CN101602685A - With the shellfish processing waste is the calcium-glutamate chelate synthesis method in calcium source - Google Patents
With the shellfish processing waste is the calcium-glutamate chelate synthesis method in calcium source Download PDFInfo
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- CN101602685A CN101602685A CNA2009101510231A CN200910151023A CN101602685A CN 101602685 A CN101602685 A CN 101602685A CN A2009101510231 A CNA2009101510231 A CN A2009101510231A CN 200910151023 A CN200910151023 A CN 200910151023A CN 101602685 A CN101602685 A CN 101602685A
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- glutamate chelate
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Abstract
The present invention relates to the shell is the novel method that calcium-glutamate chelate is synthesized in the calcium source.Main process comprises shell pre-treatment, synthetic, purifying, stoving process step.Earlier with shell with 0.05M salt acid soak, oven dry, pulverizing and elutriation handle calcium source oyster shell whiting, by L-glutamic acid and oyster shell whiting (the lime carbonate calcium contents is in 95%) mol ratio is 2: 1.0~1.2 batchings, and add the distilled water of 30~35 times of oyster shell whiting weight, stirring also is heated to 70~75 ℃, insulation chelating 1.0~1.5 hours, cooling, suction filtration; The gained clear liquid is evaporated to the stiff paste shape, adds 85~90% ethanol, stir standing over night; Suction filtration, insolubles 95% ethyl alcohol recrystallization, suction filtration; Above-mentioned gained crystallization is promptly got product of calcium-glutamate chelate in 130 ℃ of oven dry.Technology of the present invention is easy, but the multiple shell of higher value application, and product can be used as calsium supplement, for uses such as salt agent and seasoningss.
Description
Technical field:
The present invention relates to a kind of shellfish processing waste (oyster shells, scallop shell etc.) that utilizes for the calcium source, through high-valued, clean processing step, what realize the shellfish processing waste comprehensive utilization is the calcium-glutamate chelate synthesis method in calcium source with the shellfish processing waste.
Background technology:
The sickness rate of diseases such as the hypertension that the sodium salt picked-up is too high and calcium deficiency causes aspect diet, obesity increases year by year and the trend of becoming younger occurs, and modern medicine has proved that also calcium deficiency is bigger than the hazardness of high sodium.Therefore, the raising of calcium contents is to solve one of main path of calcium deficiency problem in the food.
At present, widely used calcium-supplementing preparation majority is a calcium salt, as calcium phosphate, lime carbonate, calglucon, calcium acetate, calcium lactate etc.With these calcium salts relatively, absorption, toxicity are little more and more to be subjected to extensive attention to calcium amino acid chelate because of being easy to.The calcium amino acid chelate constructional feature is that per two amino acid moleculars are sequestered in by chelating technology with a calcium ion, the calcium constituent that is positioned at five-ring inner complex center can pass through the intestinal villi brush border, integral form with amino acid or peptide directly absorbs from intestinal mucosa, thereby exempt from some physical and chemical factors, as the pH value, lipid, fiber, oxalic acid, oxide compound, phytic acid, the influence of phosphoric acid salt and mycotoxin etc., thereby can effectively be absorbed, its biology utilization ratio height, thus it is poorly soluble to efficiently solve traditional calcium source, specific absorption is low, side effect is big, produce problems such as calculus.
China's fishery products aboundresources has accounted for 36% of world's fishery products total amount.Wherein, a large amount of wastes (oyster shells, scallop shell etc.) of producing of shellfish processing still remain Application and Development.The present invention is conceived to the higher value application of shellfish processing waste; utilize it to enrich the calcium source and prepare the high purity calcium-glutamate chelate; not only can be used as liver and gall diseases adjuvant drug, calsium supplement; can be used as again for salt agent and seasonings and use; thereby it is turned waste into wealth, also significant to the protection environment simultaneously.
Summary of the invention:
The object of the present invention is to provide a kind of novel method of synthesizing calcium-glutamate chelate with the shell for the calcium source.
To achieve these goals, main process of the present invention comprises shell pre-treatment, synthetic, purifying, stoving process step, wherein
Shell pre-treatment: shell is scrubbed adsorptives such as removing shell surface silt with 0.05M salt acid soak after 1 hour, through 100 ℃ of oven dry, pulverized 60 mesh sieves, handle promptly to get through the tap water flying method again and synthesize calcium-glutamate chelate usefulness calcium source oyster shell whiting;
Synthetic: by L-glutamic acid and oyster shell whiting (the lime carbonate calcium contents is in 95%) mol ratio is 2: 1.0~1.2 batchings, and add the distilled water of 30~35 times of oyster shell whiting weight, stirring also is heated to 70~75 ℃, insulation chelating 1.0~1.5 hours, make the L-glutamic acid complete reaction, cooling, suction filtration is removed excessive oyster shell whiting;
Purifying: above-mentioned suction filtration gained clear liquid is evaporated to the stiff paste shape, adds 85~90% ethanol, stir standing over night.Suction filtration, insolubles 95% ethyl alcohol recrystallization, suction filtration;
Oven dry: above-mentioned gained crystallization is dried in 130 ℃ of baking ovens, promptly get product of calcium-glutamate chelate.
The present invention compared with prior art, its technological process is simple, shell need not the calcining, building-up process need not artificial conditioned reaction liquid pH, oyster shell whiting utilization ratio height, the good (white of products obtained therefrom quality, Yi Rong, chelation percent is up to 94.5%), but the shell of the multiple shellfish processing waste of higher value application.
Embodiment:
The present invention is further elaborated below by example:
Example 1: adsorptives such as removing shell surface silt is scrubbed in the immersion in the 0.05M hydrochloric acid soln of oyster shells 120 grams after 1 hour, through 100 ℃ of oven dry, pulverized 60 mesh sieves, handle promptly to get through the tap water flying method again and synthesize calcium-glutamate chelate with calcium source oyster shell whiting 100 grams.100 gram calcium source oyster shell whitings and 265 gram L-glutamic acid, 3 liters of distilled water are mixed, stir and be heated to 72 ℃, be incubated chelating 1.0 hours, cool off suction filtration; Above-mentioned suction filtration gained clear liquid is evaporated to the stiff paste shape, adds 90% ethanol, stir standing over night.Suction filtration is with gained throw out 95% ethyl alcohol recrystallization, suction filtration; Above-mentioned gained crystallization is dried in 130 ℃ of baking ovens, promptly get calcium-glutamate chelate (C
10H
16N
2CaO
82H
2O) product 299 grams.
Example 2: step and method are with example 1, and raw material is chosen scallop shell or CONCHA MERETRICID SEU CYCLINAE, and the quality of its preparation product of calcium-glutamate chelate is identical with the oyster shells raw material.
Claims (4)
1, is the calcium-glutamate chelate synthesis method in calcium source with the shellfish processing waste, comprises the steps:
Shell pre-treatment: shell is scrubbed adsorptives such as removing shell surface silt with 0.05M salt acid soak after 1 hour, through 100 ℃ of oven dry, pulverized 60 mesh sieves, handle promptly to get through the tap water flying method again and synthesize calcium-glutamate chelate usefulness calcium source oyster shell whiting;
Synthetic: by L-glutamic acid and oyster shell whiting (the lime carbonate calcium contents is in 95%) mol ratio is 2: 1.0~1.2 batchings, and add the distilled water of 30~35 times of oyster shell whiting weight, stirring also is heated to 70~75 ℃, insulation chelating 1.0~1.5 hours, make the L-glutamic acid complete reaction, cooling, suction filtration is removed excessive oyster shell whiting;
Purifying: above-mentioned suction filtration gained clear liquid is evaporated to the stiff paste shape, adds 85~90% ethanol, stir standing over night.Suction filtration, insolubles 95% ethyl alcohol recrystallization, suction filtration again;
Oven dry: above-mentioned gained crystallization is dried in 130 ℃ of baking ovens, promptly get product of calcium-glutamate chelate.
2, as claimed in claim 1 is the calcium-glutamate chelate synthesis method in calcium source with the shellfish processing waste, it is characterized in that shell is used to prepare calcium-glutamate chelate through preprocessing process such as elutriation washings again through diluted acid immersion, pulverizing.
3, as claimed in claim 1 is the calcium-glutamate chelate synthesis method in calcium source with the shellfish processing waste, it is characterized in that building-up process adopts distilled water, and calcium source oyster shell whiting is excessive 10~20%, 70-75 ℃, and insulation chelating 1.0~1.5 hours; 85~90% ethanol are adopted in calcium-glutamate chelate crystallization for the first time, and recrystallization adopts 95% ethanol.
4, as claimed in claim 1 is the calcium-glutamate chelate synthesis method in calcium source with the shellfish processing waste, it is characterized in that shell comprises shellfish processing wastes such as oyster shells, scallop shell, CONCHA MERETRICID SEU CYCLINAE.
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CN2009101510231A CN101602685B (en) | 2009-06-30 | 2009-06-30 | Calcium-glutamate chelate synthesis method using shellfish processing waste as calcium source |
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CN2009101510231A CN101602685B (en) | 2009-06-30 | 2009-06-30 | Calcium-glutamate chelate synthesis method using shellfish processing waste as calcium source |
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CN101602685B CN101602685B (en) | 2012-06-27 |
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Cited By (10)
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CN102442871A (en) * | 2010-10-12 | 2012-05-09 | 青岛大学 | Preparation method of composite calcium amino acid chelate by hems of shells and scallops as raw materials |
CN102499337A (en) * | 2011-10-14 | 2012-06-20 | 浙江大学 | Preparation method of bioactive calcium jelly by using procambarus clarkii shells |
CN103848748A (en) * | 2014-04-01 | 2014-06-11 | 王子荣 | Glutamic acid chelated calcium prepared by using eggshells as calcium source and preparation method of glutamic acid chelated calcium |
CN104086454A (en) * | 2014-07-22 | 2014-10-08 | 福州大学 | Glutamic acid chelated calcium product prepared from shell and preparation method thereof |
CN105084944A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared by utilizing shells as well as preparation method and application thereof |
CN105085051A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared from oyster shell, and preparation method and application thereof |
CN103408604B (en) * | 2013-08-12 | 2016-07-13 | 青岛大学 | The alginic acid monosaccharide calcium synthetic method being raw material with shell and alginic acid |
CN106117069A (en) * | 2016-06-17 | 2016-11-16 | 宜兴市前成生物有限公司 | A kind of method preparing L glutamate chelate potassium one water thing |
CN110283090A (en) * | 2019-07-02 | 2019-09-27 | 广东海洋大学 | A kind of preparation method of L-phenylalanine chelating calcium powder and its L-phenylalanine of preparation chelate calcium tablet |
CN112795612A (en) * | 2021-03-10 | 2021-05-14 | 合肥工业大学 | Preparation method for extracting peptide chelated calcium by combined conversion of enzymolysis and chelation |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004050664A1 (en) * | 2002-12-05 | 2004-06-17 | Md Bioalpha Co., Ltd. | Method for preparation of amino acid chelate |
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2009
- 2009-06-30 CN CN2009101510231A patent/CN101602685B/en not_active Expired - Fee Related
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102442871A (en) * | 2010-10-12 | 2012-05-09 | 青岛大学 | Preparation method of composite calcium amino acid chelate by hems of shells and scallops as raw materials |
CN102499337A (en) * | 2011-10-14 | 2012-06-20 | 浙江大学 | Preparation method of bioactive calcium jelly by using procambarus clarkii shells |
CN103408604B (en) * | 2013-08-12 | 2016-07-13 | 青岛大学 | The alginic acid monosaccharide calcium synthetic method being raw material with shell and alginic acid |
CN103848748B (en) * | 2014-04-01 | 2015-12-30 | 王子荣 | A kind of employing birds, beasts and eggs shell class is that calcium-glutamate chelate and preparation method thereof is prepared in calcium source |
CN103848748A (en) * | 2014-04-01 | 2014-06-11 | 王子荣 | Glutamic acid chelated calcium prepared by using eggshells as calcium source and preparation method of glutamic acid chelated calcium |
CN104086454A (en) * | 2014-07-22 | 2014-10-08 | 福州大学 | Glutamic acid chelated calcium product prepared from shell and preparation method thereof |
CN105085051A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared from oyster shell, and preparation method and application thereof |
CN105084944A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared by utilizing shells as well as preparation method and application thereof |
CN106117069A (en) * | 2016-06-17 | 2016-11-16 | 宜兴市前成生物有限公司 | A kind of method preparing L glutamate chelate potassium one water thing |
CN110283090A (en) * | 2019-07-02 | 2019-09-27 | 广东海洋大学 | A kind of preparation method of L-phenylalanine chelating calcium powder and its L-phenylalanine of preparation chelate calcium tablet |
CN110283090B (en) * | 2019-07-02 | 2023-03-28 | 广东海洋大学 | Preparation method of L-phenylalanine chelated calcium powder and L-phenylalanine chelated calcium tablet prepared by same |
CN112795612A (en) * | 2021-03-10 | 2021-05-14 | 合肥工业大学 | Preparation method for extracting peptide chelated calcium by combined conversion of enzymolysis and chelation |
CN112795612B (en) * | 2021-03-10 | 2022-07-12 | 合肥工业大学 | Preparation method for extracting peptide chelated calcium by combined conversion of enzymolysis and chelation |
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