CN111675627A - Preparation method of calcium aspartate - Google Patents
Preparation method of calcium aspartate Download PDFInfo
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- CN111675627A CN111675627A CN202010587808.XA CN202010587808A CN111675627A CN 111675627 A CN111675627 A CN 111675627A CN 202010587808 A CN202010587808 A CN 202010587808A CN 111675627 A CN111675627 A CN 111675627A
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- calcium
- aspartate
- calcium aspartate
- preparation
- homogenization
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- 229940034055 calcium aspartate Drugs 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OPSXJNAGCGVGOG-DKWTVANSSA-L Calcium L-aspartate Chemical compound [Ca+2].[O-]C(=O)[C@@H](N)CC([O-])=O OPSXJNAGCGVGOG-DKWTVANSSA-L 0.000 title claims abstract 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- 238000000265 homogenisation Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 9
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 8
- 229960005261 aspartic acid Drugs 0.000 claims description 8
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 5
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000007873 sieving Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- GYUKEMYHXWICKF-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;calcium Chemical compound [Ca].OC(=O)[C@@H](N)CC(O)=O GYUKEMYHXWICKF-DKWTVANSSA-N 0.000 description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 19
- 229960005069 calcium Drugs 0.000 description 17
- 239000011575 calcium Substances 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- 229960003563 calcium carbonate Drugs 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229940024606 amino acid Drugs 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 235000003704 aspartic acid Nutrition 0.000 description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 210000000936 intestine Anatomy 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 208000037147 Hypercalcaemia Diseases 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 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 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229940069978 calcium supplement Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 210000002064 heart cell Anatomy 0.000 description 1
- 230000000148 hypercalcaemia Effects 0.000 description 1
- 208000030915 hypercalcemia disease Diseases 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 210000004347 intestinal mucosa Anatomy 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000005229 liver cell Anatomy 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 210000000813 small intestine Anatomy 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of bioengineering, and particularly relates to a preparation method of calcium aspartate, which specifically comprises the following steps: s1, reacting raw materials; s2, primary homogenizing; s3, homogenizing for the second time; s4, drying, sieving and packaging. The preparation method of the calcium aspartate provided by the invention has the advantages that the cost and the reaction efficiency are considered, the high-purity calcium aspartate is obtained by compounding the calcium carbonate and the calcium hydroxide, the economic value is better, the resources are fully utilized, and the social benefit is greater; the preparation method is simple and convenient, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of bioengineering, and particularly relates to a preparation method of calcium aspartate.
Background
Calcium is a major element essential to the human body. It not only constitutes the bones and teeth of the human body, but also participates in various physiological activities. According to the research data of related nutrition, the residents in China generally have insufficient calcium and nutrition, the related diseases caused by the calcium deficiency are known by the public, and the attention of people is gradually drawn to the calcium supplement. At present, calcium agents sold in the market include calcium carbonate, calcium lactate, calcium hydrogen phosphate, calcium citrate, amino acid chelated calcium and the like.
The calcium aspartate is one of amino acid chelated calcium, and is prepared by refining every two amino acid molecules and one calcium ion under the special conditions of high pressure and high frequency. The chelated calcium molecule has stable structure, the calcium atom is connected with the nitrogen atoms in the two amino acid molecules by a coordination bond and is connected with the oxygen atom of the carboxyl group by a covalent bond to form two five-membered rings with stable structure, the special chelated structure not only ensures that the calcium atom is not easily influenced by acid and alkali in the stomach and intestine, but also ensures that the chelated calcium can be covalently combined with glutathione on the cell membrane of the small intestine mucosa and directly enters the intestinal mucosa to be completely absorbed by the human body.
The aspartic acid chelated calcium has the following characteristics: 1. the absorption rate is up to more than 95 percent and is 3 to 4 times of that of other calcium products; 2. is easy to dissolve in water, and the solubility of the calcium carbonate is 400 times of that of edible calcium carbonate, so that the calcium carbonate is easier to absorb by a human body; 3. vitamin D is not needed to be added, no precipitate is generated, no calculus is formed, and the method is safer; 4. the pH value (pH value) is neutral, basically accords with the pH value of a human body, and has no stimulation to the stomach and intestine; 5. after entering blood, a slow flowing calcium reservoir is formed, hypercalcemia cannot be caused by high plasma calcium concentration, and waste cannot be caused by kidney discharge; 6. has good protection and repair effects on damaged heart and liver cells, accelerates the excretion of in vivo metabolites, and improves the immunity of human bodies.
The inorganic calcium source for the preparation of calcium aspartate is generally calcium oxide or calcium hydroxide or calcium carbonate. The calcium carbonate has poor solubility, the yield of the calcium aspartate prepared by singly using the calcium carbonate as a raw material is relatively low, and the reaction efficiency is slow; the price of calcium hydroxide is relatively high, and the preparation of calcium aspartate by only using calcium hydroxide as a raw material has the disadvantage of production cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing calcium aspartate by compounding calcium carbonate and calcium hydroxide as an inorganic calcium source.
The preparation method of the calcium aspartate specifically comprises the following steps:
s1, mixing 0.9-1.1 parts of L-aspartic acid, 0.1-0.3 part of calcium carbonate, 0.1-0.3 part of calcium hydroxide and 3.2 parts of pure water according to parts by weight, and reacting at 65-85 ℃ and pH of 5.3-6.0 for 0.5-1 h; when the pH value of the reaction liquid is 6.1-6.5, preserving the heat for 5-10 min;
s2, primary homogenization: filtering the reaction solution obtained in the step S1 under 60-80MPa, and homogenizing for 30-60 min;
s3, secondary homogenization: filtering the reaction solution after primary homogenization at 90-130MPa, and then homogenizing for 150-300 min;
and S4, standing and precipitating the reaction solution after secondary homogenization, separating to obtain a supernatant, and drying to obtain the calcium aspartate.
Preferably, the filtration in S2 is performed by a 100-mesh screen, and the feeding speed during homogenization is 500-1000L/h; the filtration in step S3 is performed by a 500-mesh screen, and the feeding speed during homogenization is 120-200L/h.
Preferably, the drying in S4 is spray drying at 250 ℃ and 180 ℃, and the water content of the dried calcium aspartate is less than or equal to 5%.
Preferably, the particle size of the calcium aspartate in S4 is 60-120 meshes.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the calcium aspartate comprehensively considers the cost of the calcium carbonate and the reaction rate of the raw materials, the calcium carbonate is low in price but is insoluble in water, and when the calcium carbonate is used as the raw material to react with the aspartic acid, the solubility is not high, so that the reaction efficiency is influenced, and the energy consumption is improved; insoluble calcium carbonate is easy to agglomerate in the reaction kettle, and the heat transfer of the reaction kettle is influenced; calcium hydroxide as a strong base reacts with aspartic acid more easily and fully, has certain solubility in water, has reaction efficiency far higher than that of calcium carbonate, but as an inorganic calcium source, has a price far higher than that of calcium carbonate, and causes the product cost to rise; the invention gives consideration to the cost and the reaction efficiency, and the high-purity calcium aspartate is obtained by compounding the calcium carbonate and the calcium hydroxide, thereby having better economic value, fully utilizing resources and having greater social benefit; the preparation method is simple and convenient, and is suitable for large-scale industrial production.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following embodiments are further described, but the present invention is not limited to the following embodiments.
Example 1
The preparation method comprises the following steps:
s1, burdening reaction: adding the raw materials into a reaction kettle according to a proportion, and reacting for 0.5h at 65 ℃ and pH of 5.3; when the pH value of the reaction liquid is 6.1, preserving the temperature for 5 min;
s2, primary homogenization: filtering the reaction solution through a 100-mesh pipeline filter under the condition of 60MPa, then feeding the reaction solution into a homogenizer, controlling the feeding speed to be 500L/h, homogenizing for 30min, and then collecting the filtrate;
s3, secondary homogenization: filtering the filtrate obtained in the step S2 by using a 500-mesh screen under the condition of 90MPa, then feeding the filtrate into a homogenizer, controlling the feeding speed to be 120L/h, homogenizing for 150min, and standing the obtained homogenized material liquid overnight;
s4, spray drying: drying the supernatant of the calcium aspartate after standing by using an instantaneous high-temperature technology of spray drying at the temperature of 200 ℃, and controlling the water content of the product to be not higher than 5%;
s5, sieving: and sieving the spray-dried calcium aspartate powder by a sieve of 80 meshes, and subpackaging into 90 g/barrel to obtain the finished calcium aspartate.
The detection method is carried out according to the indexes of GB 29226: the product contains calcium 12.8%, L-aspartic acid 82.2%, pH 7.05, water 4.51%, lead 0.09mg/kg, and total arsenic 0.13 mg/kg.
Example 2
The preparation method comprises the following steps:
s1, burdening reaction: adding the raw materials into a reaction kettle according to a proportion, and reacting for 1.0h at 85 ℃ and pH of 6.0; when the pH value of the reaction liquid is 6.5, preserving the temperature for 10 min;
s2, primary homogenization: filtering the reaction solution through a 100-mesh pipeline filter under the condition of 80MPa, feeding the reaction solution into a homogenizer at a feeding speed of 1000L/h, and collecting filtrate after homogenizing for 60 min;
s3, secondary homogenization: filtering the primary homogenized reaction solution by using a 500-mesh screen under the condition of 130MPa, then feeding the filtered reaction solution into a homogenizer at a feeding speed of 200L/h, homogenizing for 300min, and standing the homogenized material solution overnight;
s4, spray drying: drying the supernatant of the calcium aspartate after standing by using an instant drying technology of spray drying at 180 ℃, and controlling the water content of the product to be not higher than 5%;
s5, sieving: the calcium aspartate powder after spray drying is sieved by a sieve of 80 meshes and is subpackaged into 90 g/barrel to obtain the finished product.
The detection method is carried out according to the indexes of GB 29226: the product contains calcium 12.7%, L-aspartic acid 82.3%, pH 7.00, water 4.38%, lead 0.05mg/kg, and total arsenic 0.15 mg/kg.
Example 3
The preparation method comprises the following steps:
s1, burdening reaction: adding the raw materials into a reaction kettle according to a proportion, and reacting for 1h at 70 ℃ and pH of 5.5; when the pH value of the reaction liquid is 6.5, preserving the temperature for 8 min;
s2, primary homogenization: filtering the reaction solution through a 100-mesh pipeline filter under the condition of 70MPa, feeding the reaction solution into a homogenizer at the feeding speed of 800L/h, and collecting filtrate after homogenizing for 60 min;
s3, secondary homogenization: filtering the primary homogenized reaction solution by using a 500-mesh screen under the condition of 120MPa, then feeding the filtered reaction solution into a homogenizer at the feeding speed of 150L/h, homogenizing for 200min, and standing the homogenized material solution overnight;
s4, spray drying: drying the supernatant of the calcium aspartate after standing by using an instant drying technology of spray drying at 250 ℃, and controlling the water content of the product to be not higher than 5%;
s5, sieving: and (3) sieving the spray-dried calcium aspartate powder by a sieve of 80 meshes, and subpackaging into 90 g/barrel to obtain the finished product.
The detection method is carried out according to the indexes of GB 29226: the product contains calcium 12.5%, L-aspartic acid 82.0%, pH 7.02, water 4.43%, lead 0.03mg/kg, and total arsenic 0.11 mg/kg.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments of the present invention have been described for the purpose of preventing redundancy, but once the basic inventive concept is known, those skilled in the art may make other variations and modifications to the embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. The preparation method of calcium aspartate is characterized by comprising the following steps:
s1, mixing 0.9-1.1 parts of L-aspartic acid, 0.1-0.3 part of calcium carbonate, 0.1-0.3 part of calcium hydroxide and 3.2 parts of pure water according to parts by weight, and reacting at 65-85 ℃ and pH of 5.3-6.0 for 0.5-1 h; when the pH value of the reaction liquid is 6.1-6.5, preserving the heat for 5-10 min;
s2, primary homogenization: filtering the reaction solution obtained in the step S1 under 60-80MPa, and homogenizing for 30-60 min;
s3, secondary homogenization: filtering the reaction solution after primary homogenization at 90-130MPa, and then homogenizing for 150-300 min;
and S4, standing and precipitating the reaction solution after secondary homogenization, separating to obtain a supernatant, and drying to obtain the calcium aspartate.
2. The method for preparing calcium aspartate according to claim 1, wherein the filtration in S2 is performed by passing through a 100-mesh screen, and the feeding speed during homogenization is 500-1000L/h; the filtration in step S3 is performed by a 500-mesh screen, and the feeding speed during homogenization is 120-200L/h.
3. The method for preparing calcium aspartate according to claim 1, wherein the drying in S4 is spray drying at 180 ℃ and 250 ℃, and the water content of the dried calcium aspartate is 5% or less.
4. The method for producing calcium aspartate according to claim 1, wherein the particle size of the calcium aspartate in S4 is 60 to 120 mesh.
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Cited By (1)
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CN115073315A (en) * | 2022-07-06 | 2022-09-20 | 淄博润聚生物科技有限公司 | Synthetic method of sodium aspartate and calcium aspartate |
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