CN104151154B - A kind of production method of citric acid monohydrate crystal - Google Patents
A kind of production method of citric acid monohydrate crystal Download PDFInfo
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- CN104151154B CN104151154B CN201410376663.3A CN201410376663A CN104151154B CN 104151154 B CN104151154 B CN 104151154B CN 201410376663 A CN201410376663 A CN 201410376663A CN 104151154 B CN104151154 B CN 104151154B
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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
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
The invention discloses a kind of production method of citric acid monohydrate crystal, wherein, the method comprises, can generate under the condition of citric acid monohydrate crystal, citric acid solution is carried out at least two-stage crystallization, and the magma liquid that every grade of crystallization is obtained carries out classification, the magma liquid of the crystal that contains greater particle size that classification is obtained carries out next stage crystallization, wherein, the crystallization temperature of upper level crystallization is higher than the crystallization temperature of next stage crystallization. By technique scheme, realize continuous production Citric Acid Mono, the citric acid monohydrate crystal epigranular obtaining, bulk density is high, and the low object of cost.
Description
Technical field
The present invention relates to a kind of production method of citric acid monohydrate crystal.
Background technology
Citric Acid Mono is mainly used in food, beverage industry, as acid, flavor enhancement, anticorrisive agent andAntistaling agent. Also in chemical industry, cosmetic industry and washing industry, be used as antioxidant, plasticizer andWashing agent. The production method of current industrial Citric Acid Mono is mainly the method for batch (-type) crystallization, concreteComprise: first citric acid fermentation broth is obtained to citric acid clear liquid through Separation of Solid and Liquid, citric acid clear liquid is through hydrogen calciumAfter method (calcium salt method) extraction, acidolysis, decolouring, obtain the citric acid solution of purifying, then by the lemon of purifyingThe heating of lemon acid solution is concentrated, then gained citric acid concentrate is put into multiple crystallizers in batches, by coolingMake citric acid concentrate reach hypersaturated state, crystal is separated out, and carry out Separation of Solid and Liquid, thereby obtainThe wet crystal of Citric Acid Mono and From Mother Liquor of Crystallizing Citric Acid.
But, adopting the production method of above-mentioned citric acid monohydrate crystal, crystal grain is inhomogeneous, it is close to pile upSpend low; For periodic crystallisation, hand labor intensity is large, and production cost is higher.
Summary of the invention
The object of the invention is to overcome the citric acid monohydrate crystal granularity that prior art produces inhomogeneous, pile upDensity is low, and the high defect of production cost, and a kind of citric acid monohydrate crystal epigranular obtaining is provided,Bulk density is high, and the production method of the low citric acid monohydrate crystal of production cost.
The present inventor's discovery, the method for existing explained hereafter citric acid monohydrate crystal is all by heatingThe direct step of citric acid solution after concentrated is cooled to 15 DEG C of left and right, and cooling so fast can make a waterCitric acid is instantaneous separates out in large quantities, and the Citric Acid Mono of separating out does not have time enough according to certain ruleCarry out the arrangement of crystal formation, just can be stacked disorderly, therefore, can cause the Citric Acid Mono obtainingCrystal grain is inhomogeneous, and crystal not of uniform size also makes its bulk density step-down. Even if the later stage extends againThe one-tenth of crystal is long-time, the change on the crystal grain recurring structure that is also difficult to make to have formed. In addition,The method of existing production citric acid monohydrate crystal is all step technique, is all in a crystallizing tankCrystallization, produces after a collection of citric acid crystal, carries out Separation of Solid and Liquid, then carries out the production of next tank, like thisThe production efficiency of the mode of production lower, equipment for separating liquid from solid centrifuge or for a long time idle running, or needShut down, long-time idle running causes power consumption to increase, and restarts also very power consumption when shutdown, after shutdown, reachesConsuming time also long to stable state, generally need to about 20-40 minute, further cause power consumption increase.
The present inventor finds through a large amount of research, citric acid solution is carried out at least twice knotCrystalline substance, and the crystallization temperature of upper level crystallization is greater than the crystallization temperature of next stage crystallization, makes like this lemon acid-solubleLiquid carries out substep decrease temperature crystalline, and on the one hand, in each step, Citric Acid Mono molecule can not look like existing skillArt is separated out like that in large quantities, makes the Citric Acid Mono molecule of separating out have time enough and space to carry out crystalline substanceThe arrangement of type and growth, thus comparatively rule, the more uniform Citric Acid Mono crystalline substance of crystal grain can be formedBody. The present inventor also finds, the magma liquid after every one-level crystallization is carried out to classification, will containThe magma liquid of the crystal of large particle diameter is directly squeezed into next stage and is continued crystallization, and repeat this step until lastLevel, can screen step by step according to the size of the citric acid monohydrate crystal obtaining like this, makes finalCan obtain that particle is large and crystal grain is even, the citric acid monohydrate crystal that bulk density is high. And thisInvention by carry out crystallization at least 2 crystallizing tanks, by constantly in the first order crystallizing tank stream add lemonLemon acid solution, thus step production technology is changed into the production technology of continous way, and by controllingThe flow velocity of citric acid, with the time of crystallization control, has been saved manpower so greatly, and utilization rate of equipment and installations is higher,Thereby provide cost savings.
Based on above discovery, the invention provides a kind of production method of citric acid monohydrate crystal, wherein,The method comprises, generating under the condition of citric acid monohydrate crystal, citric acid solution is carried out at leastTwo-stage crystallization, and the magma liquid that every grade of crystallization is obtained carries out classification, and containing that classification is obtained is largerThe magma liquid of the crystal of particle diameter carries out next stage crystallization, wherein, the crystallization temperature of upper level crystallization higher than underThe crystallization temperature of one-level crystallization.
Preferably, the crystallization temperature of first order crystallization is 30-35 DEG C.
More preferably, the differences in crystallisation temperature of adjacent two-stage crystallization is 3-10 DEG C, is preferably 5-8 DEG C.
Further preferably, in described citric acid solution, the content of citric acid is 64-72 % by weight, more excellentSelect 69-71 % by weight.
By technique scheme, under the condition that citric acid solution is reduced gradually in temperature, carry out substep knotCrystalline substance, and every grade of crystallization is obtained to magma liquid carry out classification according to the size of Citric Acid Mono particle, thereby makeObtain the citric acid monohydrate crystal epigranular finally obtaining, bulk density is high. And by prior art intermittentlyThe Citric Acid Mono production technology of formula is improved to the production technology of continous way, makes the utilization rate of equipment greatlyImprove, hand labor intensity reduces greatly, thereby has reduced production cost.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is the MIcrosope image of the citric acid monohydrate crystal that obtains according to the method for embodiment 1, amplifies40 times;
Fig. 2 is the MIcrosope image of the citric acid monohydrate crystal that obtains according to the method for comparative example 1, amplifies40 times.
Fig. 3 is the process chart of the production citric acid monohydrate crystal of embodiment 1, wherein,
1, feeding liquid
11, one-level crystallizer 12, one-level stir
13, magma liquid 14, one-level clasfficiator are returned in one-level clasfficiator upper end
15, one-level clasfficiator lower end out-feed liquid 16, one-level crystallizer out-feed liquid
21, secondary crystallization device 22, secondary stir
23, magma liquid 24, secondary clasfficiator are returned in secondary clasfficiator upper end
25, secondary clasfficiator lower end out-feed liquid 26, secondary crystallization device out-feed liquid
31, three grades of crystallizers 32, three grades of stirrings
33, magma liquid 34, three grades of clasfficiators are returned in three grades of clasfficiator upper ends
35, three grades of clasfficiator lower end out-feed liquids 36, three grades of crystallizer out-feed liquids
41, level Four crystallizer 42, level Four stir
43, magma liquid 44, four-stage grading device are returned in four-stage grading device upper end
45, four-stage grading device lower end out-feed liquid 46, level Four crystallizer out-feed liquid
51, Pyatyi crystallizer 52, Pyatyi stir
53, magma liquid 54, Pyatyi clasfficiator are returned in Pyatyi clasfficiator upper end
55, Pyatyi clasfficiator lower end out-feed liquid 56, Pyatyi crystallizer out-feed liquid
6, centrifuge
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of production method of citric acid monohydrate crystal, wherein, the method comprises,Can generate under the condition of citric acid monohydrate crystal, citric acid solution is carried out at least two-stage crystallization, andThe magma liquid that every grade of crystallization is obtained carries out classification, the crystalline substance of the crystal that contains greater particle size that classification is obtainedSlurries carry out next stage crystallization, and wherein, the crystallization temperature of upper level crystallization is higher than the crystallization of next stage crystallizationTemperature.
According to the present invention, described " can generate the condition of citric acid monohydrate crystal " refers to " can be continuousGenerate the condition of citric acid monohydrate crystal ". Described continuous production can by crystallization crystallizing tank usedNumber and the progression of crystallization are identical and realize. For example, in a crystallizing tank, carry out after crystallization at the corresponding levels gainedThe crystallizing tank that can enter next stage after magma liquid is classified carries out next stage crystallization, and at the corresponding levels knot nowBrilliant tank continues to accept magma liquid from upper level to proceed crystallization at the corresponding levels, wherein, ties in the first orderIn brilliant tank, citric acid solution to be crystallized joins in one-level crystallizing tank in the mode adding continuously.
In the present invention, described " generating under the condition of citric acid monohydrate crystal " refers to, crystallizationCondition, it is citric acid monohydrate crystal that for example temperature makes the citric acid crystal of separating out. Those skilled in the artKnown, under the condition that is not more than 36.6 DEG C, the crystal of separating out in citric acid solution is Citric Acid Mono crystalline substanceBody.
Under normal circumstances, treat that the temperature of the citric acid solution of decrease temperature crystalline is generally 36-45 DEG C, the present inventionInventor find, generating at the temperature of citric acid monohydrate crystal, by the crystallization of first order crystallizationTemperature remains in higher level, not only can make Citric Acid Mono molecule successfully separate out, and analyseThe citric acid molecule amount going out, owing to greatly reducing, makes it have time enough and space to carry out the row of crystal formationRow, thus it is more regular to make to obtain the arrangement of citric acid monohydrate crystal, and particle is more even. Therefore,Under preferable case, the crystallization temperature of first order crystallization is 30-35 DEG C. Preferably, described in, treat decrease temperature crystallineThe temperature of citric acid solution and the temperature difference of the crystallization temperature of one-level crystallization be 6-10 DEG C.
According to the present invention, although in adjacent two-stage, the crystallization temperature of upper level crystallization is tied higher than next stageBrilliant crystallization temperature can realize goal of the invention of the present invention. But the present inventor finds, when adjacentThe differences in crystallisation temperature of two-stage crystallization is 3-10 DEG C, while being preferably 5-8 DEG C, described Citric Acid Mono moleculeThe law of development of the amount of separating out and speed of separating out and citric acid monohydrate crystal can be coordinated further, fromAnd it is more regular that the citric acid monohydrate crystal that obtains is arranged, crystal grain is more even.
The method according to this invention, described citric acid solution be preferably at the temperature of 45-100 DEG C, heat denseBeing reduced to citric acid concentration is 64-72 % by weight, and preferably the citric acid solution of 69-71 % by weight, heats denseThe operating condition of contracting can be normal pressure or vacuum.
According to the present invention, except the crystallization temperature of citric acid crystallization being controlled in the process of every grade of crystallizationInside and outside scope of the present invention, have no particular limits for other condition of crystallization, as long as it ensure lemonThe total time of acid crystal is 7-15 hour. The control of described time can be by controlling every grade of crystallizationCrystallizer in the flow velocity (with respect to the crystallizer of 10 liter capacities) of magma liquid realize above-mentioned purpose,In preferred situation, in order to ensure that Citric Acid Mono can analysed fully in the process of every one-level crystallizationGo out, every grade of charging rate is consistent with discharging speed, for example, can be 2-5m3/ h. Preferably, every grade of knotBrilliant crystallization time is 2-5 hour.
According to the present invention, the progression that in theory citric acid solution is carried out to crystallization is more, gained one water lemonThe particle of acid crystal is just more even, and the larger water lemon of particle diameter containing in every grade of magma liquid obtainingThe ratio of lemon acid crystal is larger, thus make final mass preferably citric acid monohydrate crystal outputHigh. But the present inventor finds according to practical production experience, and citric acid solution is carried out to 2 grades of crystallizationsCan realize goal of the invention of the present invention, preferably carry out the crystallization of 3-5 level. Under preferred crystallization progression,Can either ensure that citric acid monohydrate crystal particle is more even, the particle diameter containing in the magma liquid that every grade obtainsThe ratio of larger citric acid monohydrate crystal is also higher, can also save unnecessary operating procedure.
Wherein, taking 5 grades of crystallizations of Fig. 3, as example, the present invention will be described in detail, but the present invention is notBe limited to this. Concrete, feeding liquid 1 (citric acid solution to be crystallized) joins one-level crystallization continuouslyIn device 11, stir and carry out one-level crystallization 12 times in one-level, the magma liquid obtaining goes out as one-level crystallizerFeed liquid 16 enters continuously one-level clasfficiator 14 and carries out classification, and wherein, what classification obtained contains greater particle sizeThe magma liquid of crystal enter continuously in secondary crystallization device 21 and carry out as one-level clasfficiator lower end out-feed liquidSecondary crystallization, what classification obtained contain compared with the magma liquid of the crystal of small particle diameter returns as one-level clasfficiator upper endReturn magma liquid 13 and be back to continuously in one-level crystallizer 11 and proceed one-level crystallization, by that analogy, straightTo Pyatyi clasfficiator 54, after classification, contain the magma liquid of crystal of greater particle size as Pyatyi clasfficiator lower endOut-feed liquid 55 enters centrifuge 6 continuously to carry out Separation of Solid and Liquid and obtains citric acid monohydrate crystal of the present invention.Wherein, speed those skilled in the art that feeding liquid 1 enters in one-level crystallizer can be according to actual conditionsAdjust.
In the present invention, have no particular limits for the state in every grade of crystallization process, for example, Ke YiUnder the condition stirring, carry out, also can under the condition stirring, not carry out. In preferred situation, in order to makeThe citric acid monohydrate crystal particle obtaining is more even dispersedly in magma liquid, thereby is more conducive to separate outCitric Acid Mono molecule attached, every grade of crystallization is all carried out under the condition stirring. For the speed stirringCan be the speed of the stirring for Citric Acid Mono crystallization of this area routine, for example, Ke Yiwei20-25rpm。
According to the present invention, to the standard that obtains citric acid monohydrate crystal and carry out classification not being had after every grade of crystallizationHave special restriction, those skilled in the art can adjust according to the needs of actual production. Preferably feelingsUnder condition, the particle diameter of the crystal of the greater particle size that after first order crystallization, classification obtains is 425-600 μ m; And phaseIn adjacent two-stage, the particle diameter of the crystal of the greater particle size that next stage classification obtains is that upper level classification obtainsThe 1.2-1.7 of the particle diameter of the crystal of large particle diameter doubly. The Citric Acid Mono obtaining in this preferred situationCrystal grain is no matter from the size of particle or from the queueing discipline aspect of crystal formation, its commercial value is higher.
According to the present invention, for the locating compared with the magma liquid of the crystal of small particle diameter of containing obtaining after every grade of classificationReason mode has no particular limits, and for example, can be carried out preparing corresponding one after Separation of Solid and LiquidWater citric acid crystal grain; Also can be returned with the magma liquid of this grade and be mixed, and again be carried out crystallization.Preferred the latter's processing mode in the present invention.
According to the present invention, can realize classification by variety of way, for example, magma liquid is sieved or byClasfficiator (hydrocyclone or spiral classifier) carries out classification. Under preferable case, described classification is at waterIn power cyclone, carry out. More preferably, carry out classification in hydroseparator time, the condition of described classificationComprising: the feed pressure of magma liquid is 0.2-0.4MPa, is the hydrocyclone of 10 liters with respect to volume,The pan feeding speed of magma liquid is 2-10m3/ h. The present inventor finds, method of the present invention can beIn crystallization process, control the uniformity of crystal, thereby save the follow-up operation of sieving, therefore, side of the present inventionMethod has improved the production efficiency of citric acid monohydrate crystal largely.
The present inventor's discovery, while adopting above-mentioned preferred hydrocyclone to carry out classification, lastCrystalline content in the magma liquid for the treatment of Separation of Solid and Liquid obtaining after level crystallization is about 45-55 % by weight, with existingThere is method for crystallising to obtain the content of crystal in magma liquid basic identical, therefore, in a preferred embodiment,Method of the present invention can not increase the burden of follow-up solid-liquid separation step, can ensure production efficiency and energyUnder the prerequisite of consumption, improve the quality of crystal product.
Due to citric acid solution nature crystallization, can produce a large amount of tiny nucleus, nucleus too much causes crystal rawSlowly long, the particle of the anhydrous citric acid crystal that the crystal system initial stage forms is little, therefore, and side of the present inventionMethod preferably also comprises: in the magma liquid of first order crystallization, add Citric Acid Mono crystal seed. Wherein, to oneThe addition of water citric acid crystal seed has no particular limits, in preferred situation, with respect to 1kg theory oneThe output of water citric acid crystal, the addition of described Citric Acid Mono crystal seed is 600-700mg, is preferably620-650mg. The output of theoretical citric acid monohydrate crystal is according to the citric acid solution lemon for crystallizationThe output of the citric acid monohydrate crystal that the content theory of lemon acid calculates.
In the present invention, citric acid solution can be potato dry powder, tapioca starch, corn flour, dehydrated potato powder, shallow lakeThe raw material such as powder and glucose mother liquid, through microorganism fermentations such as aspergillus nigers, zymotic fluid process Separation of Solid and Liquid, thenThe citric acid solution obtaining after calcium salt method, suction-joint method or chromatographic purification and after concentrated, can be alsoObtain after soluble in water by purity being not less than to the citric acid solid of 99 % by weight. Described lemon is acid-solubleIn liquid, the content of citric acid can be 64-72 % by weight, preferably 69-71 % by weight, the purity of citric acidGenerally be not less than 99 % by weight. The purity of described citric acid refers to directly removes above-mentioned citric acid solutionThe weight percentage of citric acid in gained solid product after solvent. Its Raw, microorganism, fermentation barPart and purification condition can be any for obtaining the thing of citric acid solution for what those skilled in the art will know thatMatter and condition, do not repeat them here.
The method according to this invention also comprises, what the magma liquid classification of afterbody crystallization was obtained containsThe magma liquid of the crystal of large particle diameter carries out Separation of Solid and Liquid, obtains the wet crystal of Citric Acid Mono and citric acid crystallizationMother liquor. The wet crystal of gained Citric Acid Mono can obtain Citric Acid Mono crystalline substance after removing free water by dryBody; Gained From Mother Liquor of Crystallizing Citric Acid can recycle two to three times, so that raw material is fully applied.Described Separation of Solid and Liquid, dry method and condition of removing free water can adopt various side known in the artMethod and condition, do not repeat them here.
Below will describe the present invention by embodiment.
The size distribution of citric acid monohydrate crystal adopts order to count analytical method and records;
The bulk density of citric acid monohydrate crystal adopts natural sedimentation to record, and assay method is: by be measuredSample is poured in 1L graduated cylinder, and volume is weighed after reaching 1L, does not apply artificial or mechanical oscillation in this process,The bulk density obtaining is bulk density;
Crystal pattern similarly is that take pictures obtains employing Olympus microscope (OLIMPUSCx31 type);
The ratio that the quality of 10-20 order crystal grain accounts for total crystal grain quality is larger, and the flat of crystal is describedAll granularity is larger, and quality is higher, and crystal product agglomeration resistance ability is stronger.
Embodiment 1
The present embodiment is for illustrating the production method of citric acid monohydrate crystal provided by the invention.
Carry out the production of citric acid monohydrate crystal according to the mode in table 1. Wherein, levels grain graininessSize, refers to that 98% above particle reaches this requirement.
Table 1
Wherein, in the citric acid solution adding in one-level crystallization, citric acid content is 71 % by weight, andThe incipient stage of first order crystallization adds Citric Acid Mono crystal seed, wherein, and with respect to the theoretical water lemon of 1kgThe output of lemon acid crystal, the addition of described Citric Acid Mono crystal seed is 635mg. Level V crystallization is dividedLevel obtains magma liquid and within centrifugal 20 minutes, carries out Separation of Solid and Liquid with the rotating speed of 800rpm, afterwards by separating obtainedSolid is dried 15 minutes with the temperature of 32 DEG C. After dry, producing citric acid crystal product size distribution distributesAs shown in table 5, the bulk density of crystal is 1070kg/m3. The microscope of gained citric acid monohydrate crystalAs shown in Figure 1, detailed process as shown in Figure 3 for picture.
Embodiment 2
The present embodiment is for illustrating the production method of citric acid monohydrate crystal provided by the invention.
Carry out the production of citric acid monohydrate crystal according to the mode in table 2. Wherein, levels grain graininessSize, refers to that 98% above particle reaches this requirement.
Table 2
Wherein, in the citric acid solution adding in one-level crystallization, citric acid content is 70 % by weight, andThe incipient stage of first order crystallization adds Citric Acid Mono crystal seed, wherein, and with respect to the theoretical water lemon of 1kgThe output of lemon acid crystal, the addition of described Citric Acid Mono crystal seed is 620mg. Fourth stage crystallization is dividedLevel obtains magma liquid and within centrifugal 22 minutes, carries out Separation of Solid and Liquid with the rotating speed of 800rpm, afterwards by separating obtainedSolid is dried 16 minutes with the temperature of 35 DEG C. After dry, producing citric acid crystal product size distribution distributesAs shown in table 5, the bulk density of crystal is 1060kg/m3. The microscope of gained citric acid monohydrate crystalPicture is similar to Example 1.
Embodiment 3
The present embodiment is for illustrating the production method of citric acid monohydrate crystal provided by the invention.
Carry out the production of citric acid monohydrate crystal according to the mode in table 3. Wherein, levels grain graininessSize, refers to that 98% above particle reaches this requirement.
Table 3
Wherein, in the citric acid solution adding in one-level crystallization, citric acid content is 69 % by weight, andThe incipient stage of first order crystallization adds Citric Acid Mono crystal seed, wherein, and with respect to the theoretical water lemon of 1kgThe output of lemon acid crystal, the addition of described Citric Acid Mono crystal seed is 650mg. Third level crystallization is dividedLevel obtains magma liquid and within centrifugal 22 minutes, carries out Separation of Solid and Liquid with the rotating speed of 800rpm, afterwards by separating obtainedSolid is dried 20 minutes with the temperature of 32 DEG C. After dry, producing citric acid crystal product size distribution distributesAs shown in table 5, the bulk density of crystal is 1050kg/m3. The microscope of gained citric acid monohydrate crystalPicture is similar to Example 1.
Embodiment 4
The present embodiment is for illustrating the production method of citric acid monohydrate crystal provided by the invention.
Carry out the crystallization of citric acid monohydrate crystal according to the method for embodiment 1, different, points two gradingRow crystallization, the condition of crystallization is as shown in the table.
Table 4
After dry, produce the distribution of citric acid crystal product size distribution as shown in table 5, the bulk density of crystalFor 950kg/m3. The uniformity coefficient of gained citric acid monohydrate crystal is poor compared with embodiment, but is better than comparative example 1.
Embodiment 5
The present embodiment is for illustrating the production method of citric acid monohydrate crystal provided by the invention.
Carry out the crystallization of citric acid monohydrate crystal according to the method for embodiment 1, different, every grade of crystallizationCrystallization time be respectively 1.5 hours, 1 hour, 2 hours, 1.5 hours, 1.5 hours. Raw after dryThe citric acid monohydrate crystal Granularity Distribution of producing is as shown in table 5, and the bulk density of crystal is 960kg/m3. The uniformity coefficient of gained citric acid monohydrate crystal is similar to Example 4.
Comparative example 1
This comparative example is for illustrating the production method of the citric acid monohydrate crystal that prior art provides.
Carry out the crystallization of citric acid monohydrate crystal according to the method for embodiment 1, different, by citric acidSolution only carries out one-level crystallization, also, the temperature of citric acid solution is directly reduced to 15 DEG C and carries out crystallization18 hours, and the crystal in magma liquid is not carried out to classification after crystallization. The water lemon producing after dryAcid crystal Granularity Distribution is as shown in table 5, and the bulk density of crystal is 880kg/m3, gained one waterThe microscope picture of citric acid crystal as shown in Figure 2.
Table 5
By embodiment 1-5 is compared and can be found out with comparative example 1, adopt method of the present invention,Citric acid solution is carried out at least 2 grades of crystallizations, and the magma liquid after crystallization is carried out to classification, final instituteThe size distribution of citric acid monohydrate crystal is comparatively even, and percent crystallization in massecuite and crystal accumulation density are alsoHigh. In addition, due to the production technology that method of the present invention is continous way, raw with the batch (-type) of prior artProduction. art is compared, and the utilization rate of equipment is high, and equipment can not exist the process that shutdown is restarted frequently,Greatly reduced power consumption, therefore, manufacturing cost is lower. Embodiment 1 is compared with embodiment 4-5 canTo find out, under the FCTA temprature of preferred crystallization sum of series citric acid solution and by every grade of crystallizationTime be controlled in the preferred scope of the present invention, the size distribution of final gained citric acid monohydrate crystal isFor evenly, and percent crystallization in massecuite and crystal accumulation density also higher.
Can find out by Fig. 1 of embodiment 1 and Fig. 2 of comparative example 1, adopt of the present invention inventionThe granular size of the citric acid monohydrate crystal arriving is more even.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned realityExecute the detail in mode, within the scope of technical conceive of the present invention, can be to technical side of the present inventionCase is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode. For fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a continuous producing method for citric acid monohydrate crystal, is characterized in that, the method comprises,Generating under the condition of citric acid monohydrate crystal, citric acid solution is carried out at least two-stage crystallization, andAnd the magma liquid that every grade of crystallization is obtained carries out classification, the crystal that contains greater particle size that classification is obtainedMagma liquid carries out next stage crystallization, and wherein, the crystallization temperature of upper level crystallization is higher than the knot of next stage crystallizationBrilliant temperature;
Wherein, the differences in crystallisation temperature of adjacent two-stage crystallization is 3-10 DEG C;
Wherein, the crystallization temperature of first order crystallization is 30-35 DEG C;
Wherein, the crystallization time of every grade of crystallization is 2-5 hour;
The particle diameter of the crystal of the greater particle size that wherein, first order CRYSTAF obtains is 425-600 μ m; PhaseIn adjacent two-stage, the particle diameter of the crystal of the greater particle size that next stage classification obtains is that upper level classification obtainsThe 1.2-1.7 of the particle diameter of the crystal of large particle diameter doubly.
2. method according to claim 1, wherein, carries out the crystallization of 3-5 level by citric acid solution.
3. method according to claim 1 and 2, wherein, the crystallization temperature of adjacent two-stage crystallizationPoor is 5-8 DEG C.
4. method according to claim 1, wherein, the method also comprises, classification is obtainedContain compared with the magma liquid of the crystal of small particle diameter and return to mix for the magma liquid of crystallization with this grade, and againCarry out crystallization.
5. according to the method described in 1 or 2 of claims, wherein, every grade of bar that crystallization is all being stirredUnder part, carry out; The speed stirring is 20-25rpm.
6. method according to claim 1 and 2, wherein, described classification is in hydrocycloneCarry out, the condition of described classification comprises: the feed pressure of magma liquid is 0.2-0.4MPa, with respect to volumeBe the hydrocyclone of 10 liters, the pan feeding speed of magma liquid is 2-10m3/h。
7. method according to claim 1, wherein, the method also comprises, in first order crystallizationMagma liquid in add Citric Acid Mono crystal seed, with respect to the output of the theoretical citric acid monohydrate crystal of 1kg,The addition of described Citric Acid Mono crystal seed is 600-700mg.
8. method according to claim 7, wherein, with respect to the theoretical Citric Acid Mono crystalline substance of 1kgThe output of body, the addition of described Citric Acid Mono crystal seed is 620-650mg.
9. method according to claim 1, wherein, in described citric acid solution, citric acid containsAmount is 64-72 % by weight.
10. method according to claim 9, wherein, in described citric acid solution, citric acid containsAmount 69-71 % by weight.
11. methods according to claim 1, wherein, the method also comprises, afterbody is tiedThe magma liquid of the crystal that contains greater particle size that brilliant magma liquid classification obtains carries out Separation of Solid and Liquid, obtains oneThe wet crystal of water citric acid and From Mother Liquor of Crystallizing Citric Acid.
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