CN101893564B - Monitoring device for monitoring crystallization process and crystallization device having same - Google Patents
Monitoring device for monitoring crystallization process and crystallization device having same Download PDFInfo
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- CN101893564B CN101893564B CN 200910205485 CN200910205485A CN101893564B CN 101893564 B CN101893564 B CN 101893564B CN 200910205485 CN200910205485 CN 200910205485 CN 200910205485 A CN200910205485 A CN 200910205485A CN 101893564 B CN101893564 B CN 101893564B
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Abstract
The invention discloses a monitoring device for monitoring the crystallization process of a crystallization system. The monitoring device can be arranged on the outer side of a cylindrical container which can accommodate the crystallization system and comprises a laser transmitter, at least two laser receivers and a computing unit, wherein the at least two laser receivers are arranged in a way of forming angles of certain degrees with the laser transmitter and can monitor different crystallization stages of the crystallization system respectively; the computing unit can compute the laser intensities of the receivers respectively; and the laser transmitter and the laser receivers are arranged on the same radial cross section outside the cylindrical container. The crystallization device of the invention can dynamically monitor the turbidity change of the system at a starting crystallization stage, a middle crystallization stage and a latter half crystallization stage.
Description
Technical field
The present invention relates to a kind of monitoring device for monitoring crystallizing system crystallization process, also relate to a kind of crystallizer with this monitoring device.
Background technology
Crystallization process is the phase transition process of the heat and mass of a complexity, the feed liquid system becomes muddiness by clarification when nucleation process begins, along with the increase of crystal grain number in the feed liquid system and the increase of crystal particle diameter, the muddy degree of system is also increasing, after crystallization reaction reached equilibrium state, the turbidity of system no longer changed.Therefore, the situation of change of system turbidity can reflect the crystalline condition of system to a great extent, and its research for crystallization processes is significant.
But, traditional crystallizer all needs to take a sample from crystallizing system first when detecting the crystallizing system turbidity, and then detect the crystallizing system turbidity with specialized equipment, the problem that this crystallizer exists is that the data that record have certain hysteresis quality, can't accurately judge the crystalline condition of particular point in time, and because this detection mode needs off-line operation, so it is also very inconvenient to operate.
In order to overcome the defects of crystallizer; a kind of improved crystallization apparatus is provided in the prior art; thereby it changes the drop out point of determining crystal by the turbidity that the laser-transmitting method detects crystallizing system online; such as document " research of 6-APA reactive crystallization macroscopic property " (Gong Junbo etc.; " chemical industry and engineering "; 2004; 21; 34-36) with " thermodynamics of crystallization of procaine penicillin " (Lu Jie and Wang Jingkang; " colleges and universities' chemical engineering journal ", 1999,13; reported the method identification crystallization starting point that adopts laser-transmitting 189-192), to measure the maximum degree of supersaturation of crystallizing system.Although these methods have reached the purpose of online detection, but because their detection sensitivity is very low, the turbidity scope that can detect is also very little, so they are only applicable to the detection of crystallization turbidity in mid-term, detects and can't change the turbidity of crystallization overall process.
Summary of the invention
The purpose of this invention is to provide a kind of monitoring device that can monitor the crystallization overall process of crystallizing system.
For achieving the above object, the invention provides a kind of monitoring device, this device can be installed in the outside of the hydrostatic column that can hold crystallizing system, it comprise a generating laser, from least two laser pickoffs can monitoring respectively the different crystallization stages of crystallizing system of the angled setting of this generating laser and the computing unit that can calculate respectively the receiver laser intensity, described generating laser and laser pickoff are arranged on the outer same radial cross-section of hydrostatic column.
Preferably, laser pickoff of the present invention comprises the first laser pickoff and the second laser pickoff, take the center of circle of described hydrostatic column radial cross-section as basic point, the angle that described the first laser pickoff becomes with generating laser is α, 45 degree≤α≤90 degree, further preferred α equals 90 degree, and the angle that described the second laser pickoff becomes with generating laser is β, and β equals 180 degree.
Preferably, laser pickoff of the present invention also comprises the 3rd laser pickoff, and take the center of circle of described hydrostatic column radial cross-section as basic point, its angle that becomes with generating laser is γ, and 0 degree＜γ≤30 degree, further preferred γ are 15 degree.
Preferably, described the second laser pickoff is the transmission receiver, and the first laser pickoff and the 3rd laser pickoff are the scattering receivers.
Another object of the present invention provides a kind of crystallizer.This crystallizer comprises that one can hold the hydrostatic column of crystallizing system, also comprises a monitoring device provided by the invention.
Described computing unit links to each other with laser pickoff, and can the laser intensity that each laser pickoff receives be calculated respectively, thereby the change curve of the laser intensity that each receiver receives is shown.For example, in one embodiment of the invention, computing unit can illustrate voltage signal that laser pickoff receives with respect to the curve map of ω, and wherein ω refers to that organic solvent is with respect to the volume ratio of water in the crystallizing system.
The part that described hydrostatic column passes through at laser optical path at least is to be made of the permeable material of light.For example, the hydrostatic column overwhelming majority all is to be made by the steel that are suitable for chemical reaction, is made by glass at the position that light path is passed through.
Preferably, described crystallizer further comprises the stirring apparatus that can stir crystallizing system, can heat or the temperature control equipment of crystallisation by cooling system, can regulate the pH control device of potential of hydrogen and can control the volume control device that adds flow quantity.Described stirring apparatus can be chemical field magnetic stirring apparatus commonly used, also can be mechanical stirring device, and other any chemical field stirring apparatus commonly used, and described stirring apparatus is arranged on any appropriate location that does not affect laser detection.Described temperature control equipment can be this area chuck that can lead to refrigerant or heating agent commonly used, also can be other chemical field any device that can regulate the crystallizing system temperature commonly used.Described volume control device can be adjusted in real time to the dissolved agent in the crystallizing system and reaction reagent flow.
Monitoring device of the present invention is by arranging a plurality of laser pickoffs, can monitor for the different turbidity scopes of crystallizing system respectively, wherein, the scattering receiver that is arranged on 45～90 degree is relatively sensitiveer when the system turbidity is lower, can be used for Real Time Monitoring is carried out in the turbidity variation of Initial stage of crystallization; The transmission receiver sensitivity when the system turbidity is higher that is arranged on 180 degree is higher, can be used for the turbidity variation of process in the middle of the crystallization is monitored; Be arranged on greater than 0 the degree less than or equal to 30 the degree the sensitivity of scattering receiver when the system turbidity is very high higher, can monitor the system turbidity of crystallization the second half.In use, can open simultaneously 2 or 3 receivers, computing unit changes the turbidity of each receiver does independent calculating, and the change curve of the laser intensity that each receiver detects is shown.The experimenter can determine best crystallization condition according to the curvilinear motion situation.
Description of drawings
Fig. 1: the structural representation of crystallization apparatus of the present invention;
Fig. 2: the longitudinal sectional drawing of Fig. 1 crystallization apparatus;
Fig. 3: Fig. 1 crystallization apparatus is in the longitudinal section view on generating laser, the first laser pickoff and plane, the second laser pickoff place;
Fig. 4: the vertical view of Fig. 1 crystallization apparatus end socket;
Fig. 5: the U that the first receiver (90 degree) detects and the graph of a relation between the ω;
Fig. 6: the U that the second receiver (180 degree) detects and the graph of a relation between the ω;
Fig. 7: the U that the 3rd receiver (15 degree) detects and the graph of a relation between the ω;
Fig. 8: the U that the first receiver (45 degree) detects and the graph of a relation between the ω;
Fig. 9: the U that the first receiver (60 degree) detects and the graph of a relation between the ω;
Figure 10: the U that the 3rd receiver (30 degree) detects and the graph of a relation between the ω;
Figure 11: the U that the 3rd receiver (7 degree) detects and the graph of a relation between the ω;
Figure 12: the U that Comparative Examples receiver (40 degree) detects and the graph of a relation between the ω.
Caption: ω refers to the volume ratio of acetone and water in the solution, and U is voltage.
Embodiment
In order to make those skilled in the art understand better technical scheme of the present invention, the present invention is described in further detail below in conjunction with the drawings and specific embodiments.
As illustrated in fig. 1 and 2, crystallization apparatus comprises base 1, hydrostatic column 2, generating laser 3, the first laser pickoff 4, the second laser pickoff 5 and computing unit (not shown).
Wherein, container 2 can all be made by glass, and the part of perhaps passing through at laser optical path is at least made by glass.In 1/5th height inserted bases 1 of crystallisation vessel 2 bottoms, be provided with generating laser 3, the first laser pickoff 4 and the second laser pickoff 5 at base 1 same plane.The central angle alpha that becomes between described the first laser pickoff 4 and the generating laser 3 is 90 degree, and α can also get arbitrarily angled between 45～90 degree; The central angle β that becomes between described the second laser pickoff 5 and the generating laser 3 equals 180 degree.
Wherein, described generating laser 3 can be solid state laser or gas laser etc., and the laser that its produces is vertical with chamber wall and pass through crystallizing system.Described laser pickoff can be photoresistance, photodiode or phototriode etc., external low tension loop and with voltage check device.
Described laser pickoff is connected to a computing unit, and the laser intensity that described computing unit can receive a plurality of laser pickoffs respectively calculates, and then the change curve of the laser intensity that each laser pickoff receives is shown.The change curve of the laser intensity that the experimenter can receive according to each laser pickoff is judged best crystallization condition.
According to actual needs, crystallization apparatus of the present invention can also arrange the 3rd laser pickoff 6 on the plane with generating laser 3, the first laser pickoff 4 and the second laser pickoff 5 places, central angle unity gamma 5 degree of described the 3rd laser pickoff 6 and 3 one-tenth of generating lasers, described γ can also be got greater than 0 arbitrarily angled to less than or equal between 30 degree.
Crystallization apparatus of the present invention is by arranging a plurality of laser pickoffs, can monitor for the different turbidity of crystallizing system, wherein, the scattering receiver that is arranged on 45～90 degree is relatively sensitiveer when the system turbidity is lower, can be used for Real Time Monitoring is carried out in the turbidity variation of Initial stage of crystallization; The transmission receiver sensitivity when the system turbidity is higher that is arranged on 180 degree is higher, can be used for the turbidity variation of process in the middle of the crystallization is monitored; Be arranged on greater than 0 the degree less than or equal to 30 the degree the sensitivity of scattering receiver when the system turbidity is very high higher, can monitor the system turbidity of crystallization the second half.In use, can open simultaneously three receivers.The experimenter can judge according to the change in electric that each receiver of comparison detects the development situation of crystallization.
For more effective and monitor expediently and regulate crystallizing system, crystallization apparatus of the present invention also comprises end socket 7, be fixed together by connecting rod 8 between end socket 7 and container 2 and the base 1, described end socket 7 is provided with conductivity meter socket 9, pH meter socket 10, thermometer socket 11 and sample tap 12.Also further be provided with acid-adding port 13 on the described end socket 7, add alkali mouth 14, filling opening 15, be fixed with the tubule (not shown) on the described opening, emulsion tube can be connected in the purpose that realizes acid adding, adds alkali and add reaction dissolvent by constant flow pump again on the tubule.By electric machine support 16 direct current generator 17 is installed on the end socket 7, electric machine support 16 is threaded connection on end socket 7, the lower end of direct current generator 17 is connected with paddle main shaft 18, the upper end of paddle main shaft 18 is connected by shaft joint 19 with motor 17, its lower end links to each other with stirring vane 20, stirring vane 20 has various shape, such as anchor formula, Ping Yeshi and push type etc.Be provided with the chuck 21 that can lead to refrigerant or heating agent on the container 2, thereby can regulate the temperature of crystallizing system.
Take by weighing the 2g cephalosporin C Sodium, add the 100ml deionized water, filter the aqueous solution of the cephalosporin C Sodium that obtains clarifying after the dissolving.Solution is poured in the crystallization reactor of the present invention, and temperature constant is 25 degree, and speed of agitator is 150RPM, adds acetone with constant flow pump with the flow of 3ml/min in reactor.Record respectively the output voltage of 90 degree, 180 degree and 15 these three laser pickoffs of degree, the volume ratio with ω represents acetone and water in the crystallizing system obtains output voltage U to the curve of ω, respectively shown in Fig. 5,6 and 7.As shown in Figure 5, at ω=1.55 places, vertical line left side, crystallization does not begin, and main manifestations is but that the crystallizing system volume increases the process that does not also have solid particle to separate out, so curve decline and more and more milder.On the vertical line right side, the crystallization nucleation process begins, nucleus is constantly separated out, the turbidity of system increases, so the output voltage increase, and curve begins to rise, and the output voltage of second, third laser pickoff of this moment does not change, illustrate that the first laser pickoff is more sensitive than second, third receiver under low turbidity condition, point of inflexion on a curve can be determined the drop out point of crystal more accurately, and drop out point with this understanding is ω=1.55.
Carrying out along with crystallization, cephalosporin C Sodium crystal number in the system is more and more, crystal particle diameter is increasing, turbidity in the system is also more and more higher, because crystal grain is stronger to effects such as the multiple scattering of laser, diffraction in this moment crystallizing system, therefore the variation of the first laser pickoff output voltage is significantly not regular.The change curve of the second laser pickoff then as shown in Figure 6, rule comparatively expressively, this is based on the transmission principle design because of the second laser pickoff, this moment, crystal grain was less to multiple scattering, the diffraction interference of laser, and the second receiver can calculate according to the Lambert-Beer law turbidity of solution system.
Along with constantly separating out of crystal, the variation of the second laser pickoff output voltage tends towards stability, shown in the second vertical line (ω=2.30) right side of Fig. 6, and this moment the 3rd laser pickoff output voltage still on the rise, illustrate that crystallization still carrying out.This shows, under higher turbidity, the second laser pickoff can not reflect that the 3rd laser pickoff is the variation of reactive crystallization process preferably when the system turbidity changed.As shown in Figure 7, locate in the position (ω=2.50) of the second vertical line, curve levels off to flat line, and this moment, crystallization reaction reached balance, and crystal is no longer separated out or grown up, and therefore, can determine that the terminal point of crystallization reaction is ω=2.50 by the 3rd laser pickoff.
Operate according to the method identical with embodiment 2, difference only is that the central angle alpha that the first laser pickoff becomes with generating laser equals 45 degree.Obtain the change curve of the first laser pickoff as shown in Figure 8, the ω the when crystal among the figure shown in the vertical line is separated out=1.70.
Operate according to the method identical with embodiment 2, difference only is that the central angle alpha that the first laser pickoff becomes with generating laser equals 60 degree.Obtain the change curve of the first laser pickoff as shown in Figure 9, the ω the when crystal among the figure shown in the vertical line is separated out=1.62.
Operate according to the method identical with embodiment 2, difference only is that the central angle γ that the 3rd laser pickoff becomes with generating laser equals 30 degree.Obtain the change curve of the 3rd laser pickoff as shown in figure 10, the ω the when crystallization reaction among the figure shown in the vertical line reaches balance=2.40.
Operate according to the method identical with embodiment 2, difference only is that the central angle γ that the 3rd laser pickoff becomes with generating laser equals 7 degree.Obtain the change curve of the 3rd laser pickoff as shown in figure 11, the ω the when crystal among the figure shown in the vertical line is separated out=2.45.
Comparative Examples
Operate according to the method identical with embodiment 2, difference is to become 40 degree central angle places that one laser pickoff is set with generating laser.The change curve of this laser pickoff as shown in figure 12.The change curve of Figure 12 does not present certain regularity, the state variation that it can not the reactive crystallization system.
Claims (8)
1. monitoring device that is used for monitoring crystallizing system crystallization process, described monitoring device can be installed in the outside of the hydrostatic column that can hold crystallizing system, it is characterized in that, this monitoring device comprise a generating laser, from least two laser pickoffs can monitoring respectively the different crystallization stages of crystallizing system of the angled setting of this generating laser and the computing unit that can calculate respectively the receiver laser intensity, described generating laser and laser pickoff are arranged on the outer same radial cross-section of hydrostatic column;
Described laser pickoff comprises the first laser pickoff and the second laser pickoff, the angle that described the first laser pickoff becomes with generating laser is α, 45 degree≤α≤90 degree, the angle that described the second laser pickoff becomes with generating laser is β, β equals 180 degree;
Described the first receiver is the scattering receiver, and described the second laser pickoff is the transmission receiver.
2. monitoring device as claimed in claim 1 is characterized in that α is 90 degree.
3. monitoring device as claimed in claim 1 or 2 characterized by further comprising the 3rd laser pickoff, and its angle that becomes with generating laser is γ, 0 degree＜γ≤30 degree, and described the 3rd laser pickoff is the scattering receiver.
4. monitoring device as claimed in claim 3 is characterized in that γ is 15 degree.
5. a crystallizer comprises the hydrostatic column that can hold crystallizing system, it is characterized in that, also comprises each described monitoring device such as claim 1-4.
6. crystallizer as claimed in claim 5 is characterized in that, described computing unit can illustrate signal that laser pickoff receives along with the curve map of crystallization reaction change in process.
7. crystallizer as claimed in claim 5 is characterized in that, the part that described hydrostatic column passes through at laser optical path at least is to be made of the permeable material of light.
8. such as the arbitrary described crystallizer of claim 5-7, it is characterized in that, described crystallizer also comprises mixing control device, temperature control equipment, pH regulating device, and can control the volume control device that adds flow quantity.
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| CN 200910205485 CN101893564B (en) | 2009-10-19 | 2009-10-19 | Monitoring device for monitoring crystallization process and crystallization device having same |
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| CN101893564B true CN101893564B (en) | 2013-02-06 |
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| CN105498657B (en) * | 2015-12-31 | 2017-12-22 | 连云港拜尔特化工有限公司 | A kind of reactor concentration monitoring device |
| CN110914672A (en) | 2017-04-20 | 2020-03-24 | 生物梅里埃公司 | Optical test platform |
| CN111289557A (en) * | 2020-02-27 | 2020-06-16 | 鞍钢矿业爆破有限公司 | Arduino-based method and system for measuring crystallization point of ammonium nitrate solution |
| CN113125493B (en) * | 2021-04-15 | 2023-09-12 | 濮阳市盛源能源科技股份有限公司 | Instrument for analyzing maleic anhydride crystallization point |
Citations (5)
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| CN1501065A (en) * | 2002-11-19 | 2004-06-02 | 友达光电股份有限公司 | Polysilicon film crystallization quality detecting apparatus, detecting and controlling method therefor |
| JP2006275901A (en) * | 2005-03-30 | 2006-10-12 | Seiko Epson Corp | Device and method for crystal evaluation |
| WO2007121363A3 (en) * | 2006-04-13 | 2008-05-08 | Univ Mississippi | An optical apparatus for simultaneously measuring the scattering and concentration signals of macromolecules in a flow cell |
| CN201210142Y (en) * | 2008-05-09 | 2009-03-18 | 天津理工大学 | Experiment device for monitoring crystallization process of vitamin B12 by improved laser method |
| CN201543263U (en) * | 2009-10-19 | 2010-08-11 | 上海医药工业研究院 | Monitoring device for monitoring crystallization process and crystallization equipment equipped with same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1501065A (en) * | 2002-11-19 | 2004-06-02 | 友达光电股份有限公司 | Polysilicon film crystallization quality detecting apparatus, detecting and controlling method therefor |
| JP2006275901A (en) * | 2005-03-30 | 2006-10-12 | Seiko Epson Corp | Device and method for crystal evaluation |
| WO2007121363A3 (en) * | 2006-04-13 | 2008-05-08 | Univ Mississippi | An optical apparatus for simultaneously measuring the scattering and concentration signals of macromolecules in a flow cell |
| CN201210142Y (en) * | 2008-05-09 | 2009-03-18 | 天津理工大学 | Experiment device for monitoring crystallization process of vitamin B12 by improved laser method |
| CN201543263U (en) * | 2009-10-19 | 2010-08-11 | 上海医药工业研究院 | Monitoring device for monitoring crystallization process and crystallization equipment equipped with same |
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