CN117865792A - Preparation method of ferrous potassium citrate - Google Patents
Preparation method of ferrous potassium citrate Download PDFInfo
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- CN117865792A CN117865792A CN202311836094.1A CN202311836094A CN117865792A CN 117865792 A CN117865792 A CN 117865792A CN 202311836094 A CN202311836094 A CN 202311836094A CN 117865792 A CN117865792 A CN 117865792A
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- ferrous
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- potassium citrate
- ferrous sulfate
- citric acid
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- 229960002635 potassium citrate Drugs 0.000 title claims abstract description 90
- 239000001508 potassium citrate Substances 0.000 title claims abstract description 90
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 title claims abstract description 90
- 235000011082 potassium citrates Nutrition 0.000 title claims abstract description 90
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 43
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 43
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011640 ferrous citrate Substances 0.000 claims abstract description 39
- 235000019850 ferrous citrate Nutrition 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 15
- 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 abstract 4
- 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 description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 229960004106 citric acid Drugs 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- OBKARMSLSGWHQK-UHFFFAOYSA-K tripotassium;2-hydroxypropane-1,2,3-tricarboxylate;dihydrate Chemical group O.O.[K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OBKARMSLSGWHQK-UHFFFAOYSA-K 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229960001781 ferrous sulfate Drugs 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 12
- 229960003975 potassium Drugs 0.000 abstract description 12
- 229910052700 potassium Inorganic materials 0.000 abstract description 12
- 239000011591 potassium Substances 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 75
- 239000000047 product Substances 0.000 description 40
- 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 37
- 239000000706 filtrate Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 24
- 229910001448 ferrous ion Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- JHYAVWJELFKHLM-UHFFFAOYSA-H tetrasodium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O JHYAVWJELFKHLM-UHFFFAOYSA-H 0.000 description 6
- 208000000913 Kidney Calculi Diseases 0.000 description 5
- 206010029148 Nephrolithiasis Diseases 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 208000019025 Hypokalemia Diseases 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 208000024896 potassium deficiency disease Diseases 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006545 glycolytic metabolism Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000015097 nutrients Nutrition 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
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- DYPHJEMAXTWPFB-UHFFFAOYSA-N [K].[Fe] Chemical compound [K].[Fe] DYPHJEMAXTWPFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003355 alkalizing urine Effects 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of ferrous potassium citrate, which comprises the following steps: s1, respectively preparing a ferrous sulfate solution, a citric acid solution and a potassium citrate solution; sulfuric acid and elemental iron are added in the preparation process of the ferrous sulfate solution; s2, adding simple substance iron into the citric acid solution, slowly adding ferrous sulfate solution, and reacting for 20-40 min at the temperature of above 95 ℃ to obtain ferrous citrate solution; s3, slowly adding a potassium citrate solution into the ferrous citrate solution, reacting at 90-100 ℃ for 60-80 min to obtain the ferrous potassium citrate solution, and then preparing the ferrous potassium citrate product. The preparation method has the advantages of less introduced impurities, higher product purity and about 95 percent of product yield, and the prepared ferrous potassium citrate product is yellow green crystal powder, the potassium mass percent is 25-35 percent, and the ferrous iron mass percent is 10-15 percent.
Description
Technical Field
The invention belongs to the technical field of food processing, and particularly relates to a preparation method of ferrous potassium citrate.
Background
Citric acidThe food has good palatability, has the function of increasing appetite, can directly participate in glycolytic metabolism, releases energy and provides heat energy for animals. Fe in living body 2+ The absorption of the iron citrate is superior to that of Fe, so the iron citrate is an easy-to-absorb and high-efficiency iron preparation. From its composition, ferrous citrate retains a carboxyl group, remains acidic, and when consumed, stomach acid (H + ) Ferrous iron in the ferrous citrate can be released in the form of ferrous ions. The free citric acid still has the effect of maintaining the acidity of digestive juice, and the citrate has the growth promoting effect superior to sulfate radical. Potassium citrate can be used for controlling uric acid or cystine from kidney stones in medical treatment, and can be used for preventing and treating hypokalemia and alkalizing urine. In recent years, as current consumption and life behavior habits are increasingly pursued to be fast, people in the general population generally have fast food and fast-paced life habits, and people with physical conditions of kidney sand and kidney stones in the population are higher and higher, the product of ferrous potassium citrate is prepared, and can be better applied to the pharmaceutical industry and the food nutrition industry, added into foods and medicines, has good taste, promotes glycolytic metabolism of human bodies, can supplement nutrient potassium ions required by the human bodies while daily supplementing iron nutrients, can play a role of supplementing iron, simultaneously control or improve the appearance of kidney stones in the human bodies, and can also effectively prevent hypokalemia and urine alkalization of the human bodies.
The prior art does not report about the preparation method of ferrous potassium citrate. The applicant provides a preparation method of sodium ferrous citrate similar to potassium ferrous citrate in 2021, which comprises the steps of adding sulfuric acid and elemental iron into ferrous sulfate solution, reacting at 25-35 ℃, carrying out solid-liquid separation to obtain filtrate a after the reaction is finished, mixing the filtrate a with sodium citrate solution for reaction, adding sodium bisulfate accounting for 5-10% of the mass of ferrous sulfate, carrying out reaction at 85-95 ℃ for 60-80 min, carrying out solid-liquid separation, concentrating, crystallizing and drying the filtrate to obtain the sodium ferrous citrate product. The applicant finds that the product yield and purity are lower when the method is used for producing the ferrous potassium citrate, and the method is not suitable for producing the ferrous potassium citrate and needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of ferrous potassium citrate for solving the defects in the prior art.
The invention aims at realizing the following technical scheme:
the preparation method of the ferrous potassium citrate comprises the following steps:
s1, respectively preparing a ferrous sulfate solution, a citric acid solution and a potassium citrate solution; sulfuric acid and elemental iron are added in the preparation process of the ferrous sulfate solution;
s2, adding simple substance iron into the citric acid solution, slowly adding the ferrous sulfate solution, and reacting for 20-40 min at the temperature of above 95 ℃ to obtain a ferrous citrate solution;
s3, slowly adding the potassium citrate solution into the ferrous citrate solution, and reacting at 90-100 ℃ for 60-80 min to obtain the ferrous potassium citrate solution;
s4, preparing the ferrous potassium citrate solution into a ferrous potassium citrate product;
the amount of the reaction materials is 1 (3-3.1) in terms of the molar ratio of ferrous sulfate, citric acid and potassium citrate in the solution (1-1.1).
Preferably, the ferrous sulfate is ferrous sulfate heptahydrate, and the ferrous sulfate solution is prepared by the following steps:
taking deionized water, firstly adding sulfuric acid, then adding ferrous sulfate heptahydrate and elemental iron, fully stirring until the solution is clear, and filtering to obtain a ferrous sulfate solution;
the sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95%;
the addition amount of the ferrous sulfate heptahydrate is 40-60% of the mass of the deionized water;
the addition amount of the sulfuric acid is 0.45-0.65% of the mass of the ferrous sulfate heptahydrate.
Preferably, the citric acid is citric acid monohydrate, and the citric acid solution is prepared by the following steps:
adding citric acid monohydrate into deionized water, heating to 50-70 ℃, fully stirring until the solution is clear, and filtering to obtain the citric acid solution;
the addition amount of the citric acid monohydrate is 60-90% of the mass of the deionized water.
Preferably, in the ferrous sulfate solution, the addition amount of the simple substance iron is 0.45-0.65% of the addition mass of the ferrous sulfate heptahydrate;
the addition amount of the simple substance iron in the step S2 is 0.45-0.65% of the addition mass of the ferrous sulfate heptahydrate.
Preferably, the charging time of the ferrous sulfate solution in the step S2 is 15-25 min, and the reaction time after charging is 20-40 min.
Preferably, the potassium citrate is potassium citrate dihydrate, and the potassium citrate solution is prepared by the following steps:
adding deionized water into potassium citrate dihydrate, fully stirring until the solution is clear, and filtering to obtain the potassium citrate solution;
the adding amount of the potassium citrate dihydrate is 35-50% of the mass of the deionized water.
Preferably, the potassium citrate solution in the step S3 is fed for 10-20 min, and the reaction time after feeding is 60-80 min.
Preferably, step S4 further includes:
and filtering, concentrating and drying the ferrous potassium citrate solution to obtain a ferrous potassium citrate product.
Preferably, the drying is vacuum drying, the temperature is 55-65 ℃, and the time is 16-18 h.
The potassium ferrous citrate obtained by the application chelates potassium ions and ferrous citrate together, can play a role in iron supplement during use, simultaneously control or improve the appearance of kidney stones of a human body, and can also effectively prevent and treat hypokalemia of the human body and the appearance of urine alkalization. The preparation method has the advantages of less introduced impurities, higher product purity and about 95 percent of product yield, and the prepared ferrous potassium citrate product is yellow green crystal powder, the potassium mass percent is 25-35 percent, and the ferrous iron mass percent is 10-15 percent.
Detailed Description
The invention provides a preparation method of ferrous potassium citrate, which comprises the following steps:
s1, respectively preparing a ferrous sulfate solution, a citric acid solution and a potassium citrate solution; sulfuric acid and elemental iron are added in the preparation process of the ferrous sulfate solution; the ferrous sulfate solution is added with simple substance iron and sulfuric acid to prevent ferrous ions in the ferrous sulfate from being oxidized into ferric iron;
s2, adding simple substance iron into the citric acid solution, slowly adding ferrous sulfate solution, and reacting for 20-40 min at the temperature of above 95 ℃ to obtain ferrous citrate solution; the addition of elemental iron during the reaction can also prevent the formation of ferric iron during the reaction; the ferrous sulfate is slowly added into the citric acid solution to make the ferrous sulfate fully contact and react with excessive citric acid, so that the ferrous citrate is generated to the greatest extent;
s3, slowly adding a potassium citrate solution into the ferrous citrate solution, and reacting at 90-100 ℃ for 60-80 min to obtain the ferrous potassium citrate solution; the potassium citrate solution is slowly added into the ferrous citrate to ensure the stability of the ferrous citrate, prevent ferrous ions from being oxidized and ensure the ferrous content in the ferrous potassium citrate;
s4, preparing a ferrous potassium citrate solution into a ferrous potassium citrate product;
the material consumption is 1 (3-3.1) in terms of the molar ratio of ferrous sulfate, citric acid and potassium citrate in the solution (1-1.1). The excessive citric acid is used for fully reacting with ferrous sulfate, consuming all ferrous sulfate and improving the yield of the ferrous citrate; the potassium citrate is used in excess to promote the sufficient reaction and chelation with ferrous citrate, thereby further improving the product yield.
The application firstly adopts ferrous sulfate solution and citric acid solution to react and prepare ferrous citrate, then reacts with potassium citrate to obtain ferrous potassium citrate, and compared with the ferrous sodium citrate prepared by adopting ferrous sulfate and sodium citrate to react in one step in the preparation process of ferrous sodium citrate in the prior art, the application adopts two steps to prepare ferrous potassium citrate, can fully participate in the reaction of ferrous ions, supplements the content of ferrous ions while reducing the content of ferric ions, generates relatively stable ferrous citrate with high purity, promotes the subsequent chelation stability with potassium ions, and improves the purity and yield of ferrous potassium citrate.
The material which is used for chelating citric acid with iron ions and potassium ions is not available in the market at present, and the invention is used for synthesizing ferrous potassium citrate through the first reaction, can supplement iron ions and potassium ions simultaneously, provides an acidic environment, is a good iron-potassium supplementing preparation, can promote the absorption efficiency of organisms to nutrition, better promote the growth of organisms, and can also control the generation of kidney stones of the organisms or prevent hypokalemia and urine alkalization.
Preferably, the ferrous sulfate adopts ferrous sulfate heptahydrate which is low in price and wide in source, and the acidic ferrous sulfate solution is prepared by the following steps:
taking deionized water, firstly adding sulfuric acid, then adding ferrous sulfate heptahydrate and elemental iron, fully stirring until the solution is clear, and filtering to obtain a ferrous sulfate solution. Firstly, sulfuric acid is added to provide an acidic environment to promote the dissolution of ferrous sulfate heptahydrate, and meanwhile, an acidic reaction environment is provided for ferric iron in the simple substance iron reduction solution.
The sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95%; the addition of the ferrous sulfate heptahydrate is 40-60% of the mass of the deionized water; the addition amount of the sulfuric acid is 0.45-0.65% of the mass of the ferrous sulfate heptahydrate.
Preferably, the citric acid is citric acid monohydrate, and the citric acid solution is prepared by the following steps:
adding citric acid monohydrate into deionized water, heating to 50-70 ℃ to promote dissolution of citric acid monohydrate, fully stirring until the solution is clear, and filtering to obtain a citric acid solution; the addition amount of citric acid monohydrate is 60-90% of the mass of deionized water.
Preferably, the simple substance iron is preferably simple substance iron powder, and the simple substance iron is used as an antioxidant, so that no new impurities are introduced, and the product purity is prevented from being influenced. In the ferrous sulfate solution, the addition of the simple substance iron is 0.45-0.65% of the addition mass of the ferrous sulfate heptahydrate; the addition amount of the simple substance iron in the step S2 is 0.45 to 0.65 percent of the addition mass of the ferrous sulfate heptahydrate.
The feeding time of the ferrous sulfate solution in the step S2 is 15-25 min, and the reaction time after feeding is 20-40 min. By limiting the feeding time and the reaction time, ferrous sulfate and citric acid can be slowly and fully reacted, the yield is improved, meanwhile, the long-time reaction is avoided, the experimental resources are wasted, and the preparation cost of the product is reduced.
Preferably, the potassium citrate is potassium citrate dihydrate, and the potassium citrate solution is prepared by the steps of:
adding deionized water into potassium citrate dihydrate, fully stirring until the solution is clear, and filtering to obtain a potassium citrate solution; the addition amount of the potassium citrate dihydrate is 35-50% of the mass of the deionized water.
When the method is used for preparing the reaction solution, the materials are dissolved and then filtered, so that raw materials such as ferrous sulfate, antioxidants and the like which are not fully dissolved and insoluble impurities are effectively prevented from being contained in the solution, and the purity of a final product is prevented from being influenced in a reaction system.
Preferably, the potassium citrate solution in the step S3 is fed for 10-20 min, and the reaction time after feeding is 60-80 min.
Preferably, step S4 further includes:
and filtering, concentrating and drying the ferrous potassium citrate solution to obtain a ferrous potassium citrate product. Further preferably, the drying is vacuum drying, the drying temperature is 55-65 ℃ and the drying time is 16-18 h. The adoption of vacuum drying can effectively prevent the oxidation of potassium ferrous citrate due to contact with oxygen in the air.
Example 1
The preparation method of the ferrous potassium citrate provided by the embodiment comprises the following steps:
step A, 200ml of deionized water is measured in a 1L beaker, 0.5g of concentrated sulfuric acid (the mass fraction is 98%) is added, 100g of ferrous sulfate heptahydrate is added in an aqueous solution, then 0.6g of iron powder is added, the mixture is fully stirred at normal temperature, and the mixture is filtered after the material is dissolved and clarified, so as to obtain filtrate (1);
step B, 300ml of deionized water is measured in a 1L beaker, 227g of citric acid monohydrate is added, the temperature is raised to 60 ℃, the materials are fully stirred until the materials are completely dissolved and clarified, and the filtration is carried out to obtain filtrate (2);
and C, heating the filtrate (2) to 95 ℃ in a water bath, adding 0.5g of iron powder, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate for 20min, and carrying out heat preservation reaction for 30min to obtain a ferrous citrate solution as filtrate (3) after the reaction is completed.
Step D, 200ml of deionized water is weighed in a 1L beaker, 85g of potassium citrate dihydrate is weighed and added into water, and the mixture is sufficiently stirred and clarified and then filtered to obtain filtrate (4);
step E, heating the filtrate (3) to about 95 ℃ in a water bath, slowly adding the filtrate (4) into the filtrate gradually for 15min, and then carrying out heat preservation reaction for 60min;
and F, after the reaction is finished, filtering, concentrating the filtrate, crystallizing, and vacuum drying at 60 ℃ for 16 hours to obtain a ferrous potassium citrate product.
Comparative example 1
The procedure of example 1 is followed except that in step C, the water bath is heated to a temperature of 60 ℃.
Comparative example 2
The procedure of example 1 is followed except that in step C, the water bath is heated to a temperature of 80 ℃.
Comparative example 3
The procedure of example 1 is followed except that in step C, the water bath is heated to a temperature of 90 ℃.
The experimental process phenomenon in step C of example 1 and comparative examples 1 to 3 was compared and analyzed, and the ferrous ion content and the product yield of the obtained ferrous potassium citrate product were analyzed, and the results are shown in table 1.
TABLE 1 influence of different reaction temperatures on Potassium ferrous citrate products
As can be seen from the data in Table 1, the reaction temperature in step C has a greater influence on the formation of ferrous citrate, and the higher the temperature, the more favorable the reaction is for the formation of ferrous citrate, so that the higher the yield of the subsequent synthesis of ferrous potassium citrate, the higher the ferrous iron content in the product, and therefore the temperature for synthesizing ferrous citrate in step C should be controlled to be above 95 ℃.
Comparative example 4
The procedure of example 1 was followed except that in step C, the reaction time was kept at 60 minutes after the addition of the ferrous sulfate heptahydrate solution.
Comparative example 5
The procedure of example 1 was followed except that in step C, the reaction time was kept at 90 minutes after the addition of the ferrous sulfate heptahydrate solution.
Comparative example 6
The procedure of example 1 was followed except that in step C, the reaction time was kept at 120 minutes after the addition of the ferrous sulfate heptahydrate solution.
The experimental process phenomenon in step C of example 1 and comparative examples 4 to 6 was analyzed in comparison, and the ferrous ion content and the product yield of the obtained ferrous potassium citrate product were analyzed, and the results are shown in table 2.
TABLE 2 influence of different reaction times on the Potassium ferrous citrate product
The data in table 2 can be compared, the reaction time in the step C has smaller influence on the generation of ferrous citrate and on the content of ferrous ions in the final product ferrous potassium citrate, so that the reaction time for synthesizing ferrous citrate in the step C by experiment is determined to be about 30min, thereby ensuring the relatively complete synthesis of ferrous citrate, saving resources and reducing the production cost of the product.
Comparative example 7
The iron powder added in the step A and the step C is removed in the comparative example, so that the influence of the iron powder on the content of ferrous ions in the preparation of the ferrous potassium citrate product is investigated, and the specific experimental steps are as follows:
step A, 200ml of deionized water is measured in a 1L beaker, 0.5g of concentrated sulfuric acid (the mass fraction is 98%) is added, 100g of ferrous sulfate heptahydrate is added, the mixture is fully stirred at normal temperature, and the mixture is filtered after the mixture is dissolved and clarified, so as to obtain filtrate (1);
step B, 300ml of deionized water is measured in a 1L beaker, 227g of citric acid monohydrate is added, the temperature is raised to 60 ℃, the materials are fully stirred until the materials are completely dissolved and clarified, and the filtration is carried out to obtain filtrate (2);
and C, heating the filtrate (2) to 95 ℃ in a water bath, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate, wherein the adding time is 20min, and carrying out heat preservation reaction for 30min, so that the ferrous citrate solution is obtained as filtrate (3) after the reaction is completed.
Step D, 200ml of deionized water is weighed in a 1L beaker, 85g of potassium citrate dihydrate is weighed and added into water, and the mixture is sufficiently stirred and clarified and then filtered to obtain filtrate (4);
step E, heating the filtrate (3) to about 95 ℃ in a water bath, slowly adding the filtrate (4) into the filtrate gradually for 15min, and then carrying out heat preservation reaction for 60min;
and F, after the reaction is finished, filtering, concentrating the filtrate, crystallizing, and vacuum drying at 60 ℃ for 16 hours to obtain a ferrous potassium citrate product.
The experimental phenomena of example 1 and comparative example 7 were compared and analyzed, and the ferrous iron content ion and the product yield of the obtained ferrous potassium citrate product were analyzed, and the results are shown in table 3.
TABLE 3 influence of iron free powder on Potassium ferrous citrate product
| Sample numbering | Example 1 | Comparative example 7 |
| Reaction temperature/. Degree.C | 95℃ | 95℃ |
| Reaction time/min | 30min | 30min |
| Ferrous ion content/% | 12.22 | 6.52 |
| Product yield/% | 96.5 | 85.2 |
As can be seen from comparison of the data in Table 3, the removal of the iron powder added in step A and step C has a relatively large effect on the ferrous iron content of the final product, ferrous potassium citrate, and therefore the iron powder addition in step C is necessary.
Comparative example 8
The procedure of example 1 was followed except that in step E, the filtrate (4) was added, and the reaction time was kept at 30 minutes.
Comparative example 9
The procedure of example 1 was followed except that in step E, the filtrate (4) was added, and the reaction time was kept at 90 minutes.
Comparative example 10
The procedure of example 1 was followed except that in step E, the filtrate (4) was added, and the reaction time was kept at 120 minutes.
Step E of example 1 and comparative examples 8 to 10 were subjected to comparative analysis, and the ferrous ion content, potassium ion content and product yield of the obtained ferrous potassium citrate product were analyzed, and the results are shown in Table 4.
TABLE 4 influence of different reaction times on the Potassium ferrous citrate product
| Sample numbering | Example 1 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Reaction temperature/. Degree.C | 95℃ | 95℃ | 95℃ | 95℃ |
| Reaction time/min | 60min | 30min | 90min | 120min |
| Ferrous ion content/% | 12.22 | 6.52 | 11.12 | 10.86 |
| Potassium ion content/% | 30.95 | 20.57 | 28.69 | 29.12 |
| Product yield/% | 96.5 | 63.6 | 93.2 | 92.0 |
As can be seen from comparison of the data in table 4, the reaction time in step E has a certain influence on the content of ferrous ions in the final product potassium ferrous citrate, and the reaction time is too long, and part of ferrous ions are oxidized, and the product yield is reduced, so that the reaction time for synthesizing the potassium ferrous citrate in step E is determined to be about 60 minutes.
Comparative example 11
This comparative example attempted to prepare ferrous potassium citrate according to a presently disclosed preparation process similar to that of ferrous sodium citrate, comprising the steps of:
step A, 200ml of deionized water is measured in a 1L beaker, 0.2g of concentrated sulfuric acid is added, 100g of ferrous sulfate heptahydrate is added, 0.2g of iron powder is added, and filtration is carried out after full stirring and clarification, so as to obtain filtrate (1);
step B, weighing 400ml of deionized water in a 1L beaker, slowly adding 200g of potassium citrate, fully stirring and clarifying, and filtering to obtain filtrate (2);
step C, heating the filtrate (2) to about 90 ℃ in a water bath, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate, adding 6g of potassium hydrogen sulfite as an antioxidant into the mixture for 15min, and then carrying out heat preservation reaction for 70min;
step D, after full reaction, filtering the reaction solution, heating and concentrating the filtrate to about 200mL, and filtering to obtain a large amount of precipitated products;
and E, placing the wet material into a vacuum drying oven for drying at 50 ℃ to obtain a potassium ferrous citrate product.
The experimental phenomena of example 1 and comparative example 11 were compared and analyzed, and the ferrous iron content ion and the product yield of the obtained ferrous potassium citrate product were analyzed, and the results are shown in table 5.
TABLE 5 influence of different preparation processes on the formation of ferrous potassium citrate product
| Sample numbering | Example 1 | Comparative example 11 |
| Reaction temperature/. Degree.C | 95℃ | 90℃ |
| Reaction time/min | 60min | 70min |
| Ferrous ion content/% | 12.22 | 10.07 |
| Potassium ion content/% | 30.95 | 20.13 |
| Product yield/% | 96.5 | 88.2 |
The data in table 5 can be compared, and the process using the example is superior to the process using the comparative example in that the ferrous potassium citrate product is prepared according to the preparation process for similarly preparing ferrous sodium citrate, potassium citrate is directly reacted with ferrous sulfate, the ferrous ion has reduced oxidation loss content, and the ferrous ion participates in the reaction to be not high and unstable, so that the content of ferrous ion in the ferrous potassium citrate product and the product yield are obviously reduced.
Example 2
The preparation method of the ferrous potassium citrate provided by the embodiment comprises the following steps:
step A, 200ml of deionized water is measured in a 1L beaker, 0.45g of concentrated sulfuric acid (the mass fraction is 98%) is added, 100g of ferrous sulfate heptahydrate is added in an aqueous solution, then 0.45g of iron powder is added, stirring is carried out fully at normal temperature, and filtering is carried out after the materials are dissolved and clarified, thus obtaining filtrate (1);
step B, 300ml of deionized water is measured in a 1L beaker, 227g of citric acid monohydrate is added, the temperature is raised to 60 ℃, the materials are fully stirred until the materials are completely dissolved and clarified, and the filtration is carried out to obtain filtrate (2);
and C, heating the filtrate (2) to 98 ℃ in a water bath, adding 0.45g of iron powder, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate for 20min, and carrying out heat preservation reaction for 40min to obtain a ferrous citrate solution as a filtrate (3) after the reaction is completed.
Step D, 200ml of deionized water is weighed in a 1L beaker, 85g of potassium citrate dihydrate is weighed and added into water, and the mixture is sufficiently stirred and clarified and then filtered to obtain filtrate (4);
step E, heating the filtrate (3) to about 95 ℃ in a water bath, slowly adding the filtrate (4) into the filtrate gradually for 15min, and then carrying out heat preservation reaction for 80min;
and F, after the reaction is finished, filtering, concentrating the filtrate, crystallizing, and vacuum drying at 60 ℃ for 16 hours to obtain a ferrous potassium citrate product.
Example 3
The preparation method of the ferrous potassium citrate provided by the embodiment comprises the following steps:
step A, 200ml of deionized water is measured in a 1L beaker, 0.6g of concentrated sulfuric acid (the mass fraction is 98%) is added, 100g of ferrous sulfate heptahydrate is added in an aqueous solution, then 0.6g of iron powder is added, the mixture is fully stirred at normal temperature, and the mixture is filtered after the material is dissolved and clarified, so as to obtain filtrate (1);
step B, 300ml of deionized water is measured in a 1L beaker, 234g of citric acid monohydrate is added, the temperature is raised to 60 ℃, the materials are fully stirred until the materials are completely dissolved and clarified, and the filtration is carried out to obtain filtrate (2);
and C, heating the filtrate (2) to 98 ℃ in a water bath, adding 0.6g of iron powder, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate for 20min, and carrying out heat preservation reaction for 40min to obtain a ferrous citrate solution as a filtrate (3) after the reaction is completed.
Step D, 200ml of deionized water is weighed in a 1L beaker, 90g of potassium citrate dihydrate is weighed and added into water, and the mixture is sufficiently stirred and clarified and then filtered to obtain filtrate (4);
step E, heating the filtrate (3) to about 98 ℃ in a water bath, slowly adding the filtrate (4) into the filtrate gradually for 15min, and then carrying out heat preservation reaction for 60min;
and F, after the reaction is finished, filtering, concentrating the filtrate, crystallizing, and vacuum drying at 60 ℃ for 16 hours to obtain a ferrous potassium citrate product.
Example 4
The preparation method of the ferrous potassium citrate provided by the embodiment comprises the following steps:
step A, 200ml of deionized water is measured in a 1L beaker, 0.5g of concentrated sulfuric acid (the mass fraction is 98%) is added, 100g of ferrous sulfate heptahydrate is added in an aqueous solution, then 0.5g of iron powder is added, the mixture is fully stirred at normal temperature, and the mixture is filtered after the material is dissolved and clarified, so as to obtain filtrate (1);
step B, 300ml of deionized water is measured in a 1L beaker, 230g of citric acid monohydrate is added, the temperature is raised to 60 ℃, the materials are fully stirred until the materials are completely dissolved and clarified, and the filtration is carried out to obtain filtrate (2);
and C, heating the filtrate (2) to 96 ℃ in a water bath, adding 0.5g of iron powder, dropwise adding a ferrous sulfate heptahydrate solution into the filtrate for 20min, and carrying out heat preservation reaction for 30min to obtain a ferrous citrate solution as filtrate (3) after the reaction is completed.
Step D, 200ml of deionized water is weighed in a 1L beaker, 87g of potassium citrate dihydrate is weighed and added into water, and filtration is carried out after full stirring and clarification, so as to obtain filtrate (4);
step E, heating the filtrate (3) to about 95 ℃ in a water bath, slowly adding the filtrate (4) into the filtrate gradually for 15min, and then carrying out heat preservation reaction for 60min;
and F, after the reaction is finished, filtering, concentrating the filtrate, crystallizing, and vacuum drying at 55 ℃ for 18 hours to obtain a ferrous potassium citrate product.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. The preparation method of the ferrous potassium citrate is characterized by comprising the following steps of:
s1, respectively preparing a ferrous sulfate solution, a citric acid solution and a potassium citrate solution; sulfuric acid and elemental iron are added in the preparation process of the ferrous sulfate solution;
s2, adding simple substance iron into the citric acid solution, slowly adding the ferrous sulfate solution, and reacting for 20-40 min at the temperature of above 95 ℃ to obtain a ferrous citrate solution;
s3, slowly adding the potassium citrate solution into the ferrous citrate solution, and reacting at 90-100 ℃ for 60-80 min to obtain the ferrous potassium citrate solution;
s4, preparing the ferrous potassium citrate solution into a ferrous potassium citrate product;
the amount of the reaction materials is 1 (3-3.1) in terms of the molar ratio of ferrous sulfate, citric acid and potassium citrate in the solution (1-1.1).
2. The method for preparing ferrous potassium citrate according to claim 1,
the ferrous sulfate is ferrous sulfate heptahydrate, and the ferrous sulfate solution is prepared by the following steps:
taking deionized water, firstly adding sulfuric acid, then adding ferrous sulfate heptahydrate and elemental iron, fully stirring until the solution is clear, and filtering to obtain a ferrous sulfate solution;
the sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95%;
the addition amount of the ferrous sulfate heptahydrate is 40-60% of the mass of the deionized water;
the addition amount of the sulfuric acid is 0.45-0.65% of the mass of the ferrous sulfate heptahydrate.
3. The method for preparing ferrous potassium citrate according to claim 1,
the citric acid is citric acid monohydrate, and the citric acid solution is prepared by the following steps:
adding citric acid monohydrate into deionized water, heating to 50-70 ℃, fully stirring until the solution is clear, and filtering to obtain the citric acid solution;
the addition amount of the citric acid monohydrate is 60-90% of the mass of the deionized water.
4. The method for preparing ferrous potassium citrate according to claim 2,
in the ferrous sulfate solution, the addition of the simple substance iron is 0.45-0.65% of the added mass of the ferrous sulfate heptahydrate;
the addition amount of the simple substance iron in the step S2 is 0.45-0.65% of the addition mass of the ferrous sulfate heptahydrate.
5. The method for preparing ferrous potassium citrate according to claim 1,
and step S2, the charging time of the ferrous sulfate solution is 15-25 min, and the reaction time after charging is 20-40 min.
6. The method for preparing ferrous potassium citrate according to claim 1,
the potassium citrate is potassium citrate dihydrate, and the potassium citrate solution is prepared by the following steps:
adding deionized water into potassium citrate dihydrate, fully stirring until the solution is clear, and filtering to obtain the potassium citrate solution;
the adding amount of the potassium citrate dihydrate is 35-50% of the mass of the deionized water.
7. The method for preparing ferrous potassium citrate according to claim 1,
and step S3, the feeding time of the potassium citrate solution is 10-20 min, and the reaction time after feeding is 60-80 min.
8. The method for preparing ferrous potassium citrate according to claim 1,
step S4 further comprises:
and filtering, concentrating and drying the ferrous potassium citrate solution to obtain a ferrous potassium citrate product.
9. The method for preparing ferrous potassium citrate according to claim 8,
the drying adopts vacuum drying, the temperature is 55-65 ℃ and the time is 16-18 h.
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