CN101973899A - Novel production process of nanometer calcium amino acid chelate with high efficiency - Google Patents
Novel production process of nanometer calcium amino acid chelate with high efficiency Download PDFInfo
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- CN101973899A CN101973899A CN 201010279421 CN201010279421A CN101973899A CN 101973899 A CN101973899 A CN 101973899A CN 201010279421 CN201010279421 CN 201010279421 CN 201010279421 A CN201010279421 A CN 201010279421A CN 101973899 A CN101973899 A CN 101973899A
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- amino acid
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Abstract
The invention discloses a novel production process of nanometer calcium amino acid chelate based on the energy conversion of a chelant (amino acid) and the calcium ions. The process comprises the following steps: preparing the calcium compound and the chelant (amino acid) of the reactants into a water suspension solution with a proper grammole proportion; injecting the solution into an SY-NANO high pressure fluid nano-grinding after the pretreatment; performing the strong impacting pressure, the instantaneous high temperature and the ultrahigh frequency ultrasonic wave together on the suspension solution based on the cavitation collapse action principle to break the covalent bond of the amino acid to form the dentate; obtaining the calcium amino acid chelate by the chelation reaction of the dentate and the calcium ions. The key point of the invention lies in applying the Nanotechnology into the production of the calcium amino acid chelate, and improving the relevant parameters of the chelation reaction simultaneously. The novel process has the advantages of short period, high efficiency and continuous production. The annual output of one production line can reach 200 tons. The invention has significant economic value and social significance on the quality improvement of the calcium supplementation products and the health advancement of the people.
Description
Technical field
The present invention relates to a kind of efficient nano calcium amino acid chelate new process of production.
Background technology
Calcium be ensure baby's normal development, to keep the person of growing up healthy and to delay the elderly's aging course necessary; It seems that totally its in-vivo content is not high, but be absolutely necessary; Calcium constituent will be kept certain proportion relation in vivo, in case overbalance, the people know from experience various diseases.We know that calcium is the highest metallic element of in-vivo content, 2% (1200-1400 gram) of about percentage of liveweight, and wherein about 99% is distributed in bone and the tooth, and all the other 1% exist in extracellular fluid, blood and the soft tissue with free or bonded ionic condition.Calcium is not only the main component that constitutes human body bone ilium and tooth, and its physiological function is many-sided.The shortage of calcium can cause multiple disease, and is particularly particularly outstanding to baby, pregnant woman and the elderly's influence.Baby's dysplasia, bowlegs, pigeon breast, rickets, of short and small stature; Be easy to get osteoporosis etc. of old man is all sent out because of calcium deficiency causes.China's nutrition reconnaissance information for the third time shows: account for 50% in Chinese children calcium deficiency or calcium under-nutrition person.Usually the needed by human body metallic element mainly absorbs from food, approximately need every day 400 milligrams calcium to upgrade as the grownup, but generally speaking, the calcium that people absorb from food only has the 150-200 milligram, and that insufficient section can only replenish by taking calcium preparation.Therefore, the calcium constituent quantity not sufficient that human body still will absorb from food then can only remedy by taking corresponding calcium preparation, to keep the state of health of health.
Traditional calcium preparation is of a great variety on the market, and rough segmentation is nothing more than inorganic calcium salt such as lime carbonate, secondary calcium phosphate etc.Also having with shell, pearl oyster, bone meal is Calcium of intensifiens (based on calcium hydroxide) and the organic acid calcium salt that raw material is made, as calglucon, citrate of lime, calcium lactate, threonic acid calcium etc.These calcium preparations are ingested and all will be dissociated into calcium ion behind the gi tract, then by carrying calsequestrin again by intestinal absorption, the calcium preparation of this ionic absorption pattern is exactly nearly all calcium-supplementing preparation of supplying in the market, also is traditional calsium supplement of continuing to use decades, and they have following shortcoming:
1. the general indissoluble of traditional calsium supplement is separated, and what some alkalescence was stronger has intense stimulus to stomach.
2. traditional calsium supplement quality is difficult to be controlled, and the heavy metal lead that contains, arsenic etc. usually exceed standard.
3. the ionic calcium agent is adapted at absorbing under the sour environment, but little enteron aisle is alkalescence, and the calcium agent is difficult for dissolving, so absorb difficulty.
The ionic calcium agent often disturb by composition in the meals (as oxalic acid etc.), influence the absorption of calcium agent.
In view of the various shortcoming and defect that traditional calcium preparation exists, therefore researching and developing new calcium preparation and setting up new production process has realistic meaning very much.
Put into practice for many years through the doctor patient, generally believe that calcium amino acid chelate is the outstanding person in known numerous calcium-supplementing preparation, so be subjected to favoring widely.U.S. food management association once was defined as with regard to amino-acid chelate in 1987: the metal ion of soluble metallic salt and the amino product that forms coordinate bond, metal ion and amino acid whose mol ratio are 1: 2~1: 3, various amino acid whose molecular-weight average are approximately 150, and its inner complex molecular weight is no more than 800.In brief, inner complex is metal ion and has the amino acids formed a kind of heterocycle structure material of unpaired electron part.The structure of inner complex is determined by synthesis condition.Chelatropic reaction must carry out under appropriate condition, and these conditions comprise the mol ratio of metal ion and part, the pH value of medium during reaction (as the aqueous solution) and dissolubility of reactants etc.By effective synthetic method, the nano-aminophenol inner complex that obtains is a kind of metastable compound, and wherein Sauerstoffatom in metal ion and the a-amino acid carboxyl and alpha-amino nitrogen form a five-membered ring structure.This five-membered ring structure is to be made of the nitrogen-atoms in the carbon atom of the Sauerstoffatom of atoms metal, carboxyl, carbonyl, alpha-carbon atom and the alpha-amino group.Practical structures depends on whether the mol ratio of metal ion and part and metal ion form coordinate bond with carboxyl oxygen.
Up to now; the preparation method of calcium amino acid chelate; mainly contain chemical synthesis, electrolysis one semi-transparent embrane method and ion exchange method etc.; the subject matter of these methods: reaction is slow, the time is long, productive rate is low; reaction not exclusively; and remove and not participate in difficulty of synthetic residual reactant, therefore, large-scale production is difficulty.
Summary of the invention
The object of the present invention is to provide a continuity efficient, quick, mass-producing to produce the chelated calcium novel process of nano-aminophenol.
Efficient nano calcium amino acid chelate new process of production provided by the invention is for being the wet processing of reaction medium with water, may further comprise the steps: calcium cpd and amino acid are suspended in water make suspension, the pH value of this suspension is transferred on the described amino acid whose iso-electric point, the granularity of suspended particle is less than 30 microns in this suspension, calcium constituent in the described calcium cpd and described amino acid whose mol ratio are 1: 2~3, and the ratio of the weight of described calcium cpd and amino acid whose weight and water is 25~35: 75~85; Described suspension pumped into carry out chelatropic reaction in the high pressure fluid nanometer mill and obtain limpid solution, reaction conditions is as follows: operating pressure is controlled at 100~120MPA, rotating speed 250~350r/min, 70~90 ℃ of temperature, ultrasonic frequency 50~70Hz; Dry described solution obtains white crystal, and this white crystal is nano-aminophenol chelating calcium.
The pH value of described suspension is preferably 7.2~7.5.
Described amino acid can be for being selected from L-Ala, Aspartic Acid, amino-succinamic acid, L-glutamic acid, glu famine, arginine, Methionin, Histidine, glycine, proline(Pro) and the oxyproline one or more.Also can be small-molecule peptide.
Described amino acid is preferably the L-Aspartic Acid.
Described calcium cpd is preferably Ca (OH)
2And/or CaO.
Preferably, described high pressure fluid nanometer mill is SY-NANO high pressure fluid nanometer mill, during described suspension grinds with 150~250 liters/hour the described SY-NANO high pressure fluid of input speed pump people nanometer by high-pressure pump.More preferably, described operating pressure is controlled at 105~115MPA, and described rotating speed is 280~320r/min, and described input speed is 180~220 liters/hour.
Preferably, calcium constituent in the described calcium cpd and described amino acid whose mol ratio are 1: 2.1~2.4, and the ratio of the weight of described calcium cpd and amino acid whose weight and water is 30: 75~85.
Utilize the nano-aminophenol chelating calcium molecular structure of prepared provided by the invention more stable, solubility property is good, absorb easily, the bioavailability height, calcium contents is about 10~15%, poisonous metal constituent contents such as mercury, lead, arsenic and chromium are substantially free of impurity such as muriate and vitriol well below national standard.Therefore, after processed, product can be directly used in food or medicine.
Embodiment
Efficient nano calcium amino acid chelate new process of production provided by the invention adopts wet processing to prepare Aspartic Acid chelating calcium, is reaction medium, carrier wave body and energy carrier with water.The synthetic of nano-aminophenol inner complex is to carry out in nano molecular energy transformation container (high pressure fluid nanometer mill).In the embodiment of introducing below, employed high pressure fluid nanometer mill is SY-NANO (equipment chain name) high pressure fluid nanometer mill, cardinal principle is: will be through the certain density chelating amino acids agent and the calcium cpd suspension of pulverizing, homogeneous, filtration treatment, and the solid granularity should be less than 30 microns in the suspension; Inject in the nano molecular energy container with high-pressure pump then; utilize this equipment air pocket principle of caving in; produce very strong percussive pressure; the ultrasonic wave of TRANSIENT HIGH TEMPERATURE and ultra high frequency; acting in conjunction is in metallic compound and part amino acid; make solia particle or the fragmentation of liquid droplet in the liquid or be dispersed into nanometer scale, cause amino acid covalent linkage homolysis to form aglucon and metal ion (central ion) hair tonic chelatropic reaction, generate the nano-aminophenol inner complex.Further, preferable a kind of embodiment may further comprise the steps successively: raw material is chosen (food grade: calcium cpd, amino acid, pure water); Prepare burden in proportion; Drop into stirrer (stirring 30-40min); Suspension filtered (filter screen 400 orders); Transfer pH (7.4); Filtrate pumps into the SY-200L high pressure homogenizer; Homogenizing fluid pumps in the SY-NANO high pressure fluid nanometer mill (rotating speed 300r/min); Nanometer chelating calcium liquid spraying drying (210 ℃ of air intakes, 90 ℃ of air-out); Quality inspection; Metering packing; Deep processing or warehouse-in store.
Below by embodiment the present invention is further specified.The conditioned disjunction step of not listing in following examples is all consistent with above description.
Embodiment 1
Will be through selected Ca (OH)
2With the L-Aspartic Acid, by 1: 2.2 batching of mole ratio, reactant and pure water be to mix at 30: 80 with part by weight, fully stir, the acidity of suspension is transferred to PH7.4, and through colloidal mill, clarifixator is handled, reactant is fully dissolved and disperse, remove bigger particle in the suspension through the filter elimination again, guarantee that the solid substance granularity is less than 30 microns, then in the suspension, suspension of reactants is pumped in the SY-NANO high pressure fluid nanometer mill, its operating pressure is controlled at about 110MPA, rotating speed 300r/min, 70~90 ℃ of temperature, ultrasonic frequency 50~70Hz input speed is per hour 200 liters, all the chelatropic reaction processes are finished in that the nanometer materialization is indoor, and are last, obtain limpid L-Aspartic Acid and sting and close calcium solution, reaction solution is spray-dried, obtains white crystalline powder shape product.
Embodiment 2
Except Ca (OH)
2With the L-Aspartic Acid by outside mole ratio 1: 2.5 batching, other condition is all identical with enforcement 1 with schedule of operation.
Embodiment 3
Except with Ca (OH)
2Replace with CaO, by outside 1: 2.2 batching of mole ratio, other condition is all identical with enforcement 1 with schedule of operation with CaO and L-Aspartic Acid.
Embodiment 4
Except the L-Aspartic Acid is replaced with the L-Ala, other condition is all identical with enforcement 1 with schedule of operation.
Embodiment 5
Except the L-Aspartic Acid is replaced with the amino-succinamic acid, other condition is all identical with enforcement 1 with schedule of operation.
Embodiment 6
Except the L-Aspartic Acid is replaced with the L-glutamic acid, other condition is all identical with enforcement 1 with schedule of operation.
Embodiment 7
Except the L-Aspartic Acid is replaced with the arginine, other condition is all identical with enforcement 1 with schedule of operation.
Embodiment 8
Except the L-Aspartic Acid is replaced with the glycine, other condition is all identical with enforcement 1 with schedule of operation.
The product that embodiment 1~8 obtains is white powder, odorless, and slightly salty delicate flavour, soluble in water, the visible impurity of no naked eyes does not have impurity such as vitriol, muriate.Through infrared spectra and EFI mass spectroscopy, be and contain calcium chelate.The L-asparagus fern calcium amino acid chelate that the chemical structure analysis result obtains with embodiment 1 and 2 is that example is described as follows: described L-asparagus fern calcium amino acid chelate molecular formula is Ca[HCOOCH (NH
2) CH
2COO]
2, molecular weight is 304.2, structure is as follows:
The physical and chemical index of the product that embodiment 1~8 obtains is as shown in table 1 below:
Table 1 physical and chemical index
Each data obtains with conventional determining method in the table 1, meets state-set standard (GB/T).
The mensuration of calcium: EDTA (ethylenediamine tetraacetic acid (EDTA)) complexometry and calcium meter colorimetry; Determined amino acid: triumphant formula nitriding; Specific rotation is measured: the specific rotation instrument is measured; Moisture determination: dry weighting method; Determining heavy metals: determining heavy metals instrument.
By above analysis as can be known, except that the nano-aminophenol inner complex, by product has only water in the reaction product of the present invention, does not produce any deleterious byproduct.Its synthetic product calcium amino acid chelate molecular structure stabilized, good water solubility absorbs easily; Heavy metal content such as lead, mercury, arsenic are well below national standard; So, just can be directly used in pharmacy or food-processing after the product dehydration.
Claims (8)
1. efficient nano calcium amino acid chelate new process of production, for being the wet processing of reaction medium with water, it is characterized in that, may further comprise the steps: calcium cpd and amino acid are suspended in water make suspension, the pH value of this suspension is transferred on the described amino acid whose iso-electric point, the granularity of suspended particle is less than 30 microns in this suspension, calcium constituent in the described calcium cpd and described amino acid whose mol ratio are 1: 2~3, and the ratio of the weight of described calcium cpd and amino acid whose weight and water is 25~35: 75~85; Described suspension pumped into carry out chelatropic reaction in the high pressure fluid nanometer mill and obtain limpid solution, reaction conditions is as follows: operating pressure is controlled at 100~120MPA, rotating speed 250~350r/min, 70~90 ℃ of temperature, ultrasonic frequency 50~70Hz; Dry described solution obtains white crystal, and this white crystal is nano-aminophenol chelating calcium.
2. efficient nano calcium amino acid chelate new process of production according to claim 1 is characterized in that the pH value of described suspension is 7.2~7.5.
3. efficient nano calcium amino acid chelate new process of production according to claim 1, it is characterized in that described amino acid is to be selected from L-Ala, Aspartic Acid, amino-succinamic acid, L-glutamic acid, glu famine, arginine, Methionin, Histidine, glycine, proline(Pro) and the oxyproline one or more.
4. efficient nano calcium amino acid chelate new process of production according to claim 1 is characterized in that described amino acid is the L-Aspartic Acid.
5. efficient nano calcium amino acid chelate new process of production according to claim 1 is characterized in that, described calcium cpd is Ca (OH)
2And/or CaO.
6. according to each described efficient nano calcium amino acid chelate new process of production of claim 1~5, it is characterized in that, described high pressure fluid nanometer mill is SY-NANO high pressure fluid nanometer mill, during described suspension grinds with 150~250 liters/hour the described SY-NANO high pressure fluid of input speed pump people nanometer by high-pressure pump.
7. efficient nano calcium amino acid chelate new process of production according to claim 6 is characterized in that described operating pressure is controlled at 105~115MPA, and described rotating speed is 280~320r/min, and described input speed is 180~220 liters/hour.
8. efficient nano calcium amino acid chelate new process of production according to claim 6, it is characterized in that, calcium constituent in the described calcium cpd and described amino acid whose mol ratio are 1: 2.1~2.4, and the ratio of the weight of described calcium cpd and amino acid whose weight and water is 30: 75~85.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104000191A (en) * | 2014-02-07 | 2014-08-27 | 岳智广 | A novel chelated calcium |
CN106187798A (en) * | 2016-07-21 | 2016-12-07 | 西安利君制药有限责任公司 | A kind of chelated calcium preparation method of aminoacid nanometer |
CN106631848A (en) * | 2017-01-03 | 2017-05-10 | 河北农业大学 | Method for preparing calcium lysine chelate with shell of Argopecten irradias as calcium source |
CN106858610A (en) * | 2017-03-01 | 2017-06-20 | 岳智广 | The preparation method of a kind of amino acid chelated calcium and including the chelated calcium calcium-supplementing preparation |
CN107417556A (en) * | 2017-05-23 | 2017-12-01 | 王广生 | L aspartase calciums and preparation method thereof |
CN111592024A (en) * | 2020-04-24 | 2020-08-28 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
CN113004163A (en) * | 2021-03-17 | 2021-06-22 | 三亚百泰生物科技有限公司 | Preparation method and equipment of nano amino acid chelated calcium |
CN114230685A (en) * | 2021-12-21 | 2022-03-25 | 美泰科技(青岛)股份有限公司 | Preparation process of chondroitin sulfate chelated calcium with anti-osteoporosis function |
CN115611759A (en) * | 2022-12-08 | 2023-01-17 | 维卓(嘉兴)营养品有限公司 | Preparation method of (R) -3-aminobutyric acid chelated calcium |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104000191A (en) * | 2014-02-07 | 2014-08-27 | 岳智广 | A novel chelated calcium |
CN106187798A (en) * | 2016-07-21 | 2016-12-07 | 西安利君制药有限责任公司 | A kind of chelated calcium preparation method of aminoacid nanometer |
CN106631848A (en) * | 2017-01-03 | 2017-05-10 | 河北农业大学 | Method for preparing calcium lysine chelate with shell of Argopecten irradias as calcium source |
CN106858610A (en) * | 2017-03-01 | 2017-06-20 | 岳智广 | The preparation method of a kind of amino acid chelated calcium and including the chelated calcium calcium-supplementing preparation |
CN106858610B (en) * | 2017-03-01 | 2018-05-22 | 岳智广 | The preparation method of a kind of amino acid chelated calcium and including the chelated calcium calcium-supplementing preparation |
CN107417556A (en) * | 2017-05-23 | 2017-12-01 | 王广生 | L aspartase calciums and preparation method thereof |
CN111592024A (en) * | 2020-04-24 | 2020-08-28 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
CN111592024B (en) * | 2020-04-24 | 2022-09-06 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
CN113004163A (en) * | 2021-03-17 | 2021-06-22 | 三亚百泰生物科技有限公司 | Preparation method and equipment of nano amino acid chelated calcium |
CN114230685A (en) * | 2021-12-21 | 2022-03-25 | 美泰科技(青岛)股份有限公司 | Preparation process of chondroitin sulfate chelated calcium with anti-osteoporosis function |
CN114230685B (en) * | 2021-12-21 | 2022-12-20 | 美泰科技(青岛)股份有限公司 | Preparation process of chondroitin sulfate chelated calcium with anti-osteoporosis function |
CN115611759A (en) * | 2022-12-08 | 2023-01-17 | 维卓(嘉兴)营养品有限公司 | Preparation method of (R) -3-aminobutyric acid chelated calcium |
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