CN1997596A - 基于硫酸铁的磷酸盐吸附剂 - Google Patents
基于硫酸铁的磷酸盐吸附剂 Download PDFInfo
- Publication number
- CN1997596A CN1997596A CNA2005800214599A CN200580021459A CN1997596A CN 1997596 A CN1997596 A CN 1997596A CN A2005800214599 A CNA2005800214599 A CN A2005800214599A CN 200580021459 A CN200580021459 A CN 200580021459A CN 1997596 A CN1997596 A CN 1997596A
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- CN
- China
- Prior art keywords
- composition
- iron
- preparation
- iii
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 12
- 239000010452 phosphate Substances 0.000 title abstract description 12
- 239000003463 adsorbent Substances 0.000 title abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title description 3
- 229910000358 iron sulfate Inorganic materials 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 241001465754 Metazoa Species 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 95
- 239000000725 suspension Substances 0.000 claims description 48
- 229910052742 iron Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 150000001720 carbohydrates Chemical class 0.000 claims description 18
- 235000014633 carbohydrates Nutrition 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004021 humic acid Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 239000002594 sorbent Substances 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 8
- 229960004887 ferric hydroxide Drugs 0.000 claims description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 201000005991 hyperphosphatemia Diseases 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 238000007911 parenteral administration Methods 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 150000003016 phosphoric acids Chemical class 0.000 description 18
- 239000011734 sodium Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000004255 ion exchange chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229940045511 barium chloride Drugs 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- -1 iron nitrate compound Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 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 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000004913 chyme Anatomy 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007902 hard capsule Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000007901 soft capsule Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/26—Iron; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
-
- 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
- A61P3/12—Drugs for disorders of the metabolism for electrolyte homeostasis
- A61P3/14—Drugs for disorders of the metabolism for electrolyte homeostasis for calcium homeostasis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/08—Plasma substitutes; Perfusion solutions; Dialytics or haemodialytics; Drugs for electrolytic or acid-base disorders, e.g. hypovolemic shock
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Food Science & Technology (AREA)
- Epidemiology (AREA)
- Hematology (AREA)
- Hydrology & Water Resources (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Diabetes (AREA)
- Mycology (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Nutrition Science (AREA)
- Obesity (AREA)
- Rheumatology (AREA)
- Endocrinology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Medicinal Preparation (AREA)
- Compounds Of Iron (AREA)
- Fodder In General (AREA)
Abstract
本发明涉及一种制备新组合物的方法,且涉及所述组合物作为磷酸盐吸附剂的用途,尤其用于人类和动物中的施用。
Description
本发明涉及一种制备新组合物的方法,且涉及该组合物作为磷酸盐吸附剂的用途,尤其用于人类和动物中的施用。
由EP0868125可得知用于来自含水介质的磷酸盐的吸附剂,该吸附剂包含由碳水化合物和/或腐殖酸稳定的多核β-氢氧化铁。该产物的制备是通过将氯化铁(III)溶液与碱(尤其是苏打溶液)反应且在所得氢氧化铁老化之前加入碳水化合物或腐殖酸。在沉淀中必须采用氯化铁(III)溶液,因为氯离子的存在对于形成β-氢氧化铁(四方纤铁矿)是必不可少的。推测碳水化合物或腐殖酸的加入引起新制备的β-氢氧化铁的稳定化,其结果是所得材料与老化β-氢氧化铁与碳水化合物或腐殖酸的混合物相比,表现出优异的磷酸盐吸附容量。
然而,在根据EP0868125制备磷酸盐吸附剂过程中,将氯化铁(III)用作起始材料出现了问题。例如,氯化铁(III)的使用导致装置中由于存在氯离子的腐蚀问题。此外,氯化铁(III)成本相对较高。
因此,希望提供不会由于使用氯化铁(III)作为起始材料而表现出上述缺点的磷酸盐吸附剂。同时,该磷酸盐吸附剂应具有与根据EP0868125的材料基本相同的磷酸盐吸附容量。
本发明人现已令人惊奇地发现通过使用硫酸铁和/或硝酸铁化合物作为起始材料,可能在不使用氯化铁(III)的情况下(例如通过碳水化合物或腐殖酸)获得明显同样稳定的氢氧化铁,且其磷酸盐吸附容量基本上相应于EP0868125的材料的容量。在该发现的基础上,本发明人完成了本专利申请。
因此本发明提供了一种制备组合物的方法,包括以下步骤:
a)将至少一种碱加入含硫酸盐和/或硝酸盐的铁(III)盐水溶液以形成氢氧化铁沉淀,
b)任选用水洗涤所得沉淀一次或多次,产生氢氧化铁的含水悬浮液,
c)向所得含水悬浮液加入至少一种另一成分,该成分抑制步骤b)中所得的氢氧化铁沉淀的老化,
d)干燥步骤c)中所得的组合物。
在步骤a)中,含硫酸盐和/或硝酸盐的铁(III)盐水溶液与至少一种碱反应以形成氢氧化铁沉淀。
含硫酸盐的铁(III)盐水溶液可具体为硫酸铁(III)(Fe(SO4)3)(包括其水合物)的水溶液。然而还可以采用其它含硫酸盐的铁(III)盐水溶液,例如铁明矾溶液,如KFe(SO4)2或NH4Fe(SO4)2。还可根据本发明采用含硫酸的硫酸亚铁(II)溶液,例如用硝酸对其进行氧化。
优选使用的含硫酸盐的铁(III)盐水溶液浓度约3-16wt.%,基于铁量。
含硝酸盐的铁(III)盐水溶液可具体为硝酸铁(III)(Fe(NO3)3)(包括其水合物)的水溶液。
优选使用的含硝酸盐的铁(III)盐水溶液浓度约3-16wt.%,基于铁量。
有利地选择在步骤a)中加入的碱量使得建立至少约3,优选至少约6的pH值。有利的是,从经济角度出发,碱的用量使得铁尽可能彻底地从溶液沉淀。因此,通常该工序在不超过约10的pH值实施。从经济角度出发,更高的pH值不再有利。因此,在步骤a)中建立的pH值优选约3-10,更优选约5-8。
碱金属和/或碱土金属化合物优选用作步骤a)中的碱。尤其优选这些化合物是碱或碱土金属的氢氧化物或碳酸盐。更加优选碱金属碳酸盐、碱金属碳酸氢盐和碱金属氢氧化物,尤其优选钠。这些碱有利地且优选地以含水溶液形式使用,优选具有约0.01-2mol/l的摩尔浓度。然而,也可将碱以固体形式加入该含硫酸盐和/或硝酸盐的铁(III)盐溶液。
最优选氢氧化钠、碳酸钠和/或碳酸氢钠用作步骤a)中的碱,优选以其水溶液形式。
与碱的反应优选不在高温进行,因为这可能导致形成的氢氧化物加速老化。反应中的温度优选维持在10-40℃,更优选20-30℃;甚至更优选反应在室温(25℃)进行。可有利地允许悬浮液在沉淀之后短暂静置。在实践中,可使悬浮液在室温或以下静置例如1-5小时。在该期间,可搅拌悬浮液。
随后,优选用水洗涤所得沉淀一次,优选数次,在每种情况下,洗涤/悬浮操作之后优选通过滗析、过滤、离心和/或通过反渗透工艺例如膜过滤将水除去。并不干燥所得潮湿产物。潮湿产物悬浮于水中。水量并不关键;优选地,该工序使得所得悬浮液的铁含量(以Fe计算)至多为10wt.%,尤其优选2-8wt.%。
在加入其它组分之前,所得氢氧化铁含水悬浮液优选具有大约6.5-7.5范围的接近中性pH值。较低pH值会导致氢氧化铁再次部分进入溶液。较高pH值是不合需要的,因为这可能导致步骤c)中络合物的形成。
根据本发明的工艺尤其优选以这样的方式进行:在步骤c)中加入其它组分之前,基本没有氢氧化铁出现老化。在沉淀老化期间,经常发生最初随机就位的分子重新组合以形成或多或少的规则晶格。在大多数情况下,沉淀的老化不仅包括结晶,还包括由于奥斯特瓦尔德(ostwald)熟化导致的颗粒增大。
在步骤c)中,向以上获得的悬浮液加入至少一种其它组分,该组分抑制上述在步骤b)中获得的氢氧化铁沉淀的老化。抑制氢氧化铁老化的该组分可优选选自碳水化合物、碳水化合物衍生物和腐殖酸。该组分优选以固体形式加入,但是以含水溶液形式加入在原则上也是可行的。
根据本发明,尤其优选用作进一步老化抑制组分的是碳水化合物,例如各种碳水化合物和糖,例如琼脂糖、葡聚糖、糊精、麦芽糖糊精、糊精衍生物、葡聚糖衍生物、淀粉、纤维素如微晶纤维素和纤维素衍生物、蔗糖、麦芽糖、乳糖或甘露醇。
尤其优选淀粉、蔗糖、糊精和/或其混合物。最优选淀粉、蔗糖或其混合物。非常优选蔗糖和至少一种特别选自淀粉、麦芽糖糊精和纤维素尤其是微晶纤维素的其它组分的混合物。不受一种理论束缚,推测认为额外组分的功能是稳定新鲜配制的沉淀氢氧化铁,由此防止氢氧化铁沉淀的老化。
优选选择碳水化合物或腐殖酸的量使得每g铁(以Fe计算)加入至少0.5g,优选至少1g抑制氢氧化铁老化的其它组分,例如碳水化合物或腐殖酸。优选地,所得组合物的铁含量不应超过50wt.%,优选不超过约40wt.%。所得组合物的铁含量应当优选至少20wt.%。抑制氢氧化铁老化的组分(例如碳水化合物和/或腐殖酸)的最大含量不受任何限制,主要由经济原因决定。所述含量优选约5-60wt.%,更优选约20-60wt.%。
在步骤c)中加入抑制氢氧化铁老化的组分之后,以本身已知的方式干燥所得含水悬浮液。可例如通过真空浓缩或者喷雾干燥进行干燥。
在根据本发明方法的一个优选实施方案中,至少一种钙盐在根据本发明获得的组合物干燥之前或者之后加入。合适的钙盐是例如无机或有机酸的盐,尤其是醋酸钙。钙盐的加入增加了磷酸盐结合容量,尤其是在较高pH值时。在大于5的pH值使用提供有钙盐的这些吸附剂是特别有利的,因为随后甚至完整的磷酸盐结合容量得以保持。已经显示每g铁加入400mg-2g,例如约1g的钙盐,尤其是醋酸钙,是特别有利的。
根据本发明获得的材料基本上是氢氧化铁和抑制氢氧化铁老化的组分如碳水化合物或腐殖酸的物理混合物。如上已经所述,推测抑制氢氧化铁老化的组分与新鲜沉淀的氢氧化铁接触且使得氢氧化铁稳定化,从而材料不发生老化,而老化会降低磷酸盐吸附能力。络合物形成,如DE4239442中所述,不会在根据本发明选择的添加含水悬浮液的条件下发生,因为形成络合物在例如碳水化合物加入氢氧化铁期间需要强碱条件。
根据本发明方法获得的组合物优选用于制备用于来自含水溶液的磷酸盐的吸附剂。优选地,通过根据本发明的方法获得的组合物制备用于人类或动物中的口服和/或肠胃外施用的制剂。特别地,根据本发明获得的组合物用于制备预防和/或治疗高磷酸盐血状态(hyperphosphataemicstate)的制剂。特别优选地,根据本发明获得的组合物用于制备预防和/或治疗透析患者的制剂。
为该目的,根据本发明方法获得的组合物以本身已知的方式配制成药学剂型,例如用于口服。其可以原样配制或者与常规的药学添加剂如常规载体或者辅助物质一起配制。例如,可进行包囊,其可采用药学领域中所用的常规材料(例如硬或软胶囊)作为包囊剂。根据本发明获得的组合物微囊化也是可能的。还可以任选结合辅助物质和添加剂,以颗粒、片剂、锭剂、填充成囊剂、以凝胶形式或者以粘剂(stick)形式提供吸附剂。根据本发明获得的组合物的日剂量例如为1-3g,优选约1.5g,基于铁。
根据本发明获得的组合物也适用于吸附结合到食品中的磷酸盐;为此目的,其可以例如混合到食品中。为该目的,可制备例如以上针对药物所述的配方。
根据本发明获得的组合物特别适于用作吸附剂,尤其用于来自体液、食糜和食品的无机的和结合食品的磷酸盐。其具有类似于根据EP0868125所得试剂的磷酸盐吸附能力,制备简单且廉价。
本发明进一步涉及根据本发明方法获得的吸附剂。
通过使用硫酸铁和/或硝酸铁作为起始材料,根据本发明可以获得氯化物含量特别低的组合物,该氯化物仅以痕量存在于组合物中。该氯化物含量尤其低于四方纤铁矿的常规氯化物含量。因此本发明也涉及含有氢氧化铁(III)以及选自碳水化合物和腐殖酸的至少一种组分的组合物,该组合物含有少于0.05wt.%,优选少于0.03wt.%,更优选少于0.01wt.%的氯化物。
通过以下实施例更加详细地解释本发明:
实施例1
444g硫酸铁(III)溶液(11.3%w/w Fe)在20-30分钟内,搅拌下(叶片型搅拌器)滴加到1160g苏打溶液(d20=1.185g/ml)。悬浮液再搅拌1小时。此后将2升水搅拌下加入悬浮液;静置混合物,随后滗析掉上清液。该工序重复5次。以这种方式,获得铁含量4.0%(w/w)(通过配位滴定法确定)的1238g悬浮液。加入蔗糖和淀粉各73.9g到1238g上述悬浮液。随后于60℃在旋转蒸发器中浓缩悬浮液,且于50℃高真空干燥。获得铁含量21.5%(w/w)的223g粉末。
磷酸盐吸附容量的确定:将10ml磷酸钠溶液(13.68g/l Na3PO4×12H2O)加入根据以上实施例制备的233mg材料(对应于0.9mmol铁)(摩尔比Fe∶P=1∶0.4)。在调节pH值之后,允许悬浮液在37℃反应2小时。随后离心悬浮液;滗析掉上清液且用蒸馏水补足到25ml,且确定其磷含量。根据该实施例制备的材料的磷酸盐吸附,由离子色谱法确定,在3.0的pH是0.20mg P/mg Fe和在5.5的pH是0.16mg P/mg Fe。
实施例2
439g硫酸铁(III)溶液(11.5%w/w Fe)在20-30分钟内,搅拌下(叶片型搅拌器)滴加到1014ml氢氧化钠溶液(9.6%w/v)。悬浮液再搅拌1小时。此后将2升水搅拌下加入悬浮液;静置混合物,随后滗析掉上清液。重复该工序直到滗析掉的上清液没有硫酸盐(用氯化钡控制)。以这种方式,获得铁含量2.74%(w/w)(通过配位滴定法确定)的1606g悬浮液。加入蔗糖和淀粉各66.0g到1606g上述悬浮液。随后于60℃在旋转蒸发器中浓缩悬浮液,且于50℃真空干燥。获得铁含量22.2%(w/w)的190g粉末。
磷酸盐吸附容量的确定:将10ml磷酸钠溶液(13.68g/l Na3PO4×12H2O)加入根据该实施例制备的226mg材料(对应于0.9mmol铁)(摩尔比Fe∶P=1∶0.4)。在调节pH值之后,使悬浮液在37℃反应2小时。随后离心悬浮液;滗析掉上清液且用蒸馏水补足到25ml,且确定其磷含量。
根据实施例1制备的材料的磷酸盐吸附,由离子色谱法确定,在3.0的pH是0.19mg P/mg Fe和在5.5的pH是0.15mg P/mg Fe。
实施例3
535g硝酸铁(III)溶液(9.7%w/w Fe)在20-30分钟内,搅拌下(叶片型搅拌器)滴加到1200g苏打溶液(d20=1.185g/ml)。悬浮液再搅拌1小时。随后将悬浮液转移到滤袋且通过用水连续清洗3小时进行洗涤(3小时后洗涤水的电导率约300μS/cm)。以这种方式,获得铁含量4.3%(w/w)(通过配位滴定法确定)的923g悬浮液。加入蔗糖和淀粉各60.1g到923g上述悬浮液。随后于60℃在旋转蒸发器中浓缩悬浮液,且于50℃真空干燥。获得铁含量22.3%(w/w)的172g粉末。
磷酸盐吸附容量的确定:将10ml磷酸钠溶液(13.68g/l Na3PO4×12H2O)加入根据该实施例制备的225mg材料(对应于0.9mmol铁)(摩尔比Fe∶P=1∶0.4)。在调节pH值之后,允许悬浮液在37℃反应2小时。随后离心悬浮液;滗析掉上清液且用蒸馏水补足到25ml,且确定其磷含量。根据该实施例制备的材料的磷酸盐吸附,由离子色谱法确定,在3.0的pH是0.21mg P/mg Fe和在5.5的pH是0.17mg P/mg Fe。
实施例4
234g硫酸铁(III)溶液(11.4%w/w Fe)在20-30分钟内,搅拌下(叶片型搅拌器)滴加到615g苏打溶液(d20=1.185g/ml)。悬浮液再搅拌1小时。随后将悬浮液转移到滤袋且通过用水连续清洗约3小时进行洗涤(用氯化钡测试硫酸盐的缺乏)。以这种方式,获得铁含量6.0%(w/w)(通过配位滴定法确定)的470g悬浮液。加入蔗糖和麦芽糖糊精各21.1g到470g上述悬浮液。随后于60℃在旋转蒸发器中浓缩悬浮液,且于50℃高真空干燥。获得铁含量20.3%(w/w)的66g粉末。
磷酸盐吸附容量的确定:将10ml磷酸钠溶液(13.68g/l Na3PO4×12H2O)加入根据该实施例制备的247mg材料(对应于0.9mmol铁)(摩尔比Fe∶P=1∶0.4)。在调节pH值之后,允许悬浮液在37℃反应2小时。随后离心悬浮液;滗析掉上清液且用蒸馏水补足到25ml,且确定其磷含量。根据该实施例制备的材料的磷酸盐吸附,由离子色谱法确定,在3.0的pH是0.21mg P/mg Fe和在5.5的pH是0.17mg P/mg Fe。
实施例5
223g硫酸铁(III)溶液(11.3%w/w Fe)在20-30分钟内,搅拌下(叶片型搅拌器)滴加到585g苏打溶液(d20=1.185g/ml)。悬浮液再搅拌1小时。随后将悬浮液转移到滤袋且通过用水连续清洗3小时进行洗涤(用氯化钡测试硫酸盐的缺乏)。以这种方式,获得铁含量6.0%(w/w)(通过配位滴定法确定)的447g悬浮液。加入蔗糖和结晶纤维素各20.6g到447g上述悬浮液。随后于60℃在旋转蒸发器中浓缩悬浮液,且于50℃高真空干燥。获得铁含量20.6%(w/w)的65g粉末。
磷酸盐吸附容量的确定:将10ml磷酸钠溶液(13.68g/l Na3PO4×12H2O)加入根据该实施例制备的244mg材料(对应于0.9mmol铁)(摩尔比Fe∶P=1∶0.4)。在调节pH值之后,允许悬浮液在37℃反应2小时。随后离心悬浮液;滗析掉上清液且用蒸馏水补足到25ml,且确定其磷含量。根据该实施例制备的材料的磷酸盐吸附,由离子色谱法确定,在3.0的pH是0.20mg P/mg Fe和在5.5的pH是0.17mg P/mg Fe。
Claims (23)
1.制备组合物的方法,包括以下步骤:
a)将至少一种碱加入含硫酸盐和/或硝酸盐的铁(III)盐水溶液以形成氢氧化铁沉淀,
b)任选用水洗涤所得沉淀一次或多次,产生氢氧化铁的含水悬浮液,
c)向所得含水悬浮液加入至少一种其它成分,该成分抑制步骤b)中所得氢氧化铁沉淀的老化,
d)干燥步骤c)中所得的组合物。
2.根据权利要求1的方法,特征在于采用含硫酸盐的铁(III)盐溶液。
3.根据权利要求1或2的方法,特征在于抑制氢氧化铁沉淀老化的该其它组分选自碳水化合物、碳水化合物衍生物和腐殖酸。
4.根据权利要求1-3任一项的方法,特征在于铁(III)盐溶液是硫酸铁(III)水溶液。
5.根据权利要求1-3任一项的方法,特征在于铁(III)盐溶液是硝酸铁(III)水溶液。
6.根据权利要求1-5任一项的方法,特征在于在步骤a)中建立的pH值至少为3。
7.根据权利要求1-6任一项的方法,特征在于所得组合物含有不超过50wt.%的铁。
8.根据权利要求1-7任一项的方法,特征在于该碱选自碱金属和碱土金属化合物。
9.根据权利要求1-8任一项的方法,特征在于该碱选自碱金属氢氧化物和碱金属碳酸盐。
10.根据权利要求1-9任一项的方法,特征在于碱金属碳酸盐水溶液、碱金属碳酸氢盐水溶液或碱金属氢氧化物水溶液用作步骤a)中的碱。
11.根据权利要求1-10任一项的方法,特征在于在步骤a)中建立的pH值至少为6。
12.根据权利要求1-11任一项的方法,特征在于氢氧化钠、碳酸钠和/或碳酸氢钠用作步骤a)中的碱。
13.根据权利要求1-12任一项的方法,特征在于抑制氢氧化铁老化的该其它组分选自淀粉、蔗糖和糊精。
14.根据权利要求1-13任一项的方法,特征在于在该组合物干燥之前或之后加入至少一种钙盐。
15.根据权利要求1-14任一项的方法,特征在于在步骤c)中加入其它组分之前,基本没有发生氢氧化铁的老化。
16.根据权利要求1-15任一项的方法,特征在于所得组合物在进一步的步骤e)中被配制为药学剂型。
17.根据权利要求1-16任一项可得的组合物在制备用于来自含水溶液的磷酸盐的吸附剂中的用途。
18.根据权利要求1-16任一项可得的组合物在制备用于人类或动物中口服和/或肠胃外施用的制剂中的用途。
19.根据权利要求1-16任一项可得的组合物在制备用于预防和/或治疗高磷酸盐血状态的制剂中的用途。
20.根据权利要求17-19任一项在制备用于预防和/或治疗透析患者的制剂中的用途。
21.根据权利要求1-16任一项的方法可得的吸附剂。
22.根据权利要求1-16任一项所得组合物在制备与食品混合的吸附剂中的用途。
23.含有氢氧化铁(III)以及选自碳水化合物和腐殖酸中的至少一种组分的组合物,特征在于其含有少于0.05wt.%的氯化物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004031181A DE102004031181A1 (de) | 2004-06-28 | 2004-06-28 | Phosphatadsorbens |
DE102004031181.1 | 2004-06-28 | ||
PCT/EP2005/052861 WO2006000547A2 (de) | 2004-06-28 | 2005-06-21 | Verfahren zur herstellung eines phosphatadsorbens auf eisensulfat-basis |
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CN1997596A true CN1997596A (zh) | 2007-07-11 |
CN1997596B CN1997596B (zh) | 2011-03-30 |
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US (2) | US20090169645A1 (zh) |
EP (1) | EP1899270B1 (zh) |
JP (1) | JP4997107B2 (zh) |
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AR (1) | AR049522A1 (zh) |
AU (1) | AU2005256617C1 (zh) |
BR (1) | BRPI0512636A (zh) |
CA (1) | CA2571364C (zh) |
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HK (1) | HK1108422A1 (zh) |
MX (1) | MX2007000335A (zh) |
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UA (1) | UA92894C2 (zh) |
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2004
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- 2005-06-21 US US11/571,305 patent/US20090169645A1/en not_active Abandoned
- 2005-06-21 EP EP05753905.8A patent/EP1899270B1/de active Active
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- 2005-06-21 CN CN2005800214599A patent/CN1997596B/zh not_active Expired - Fee Related
- 2005-06-21 WO PCT/EP2005/052861 patent/WO2006000547A2/de active Application Filing
- 2005-06-21 AU AU2005256617A patent/AU2005256617C1/en not_active Ceased
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- 2005-06-21 UA UAA200614017A patent/UA92894C2/ru unknown
- 2005-06-24 TW TW094121167A patent/TWI351926B/zh not_active IP Right Cessation
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- 2007-01-26 ZA ZA200700767A patent/ZA200700767B/xx unknown
- 2007-12-14 HK HK07113656.1A patent/HK1108422A1/xx not_active IP Right Cessation
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CN107397810B (zh) * | 2016-05-19 | 2021-08-24 | 欣凯医药化工中间体(上海)有限公司 | 基于铁的氢氧化物-桃胶的磷结合剂、其制备方法及其应用 |
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WO2006000547A3 (de) | 2006-06-22 |
DE102004031181A1 (de) | 2006-01-19 |
BRPI0512636A (pt) | 2008-03-25 |
UA92894C2 (ru) | 2010-12-27 |
HK1108422A1 (en) | 2008-05-09 |
TW200603746A (en) | 2006-02-01 |
WO2006000547A2 (de) | 2006-01-05 |
TWI351926B (en) | 2011-11-11 |
KR20070031420A (ko) | 2007-03-19 |
RU2007103154A (ru) | 2008-08-10 |
CA2571364C (en) | 2013-05-14 |
US20090169645A1 (en) | 2009-07-02 |
CA2571364A1 (en) | 2006-01-05 |
RU2344083C2 (ru) | 2009-01-20 |
AU2005256617C1 (en) | 2011-03-10 |
US20140335202A1 (en) | 2014-11-13 |
EP1899270B1 (de) | 2019-02-27 |
CN1997596B (zh) | 2011-03-30 |
ES2718458T3 (es) | 2019-07-02 |
MX2007000335A (es) | 2007-03-12 |
AR049522A1 (es) | 2006-08-09 |
EP1899270A2 (de) | 2008-03-19 |
NZ552247A (en) | 2010-06-25 |
JP4997107B2 (ja) | 2012-08-08 |
NO20070391L (no) | 2007-03-20 |
JP2008504344A (ja) | 2008-02-14 |
ZA200700767B (en) | 2008-09-25 |
KR101122752B1 (ko) | 2012-03-23 |
AU2005256617B2 (en) | 2010-08-26 |
AU2005256617A1 (en) | 2006-01-05 |
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