CN116573998A - Preparation method of spherical calcium citrate crystals with adjustable granularity - Google Patents
Preparation method of spherical calcium citrate crystals with adjustable granularity Download PDFInfo
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- CN116573998A CN116573998A CN202210961370.6A CN202210961370A CN116573998A CN 116573998 A CN116573998 A CN 116573998A CN 202210961370 A CN202210961370 A CN 202210961370A CN 116573998 A CN116573998 A CN 116573998A
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- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 title claims abstract description 57
- 239000001354 calcium citrate Substances 0.000 title claims abstract description 56
- 235000013337 tricalcium citrate Nutrition 0.000 title claims abstract description 56
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 50
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 11
- VMLAJPONBZSGBD-UHFFFAOYSA-L calcium;hydrogen carbonate;hydroxide Chemical compound [OH-].[Ca+2].OC([O-])=O VMLAJPONBZSGBD-UHFFFAOYSA-L 0.000 claims abstract description 11
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 235000013373 food additive Nutrition 0.000 claims description 3
- 239000002778 food additive Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 abstract description 16
- 238000010364 biochemical engineering Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 49
- 238000009826 distribution Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 239000012798 spherical particle Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229940069978 calcium supplement Drugs 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 235000013350 formula milk Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 210000004211 gastric acid Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 208000024335 physical disease Diseases 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/20—Agglomerating; Granulating; Tabletting
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/20—Agglomerating; Granulating; Tabletting
- A23P10/28—Tabletting; Making food bars by compression of a dry powdered mixture
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/194—Carboxylic acids, e.g. valproic acid having two or more carboxyl groups, e.g. succinic, maleic or phthalic acid
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P3/00—Drugs for disorders of the metabolism
- A61P3/02—Nutrients, e.g. vitamins, minerals
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
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- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention belongs to the field of biochemical engineering, and particularly relates to a preparation method of spherical calcium citrate crystals with adjustable granularity. The preparation method comprises the following steps: (1) Preparing a citric acid-water solution with the concentration of 0.01-0.2 g/mL and a calcium carbonate-water suspension with the concentration of 0.01-0.3 g/mL; (2) And (3) dropwise adding the calcium carbonate-water suspension into the citric acid-water solution, and stirring, reacting and crystallizing until the pH is 3.5-5 to obtain spherical calcium citrate particles. The particle size regulation and control of the calcium citrate is realized by controlling the reaction temperature and the drop rate of calcium carbonate suspension drops, and spherical calcium citrate particles with average particle size ranging from 30 to 170 microns and more uniform particle size can be obtained. The product has good particle uniformity and high fluidity, and the repose angle is 28-32 degrees. The preparation process is simple, green, environment-friendly and pollution-free.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a preparation method of spherical calcium citrate crystals with adjustable granularity.
Background
Calcium is an essential element of human body and participates in the whole life process of human body. The intake of enough calcium daily can maintain the normal metabolism of the human body and simultaneously effectively avoid the occurrence of physical diseases.
The calcium citrate (CAS: 813-94-5) is used as organic acid calcium with better biocompatibility, does not generate stimulation effect on intestines and stomach after being neutralized by gastric acid, has a certain degree of defects compared with inorganic acid calcium, and is a more ideal food calcium supplement product.
The calcium citrate products obtained in the market are irregular in morphology and uneven in particle size distribution, the taste of the calcium citrate products serving as food additives or calcium supplements is affected, and the calcium citrate with good morphology and even particle size distribution is required to be controlled through a crystallization process. CN104529754a provides a method for preparing amorphous calcium citrate; CN104355991a provides a method for preparing fibrous calcium citrate. CN104402705a provides a preparation method of spherical calcium citrate, but the preparation method is complex, the prepared spherical particles are formed by self-assembly of flaky crystals, freeze drying is required to ensure the stability of the spherical crystals, the particle size of the spherical product is not uniform, and the required production raw materials are expensive, so that industrialization is not easy to realize. According to the invention, a dropping mode of adding calcium carbonate into citric acid is adopted, and a spherical calcium citrate product with uniform particle size distribution, more stable morphology and compactness is obtained by controlling the dropping speed, and meanwhile, the calcium citrate products with different particle sizes are obtained by regulating and controlling the temperature according to the product requirement.
Disclosure of Invention
The market demand for calcium citrate with the advantage of high bioavailability will continue to rise over time. Because calcium citrate is commonly used for daily high-end calcium supplement, including calcium tablet preparation, and is mixed with other food raw materials such as infant formula milk powder, health care products, beverages, dairy products and the like, the calcium citrate granules are required to have better fluidity, compoundability, suspension property, excellent texture and other food functions, so that the quality requirements of the market on foods are met. The appearance and the particle size distribution of the product are important indexes of the current calcium citrate product, wherein the excellent mouthfeel needs to have the high fluidity, small particle size and narrow particle size distribution of the spherical product so as to eliminate the dry and sand feeling generated in the eating process; tableting formulations require high flow products to reduce sticking residues on the tablet press. However, calcium citrate produced in the industry at present is easy to agglomerate, so that the morphology and the particle size distribution are uneven, and the market value of the calcium citrate is seriously influenced. In order to overcome the problems in the prior art, the invention provides a preparation method of spherical calcium citrate with stable and adjustable granularity, which reduces the difficulty of downstream processing and reduces the production energy consumption and dust pollution of products. The calcium citrate product obtained by the process has the advantages of uniform particle size distribution, stable morphology, no agglomeration, good fluidity, low price of production raw materials, simple process, green and environment-friendly performance, and can realize large-scale production.
The technical scheme of the invention is as follows:
(1) Preparing a citric acid-water solution with the concentration of 0.03-0.2 g/mL and a calcium carbonate-water suspension with the concentration of 0.03-0.3 g/mL;
(2) And (3) dropwise adding the calcium carbonate-water suspension into the citric acid-water solution, and stirring, reacting and crystallizing until the pH is 3.5-5 to obtain spherical calcium citrate particles.
And (3) dripping the calcium carbonate suspension into the prepared citric acid solution according to a certain dripping rate, stirring in the whole process to ensure complete reaction, and finishing experiments for 0.3-1h (for example, 0.3h, 0.5h, 0.8h, 1h and the like) after the dripping of the calcium carbonate suspension is finished, thus obtaining the spherical calcium citrate particles.
The molar ratio relationship of the two reactants in the step (1) is calcium carbonate: citric acid=1.3 to 1.47:1, ensuring the pH value of the end point to be 3.5-5.
And (3) converting the dropping speed of the calcium carbonate suspension in the step (2) according to the absolute dropping speed (namely the dropping time) for 30-180min.
Preferably, the dripping time is respectively as follows at different temperatures: 150-180min at 20deg.C; 100-130min at 40 ℃; 50-70min at 60 ℃; 30-40min at 80deg.C.
The stirring rate in the step (2) is maintained at 200 to 350rpm (e.g., 200rpm, 250rpm, 300rpm, 350 rpm).
The particle size of the spherical product in the step (2) can be adjusted by changing the reaction temperature: with the increase of the temperature, the reaction rate and the crystal growth rate of the calcium citrate are accelerated, and the spherical product with large particle size is obtained. When the reaction temperature is controlled at 20. At 40, 60 and 80 ℃, the average particle diameter (D) v (50) 29.6 microns, 68.1 microns, 116 microns, 173 microns, respectively.
The preparation method further comprises the steps of sequentially carrying out solid-liquid separation and drying on the substances obtained by the reaction crystallization. The solid-liquid separation mode is vacuum filtration. The drying method adopts normal pressure drying, the temperature is 50-55 ℃ (such as 50 ℃, 55 ℃ and the like), and the drying time is 12-24 hours (such as 12 hours, 16 hours, 20 hours, 24 hours and the like).
The calcium citrate spherical product has high particle mobility, the repose angle is between 28 and 32 degrees, and the test standard of the repose angle is GB/T11986-1989. The Span number representing the particle size distribution is calculated as in formula (1), wherein d 90 、d 10 、d 50 The volume fractions are respectively 10%, 50% and 90% of the cumulative particle size distribution, and a smaller Span value indicates a more uniform particle size distribution.
Span＝(d 90 -d 10 )/d 50 (1)
Further analysis, the invention also provides application of the calcium citrate spherical product: can be applied in the food field, including as a tabletting preparation, a food calcium enhancer and the like. The spherical product has better powder performance, improves the tabletting performance of the calcium supplement product and has the taste as a food calcium enhancer.
Compared with the current preparation method of calcium citrate, the method has the following beneficial effects:
a) The morphology of the crystals of calcium citrate obtained by the method is spherical, compared with other morphologies (for example: fibrous, blocky and powdery) greatly improves the powder properties of products such as morphology, fluidity and the like, and is also more beneficial to downstream processing treatment of the products.
b) Compared with the existing self-assembled spherical crystal, the spherical calcium citrate product prepared by the method has the advantages of better particle size distribution and difficult breakage, further simplifies the post-treatment process of the product, and simultaneously has better particle size distribution and uniform morphology as a food additive.
c) Compared with the reported spherical calcium citrate preparation process, the method effectively creates a reaction crystallization system for controlling the nucleation growth of the calcium citrate crystals, and has the advantages of low raw material price, simple process parameter control, no byproduct generation and the like. The particle size of the spherical particles obtained by the method is controlled based on the reaction temperature, and the corresponding reaction temperature can be selected according to the product requirement. The process scheme for tamping is provided to promote the calcium citrate to enter into a high-end calcium supplement product line.
Drawings
Fig. 1: SEM photograph of spherical calcium citrate in example 1 of the present invention (scale 20 μm);
fig. 2: SEM photograph of spherical calcium citrate in example 2 of the present invention (scale 50 μm);
fig. 3: SEM photograph of spherical calcium citrate in example 3 of the present invention (scale 100 μm);
fig. 4: SEM photograph of spherical calcium citrate in example 4 of the present invention (scale 100 μm);
fig. 5: particle size characterization graphs were performed using a markov 3000 for inventive examples 1, 2, 3, 4.
Fig. 6: XRD patterns of calcium citrate are prepared in the embodiment of the invention.
Detailed Description
Example 1:
(1) At 20 ℃, a mixed solution of 0.03g/mL of citric acid and water is prepared, and the mixture is stirred until the citric acid is completely dissolved in the water. A0.03 g/mL calcium carbonate-water suspension was prepared and stirred until the calcium carbonate was suspended in water. The molar ratio relation of the calcium carbonate and the citric acid is 1.4:1, a step of;
(2) Adding the calcium carbonate suspension into the citric acid solution at the same dropping speed within 1.5h, controlling the reaction temperature at 20 ℃, and maintaining the stirring speed of 250rpm until the dropping of the calcium carbonate suspension is completed for 1.5h, so that solid particles nucleate and grow into stable spherical particles;
(3) Vacuum filtering, washing with water, and drying at 50deg.C for 24 hr to obtain dried calcium citrate granule.
An electron microscope morphology characterization graph (SEM model HITACHI, TM3000, japan) of the product is shown in FIG. 1; XRD patterns (XRD model R-AXIS-RAPID, rigaku, japan) of the product are shown in figure 6; figure 5 shows that the spherical calcium citrate product has an average particle size of 29.6 microns, a Span number of 0.87 and an angle of repose of 32.
Example 2:
(1) At 40 ℃, a mixed solution of 0.01g/mL of citric acid-water is prepared, and stirred until the citric acid is completely dissolved in the water. Preparing a 0.01g/mL calcium carbonate-water suspension, and stirring until the calcium carbonate is suspended in water, wherein the molar ratio relationship of the calcium carbonate and the citric acid is 1.42:1, a step of;
(2) Adding the calcium carbonate suspension into the citric acid solution at the same dropping speed within 1h, controlling the reaction temperature at 40 ℃, and maintaining the stirring speed at 300rpm until the dropping of the calcium carbonate suspension is finished for 0.5h, so that solid particles nucleate and grow into stable spherical particles;
(3) Vacuum filtering, washing with water, and drying at 50deg.C for 16 hr to obtain dried calcium citrate granule.
The electron microscope morphology characterization graph of the product is shown in figure 2; fig. 5 shows the mean particle size of the spherical calcium citrate product of 68.1 μm, span number of 0.90, angle of repose of 31 °, test method as in example 1.
Example 3:
(1) At 60 ℃, a mixed solution of 0.15g/mL of citric acid-water is prepared, and stirred until the citric acid is completely dissolved in the water. Preparing a 0.3g/mL calcium carbonate-water suspension, and stirring until the calcium carbonate is suspended in water, wherein the molar ratio relationship of the calcium carbonate and the citric acid is 1.47:1, a step of;
(2) Adding the calcium carbonate suspension into the citric acid solution at the same dropping speed within 0.8h, controlling the reaction temperature at 60 ℃, and maintaining the stirring speed of 300rpm until the dropping of the calcium carbonate suspension is finished for 0.5h, so that solid particles nucleate and grow into stable spherical particles;
(3) Vacuum filtering, washing with water, and drying at 55deg.C for 12 hr to obtain dried calcium citrate granule.
An electron microscope morphology characterization graph (SEM model HITACHI, TM3000, japan) of the product is shown in FIG. 3; fig. 5 shows the mean particle size of the spherical calcium citrate product of 116 microns, span number of 0.81, angle of repose of 30 deg., test method as in example 1.
Example 4:
(1) At 80 ℃, a mixed solution of 0.1g/mL of citric acid-water is prepared, and stirred until the citric acid is completely dissolved in the water. Preparing a 0.5g/mL calcium carbonate-water suspension, and stirring until the calcium carbonate is suspended in water, wherein the molar ratio relationship of the calcium carbonate and the citric acid is 1.45:1, a step of;
(2) Adding the calcium carbonate suspension into the citric acid solution at the same dropping speed within 0.8h, controlling the reaction temperature at 80 ℃, and maintaining the stirring speed of 250rpm until the dropping of the calcium carbonate suspension is finished for 0.5h, so that solid particles nucleate and grow into stable spherical particles;
(3) Vacuum filtering, washing with water, and drying at 50deg.C for 16 hr to obtain dried calcium citrate granule.
An electron microscope morphology characterization graph (SEM model HITACHI, TM3000, japan) of the product is shown in FIG. 4; fig. 5 shows that the spherical calcium citrate product has an average particle size of 173 microns, a Span number of 0.77, an angle of repose of 28 deg., and the test method is the same as in example 1.
Comparative example 1:
the only difference from example 1 is that the dropping rate of the calcium carbonate suspension was changed to reduce the dropping time from 1.5 hours to 0.2 hours.
The product particles had an average particle size of 53 microns, span number of 1.26, angle of repose of 46 °, and severe agglomeration and poor sphericity. The test method was the same as in example 1.
Comparative example 2:
the difference from example 1 is that the calcium carbonate suspension and the citric acid concentration are each changed to 0.3g/mL, and other experimental conditions are the same as those of example 1.
The appearance of a large amount of fine crystals of the product causes the solution in the crystallizer to gradually gel until the last stirring paddle cannot stir suspended matters in the crystallizer, the appearance of the final product is characterized by sphere, short rod shape, needle shape and the like, and the repose angle of the product is 48 degrees.
Comparative example 3:
the difference from example 3 was that the stirring rate of the reaction crystals was changed to 600rpm, and other experimental conditions were ensured to be the same as in example 3.
The product has short flaky broken crystals and spherical crystals, and the surface of the spherical crystals is found to have polished marks through the electron microscope characterization, the average particle size of the product is reduced to 84 microns, and the particle size shows extremely uneven distribution of the double-peak distribution size.
Comparative example 4:
the water-soluble calcium salt and citrate proposed in the patent application CN104402705A are mixed and crystallized to obtain self-assembled agglomerated spherical particles and dispersed flaky crystals which can not be electrostatically attracted to agglomerate, and the particle size of the product is distributed between 10 and 100 microns (large spherical crystals and small dispersed flaky crystals).
As is clear from a comparison of example 1 and comparative example 1, when the drop time of the reactant calcium carbonate suspension is too short, the product appears to agglomerate, the sphericity is poor, the fluidity is reduced, and the average particle diameter is significantly increased, because the drop time is too short due to the excessively fast drop rate, the crystal growth sites are increased due to the increased supersaturation, and the powder performance of the product is reduced while the formation of the cauliflower-shaped spherical crystals (agglomerated crystals) is promoted.
As is clear from the comparison between the example 1 and the comparative example 2, when the initial concentration of the reactant components in the solution is out of the limit of the present invention, abnormal pasty phenomenon occurs, mass transfer and fluidity of the system are seriously affected, and the subsequent solid-liquid separation and drying time period is greatly prolonged, and the morphology of the product is observed to have a spherical shape and a short rod shape by a microscope, so that if pasty abnormal phenomenon occurs, the process efficiency and powder performance of the product are seriously affected.
As is clear from a comparison of example 3 and comparative example 3, when the stirring rate of the reaction operation exceeds the limit of the present invention, the shear force at each position in the system changes. The spherulites formed by the long flaky crystals are broken by larger shearing force in the growth process, so that a large number of broken crystals appear in the product, the particle size is changed, and the quality of the calcium citrate product is seriously affected.
As can be seen from the comparison of examples 1-4 and comparative example 4, the patent adopts citric acid and calcium carbonate to react and crystallize, regulates and controls the dripping speed to obtain spherical crystals with uniform particle size distribution, uniform morphology and stability, improves the powder performance of the spherical crystals, and is beneficial to realizing industrialized amplification.
According to the preparation method of the spherical calcium citrate with adjustable granularity, disclosed and provided by the invention, a person skilled in the art can select the temperature, the concentration of citric acid and calcium carbonate, the dripping speed and the residence time under the reaction crystallization system to obtain a calcium citrate product with good sphericity by referring to the content of the content, and can obtain the spherical calcium citrate with different particle sizes by adjusting the temperature as a key parameter. While the method of the present invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and combinations of the methods and products described herein can be made to practice the present technology without departing from the spirit or scope of the invention. It is expressly noted that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.
Claims (10)
1. The preparation method of the spherical calcium citrate crystal with adjustable granularity is characterized by comprising the following steps of:
(1) Preparing a citric acid-water solution with the concentration of 0.03-0.2 g/mL and a calcium carbonate-water suspension with the concentration of 0.03-0.3 g/mL;
(2) And (3) dropwise adding the calcium carbonate-water suspension into the citric acid-water solution, and stirring, reacting and crystallizing until the pH is 3.5-5 to obtain spherical calcium citrate particles.
2. The method of claim 1, wherein the molar ratio of calcium carbonate in the calcium carbonate-water suspension to citric acid in the citric acid-water solution in step (1) is 1.3-1.47.
3. The method according to claim 1, wherein the dropping time in the step (2) is 30 to 180 minutes.
Preferably, the dripping time is respectively as follows at different temperatures: 150-180min at 20deg.C; 100-130min at 40 ℃; 50-70min at 60 ℃; 30-40min at 80deg.C.
4. The method according to claim 1, wherein the stirring rate in the step (2) is 200 to 350rpm.
5. The method according to claim 1, wherein the curing time after the completion of the dropwise addition of the reactant in step (2) is 0.3 to 1h.
6. The method according to claim 1, wherein the step (2) further comprises sequentially subjecting the product obtained by the reaction crystallization to solid-liquid separation, washing and drying.
7. The method according to claim 1, wherein the solid-liquid separation is vacuum filtration.
8. The preparation method according to claim 1, wherein the drying mode is normal pressure drying, the drying temperature is 50-55 ℃, and the drying time is 12-24h.
9. The preparation method according to claim 1, wherein the spherical calcium citrate particles with adjustable particle size are obtained.
10. Use of the spherical calcium citrate particles according to claim 9 in a food additive.
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