CN108059596A - A kind of preparation method of high-purity citric acid iron ammonium - Google Patents
A kind of preparation method of high-purity citric acid iron ammonium Download PDFInfo
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- CN108059596A CN108059596A CN201711466933.XA CN201711466933A CN108059596A CN 108059596 A CN108059596 A CN 108059596A CN 201711466933 A CN201711466933 A CN 201711466933A CN 108059596 A CN108059596 A CN 108059596A
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- Prior art keywords
- iron
- citric acid
- reaction
- ammonium
- purity
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 title claims abstract description 9
- 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 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical class [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960002413 ferric citrate Drugs 0.000 claims abstract description 21
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 21
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000000502 dialysis Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- -1 iron ion Chemical class 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 6
- 102000003939 Membrane transport proteins Human genes 0.000 claims abstract description 5
- 108090000301 Membrane transport proteins Proteins 0.000 claims abstract description 5
- 230000009061 membrane transport Effects 0.000 claims abstract description 5
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000008235 industrial water Substances 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 8
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 244000131522 Citrus pyriformis Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 235000005979 Citrus limon Nutrition 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 4
- 239000011640 ferrous citrate Substances 0.000 description 4
- 235000019850 ferrous citrate Nutrition 0.000 description 4
- 201000006747 infectious mononucleosis Diseases 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 229940124344 antianaemic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of high-purity citric acid iron ammonium, include the following steps：Step 1: a certain amount of iron hydroxide is placed in dialysis bag made of collodion establishes Liquid Membrane Transport system, the rate of release of iron ion is controlled by Liquid Membrane Transport, and then controls the forming quantity of ferric citrate nucleus and the growth rate of crystal；Step 2: proportionally citric acid and ammonium hydroxide wiring solution-forming are placed in reactor, entire reactor is placed in ultrasonic disperser, and the dialysis bag for filling iron hydroxide prepared in step 1 is placed in the reactor, ultrasonic reaction 5 60 minutes；Step 3: it is that the reaction system after reaction is obtained into the ferric citrate product of high-purity using being evaporated under reduced pressure, by the way of re-dry.The present invention integrates the ferric citrate product of the technical controllings synthesis high-purities such as the release of dialysis control iron ion, ultrasonic disperse and vacuum distillation for the first time, which has many advantages, such as energy-efficient, environmentally protective, industrial water reusable edible.
Description
Technical field
The invention belongs to field of food science, and in particular to a kind of preparation side as food additive citric acid iron ammonium
Method.
Background technology
Ferric citrate is also known as Ferric Ammonium Citrate, have brown and green two kinds, have it is odorless, have saline taste and iron taste, pole
The easy moisture absorption, it is more unstable under solution state because light can be reduced into ferrous salt, it is soluble easily in water, it is organic molten insoluble in ethyl alcohol, ether etc.
Agent, aqueous solution are in neutrality, and green is more easy to chance light compared with brown and is reduced.The squamaceous ferric citrate iron-holder of brown is higher, and
The squamaceous ferric citrate iron-holder of green is relatively low.Ferric citrate is photochemistry sensitization substance, and green is more easy to compared with brown
It is photosensitive.Ferric citrate is a kind of excellent nutrition fortifier, can be used as antianaemics, treats hypoferric anemia, is widely used in
The numerous areas such as food additives, medicine.
Preparation method in relation to ferric citrate is concentrated mainly on two kinds of acid-base neutralization method and oxidation-reduction method.For example, specially
Sharp Application No. CN2017107227359 discloses a kind of ferric citrate preparation process, and lemon is prepared by raw material of ferrous sulfate
Lemon acid iron ammonium, is as follows：1. ferrous sulfate is added to the water, then stirring and dissolving；It is 2. aqueous sodium carbonate is slow
It adds in ferrous sulfate solution, at room temperature fully reaction 1-2h；3. filtering, sediment is washed with water, until sulfate radical-free ion
Until detection, after addition water stirs evenly, then citric acid is added in above-mentioned sediment, is stirred to react 1-2h；4. it adds in double
Oxygen water is aoxidized, and is then added in ammonium hydroxide or is passed through ammonia, is stirred to react and adjusts pH to 6-8, then react 0.5-1h；5. heating
It is concentrated into, cools down, add ammonium hydroxide, 6. are spray-dried in 130-150 DEG C of drying or 190-200 DEG C to get ferric citrate product.
Number of patent application CN2010101798256 discloses a kind of industrialized production pollution-free food salt anticaking agent lemon
The method of sour iron ammonium, food-grade ammonium citrate is dissolved in deionized water, and heating makes ammonium citrate all dissolve, filtering；It is filtering
The iron hydroxide powder of certain mass is added in liquid, is warming up to 85-90 DEG C, is stirred 45-50 minutes until solution is sticky paste；
Sticky paste is put into baking oven and is dried, oven temperature is 70-75 DEG C, packaging of sieving after drying, you can obtain the lemon
Lemon acid iron ammonium, surveys its iron content.Present invention accomplishes industrialized productions, and process route is short, saving production cost, in production process
There is no ammonium hydroxide to participate in reaction, do not have the leakage contribution environment of ammonia, concentrate and take less, it is energy saving.The level that product reaches,
Meet the standard of Chinese Pharmacopoeia (95 years) and British Pharmacopoeia BP73 iron contents for 20.5-22.5%.
Number of patent application CN2009101727084 discloses a kind of production method of ferric citrate, by water, citric acid,
Iron powder is prepared according to the following steps：1. water will be stated, citric acid is placed in mixing plant and is warming up to 60 DEG C；2. open the mixing plant
Add in insulated and stirred after iron powder is to slowly warm up to 80 DEG C, reaction generation ferrous citrate；3. second step resulting material is cooled to
40 DEG C add in hydrogen peroxide oxidation to no ferrous ion；4. it is passed through after ammonia is neutralized to pH >=7 to high iron compound obtained by the 3rd step
It is filtered to remove impurity and is concentrated into paste；5. concentrate obtained by the 4th step is placed in drying in oven, 80 DEG C of drying temperature.The present invention
Advantage is, by the use of hydrogen peroxide as oxidant, to pass through scientific matching and production technology instead of ferrous sulfate using iron powder；Make preparation
Process, which avoids, brings the impurity such as chlorion and sulfate ion into, avoids among the iron hydroxide for generating and being difficult to be dehydrated and washing
Product enormously simplifies production process, reduces production cost, improves the production efficiency of ferric citrate.
In addition, Zhang Taiping etc. (Zhang Taiping, preparation method [J] high continuing education journals of ten thousand such as iron of fine quality ferric citrates,
2004,17 (1):Hydroxide 37-38.) is obtained by the reaction with liquid caustic soda after sodium chlorate aoxidizes using ferrous sulfate in acid condition
Iron.Iron hydroxide is dissolved in citric acid.It is neutralized with ammonia, through being dried to obtain product ferric citrate.Equipped with blender
16.7g ferrous sulfate heptahydrates and 40ml distilled water are added in three-necked bottle.Blender is started, adds in sulfuric acid 3ml slowly under stiring,
Sodium chlorate 1g is added, is vigorously stirred.Water-soluble heating, temperature rise to 80 DEG C or more, add sodium chlorate 1g, and stirring is until reaction
It is not in that ferrous reaction (does not take a small amount of reaction solution to terminate and examined with the potassium ferricyanide.Add in potassium ferricyanide weak solution, vibration, not in indigo plant
Color).Obtain ferrum sulfuricum oxydatum solutum.Sodium hydroxide l0g (being dissolved in wiring solution-forming in a certain amount of distilled water) is added in into solution.Acutely stir
It mixes, in 80~90 DEG C of when solution becomes clarification, filtering adds distillation water washing to sulfate ion and chlorion for temperature control
It meets the requirements and (takes a small amount of solution that the BaCl of acidifying is added dropwise respectively2、AgNO3, until solution is generated without white precipitate), it drains
Ferric hydroxide precipitate.Citric acid is divided into three parts of 9.6g, 12.6g, 25.2g inequality, respectively with iron hydroxide and a certain amount of
Distilled water is added in three-necked bottle.Stirring, temperature are controlled at 95 DEG C or more, when heat preservation 1 is small.Then it is cooled to 50 DEG C, is added with stirring
Ammonium hydroxide 40ml.Static more than 48h takes supernatant liquor filtering filtrates to be condensed into paste.In less than 80 DEG C dry product citric acids
Iron ammonium.
(Wang Yu, Yan Jing, Wang Xuewei wait synthetic method [J] Chemical Engineering Technologies of salt anticaking agent ferric citrates to Wang Yu etc.
With exploitation, 2014 (7):25-27.) by 43g FeSO4·7H2O is dissolved in 100mL pure water, is added slowly with stirring
H2SO430%H is added dropwise in 4mL2O279g is heated to 90 DEG C, uses K3[Fe(CN)6] examine Fe2+It is oxidized to Fe3+Degree (oxidation
Blueness should not occur when completely), obtain ferrum sulfuricum oxydatum solutum.Certain temperature is controlled, 5% ammonium hydroxide 150mL is added dropwise under stiring, acutely
Stirring when solution viscosity reduces, gained is precipitated and filters and is washed 4~5 times with decantation with 70~80 DEG C of hot water, detected
Sulfate radical meets the requirements, and standing discards supernatant liquor and obtains brownish red slurry.A certain amount of ammonium citrate is taken to crystallize, is added to above-mentioned
In the slurry of iron hydroxide, stirring and dissolving.80 DEG C are warming up to, insulated and stirred reaction 3h obtains rufous clear solution, mistake
Filter, filter vacuum are concentrated into paste, are transferred to 70 DEG C of oven dryings, obtain rufous loose particles or flakey product.
Wang Yu etc. (Wang Yu, Yan Jing, Li Zechun, new process research [J] Chemical Engineers that ferric citrates is waited to synthesize,
2014,28 (11):76-78.) citric acid is dissolved in a certain amount of water, adds in reduced iron powder by several times at 80~85 DEG C, stirring is anti-
It answers, generates the white precipitate of ferrous citrate.Ammonium hydroxide is added dropwise under stirring into ferrous citrate, dissolves ferrous citrate.Room
Quantitative H is slowly added dropwise under temperature into solution2O, then rises to certain temperature insulation reaction, and oxidation obtains ferric citrate.It is molten
Liquid is filtered and is concentrated in vacuo, and until liquid formation paste, is transferred in baking oven below 80 DEG C and is drying to obtain product citric acid
Iron ammonium.Citric acid is 1.1 with iron powder rate of charge:L, reaction time 3h, 80 DEG C of reaction temperature select H2O2Excessive 20%, reaction temperature
60 DEG C of degree, reaction time 1.5h are optimum reaction condition.
It is found by investigating, ferric citrate has boundless application prospect in food, medicine and other fields, has caused
The attention of researcher and relevant enterprise.Explore the ferric citrate that convenient, efficient green synthesis process prepares high-purity
Product will bring objective Social benefit and economic benefit.
The content of the invention
It is an object of the invention to：A kind of preparation method of high-purity citric acid iron ammonium is proposed, in process of production without useless
Liquid generates, and the product of acquisition has the characteristics that purity height, good dispersion, of low cost, and one kind is provided for food additives field
The ferric citrate additive of high-quality.
The present invention proposes a kind of preparation method of high-purity citric acid iron ammonium, includes the following steps：
Step 1: a certain amount of iron hydroxide is placed in dialysis bag made of collodion establishes Liquid Membrane Transport system, pass through
Liquid Membrane Transport controls the rate of release of iron ion, and then controls the forming quantity of ferric citrate nucleus and the growth speed of crystal
Rate；
Step 2: it is 1 according to the molar ratio of citric acid and ammonium hydroxide：1 by citric acid and ammonium hydroxide wiring solution-forming, is placed in reaction
In device, entire reactor is placed in ultrasonic disperser, and the dialysis bag for filling iron hydroxide prepared in step 1 is placed in this
In reactor, wherein, the molal quantity of iron hydroxide is identical with the molal quantity of citric acid, ultrasonic reaction 5-60 points at normal temperatures of system
Clock；
Step 3: by the reaction system after reaction using vacuum distillation, again in baking oven 80-95oThe mode of C dryings, obtains
The ferric citrate product of high-purity.
As an optimization：The power of the ultrasonic disperser is 50-300W.
The invention has the advantages that：
1st, the technique of the release of dialysis control iron ion, ultrasound and vacuum distillation is put forward for the first time, prepares the lemon of high-purity
Sour iron ammonium product；
2nd, the present invention effectively controls the generation of ferric citrate double salt, system using dialysis bag control iron ion release
In there is no extra iron hydroxide substance, be conducive to recycling for water in reaction system；
3rd, disperse in present invention process by ultrasonic wave, not only contribute to the homodisperse of system, and can speed up anti-
Answer progress；
4th, since this method is by the way of being concentrated under reduced pressure, reaction process is greatly accelerated, improves production efficiency, is saved
The energy.
5th, the technical process that the present invention uses is generated without waste water, solid waste, belongs to environmentally protective production technology.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, so that the technology of this field
Personnel can be better understood from advantages and features of the invention, so as to make apparent boundary to protection scope of the present invention
It is fixed.Embodiment described in the invention is only part of the embodiment of the present invention, instead of all the embodiments, based on the present invention
In embodiment, the every other implementation that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Embodiment 1：
The iron hydroxide of 10.7g is placed in using in dialysis bag made of collodion, is sealed after exporting again by the dialysis bag
It is placed in beaker.The solution being made into beaker containing 29.4g Citric Acid Monos and 0.6g ammonia, entire reactor are placed in ultrasonic wavelength-division
It dissipates in device.The dialysis bag for filling iron hydroxide prepared by the first step is placed in the reactor, and the power of ultrasonic wave is 50w, instead
It is 5 minutes between seasonable.After reaction, reaction system is obtained into the ironic citrate of high-purity using being evaporated under reduced pressure, after re-dry
Ammonium product.
Embodiment 2
The iron hydroxide of 10.7g is placed in using in dialysis bag made of collodion, is sealed after exporting again by the dialysis bag
It is placed in beaker.The solution being made into beaker containing 27.3g Citric Acid Monos and 0.2g ammonia, entire reactor are placed in ultrasonic wavelength-division
It dissipates in device.The dialysis bag for filling iron hydroxide prepared by the first step is placed in the reactor, and the power of ultrasonic wave is 200w, instead
It is 30 minutes between seasonable.After reaction, reaction system is obtained into the citric acid of high-purity using being evaporated under reduced pressure, after re-dry
Iron ammonium product.
Embodiment 3
The iron hydroxide of 10.7g is placed in using in dialysis bag made of collodion, is sealed after exporting again by the dialysis bag
It is placed in beaker.The solution being made into beaker containing 28.0g Citric Acid Monos and 0.3g ammonia, entire reactor are placed in ultrasonic wavelength-division
It dissipates in device.The dialysis bag for filling iron hydroxide prepared by the first step is placed in the reactor, and the power of ultrasonic wave is 100w, instead
It is 60 minutes between seasonable.After reaction, reaction system is obtained into the citric acid of high-purity using being evaporated under reduced pressure, after re-dry
Iron ammonium product.
Comparative example
The solution that the iron hydroxide of 10.7g, 29.4g Citric Acid Monos and 0.6g ammonia are made into, is added to same beaker
In, it after stirring, is concentrated and dried, obtains ferric citrate product.
Claims (2)
1. a kind of preparation method of high-purity citric acid iron ammonium, it is characterised in that：Include the following steps：
Step 1: a certain amount of iron hydroxide is placed in dialysis bag made of collodion establishes Liquid Membrane Transport system, pass through liquid film
It transmits to control the rate of release of iron ion, and then controls the forming quantity of ferric citrate nucleus and the growth rate of crystal；
Step 2: it is 1 according to the molar ratio of citric acid and ammonium hydroxide：1 by citric acid and ammonium hydroxide wiring solution-forming, is placed in reactor
In, entire reactor is placed in ultrasonic disperser, and it is anti-that the dialysis bag for filling iron hydroxide prepared in step 1 is placed in this
It answers in device, wherein, the molal quantity of iron hydroxide is identical with the molal quantity of citric acid, ultrasonic reaction 5-60 points at normal temperatures of system
Clock；
Step 3: the reaction system after reaction is obtained high-purity using vacuum distillation, again in a manner that 80-95 DEG C of baking oven is dry
The ferric citrate product of degree.
2. the preparation method of high-purity citric acid iron ammonium according to claim 1, it is characterised in that：The ultrasonic wavelength-division
The power for dissipating device is 50-300W.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2200236A1 (en) * | 1972-09-21 | 1974-04-19 | Miles Lab | Ferric ammonium citrate prepn - from calcium citrate, ferric sulphate and ammonia |
| CN101898956A (en) * | 2010-05-24 | 2010-12-01 | 南通市飞宇精细化学品有限公司 | Method for industrial production of antitackiness agent ammonium ferric citrate for green food edible salt |
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2017
- 2017-12-29 CN CN201711466933.XA patent/CN108059596B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2200236A1 (en) * | 1972-09-21 | 1974-04-19 | Miles Lab | Ferric ammonium citrate prepn - from calcium citrate, ferric sulphate and ammonia |
| CN101898956A (en) * | 2010-05-24 | 2010-12-01 | 南通市飞宇精细化学品有限公司 | Method for industrial production of antitackiness agent ammonium ferric citrate for green food edible salt |
Non-Patent Citations (1)
| Title |
|---|
| 周鹏等: "《简易复合渗析装置的制作及其在氢氧化铁溶胶纯化中的应用》", 《山东化工》 * |
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