CN115894266A - Preparation method of sodium ferric ethylene diamine tetraacetate - Google Patents
Preparation method of sodium ferric ethylene diamine tetraacetate Download PDFInfo
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- CN115894266A CN115894266A CN202211509651.4A CN202211509651A CN115894266A CN 115894266 A CN115894266 A CN 115894266A CN 202211509651 A CN202211509651 A CN 202211509651A CN 115894266 A CN115894266 A CN 115894266A
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- sodium
- carbonate
- ferrous
- edta
- ferrous sulfate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 title claims abstract description 45
- 235000019268 ferrous carbonate Nutrition 0.000 claims abstract description 85
- 239000004277 Ferrous carbonate Substances 0.000 claims abstract description 84
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims abstract description 84
- 229960004652 ferrous carbonate Drugs 0.000 claims abstract description 84
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims abstract description 84
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 76
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 235000017550 sodium carbonate Nutrition 0.000 claims description 38
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 34
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 25
- 239000011790 ferrous sulphate Substances 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 25
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 19
- 229940001593 sodium carbonate Drugs 0.000 claims description 14
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical class [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 claims description 11
- SRFKWQSWMOPVQK-UHFFFAOYSA-K sodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(2+) Chemical compound [Na+].[Fe+2].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O SRFKWQSWMOPVQK-UHFFFAOYSA-K 0.000 claims description 10
- 235000013555 soy sauce Nutrition 0.000 claims description 9
- 235000013305 food Nutrition 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000013373 food additive Nutrition 0.000 claims description 4
- 239000002778 food additive Substances 0.000 claims description 4
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims description 4
- WVLDCUJMGWFHGE-UHFFFAOYSA-L iron(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O WVLDCUJMGWFHGE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- XJECNSWAHCMYNZ-UHFFFAOYSA-N C=C.[Fe].[Na] Chemical group C=C.[Fe].[Na] XJECNSWAHCMYNZ-UHFFFAOYSA-N 0.000 claims description 3
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000013409 condiments Nutrition 0.000 claims description 2
- GLYUSNXFOHTZTE-UHFFFAOYSA-L disodium;carbonate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O GLYUSNXFOHTZTE-UHFFFAOYSA-L 0.000 claims description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims description 2
- 229940018038 sodium carbonate decahydrate Drugs 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 49
- 229910052742 iron Inorganic materials 0.000 abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 20
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000009920 chelation Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 70
- 239000000047 product Substances 0.000 description 61
- 239000011734 sodium Substances 0.000 description 26
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 25
- 229910052708 sodium Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 238000004064 recycling Methods 0.000 description 20
- 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 17
- 229960001484 edetic acid Drugs 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000012535 impurity Substances 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- LKZLBQPNDYMRJE-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron;sodium Chemical compound [Na].[Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LKZLBQPNDYMRJE-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 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 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- ASHFQILZQVAPMW-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron Chemical compound [Na+].[Na+].[Fe].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ASHFQILZQVAPMW-UHFFFAOYSA-L 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 240000008397 Ganoderma lucidum Species 0.000 description 1
- 235000001637 Ganoderma lucidum Nutrition 0.000 description 1
- 206010070840 Gastrointestinal tract irritation Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of sodium ferric ethylenediamine tetraacetate, and relates to the technical field of ferric salt preparation. The method comprises the following steps: mixing the ferrous sulfate heptahydrate solution with carbonate or sodium bicarbonate to react to obtain ferrous carbonate, then mixing the ferrous carbonate with EDTA salt solution, and heating to boil to obtain the ethylenediaminetetraacetic acid ferric sodium salt. The iron content of the prepared sodium ferric ethylene diamine tetraacetate meets the requirement, the product yield is high, and the chelation degree of the product is not interfered by the complex breaking action of oxidants such as hydrogen peroxide, so that the purity of the product is improved. In addition, the preparation method is simple and easy to implement, short in flow and low in cost.
Description
Technical Field
The invention relates to the technical field of iron salt preparation, and particularly relates to a preparation method of ethylenediaminetetraacetic acid (EDTA) ferric sodium salt.
Background
Ethylenediaminetetraacetic acid sodium iron (EDTA), also known as sodium iron (EDTA), has a molecular formula of C 10 H 12 FeN 2 NaO 8 ·3H 2 O, molecular weight 421.09, as a pale yellowish crystalline powder. It is not changed during processing and storage, and is soluble in water and acid. The EDTA iron sodium has the advantages of good taste and no gastrointestinal irritation, and when used as food additive, it does not affect the sensory and physicochemical qualities of food. As a new iron salt, sodium iron EDTA is considered by more and more nutrition experts as the most promising iron nutrition enhancer due to its good stability and bioavailability.
At present, although there are reports on the preparation method of sodium ferric ethylenediamine tetraacetate, the existing method has the following defects: for example: the antral ganoderma lucidum discloses a new method using FeCl 3 And Na 2 EDTA、EDTA、NaOH、NaHCO 3 The process for preparing the EDTA iron sodium by using the ferric chloride method is used as a raw material, a large amount of chloride ions are easy to remain in the EDTA iron sodium prepared by using the ferric chloride method, reaction equipment is easy to corrode, and the yield is lower by about 70%. Stalin, et al, discloses a process for preparing EDTAT iron sodium by using ferric sulfate and EDTA4 Na; the product prepared by the ferric sulfate method contains a large amount of sodium sulfate impurities, which affects the purity of the product, and the product is easy to generate precipitate when dissolved in soy sauce. Therefore, the production process of the ethylenediaminetetraacetic acid ferric sodium salt with low research and development cost, short flow, high yield and high purity has practical significance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of ethylenediaminetetraacetic acid ferric sodium salt so as to improve the purity and yield of ethylenediaminetetraacetic acid ferric sodium salt.
The invention is realized by the following steps:
the invention provides a preparation method of ethylenediaminetetraacetic acid ferric sodium salt, which comprises the following steps: mixing the ferrous sulfate heptahydrate solution with carbonate or sodium bicarbonate to react to obtain ferrous carbonate, then mixing the ferrous carbonate with EDTA salt solution, heating to boil to obtain the ethylenediaminetetraacetic acid ferric sodium salt. The carbonate is sodium carbonate, sodium carbonate decahydrate or sodium carbonate heptahydrate.
The invention provides a new preparation route, which comprises the steps of firstly preparing ferrous carbonate on site, reacting the ferrous carbonate with an EDTA salt solution to generate EDTA ferrous salt due to the activity of the ferrous carbonate, and oxidizing the prepared EDTA ferrous salt into EDTA ferric sodium without an additional oxidant particularly by a boiling oxidation mode. The iron content of the ethylenediaminetetraacetic acid ferric sodium salt meets the requirement, and the chelation degree of the product is not interfered by the complex breaking cooperation of oxidants such as hydrogen peroxide, so that the purity of the product is improved. In addition, the preparation method is simple and easy to implement, short in flow and low in cost.
Compared with the existing ferric trichloride method and ferrous sulfate method, the preparation method provided by the invention has the advantages of less impurity ions of the product, no residual chloride ions, no equipment corrosion problem, and greatly improved product purity based on the characteristic of less impurity of the product.
The sodium ferric ethylenediamine tetraacetate prepared by the preparation method provided by the invention has strong product stability, can be dissolved in foods including soy sauce, and does not generate precipitate.
The inventor adopts a method for preparing ferrous carbonate on site, can keep the activity of the ferrous carbonate, and if the finished product of ferrous carbonate is directly added to be mixed and reacted with EDTA salt solution, because the finished product of ferrous carbonate is easy to oxidize to generate ferric oxide and the like which are difficult to preserve, and the ferric oxide and the like lose the activity and cannot fully react with the EDTA salt solution, the purity and the yield of the product of the sodium iron ethylene diamine tetracetate are reduced.
The carbonate cannot be selected from potassium carbonate, the solubility of potassium sulfate generated after reaction is far less than that of sodium sulfate, and the potassium sulfate is likely to be separated out together with ferrous carbonate, so that the sulfate amount in the product is increased, and the product purity is influenced; ammonium carbonate is easy to decompose when heated, and the final product possibly has an ammonium taste.
In a preferred embodiment of the present invention, the ferrous sulfate solution is an aqueous solution prepared from ferrous sulfate monohydrate, ferrous sulfate pentahydrate, ferrous sulfate hexahydrate, ferrous sulfate heptahydrate, or ferrous sulfate dodecahydrate.
In a preferred embodiment of the present invention, the ferrous sulfate solution is a ferrous sulfate heptahydrate solution prepared from ferrous sulfate heptahydrate; the carbonate is sodium carbonate.
The mixing mass ratio of the sodium carbonate to the ferrous sulfate heptahydrate in the ferrous sulfate heptahydrate solution is 30-40. For example, the mixing mass ratio is 30-35; or 32-40; or 35.
The inventor finds that under the condition of the mixing mass ratio, the synthesized ferrous carbonate has more content and can fully react with EDTA salt, and the iron content in the EDTA ferric sodium salt is kept at a higher level.
If the addition amount of the sodium carbonate and the ferrous sulfate heptahydrate is reduced until the mixing addition ratio of the sodium carbonate and the ferrous sulfate heptahydrate is lower than the mixing mass ratio, the sodium iron phosphate cannot completely react with the glycine, and the iron content in the sodium iron ethylenediaminetetraacetate is kept at a low level.
If the addition amount of the sodium carbonate and the ferrous sulfate heptahydrate is increased until the mixing addition ratio of the sodium carbonate and the ferrous sulfate heptahydrate exceeds the mixing mass ratio, impurities are introduced to reduce the iron content of the product. Therefore, when the adding amount of the ferrous sulfate and the soda ash is in the range, the iron content of the product is the highest, and no waste is caused.
In the preferred embodiment of the invention, ferrous sulfate heptahydrate is mixed with water to obtain a ferrous sulfate heptahydrate solution, and the mixing mass ratio of the sodium carbonate, the ferrous sulfate heptahydrate and the water is 30-40: 300-400.
In a preferred embodiment of the present invention, the reaction conditions for preparing ferrous carbonate are as follows: reacting at 70-80 ℃. At the above temperatures, which contribute to obtaining a good activity of the ferrous carbonate, for example at 72-80 ℃ or at 75-80 ℃.
In an alternative embodiment, the reaction time for the preparation of ferrous carbonate is 20-40min. Such as 25-30min, or 30-40min. The preparation method provided by the invention has fewer steps and less time consumption.
In an alternative embodiment, the reaction time for the preparation of ferrous carbonate is 25-30min.
In an optional embodiment, after the reaction for preparing the ferrous carbonate is finished, the method further comprises performing suction filtration on the reaction solution after the reaction to obtain ferrous carbonate crystals.
In the preferred embodiment of the invention, the mixing mass ratio of the ferrous carbonate to the EDTA salt solution is 30-40:392-506.
In the preferred embodiment of the invention, the oxidation reaction is carried out by heating the mixed solution of ferrous carbonate and EDTA solution to boiling and reacting for 20-30min under heat preservation. The heating to boiling means: the mixed liquid is heated to bring the mixed liquid into a boiling state.
In a preferred embodiment of the present invention, the incubation reaction is carried out by mixing a mixture of ferrous carbonate and EDTA salt solution with an oxidizing agent.
In an alternative embodiment, the oxidizing agent is hydrogen peroxide, ozone, potassium permanganate, or manganese dioxide.
In an optional embodiment, when the oxidizing agent is selected from hydrogen peroxide, the mixing mass ratio of the mixed solution of the ferrous carbonate and the EDTA salt solution to the oxidizing agent is 30-40: 30-60.
In a preferred embodiment of the present invention, the oxidation reaction further comprises a cooling step after the oxidation reaction, wherein the cooling step is carried out until the oxidation reaction is crystallized;
in an alternative embodiment, the cooling step is followed by a filtration step to obtain sodium iron ethylenediaminetetraacetate, and the filtrate is recycled; for example, the filtrate is added into a mixed solution of ferrous carbonate and EDTA salt solution (after the reaction is clarified), and is used for preparing the sodium ferric ethylenediamine tetraacetate again.
The filtrate is recycled, so that the product yield can be greatly improved and can reach over 90 percent.
The EDTA salt solution is EDTA monosodium salt solution.
In a preferred embodiment of the invention, the EDTA salt solution is prepared by:
mixing EDTA, water and sodium hydroxide, and reacting at 90-95 ℃; the mass ratio of EDTA, water and sodium hydroxide is 80-90. Compared with the reaction of sodium carbonate and EDTA, the reaction time of the method is shorter, and the reaction can be fully carried out without heating.
In an alternative embodiment, EDTA, water and sodium hydroxide are reacted at 90-95 deg.C for 30-35min.
The invention also provides the application of the sodium ferric ethylenediamine tetraacetate prepared by the preparation method of the sodium ferric ethylenediamine tetraacetate in preparing the food additive;
in an alternative embodiment, the food product is a liquid condiment;
in an alternative embodiment, the food product is soy sauce.
Compared with the sodium ferric ethylenediamine tetraacetate product prepared by the ferrous sulfate method, the preparation method of the sodium ferric ethylenediamine tetraacetate provided by the invention has the advantages of higher chelation degree, stronger stability and higher solubility, and can be dissolved in soy without generating precipitate.
The invention has the following beneficial effects:
the invention provides a novel preparation route of ethylene diamine tetraacetic acid ferric sodium, which can ensure that ferrous carbonate has certain activity and can react with EDTA salt solution to generate EDTA ferrous salt by preparing ferrous carbonate on site. The iron content of the prepared sodium ferric ethylene diamine tetraacetate meets the requirement, and the chelation degree of the product is not interfered by the complex breaking action of oxidants such as hydrogen peroxide, so that the purity of the product is improved. In addition, the preparation method is simple and easy to implement, short in flow and low in cost.
Compared with the existing ferric trichloride method and ferrous sulfate method, the preparation method provided by the invention has the advantages of less impurity ions of the product, no residual chloride ions, no equipment corrosion problem, and greatly improved product purity based on the characteristic of less impurity of the product.
The sodium ferric ethylenediamine tetraacetate prepared by the preparation method provided by the invention has strong product stability, can be dissolved in foods including soy sauce, does not generate precipitate, and can be used for preparing food additives.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 80 parts of ferrous sulfate heptahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and performing suction filtration after the reaction is finished to obtain a ferrous carbonate crystal.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after reaction clarification, heating to boiling and preserving heat for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid iron sodium product, and meanwhile, recycling the filtrate to improve the yield. The filtrate can be added after the ferrous carbonate and EDTA salt react completely and become clear in the next preparation.
Example 2
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 35 portions of soda ash are added into a mixture of 80 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 3
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
according to the weight portion, 30 portions of soda ash are added into a mixture of 80 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 4
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
according to the weight portion, 30 portions of soda ash are added into the mixture of 75 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 5
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 30 portions of soda ash are added into the mixture of 70 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at the temperature of 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 6
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
according to the weight portion, 35 portions of soda ash are added into the mixture of 70 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 14 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 7
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 35 portions of soda ash are added into the mixture of 70 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 85 parts of EDTA and 400 parts of water, 14 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 8
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 35 portions of soda ash are added into the mixture of 70 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 80 parts of EDTA and 400 parts of water was added 12 parts of sodium hydroxide, and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 9
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 30 portions of soda ash are added into the mixture of 75 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 85 parts of EDTA and 400 parts of water, 12 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Example 10
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 75 parts of ferrous sulfate heptahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and performing suction filtration after the reaction is finished to obtain a ferrous carbonate crystal.
To a mixture of 80 parts of EDTA and 400 parts of water, 15 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 1
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 30 portions of soda ash are added into the mixture of 60 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at the temperature of 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 2
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
according to the weight portion, 50 portions of soda ash are added into the mixture of 90 portions of ferrous sulfate heptahydrate and 400 portions of water, the mixture reacts for 30min at the temperature of 80 ℃, and ferrous carbonate crystals are obtained after the reaction is finished and the filtration is carried out.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 3
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
to a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding 40 parts of ferrous carbonate into the mixed solution, after the reaction is clarified, heating to boiling, carrying out heat preservation reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and meanwhile, recycling the filtrate to improve the yield.
Comparative example 4
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 80 parts of ferrous sulfate heptahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and performing suction filtration to obtain ferrous carbonate crystals after the reaction is finished.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after reaction clarification, adding 60 parts of hydrogen peroxide, fully oxidizing, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid iron sodium product, and simultaneously recycling the filtrate to improve the yield.
Comparative example 5
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
to a mixture of 90 parts of EDTA and 400 parts of water, 64 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding 50 parts of ferric chloride into the mixed solution, after the reaction is clarified, heating to boiling, preserving heat, reacting for 30min, cooling, crystallizing, filtering to obtain an ethylenediaminetetraacetic acid ferric sodium salt product, and meanwhile, recycling the filtrate.
Comparative example 6
According to the weight portion, 100 portions of hydrogen peroxide are added into the mixture of 80 portions of ferrous sulfate heptahydrate and 400 portions of water, and the mixture is fully reacted for 2 hours, and then the ferric sulfate solution is filtered and filtered after the reaction is completed.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And slowly adding the ferric sulfate solution prepared in the previous step into the mixed solution, reacting and clarifying, heating to boiling, performing heat preservation reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid sodium iron product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 7
The embodiment provides a preparation method of food-grade sodium ferric ethylenediamine tetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 80 parts of ferrous sulfate heptahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and performing suction filtration to obtain ferrous carbonate crystals after the reaction is finished.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, reacting and clarifying, heating to boiling, keeping the temperature, reacting for 30min, cooling, crystallizing, and filtering to obtain the product of the sodium iron ethylenediaminetetraacetate.
Comparative example 8
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 50 parts of ferrous sulfate monohydrate and 400 parts of water in parts by weight, reacting at 80 ℃ for 30min, and performing suction filtration after the reaction is finished to obtain a ferrous carbonate crystal.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 9
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 70 parts of ferrous sulfate pentahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and filtering after the reaction is finished to obtain ferrous carbonate crystals.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after the reaction is clarified, heating to boiling and preserving the temperature for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid ferric sodium product, and simultaneously recovering and recycling the filtrate to improve the yield.
Comparative example 10
The embodiment provides a preparation method of food-grade sodium iron ethylenediaminetetraacetate, which comprises the following steps:
adding 40 parts of soda ash into a mixture of 75 parts of ferrous sulfate hexahydrate and 400 parts of water according to parts by weight, reacting at 80 ℃ for 30min, and filtering after the reaction is finished to obtain ferrous carbonate crystals.
To a mixture of 90 parts of EDTA and 400 parts of water, 16 parts of sodium hydroxide was added and the mixture was reacted at 90 ℃ for 30min. And then slowly adding the ferrous carbonate prepared in the previous step into the mixed solution, after reaction clarification, heating to boiling and preserving heat for reaction for 30min, cooling, crystallizing, filtering to obtain an ethylene diamine tetraacetic acid iron sodium product, and meanwhile, recycling the filtrate to improve the yield.
Experimental example 1
The effect of different weight additions of ferrous sulfate and soda ash on iron content is shown in table 1. The detection method of the iron content is shown by reference to 5.4 in the national standard GB 22557-2008.
Comparing table 1, it can be seen that the higher the iron content of the product as the weight of ferrous sulfate and soda increases, because the more ferrous carbonate synthesized the more sufficient iron content to react with glycine. However, the content of the ferrous sulfate and the soda ash is reduced after the adding amount of the ferrous sulfate and the soda ash exceeds the proportioning of the embodiment 1, because impurities are introduced when the adding amount of the ferrous sulfate and the soda ash is too large, the content of the iron in the product is reduced. Therefore, the iron content of the product is the highest when the adding amount of the ferrous sulfate and the soda ash is in the range given in the embodiment, and no waste is caused.
Table 1 results of the effect of different weights of added ferrous sulfate and soda ash on the iron content.
| Number of | Example 1 | Comparative example 1 | Comparative example 2 |
| Ferrous sulfate and sodium carbonate | 80 parts and 45 parts of | 60 parts by weight and 30 parts by weight | 90 parts and 50 parts |
| Iron content | 12.96％ | 11.32％ | 12.45％ |
Experimental example 2
The reaction conditions of the now synthesized ferrous carbonate and the use of the finished ferrous carbonate with monosodium glycin EDTA are shown in table 2.
As can be seen from the comparison of Table 2, the activity of the currently prepared ferrous carbonate can be maintained and can directly react with monosodium EDTA, while the ferrous carbonate product is easily oxidized to generate ferric oxide, etc., which is difficult to preserve and the activity of the product is lost and cannot sufficiently react with monosodium EDTA.
TABLE 2 statistics of the reaction of ferrous carbonate and monosodium EDTA
| Number of | Example 1 | Comparative example 3 |
| Whether or not ferrous carbonate is synthesized at present | Is that | Whether or not |
| Color of ferrous carbonate | Dark green | Brown colour |
| Reaction phenomenon | With generation of bubbles | No phenomenon |
| Iron content | 12.96％ | 10.26％ |
Experimental example 3
This experimental example verifies whether sodium ferrous EDTA can be oxidized into ferrous EDTA autonomously, see Table 3.
As can be seen from the comparison of the table 3, EDTA ferrous sodium of experimental design is very easily oxidized into EDTA ferric sodium, and the EDTA ferric sodium can be completely oxidized without adding hydrogen peroxide, so that the iron content meets the requirement, and the chelation degree of the product cannot be interfered by the hydrogen peroxide complexation.
Table 3 statistics of the effect of boiling and hydrogen peroxide oxidation on iron content.
| Numbering | Example 1 | Comparative example 4 |
| Dripping 1% water solution into potassium ferricyanide to change it into blue | Whether or not | Whether or not |
| Iron content | 12.96％ | 12.75％ |
Experimental example 4
This example verifies the dissolution of 2g of ferric sodium EDTA prepared by different methods in 100ml soy sauce, as shown in Table 4.
As is clear from comparison of Table 4, the EDTA iron sodium prepared by the process and the ferric chloride method was dissolved in soy sauce without producing precipitates, while the ferric sulfate method dissolved precipitates in soy sauce. The product prepared by the invention has high chelating degree and stronger stability.
Table 4 statistical table of the dissolution of sodium ferric EDTA prepared by different methods in soy sauce.
| Numbering | Example 1 | Comparative example 5 | Comparative example 6 |
| Method | In-situ ferrous carbonate production method | Iron chloride process | Iron sulfate process |
| Whether or not there is a precipitate | Is free of | Is composed of | Is provided with |
Experimental example 5
This experimental example verifies the chloride ion and sulfate content of the EDTA iron sodium prepared by different methods. See table 5.
As can be seen from comparison of Table 5, the impurity ion content of the product prepared by the method is far lower than that of the product prepared by other methods, so that the product prepared by the method has high purity.
Table 5 statistical table of chloride and sulfate content of EDTA iron sodium prepared by different methods.
| Number of | Example 1 | Comparative example 5 | Comparative example 6 |
| Method | In-situ ferrous carbonate production method | Ferric chloride process | Iron sulfate process |
| Chloride ion | Is free of | 1.56％ | Is composed of |
| Sulfates of sulfuric acid | 0.05％ | Is composed of | 2.12％ |
Experimental example 6
This example demonstrates the effect of mother liquor recycle on product yield, as shown in table 6. The results show that the product yield can be significantly improved by mother liquor recycling.
Table 6 results table of the effect of mother liquor recycle on product yield.
Experimental example 7
The experimental example verifies the influence of different ferrous sulfate on the quality of the synthesized ferrous carbonate and the iron content of the product, and the influence is shown in a table 7. The result shows that the ferrous carbonates prepared from different ferrous sulfates have the same quality and can be used for preparing EDTA iron sodium, and the iron content of the product meets the requirement.
TABLE 7 influence of different ferrous sulfates on the iron content of the product
| Numbering | Example 1 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Ferrous sulfate species | Ferrous sulfate heptahydrate | Ferrous sulfate monohydrate | Ferrous sulfate pentahydrate | Ferrous sulfate hexahydrate |
| Color of ferrous carbonate | Deep green color | Deep green color | Dark green | Dark green |
| Iron content | 12.96％ | 12.59％ | 12.87％ | 12.73％ |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the sodium iron ethylene diamine tetraacetate is characterized by comprising the following steps: mixing a ferrous sulfate solution with carbonate or sodium bicarbonate to react to obtain ferrous carbonate, then mixing the ferrous carbonate with an EDTA salt solution, and heating to boil to obtain ethylenediaminetetraacetic acid ferric sodium salt; the carbonate is sodium carbonate, sodium carbonate decahydrate or sodium carbonate heptahydrate.
2. The method of claim 1, wherein the ferrous sulfate solution is an aqueous solution prepared from ferrous sulfate monohydrate, ferrous sulfate pentahydrate, ferrous sulfate hexahydrate, ferrous sulfate heptahydrate, or ferrous sulfate dodecahydrate;
preferably, the ferrous sulfate solution is a ferrous sulfate heptahydrate solution prepared from ferrous sulfate heptahydrate; the carbonate is sodium carbonate;
the mixing mass ratio of the sodium carbonate to the ferrous sulfate heptahydrate in the ferrous sulfate heptahydrate solution is 30-40.
3. The preparation method of sodium ferric ethylenediamine tetraacetate according to claim 2, characterized in that the ferrous sulfate heptahydrate is mixed with water to obtain a ferrous sulfate heptahydrate solution, and the mixing mass ratio of the sodium carbonate, the ferrous sulfate heptahydrate and the water is 30-40: 300-400.
4. The method for preparing ethylenediaminetetraacetic acid ferric sodium salt as claimed in claim 1, wherein the reaction conditions for preparing ferrous carbonate are: reacting at 70-80 ℃;
preferably, the reaction time for preparing the ferrous carbonate is 20-40min;
preferably, the reaction time for preparing the ferrous carbonate is 25-30min;
preferably, after the reaction for preparing the ferrous carbonate is finished, the method further comprises the step of carrying out suction filtration on the reaction liquid after the reaction to obtain ferrous carbonate crystals.
5. The method for preparing ethylenediaminetetraacetic acid ferric sodium salt according to claim 1, wherein the mixing mass ratio of the ferrous carbonate to the EDTA salt solution is 30-40:392-506.
6. The method for preparing ethylenediaminetetraacetic acid ferric sodium salt as claimed in claim 5, wherein the mixed solution of ferrous carbonate and EDTA salt solution is heated to boiling, and the reaction is carried out for 20-30min under heat preservation.
7. The method of claim 6, further comprising a cooling step after the incubation reaction, wherein the cooling step is performed until crystallization.
8. The method for preparing ethylenediaminetetraacetic acid ferric sodium salt as claimed in claim 7, wherein, the cooling step is followed by a filtering step to obtain ethylenediaminetetraacetic acid ferric sodium salt, and the filtrate is recycled;
preferably, the filtrate is added into the mixed solution of ferrous carbonate and EDTA salt solution for preparing the sodium ferric ethylenediamine tetraacetate again.
9. The method of claim 1, wherein the EDTA salt solution is a monosodium EDTA solution;
preferably, the EDTA salt solution is prepared by the following method:
mixing EDTA, water and sodium hydroxide, and reacting at 90-95 ℃; the mass ratio of EDTA, water and sodium hydroxide is (80-90);
preferably, EDTA, water and sodium hydroxide are reacted at 90-95 ℃ for 30-35min.
10. Use of sodium iron ethylenediaminetetraacetate, prepared by the process as defined in any one of claims 1 to 9, in the preparation of a food additive;
preferably, the food product is a liquid condiment;
preferably, the food product is soy sauce.
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| CN105294469A (en) * | 2015-11-24 | 2016-02-03 | 上海永通化工有限公司 | Preparation method for iron sodium ethylene diamine tetraacetate |
| CN109369426A (en) * | 2018-12-06 | 2019-02-22 | 郑州瑞普生物工程有限公司 | A kind of preparation method of high-quality ethylenediamine tetra-acetic acid zinc sodium |
| CN114436811A (en) * | 2021-12-27 | 2022-05-06 | 郑州瑞普生物工程有限公司 | Preparation method of sodium ferrous citrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PL257279A1 (en) * | 1985-12-31 | 1987-09-21 | Lubelska Polt | Method of obtaining sodium/iron versenate |
| CN101481319A (en) * | 2009-02-04 | 2009-07-15 | 北京维他科技有限公司 | Method for drying super-fine sodium iron ethylenediaminetetraacetate (NaFeEDTA) product capable of rapidly dissolvable |
| CN105294469A (en) * | 2015-11-24 | 2016-02-03 | 上海永通化工有限公司 | Preparation method for iron sodium ethylene diamine tetraacetate |
| CN109369426A (en) * | 2018-12-06 | 2019-02-22 | 郑州瑞普生物工程有限公司 | A kind of preparation method of high-quality ethylenediamine tetra-acetic acid zinc sodium |
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