CN1060817C - Electrolytic separating process for ilmenite - Google Patents
Electrolytic separating process for ilmenite Download PDFInfo
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- CN1060817C CN1060817C CN97117202A CN97117202A CN1060817C CN 1060817 C CN1060817 C CN 1060817C CN 97117202 A CN97117202 A CN 97117202A CN 97117202 A CN97117202 A CN 97117202A CN 1060817 C CN1060817 C CN 1060817C
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- ilmenite
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Abstract
The present invention provides an electrolytic dialysis separating method for ilmenite, which belongs to the technical field of the wet production of titanium dioxide and iron oxide. An electrolytic dialysis tank with an anion exchange diaphragm is used, diluted acid is used as a separating medium, and electric leaching is carried out to the ilmenite in an anode region. Iron ions are selectively leached, and iron and titanium are separated; the separation of the iron and a mother solution and the recovery of the acid are carried out in a cathode region, the iron ions are conveyed back to the anode region for circular use through the anion exchange diaphragm under the action of electric field force, and titanium oxide and the iron oxide or pure iron powder can be simultaneously produced. The present invention has the advantages of good comprehensive benefit, no pollution, high quality of products, no restriction of raw materials for the production of the iron oxide, etc.
Description
The invention relates to a method for separating ferrotitanium from ilmenite, belonging to the wet production of titanium dioxide and iron oxide
The technical field is as follows.
Titanium dioxide and ferric oxide are two large chemical basic raw materials, and the sulfuric acid method is a main method for producing titanium dioxide by a traditional wet method. The method separates iron in the ilmenite to obtain ferrous sulfate with low value, and generates a large amount of waste acid in the production process, which needs to be discharged and treated, so that the production cost is high and the environmental pollution is serious, and the production method almost faces the desperate situation. The existing wet production process of iron oxide uses the waste iron sheet as a main raw material, so that the production scale and the yield of the iron oxide are limited by the resources and the quality of the waste iron sheet.
The invention aims to simultaneously solve the defects of the existing titanium dioxide and ferric oxide production method and provide the ilmenite electrolytic dialysis separation method which is used for separating ilmenite by an electrolytic dialysis method, simultaneously obtaining titanium dioxide and ferric oxide, not discharging waste acid, having high product quality, not being limited by waste iron scale resources and having good comprehensive benefits.
The technical scheme of the invention is as follows: the electrolytic dialysis separation method of ilmenite is characterized in that the ilmenite is separated by adopting the electrolytic dialysis method, an anion exchange diaphragm is divided into an anode area and a cathode area, and in an electrolytic dialysis tank which takes dilute sulfuric acid or dilute hydrochloric acid as a separation medium, the iron-titanium separation, the generation of iron oxide or the reduction and purification of iron and the recycling of acid of the ilmenite are simultaneously completed by utilizing the oxidation of the anode area, the reduction of the cathode area and the dialysis ofthe anion exchange diaphragm. The anode area of the electrodialytic cell is an acidolysis area, and the cathode area is a hydrolysis area; firstly, separating iron and titanium from ilmenite in the anode region of an electrodialytic cell, adding ilmenite into the anode region of the electrodialytic cell containing dilute sulfuric acid or dilute hydrochloric acid (one of the two acids can be selected according to actual requirements) according to a certain mineral acid ratio, selectively dissolving iron in ilmenite by the dilute sulfuric acid or the dilute hydrochloric acid through electrochemical oxidation, and separating the dissolved iron from solid-phase titanium dioxide insoluble in dilute acid (namely simultaneously generating liquid FeSO)4、Fe2(SO4)3Or FeCl2，FeCl3And solid phase TiO2) The PH value of the anode area is controlled to be 1-2 (the specific value is determined according to actual needs, so that ferrous ions are completely oxidized into ferric ions), and the dissolved ferrous ions (FeSO)4Or FeCl2) Total oxidation to ferric ion [ Fe]2(SO4)3Or FeCl3]The one-step oxidation method is realized, and a two-step oxidation method in the process of producing the ferric oxide by a flow transfer wet method is not needed; after the oxidation of the iron ions is finished, solid-liquid separation and filtration are carried out,dissolving iron in the liquid phase, and leaving titanium dioxide in the solid phase; the separated mother liquor is sent to a cathode area of an electrodialytic cell, the pH value of the cathode area is controlled to be 2-3 (the specific data is actually determined, and the iron ions are fully hydrolyzed and precipitated), and common iron oxide seed crystals (promoting the hydrolysis and crystallization of the iron ions into a solid phase) are added, wherein the seed crystals can be Fe according to different products2O3FeOH or Fe (OH)3]Hydrolyzing and precipitating iron ions to form solid-phase iron oxide (Fe)2O3) At the moment, sulfate ions or hydrochloric acid ions in the catholyte return to the anode region through the anion exchange membrane under the action of the electric field force; when sulfate radical or hydrochloride radical ion in the cathode region is reduced to the standard of discharge, dewatering and filtering to obtain ferric oxide filter cake, washing and dryingThe iron oxide for non-pigment is produced by the conventional process of (100-105 ℃) and crushing (to Taylor sieve-325 meshes) (iron oxide red FeO can be obtained by controlling different crystal seeds, hydrolysis and precipitation conditions (namely PH value)3Iron oxide yellow Fe2O3nH2O or black iron oxide Fe3O4](ii) a Or controlling the cathode potential to be greater than the precipitation potential of iron (the potential of iron is generally 2-4V), so that iron ions in the cathode zone mother liquor are directly reduced into metallic iron, precipitated by a cathode, and then subjected to conventional hydrogen reduction (carried out at 700-800 ℃) and crushing processes to produce pure iron powder; solid phase (TiO) separated from solid in anode region2And a small amount of ilmenite with insufficient reaction) is washed with water, then magnetic separation is carried out, the residual ilmenite obtained by magnetic separation is returned to an anode region for continuous acidolysis, sulfuric acid with the mass percentage concentration of 94% or hydrochloric acid with the mass percentage concentration of 28% (one acid is selected as required for acidolysis in the anode region) is added to the nonmagnetic titanium dioxide material with the high acid solubility (dissolved in high-concentration acid) separated by magnetic separation for acid dissolution, hydrolysis and solid-liquid separation filtration are carried out,the separated dilute acid liquid phase is sent to the anode region for recycling, the separated solid phase (metatitanic acid) is subjected to conventional washing bleaching, salt treatment, calcination (800-900 ℃), grinding (to a Taylor sieve-200 mesh screen) and surface treatment process (the freezing separation process in the conventional acid titanium dioxide production process is not required) to produce titanium dioxide for pigments; or will beThe titanium dioxide nonmagnetic material is subjected to conventional drying (carried out at 100-105 ℃) and crushing (to a Taylor sieve of-320 meshes) processes to produce titanium dioxide for non-pigments. The iron oxide filter cake obtained by filtering in the cathode zone can be subjected to a standard process of washing, salt treatment, drying (carried out at 100-105 ℃, grinding to a Taylor sieve of-325 meshes) and surface treatment to produce iron oxide for pigments; the non-pigment titanium dioxide can be calcined (and added with a crystal form converter ZnO) at 900-920 ℃ to produce the artificial rutile by the conventional process. The concentration of a separation medium dilute sulfuric acid or dilute hydrochloric acid in the ilmenite electrolytic dialysis separation method is 18-24% (mass percentage concentration, selected according to actual needs), the mass ratio of mineral acid added into an anode region for reaction is 1: 4-6 (only iron is dissolved completely), and the reaction temperature is 100-110 ℃ (when needed, the ilmenite can be fully reacted, and the ilmenite can be heated by a known method such as a steam heating method and the like). Hydrated titanium dioxide seed crystals may also be added to the anode zone to allow a small amount of dilute acid-soluble titanium dioxide to precipitate back to the solid phase (titanium dioxide is substantially insoluble in dilute acid) to improve recovery and product quality. When the metallic iron is directly reduced, the cathode potential is controlled to be more than 2-4V, so that the iron ions inthe mother liquor are fully reduced.
The attached drawing is a process flow chart of the invention.
Examples of the present invention are further illustrated below.
Example 1: the electrolytic dialysis separation method for ilmenite separates titanium and iron by an electrolytic dialysis method, and completes the separation of iron and titanium, the generation of iron oxide or the reduction and purification of iron, and the recycling of sulfuric acid in an electrolytic dialysis tank which is divided into an anode area and a cathode area by an anion exchange diaphragm and takes sulfuric acid with the mass percentage concentration of 24% as a separation medium. The anode area of the electrodialytic cell is an acidolysis area, and the cathode area is a hydrolysis area. Firstly, separating iron and titanium of ilmenite at an anode of an electrodialytic cell, adding ilmenite into an anode area according to the mass ratio of mineral acid to the anode area of 1: 6, controlling the reaction humidity to be 110 ℃ by adding steam into the electrodialytic cell, selectively dissolving iron in the ilmenite by dilute sulfuric acid, separating the iron from solid-phase titanium dioxide insoluble in balanced acid, and controlling the pH value of the anode area to be 2 so that all dissolved ferrous ions are oxidized into ferric ions, thereby realizing the one-step oxidation method of ferric oxide. The reaction formula is as follows:
separation of
Oxidation of 2FeSO4+SO4 -2→Fe2(SO4)3
After the iron ion oxidation is finished, carrying out solid-liquid separation, sending the separated mother liquor to the cathode area of an electrolytic dialysis tank, controlling the pH to be 3, and adding Fe2O3Seed crystal to hydrolyze and precipitate iron ions to generate solid-phase iron oxide (Fe)2O3) And (4) precipitating. The reaction formula is as follows:
hydrolysis
Precipitation of
When the sulfate ion in the cathode area is reduced to the discharge standard, dehydration filtration is carried out to obtain iron oxide (Fe)2O3) Washing the filter cake, drying at 105 deg.C, pulverizing to 325 mesh, and making into iron oxide red (Fe) for non-pigment2O3)。
Solid phase (TiO) separated from solid in anode region2) After water washing, magnetic separation is carried out, the magnetically separated residual ilmenite is returned to the anode region for continuous acidolysis, sulfuric acid with the mass percentage concentration of 94 percent is added into the magnetically separated high-acid-solubility titanium dioxide nonmagnetic material for acid dissolution treatment, and then hydrolysis and solid-liquid separation are carried out, wherein the reaction formula is as follows:
acid soluble
Hydrolysis
The separated sulfuric acid is sent to an anode area for circulationRing use, separated solid phase (H)2TiO3) The titanium dioxide for the pigment is prepared by the processes of conventional washing and bleaching, salt treatment, calcination at 900 ℃, grinding to a Taylor sieve of 200 meshes and surface treatment. The method does not need the traditional working procedure of freezing and separating ferrous sulfate.
Example 2: the sulfuric acid with the mass percent concentration of 18 percent is adopted as a separation medium, ilmenite is added according to the mineral acid ratio of 1: 4, the reaction temperature is controlled at 100 ℃, the PH value of the anode area is controlled to be 1, and other process methods before the iron ion oxidation is finished are the same as example 1.
After the iron ions are oxidized, solid-liquid separation is carried out, the separated mother liquor is sent to the cathode area of an electrolytic dialysis tank, the cathode potential is controlled to be 4V, so that the iron ions in the mother liquor are reduced into metallic iron, the metallic iron is separated out from the cathode, and then the pure iron powder is prepared by carrying out hydrogen reduction at 700 ℃ by the conventional process and then crushing.
And (3) washing the solid phase separated from the anode region with water, carrying out magnetic separation, returning the magnetically-separated residual ilmenite to the anode region for continuous acidolysis, and carrying out conventional drying (at 105 ℃) and crushing (to a Taylor sieve of 200 meshes) on the magnetically-separated high-acid-solubility titanium dioxide nonmagnetic material to obtain the titanium dioxide for the non-raw material. Then adding a crystal form conversion agent (ZnO) by a conventional process and calcining at 900 ℃ to prepare the artificial rutile.
Example 3: the separation medium is hydrochloric acid with the mass percentage concentration of 24 percent, the rest process methods are the same as the example 1, and the reaction formula is as follows:
anode field separation
Oxidation by oxygen
Cathode zone hydrolysis
Precipitation of
The reaction formula when hydrochloric acid is added to prepare titanium dioxide for the pigment is as follows:
acid soluble
Hydrolysis
Example 4: the separation medium is hydrochloric acid with the mass percent concentration of 18 percent, and the rest process method is the same as the example 2. The reaction formula is as follows:
anode field separation
Oxidation by oxygen
Cathode zone hydrolysis
Precipitation of
Example 5: the separation medium is sulfuric acid with the mass percent concentration of 20%, ilmenite is added according to the mineral acid ratio of 1: 5, the reaction temperature is controlled at 105 ℃, the pH value of the anode region is controlled to be 1, and the rest processes are the same as in example 1. Controlling the pH value of the cathode region to be 2 and adding FeOOH seed crystal to obtain the iron oxide (F)2O3·nH2O) filter cake, washing according to conventional process, salt treating, drying at 105 deg.C, grinding to obtain iron oxide (F) for pigment2O3·nH2O)。
Example 6: the separation medium is sulfuric acid with the mass percentage concentration of 20 percent, ilmenite is added according to the mineral acid ratio of 1: 5, the reaction temperature is controlled at 105 ℃, the PH value of the anode region is controlled to be 1.5, and the rest processes are the same as the example 1. Controlling the cathode pH to 2.5 and adding Fe (OH)3Seed crystal to obtain iron oxide (Fe)3O4) After the filter cake is washed and salted according to the conventional process, dried at 105 ℃ and ground to the surface of a Taylor sieve with 325 meshesPreparing iron oxide (Fe) for pigment3O4)。
The present invention adopts the electrolytic dialysis separation method to separate iron and titanium from ilmenite, so that the separation of iron and titanium, the generation of ferric oxide or the reduction and purification of iron and the recycling of acid can be simultaneously completed in an electrolytic bath, ferrous ions can be further oxidized to generate ferric oxide under the action of electrochemical oxidation, and ferric oxide can be produced while titanium dioxide is produced, so the present invention has the advantages of good comprehensive benefit, low production cost, no environmental pollution, high product quality, no limitation of waste iron sheet resources for producing ferric oxide, etc.
Claims (5)
1. An electrolytic dialysis separation method for ilmenite is characterized in that the ilmenite is separated by the electrolytic dialysis method, and in an electrolytic dialysis tank which is divided into an anode area and a cathode area by an anion exchange diaphragm and takes dilute sulfuric acid or dilute hydrochloric acid as a separation medium, the iron and titanium separation, the generation of iron oxide or the reduction and purification of iron and the recycling of acid of the ilmenite are simultaneously completed by utilizing the oxidation of the anode area, the reduction of the cathode area and the dialysis of the anion exchange diaphragm; the method comprises the following steps that an anode area of an electrodialytic cell is an acidolysis area, a cathode area of the electrodialytic cell is a hydrolysis area, firstly, iron and titanium of ilmenite are separated in the anode area of the electrodialytic cell, dilute sulfuric acid or dilute hydrochloric acid selectively dissolves out iron in the ilmenite through electrochemical oxidation, the iron is separated from solid-phase titanium dioxide insoluble in dilute acid, the pH value of the anode area is controlled to be 1-2, and the dissolved ferrous ions are completely oxidized into ferric ions; after the iron ions are oxidized, carrying out solid-liquid separation and filtration, sending the separated mother liquor to a cathode area of an electrolytic dialysis tank, controlling the pH value of the cathode area to be 2-3, adding common iron oxide seed crystals to hydrolyze and precipitate the iron ions into solid-phase iron oxide, returning sulfate radicals or hydrochloric acid radical ions in the cathode area to an anode area through an anion exchange membrane under the action of an electric field, reducing the sulfate radicals or hydrochloric acid radical ions in the cathode area to a discharge standard, carrying out filtration and dehydration to obtain an iron oxide filter cake, and carrying out washing, drying, crushing and other conventional processes on the filter cake to produce the iron oxide for non-pigments; or controlling the cathode potential to be larger than the precipitation potential of iron to directly reduce iron ions in the mother liquor in the cathode area into metallic iron, precipitating from the cathode, and producing pure iron powder by the conventional hydrogen reduction and crushing process; washing solid-phase substances obtained by solid-liquid separation in the positive-negative region with water, performing magnetic separation, and returning the magnetically-separated residual ilmenite to the positive region for continuous acidolysis; adding 94% sulfuric acid or 28% hydrochloric acid into the high-acid-solubility titanium dioxide nonmagnetic material separated by magnetic separation for acid dissolution, then carrying out hydrolysis and solid-liquid separation, sending the separated dilute acid to an anode area for recycling, and carrying out conventional washing bleaching, salt treatment, calcination, grinding and surface treatment on the separated solid phase to produce titanium dioxide for pigment; or the titanium dioxide non-magnetic material is subjected to conventional drying and crushing processes to produce the titanium dioxide for the non-pigment.
2. The electrolytic dialysis separation method of ilmenite according to claim 1, characterized in that the concentration of dilute sulfuric acid or hydrochloric acid is 18-24%, the mass ratio of ilmenite and acid reacted in the anode zone is 1: 4-6, and the reaction temperature is 100-110 ℃.
3. An ilmenite electrolytic dialysis separation process according to claim 1 or 2, characterized in that the iron oxide cake dewatered by filtration from the cathode zone is further subjected to conventional processes of washing, salt treatment, grinding, surface treatment to produce iron oxide for pigments; the non-pigmenting titanium dioxide may be further calcined by conventional techniques to produce synthetic rutile.
4. An ilmenite electrolytic dialysis separation process according to claim 1 or 2, characterized in that the anode zone is additionally provided with a seed crystal of hydrated titanium dioxide to precipitate a small amount of titanium dioxide dissolved in dilute acid as a solid phase.
5. An ilmenite electrolytic dialysis separation process according to claim 3, characterized in that the anode zone is additionally seeded with hydrated titanium dioxide to precipitate a small amount of titanium dioxide dissolved in dilute acid as a solid phase.
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| CN97117202A CN1060817C (en) | 1997-08-08 | 1997-08-08 | Electrolytic separating process for ilmenite |
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| CN97117202A CN1060817C (en) | 1997-08-08 | 1997-08-08 | Electrolytic separating process for ilmenite |
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| CN1060817C true CN1060817C (en) | 2001-01-17 |
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| CN101116785B (en) * | 2007-08-31 | 2010-12-15 | 乐昌市银星化工有限公司 | Floating ball self-sucking titanium liquid-cleaning technique |
| CN109518225B (en) * | 2019-01-16 | 2020-10-02 | 北京矿冶科技集团有限公司 | Method for separating ferrous iron and cobalt nickel in solution |
| CN113354171B (en) * | 2021-05-13 | 2022-11-08 | 西北矿冶研究院 | Process method for deep dearsenization from copper smelting waste acid |
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| CN1134730A (en) * | 1993-09-07 | 1996-10-30 | 技术资源有限公司 | Upgrading titaniferous materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1134730A (en) * | 1993-09-07 | 1996-10-30 | 技术资源有限公司 | Upgrading titaniferous materials |
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