CN102336646B - A kind of preparation method of Ferrox - Google Patents
A kind of preparation method of Ferrox Download PDFInfo
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- CN102336646B CN102336646B CN201010232984.8A CN201010232984A CN102336646B CN 102336646 B CN102336646 B CN 102336646B CN 201010232984 A CN201010232984 A CN 201010232984A CN 102336646 B CN102336646 B CN 102336646B
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Abstract
The invention discloses a kind of preparation method of Ferrox.The method comprises the steps: the divalent iron salt aqueous solution and antioxidant to stir to remove ferric ion, then with containing the oxalate denominationby aqueous solution Homogeneous phase mixing mixing solutions is obtained, this mixing solutions is stirred ageing 0.5 ~ 4 hour at 5 DEG C ~ 90 DEG C, filter afterwards, the washing of precipitate that filtration is obtained, drying; Wherein, described antioxidant is oxammonium hydrochloride and/or xitix.The method is simple and efficient to handle, and obtained Ferrox purity is high, and ferric iron content is low and have single rhombic form.
Description
Technical field
The present invention relates to a kind of preparation method of Ferrox.
Background technology
Ferrox is a kind of industrial chemicals, is all widely used in fields such as pottery, glass, photosensitive, battery material productions.In recent years, along with the increase in demand of power lithium-ion battery exploitation, the lithium iron phosphate positive material with high security obtains the extensive concern of researchist, and strength youngster causes a large amount of research and development and the production of LiFePO 4 material.Typical iron lithium phosphate synthetic method is generally with lithium salts, divalent iron salt and phosphoric acid salt for raw material, they is mixed by certain mode, then sinters under protection of inert gas and forms.Wherein, Ferrox, owing to can not remain other ion in roasting process, is thus often widely used as the source of iron supplier into synthesizing iron lithium phosphate.Regrettably, in existing Ferrox commodity, the synthesis that the product of Ferrox does not aim at iron lithium phosphate makes, and its product generally has the shortcoming that granularity is bigger than normal, purity is on the low side, crystalline structure is impure; Meanwhile, in Ferrox, ferric existence can cause the composition of iron lithium phosphate impure, and the electrochemistry of iron lithium phosphate can be caused further to reduce matter.Therefore, research synthesis have high purity, single crystal form, small particle size Ferrox product quite important for the synthesis of iron lithium phosphate.
Chinese patent CN200610097170.1 discloses a kind of production method of the Ferrox being used for synthesizing iron lithium phosphate, the method with ferrous sulfate and oxalic acid for raw material, one or both by adding in inhibitor polysaccharide, glucose, sucrose and polyvalent alcohol, and further control ph processes ferrous sulfate to prevent the hydrolysis of iron ion, then the copperas solution of process and oxalic acid or ammonium oxalate are mixed with Ferrox.This invention controls particle diameter and the crystal formation of Ferrox in preparation process by controlling reaction conditions, in this process, the method especially by logical ammonia changes ammonium acid ratio, and this operation controls complicated, not easy-operating shortcoming.
Summary of the invention
It is impure and easily containing ferric iron that technical problem to be solved by this invention overcomes the ferrous crystal formation of prior art mesoxalic acid, or the Ferrox method concrete operations being exclusively used in iron lithium phosphate of preparation control complicated, not easy-operating defect, there is provided a kind of simple and efficient to handle, and obtained Ferrox purity is high, ferric iron content is low and have the preparation method of the Ferrox of single rhombic form.
The preparation method of Ferrox of the present invention, comprise the steps: the divalent iron salt aqueous solution and antioxidant to stir to remove ferric ion, then with containing the oxalate denominationby aqueous solution Homogeneous phase mixing mixing solutions is obtained, this mixing solutions is stirred 0.5 ~ 4 hour at 5 DEG C ~ 90 DEG C, filter afterwards, the washing of precipitate that filtration is obtained, drying; Wherein, described antioxidant is oxammonium hydrochloride and/or xitix.
In the present invention, contriver through the particularly preferred antioxidant of great many of experiments can be effectively ferrous iron by the ferric iron direct-reduction existed in ferrous iron raw material, and can prevent from the oxygen in air and ferrous iron from reacting generating ferric iron, therefore effectively control ferrous stability, ensure that the synthesis of high-purity oxalic acid ferrous iron.Consumption those skilled in the art of described antioxidant should know and to adjust according to the ferric content of impurity in raw material divalent iron salt, be as the criterion with economical and effective, preferably the consumption of antioxidant is 0.1% ~ 10% of divalent iron salt total amount molar percentage, and better is 1% ~ 10%.
In the present invention, described divalent iron salt is the conventional divalent iron salt in this area, is preferably ferrous sulfate and/or iron protochloride.The ferrous iron concentration of the described divalent iron salt aqueous solution is preferably 0.56g/L ~ 140g/L.
In the present invention, the churning time of described stirring removing ferric ion is preferably 1 ~ 2 hour.
In the present invention, the source of described oxalate denominationby is the material that this area routine uses containing oxalate denominationby, is preferably one or more in oxalic acid, ammonium oxalate and sodium oxalate.The oxalate denominationby concentration of the described oxalate denominationby aqueous solution is preferably 0.88g/L ~ 220g/L.
In the present invention, the described divalent iron salt aqueous solution and the consumption of the oxalate denominationby aqueous solution are preferably for the mol ratio of divalent iron salt processed and oxalate denominationby is 1: 1.
Agents useful for same of the present invention and raw material are all commercially.
On the basis meeting this area general knowledge, each technical characteristic above-mentioned in the present invention arbitrary combination can obtain present pre-ferred embodiments.
Positive progressive effect of the present invention is: the preparation method that the invention provides a kind of Ferrox.The method is simple and efficient to handle, obtained Ferrox purity is high, be greater than 99.5%, wherein ferric iron content is low, single rhombic form, meet the quality requirements of lithium ion battery iron lithium phosphate synthesis to Ferrox completely, can be used widely in fields such as pottery, magneticsubstance, light reaching the film, glass.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the Ferrox that embodiment 1 obtains.
Fig. 2 is the SEM photo of the Ferrox that embodiment 1 obtains.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
(1) prepare with distilled water the copperas solution 500ml that ferrous iron concentration is 2.8g/L, add 2.5 × 10
-4mol oxammonium hydrochloride solid, stirs 2 hours;
(2) prepare with distilled water the oxalic acid solution 500ml that oxalate denominationby concentration is 4.4g/L;
(3) control above-mentioned oxalic acid solution 5 DEG C, at whipped state, step (1) is obtained solution and add wherein, stir 4 hours, obtain yellow mixing solutions, filter, throw out distilled water wash 3 ~ 4 times, dry at 110 DEG C, obtain Ferrox product.
Detect this sample (measuring method see reaction times of: synthesis of oxalic acid ferrous iron on the impact of composition, Liaoming Petrochemical Univ's journal, 2005,4:1 ~ 4), the purity recording Ferrox is 99.6%.
Detect through Powder XRD pattern, wherein, detecting instrument is Rigaku2200X x ray diffractometer x, and CuK α is used in test
1as target, wavelength is 0.1540nm, step-length 0.020, probe temperature is normal temperature, result as shown in Figure 1, as can be seen from the figure, sample is at 18.3 °, 23.0 °, 28.5 °, 34.3 °, 37.6 °, 42.7 °, 45.2 °, 48.2 °, 57.1 °, and 60.2 ° have diffraction peak, by with document " Synthesisofmagnetitenanoparticlesbythermaldecompositiono fferrousoxalatedihydrate " (J.Mater.Sci2008, 43:5123-5130) contrast finds: (202) of the corresponding rhombic system Ferrox of these peaks difference, (004), (400), (022), (206), (224), (602), (026), and (228) crystal face (426), in addition, exist without any assorted peak, illustrate that gained sample is pure rhombic form Ferrox thus, meanwhile, through SEM photo observation as shown in Figure 2, Ferrox particle shape is square column type.
Embodiment 2
(1) prepare with distilled water the copperas solution 500ml that ferrous iron concentration is 28g/L, add 5 × 10
-3mol xitix solid, stirred after 2 hours;
(2) prepare with distilled water the ammonium oxalate solution 500ml that oxalate denominationby concentration is 44g/L;
(3) control above-mentioned ammonium oxalate solution 50 DEG C, at whipped state, step (1) is obtained solution and add wherein, stir 1 hour, yellow mixing solutions, filter, throw out distilled water wash 3 ~ 4 times, dry at 110 DEG C, obtain Ferrox product.
After testing in (method is with embodiment 1) this sample, the purity of Ferrox is 99.7%, and the crystal formation of Ferrox is single orthorhombic structure, and Ferrox particle shape is square column type.
Embodiment 3
(1) prepare with distilled water the copperas solution 500ml that ferrous iron concentration is 140g/L, add 6.25 × 10
-2mol oxammonium hydrochloride and 6.25 × 10
-2mol xitix solid, stirs 2 hours;
(2) prepare with distilled water the sodium oxalate solution 500ml that oxalate denominationby concentration is 220g/L;
(3) control above-mentioned sodium oxalate solution 90 DEG C, at whipped state, step (1) is obtained solution and add wherein, stir 0.5 hour, yellow mixing solutions, filter, throw out distilled water wash 3 ~ 4 times, dry at 110 DEG C, obtain Ferrox product.
After testing in (method is with embodiment 1) this sample, the purity of Ferrox is 99.8%, and the crystal formation of Ferrox is single orthorhombic structure, and Ferrox particle shape is square column type.
Embodiment 4
(1) prepare with distilled water the solution of ferrous chloride 500ml that ferrous iron concentration is 112g/L, add 5.0 × 10
-2mol oxammonium hydrochloride solid, stirs 2 hours;
(2) prepare with distilled water the sodium oxalate solution 500ml that oxalate denominationby concentration is 176g/L;
(3) control above-mentioned sodium oxalate solution 50 DEG C, at whipped state, step (1) is obtained solution and add wherein, stir 2 hours, yellow mixing solutions, filter, throw out distilled water wash 3 ~ 4 times, dry at 110 DEG C, obtain Ferrox product.
After testing in (method is with embodiment 1) this sample, the purity of Ferrox is 99.7%, and the crystal formation of Ferrox is single orthorhombic structure, and Ferrox particle shape is square column type.
Embodiment 5
(1) prepare with distilled water the solution of ferrous chloride 500ml that ferrous iron concentration is 0.56g/L, add 5.0 × 10
-4mol oxammonium hydrochloride solid, stirs 1 hour;
(2) prepare with distilled water the sodium oxalate solution 500ml that oxalate denominationby concentration is 0.88g/L;
(3) control above-mentioned sodium oxalate solution 90 DEG C, at whipped state, step (1) is obtained solution and add wherein, stir 2 hours, yellow mixing solutions, filter, throw out distilled water wash 3 ~ 4 times, dry at 110 DEG C, obtain Ferrox product.
After testing in (method is with embodiment 1) this sample, the purity of Ferrox is 99.7%, and the crystal formation of Ferrox is single orthorhombic structure, and Ferrox particle shape is square column type.
Claims (33)
1. the preparation method of a Ferrox, it is characterized in that: it comprises the steps: the divalent iron salt aqueous solution and antioxidant to stir to remove ferric ion, then with containing the oxalate denominationby aqueous solution Homogeneous phase mixing mixing solutions is obtained, this mixing solutions is stirred ageing 0.5 ~ 4 hour at 5 DEG C ~ 90 DEG C, filter afterwards, the washing of precipitate that filtration is obtained, drying; Wherein, described antioxidant is oxammonium hydrochloride and/or xitix; The described divalent iron salt aqueous solution and the consumption of the oxalate denominationby aqueous solution be to the mol ratio of divalent iron salt and oxalate denominationby be 1:1.
2. preparation method as claimed in claim 1, is characterized in that: the consumption of described antioxidant is 0.1% ~ 10% of divalent iron salt total amount molar percentage.
3. preparation method as claimed in claim 1 or 2, is characterized in that: described divalent iron salt is ferrous sulfate and/or iron protochloride.
4. preparation method as claimed in claim 1 or 2, is characterized in that: the source of described oxalate denominationby is one or more in oxalic acid, ammonium oxalate and sodium oxalate.
5. preparation method as claimed in claim 3, is characterized in that: the source of described oxalate denominationby is one or more in oxalic acid, ammonium oxalate and sodium oxalate.
6. preparation method as claimed in claim 1 or 2, is characterized in that: the ferrous iron concentration of the described divalent iron salt aqueous solution is 0.56g/L ~ 140g/L.
7. preparation method as claimed in claim 3, is characterized in that: the ferrous iron concentration of the described divalent iron salt aqueous solution is 0.56g/L ~ 140g/L.
8. preparation method as claimed in claim 4, is characterized in that: the ferrous iron concentration of the described divalent iron salt aqueous solution is 0.56g/L ~ 140g/L.
9. preparation method as claimed in claim 5, is characterized in that: the ferrous iron concentration of the described divalent iron salt aqueous solution is 0.56g/L ~ 140g/L.
10. preparation method as claimed in claim 1 or 2, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
11. preparation methods as claimed in claim 3, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
12. preparation methods as claimed in claim 4, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
13. preparation methods as claimed in claim 5, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
14. preparation methods as claimed in claim 6, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
15. preparation methods as claimed in claim 7, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
16. preparation methods as claimed in claim 8, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
17. preparation methods as claimed in claim 9, is characterized in that: the oxalate denominationby concentration of the described oxalate denominationby aqueous solution is 0.88g/L ~ 220g/L.
18. preparation methods as claimed in claim 1 or 2, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
19. preparation methods as claimed in claim 3, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
20. preparation methods as claimed in claim 4, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
21. preparation methods as claimed in claim 5, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
22. preparation methods as claimed in claim 6, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
23. preparation methods as claimed in claim 7, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
24. preparation methods as claimed in claim 8, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
25. preparation methods as claimed in claim 9, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
26. preparation methods as claimed in claim 10, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
27. preparation methods as claimed in claim 11, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
28. preparation methods as claimed in claim 12, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
29. preparation methods as claimed in claim 13, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
30. preparation methods as claimed in claim 14, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
31. preparation methods as claimed in claim 15, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
32. preparation methods as claimed in claim 16, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
33. preparation methods as claimed in claim 17, is characterized in that: the churning time of described stirring removing ferric ion is 1 ~ 2 hour.
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| CN102815745A (en) * | 2012-09-05 | 2012-12-12 | 山东东佳集团股份有限公司 | Water washing process for producing titanium dioxide by using sulfuric acid method which uses ascorbic acid to remove high-valence iron |
| CN103439324B (en) * | 2013-08-13 | 2015-11-11 | 武汉钢铁(集团)公司 | The rapid assay methods of iron content in continuous casting covering slag |
| CN104617290B (en) * | 2013-11-04 | 2017-02-08 | 中国科学院大连化学物理研究所 | Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material |
| CN110484748B (en) * | 2019-09-06 | 2020-09-11 | 中南大学 | Method for selectively recovering silver from waste circuit board |
| CN112340918A (en) * | 2020-11-11 | 2021-02-09 | 山东云水环保科技有限公司 | Method for recycling steel pickling rust removal waste liquid |
| CN113753961B (en) * | 2021-07-30 | 2022-08-12 | 安徽丰原锂电能源有限公司 | Method for purifying ferrous sulfate and preparing iron phosphate |
| CN114105759B (en) * | 2021-08-05 | 2022-09-13 | 中南大学 | Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot |
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| GB393531A (en) * | 1932-04-28 | 1933-06-08 | Curtin Howe Corp | Improvements in and relating to the production and regeneration of solutions of ferric oxalate |
| CN101129351A (en) * | 2006-08-25 | 2008-02-27 | 内蒙古百金纳投资有限责任公司 | Iron supplement composition, its preparing method and application of the same |
| CN100488937C (en) * | 2006-10-28 | 2009-05-20 | 李传友 | Production method of ferrous oxalate special for ferrous lithium phosphate |
| CN101058536B (en) * | 2007-01-24 | 2010-12-08 | 湖南化工研究院 | Method of preparing ultramicro ferrous oxalate |
| CN101059496B (en) * | 2007-05-22 | 2011-12-07 | 西南政法大学司法鉴定中心 | Method for identifying iron gall ink writing relative formation time |
| CN100540465C (en) * | 2007-07-23 | 2009-09-16 | 河北工业大学 | The hydro-thermal synthetic preparation method of lithium ion battery anode material lithium iron phosphate |
| CN101376626B (en) * | 2007-08-28 | 2011-05-25 | 比亚迪股份有限公司 | Preparation of iron oxalate hydrous salt crystal |
| CN101462944B (en) * | 2007-12-17 | 2012-12-12 | 比亚迪股份有限公司 | Iron oxalate crystal and preparation thereof |
| CN101386575B (en) * | 2008-07-04 | 2012-06-20 | 合肥国轩高科动力能源有限公司 | Method for preparing iron oxalate |
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