CN106660824B - The method for preparing molysite - Google Patents
The method for preparing molysite Download PDFInfo
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- CN106660824B CN106660824B CN201580036889.1A CN201580036889A CN106660824B CN 106660824 B CN106660824 B CN 106660824B CN 201580036889 A CN201580036889 A CN 201580036889A CN 106660824 B CN106660824 B CN 106660824B
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- molysite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of method that electrolysis method prepares the molysite such as ferric sulfate, iron chloride, bodied ferric sulfate, poly-ferric chloride, poly-ferric sulfate chloride, and the basicity of product can use electrolytic process and be readily controlled.In the electrolytic cell using anion-exchange membrane as electrolyte membrane, while anode chamber's output molysite product, cathode chamber output is electrolysed the products such as pure iron, hydrogen, zinc.The raw material sources such as required ferrous sulfate, frerrous chloride, waste hydrochloric acid, Waste Sulfuric Acid are in the by-product or waste of the industries such as titanium dioxide, circuit board and stainless steel etching, steel.
Description
Technical field
The invention belongs to inorganic chemical industries and field of hydrometallurgy, in particular to prepare the method for molysite.
Background technique
The industries such as titanium dioxide, circuit board and stainless steel etching, steel generate tens million of tons of ferrous sulfate, protochloride every year
Iron, spent acid become heavy environmental pressure.It is former that the industry such as molysite, pure iron, hydrogen can be converted it into using electrolytic process
Material, realizes the recycling of waste.
Molysite, i.e. trivalent iron salt are divided into ferric salt, alkali formula molysite, acid molysite.The purposes of acid molysite is less, positive iron
Salt and alkali formula molysite are the very big water purification agents of dosage.It is well known that iron ion encounters, hydroxide ion is easy to form to be insoluble in water
Precipitating, but contain a large amount of iron ions and a large amount of hydroxide ion (hydroxyls simultaneously if taking specific method but and can be made
Base) soluble alkaline molysite, and the solubility of this alkali formula molysite is very big.This alkali formula molysite is really a kind of inorganic
High molecular polymer, therefore often referred to as polymeric iron, water purification performance are very good.Ferric sulfate, bodied ferric sulfate, gathers iron chloride
Close iron chloride, poly-ferric sulfate chloride this five kinds of molysite occupy the overwhelming majority of molysite usage amount, wherein again with polyaluminum sulfate
The dosage of iron is maximum.
The concept of basicity is introduced in molysite field, the numerical value of basicity is equal to hydroxide ion (hydroxyl) institute in molysite
The ratio between electrically charged quantity absolute value of electrically charged quantity absolute value and whole iron ions institute.Since the measurement of basicity generallys use acid
The basicity of alkali titration, acid salt can be expressed as negative value, can thus unify to use each of basicity B quantificational expression molysite
Kind state: B=0 is ferric salt, and B > 0 is alkali formula molysite, and B < 0 is acid molysite.In water purification agent field, the basicity of molysite and
Concentration becomes the most important parameter of characterization molysite performance.Basicity appropriate is conducive to improve the water purification ability of molysite, still
It is unstable that excessively high basicity will lead to molysite.Molysite product design is improved for reducing evaporation, transport, storage etc. cost
Have a most important influence, thus control basicity in the desired range within and the raising concentration pass that is molysite technology of preparing as far as possible
Where key.
Chemical oxidization method, which prepares molysite technology, more comprehensive summary1,2,3,4, such methods need to consume sub-
Raw material except molysite；Basicity is controlled by adjusting acid amount or alkali number, foreign ion is readily incorporated, is easy to happen alkali
Local over-concentration causes precipitating to generate.
Fang Yihe etc.5Have studied the electrolytic process of ferrous sulfate system, for pickle liquor utilization provide one it is new
Method does not introduce foreign ion.Major defect is: not controlling the range of basicity；Using with a large amount of free acids
Ferrous sulfate solution as raw material, need first to neutralize a part of free acid with steel scrap, be neutralized again with iron hydroxide after electrolysis
Fall remaining free acid, and the cost of steel scrap and iron hydroxide is all very high；Using low temperature process, product design is low, gained anode
Product iron concentration is no more than 100g/L.
There is document to disclose the electrolytic process of ferrous chloride waste fluid obtained by leaching copper6, but it is principally dedicated to cathodic process, anode
Process is not disclosed in detail, more without reference to the control to basicity.Due to using low temperature process, gained anode product design
Low, iron concentration is lower than 130g/L.
The phenomenon that existing document all can make the basicity of molysite increase without open anion-exchange membrane, more not to it
It is utilized and is controlled, typically without the basicity control problem in the electrolytic process of open preparation high concentration molysite.
Technical problem
Electrolysis method preparation have desired basicity molysite product be the invention solves most important problem.
Solution to the problem
Technical solution
The technical scheme adopted by the invention is that:
Molysite is prepared using electrolysis method, the ferrous salt in anodic oxidation anolyte becomes molysite, hands over using anion
Film diaphragm is changed to increase the basicity of molysite.
Further, basicity is controlled using diaphragm two sides pressure difference.
Further, 50 DEG C of anolyte temperature >.
Further, anolyte iron content >=150g/L, temperature >=60 DEG C, preferably >=80 DEG C.
Further, diaphragm cathode side pressure > diaphragm anode-side pressure.
Further, active material of positive electrode is carbon material, preferably graphite；Anode substrate material is good conductor material, excellent
It is selected as graphite.
Further, catholyte is containing a kind of or several in sulfuric acid, hydrochloric acid, ferrous sulfate, frerrous chloride, zinc sulfate
The solution of kind.
Further, catholyte chlorine ion concentration >=4mol/L.
Document 5 points out that the free acid of anode chamber can move to cathode chamber.But experiment discovery, when anolyte free acid content
It is less or be free of free acid when, anion-exchange membrane can catalysed promoted iron ion formed alkali formula molysite, that is, increase anode
The basicity of molysite in liquid.In the identical situation of other electrolytic conditions, anolyte iron concentration is bigger, this catalysed promoted
Effect is more obvious, and is more conducive to the basicity for improving molysite, especially when iron concentration is in 150g/L or more, the increasing of basicity
Add more rapid.This phenomenon is difficult to be explained with the hydrolysis theory of iron ion merely.The present invention is reached using this phenomenon
Prepare the purpose with certain basicity molysite naturally using electrolytic process, preparation process is uniform and stable, avoids office
Portion's alkali overrich, and other raw materials need not be used.
Excessive basicity is unfavorable for preparing ferric salt and low basicity alkali formula molysite, so that needing to be added relatively large
Acid be corrected, therefore, it is desirable to by basicity control within limits.Controlled in the present invention word be it is two-way, both referred to
Control basicity becomes larger, and also refers to that control basicity becomes smaller, without that should be understood merely as inhibiting by control.
The pressure of diaphragm two sides can have an impact basicity.Definition:
Δ P=diaphragm anode-side pressure-diaphragm cathode side pressure=diaphragm two sides resultant force/diaphragm area
Experiment shows that the numerical value of Δ P and basicity have positive correlation, and Δ P numerical value is bigger, is more conducive to increase alkali
Degree, on the contrary it is then be conducive to reduction basicity.
Δ P < 0 is conducive to the design and manufacture of large scale electrolytic cell, because anode-side is easy design, support construction props up film
Support.
Experiment discovery improves catholyte chlorine ion concentration and is also beneficial to reduce basicity.When chlorine ion concentration is more than
When 4mol/L, this effect becomes very prominent, can prepare basicity close to ferric salt product.
The viscosity of iron salt solutions increases sharply with the raising of concentration and basicity, and the increase of viscosity was for being electrolysed
Cheng Feichang is unfavorable.When viscosity is larger, anodic current efficiency declines rapidly, and side reaction is violent, wastes electric energy.And side reaction is raw
At acidic materials, control of the severe jamming for basicity.The increase of viscosity also results in conductivity decline, and power consumption rises.
For iron salt solutions, the viscosity of solution can be reduced by increasing temperature, but this influence is not linear.In 0-100
In the range of DEG C, the viscosity of iron salt solutions declined rapidly before this, to 50 DEG C after downward trend tend to slowly, therefore for concentration compared with
High anolyte, preferred electrolysis temperature should be at 50 DEG C or more.The volume change of electrolytic process Anodic liquid is little, therefore electricity
Iron-content before solving in anolyte determines the iron-content of final anode liquid product substantially, and difference is only that electrolysis is preceding main
It is ferrous iron, is mainly ferric iron after electrolysis.
It can inhibit side reaction using high-temperature electrolysis, using the active material of positive electrode of high activity.
Anode material includes mainly functionally basis material and active material two parts, selects suitable anode activity material
Material has key effect for inhibiting side reaction and then improving product design.Basis material and active material can be identical, such as
Basis material and active material are all graphite plates when using graphite plate as anode；It can also be different, such as titanium-based is respectively adopted
Anode and graphite particle7,8。
Many experiments show that carbon material has outstanding electro-chemical activity to ferrous ions, this is primarily due to carbon
Self character.Amorphous carbon, graphite, vitreous carbon have preferable electro-chemical activity, but amorphous carbon electric conductivity is poor, glass
Carbon is prohibitively expensive.The purpose of for anticorrosive, increase specific surface area, increase hydrophily, carbon anode active material often adds it
His ingredient, change physics or geometric shape, carry out physics or chemical processing etc., at this time active material there are shapes
Formula is although different, but play main electro-chemical activity is still carbon material.Claims of the invention is not because this
The difference of existence form and be restricted.For example, the method increase corrosion resistance for immersing organic matter can be used in graphite plate electrode；Stone
Plate, graininess, filiform can be made in the hope of changing specific surface area in ink.These kinds all without changing main active material of positive electrode
Class, thus this kind of active material of positive electrode is still within the scope of claims of the invention.
Suitable in-depth study has been carried out in the cathodic process of cathodic process, especially hydrogen ion and ferrous ion.This
The electrolytic conditions such as concentration, temperature, pH, the current density of class cathodic process are all with practical value in quite a wide range of interior variation.
Such as ferrous sulfate, in pH < 5.5, concentration from close to 0 to saturation, temperature in the broad spectrum from room temperature to boiling all
There is practical application value.
Relative to low-temperature electrolytic9, catholyte works under high temperature and advantageously reduces power consumption, can use biggish electricity
Current density10, but the temperature tolerance of anion-exchange membrane is required to improve.The heat resistance of anion-exchange membrane should with it is used
Temperature range is adapted.In order to prepare the pure iron product of property, catholyte may there are larger with anolyte
The temperature difference.Obviously, the lesser temperature difference is conducive to reduce energy consumption.The current density of cathodic process mainly by cathode product require and
The constraint of anion exchange film properties, excessively high current density will shorten the service life of film.
Bibliography:
[1] Du Xinfang, Chen Yuyong, ferric sulfate trial-production and application, using chemical industry [J], 2011, (7), 1301-1302
[2]Clair；Rene (Martigues, FR), Gallet；Alain (Lavera, FR), Production of
Concentrated aqueous solutions of ferric chloride [P], US5527515,1995
[3] the commonplace pavilion of Pan, Wu Jinfeng, the research and progress of bodied ferric sulfate technology of preparing, Treatment of Industrial Water magazine [J],
2009 (9), 1-5
[4] white strong, the preparation and application of inorganic macromolecule flocculant poly iron chloride, China environmental protection industry [J], 2009,
(2), 38-41
[5] Fang Yihe, Liang Shengfei, Li Ziqiang, Electrolytic Treatment of Waste Sulfuric Acid Pickling Solution With Anion Exchange Membrane, steel [J],
1983, (8), 42-45
[6] Hunan east tungsten ore, Central-South China Institute of Mining and Metallurgy, ferric trichloride soak copper byproduct-electrolytic iron powder, and non-ferrous metal (selects smelting portion
Point) [J], 1978, (2), 64-65
[7] V.Jiricny, A.Roy, J.W.Evans, Copper electrowinning using spouted-bed
Electrodes:Part I.Experiments with oxygen evolution or matte oxidation at the
Anode, Metallurgical and Materials Transactions.B [J], 2002,33 (5), 669-676
[8] V.Jiricny, A.Roy, J.W.Evans, Copper electrowinning using spouted-bed
Electrodes:Part II.Copper electrowinning with ferrous ion oxidation as the
Anodic reaction, Metallurgical and Materials Transactions.B [J], 2002,33 (5), 677-
683
[9] W.M.Shafer, C.R.Harr, Electrolytic Iron Powders-Production and
Properties, Journal of The Electrochemical Society [J], 1958,105 (7), 413-417
[10] Mostad E, Rolseth S., Thonstad J., Electrowinning of iron from
Sulphate solutions, Hydrometallurgy, 2008,90 (2-4), 213-220
Advantageous effect of the invention
Beneficial effect
The electric energy of two electrodes of cathode and anode is utilized in the present invention simultaneously, can carry out to the basicity of molysite product effective
Control, molysite product iron-content is up to 150g/L or more.
To the brief description of accompanying drawing
Detailed description of the invention
Fig. 1 is for the viscosity of iron chloride and ferric sulfate as temperature increases and reduced trend curve.
Implement the most preferred embodiment of the invention
Preferred forms of the invention
Using two-compartment cell of the anion-exchange membrane as diaphragm is had, electrolyte can be recycled.To be easy to implement Δ P
< 0, anode chamber are closed structure.The liquid level difference of two Room can also be used to realize the control to Δ P.Anode is thick using 1cm
The graphite plate of degree or the reticulated vitreous carbon of 0.5cm thickness 45PPI, graphite plate surface are provided with the sulculus that sectional area is 2mm*2mm
As diversion trench, separation 5mm.Cathode uses 304 stainless steel plates.Agents useful for same is that analysis is pure.
Embodiment 1
Catholyte: ferrous sulfate 1200g, ammonium sulfate 160g add water to 2L.Anolyte: ferrous sulfate 600g adds water 300g
Suspension is made as anolyte, -20kPa < Δ P < -30kPa, 80 DEG C of anode temperature.Graphite sheet anode.The electrolysis that is powered is straight
To anolyte ferrous ion content < 0.05mol/L, the iron ion content 175g/L of anolyte, B=5.0%, cathode analysis are obtained
Pure iron 57g out.
Inventive embodiments
Embodiments of the present invention
Embodiment 2
Catholyte: ferrous sulfate 1.5mol/L, 600mL.Anolyte: frerrous chloride 202g adds water to 500mL, temperature 80-
85 DEG C, 150Pa < Δ P < 200Pa.Graphite sheet anode.It is powered and is electrolysed until anolyte ferrous ion content < 0.05mol/L,
Obtain the iron ion content 105g/L, B=1.1% of anolyte.
Embodiment 3
Catholyte: ferrous sulfate 1.8mol/L, 1L.Anolyte: 200ml polymeric ferrous sulphate solution (iron concentration
4.16mol/L, B=7.7%), 200g water and 400g ferrous sulfate, 200Pa < Δ P < 300Pa, anode temperature 60- is added
80℃.Graphite sheet anode.Electrolysis be powered until anolyte ferrous ion content < 0.05mol/L, anolyte iron ion content
253g/L, B=12.8%.
Embodiment 4
Catholyte: ferrous sulfate 1.5mol/L, 2L, pH=2.5.Anolyte: ferrous sulfate 2.88mol/L, 0.625L, temperature
Degree control is at 80-100 DEG C, -70kPa < Δ P < -100kPa.Graphite sheet anode.Electrolysis be powered until anolyte ferrous ion contains
< 0.05mol/L is measured, anolyte adds ferrous sulfate heptahydrate 150g, then is powered until anolyte ferrous ion content <
0.01mol/L, always there are pure iron 57g, and gained bodied ferric sulfate density is 1.502g/cm3, B=5.0%.
Embodiment 5
Catholyte: 2.2mol/L sulfuric acid, 1L.Anolyte: ferrous sulfate 310g adds water 300g that anolyte, temperature 80 is made
DEG C, 100Pa < Δ P < 200Pa.Reticulated Vitreous carbon anode.Electrolysis be powered until anolyte ferrous ion content < 0.05mol/
L, anolyte iron ion content 125g/L, B=3.0%, cathode product is hydrogen.
Embodiment 6
Catholyte: 2.0mol/L hydrochloric acid, 1L.Anolyte: ferrous sulfate 305g adds water 310g that anolyte, temperature 80 is made
DEG C, 100Pa < Δ P < 200Pa.Graphite sheet anode.Electrolysis be powered until anolyte ferrous ion content < 0.05mol/L, sun
Pole liquid iron ion content 130g/L, B=1.3%, cathode product is hydrogen.
Embodiment 7
Catholyte: solution of ferrous chloride 3.5mol/L, pH=0.5.Anolyte: frerrous chloride 4.1mol/L, 400mL, temperature
70-80 DEG C, -250Pa < Δ P < -350Pa of degree, graphite sheet anode.Electrolysis be powered until anolyte ferrous ion content <
0.1mol/L measures ferric chloride solution iron content 162g/L, B=0.
Embodiment 8
Catholyte: 0.5mol frerrous chloride and 0.5mol zinc sulfate add water to 0.5L, pH=1.5.Anolyte: 125g sulfuric acid
Ferrous iron adds water to 0.2L, and 40 DEG C, -50Pa < Δ P < 50Pa, air stirring.Electrolysis be powered until anolyte ferrous ion content
< 0.1mol/L, anolyte iron ion content 120g/L, B=5.2%.
Claims (22)
1. the method for preparing molysite, the method is using the ferrous ion in anodizing oxidizing anode electrolyte, feature
Be: using the solution or suspension of ferrous sulfate or protochloride molysite as initial anolyte, 50 DEG C of temperature >, using yin from
Proton exchange increases the basicity of molysite as electrolyte membrane, so that basicity >=0 of the molysite of preparation.
2. the method as described in claim 1, it is characterised in that: controlled using diaphragm two sides pressure difference basicity.
3. the method as described in claim 1, it is characterised in that: anolyte iron content >=150g/L, temperature >=60 DEG C.
4. the method as described in claim 1, it is characterised in that: anolyte iron content >=150g/L, temperature >=80 DEG C.
5. the method as described in claim 1, it is characterised in that: diaphragm cathode side pressure > diaphragm anode-side pressure.
6. method according to claim 2, it is characterised in that: diaphragm cathode side pressure > diaphragm anode-side pressure.
7. method as claimed in claim 3, it is characterised in that: diaphragm cathode side pressure > diaphragm anode-side pressure.
8. method as claimed in claim 4, it is characterised in that: diaphragm cathode side pressure > diaphragm anode-side pressure.
9. such as method of any of claims 1-8, it is characterised in that: catholyte is to contain sulfuric acid, hydrochloric acid, sulphur
The solution of at least one of sour ferrous iron, frerrous chloride, zinc sulfate substance.
10. such as method of any of claims 1-8, it is characterised in that: active material of positive electrode is carbon material, anode base
Body material is good conductor material.
11. method as claimed in claim 9, it is characterised in that: active material of positive electrode is carbon material, and anode substrate material is good
Conductor material.
12. method as claimed in claim 10, it is characterised in that: carbon material is graphite, and good conductor material is graphite.
13. method as claimed in claim 11, it is characterised in that: carbon material is graphite, and good conductor material is graphite.
14. method as claimed in claim 10, it is characterised in that: carbon material is vitreous carbon.
15. method as claimed in claim 11, it is characterised in that: carbon material is vitreous carbon.
16. method as claimed in claim 9, it is characterised in that: catholyte chloride ion content >=4mol/L.
17. method as claimed in claim 10, it is characterised in that: catholyte chloride ion content >=4mol/L.
18. method as claimed in claim 11, it is characterised in that: catholyte chloride ion content >=4mol/L.
19. method as claimed in claim 12, it is characterised in that: catholyte chloride ion content >=4mol/L.
20. method as claimed in claim 13, it is characterised in that: catholyte chloride ion content >=4mol/L.
21. method as claimed in claim 14, it is characterised in that: catholyte chloride ion content >=4mol/L.
22. method as claimed in claim 15, it is characterised in that: catholyte chloride ion content >=4mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2015/078712 WO2016179786A1 (en) | 2015-05-11 | 2015-05-11 | Method of preparing ferric salt |
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| CN106660824B true CN106660824B (en) | 2019-01-18 |
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| CN113477639B (en) * | 2021-06-25 | 2022-06-10 | 武钢集团昆明钢铁股份有限公司 | Method for cleaning ferric trichloride stains |
| CN114735765B (en) * | 2022-03-10 | 2023-09-01 | 成都盛威兴科新材料研究院合伙企业(有限合伙) | Production process of battery grade nickel sulfate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186773A (en) * | 1997-12-19 | 1998-07-08 | 中国科学院生态环境研究中心 | Preparing polymerised aluminum chloride by electrodialysis |
| CN101437753A (en) * | 2006-01-06 | 2009-05-20 | 耐克斯特凯姆股份有限公司 | Polyaluminum chloride and aluminum chlorohydrate, processes and compositions: high-basicity and ultra high-basicity products |
| CN101475276A (en) * | 2008-12-31 | 2009-07-08 | 莫一平 | Treatment process for ferric oxide production wastewater |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113911A (en) * | 1960-09-06 | 1963-12-10 | Armour Pharma | Process of preparing aluminum chlorhydroxides and aluminum hydroxide |
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2015
- 2015-05-11 WO PCT/CN2015/078712 patent/WO2016179786A1/en active Application Filing
- 2015-05-11 CN CN201580036889.1A patent/CN106660824B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186773A (en) * | 1997-12-19 | 1998-07-08 | 中国科学院生态环境研究中心 | Preparing polymerised aluminum chloride by electrodialysis |
| CN101437753A (en) * | 2006-01-06 | 2009-05-20 | 耐克斯特凯姆股份有限公司 | Polyaluminum chloride and aluminum chlorohydrate, processes and compositions: high-basicity and ultra high-basicity products |
| CN101475276A (en) * | 2008-12-31 | 2009-07-08 | 莫一平 | Treatment process for ferric oxide production wastewater |
Non-Patent Citations (2)
| Title |
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| 阴离子交换膜电解处理硫酸酸洗废液;方一鹤等;《钢铁》;19830831;第18卷(第8期);第42-45页 |
| 高铁絮凝剂的电合成及其在染料废水处理中的应用;郑曦;《福建师范大学学报（自然科学版）》;20020930;第18卷(第3期);第54-57页 |
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| WO2016179786A1 (en) | 2016-11-17 |
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