CN102964241A - Production method of citric acid monohydrate crystals - Google Patents
Production method of citric acid monohydrate crystals Download PDFInfo
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- CN102964241A CN102964241A CN2012105239202A CN201210523920A CN102964241A CN 102964241 A CN102964241 A CN 102964241A CN 2012105239202 A CN2012105239202 A CN 2012105239202A CN 201210523920 A CN201210523920 A CN 201210523920A CN 102964241 A CN102964241 A CN 102964241A
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Abstract
The invention relates to a production method of citric acid monohydrate crystals. The method comprises: (a) adding a citric acid concentrated liquid with the temperature of 50-100 DEG C and the concentration of 69.5-78 wt%, and reducing the temperature of the concentrated liquid to crystallize while stirring, thereby obtaining citric acid crystal size; (b) regulating the stirring speed rate to be lower than the stirring speed rate of the step (a) by 28-57% from starting to reduce the temperature of the citric acid crystal size to be 36.6 DEG C; (c) regulating the stirring speed rate to be higher than that of the step (b) by 10-55% and lower than that of the step (a) after reducing the temperature of the citric acid crystal size to be 36.6 DEG C until the crystal content exceeds 30wt% by taking the total weight of a mixture containing crystals as a standard; and (d) reducing the temperature of the citric acid crystal size to be 5-20 DEG C, and separating the crystals from the crystal size. The method provided by the invention can be used for enabling the granule diameters of the citric acid monohydrate crystals to be much uniform, relieving the scabbing phenomenon and reducing the false crystal content.
Description
Technical field
The present invention relates to a kind of production method that can access the citric acid monohydrate crystal of uniform particle diameter.
Background technology
Citric acid monohydrate Food grade is mainly used in food, beverage industry as acidic flavoring agent, seasonings and sanitas, preservation agent.Also in chemical industry, cosmetic industry and washing industry, be used as antioxidant, softening agent, washing composition.The production method of present industrial Citric acid monohydrate Food grade comprises: first citric acid fermentation broth is obtained the citric acid clear liquid through solid-liquid separation, the citric acid clear liquid is through hydrogen calcium method (calcium salt method), acid hydrolyzation, solution heating after gained is purified after the decolouring is concentrated, above-mentioned citric acid concentrated solution is put into the crystallizer decrease temperature crystalline, be provided with agitator in the crystallizer, agitator is generally an agitator, the rotating speed of agitator all the time constant (24r/min) in the whole production process, the temperature of the mixture of crystal to be contained is reduced to carries out solid-liquid separation about 13 ℃, thereby obtains the wet crystal of Citric acid monohydrate Food grade and From Mother Liquor of Crystallizing Citric Acid.
There is following shortcoming in the production method of above-mentioned citric acid monohydrate crystal:
1, crystal grain is inhomogeneous and less, and size distribution is wide, causes thus anti-caking performance poor.
2, the crystallizer inwall scabs seriously.
3, pseudo-brilliant content is more.
Size distribution is as shown in the table:
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of production method that can access the citric acid monohydrate crystal of uniform particle diameter.
The production method of citric acid monohydrate crystal provided by the invention may further comprise the steps successively:
(a) adding temperature in crystallizer is that 50-100 ℃, citric acid concentration are the citric acid concentrated solution of 68.5-78 % by weight, under agitation, makes this citric acid concentrated solution decrease temperature crystalline obtain citric acid magma liquid;
When (b) temperature of citric acid magma liquid is reduced to 36.6 ℃, the speed that stirs is adjusted into rate reduction 28-57% than the stirring of step (a);
(c) temperature of citric acid magma liquid is reduced to after 36.6 ℃, take the gross weight of the mixture that contains crystal as benchmark, from the content of crystal surpasses 30 % by weight, the speed that the speed that stirs is adjusted into than the stirring of step (b) improves 10-55%, and is lower than the speed of the stirring of step (a);
(d) temperature of citric acid magma liquid is reduced to 5-20 ℃, isolation of crystalline from described citric acid magma liquid.
The present inventor is through deeply discussing and grope and obtain in conjunction with a large amount of production practice the production method of above-mentioned Citric acid monohydrate Food grade, by the material that contains citric acid under the different states in the decrease temperature crystalline process (comprise the citric acid concentrated solution, contain the mixture of crystal etc.) is applied stirring in various degree, so that the uniform particle diameter of the citric acid monohydrate crystal that finally obtains.In addition, under the preferable case, by crystallizer being designed to the degree of mixing that two-layer agitator has further improved the material that contains citric acid, the particle diameter that makes the citric acid monohydrate crystal that obtains is homogeneous more, and can alleviate the crystallizer inwall the phenomenon that scabs, reduce pseudo-brilliant content.For example, adopt the size distribution of the citric acid monohydrate crystal (product) that obtains among the embodiment 1 of method of the present invention to be:
Wherein, expression can not be that particle diameter is greater than the material of the sieve aperture of 10 mesh sieves by 10 mesh sieves (particle diameter is 2000 microns) on 10 mesh sieves; Expression can be that particle diameter is less than the material of the sieve aperture of 80 mesh sieves by 80 mesh sieves (particle diameter is 180 microns) under 80 mesh sieves.
Description of drawings
Fig. 1 is the synoptic diagram of the embodiment of the invention 1 employed crystallizer.
Description of reference numerals
1 tank body; 2 stir shafts; 3 agitators; 4 heat-exchanging parts.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the production method of described citric acid monohydrate crystal may further comprise the steps successively:
(a) adding temperature in crystallizer is that 50-100 ℃, citric acid concentration are the citric acid concentrated solution of 68.5-78 % by weight, under agitation, makes this citric acid concentrated solution decrease temperature crystalline obtain citric acid magma liquid;
When (b) temperature of citric acid magma liquid is reduced to 36.6 ℃, the speed that stirs is adjusted into rate reduction 28-57% than the stirring of step (a);
(c) temperature of citric acid magma liquid is reduced to after 36.6 ℃, take the gross weight of the mixture that contains crystal as benchmark, from the content of crystal surpasses 30 % by weight, the speed that the speed that stirs is adjusted into than the stirring of step (b) improves 10-55%, and is lower than the speed of the stirring of step (a);
(d) temperature of citric acid magma liquid is reduced to 5-20 ℃, isolation of crystalline from described citric acid magma liquid.
According to the present invention, preferred, the speed of the stirring of described step (a) is 25-35r/min; The speed of the stirring of described step (b) is 15-18r/min; The speed of the stirring of described step (c) is 20-23r/min.
Citric acid monohydrate crystal production method with respect to constant rotational speed in the prior art, the present invention is directed to the material that contains citric acid of different states, by changing agitation power and adjusting stirring velocity, can improve mass transfer in the material that contains citric acid, heat transmission and transmission ofenergy, make more homogeneous of the citric acid monohydrate crystal particle diameter that finally obtains.
In the present invention, in the situation of not doing opposite explanation, the noun of locality of use as " on ", D score typically refers to upper and lower along the short transverse of tank body 1 as shown in Fig. 1; " interior ", " outward " refer to the inside and outside of tank body 1; " axially " refers to the direction of stir shaft 2, and " radially " refers to the diametric(al) of tank body 1, namely perpendicular to the direction of stir shaft 2.
Crystallizer used in the present invention can have following structure: comprise tank body 1; Be arranged on the stir shaft 2 in the tank body 1; Be arranged at least two agitators 3 on the described stir shaft 2; The heat-exchanging part 4 that is used for thermal exchange.
The present invention has no particular limits for tank body 1, can be to be used for the various tank bodies that crystallization is produced in the prior art, and for example the aspect ratio of described tank body can be 1-3, is preferably ellipse.In addition, described tank body generally also comprises the opening for feed that is arranged at the tank body top, the discharge port that is arranged at tank base, the manhole that communicates with tank body, insulation water layer chamber and liquidometer etc.The structure and function of these parts all can with reference to prior art, therefore repeat no more at this paper.
According to the present invention, stir shaft 2 is preferably along the central axis settings of tank body 1, radially vertical with tank body 1.Stir shaft 2 can be more piece, can connect by shaft coupling between each joint.In addition, although not shown, but in order to drive the rotation of stir shaft 2, described crystallizer also is provided with the drive unit that can drive stir shaft 2 rotations, namely, the drive unit that one end of stir shaft 2 connects can be for changing the various known drive unit of power regulation agitation speed, motor for example, and the volume adequacy of the material that contains citric acid that the peak power of motor can be stirred is as required selected.
According to the present invention, heat-exchanging part 4 can adopt known various interchanger, for example, chuck and coiled pipe etc., specifically preferably adopt in the present invention chuck to carry out heat exchange, described chuck also is provided with heat-eliminating medium entrance and heat-eliminating medium outlet, specifically can with reference to prior art, therefore repeat no more at this paper.
According to the present invention, a plurality of agitators 3 preferably are arranged on the described stir shaft 2 equally spacedly, and owing to described a plurality of agitators 3 are arranged on the same stir shaft, and by same drive unit driving, therefore the rotating speed of a plurality of agitators is all identical.
In the method for the invention, be the tank body of 1-3 for aspect ratio, preferably at stir shaft 2 two agitators 3 are set.
In the method for the invention, there is no particular limitation for the agitator 3 that adopts which kind of form.Under the preferable case, described agitator 3 comprises paddle stirrer or anchor stirrer.
In the present invention, the diameter of paddle stirrer (external diameter of blade) is preferably 0.35-0.6 with the ratio of the diameter of tank body 1, and the number of blade of paddle stirrer is preferably 2-3.The blade of described paddle stirrer can be made with band steel, to weld or to be fixed by bolts on the wheel hub, the shape of the blade of paddle stirrer can adopt various known shapes, for example, can be divided into flat-blade paddle agitator and inclined paddle type agitator according to the features of shape difference of blade.
In the present invention, described anchor stirrer is preferably the anchor frame.It can obtain large shearing force along wall when low speed rotation, but settlement prevention and wall adhere to the shape at the bottom of the bottom shape applying oval can.The diameter of anchor stirrer (when being preferably the anchor grid agitator, stirrer diameter refers to the maximum wide cut between the agitating vane) is preferably 0.9-0.98 with the ratio of the diameter of tank body 1.
In the method for the invention, for the crystallizer that two agitators 3 are set on the stir shaft 2, anchor stirrer 11 and paddle stirrer 10 arrange coaxially take stir shaft 2 as axle, preferred anchor stirrer is arranged on the lower end of stir shaft 2, preferred anchor stirrer is arranged at the bottom near tank body 1, and paddle stirrer is arranged on the top of described anchor stirrer.Among the present invention, preferred, described paddle stirrer is flat-blade paddle agitator, and described anchor stirrer is the anchor grid agitator.Preferably.The distance of flat-blade paddle agitator and anchor grid agitator is 400-1000mm, and described distance refers to the vertical range between fixed position to the fixed position of the upper ledge of anchor grid agitator and stir shaft 2 on paddle stirrer and the stir shaft 2.
Anchor stirrer is take the axial flow state as main, paddle stirrer is take the radial flow state of mixed flow as main, because existing axial flow has again radial flow, so that the liquid in the tank body can fully be stirred, mix, thereby degree of supersaturation is more even everywhere in the crystallizer.Not only economy but also effectively strengthen radial and axial flow of material in tank body 1 of containing citric acid of paddle stirrer is being set above the anchor stirrer, make the citric acid monohydrate crystal uniform particle diameter that finally obtains, in the generation of the brilliant scar that the inwall that anchor stirrer can establishment tank body 1 is set near the bottom of tank body 1, thereby boost productivity, reduce production costs and reduce the labour intensity that cleaning is safeguarded.
In the method for the invention, all agitators 3 that preferably are arranged on the stir shaft 2 all are immersed in citric acid concentrated solution or the citric acid magma liquid, can effectively produce citric acid monohydrate crystal thus.
In the present invention, the temperature used of step (a) can obtain by known method as the citric acid concentrated solution of 68.5-78 % by weight as 50-100 ℃, citric acid concentration.For example, use the raw materials such as potato dry powder, Tapioca Starch, Semen Maydis powder, potato powder, starch and glucose mother liquid, through microbial fermentations such as aspergillus nigers, fermented liquid is through solid-liquid separation, through obtaining containing the solution (citric acid concentration is generally the 10-40 % by weight) of citric acid after calcium salt method, suction-joint method or the chromatographic purification, this is contained concentrated the obtaining of solution heating of citric acid again; Also the solution (citric acid concentration can be the 10-40 % by weight) that obtains containing citric acid after soluble in water by the citric acid solid that purity is not less than 99 % by weight can be, concentrated the obtaining of solution heating of citric acid will be contained again.Above-mentioned fermentation condition and purification condition are conventionally known to one of skill in the art.
The physical significance of degree of supersaturation is consistent with the physical significance of degree of supersaturation well known in the art among the present invention, refers under a certain temperature ratio of the weight of the solute that theory can be dissolved when solvent reached capacity under the weight of the solute of actual dissolving in the solvent and this temperature.
In the method for the invention, the speed of cooling can be 1-10 ℃/h, for whole decrease temperature crystalline process, can keep constant cooling rate; Preferably, feed temperature from 50-100 ℃ be reduced to before 36.6 ℃ with faster speed cooling (6-10 ℃/h), it is slower to reach the later cooling rate of 36.6 ℃ of beginnings at feed temperature, is preferably the speed cooling with 2-6 ℃/h.
The cooling method can be preferably chuck at heat-exchanging part 4() in pass into heat-eliminating medium, heat-eliminating medium can be water, mixture of ice and water etc.
In the method for the invention, step (d) preferably is reduced to 5-20 ℃ when the temperature of citric acid magma liquid, when preferably being reduced to 10-15 ℃, and isolation of crystalline from described citric acid magma liquid.
The below will further describe in detail the present invention by specific embodiment.In following examples and the Comparative Examples, employed Citric Acid, usp, Anhydrous Powder crystal seed is that COFCO Biochemical (Anhui) Co., Ltd. produces; The size distribution of citric acid monohydrate crystal adopts order to count analytical procedure and records, and the content of Citric acid monohydrate Food grade is to measure according to GB GB1987-2007 method in " food additive citric acid " to obtain in the citric acid monohydrate crystal.
The crystallizer that present embodiment uses comprises: as shown in Figure 1, and diameter D=1700mm, the height H=2500mm of tank body, the useful volume V=6m of tank body
3The agitator that is arranged on the lower end (apart from the bottom 100mm of tank body) of stir shaft is anchor grid agitator, diameter d=1610mm, (distance apart from the anchor grid agitator is 1800mm) arranges flat-blade paddle agitator above described anchor grid agitator, and the diameter d=680mm of flat-blade paddle agitator, number of blade are 3; Heat-exchanging part adopts chuck, internal circulation cold water.
Be 38 % by weight, density 1145kg/m with citric acid (citric acid purity is 99 % by weight) concentration
3The solution that contains citric acid to be concentrated to citric acid concentration 60 ℃ of lower heating be 73 % by weight, obtain the citric acid concentrated solution.
(1) in crystallizer, adds 6m
3The citric acid concentrated solution, with the speed cooling of 10 ℃/h, the rotating speed that stir shaft drives stirring rake is 35r/min, obtains citric acid magma liquid.
When (2) temperature of citric acid magma liquid was reduced to 36.6 ℃, the adjustment of rotational speed of stir shaft was 15r/min, and the speed with cooling is adjusted into 6 ℃/h in addition.
(3) when the weight of crystal account for the mixture that contains crystal gross weight 30% the time, the adjustment of rotational speed of stir shaft is 23r/min.
(4) when the mixture that contains crystal is cooled to 10 ℃, carry out solid-liquid separation, the brilliant scar layer thickness of measuring inner tank wall is 1mm, with the gained solid obtain citric acid monohydrate crystal at 35 ℃ after being dried to constant weight, content is 99.9 % by weight, size distribution is as shown in the table:
Comparative Examples 1
Method according to embodiment 1 is produced citric acid monohydrate crystal, different is, only in the lower end of stir shaft the anchor grid agitator is set in the crystallizer, and paddle stirrer is not set, regulating electric machine power makes rotating speed constant 24r/min of being in whole decrease temperature crystalline process of stir shaft.And with the cooling speed be adjusted into 4 ℃/h.When the mixture that contains crystal is cooled to 10 ℃, carry out solid-liquid separation, the brilliant scar layer thickness of measuring inner tank wall is 15mm, with the gained solid obtain citric acid monohydrate crystal at 35 ℃ after being dried to constant weight, content is 99.5 % by weight, size distribution is as shown in the table:
In crystallizer, do not arrange the paddle stirrer (flat-blade paddle agitator), other operations with embodiment 1 are identical, the brilliant scar layer thickness of measuring inner tank wall is 10mm, with the gained solid obtain citric acid monohydrate crystal at 35 ℃ after being dried to constant weight, content is 99.7 % by weight, size distribution is as shown in the table:
Use the crystallizer of embodiment 1.
Be 38 % by weight, density 1145kg/m with citric acid (citric acid purity is 99 % by weight) concentration
3The solution that contains citric acid to be concentrated to citric acid concentration 80 ℃ of lower heating be 72 % by weight, obtain the citric acid concentrated solution.
(1) in crystallizer, adds 6m
3The citric acid concentrated solution, with the speed cooling of 8 ℃/h, the rotating speed that stir shaft drives stirring rake is 30r/min, obtains citric acid magma liquid.
When (2) temperature of citric acid magma liquid was reduced to 36.6 ℃, the rotating speed of stir shaft was 18r/min, and the speed with cooling is adjusted into 4 ℃/h in addition.
(3) when the weight of crystal account for the mixture that contains crystal gross weight 30% the time, the rotating speed of stir shaft is 22r/min.
(4) when the mixture that contains crystal is cooled to 15 ℃, carry out solid-liquid separation, the brilliant scar layer thickness of measuring inner tank wall is 1mm, with the gained solid obtain citric acid monohydrate crystal at 35 ℃ after being dried to constant weight, content is 99.9 % by weight, size distribution is as shown in the table:
Use the crystallizer of embodiment 1.
Be 38 % by weight, density 1145kg/m with citric acid (citric acid purity is 99 % by weight) concentration
3The solution that contains citric acid to be concentrated to citric acid concentration 98 ℃ of lower heating be 72 % by weight, obtain the citric acid concentrated solution.
(1) in crystallizer, adds 6m
3The citric acid concentrated solution, with the speed cooling of 6 ℃/h, the rotating speed that stir shaft drives stirring rake is 25r/min, obtains citric acid magma liquid.
When (2) temperature of citric acid magma liquid was reduced to 36.6 ℃, the rotating speed of stir shaft was 16r/min, and the speed with cooling is adjusted into 2 ℃/h in addition.
(3) when the weight of crystal account for the mixture that contains crystal gross weight 30% the time, the rotating speed of stir shaft is 20r/min.
(4) when the mixture that contains crystal is cooled to 20 ℃, carry out solid-liquid separation, the brilliant scar layer thickness of measuring inner tank wall is 1.2mm, with the gained solid obtain citric acid monohydrate crystal at 30 ℃ after being dried to constant weight, content is 99.9 % by weight, size distribution is as shown in the table:
Data by embodiment and Comparative Examples can be found out, adopt method of the present invention can obtain the citric acid monohydrate crystal of uniform particle diameter.Relatively can find out by embodiment 1-4 and Comparative Examples 1, apply in various degree stirring for the material that contains citric acid under the different states, can make the uniform particle diameter of the citric acid monohydrate crystal that obtains.Can find out by embodiment 2 and embodiment 1,3 and 4 comparison, two-layer agitator is set, the particle diameter that can make the citric acid monohydrate crystal that obtains is homogeneous more, and can reduce brilliant scar layer on the inwall of crystallizer thickness, improve the purity of crystal.
Claims (9)
1. the production method of a citric acid monohydrate crystal is characterized in that, the method may further comprise the steps successively:
(a) adding temperature in crystallizer is that 50-100 ℃, citric acid concentration are the citric acid concentrated solution of 68.5-78 % by weight, under agitation, makes this citric acid concentrated solution decrease temperature crystalline obtain citric acid magma liquid;
When (b) temperature of citric acid magma liquid is reduced to 36.6 ℃, the speed that stirs is adjusted into rate reduction 28-57% than the stirring of step (a);
(c) temperature of citric acid magma liquid is reduced to after 36.6 ℃, take the gross weight of the mixture that contains crystal as benchmark, from the content of crystal surpasses 30 % by weight, the speed that the speed that stirs is adjusted into than the stirring of step (b) improves 10-55%, and is lower than the speed of the stirring of step (a);
(d) temperature when citric acid magma liquid is reduced to 5-20 ℃, isolation of crystalline from described citric acid magma liquid.
2. method according to claim 1, wherein, the speed of the stirring of described step (a) is 25-35r/min; The speed of the stirring of described step (b) is 15-18r/min; The speed of the stirring of described step (c) is 20-23r/min.
3. method according to claim 1, wherein, described crystallizer comprises: tank body (1); Be arranged on the stir shaft (2) in the tank body (1); Be arranged at least two agitators (3) on the described stir shaft (2); The heat-exchanging part (4) that is used for thermal exchange.
4. method according to claim 3, wherein, described agitator (3) comprises paddle stirrer and anchor stirrer.
5. method according to claim 4, wherein, the ratio of the diameter of the diameter of paddle stirrer and tank body (1) is 0.3-0.6, the number of blade of paddle stirrer is 2-3; The ratio of the diameter of the diameter of anchor stirrer and tank body (1) is 0.9-0.98.
6. the described method of any one according to claim 3-5 wherein, is provided with two agitators (3) on the described stir shaft (2), anchor stirrer is arranged on the lower end of stir shaft (2), and paddle stirrer is arranged on the top of described anchor stirrer.
According to claim 6 in the described method of any one, wherein, agitator (3) is immersed in citric acid concentrated solution or the citric acid magma liquid.
8. method according to claim 1, wherein, the aspect ratio of described tank body (1) is 1-3.
9. method according to claim 1, wherein, the speed of cooling is 1-10 ℃/h; Preferably, the speed of the cooling before feed temperature is reduced to 36.6 ℃ from 50-100 ℃ is 6-10 ℃/h, and the speed that feed temperature reaches the cooling of 36.6 ℃ of beginnings is 2-6 ℃/h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104230695A (en) * | 2014-07-28 | 2014-12-24 | 中粮生物化学（安徽）股份有限公司 | Citric acid monohydrate crystals and production method thereof |
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| US5712131A (en) * | 1993-07-06 | 1998-01-27 | Bayer Corporation | Recovery of organic acid from an impure process stream by addition of strong acid or salt thereof |
| CN102234225A (en) * | 2011-05-06 | 2011-11-09 | 安徽丰原生物化学股份有限公司 | Production method for citric acid monohydrate crystal |
| CN102260166A (en) * | 2011-08-03 | 2011-11-30 | 中粮生物化学（安徽）股份有限公司 | Method for drying citrate monohydrate crystals and obtained citrate monohydrate crystals |
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Patent Citations (3)
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| US5712131A (en) * | 1993-07-06 | 1998-01-27 | Bayer Corporation | Recovery of organic acid from an impure process stream by addition of strong acid or salt thereof |
| CN102234225A (en) * | 2011-05-06 | 2011-11-09 | 安徽丰原生物化学股份有限公司 | Production method for citric acid monohydrate crystal |
| CN102260166A (en) * | 2011-08-03 | 2011-11-30 | 中粮生物化学（安徽）股份有限公司 | Method for drying citrate monohydrate crystals and obtained citrate monohydrate crystals |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230695A (en) * | 2014-07-28 | 2014-12-24 | 中粮生物化学（安徽）股份有限公司 | Citric acid monohydrate crystals and production method thereof |
| CN104230695B (en) * | 2014-07-28 | 2016-03-09 | 中粮生物化学（安徽）股份有限公司 | A kind of citric acid monohydrate crystal and production method thereof |
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