CN 107233744 B CN107233744 B CN 107233744B CN 201710435278 A CN201710435278 A CN 201710435278A CN 107233744 B CN107233744 B CN 107233744B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/18—Preparation in the form of shaped products, e.g. granules
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
Abstract
The present invention provides a kind of cooling crystallization methods of film auxiliary nucleation, belong to crystallization field of engineering technology.Solution to be crystallized is added in crystallization kettle, opens computer, stirring and temperature regulating device, while opening coolant circuit；After system is stablized, peristaltic pump is opened, solution to be crystallized is made to be delivered to membrane module；To nucleus occur in membrane module, the mother liquor with nucleus is delivered to crystallization kettle, carries out crystal growth.By the control to coolant liquid and operating condition come the growth of the generation of system regulation nucleus and crystal, to obtain ideal crystal product.
Description
Technical field
The invention belongs to crystallize field of engineering technology, especially suitable for solubility with temperature reduction and significantly reduced object
The preparation of matter.
Background technique
Crystallisation by cooling is to generate degree of supersaturation by temperature is reduced and crystallization is precipitated.In order to shorten crystallizing cycle, prevent it is quick-fried
Hair nucleation, effectively control crystal growth, obtain the more uniform crystal product of granularity, usually into solution be added right quantity and
The crystal seed of appropriate granularity, the solute for being crystallized it are only grown on the surface of the seed.Stirring appropriate is selected, occurs that crystal seed not
Coalescence more uniform can be suspended in entire solution again, and avoid secondary nucleation phenomenon as far as possible.During entire crystallization, it is necessary to
The temperature or concentration of careful control solution.
It is, in general, that ideal crystal seed should be the more complete phase of the structure obtained in same settling system, ingredient
The allomeric, should purity with higher.Additional amount, granularity, opportunity selection and pretreatment of crystal seed etc. are to final products matter
Amount has a certain impact, and product quality is caused to fluctuate.In current crystallization production, crystal seed is rule of thumb launched, it is brilliant to launching
Kind temperature, crystal seed amount and seed size lack theoretical and experimental basis.
It is referred in Chinese patent CN1736970A and CN102070625A satisfactory by launching crystal seed acquisition
Crystal product, but be to obtain satisfactory crystal product, to the time for launching crystal seed and to the matter of crystal seed in control condition
Amount and granularity have strict demand, once operating condition has deviation, will cause fluctuation to crystal product quality.Therefore the party is used
Method produces varigrained different crystal limitation very much, and expanding production is also more difficult.
It with the continuous development of membrane material and membrane science, has nowadays applied quite extensive in every field, has studied
Person has developed diversified membrane separating process for different industrial requirements.Meanwhile membrane separation technique and other technologies are handed over
Fork, fusion, innovation, can give full play to the advantage of membrane separating process, so that industrial process is more complete.The present invention makes full use of
Film as nonhomogen-ous nucleation surface, solute molecule adsorbs in film surface, to form nucleus, and be detached under shearing force,
Leave new nucleation sites.Repeatedly, effect of the film in crystallization process as nonhomogen-ous nucleation surface is enhanced.Solute is in film
Crystal is generated in component, is delivered in crystallization kettle as nucleus, is mainly modified by the selection of control and film to operating condition
Obtain ideal crystal product.The invention is used for the preparation of drug and chemical products, has greatly widened the application of crystallisation by cooling
Field.
Summary of the invention
The present invention proposes a kind of cooling crystallization method of film auxiliary nucleation, and the membrane module used is as nucleation interface, film group
It is uniformly distributed between each film inside part, film side is crystallization solution, and the other side is coolant liquid.Due to coolant liquid and liquid to be crystallized it
Between there are the temperature difference so that crystallization solution reaches degree of supersaturation in film surface, film is as nonhomogen-ous nucleation surface, and solute molecule is in film
Adsorption, to form nucleus.Nucleus is introduced into crystallizer therewith, nucleus is grown in a crystallizer, obtains crystal product.
Technical solution of the present invention:
A kind of cooling crystallization method of film auxiliary nucleation, the equipment of crystallisation by cooling of the film auxiliary nucleation used is by two circuits
Composition；
One circuit: agitating device 2 is mounted in the crystallization kettle 1 with collet, and the outlet of crystallization kettle 1 successively passes through first
The side lower port connection of valve 14, the first three-way control valve 12, the first peristaltic pump 8, thermometer and membrane module 3, membrane module 3
Side upper port is connect by thermometer 10 with 1 entrance of crystallization kettle；Wherein, the collet of crystallization kettle 1 and the first temperature control device 6 connect
It connects, the first temperature control device 6 is connect with computer 11, is accurately controlled convenient for temperature, and realization in crystallization kettle 1 is made at the uniform velocity to cool down；
Another circuit: the second valve 15, the second peristaltic pump 9 are successively passed through in the outlet of coolant bottle 5, with 3 lower end of membrane module
Mouth connection, 3 upper port of membrane module are connect with 5 entrance of coolant bottle；Wherein, coolant bottle 5 has collet, collet and the second temperature control
Device 7 connects；
Steps are as follows:
(1) solution to be crystallized of saturation is prepared, and is injected into crystallization kettle 1, agitating device 2, the first temperature control are opened
Device 6 and computer 11 maintain 30min-80min, are uniformly mixed solution to be crystallized, by computer 11 to the first temperature control device 6
Carry out accurate real-time control；The second valve 15, the second peristaltic pump 9 and the second temperature control device 7 are opened simultaneously, flow and temperature are adjusted
Degree, making coolant liquid, stable circulation flows in the loop；
(2) the first valve 14 is opened, a, b mouth of the first three-way control valve 12 are opened, closes c mouthfuls, opens the second threeway tune
B, c mouth of valve 13 are saved, a mouthfuls is closed, solution to be crystallized is delivered in membrane module 3；
(3) when being full of entire pipeline wait crystallize, the first three-way control valve 12 and the second three-way control valve 13 are opened
A, c mouth, close b mouthful, make solution to be crystallized in the loop stable circulation flowing；
(4) when there is nucleus generation in membrane module 3, the b mouth of the second three-way control valve 13 is opened, closes a mouthfuls, it will be with crystalline substance
The mother liquor of core is delivered to crystallization kettle 1, carries out crystal growth；When crystal growth to required size, to the solution in crystallization kettle 1 into
Row filtration drying obtains crystal product.
The membrane module can use hollow-fibre membrane or plate membrane.Organic film can be used, as PTFE (polytetrafluoroethylene (PTFE)),
PVDF (Kynoar), PE (polyethylene) or PP (polypropylene) etc.；Inoranic membrane, such as metal oxide film, zeolite membrane；It is compound
Film, such as polyvinyl alcohol/micro- sodium cellulose.
Beneficial effects of the present invention:
(1) crystal size is controllable, narrow particle size distribution.The present invention assists generating nucleus by film, and is transported to crystallization
Kettle, carries out crystal growth, and obtained crystalline size is uniform.
(2) process is easily controllable, easy to operate.Solution and nucleus to be crystallized can be realized by valve control in the present invention
Conveying.By regulation coolant temperature, flow velocity and solution temperature to be crystallized, flow, i.e., controllable nucleus generates and crystal growth.
Compared to the cooling crystallization technology that crystal seed is added, it is no longer necessary to crystal seed processing and select, and the choosing to condition when crystal seed is added
It selects.
(3) crystal product quality is high, has a wide range of application.The present invention proposes that one kind is novel at nuclear technology, avoids crystal seed
Reunion in solution to be crystallized and broken, by controlling the generation of nucleus and the growth of crystal, can be obtained ideal crystal
Product, the present invention expand the scope of application of cooling crystallization technology.
The present invention makes full use of the auxiliary nucleation of film, using the ancillary equipments such as peristaltic pump, temperature control device, the tune of system
Control crystal production process.The present invention changes traditional dispensing crystal seed and obtains the mode of crystal product, is generated using membrane module brilliant
Core, and be transported to crystallization kettle and carry out crystal growth, thus the high quality crystal needed for obtaining.In process of production, it avoids
The preprocessing process of crystal seed, also reduces operating condition to the influence degree of crystal product, quick for some pairs of operating conditions
The production of the substance of sense, especially temperature sensitive substance is significant.The present invention not only ensure that the quality and quantity of product, but also
Process control and easy to operate, practicability is good.
Detailed description of the invention
Fig. 1 is the equipment of crystallisation by cooling schematic diagram of film auxiliary nucleation.
In figure: 1 crystallization kettle；2 agitating devices, 3 membrane modules；4 films；5 coolant bottles；
6 first temperature control devices；7 second temperature control devices；8 first peristaltic pumps；9 second peristaltic pumps；
10 thermometers；11 computers；12 first three-way control valves；13 second three-way control valves；
14 first valves；15 second valves.
Specific embodiment
Below in conjunction with attached drawing and process regimes, a specific embodiment of the invention is further illustrated.
Embodiment 1
Take PP doughnut film production membrane module 3.Prepare the KNO containing 300g at 50 DEG C3Saturated aqueous solution, and added
Enter into crystallization kettle 1, opens agitating device 2.Computer is opened, it is 50 DEG C that first stage temperature is arranged in computer, time setting
For 1h, second stage temperature is 10 DEG C, and the time is set as 4h.Temperature control device 6 is opened, recirculated water is opened, maintains operating status 1h.
Suitable quantity of water is added in coolant bottle 5, opens the second temperature control device 7, setting temperature is 15 DEG C, adjusts the first peristaltic pump 8 and is
30rpm keeps stable circulation flowing.After running 55min, adjusting valve door 14 is opened, opens a, b mouth of the first three-way control valve 12,
C mouthfuls are closed, b, c mouth of the second three-way control valve 13 are opened, closes a mouthfuls, opens the second peristaltic pump 9, and be adjusted to 75rpm, it will
Solution to be crystallized is delivered in membrane module 3.When being full of solution in circuit, the first three-way control valve 12 and the second threeway tune are opened
A, c mouth of valve 13 are saved, closes b mouthfuls, making solution to be crystallized, stable circulation flows in the loop.After running 5min, have in membrane module 3
Subtle KNO3Nucleus generates.The b mouth of the second three-way control valve 13 is opened, closes a mouthfuls, the mother liquor with nucleus is delivered to crystallization
In kettle 1, the first peristaltic pump 8 is closed immediately, closes the b mouth of the second three-way control valve 13.Rerun 2h, with the reduction of temperature,
Nucleus is grown to the suitable crystal of granularity in crystallization kettle 1.Agitating device 2, temperature control device and computer 11 are closed, by crystallization kettle 1
In mixing liquid filtering drying obtain KNO3Crystal product.
Embodiment 2
Take PVDF plate film production membrane module 3.Prepare the CoSO containing 200g at 50 DEG C4Saturated aqueous solution, and added
Enter into crystallization kettle 1, opens agitating device 2.Computer 11 is opened, first stage temperature setting is 50 DEG C in computer 11, the time
It is set as 40min, second stage temperature setting is 20 DEG C, and the time is set as 3h.The first temperature control device 6 is opened, recirculated water is opened,
Maintain operating status 50min.Suitable quantity of water is added in coolant bottle 5, opens the second temperature control device 7, setting temperature is 15 DEG C, is adjusted
Second peristaltic pump 2 is 70rpm, and coolant liquid is made to keep Rapid Circulation steady flow.After running 30min, the first valve 14 is opened, is beaten
A, b mouth of the first three-way control valve 12 are opened, closes c mouthfuls, opens b, c mouth of the second three-way control valve 13, closes a mouthfuls, is opened compacted
Dynamic pump, and it is adjusted to 75rpm, solution to be crystallized is delivered in membrane module 3.When being full of solution in circuit, the one or three is opened
A, c mouth of logical regulating valve 12 and the second three-way control valve 13, close b mouthfuls, and making solution to be crystallized, stable circulation flows in the loop.
After running 10min, there is subtle CoSO in membrane module 34Nucleus generates.The b mouth of the second three-way control valve 13 is opened, closes a mouthfuls,
Mother liquor with nucleus is delivered in crystallization kettle 1, closes the first peristaltic pump 8 immediately, closes the b of the second three-way control valve 13
Mouthful.Rerun 3h, and with the reduction of temperature, nucleus is grown to the suitable crystal of granularity in crystallization kettle 1.Closing agitating device 2,
Mixing liquid filtering drying in crystallization kettle 1 is obtained CoSO by temperature control device and computer 114Crystal product.
Embodiment 3
Take PTFE doughnut film production membrane module 3.Prepare the NaNO containing 150g at 40 DEG C3Saturated aqueous solution, and will
It is added into crystallization kettle 1, opens agitating device 2.Computer 11 is opened, it is 40 DEG C that first stage temperature is arranged in computer 11,
Time is set as 50min, and second stage temperature is 10 DEG C, and the time is set as 3h.The first temperature control device 6 is opened, recirculated water is opened,
Maintain operating status 50min.Suitable quantity of water is added in coolant bottle 5, opens the second temperature control device 7, setting temperature is 14 DEG C, is adjusted
Peristaltic pump is 50rpm, and coolant liquid is made to keep stable circulation flowing.After running 50min, the first valve 14 is opened, opens the one or three
A, b mouth of logical regulating valve 12, close c mouthfuls, open b, c mouth of the second three-way control valve 13, close a mouthfuls, open peristaltic pump, adjust
To 60rpm.When hydraulically full in circuit, a, c mouth of the first three-way control valve 12 and the second three-way control valve 13 are opened, is closed
B mouthfuls, making solution to be crystallized, stable circulation flows in the loop.After running 10min, there is subtle NaNO in membrane module 33Nucleus produces
It is raw.It opens the b mouth of the second three-way control valve 13, closes a mouthfuls, the mother liquor with nucleus is delivered in crystallization kettle 1, closes the immediately
One peristaltic pump 8 closes the b mouth of the second three-way control valve 13.Rerun 3h, and with the reduction of temperature, nucleus is raw in crystallization kettle 1
The suitable crystal of a length of granularity.Agitating device 2, temperature control device and computer 11 are closed, the mixing liquid in crystallization kettle 1 is filtered and is dried
It is dry to obtain NaNO3Crystal product.
Claims (3)
1. a kind of cooling crystallization method of film auxiliary nucleation, which is characterized in that the film auxiliary that the cooling crystallization method uses
The equipment of crystallisation by cooling of nucleation is made of two circuits；
One circuit: agitating device (2) is mounted on the crystallization kettle (1) with collet Nei, and the outlet of crystallization kettle (1) successively passes through
The side lower port company of one valve (14), the first three-way control valve (12), the first peristaltic pump (8), thermometer and membrane module (3)
It connects, the side upper port of membrane module (3) is connect by thermometer (10) with crystallization kettle (1) entrance；Wherein, the folder of crystallization kettle (1)
Set is connect with the first temperature control device (6), and the first temperature control device (6) is connect with computer (11), is accurately controlled, is made convenient for temperature
It realizes in crystallization kettle (1) and at the uniform velocity cools down；
Another circuit: the second valve (15), the second peristaltic pump (9) are successively passed through in coolant bottle (5) outlet, with membrane module (3)
Lower port connection, membrane module (3) upper port are connect with coolant bottle (5) entrance；Wherein, coolant bottle (5) has collet, collet
It is connect with the second temperature control device (7)；
Steps are as follows:
(1) solution to be crystallized of saturation is prepared, and is injected into crystallization kettle (1), agitating device (2), the first temperature control are opened
Device (6) and computer (11) maintain 30min-80min, are uniformly mixed solution to be crystallized, by computer (11) to the first temperature control
Device (6) carries out accurate real-time control；The second valve (15), the second peristaltic pump (9) and the second temperature control device (7) are opened simultaneously,
Flow and temperature are adjusted, making coolant liquid, stable circulation flows in the loop；
(2) the first valve (14) are opened, opens a, b mouth of the first three-way control valve (12), close c mouthfuls, open the second threeway tune
B, c mouth of valve (13) are saved, a mouthfuls is closed, solution to be crystallized is delivered in membrane module (3)；
(3) when being full of entire pipeline wait crystallize, the first three-way control valve (12) and the second three-way control valve (13) are opened
A, c mouth, close b mouthful, make solution to be crystallized in the loop stable circulation flowing；
(4) when having nucleus generation in membrane module (3), the b mouth of the second three-way control valve (13) is opened, closes a mouthfuls, it will be with crystalline substance
The mother liquor of core is delivered to crystallization kettle (1), carries out crystal growth；When crystal growth to required size, to molten in crystallization kettle (1)
Liquid, which is filtered, is dried to obtain crystal product.
2. cooling crystallization method according to claim 1, which is characterized in that film (4) used in the membrane module (3)
For hollow-fibre membrane or plate membrane.
3. cooling crystallization method according to claim 2, which is characterized in that the hollow-fibre membrane or plate membrane is to have
Machine film, inoranic membrane or composite membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710435278.5A CN107233744B (en) | 2017-06-12 | 2017-06-12 | A kind of cooling crystallization method of film auxiliary nucleation |
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| CN201710435278.5A CN107233744B (en) | 2017-06-12 | 2017-06-12 | A kind of cooling crystallization method of film auxiliary nucleation |
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| CN107233744B true CN107233744B (en) | 2019-04-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107890686A (en) * | 2017-12-06 | 2018-04-10 | 大连理工大学 | A kind of high performance membrane dilution crystallization method of double unit coupling cycles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10675557B2 (en) | 2017-11-03 | 2020-06-09 | Dalian University Of Technology | Continuous crystallization method under control of multistage membrane |
| CN109794078A (en) * | 2019-03-21 | 2019-05-24 | 大连理工大学 | A kind of method and system of the automatic nucleus screening of membrane interface regulation |
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| JP3798829B2 (en) * | 1995-04-12 | 2006-07-19 | 日揮株式会社 | Crystallizer and crystallization method |
| AU2003222136A1 (en) * | 2002-04-02 | 2003-10-20 | E.I. Du Pont De Nemours And Company | Apparatus and process used in growing crystals |
| DE102013200998A1 (en) * | 2013-01-22 | 2014-07-24 | Aaa Water Technologies Ag | Crystallization system and method |
| WO2017061360A1 (en) * | 2015-10-05 | 2017-04-13 | 並木精密宝石株式会社 | Die and die pack for growing sapphire single crystals, apparatus for growing sapphire single crystals, and method for growing sapphire single crystals |
| CN106166400B (en) * | 2016-08-05 | 2018-05-08 | 大连理工大学 | A kind of dilution crystallization device and method of film auxiliary control |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107890686A (en) * | 2017-12-06 | 2018-04-10 | 大连理工大学 | A kind of high performance membrane dilution crystallization method of double unit coupling cycles |
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