CN106975239B - Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method - Google Patents
Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method Download PDFInfo
- Publication number
- CN106975239B CN106975239B CN201710364099.7A CN201710364099A CN106975239B CN 106975239 B CN106975239 B CN 106975239B CN 201710364099 A CN201710364099 A CN 201710364099A CN 106975239 B CN106975239 B CN 106975239B
- Authority
- CN
- China
- Prior art keywords
- crystal
- crystals
- mother liquor
- crystallization
- granularity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0081—Use of vibrations, e.g. ultrasound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0063—Control or regulation
Abstract
The invention discloses a crystallizer for controlling crystal granularity by ultrasonic waves and a crystallization method, and the crystallizer comprises a crystallization mother liquor container (4), wherein an external circulation pipe (5) is arranged outside the crystallization mother liquor container (4), a crystal pulp pump (3) and a sedimentation tank (6) are arranged on the external circulation pipe (5), an ultrasonic generator (1) is arranged at the bottom of the sedimentation tank (6), the sedimentation tank (6) is provided with a bypass return pipe (7) communicated with the sedimentation tank in a fluid manner, and the outlet end of the return pipe (7) is communicated with the external circulation pipe (5) in a fluid manner; and the return pipe (7) is provided with a fine grain eliminator (2). The invention effectively improves the quality of crystal products, can synchronously solve the problem of large granularity of the crystal products in the crystallization process by grinding the crystals with large granularity by ultrasonic waves, achieves the control of the granularity and the granularity distribution of the crystal products and improves the quality of the products.
Description
Technical Field
The invention belongs to the technical field of chemical application, and particularly relates to a crystallizer for controlling crystal granularity by ultrasonic waves and a crystallization method.
Background
The modern industrial crystallization technology and equipment are common core technologies for preparing high-end biomedical products, are finish machining core technologies with green and intelligent characteristics, are core technologies for realizing the improvement of the biomedical products from low-end crude products to high-end functional fine products, and are key common core technologies with active and global influences on the overall improvement of the competitiveness of the biomedical industry. Strengthening the development in this area has become a strategic high point of preemption.
The crystal size and size distribution are one of the most important indexes of crystal products, and mainly affect the solid-liquid separation during the crystallization production process, the drying process of the product, the purity of the product, the fluidity and appearance of the product, the efficacy of the product (the dissolution rate and activity of the drug), the specific requirements of the specific product (uniform, small and dispersed particle size), the yield of the product, and the like. Therefore, the control of the particle size and the particle size distribution of the crystal product in the crystallization process is one of the primary tasks of the control of the crystallization process.
The crystals with larger particle sizes have smaller relative surface area and lower surface free energy, are relatively stable in a crystallization system and are difficult to eliminate. The current method for dealing with the method comprises the following steps: firstly, the rotating speed of the stirring paddle is increased so as to smash particles with larger granularity. However, after the rotating speed of the stirring paddle is increased, all crystals in the crystallizer can be impacted, the collision efficiency among the crystals and between the crystals and the stirring paddle is difficult to control, and the particle size distribution of the crystals is increased. 2. The crystallized product is sieved, and the crystal product with large granularity is mechanically ground. The method not only increases the operation procedures and is easier to introduce impurities, but also is easy to generate a large amount of broken crystals, damages the surface and the crystal form of the crystals and reduces the product quality by mechanical grinding. The invention can directionally grind the crystal with the granularity exceeding the set value in the crystallization process, and convey the ground crystal back to the crystallization system for continuous curing, thereby realizing the control of the granularity distribution of the crystal product and leading the granularity distribution to be more concentrated.
Disclosure of Invention
The invention aims to provide a crystallizer and a crystallization method for controlling crystal granularity by ultrasonic waves, which eliminate fine crystals generated in a grinding process so as to achieve the purposes of controlling the maximum granularity of a crystal product and optimizing the granularity distribution.
The purpose of the invention is realized by the following technical scheme:
a first aspect of the present invention relates to a crystallizer for controlling the grain size of crystals by ultrasound, comprising the following components:
a crystallization mother liquor container 4, wherein an external circulation pipe 5 is arranged outside the crystallization mother liquor container 4, a crystal paddle pump 3 and a sedimentation tank 6 are arranged on the external circulation pipe 5, an ultrasonic generator 1 is arranged at the bottom of the sedimentation tank 6, the sedimentation tank 6 is provided with a bypass return pipe 7 which is in fluid communication with the sedimentation tank 6, and the outlet end of the return pipe 7 is in fluid communication with the external circulation pipe 5; the bottom end of the return pipe 7 is provided with a fine grain eliminator 2.
In a preferred embodiment of the present invention, the paddle pump 3 may also be an axial flow pump.
In the preferred embodiment of the invention, the crystal size to be ultrasonically ground is adjusted by adjusting the rotating speed of the crystal paddle pump 3; the flow rate is increased, the particle size upper limit of the ultrasonic grinding zone grinding crystal can be reduced, the flow rate is reduced, and the particle size upper limit of the ultrasonic grinding zone grinding crystal can be improved.
In a preferred embodiment of the invention, the inlet end of the return pipe 7 is provided with a filter.
In a preferred embodiment of the present invention, the number of the ultrasonic generators 1 is 1 to 10 columns, and the number of the ultrasonic generators in each column is 2 to 10.
In a preferred embodiment of the invention, the ultrasound generator 1 is operated in an intermittent mode.
In a preferred embodiment of the present invention, the ultrasonic generator 1 is provided with a frequency converter.
The working process of the invention is as follows: in the middle period stage of the crystallization process, after a large amount of crystals in the system are precipitated, continuously pumping crystal slurry from the bottom of the crystallization mother liquor container 4 through the crystal slurry pump 3 (or selecting an axial flow pump with a frequency converter) and pumping the crystal slurry into the external circulation pipe 5, then enabling the crystals with the particle size smaller than the set particle size value to be in suspension circulation in the solution by adjusting the rotating speed of the crystal slurry pump 3, flowing out of a return pipe at the top of the external circulation pipe 5, and returning to the crystallization mother liquor container 4 for continuous growth. And the crystals with the particle size exceeding the set value are deposited at the bottom of the external circulation pipe 5 and cannot return to the crystallization mother liquor container 4 from the top of the return pipe 7 for continuous crystallization. The ultrasonic generator 1 installed on the settling tank 6 is intermittently operated, the ultrasonic generator 1 is started when a certain amount of large-grained crystals are deposited at the bottom of the external circulation pipe, and the agglomerated crystals and the crystals with the granularity exceeding a set range are ground by the ultrasonic generator 1. The ultrasonic generator 1 is provided with a frequency converter to control power, and reduces energy input when grinding a fragile crystal so as to control the crushing degree of the crystal. Most of crystals with small particle size pass through the bottom of the external circulation pipe 5 when the ultrasonic generator 1 does not work, and a small part of crystals pass through the bottom of the external circulation pipe 5 quickly when the ultrasonic generator 1 works, so that the crystals are subjected to a small grinding effect by ultrasonic. The grinded crystal returns to the crystallization mother liquor container 4 along with the crystal slurry to continue growing, and irregular crystal faces generated in the grinding process are repaired or partially repaired through the curing process of the crystal. The fine grain eliminator 2 is arranged below the return pipe 7, fine crystals in the external circulation pipe 5 are led out through a filter and enter a fine grain elimination circulation system, fine grains are dissolved by a heating method, and then the fine grains are returned to the external circulation pipe through another filter in the crystallization mother liquor container 4 through a circulation pump, so that the fine grains generated in the ultrasonic grinding process are eliminated. The remaining small portion of fine crystals can be crystallized or dissolved back into the crystallization mother liquor vessel 4.
The lower limit of the crystal grain size of the ultrasonic grinding can be adjusted by setting the rotating speed of the crystal pulp pump 3, increasing the flow rate, increasing the lower limit of the grain size of the grinding crystal of the ultrasonic grinding area, reducing the flow rate and reducing the lower limit of the grain size of the grinding crystal of the ultrasonic grinding area.
The bottom of the external circulation pipe 5 is tightly attached to 1-10 columns of the ultrasonic generators 1 according to the design, 2-10 ultrasonic generators 1 are arranged on each column of the ultrasonic generators 1 according to the circumference of the external circulation pipe 5 and are used for grinding crystals deposited at the bottom of the external circulation pipe 5 due to the fact that the particle size exceeds the set particle size.
The key points of the invention are as follows: by designing the external circulation pipe 5 containing the ultrasonic generator 1, the crystals are automatically layered in the external circulation pipe 5 under the dual effects of gravity and fluid flow rate control, and the particle size of the crystals with the particle size exceeding the set upper limit is accurately reduced in a crystallization system by utilizing the grinding effect of ultrasonic waves. To avoid subsequent processing such as screening and grinding. The lower limit accessible of ultrasonic grinding's crystal size sets for at the rotational speed of brilliant stuff pump 3, increases the velocity of flow, can reduce the particle size upper limit of ultrasonic grinding district's grinding crystal, reduces the velocity of flow, can promote the particle size upper limit of ultrasonic grinding district's grinding crystal.
The invention has the beneficial effects that:
1. the quality of the crystal product is effectively improved, the problem of large granularity of the crystal product can be synchronously solved in the crystallization process by grinding the crystal with large granularity by ultrasonic waves, the granularity and the granularity distribution of the crystal product are controlled, and the product quality is improved.
2. The main body of the granularity controller is external circulation equipment, crystal mush is led out of the crystallizer for treatment only by adding a pipeline, and the granularity controller can be directly installed on the crystallizer without damaging the internal structure of the crystallizer.
3. The grinding efficiency is high, the crystal particles with large granularity are directionally ground, the crystal with small granularity is little or not ground, the energy consumption is low, the grinding efficiency is high, and excessive broken crystals are not easy to generate.
4. Compared with the traditional method for controlling the crystal granularity, which is used for screening the crystallized product according to the grain diameter after mechanically grinding, the method can be carried out on line, and impurities are not easily introduced by using an ultrasonic grinding mode.
Drawings
FIG. 1 is a schematic view of the crystallizer of the present invention;
FIG. 2 is a photograph of the crystal obtained in example 1;
FIG. 3 is the particle size distribution of crystals obtained using example 1;
FIG. 4 is a photograph of the crystal obtained in comparative example 1;
fig. 5 is a particle size distribution of the crystals obtained in comparative example 1.
In the figure: 1-an ultrasonic generator, 2-a fine grain eliminator, 3-a crystal paddle pump, 4-a crystallization mother liquor container, 5-an external circulation pipe, 6-a settling tank and 7-a return pipe.
Detailed Description
The following examples are intended to illustrate the invention, but not to further limit the scope of the invention.
Example 1
The whole crystallizer structure is shown in figure 1, wherein the volume of a crystallization mother liquor container is 120 liters, and 8 60W ultrasonic generators are arranged at the bottom of a settling tank. And (3) cooling and crystallizing the roxithromycin crystals in a crystallization mother liquor container by taking a mixed solution of ethanol and water as a solvent. 25 kg of roxithromycin is dissolved in a mixed solution of 50 kg of ethanol and 50 kg of water, and an intermittent elution crystallization experiment is carried out at the temperature of 75 ℃ at the cooling rate of 0.4 ℃/min.
And naturally precipitating crystal nuclei at 55 ℃, preserving heat for 30 minutes, then recovering the speed of 0.4 ℃/min, cooling, and simultaneously starting an ultrasonic generator, wherein the circulation volume of crystal slurry is 3.5L/min. And after the temperature is reduced to 0 ℃, the ultrasonic generator is closed, but the external circulation and the fine grain eliminator are continuously kept in an open state, and the flow of the crystal mush is kept unchanged. Meanwhile, the crystallization system is continuously stirred for 40 minutes, filtered, mother liquor is drained, and the crystals are washed by water at normal temperature and then subjected to particle size analysis. The morphology of the obtained crystals is shown in fig. 2, and the particle size distribution is shown in fig. 3. As can be seen from fig. 3, since the crystals having a large particle size are ground and the coalescence among the crystals is suppressed, the particle size of the crystals is remarkably reduced and fine crystals are substantially eliminated, and the main particle size is about 125 μm.
Comparative example 1
And (3) cooling and crystallizing the roxithromycin crystals in a 120-liter crystallizer by using a mixed solution of ethanol and water as a solvent. 25 kg of roxithromycin is dissolved in a mixed solution of 50 kg of ethanol and 50 kg of water, and an intermittent elution crystallization experiment is carried out at the temperature of 75 ℃ at the cooling rate of 0.4 ℃/min.
The crystal nucleus is naturally precipitated at 55 ℃, the temperature is kept for 30 minutes, then the speed of 0.4 ℃/min is recovered for cooling, and the ultrasonic generator and the fine grain eliminator are not started any more. Cooling to 0 deg.c, stirring for 40 min, filtering, pumping out mother liquid, washing with water at normal temperature and size analysis. The morphology of the obtained crystals is shown in FIG. 4, and the particle size distribution is shown in FIG. 5. As can be seen from FIG. 5, the crystals are larger in size due to the larger particle size of the crystals in general and the partial occurrence of coalescence, and the primary particle size exceeds 600. Mu.m.
Claims (1)
1. A crystallization method for controlling a crystal grain size by ultrasonic waves, characterized in that it uses a crystallizer for controlling a crystal grain size by ultrasonic waves, the crystallizer comprising the following components:
the crystallization mother liquor container (4), an external circulation pipe (5) is arranged outside the crystallization mother liquor container (4), a crystallization slurry pump (3) and a settling tank (6) are arranged on the external circulation pipe (5), an ultrasonic generator (1) is arranged at the bottom of the settling tank (6), the settling tank (6) is provided with a bypass return pipe (7) in fluid communication with the settling tank, and the outlet end of the return pipe (7) is in fluid communication with the external circulation pipe (5); the return pipe (7) is provided with a fine grain eliminator (2); the inlet end of the return pipe (7) is provided with a filter
The crystal slurry pump (3) is an axial flow pump; the rotating speed of the crystal slurry pump (3) is adjustable; the number of the ultrasonic generators (1) is 1-10 columns, and the number of the ultrasonic generators in each column is 2-10; a frequency converter is arranged on the ultrasonic generator (1);
the crystallization method for controlling the crystal size by ultrasonic waves comprises the following steps:
(1) Adding the crystallization mother liquor into a crystallization mother liquor container (4), and stirring by using a stirrer;
(2) After crystals are separated out from the crystallization mother liquor, continuously pumping the crystal slurry from the bottom of the crystallization mother liquor container (4) through the crystal slurry pump (3) and pumping the crystal slurry into the external circulation pipe (5);
(3) Adjusting the rotation speed of the crystal slurry pump (3) to enable small crystals with the granularity smaller than the set granularity value to circulate in suspension in the solution, flowing out of a return pipe at the top of the external circulation pipe (5), returning to the crystallization mother liquor container (4) for continuous growth, and depositing large crystals with the granularity larger than the set granularity value at the bottom of the settling tank (6);
(4) When a certain amount of large crystals are deposited at the bottom of the settling tank (6), the ultrasonic generator (1) is started to grind the large crystals into small crystals;
(5) The grinded small crystals are circulated back to the crystallization mother liquor container (4) along with the crystal slurry to continue growing, and irregular crystal faces generated in the grinding process are repaired or partially repaired through the curing process of the crystals;
(6) A part of fine crystals with finer granularity in the small crystals enter the fine crystal eliminator (2) through a filter screen at the inlet of the return pipe (7), the part of fine crystals are dissolved by heating and then enter the external circulation pipe (5) through the outlet of the return pipe (7), and finally, the crystal mush with large crystals and a part of fine crystals eliminated enters the crystallization mother liquor container (4) for recrystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710364099.7A CN106975239B (en) | 2017-05-22 | 2017-05-22 | Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710364099.7A CN106975239B (en) | 2017-05-22 | 2017-05-22 | Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106975239A CN106975239A (en) | 2017-07-25 |
| CN106975239B true CN106975239B (en) | 2023-04-14 |
Family
ID=59342659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710364099.7A Active CN106975239B (en) | 2017-05-22 | 2017-05-22 | Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106975239B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682807B (en) * | 2018-04-27 | 2020-06-19 | 多氟多新能源科技有限公司 | Lithium ion battery positive electrode material precursor and preparation method thereof, positive electrode active material, lithium ion battery and continuous reactor |
| CN110204461B (en) * | 2019-05-15 | 2022-04-05 | 西安万德能源化学股份有限公司 | Nitroguanidine crystal and microchannel crystallization process and device of nitroguanidine |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074626A (en) * | 1993-02-17 | 1993-07-28 | 中国石油化工总公司 | Eliminate the method for the parts of fine crystalline substance in the magma in the crystallizer, manufacturing coarsegrain crystal |
| CN101279213A (en) * | 2008-01-17 | 2008-10-08 | 京东方科技集团股份有限公司 | Device for circularly grinding and dispersing and method thereof |
| CN103271423A (en) * | 2013-06-05 | 2013-09-04 | 福娃集团有限公司 | Ultrasonic wave rice immersion device and immersion method |
| CN103769277A (en) * | 2014-02-14 | 2014-05-07 | 武汉科技大学 | High-efficiency circulating wet grinding device |
| CN104986796A (en) * | 2015-06-09 | 2015-10-21 | 张家港合志纳米科技有限公司 | Device system and preparation technology for preparing submicron material through continuous hydrothermal method |
| CN206965176U (en) * | 2017-05-22 | 2018-02-06 | 天津晶润锐拓科技发展有限公司 | A kind of crystallizer that crystal size is controlled by ultrasonic wave |
| CN112485165A (en) * | 2020-11-18 | 2021-03-12 | 青岛科技大学 | Online measurement device for size and shape of crystal in high solid content crystallization process |
-
2017
- 2017-05-22 CN CN201710364099.7A patent/CN106975239B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074626A (en) * | 1993-02-17 | 1993-07-28 | 中国石油化工总公司 | Eliminate the method for the parts of fine crystalline substance in the magma in the crystallizer, manufacturing coarsegrain crystal |
| CN101279213A (en) * | 2008-01-17 | 2008-10-08 | 京东方科技集团股份有限公司 | Device for circularly grinding and dispersing and method thereof |
| CN103271423A (en) * | 2013-06-05 | 2013-09-04 | 福娃集团有限公司 | Ultrasonic wave rice immersion device and immersion method |
| CN103769277A (en) * | 2014-02-14 | 2014-05-07 | 武汉科技大学 | High-efficiency circulating wet grinding device |
| CN104986796A (en) * | 2015-06-09 | 2015-10-21 | 张家港合志纳米科技有限公司 | Device system and preparation technology for preparing submicron material through continuous hydrothermal method |
| CN206965176U (en) * | 2017-05-22 | 2018-02-06 | 天津晶润锐拓科技发展有限公司 | A kind of crystallizer that crystal size is controlled by ultrasonic wave |
| CN112485165A (en) * | 2020-11-18 | 2021-03-12 | 青岛科技大学 | Online measurement device for size and shape of crystal in high solid content crystallization process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106975239A (en) | 2017-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106457061B (en) | Discontinuous crystallization unit for preparing spherical crystals | |
| CN106975239B (en) | Crystallizer for controlling crystal granularity through ultrasonic waves and crystallization method | |
| CA3053055C (en) | Method and system for producing potassium chloride by recycling byproducts | |
| Mao et al. | Enhancement of lysozyme crystallization under ultrasound field | |
| CN103212452B (en) | Method for reducing washing loss of precipitate of precipitated metal catalyst precursor and method for preparing precipitated metal catalyst therefrom | |
| CN106395916A (en) | Preparation method for ultrapure ultrafine cobalt carbonate | |
| JP2003534129A (en) | Equipment for crystal production | |
| CN106906252B (en) | Fermentation process | |
| CN102371080B (en) | Crystallizing method utilizing external circulation of crystal slurry | |
| CN104743581B (en) | Preparation technique of high-purity potassium chloride | |
| CN113230688A (en) | Large-particle nickel sulfate continuous crystallization system and method | |
| CN206965176U (en) | A kind of crystallizer that crystal size is controlled by ultrasonic wave | |
| JPH0336767B2 (en) | ||
| CN105418471A (en) | Synthetic method of carbocisteine | |
| CN110656206B (en) | Sucrose refining method capable of controlling granularity | |
| CN109052441B (en) | Method and system for removing organic matters in aluminum oxide production process | |
| CN106801144A (en) | A kind of method that heavy metal is reclaimed from sludge containing heavy metal | |
| CN105967218B (en) | A kind of preparation method of the low chlorine root cerous carbonate of hydrochloric acid system | |
| US3647396A (en) | Production of high-purity salt | |
| CN102371081B (en) | Crystallization method with a fine crystal elimination | |
| CN105111064A (en) | Method and device for recovery of terephthalic acid from polyester alkali decrement wastewater | |
| CN210230840U (en) | Artificial diamond fluidization separation equipment | |
| US5503641A (en) | Process and apparatus for preparing a potassium chloride mixture | |
| CN108863014B (en) | Method for assisting in filtering acid-soluble leached slurry of nickel-containing electroplating sludge | |
| CN105755069A (en) | Method using corn cobs to prepare xylo-oligosaccharide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Guo Zhichao Inventor after: Mao Guozhu Inventor after: Han Wenxiang Inventor after: Guo Chi Inventor after: Yang Song Inventor after: Wang Baodong Inventor after: Wang Xinchi Inventor before: Guo Zhichao Inventor before: Mao Guozhu Inventor before: Han Wenxiang Inventor before: Guo Chi Inventor before: Yang Song Inventor before: Wang Baodong Inventor before: Wang Xinchi |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |