CN117304017A - Eggshell source calcium lactate, calcium citrate, chewable tablet and preparation method thereof - Google Patents
Eggshell source calcium lactate, calcium citrate, chewable tablet and preparation method thereof Download PDFInfo
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- CN117304017A CN117304017A CN202311142262.7A CN202311142262A CN117304017A CN 117304017 A CN117304017 A CN 117304017A CN 202311142262 A CN202311142262 A CN 202311142262A CN 117304017 A CN117304017 A CN 117304017A
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- Prior art keywords
- calcium
- eggshell
- calcium lactate
- powder
- lactate
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- 210000003278 egg shell Anatomy 0.000 title claims abstract description 152
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 134
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 134
- 239000001527 calcium lactate Substances 0.000 title claims abstract description 102
- 229960002401 calcium lactate Drugs 0.000 title claims abstract description 102
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 title claims abstract description 101
- 235000011086 calcium lactate Nutrition 0.000 title claims abstract description 101
- 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 78
- 239000001354 calcium citrate Substances 0.000 title claims abstract description 78
- 235000013337 tricalcium citrate Nutrition 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007910 chewable tablet Substances 0.000 title claims description 18
- 229940068682 chewable tablet Drugs 0.000 title claims description 17
- 229960004256 calcium citrate Drugs 0.000 title description 58
- 239000000843 powder Substances 0.000 claims abstract description 82
- 239000011575 calcium Substances 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 57
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000001639 calcium acetate Substances 0.000 claims abstract description 37
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 37
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 210000000998 shell membrane Anatomy 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 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 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 31
- 229960005069 calcium Drugs 0.000 claims description 31
- 229910052791 calcium Inorganic materials 0.000 claims description 31
- 239000000796 flavoring agent Substances 0.000 claims description 30
- 235000013355 food flavoring agent Nutrition 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 18
- 235000015165 citric acid Nutrition 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 102000008186 Collagen Human genes 0.000 claims description 8
- 108010035532 Collagen Proteins 0.000 claims description 8
- 108010001441 Phosphopeptides Proteins 0.000 claims description 8
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 claims description 8
- 210000000988 bone and bone Anatomy 0.000 claims description 8
- 239000005018 casein Substances 0.000 claims description 8
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 8
- 235000021240 caseins Nutrition 0.000 claims description 8
- 229920001436 collagen Polymers 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 235000019359 magnesium stearate Nutrition 0.000 claims description 8
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound 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-YRZJJWOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229940061631 citric acid acetate Drugs 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 235000005976 Citrus sinensis Nutrition 0.000 claims description 4
- 240000002319 Citrus sinensis Species 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 4
- 229920001100 Polydextrose Polymers 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001259 polydextrose Substances 0.000 claims description 4
- 235000013856 polydextrose Nutrition 0.000 claims description 4
- 229940035035 polydextrose Drugs 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 235000019871 vegetable fat Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001055 chewing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 229940012466 egg shell membrane Drugs 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000013601 eggs Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003826 tablet Substances 0.000 description 3
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940069978 calcium supplement Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 210000004211 gastric acid Anatomy 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- -1 sodium carboxylate Chemical class 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- A61K31/59—Compounds containing 9, 10- seco- cyclopenta[a]hydrophenanthrene ring systems
- A61K31/593—9,10-Secocholestane derivatives, e.g. cholecalciferol, i.e. vitamin D3
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K38/00—Medicinal preparations containing peptides
- A61K38/16—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- A61K38/17—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- A61K38/1703—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates
- A61K38/1709—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K38/00—Medicinal preparations containing peptides
- A61K38/16—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- A61K38/17—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- A61K38/39—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin, cold insoluble globulin [CIG]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
- A61K9/0056—Mouth soluble or dispersible forms; Suckable, eatable, chewable coherent forms; Forms rapidly disintegrating in the mouth; Lozenges; Lollipops; Bite capsules; Baked products; Baits or other oral forms for animals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/205—Polysaccharides, e.g. alginate, gums; Cyclodextrin
- A61K9/2054—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
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- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Organic Chemistry (AREA)
- Epidemiology (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Zoology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Immunology (AREA)
- Nutrition Science (AREA)
- Gastroenterology & Hepatology (AREA)
- Obesity (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hematology (AREA)
- Diabetes (AREA)
- Marine Sciences & Fisheries (AREA)
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- Meat, Egg Or Seafood Products (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention provides eggshell source calcium lactate and calcium citrate, chewing tablet and its preparation method, this eggshell source calcium lactate and calcium citrate preparation method include to particle diameter < 0.074mm whole membrane eggshell powder, stir and separate the treatment in three segments, make the shell membrane separate and get eggshell powder; and heating the mother liquid of calcium lactate and the coarse liquid of calcium acetate separately, and adding Ca (OH) slowly 2 The pH is adjusted back to 8-9 for 2-3min; continuously heating, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10 until a large amount of flocculent precipitate appears; and performing suction filtration and drying to obtain a calcium lactate finished product and a calcium citrate finished product; according to the invention, the waste eggshells are used as raw materials, so that the effective industrial production of eggshell source calcium citrate and calcium lactate is realized, the yield and purity of eggshell source calcium lactate and calcium citrate are fully improved, the full recycling of eggshells is realized, and the problem of environmental pollution caused by eggshells is solved.
Description
Technical Field
The invention relates to the technical field of egg product processing, in particular to eggshell source calcium lactate, calcium citrate and chewable tablets and a preparation method thereof.
Background
Calcium is one of the most important elements in the human body. It participates in all life activities. At present, the common calcium supplementing raw material in the market is calcium carbonate, but the calcium carbonate has poor water solubility, is difficult to absorb, needs to consume gastric acid during absorption, influences the acidic environment in the stomach, and easily influences the normal digestion function of a human body.
Although eggs are widely applied to the fields of food biology, chemical light industry, medicine and the like, people often only pay attention to how to utilize edible parts such as egg white and yolk in the eggs, and eggshells accounting for 10% -12% of the whole egg mass are discarded, so that the utilization rate of eggshell resources is extremely low, and abundant calcium resources contained in the eggshells are wasted. The calcium citrate and the calcium lactate are used as novel calcium supplements, and have the advantages of high absorptivity, good solubility, low heavy metal content, good ion stability and the like. In recent years, although the method for producing calcium citrate and calcium lactate by adopting eggshell sources has been reported, the preparation method is mostly limited to laboratory small-batch production, the industrialized production of eggshell source calcium citrate and calcium lactate is influenced by more technological conditions and factors, and the existing preparation method cannot realize large-scale production, and has the problems of high production cost, low economic benefit, low product yield, difficult impurity removal, difficulty in ensuring the product purity requirement and the like. Moreover, the existing calcium supplementing tablet products in the market generally have the problems of simple formula, low pertinence and single taste.
Therefore, the industrial preparation method of the calcium citrate and the calcium lactate with the more efficient eggshell sources is searched, the production process of the calcium supplementing tablet product is optimized, and the method has important significance for solving the problem of environmental pollution caused by a large number of waste eggshells, fully utilizing eggshell waste resources and improving the side added value of poultry egg byproducts.
Disclosure of Invention
In view of the above, the invention provides an eggshell-derived calcium lactate and calcium citrate, chewable tablet and a preparation method thereof, which are used for effectively realizing industrial production of eggshell-derived calcium citrate and calcium lactate, and further used for obtaining calcium citrate and calcium lactate chewable tablet products with good efficacy and taste by taking eggshell-derived calcium citrate and calcium lactate as main raw materials.
The technical scheme of the invention is realized as follows:
a preparation method of eggshell source calcium lactate and calcium citrate comprises the following steps:
step 1: shell-membrane separation, preparing eggshell powder:
taking clean eggshells, drying at a constant temperature of 55-65 ℃ for 4-6 hours, crushing, sequentially sieving with a 80-mesh sieve and a 200-mesh sieve, adding water after sieving out full-membrane eggshell powder with the particle size smaller than 0.074mm, carrying out three-stage stirring separation treatment at a constant speed of 400-600r/min, stirring for 18-22min at the first stage, standing for 25-35min, pouring the upper liquid, and collecting shell membranes; stirring for 13-17min in the second stage, standing for 15-20min, pouring the upper liquid, and collecting the shell membrane; stirring for 8-10min in the third stage, standing for 8-12min, pouring the supernatant, collecting shell membrane, mixing the supernatant, and drying at 55-65deg.C to obtain eggshell powder;
step 2: preparing eggshell source calcium lactate concentrate and calcium acetate solid:
respectively weighing eggshell powder in the step 1, respectively slowly adding lactic acid and acetic acid, carrying out neutralization reaction to obtain calcium lactate mother liquor and calcium acetate crude liquor, and sieving with a 200-mesh sieve; heating to 85-88 deg.C, respectively, and collecting Ca (OH) 0.5-3% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously, the pH value is adjusted back to 8-9, and after 2-3min of interval; continuously heating to 90-95 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; vacuum filtering at 80-85deg.C, and drying at constant temperature less than 80deg.C to obtain calcium lactate concentrate and calcium acetate solid respectively;
step 3: eggshell source calcium lactate and calcium citrate finished products:
spray drying the calcium lactate concentrate to obtain a calcium lactate powder finished product; according to the molecular weight of 3 (1.8-2.2) of citric acid and calcium acetate, adding citric acid solution into calcium acetate for secondary neutralization reaction, drying at constant temperature below 80deg.C in a drying oven to obtain coarse product of calcium citrate, adding into boiling water above 100deg.C, filtering while hot, and drying to obtain the final product of calcium citrate.
Further, in the step 1, the mass ratio of the whole membrane eggshell powder to the water is 1:3, and the constant stirring speed of the three-stage stirring separation treatment is 500r/min.
Further illustratively, in step 2, the preparation of the calcium lactate mother liquor comprises: lactic acid is slowly added into eggshell powder according to the feed-liquid ratio of 1g to 1.85mL, water is slowly added into eggshell powder for mixing for five times, and the mixture is stirred while being added, and reacts for 2 hours at 35 ℃ to obtain calcium lactate mother liquor.
Further illustratively, in step 2, the preparation of the crude calcium acetate solution comprises: slowly adding 6mol/L acetic acid into eggshell powder according to the feed-liquid ratio of 1g to 5mL, reacting at 85 ℃ until no bubble is generated, and recovering acetic acid by a vacuum rotary evaporation device under the condition of water bath heating at 50 ℃ at the vacuum degree of 0.8MPa to obtain calcium acetate crude liquid.
Further illustrated, in the step 3, the spray drying is to spray-dry the calcium lactate concentrated solution at the temperature of more than or equal to 50 ℃, the inlet temperature of the spray drying is 140-160 ℃, the outlet temperature is 65-75 ℃, and the discharge port is sieved by a 200-mesh sieve to obtain the calcium lactate powder.
Further illustrated, in the step 3, the secondary neutralization reaction is to add citric acid into the calcium acetate concentrated solution according to the molecular weight of citric acid and calcium acetate of 3:2, react for 1.8-2.2h at 45-55 ℃, and then dry in a constant temperature drying oven at a temperature of less than 80 ℃ to obtain a crude product of calcium citrate.
The organic calcium chewable tablet is prepared from eggshell source calcium lactate and calcium citrate and comprises the following components in parts by weight: eggshell source calcium supplementing raw material 55-60g, bone collagen 1.24-1.28g, vitamin D 3 0.01-0.02g, 2.50-2.54g casein phosphopeptide, 4-6g binder, 30-32g corrigent and 0.18-0.22g lubricant magnesium stearate; the eggshell source calcium supplementing raw material is eggshell source calcium lactate or eggshell source calcium citrate.
More preferably, the binder is formed by mixing crosslinked polyvinylpyrrolidone and microcrystalline cellulose according to the mass ratio of 1:1.
More preferably, the flavoring agent comprises a flavoring agent A, a flavoring agent B and a flavoring agent C in a mass ratio of 16:1:14; wherein, the flavoring agent A is formed by mixing isomaltooligosaccharide, polydextrose and mannitol according to the mass ratio of 1:1:1; the flavoring agent B is formed by mixing citric acid, malic acid and vitamin C according to the mass ratio of 2:5:1; the flavoring agent C is prepared by mixing milk powder, vegetable fat powder, and sweet orange fruit powder at a ratio of 1:2:1.
A preparation method of the organic calcium chewable tablet containing eggshell-derived calcium lactate and calcium citrate comprises the following steps:
(1) Mixing main materials: weighing eggshell source calcium supplementing raw materials in proportion, pulverizing, sieving with 100 mesh sieve, mixing with bone collagen and vitamin D 3 Mixing with casein phosphopeptide to obtain a premix;
(2) Weighing binder, correctant and lubricant magnesium stearate according to a certain proportion, and mixing uniformly;
(3) Tabletting and molding to obtain the organic calcium chewable tablet.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, eggshells are used as raw materials, and three-section stirring separation treatment is carried out on the whole-membrane eggshell powder with a smaller particle size range at a constant stirring speed, so that efficient eggshell separation is realized, the total loss of the eggshell powder is small, the total loss of the eggshell powder can be kept below 5%, the yield of the eggshell powder is high, the yield of the eggshell powder can reach 91.88%, and the residual rate of the eggshell membrane in the eggshell is 1% -1.5%; the method has the advantages that the realized pure physical shell membrane treatment process is simpler, the cost is low, the interference and influence of the eggshell membrane in the subsequent neutralization reaction are greatly reduced, and the reaction rate of eggshells and acid is improved.
2) According to the invention, on the basis of respectively carrying out neutralization reaction on eggshell powder and lactic acid and acetic acid, the impurity is removed by virtue of high Wen Jiajian, and meanwhile, the impurity removal effect is realized more efficiently by utilizing a step-by-step callback ph mode, so that the yield and purity of the shell source calcium lactate and calcium citrate are remarkably improved, the energy consumption cost is greatly reduced, the environmental pollution caused by high-temperature calcination of eggshells is avoided, the full recycling of the eggshells under normal pressure and normal temperature is realized, waste is changed into valuables, the product calcium lactate and calcium citrate meet the national standard requirements of food-grade calcium lactate and calcium citrate, and the environmental pollution problem caused by the eggshells is solved.
Drawings
FIG. 1 shows eggshell powder (left) and eggshell membrane (right) after shell membrane separation in example 3 of the present invention;
FIG. 2 shows eggshell-derived calcium lactate (left) and eggshell-derived calcium citrate tablets (right) prepared in examples 6 and 7 of the present invention.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
A preparation method of eggshell source calcium lactate and calcium citrate comprises the following steps:
1. shell-membrane separation, preparing eggshell powder:
taking clean eggshells, drying at a constant temperature of 55 ℃ for 6 hours, crushing, sequentially sieving with a 80-mesh sieve and a 200-mesh sieve, adding water according to a mass ratio of 1:3 after sieving out full-membrane eggshell powder with a particle size smaller than 0.074mm, carrying out three-section stirring separation treatment at a constant speed of 400r/min, stirring for 22min at the first section, standing for 25min, pouring the upper liquid, and collecting shell membranes; stirring for 17min in the second stage, standing for 15min, pouring the upper liquid, and collecting the shell membrane; stirring for 10min in the third stage, standing for 8min, pouring the upper liquid, collecting shell membrane, mixing the upper liquid, and drying at 55deg.C to obtain eggshell powder;
2. preparing eggshell source calcium lactate concentrate and calcium acetate solid:
(1) Weighing eggshell powder in the step 1, slowly adding lactic acid according to the feed-liquid ratio of 1g to 1.85mL, taking water with the volume 10 times that of the eggshell powder, slowly adding and mixing for five times, stirring while adding, and carrying out neutralization reaction at 35 ℃ for 2 hours to obtain calcium lactate mother liquor; removing unreacted eggshell powder by 200 mesh sieve, heating to 85deg.C, and collecting Ca (OH) 0.5% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 8, and after 2min of interval; continuously heating to 90 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium lactate aqueous solution at 85 ℃ for suction filtration, and drying for 8 hours in a constant temperature drying oven with the temperature less than 80 ℃ to obtain calcium lactate concentrated solution;
(2) Weighing eggshell powder in the step 1, and slowly weighing according to the feed-liquid ratio of 1g to 5mLAdding 6mol/L acetic acid, carrying out neutralization reaction at 85 ℃ until no bubbles are generated, and recovering acetic acid by a vacuum rotary evaporation device under the condition of water bath heating at 50 ℃ at the vacuum degree of 0.8MPa to obtain a calcium acetate crude liquid; removing unreacted eggshell powder by 200 mesh sieve, heating to 85deg.C, and collecting Ca (OH) 0.5% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 8, and after 2min of interval; continuously heating to 90 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium acetate aqueous solution at 85 ℃ for suction filtration, and drying for 8 hours at a constant temperature of less than 80 ℃ to obtain calcium acetate solid;
3. eggshell source calcium lactate and calcium citrate finished products:
spray drying the calcium lactate concentrate to obtain a calcium lactate powder finished product;
adding citric acid solution into calcium acetate according to the molecular weight of citric acid and calcium acetate of 3:1.8, performing secondary neutralization reaction at 45 ℃ for 2.2h, drying at constant temperature below 80 ℃ in a drying oven to obtain crude calcium citrate, adding into boiling water with the temperature of above 100 ℃, filtering while hot, and drying to obtain the finished product of calcium citrate.
Example 2
A preparation method of eggshell source calcium lactate and calcium citrate comprises the following steps:
1. shell-membrane separation, preparing eggshell powder:
taking clean eggshells, drying at a constant temperature of 65 ℃ for 4 hours, crushing, sequentially sieving with a 80-mesh sieve and a 200-mesh sieve, adding water according to a mass ratio of 1:3 after sieving out full-membrane eggshell powder with a particle size smaller than 0.074mm, carrying out three-stage stirring separation treatment at a constant speed of 600r/min, stirring for 18min at the first stage, standing for 35min, pouring the upper liquid, and collecting shell membranes; stirring for 13min at the second stage, standing for 20min, pouring the upper liquid, and collecting the shell membrane; stirring for 8min in the third stage, standing for 12min, pouring the upper liquid, collecting shell membrane, mixing the upper liquid, and drying at constant temperature of 65deg.C to obtain eggshell powder;
2. preparing eggshell source calcium lactate concentrate and calcium acetate solid:
(1) Weighing eggshell powder in the step 1, slowly adding lactic acid according to the feed-liquid ratio of 1g to 1.85mL, taking water with the volume 10 times that of the eggshell powder, slowly adding and mixing for five times, stirring while adding, and carrying out neutralization reaction at 35 ℃ for 2 hours to obtain calcium lactate mother liquor; removing unreacted eggshell powder by 200 mesh sieve, heating to 88 deg.C, and collecting Ca (OH) 3% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 9, and after 3min of interval; continuously heating to 95 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium lactate aqueous solution at 80 ℃ for suction filtration, and drying for 12 hours in a constant temperature drying oven with the temperature less than 80 ℃ to obtain calcium lactate concentrated solution;
(2) Weighing eggshell powder in the step 1, slowly adding 6mol/L acetic acid according to the feed-liquid ratio of 1g to 5mL, carrying out neutralization reaction at 85 ℃ until no bubbles are generated, and recovering acetic acid by a vacuum rotary evaporation device under the condition of heating in water bath at 50 ℃ at the vacuum degree of 0.8MPa to obtain calcium acetate crude liquid; removing unreacted eggshell powder by 200 mesh sieve, heating to 88 deg.C, and collecting Ca (OH) 3% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 9, and after 3min of interval; continuously heating to 95 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium acetate aqueous solution at 80 ℃ for suction filtration, and drying for 10 hours at a constant temperature less than 80 ℃ to obtain calcium acetate solid;
3. eggshell source calcium lactate and calcium citrate finished products:
spray drying the calcium lactate concentrate to obtain a calcium lactate powder finished product;
adding citric acid solution into calcium acetate according to the molecular weight of citric acid and calcium acetate of 3:2.2, performing secondary neutralization reaction at 55 ℃ for 1.8h, oven drying at constant temperature below 80 ℃ to obtain coarse product of calcium citrate, adding into boiling water at above 100 ℃, filtering while hot, and drying to obtain the final product of calcium citrate.
Example 3
A preparation method of eggshell source calcium lactate and calcium citrate comprises the following steps:
1. shell-membrane separation, preparing eggshell powder:
taking clean eggshells, drying at a constant temperature of 60 ℃ for 5 hours, crushing, sequentially sieving with a 80-mesh sieve and a 200-mesh sieve, adding water according to a mass ratio of 1:3 after sieving out full-membrane eggshell powder with a particle size smaller than 0.074mm, carrying out three-stage stirring separation treatment at a constant speed of 500r/min, stirring for 20min at the first stage, standing for 30min, pouring the upper liquid, and collecting shell membranes; stirring for 15min in the second stage, standing for 20min, pouring the upper liquid, and collecting the shell membrane; stirring for 10min in the third stage, standing for 10min, pouring the upper liquid, collecting shell membrane, mixing the upper liquid, and drying at 60deg.C to obtain eggshell powder;
2. preparing eggshell source calcium lactate concentrate and calcium acetate solid:
(1) Weighing eggshell powder in the step 1, slowly adding lactic acid according to the feed-liquid ratio of 1g to 1.85mL, taking water with the volume 10 times that of the eggshell powder, slowly adding and mixing for five times, stirring while adding, and carrying out neutralization reaction at 35 ℃ for 2 hours to obtain calcium lactate mother liquor; removing unreacted eggshell powder by 200 mesh sieve, heating to 87 deg.C, and collecting Ca (OH) 2.5% by mass 2 ，FirstSlowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 9, and after 3min of interval; continuously heating to 95 ℃, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium lactate aqueous solution at 83 ℃ for suction filtration, and drying for 10 hours in a constant temperature drying oven with the temperature less than 80 ℃ to obtain calcium lactate concentrated solution;
(2) Weighing eggshell powder in the step 1, slowly adding 6mol/L acetic acid according to the feed-liquid ratio of 1g to 5mL, carrying out neutralization reaction at 85 ℃ until no bubbles are generated, and recovering acetic acid by a vacuum rotary evaporation device under the condition of heating in water bath at 50 ℃ at the vacuum degree of 0.8MPa to obtain calcium acetate crude liquid; removing unreacted eggshell powder by 200 mesh sieve, heating to 87 deg.C, and collecting Ca (OH) 2.5% by mass 2 Ca (OH) was slowly added at 75% of the amount of the mixture first 2 Simultaneously adjusting the pH value to 9, and after 3min of interval; continuously heating to 95 DEG CSlowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; maintaining the temperature of the calcium acetate aqueous solution at 85 ℃ for suction filtration, and drying for 9 hours at a constant temperature of less than 80 ℃ to obtain calcium acetate solid;
3. eggshell source calcium lactate and calcium citrate finished products:
spray drying the calcium lactate concentrate to obtain a calcium lactate powder finished product;
adding citric acid solution into calcium acetate according to the molecular weight of 3:2 for secondary neutralization reaction, oven drying at constant temperature below 80deg.C to obtain coarse product of calcium citrate, adding into boiling water above 100deg.C, filtering while hot, and drying to obtain final product of calcium citrate.
EXAMPLE 4 investigation of eggshell separation Effect under different Shell-membrane separation treatments
Respectively sieving the crushed eggshell powder with the particle size of less than 0.074mm and the crushed eggshell powder with the particle size of less than 0.074mm, and carrying out three-stage stirring separation treatment as in the embodiment 3; and continuously stirring and separating (45 min) the crushed eggshell powder with the particle size smaller than 0.074mm for the same stirring time as that of the embodiment 3, and measuring the respective shell-membrane separation effects of the obtained eggshell powder:
and (3) calculating recovery yields of eggshells and eggshell membranes:
eggshell powder yield W1 (%) =m1/m×100
Shell membrane yield W2 (%) =m2/m×100
Wherein: m1 is the weight of eggshell powder after shell-membrane separation, g; m2 is the weight of eggshell and eggshell membrane after shell membrane separation, g; m is the weight of the whole membrane eggshell before the separation of the shell and the membrane,
the results are shown in the following table:
TABLE 1 Shell membrane separation results of eggshell powder
As can be seen from the table, the invention carries out three-stage stirring separation treatment by combining the eggshell powder crushed to the particle size smaller than 0.074mm and constant stirring speed, so that the total loss of the eggshell powder is obviously reduced, the yield of the eggshell powder is improved, and the content of the eggshell powder in the eggshell membrane is low. After the shell and the membrane are separated, the yield of the eggshell powder can reach 91.88 percent, the yield of the eggshell membrane can reach 3.82 percent, the eggshell powder and the eggshell membrane after the shell and the membrane are separated are shown as figure 1, and the residue rate of the eggshell membrane in the eggshell is 1 to 1.5 percent after the shell and the membrane are separated; the calcium content in the shell membrane is 2% -3%.
Example 5-investigation of yield and purity of eggshell-derived organic calcium (calcium citrate and calcium lactate) under different high Wen Jiajian impurity removal procedures
Experiment group 1: the eggshell-derived calcium lactate and calcium citrate prepared by the method of example 3;
experiment group 2: the method of preparing eggshell-derived calcium lactate and calcium citrate of example 3, wherein the pH is not stepped back; the method comprises the following steps: after the temperature is raised to 87 ℃, 2 taking Ca (OH) with the mass percentage of 2.5 percent, firstlySlowly adding 75% of Ca (OH) 2 Simultaneously, directly adjusting the pH to 10, and after 3min of interval; continuously heating to 95 ℃, slowly adding the rest Ca (OH) under stirring 2 Stirring is continued until a large amount of flocculent precipitate appears;
experiment group 3: the preparation method of eggshell-derived calcium lactate and calcium citrate of example 3, wherein the impurities are removed at constant temperature with alkali; the method comprises the following steps: respectively preparing a calcium lactate mother solution and a calcium acetate crude solution, sieving with a 200-mesh sieve, directly heating to 95 ℃,quality of taking 2 Percentage of Ca (OH) 2.5%Slowly adding 75% of Ca (OH) 2 Simultaneously adjusting the pH value to 9, and after 3min of interval; slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears;
determining the yield and purity of the organic calcium under the preparation conditions of the above experiments 1 to 3, respectively; wherein:
(1) Yield calculation of organic calcium (calcium citrate and calcium lactate):
(2) And (3) measuring the content of calcium lactate:
about 0.3g of the sample (dried to constant weight at 90℃prior to the muffle furnace) was weighed, to the nearest 0.0002g, dissolved in 50mL of water to which 2mL of hydrochloric acid solution had been added, and approximately 15mL of disodium edetate standard titration solution was added dropwise with stirring by a magnetic stirrer, followed by neutralization by 5mL of sodium hydroxide solution. 1g of the calcium reagent sodium carboxylate indicator was continued to drop with the disodium edetate standard solution to the blue end point.
As a result of calculation, calcium lactate (C 6 H 10 CaO 6 ) The values are expressed in%, calculated as:
wherein: the volume of the standard titration solution of V-disodium ethylenediamine tetraacetate is measured in milliliters (mL);
c- -accurate value of disodium edetate standard titration solution concentration, unit is mole per liter (mol/L);
m- -the mass number of the sample in grams (g);
m-calcium lactate (C) 6 H 10 CaO 6 ) In grams per mole (g/mol) (m=218.2);
taking the arithmetic average value of the two parallel measurement results as the measurement result, wherein the absolute difference of the two parallel measurement results is not more than 0.3%.
(3) Calcium citrate content determination
And (5) determining the content of the calcium citrate by adopting an EDTA complexometric titration method. The calcium citrate was dried in an oven at 150 ℃ to constant weight and 0.4g of sample was accurately weighed. And (3) dropwise adding as little hydrochloric acid (1+1) as possible to dissolve the calcium citrate. Diluted to 100mL with double distilled water, 5mL of triethanolamine (30%) and 15mL of sodium hydroxide (1 mol/L) solution were added. The pH was adjusted to 13, a calcium indicator was added, and the solution was titrated with EDTA (0.05 mol/L) standard solution until the solution changed from reddish wine to blue.
Wherein H-titration consumes the volume of disodium ethylenediamine tetraacetate standard solution, mL
The actual concentration ratio of the A-EDTA standard solution is 0.05
Calcium M-citrate addition, g
8.307-8.307g of calcium citrate consumes 1mLEDTA standard solution.
The results are shown in Table 2 below:
TABLE 2 organic calcium (calcium citrate and calcium lactate) yields and purity
As can be seen from table 2 above, the yield of crude calcium lactate and the yield after purification of calcium lactate in experimental group 1 of the present invention were 70.14% and 94.83%, respectively; by using an EDTA titration method, the calcium content of the purified calcium lactate is measured to be up to 99.58%, and the requirement of food-grade calcium lactate is met by more than 98%. The yield of the coarse calcium citrate and the yield after the purification of the calcium citrate are 94.77 percent and 98.64 percent respectively; by using an EDTA titration method, the purity of the calcium citrate is measured to be 99.32 percent, and the requirement of the food-grade calcium citrate is met by more than 98 percent.
Meanwhile, the purification yield of calcium lactate and the purification yield of calcium citrate in experimental group 1 are obviously higher than those in experimental groups 2 and 3, and the method is shown that on the basis of respectively carrying out neutralization reaction on eggshell powder, lactic acid and acetic acid, the impurity is removed by high Wen Jiajian, meanwhile, the more efficient impurity removal effect is realized by utilizing a step-by-step callback ph mode, the yields of shell source calcium lactate and calcium citrate are obviously improved, the purity of products is ensured, the eggshells are fully utilized in a recycling way, waste is changed into valuable, the calcium lactate and the calcium citrate of the products meet the national standard requirements of food-grade calcium lactate and calcium citrate, and the problem of environmental pollution caused by the eggshells is solved.
Example 6-eggshell-source calcium lactate prepared in example 3, an organic calcium chewable tablet was prepared, which comprises the following components in weight ratio: eggshell source calcium lactate 59g, bone collagen 1.28g, vitamin D 3 0.01g, 2.5g casein phosphopeptide, 6g binder, 31g flavoring agent and 0.21g lubricant magnesium stearate;
wherein the binder is formed by mixing crosslinked polyvinylpyrrolidone and microcrystalline cellulose according to the mass ratio of 1:1; the flavoring agent comprises 16g of flavoring agent A, 1g of flavoring agent B and 14g of flavoring agent C; wherein, the flavoring agent A is formed by mixing isomaltooligosaccharide, polydextrose and mannitol according to the mass ratio of 1:1:1; the flavoring agent B is formed by mixing citric acid, malic acid and vitamin C according to the mass ratio of 2:5:1; the flavoring agent C is prepared by mixing milk powder, vegetable fat powder, and sweet orange fruit powder at a ratio of 1:2:1;
the preparation method comprises the following steps:
(1) Weighing eggshell source calcium lactate in proportion, pulverizing, sieving with 100 mesh sieve, mixing with bone collagen and vitamin D 3 Mixing with casein phosphopeptide to obtain a premix;
(2) Weighing binder, correctant and lubricant magnesium stearate according to a certain proportion, and mixing uniformly;
(3) Tabletting and shaping to obtain the organic calcium chewable tablet of eggshell source calcium lactate.
Example 7-eggshell-source calcium citrate prepared from example 3, an organic calcium chewable tablet was prepared, which comprises the following components in parts by weight: eggshell source calcium citrate 60g, bone collagen 1.26g and vitamin D 3 0.02g, 2.52g casein phosphopeptide, 5g binder, 31g flavoring agent and 0.2g lubricant magnesium stearate;
the adhesive is formed by mixing crosslinked polyvinylpyrrolidone and microcrystalline cellulose according to the mass ratio of 1:1;
the flavoring agent comprises 16g of flavoring agent A, 1g of flavoring agent B and 14g of flavoring agent C; wherein, the flavoring agent A is formed by mixing isomaltooligosaccharide, polydextrose and mannitol according to the mass ratio of 1:1:1; the flavoring agent B is formed by mixing citric acid, malic acid and vitamin C according to the mass ratio of 2:5:1; the flavoring agent C is prepared by mixing milk powder, vegetable fat powder, and sweet orange fruit powder at a ratio of 1:2:1;
the preparation method comprises the following steps:
(1) Weighing eggshell source calcium citrate according to a proportion, crushing, sieving with a 100-mesh sieve, mixing with bone collagen and vitamin D 3 Mixing with casein phosphopeptide to obtain a premix;
(2) Weighing binder, correctant and lubricant magnesium stearate according to a certain proportion, and mixing uniformly;
(3) Tabletting and shaping to obtain the organic calcium chewable tablet of eggshell source calcium citrate.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of eggshell source calcium lactate and calcium citrate is characterized in that: the method comprises the following steps:
step 1: shell-membrane separation, preparing eggshell powder:
taking clean eggshells, drying at a constant temperature of 55-65 ℃ for 4-6 hours, crushing, sequentially sieving with a 80-mesh sieve and a 200-mesh sieve, adding water after sieving out full-membrane eggshell powder with the particle size smaller than 0.074mm, carrying out three-stage stirring separation treatment at a constant speed of 400-600r/min, stirring for 18-22min at the first stage, standing for 25-35min, pouring the upper liquid, and collecting shell membranes; stirring for 13-17min in the second stage, standing for 15-20min, pouring the upper liquid, and collecting the shell membrane; stirring for 8-10min in the third stage, standing for 8-12min, pouring the supernatant, collecting shell membrane, mixing the supernatant, and drying at 55-65deg.C to obtain eggshell powder;
step 2: preparing eggshell source calcium lactate concentrate and calcium acetate solid:
respectively weighing eggshell powder in the step 1, respectively slowly adding lactic acid and acetic acid, carrying out neutralization reaction to obtain calcium lactate mother liquor and calcium acetate crude liquor, and sieving with a 200-mesh sieve; heating to 85-88 deg.C, respectively, and collecting Ca (OH) 0.5-3% by mass 2 Ca (OH) was slowly added at 75% of the amount of the mixture first 2 Simultaneously, the pH value is adjusted back to 8-9, and after 2-3min of interval; relay(s)Continuously heating to 90-95deg.C, slowly adding the rest Ca (OH) under stirring 2 The pH is adjusted back to 10, and stirring is continued until a large amount of flocculent precipitate appears; vacuum filtering at 80-85deg.C, and drying at constant temperature less than 80deg.C to obtain calcium lactate concentrate and calcium acetate solid respectively;
step 3: eggshell source calcium lactate and calcium citrate finished products:
spray drying the calcium lactate concentrate to obtain a calcium lactate powder finished product; according to the molecular weight of 3 (1.8-2.2) of citric acid and calcium acetate, adding citric acid solution into calcium acetate for secondary neutralization reaction, drying at constant temperature below 80deg.C in a drying oven to obtain coarse product of calcium citrate, adding into boiling water above 100deg.C, filtering while hot, and drying to obtain the final product of calcium citrate.
2. The method for preparing eggshell-derived calcium lactate and calcium citrate as claimed in claim 1, wherein: in the step 1, the mass ratio of the whole membrane eggshell powder to the water is 1:3, and the constant stirring speed of the three-stage stirring separation treatment is 500r/min.
3. The method for preparing eggshell-derived calcium lactate and calcium citrate as claimed in claim 1, wherein: in the step 2, the preparation of the calcium lactate mother liquor comprises the following steps: lactic acid is slowly added into eggshell powder according to the feed-liquid ratio of 1g to 1.85mL, water is slowly added into eggshell powder for mixing for five times, and the mixture is stirred while being added, and reacts for 2 hours at 35 ℃ to obtain calcium lactate mother liquor.
4. The method for preparing eggshell-derived calcium lactate and calcium citrate as claimed in claim 1, wherein: in the step 2, the preparation of the calcium acetate crude liquid comprises the following steps: slowly adding 6mol/L acetic acid into eggshell powder according to the feed-liquid ratio of 1g to 5mL, reacting at 85 ℃ until no bubble is generated, and recovering acetic acid by a vacuum rotary evaporation device under the condition of water bath heating at 50 ℃ at the vacuum degree of 0.8MPa to obtain calcium acetate crude liquid.
5. The method for preparing eggshell-derived calcium lactate and calcium citrate as claimed in claim 1, wherein: in the step 3, the spray drying is that the calcium lactate concentrated solution is spray dried at the temperature of more than or equal to 50 ℃, the inlet temperature of the spray drying is 140-160 ℃, the outlet temperature is 65-75 ℃, and the discharge port is sieved by a 200-mesh sieve, so as to obtain the calcium lactate powder.
6. The method for preparing eggshell-derived calcium lactate and calcium citrate as claimed in claim 1, wherein: in the step 3, the secondary neutralization reaction is to add citric acid into the calcium acetate concentrated solution according to the molecular weight of citric acid and calcium acetate of 3:2, react for 1.8-2.2h at 45-55 ℃, and dry in a constant temperature drying oven at the temperature of less than 80 ℃ to obtain a crude product of calcium citrate.
7. An organic calcium chewable tablet prepared from eggshell-derived calcium lactate and calcium citrate as defined in any one of claims 1 to 6, characterized in that: the organic calcium chewable tablet comprises the following components in parts by weight: eggshell source calcium supplementing raw material 55-60g, bone collagen 1.24-1.28g, vitamin D 3 0.01-0.02g, 2.50-2.54g casein phosphopeptide, 4-6g binder, 30-32g corrigent and 0.18-0.22g lubricant magnesium stearate;
the eggshell source calcium supplementing raw material is eggshell source calcium lactate or eggshell source calcium citrate.
8. An organocalcium chewable tablet prepared from eggshell-derived calcium lactate and calcium citrate as defined in claim 7, wherein: the adhesive is formed by mixing crosslinked polyvinylpyrrolidone and microcrystalline cellulose according to the mass ratio of 1:1.
9. An organocalcium chewable tablet prepared from eggshell-derived calcium lactate and calcium citrate as defined in claim 7, wherein: the flavoring agent comprises a flavoring agent A, a flavoring agent B and a flavoring agent C in a mass ratio of 16:1:14; wherein, the flavoring agent A is formed by mixing isomaltooligosaccharide, polydextrose and mannitol according to the mass ratio of 1:1:1; the flavoring agent B is formed by mixing citric acid, malic acid and vitamin C according to the mass ratio of 2:5:1; the flavoring agent C is prepared by mixing milk powder, vegetable fat powder, and sweet orange fruit powder at a ratio of 1:2:1.
10. The method for preparing the organic calcium chewable tablet from eggshell-derived calcium lactate and calcium citrate according to claim 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) Mixing main materials: weighing eggshell source calcium supplementing raw materials in proportion, pulverizing, sieving with 100 mesh sieve, mixing with bone collagen and vitamin D 3 Mixing with casein phosphopeptide to obtain a premix;
(2) Weighing binder, correctant and lubricant magnesium stearate according to a certain proportion, and mixing uniformly;
(3) Tabletting and molding to obtain the organic calcium chewable tablet.
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