CN104230695B - A kind of citric acid monohydrate crystal and production method thereof - Google Patents
A kind of citric acid monohydrate crystal and production method thereof Download PDFInfo
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- CN104230695B CN104230695B CN201410363494.XA CN201410363494A CN104230695B CN 104230695 B CN104230695 B CN 104230695B CN 201410363494 A CN201410363494 A CN 201410363494A CN 104230695 B CN104230695 B CN 104230695B
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- citric acid
- acid monohydrate
- monohydrate crystal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
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Abstract
The present invention relates to a kind of production method of citric acid monohydrate crystal, the method comprises: citric acid feed liquid is carried out decrease temperature crystalline, in the process of decrease temperature crystalline, in citric acid feed liquid, adds ethanol.The invention still further relates to citric acid monohydrate crystal prepared by aforesaid method.The uniform crystal particles of the citric acid monohydrate crystal that the present invention obtains, tap density and transmittance are also higher, thus improve the quality of product.
Description
Technical field
The present invention relates to a kind of production method of citric acid monohydrate crystal, and citric acid monohydrate crystal prepared by the method.
Background technology
Citric acid monohydrate Food grade is mainly used in food, beverage industry uses as acidic flavoring agent, seasonings, sanitas and preservation agent, and it can also be used for using as antioxidant, softening agent and washing composition in chemical industry, cosmetic industry and washing industry.The production method of current industrial citric acid monohydrate crystal comprises: first citric acid fermentation broth is obtained citric acid clear liquid through solid-liquid separation, again by concentrated for the solution heating of the citric acid stillness of night after calcium salt method (hydrogen calcium method), acid hydrolyzation, decolouring gained are purified, the concentration controlling concentrated solution is 68.5-72 % by weight, above-mentioned citric acid concentrated solution is put into crystallizer, citric acid concentrated solution is made to reach hypersaturated state by cooling, crystal is separated out, cool to about 13 DEG C to start to carry out solid-liquid separation, thus obtain Citric acid monohydrate Food grade and to wet crystal and From Mother Liquor of Crystallizing Citric Acid.There is the defect of the poor product quality such as transmittance is low, tap density is low in the citric acid monohydrate crystal adopting aforesaid method to produce.
Therefore, now a kind of production method that can improve the quality producies such as citric acid monohydrate crystal transmittance and tap density is badly in need of.
Summary of the invention
The object of the invention is the defect that there is the poor product quality such as transmittance is low, tap density is low in order to overcome citric acid monohydrate crystal, a kind of citric acid monohydrate crystal is provided, and the production method of this citric acid monohydrate crystal.
To achieve these goals, the invention provides a kind of production method of citric acid monohydrate crystal, the method comprises: citric acid feed liquid is carried out decrease temperature crystalline, in the process of decrease temperature crystalline, in citric acid feed liquid, adds ethanol.
Preferably, just in citric acid feed liquid, ethanol is added when decrease temperature crystalline starts.
Preferably, described ethanol joins in described citric acid feed liquid in the mode that stream adds.
Preferably, the rate of temperature fall of described decrease temperature crystalline is 2-6 DEG C/h, is more preferably 3-5 DEG C/h.
On the other hand, present invention also offers citric acid monohydrate crystal prepared by aforesaid method.
By technique scheme, ensure that the stringent environment that citric acid monohydrate crystal grows, avoid the generation of glomerocryst, sticky brilliant phenomenon, gained crystal is even, and tap density and transmittance are also higher, thus improve the quality of product.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of production method of citric acid monohydrate crystal, the method comprises: citric acid feed liquid is carried out decrease temperature crystalline, in the process of decrease temperature crystalline, in citric acid feed liquid, adds ethanol.
The present inventor finds, decrease temperature crystalline is carried out to citric acid feed liquid, wherein, in decrease temperature crystalline process, in feed liquid, add ethanol, a loose growing environment can be provided for citric acid monohydrate crystal, avoid the generation of glomerocryst, sticky brilliant phenomenon, gained crystal is even, and tap density is also higher, thus improves the quality of product.
According to the present invention, the ethanol added can be dehydrated alcohol, can be the aqueous solution of ethanol, and the present invention is to this not special restriction.In preferred situation, in order to ensure not bring too much moisture into crystallizing system, the concentration of the aqueous solution of described ethanol is not less than 90 volume %.
Although carry out decrease temperature crystalline to citric acid feed liquid, and in decrease temperature crystalline, in feed liquid, add ethanol can realize object of the present invention, but the present inventor finds, described ethanol joins in the citric acid feed liquid of cooling by the mode added by stream, can better realize object of the present invention.This mainly adds ethanol because of the mode added by stream, more effectively can increase the space between crystal, more be conducive to the growth of crystal.
According to the present invention, in the process of decrease temperature crystalline, in citric acid feed liquid, add ethanol can for when crystallization starts or after crystallization carries out for some time, ethanol is added in citric acid feed liquid, but in order to the transmittance that improves citric acid monohydrate crystal further and tap density, preferably, just in citric acid feed liquid, ethanol is added when decrease temperature crystalline starts.
According to the present invention, the flow acceleration of described ethanol can be selected in wider scope, in order to the growth better for crystal provides loose growing environment, its quality is further enhanced, preferably, with the described citric acid feed liquid of 100 parts by volume for benchmark, the speed that described stream adds be 2-6 parts by volume/hour.
In the present invention, the speed of described decrease temperature crystalline can be the selection of this area routine, but in order to improve transmittance and tap density further, to improve quality product, preferably, the rate of temperature fall of described decrease temperature crystalline is 2-6 DEG C/h, is more preferably 3-5 DEG C/h.When control rate of temperature fall is in above-mentioned preferable range, the outburst nucleation of crystal can be avoided further, reduce the generation of glomerocryst, sticky brilliant phenomenon, be more conducive to the raising of quality product.
The present inventor finds, by while control flow check add the amount of ethanol and the rate of temperature fall of decrease temperature crystalline, the speed of growth of the system environmental adaptation crystal needed for citric acid monohydrate crystal crystallization can be made, thus make crystal arrangement can ordering growth, reduce the generation of glomerocryst.
In the present invention, described decrease temperature crystalline can be realized by heat-eliminating medium, and described heat-eliminating medium can be the various material that can realize cooling down effect well known by persons skilled in the art, such as water coolant or cooling air.The preferred heat-eliminating medium of the present invention is water coolant.
In the present invention, the crystallizer for decrease temperature crystalline can be well known to a person skilled in the art jacketed type or coil pipe type crystallizer.
In addition, in order to prevent in decrease temperature crystalline process, cause owing to passing into heat-eliminating medium in the chuck of crystallizer occurring the temperature difference near the citric acid feed liquid of jacket portion and the citric acid feed liquid of middle body in crystallizer, preferably stir in decrease temperature crystalline process, be tending towards even with the temperature of the citric acid feed liquid making whole crystallizer.The mode of concrete stirring can be any-mode well known by persons skilled in the art.
In the present invention, the opportunity terminating decrease temperature crystalline can be the selection of this area routine, such as, as the near 10-15 DEG C of temperature.
In the present invention, the method also comprises carries out solid-liquid separation to the magma of decrease temperature crystalline gained, and the crystal that solid-liquid separation obtains is carried out dry step.The method of described solid-liquid separation can be the selection of this area routine, such as, by method that is centrifugal or that filter.The mode of described drying can be various drying mode well known to those skilled in the art, and such as, the drying mode of the various routines such as seasoning, forced air drying, vacuum-drying, does not repeat them here.
It should be appreciated by those skilled in the art, the Tc of Citric acid monohydrate Food grade for being less than 36.6 DEG C, when temperature is greater than 36.6 DEG C, the easy dehydration of Citric acid monohydrate Food grade becomes Citric Acid, usp, Anhydrous Powder, therefore, in solid-liquid separation and dry process, temperature should more than 36.6 DEG C, wherein, preferably, the temperature of solid-liquid separation is 10-15 DEG C, and dry temperature is 20-35 DEG C, to the not special requirement of the time of drying, as long as the citric acid monohydrate crystal of acquisition can be made fully dry.
In the present invention, in the citric acid feed liquid of preparation, the concentration of citric acid is not particularly limited, and can select in relative broad range, and the present invention is preferably 66-73 % by weight.
In the present invention, the method preparing citric acid feed liquid can for well known in the art, first citric acid fermentation broth can be obtained citric acid clear liquid through solid-liquid separation, the solution heating of the citric acid stillness of night after calcium salt method (hydrogen calcium method), acid hydrolyzation, decolouring gained are purified is concentrated, control the concentration of concentrated solution, for thus do not repeat them here.
On the other hand, present invention also offers the citric acid monohydrate crystal prepared by aforesaid method.
In the present invention, the tap density of obtained citric acid monohydrate crystal is 930-1080kg/m
3, transmittance is 98.6-99.8%.Therefore, the quality of obtained citric acid monohydrate crystal is better, and crystalline form is also better.
Below will be described the present invention by embodiment.In following examples and comparative example,
Citric acid content refers to the mass percent of citric acid in citric acid feed liquid, and citric acid content adopts conventional sodium hydroxide titration to measure;
Tap density refers to and adopts natural sedimentation to record, and be specially: poured into by testing sample in 1L graduated cylinder, volume is weighed after reaching 1L, do not apply artificial or mechanical vibration in the process, the unit weight obtained is tap density.
The measuring method of transmittance: the sample (being accurate to 0.01g) taking the standby citric acid monohydrate crystal of 50 restraints, be dissolved in water, be settled to 100mL, use 1cm cuvette, take water as blank, the transmittance measuring sample liquid under wavelength 405nm is measured value.Specifically see that GB1987-2007 measures transmittance method.
Embodiment 1
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
By 6m
3citric acid feed liquid (citric acid content is 66 % by weight) inject crystallizer carry out decrease temperature crystalline, just add ethanol to stream in citric acid feed liquid when decrease temperature crystalline starts, the stream rate of acceleration of ethanol is 0.24m
3/ hour, and to control rate of temperature fall be 4 DEG C/h, when being cooled to 12 DEG C, and at this temperature, the citric acid magma obtained is carried out centrifugation, the crystal that then will wet, 35 DEG C of dryings 12 minutes, obtains citric acid monohydrate crystal product.The tap density of the citric acid monohydrate crystal of gained is 1080kg/m
3, the transmittance of product is 99.8%.
Embodiment 2
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
By 6m
3citric acid feed liquid (citric acid content is 70 % by weight) inject crystallizer carry out decrease temperature crystalline, just add ethanol to stream in citric acid feed liquid when decrease temperature crystalline starts, the stream rate of acceleration of ethanol is 0.12m
3/ hour, and to control rate of temperature fall be 3 DEG C/h, when being cooled to 10 DEG C, and at this temperature, the citric acid magma obtained is carried out centrifugation, the crystal that then will wet, 30 DEG C of dryings 12 minutes, obtains citric acid monohydrate crystal product.The tap density of the citric acid monohydrate crystal of gained is 1070kg/m
3, the transmittance of product is 99.8%.
Embodiment 3
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
By 6m
3citric acid feed liquid (citric acid content is 73 % by weight) inject crystallizer carry out decrease temperature crystalline, just add ethanol to stream in citric acid feed liquid when decrease temperature crystalline starts, the stream rate of acceleration of ethanol is 0.36m
3/ hour, and to control rate of temperature fall be 5 DEG C/h, when being cooled to 15 DEG C, and at this temperature, the citric acid magma obtained is carried out centrifugation, the crystal that then will wet, 32 DEG C of dryings 12 minutes, obtains citric acid monohydrate crystal product.The tap density of the citric acid monohydrate crystal of gained is 1075kg/m
3, the transmittance of product is 99.7%.
Embodiment 4
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
The production of citric acid monohydrate crystal is carried out according to the method for embodiment 1, unlike, described dehydrated alcohol all joins in described crystallizer according to the add-on in embodiment 1 is disposable.The tap density of the citric acid monohydrate crystal of gained is 960kg/m
3, the transmittance of product is 98.6%.
Embodiment 5
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
The production of citric acid monohydrate crystal is carried out according to the method for embodiment 1, unlike, the stream rate of acceleration of dehydrated alcohol is 0.06m
3/ hour, the tap density of the citric acid monohydrate crystal of gained is 940kg/m
3, the transmittance of product is 98.7%.
Embodiment 6
The present embodiment is for illustration of citric acid monohydrate crystal provided by the invention and production method thereof.
The production of citric acid monohydrate crystal is carried out according to the method for embodiment 1, unlike, the stream rate of acceleration of dehydrated alcohol is 0.48m
3/ hour, the tap density of the citric acid monohydrate crystal of gained is 930kg/m
3, the transmittance of product is 98.7%.
Comparative example 1
This comparative example is for illustration of the production method of current industrial citric acid crystal.
The production of citric acid monohydrate crystal is carried out according to the method for embodiment 1, unlike, in the process of decrease temperature crystalline, do not add dehydrated alcohol.The tap density of the citric acid monohydrate crystal of gained is 880kg/m
3, the transmittance of product is 96.9%.
Embodiment 1-6 is compared can be found out with comparative example 1, and the tap density of the citric acid monohydrate crystal that the present invention produces is up to 930-1080kg/m
3, the transmittance of product is up to 98.6-99.8%, and therefore, the quality of obtained citric acid monohydrate crystal is better, and crystalline form is also better.
Embodiment 1 is compared can find out with embodiment 4, ethanol joins in citric acid feed liquid in the mode that stream adds, can improve tap density and the transmittance of the citric acid monohydrate crystal of gained further, the quality of namely obtained citric acid monohydrate crystal is better, and crystalline form is also better.
Respectively embodiment 1 is compared with embodiment 5-6 and can find out, with the described citric acid feed liquid of 100 parts by volume for benchmark, the speed that described stream adds be 2-6 parts by volume/hour, tap density and the transmittance of the citric acid monohydrate crystal of gained can be improved further, the quality of namely obtained citric acid monohydrate crystal is better, and crystalline form is also better.
Therefore, the uniform crystal particles of citric acid monohydrate crystal prepared by the present invention, tap density and transmittance are also higher, thus improve the quality of product.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (2)
1. the production method of a citric acid monohydrate crystal, the method comprises: citric acid feed liquid is carried out decrease temperature crystalline, it is characterized in that, just in citric acid feed liquid, ethanol is added when decrease temperature crystalline starts, wherein, described ethanol joins in described citric acid feed liquid in the mode that stream adds, with the described citric acid feed liquid of 100 parts by volume for benchmark, the speed that described stream adds be 2-6 parts by volume/hour, the rate of temperature fall of described decrease temperature crystalline is 3-5 DEG C/h.
2. method according to claim 1, wherein, the content of the citric acid in described citric acid feed liquid is 66-73 % by weight.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102964241A (en) * | 2012-12-07 | 2013-03-13 | 中粮生物化学（安徽）股份有限公司 | Production method of citric acid monohydrate crystals |
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| JPH0272887A (en) * | 1988-03-07 | 1990-03-13 | Res Assoc Util Of Light Oil | Separation and purification of citric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102964241A (en) * | 2012-12-07 | 2013-03-13 | 中粮生物化学（安徽）股份有限公司 | Production method of citric acid monohydrate crystals |
Non-Patent Citations (1)
| Title |
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| 柠檬酸结晶工艺探讨;李长兴;《化学工程与装备》;20120630(第6期);41-43 * |
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