CN100364548C - Iron replenisher with control released iron and its preparing method and use - Google Patents
Iron replenisher with control released iron and its preparing method and use Download PDFInfo
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- CN100364548C CN100364548C CNB2006100500811A CN200610050081A CN100364548C CN 100364548 C CN100364548 C CN 100364548C CN B2006100500811 A CNB2006100500811 A CN B2006100500811A CN 200610050081 A CN200610050081 A CN 200610050081A CN 100364548 C CN100364548 C CN 100364548C
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- Prior art keywords
- iron
- ferrous
- zeolite
- control released
- preparation
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Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 239000013589 supplement Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 150000002505 iron Chemical class 0.000 claims description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229960001781 ferrous sulfate Drugs 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 9
- 238000013270 controlled release Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 229930182817 methionine Natural products 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- 239000011773 ferrous fumarate Substances 0.000 claims description 6
- 235000002332 ferrous fumarate Nutrition 0.000 claims description 6
- 229960000225 ferrous fumarate Drugs 0.000 claims description 6
- -1 organic divalent iron salt Chemical class 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000011640 ferrous citrate Substances 0.000 claims description 5
- 235000019850 ferrous citrate Nutrition 0.000 claims description 5
- 239000004222 ferrous gluconate Substances 0.000 claims description 5
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 5
- 229960001645 ferrous gluconate Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 5
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 5
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 235000013925 ferrous lactate Nutrition 0.000 claims description 4
- 239000004225 ferrous lactate Substances 0.000 claims description 4
- 229940037907 ferrous lactate Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims 2
- 239000003814 drug Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000003674 animal food additive Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 5
- 241000283690 Bos taurus Species 0.000 abstract description 4
- 241001494479 Pecora Species 0.000 abstract description 4
- 201000010099 disease Diseases 0.000 abstract description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 210000001035 gastrointestinal tract Anatomy 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 244000144972 livestock Species 0.000 abstract description 2
- 241000272496 Galliformes Species 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 210000004877 mucosa Anatomy 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 230000000246 remedial effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 241001465754 Metazoa Species 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 8
- 241000287828 Gallus gallus Species 0.000 description 8
- 235000013601 eggs Nutrition 0.000 description 8
- 244000144977 poultry Species 0.000 description 8
- 235000013594 poultry meat Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000002354 daily effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 235000013330 chicken meat Nutrition 0.000 description 5
- 235000005911 diet Nutrition 0.000 description 5
- 230000037213 diet Effects 0.000 description 5
- 210000002303 tibia Anatomy 0.000 description 5
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- 102000001554 Hemoglobins Human genes 0.000 description 4
- 108010054147 Hemoglobins Proteins 0.000 description 4
- 235000014590 basal diet Nutrition 0.000 description 4
- 235000013345 egg yolk Nutrition 0.000 description 4
- 210000002969 egg yolk Anatomy 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 206010022971 Iron Deficiencies Diseases 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
- 238000009432 framing Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 210000002445 nipple Anatomy 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 210000000582 semen Anatomy 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 102100035882 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 206010070840 Gastrointestinal tract irritation Diseases 0.000 description 1
- 208000015710 Iron-Deficiency Anemia Diseases 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- 102100030856 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 241000736919 Pelodiscus sinensis Species 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 1
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- 102000002070 Transferrins Human genes 0.000 description 1
- 108010015865 Transferrins Proteins 0.000 description 1
- 102100033220 Xanthine oxidase Human genes 0.000 description 1
- 108010093894 Xanthine oxidase Proteins 0.000 description 1
- ZSLZBFCDCINBPY-ZSJPKINUSA-N acetyl-CoA Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSC(=O)C)O[C@H]1N1C2=NC=NC(N)=C2N=C1 ZSLZBFCDCINBPY-ZSJPKINUSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 230000036750 egg laying performance Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 229940082629 iron antianemic preparations Drugs 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001711 laumontite Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 235000016709 nutrition Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Fodder In General (AREA)
Abstract
The present invention discloses an iron replenisher of slow release control type iron and a preparation method and a purpose thereof. The iron replenisher is zeolite containing active iron, and the content of iron in the zeolite is 1.5% to 10% according to the percentage by weight. In the preparation method, zeolite containing active iron is prepared by the procedures of the adsorption and the ion exchange reaction between a divalent molysite and natural artificially synthesized zeolite, filtering, drying and pulverizing. The preparation method has the advantages of simple technological process, low production cost and easy popularization and implementation. Because carrier zeolite has the characteristics of good biocompatibility and gastrointestinal tract mucosa compatibility, regular intercommunicating pore canal structure and cage space, high surface activity, large specific surface area, etc., iron carried by the carrier zeolite has a slow release control function, and the absorption and the utilization rate of iron is greatly raised. The slow release control type iron prepared by the present invention can be used as a feed additive applied to iron replenishment for fowls, aquatic livestock, cattle, sheep, etc., and can be also used for preparing human oral taking iron replenishment health products or medicines for treating human diseases by administration of remedial iron. The slow release control type iron has wide application range.
Description
Technical field
The present invention relates to iron supplement agent of a kind of control released iron and its production and use.
Background technology
Ferrum is the essential a kind of trace element of animal, is the essential constituent of hemoglobin and Myoglobin, and active closely related with cytochrome enzyme, peroxidase, catalase, S-acetyl-coenzyme-A, succinate dehydrogenase, xanthine oxidase.Ferrum participates in the normal transport of oxygen in the body tissue, directly influences the energy and the protein metabolism of body, but also can influence the immune function and the reproductive performance of animal body.Iron content in the conventional feed is higher, says on the Dan Congliang, can satisfy the animal needs.But the utilization rate of ferrum is extremely low in the plant feed, and the intensification degree of aquaculture is more and more higher, and the effort of breeding and nutrition two aspects makes the speed of growth of poultry increase substantially.Thereby, must manually add part ferrum, could satisfy the needs of poultry.Artificial add be called iron additive.So far, three phases has been experienced in the development of iron additive, and three generation products is arranged accordingly.First generation product is an inorganic iron: ferrous sulfate, ferrous carbonate, ferric oxide, iron chloride, ferrous chloride etc.; Second filial generation product is an organic salt ferrum: ferric lactate, ferrous fumarate, ferrous citrate, Fumaric acid ferrum etc.; The third generation is protein sources or iron-amino acid chelate: methionine chelate ferrum, threonine chelated ferrum, ferrum glycinate etc.
Iron deficiency or ferrum utilize when bad in the human body, then iron deficiency or iron deficiency anemia can occur, particularly give the child more than 4 months, and the harm that the women of gestation, lactication, menstrual phase brings is very serious.The ferrous-fortifier that China's approval is used mainly contains ferrous sulfate, ferric citrate, ferric ammonium citrate, ferrous fumarate ammonium, Ferrous gluconate, ferrous lactate etc.Weigh food and mainly see its performance with the quality of ferrous-fortifier, generally comprise following 2 aspects: being to see its relative bioavailability on the one hand, is to see color or the taste that whether changes food after it adds on the other hand.The dissolubility of relative bioavailability and ferrous-fortifier has confidential relation, ordinary circumstance, every Fe that changes in the intestines and stomach easily
2+Just being absorbed easily of ionic condition.But from the ferrous-fortifier of present use, dissolubility is good usually, and bioavailability is higher, and often the probability to food color and changing odor is also bigger.And iron supplement agent such as ferrous sulfate, Ferrous gluconate often can produce the endogenous free radical, the cell membrane damage that causes the peroxidating of cell membrane lipid to cause in vivo with side effect such as gastrointestinal irritation and rust flavor and ferrum (II).Therefore various countries' research worker is being sought the iron enriched nutrient that side effect is little, bioavailability is high always for many years.
The control slow-released system has selectivity and controllability to release position, speed and the mode of medicine, pesticide, fertilizer, spice, can realize the targeting transmission and the control slow release of object, improve its utilization rate and action effect, the research and the application of control slow-releasing system will bring new technological revolution to relevant industries.The control slow release method is also representing great application prospect and theory significance aspect the research and development of feed additive, it can promote the high performance and the environmental friendlinessization of product, will provide material and technical guarantee for sustainable development of animal husbandry on new level.
The key of control slow release method is the selection of controlled release carrier.Zeolite is the aluminosilicate with regular pore canal structure of natural existence of a class or synthetic, and its chemical composition is: M
2/nAl
2O
3XxSiO
2YH
2O, wherein M represents metal cation, and n is the valence state of metal cation, and x is a silica alumina ratio, and y is the saturation moisture subnumber.Natural zeolite is because of minerogentic condition difference complex structure, and the zeolite molecular sieve of synthetic is simple in structure, controlled.Constitute the most basic construction unit TO of molecular sieve
4(T=Si, Al or other element) tetrahedron not only can be interconnected to quaternary, cell rings such as hexa-atomic via oxo bridge, can also further be unified into dicyclo, the further connection of these single, double rings just forms panoramic porous zeolite material framing structures such as cage shape or different dimension pore canal system.For example eight yuan of oxygen member ring systems comprise erionite, chabasie, α-zeolite, and these zeolites are mesoporous material, comprise the supercage that interconnects in the pore canal system; The ten-ring system claims mesopore zeolite again, comprises natural laumontite and a large amount of synthetic silica-rich zeolites, contains five yuan of oxygen rings in their framing structure, and the pore canal system major part is the single hole road of non-intersection; Double hole channel system zeolite has the internal communication duct of ten binary and perforate of eight yuan of oxygen rings or ten yuan and the eight yuan first perforates of oxygen, and as clinoptilolite, modenite, foresite etc., this class zeolite has mesoporous and two kinds of apertures of micropore.Because zeolite has good biocompatibility and gastrointestinal tract mucous affinity, the intercommunication pore passage structure and the cage shape space of rule, characteristics such as high surface and huge specific surface area make it very to be suitable as the control slow-released carrier.
Summary of the invention
The purpose of this invention is to provide iron supplement agent of a kind of control released iron and its production and use.
The iron supplement agent of control released iron is to adopt divalent iron salt and a kind of zeolite that contains active iron natural or that the artificial synthetic zeolite is prepared from through absorption, ion-exchange reactions, and by weight percentage, the content of ferrum in zeolite is 1.5～10%.
The preparation method of the iron supplement agent of control released iron of the present invention may further comprise the steps:
1) zeolite is ground to greater than 300 orders, adds water and stir, make concentration and be 1%～10% suspension slurry;
2) with iron-holder be the divalent iron salt of zeolite weight 1.5～10%, slowly add in the suspension slurry of step 1) that the pH value that detects and regulate ore pulp is 3.0～6.5, room temperature reaction 4～10 hours in stirring down;
3) detection step 2) pH value of serosity is regulated with alkaline solution, and making slurry pH value is 7.0～8.5; Wash 2～5 times, filter or centrifuge dehydration;
4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the agent of controlled release type iron supplement.
The said zeolite of the present invention can be natural or artificial synthetic zeolite.Synthetic zeolite is the commercial goods or adopts known preparation method preparation that its technology of preparing is well-known.
The said divalent iron salt of the present invention is inorganic divalent iron salt or organic divalent iron salt, inorganic divalent iron salt can be ferrous chloride, ferrous nitrate or ferrous sulfate, and organic divalent iron salt can be glycine ferrous, ferrous citrate, ferrous fumarate, Ferrous gluconate, ferrous lactate, ferrous lysine chelate or ferrous methionine.Said alkaline solution is that concentration is the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or the potassium bicarbonate of 0.5～10moL/L.
The serosity dewatering process of preparation method, but treatment in accordance with local conditions are selected for use centrifugal or method such as filtration is dewatered.The filter cake of dehydration back gained can use conventional drying plant drying.The iron supplement agent of the control released iron after the oven dry is block, can select for use conventional disintegrating apparatus to be crushed to granularity greater than 300 orders.
The iron supplement agent of control released iron is as poultry, aquatic animal, cattle, sheep iron supplement feed additive.
The iron supplement agent of control released iron is used as the human oral iron supplement of preparation and treats the health product or the medicine of human diseases by the ferrum of drug treatment.
The present invention has the following advantages:
(1) because the carrier zeolite has good biocompatibility and gastrointestinal tract mucous affinity, the intercommunication pore passage structure and the cage shape space of rule, characteristics such as high surface and huge specific surface area make it that the ferrum of institute's load is had the control slow releasing function, thereby have improved the absorption rate of ferrum greatly.
(2) the present invention adopts divalent iron salt and natural or artificial synthetic zeolite's absorption, ion-exchange reactions, after filtration, dry, pulverize and make the zeolite that contains active iron, this method technological process is simple, low production cost is easy to promotion and implementation.
(3) the prepared iron supplement agent of the present invention can be used as the iron supplement that feed additive is applied to poultry, aquatic animal, cattle, sheep etc.; Also can be used for preparing human oral iron supplement and treat the health product or the medicine of human diseases by the ferrum of drug treatment, the scope of application is extensive.
(4) iron supplement feed additive of the present invention is easy to mix with feedstuff, forms homodisperse system, and is easy to use.
The specific embodiment
The present invention is further described in conjunction with following example.
Embodiment 1
1) clinoptilolite that will originate from Jinyun county, Zhejiang province is ground to 500 orders, adds water and stirs, and makes concentration and be 10% suspension slurry;
2) with iron-holder be the ferrous chloride of zeolite weight 2% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 3.0, room temperature reaction 4 hours;
3) detection step 2) pH value of serosity is regulated with the aqueous sodium carbonate of 0.5moL/L, and making slurry pH value is 7.0; Wash filtering means dehydration 4 times;
4) filter cake of step 3) gained is dried, is crushed to 600 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in zeolite is 2%.
Different sources of iron are to the influence of laying hen egg laying performance and egg iron content:
Select Luo Man laying hen 450 plumages of 380 age in days health, be divided into five groups at random, establish three repetitions for every group, every group 90 plumage, each repeats 30 plumages.Wherein one group is matched group, be to add iron content 80mg/kg (ferrous sulfate) in the basal diet, four groups is test group in addition, adds iron content 80mg/kg (ferrum glycinate), 160mg/kg (ferrum glycinate), 600mg/kg (ferrous sulfate), 80mg/kg (control released iron) respectively in basal diet.Adopt three layers of full ladder to raise in cages, free choice feeding and drinking-water, illumination is 16L+8B.1 week of preliminary trial period, just trying 9 weeks of phase, feeding period interocclusal record feed intake, extremely eliminate chicken number, the number of laying eggs, broken egg number, total egg size and average egg weight etc.When feeding experiment finishes, get 24 pieces of eggs (each repeats 8 pieces) at random, measure the egg yolk iron content for every group.
Feeding experiment result shows, compares with contrast (80mg/kg ferrous sulfate group), and the ferrum glycinate and the control released iron that add 80mg/kg make laying rate improve 2.6% (P=0.1) and 4.7% (P＜0.05) respectively; 80mg/kg, 160mg/kg ferrum glycinate and 80mg/kg control released iron make rate of broken eggs reduce by 38.5% (P＜0.05), 34.2% (P＜0.05) and 41.3% (P＜0.05) respectively; Different sources of iron to average egg weight, feedstuff-egg ratio, extremely eliminate rate etc. and all do not make significant difference.
Egg yolk iron content measurement result shows, compare with matched group, 80mg/kg ferrum glycinate, 160mg/kg ferrum glycinate, 600mg/kg ferrous sulfate, 80mg/kg control released iron make that iron content has improved 8.4% (P＞0.05) respectively in the egg yolk, 35.6% (P＜0.01), 41.3% (P＜0.01) and 43.2% (P＜0.01).This shows that the 80mg/kg control released iron makes the deposition of egg yolk ferrum reach the effect of 160mg/kg ferrum glycinate and 600mg/kg ferrous sulfate.
Embodiment 2
1) commercially available ZSM-5 type zeolite molecular sieve is ground to 300 orders, adds water and stir, make concentration and be 5% suspension slurry;
2) with iron-holder be the ferrous nitrate of zeolite weight 5% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 4.5, room temperature reaction 6 hours;
3) detection step 2) pH value of serosity is regulated with the sodium hydrate aqueous solution of 10moL/L, and making slurry pH value is 7.5; Wash filtering means dehydration 3 times;
4) filter cake of 1 step 3) gained is dried, is crushed to 300 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in zeolite is 5%.
Different sources of iron are to the influence of suckling pig growth, metabolism and environment:
Select that the source is identical, feeding and management condition is identical, breed the achievement no significant difference in the past and be the assorted greatly sow of 15 head lengths of the 3rd parity, with 15 nests that produced after the semen deposition of same Du Luoke boar semen the close and inapparent DLY piglet of birth weight difference of totally 150 ages in days be for trying pig.Connect every group 5 nest and be divided into 3 groups at random, the I group is the ferrous sulfate group, and the II group is the ferrous methionine group, and the III group is the control released iron group.It is identical that each organizes the feeding and management program, the environmental condition unanimity.Connect nest and raise with the single hurdle of mother in same suckling house, pig house and sports ground are cement flooring nature suckling, and nursing sow all feeds identical diet.Piglet 3 age in days water supply start iron supplement, each group supplies the corresponding iron preparation aqueous solution of iron content 1000mg/L respectively, dripping on sow nipple (each nipple drips 1mL at every turn, drips sooner or later every day 2 times) when adopting lactication is sucked by piglet and places tank to appoint a piglet freely to drink the method that combines and carry out.7 ages in days begin to lure material, and 10 ages in days change by the diet iron supplement.3 basic diets of group are identical, add the different iron preparations of 100mg/kg respectively, and it is quantity-unlimiting that free choice feeding and drinking-water, diet are pressed the nest metering, finishes test during the wean of 35 ages in days.
The result shows: the indexs such as body weight, daily gain, body condition behavior grade, blood hemoglobin value, plasma transferrins content, blood plasma and liver iron of II, III group piglet when 35 age in days off-tests all remarkable (P＜0.05 or P＜0.01) is higher than the I group; In food consumption, diarrhoea incidence rate, defecation amount, the excrement iron-holder and row's ferrum amount then significantly (P＜0.05 or P＜0.01) be lower than the I group.III organize 35 age in days body weight, daily gain and hemoglobin also significantly (P＜0.05) be higher than the II group, but all the other indexs do not have significant difference (P＞0.05) between II group and III group, illustrate that control released iron and ferrous methionine can obviously improve the health status of piglet, growth promoter, the price of deed and blood physiology biochemical indicator, promote ferrum in intravital absorption of pig and utilization, reduce row's ferrum amount in defecation amount and the excrement.With regard to control released iron and ferrous methionine comparatively speaking, the former is better than the latter again to the iron supplement effect of suckling pig, is especially improving aspect piglet daily gain and the content of hemoglobin effect significantly (P＜0.05).
Feces of livestock and poultry to the pollution of atmosphere, water source and soil in fact and the ecological environment of we being depended on for existence constituted threat, and also seriously limited the sustainable development of intensification animal husbandry.In this test in the I that surveys group defecation amount, the excrement iron-holder and row's ferrum total amount all significantly (P＜0.05) be higher than the II group and III organizes, this not only further specify this class inorganic salt of ferrous sulfate in the piglet body absorption rate far below control released iron and ferrous methionine, and since in the diet various compositions all to be that mutual restriction is collaborative mutually again play a role.The unbalance absorption and the utilization that all might reduce other compositions of any composition.This had both wasted resource, had increased production cost, had reduced the effective supply of body nutrient again, influence the balance and stability of growth of animals or poultry, metabolism and organismic internal environment, also can aggravate pollution to environment because of having increased excretion.
Embodiment 3
The preparation: according to " modification of mesopore molecular sieve MCM-41 and sign under the temperate condition " (Zheng Shan, high Lian, Guo Jingkun. Journal of Inorganic Materials, 2000,15 (5): method 844-848) prepares mesopore molecular sieve MCM-41.
1) the mesopore molecular sieve MCM-41 that obtains in the preliminary step is ground to 300 orders, adds water and stir, make concentration and be 1% suspension slurry;
2) with iron-holder be the glycine ferrous of MCM-41 weight 10% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 6.5, room temperature reaction 10 hours;
3) detection step 2) pH value of serosity is regulated with the potassium hydroxide aqueous solution of 5moL/L, and making slurry pH value is 8.5; Wash centrifuge dehydration 5 times;
4) filter cake of step 3) gained is dried, is crushed to 400 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in MCM-41 is 10%.
Control released iron is to the relative biological value of AA broiler:
1 age in days commodity by completely random single-factor design method, are established three processing for the AA broiler, add standard ferrum platform thing (analytical pure FeSO successively on the basis of basal diet
4.7H
2O), control released iron and commercially available ferrous methionine.5 levels are established in each processing, and the ferrum addition is respectively 0,20,40,60,80mg/kg, and each level is established 3 repetitions.Each repeats to account for a non-plating iron material breeding cage, supports 4 chickens.Male and female half and half.Experimental period was three weeks, and first week was preliminary trial period, all test chickens basal diet of all feeding.Just the examination phase was two weeks, the corresponding test daily ration of feeding.When just the examination phase begins and finishes, be respectively that unit weighs to test chicken with the repeating groups.Calculate average daily gain and feed consumption.During off-test, each 1 approaching of male and female chicken of selection and this group body weight is butchered in each repeating groups, strips right lower limb tibia, merges back its ash of survey and weighs.The reuse atomic absorption spectrophotometry is surveyed tibia ash iron content.
Adopt slope ratio method to calculate relative biological value.With analytical pure FeSO
4.7H
2O is a reference standard, calculates the regression slope of other source of iron when its regression straight line slope is 100, and this is hypothesis reference standard analytical pure FeSO
4.7H
2The biological value of O is 100 o'clock, and the relative biological value of other source of iron the results are shown in Table 1.
The relative biological value of the different sources of iron of table 1
| Index is handled | CuSO 4.5H 2O | Control released iron | Ferrous methionine |
| Iron deposition in the heavy tibia ash of the daily gain tibia ash iron content tibia | 100 100 100 100 | 228 320 141 198 | 195 294 125 208 |
Embodiment 4
1) commercially available 4A type zeolite molecular sieve is ground to 400 orders, adds water and stir, make concentration and be 8% suspension slurry;
2) with iron-holder be the ferrous citrate of zeolite weight 1.5% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 4.0, room temperature reaction 6 hours;
3) detection step 2) pH value of serosity is regulated with the wet chemical of 2moL/L, and making slurry pH value is 7.5; Wash centrifuge dehydration 2 times;
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in zeolite is 1.5%.
Embodiment 5
1) epidesmine that will originate from Guangxi is ground to 600 orders, adds water and stirs, and makes concentration and be 4% suspension slurry;
2) with iron-holder be the ferrous lysine chelate of zeolite weight 2.5% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 4.5, room temperature reaction 10 hours;
3) detection step 2) pH value of serosity is regulated with the sodium hydrate aqueous solution of 6moL/L, and making slurry pH value is 7.0; Wash centrifuge dehydration 4 times;
4) filter cake of step 3) gained is dried, is crushed to 600 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in zeolite is 2.5%.
Embodiment 6
The preparation: according to " the ZSM-5 zeolite molecular sieve of non-amine method synthesizing high-silicon aluminum ratio and high-crystallinity " (Xiang Shouhe, Liu Shuquan, Wang Jingzhong, Li He is noisy etc. national inventing patent Granted publication 1046922C) method prepare the ZSM-5 zeolite molecular sieve.
1) the ZSM-5 zeolite molecular sieve that obtains in the preliminary step is ground to 300 orders, adds water and stir, make concentration and be 6% suspension slurry;
2) with iron-holder be the ferrous fumarate of zeolite weight 4% in stirring the suspension slurry that slowly adds step 1) down, the pH value that detects and regulate ore pulp is 4.5, room temperature reaction 4 hours;
3) detection step 2) pH value of serosity is regulated with the potassium hydroxide aqueous solution of 6moL/L, and making slurry pH value is 8.0; Wash centrifuge dehydration 4 times;
4) filter cake of step 3) gained is dried, is crushed to 400 orders, obtain the agent of controlled release type iron supplement, by weight percentage, the content of ferrum in zeolite is 4%.
The iron supplement agent of control released iron as the using method of the iron supplement feed additive of poultry, aquatic animal, cattle, sheep is: admix (in ferrum) in poultry, the aquatic animal feed by following additive capacity: pig 40～100mg/kg, broiler 50～80mg/kg, laying hen 60～100mg/kg, fish 20～80mg/kg, Trionyx sinensis Wiegmann 40～100mg/kg, shrimp 50～100mg/kg.
The iron supplement agent of control released iron is used to prepare human oral iron supplement and treats obeying 1～2 time health product and medicine day of human diseases by the ferrum of drug treatment, and a day dosing is advisable with ferrum amount 10～50mg/d.
Claims (7)
1. the iron supplement agent of a control released iron, it is characterized in that it is to adopt divalent iron salt and a kind of zeolite that contains active iron natural or that the artificial synthetic zeolite is prepared from through absorption, ion-exchange reactions, by weight percentage, the content of ferrum in zeolite is 1.5～10%.
2. the iron supplement agent of a kind of control released iron according to claim 1 is characterized in that described divalent iron salt is inorganic divalent iron salt or organic divalent iron salt.
3. the iron supplement agent of a kind of control released iron according to claim 2, it is characterized in that described inorganic divalent iron salt is ferrous chloride, ferrous nitrate or ferrous sulfate, organic divalent iron salt is glycine ferrous, ferrous citrate, ferrous fumarate, Ferrous gluconate, ferrous lactate, ferrous lysine chelate or ferrous methionine.
4. the preparation method of the iron supplement agent of a control released iron as claimed in claim 1 is characterized in that the step of method is as follows:
1) zeolite is ground to greater than 300 orders, adds water and stir, make concentration and be 1%～10% suspension slurry;
2) with iron-holder be the divalent iron salt of zeolite weight 1.5～10%, slowly add in the suspension slurry of step 1) that the pH value that detects and regulate ore pulp is 3.0～6.5, room temperature reaction 4～10 hours in stirring down;
3) detection step 2) pH value of serosity is regulated with alkaline solution, and making slurry pH value is 7.0～8.5; Wash 2～5 times, filter or centrifuge dehydration;
4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the agent of controlled release type iron supplement.
5. the preparation method of the iron supplement agent of a kind of control released iron according to claim 4 is characterized in that described divalent iron salt is inorganic divalent iron salt or organic divalent iron salt.
6. the preparation method of the iron supplement agent of a kind of control released iron according to claim 5, it is characterized in that described inorganic divalent iron salt is ferrous chloride, ferrous nitrate or ferrous sulfate, organic divalent iron salt is glycine ferrous, ferrous citrate, ferrous fumarate, Ferrous gluconate, ferrous lactate, ferrous lysine chelate or ferrous methionine.
7. the preparation method of the iron supplement agent of a kind of control released iron according to claim 4 is characterized in that described alkaline solution is that concentration is the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or the potassium bicarbonate of 0.5～10moL/L.
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