CN113818037B - Electrolysis device for electrolyzing trivalent titanium by sulfuric acid method titanium white - Google Patents
Electrolysis device for electrolyzing trivalent titanium by sulfuric acid method titanium white Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 109
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 98
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 23
- 235000010215 titanium dioxide Nutrition 0.000 title claims description 44
- 230000008569 process Effects 0.000 claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 5
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 abstract description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 238000006722 reduction reaction Methods 0.000 description 33
- 239000000843 powder Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 12
- 239000011790 ferrous sulphate Substances 0.000 description 11
- 235000003891 ferrous sulphate Nutrition 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- -1 titanium ions Chemical class 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 208000000649 small cell carcinoma Diseases 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HFDCVHDLKUZMDI-UHFFFAOYSA-N sulfuric acid titanium Chemical compound [Ti].OS(O)(=O)=O HFDCVHDLKUZMDI-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to an electrolytic device for ferric iron in titanium sulfate solution after acidolysis of titanium dioxide, which is formed by overlapping unit reactors and pressurizing and sealing the unit reactors at the first stage and the last stage, wherein the outer sides of the unit reactors at the first stage are provided with sealing heads, the unit reactors are divided into an anode and a cathode, each unit reactor consists of a reticular electrode and a plate frame, the reticular electrode is arranged at the longitudinal middle point of the plate frame, electrolyte flows through the reticular electrode, the cathode reactors and the anode reactors are alternately and hermetically combined, an ionic membrane is arranged between the cathode reactors and the anode reactors, and the overlapping group number of the unit reactors is more than or equal to 10; the electrode is a titanium tantalum-plated electrode. The electrolysis device of the invention greatly reduces the cost of the existing sulfuric acid process titanium dioxide process, and improves the purity of the product and the environmental protection of the process.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to an electrolytic device used in a reduction process of ferric iron in a titanium sulfate solution after acidolysis of titanium dioxide by a sulfuric acid method.
Background
The sulfuric acid process and the chlorination process are main processes for producing titanium pigment, and the sulfuric acid process has the advantages of low raw material price, low product cost, less investment and simple equipment. The quality of sulfuric acid process products has been greatly improved over decades of improvement. The titanium white production by the sulfuric acid method is adopted, wherein the first step of the process is to mix ilmenite and sulfuric acid for acidolysis reaction, namely, ilmenite and sulfuric acid are reacted, and titanium in minerals is converted into soluble sulfate so as to be separated from other impurities. The chemical reaction principle of the process is as follows:
TiO2+H2SO4＝TiOSO4+H2O
FeO+H2SO4＝FeSO4+H2O
Fe2O3+3H2SO4＝Fe2(SO4)3+3H2O
The solid generated by the reaction is washed by water to become a solution containing titanyl sulfate, ferrous sulfate and a large amount of Fe 3+ impurities, and the solution is acidolysis titanium solution. During the production process, a certain amount of iron is added, ferric iron is reduced into ferrous iron, and ferrous iron is removed by separation. If the hydrolysis reaction is directly carried out without removing these ferric impurities, a titanium white product of excellent quality cannot be obtained.
The current technology is to add reduced iron powder into the titanium sulfate solution to reduce Fe 3+ in the solution into Fe 2+ and reduce a small amount (1-3 g/L) of TI 4+ to meet the technological requirements of the subsequent procedures. Whether iron sheets, scrap iron or iron powder, the quality of the titanium white finished product is finally affected due to impurities, greasy dirt and nonferrous metal impurities contained in the titanium white powder. In addition, the Fe powder is adopted for reduction, the reaction is severe, the temperature rise is rapid, the hydrolysis reaction is advanced due to the fact that the titanium sulfate solution has thermal instability, especially the local excessively high temperature can lead to the occurrence of the hydrolysis reaction, partial titanium sulfate hydrolysate is formed in the titanium sulfate solution, most of the partial hydrolysate is removed by the impurity removing procedures such as subsequent filtration and the like to cause the loss of titanium, and the hydrolysate which is not removed in a small part can enter the critical process of the titanium white by the sulfuric acid method for hydrolysis, and the hydrolysate existing before the start of the hydrolysis is guided in order to bring bad crystallization centers in the process of the hydrolysis, so that the grain size distribution of the product is finally influenced, and the optical property is further influenced. Thus, the use of iron reduction requires strict control of the temperature rise conditions, and the process conditions are operated severely. The reduced iron powder is adopted for reduction, iron powder and sulfuric acid are additionally added into the materials, ferrous sulfate obtained by the reaction is dissolved in the titanium sulfate mother liquor, the concentration of the ferrous sulfate in the mother liquor is greatly higher than the requirement of the subsequent hydrolysis process, and the cooling crystallization is additionally carried out to remove redundant ferrous sulfate in the mother liquor. In addition, under the condition that an ore source with 10 percent of Fe 3+ content is generally adopted, the reduction process of the sulfuric acid process titanium white in the sulfuric acid titanium solution after acidolysis needs to consume the reduced iron powder with the cost of 200 yuan/ton of titanium white, and the reduction cost is higher.
Electrolytic trivalent titanium has attracted attention of those skilled in the art as an effective alternative to iron powder reduction processes because of the absence of added iron. The process only uses mother liquor electrolysis to generate reduction, can reduce the generation of ferrous sulfate byproducts caused by the addition of reduced iron powder, saves iron resources, and has the advantages that the existing electrolysis method is used for directly electrolyzing ferric iron solution and also electrolyzing titanium sulfate solution prepared by electrolysis, but the electrolysis is usually performed by adopting a single-stage electrolysis chamber provided with an ion diaphragm, the operation stability is poor, the operation cost is high, the method is only suitable for a small-cell reaction chamber under laboratory conditions at present, the required electrolyte cannot be obtained by direct amplification, the application cost can be greatly increased, and the reduction process exceeds that of directly adding iron powder, so that the method cannot be put into industrial production at all.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the impurity of an iron reducing agent product adopted in the production process of titanium dioxide by a sulfuric acid method is high, the cost is too high, and the quality is influenced by local overheating of a titanium sulfate solution caused by reaction heat in the reduction process. By adding the electrolytic device in the process, the trivalent titanium electrolysis process which does not introduce impurities, has low cost and simple process and can be directly applied to the actual production process and the electrolytic device adopted by the trivalent titanium electrolysis process are further provided.
The invention provides an electrolysis device for a sulfuric acid process titanium white electrolysis trivalent titanium process, which is formed by overlapping unit reactors and pressurizing and sealing the unit reactors at the first stage and the last stage, wherein the outer sides of the unit reactors at the last stage are provided with sealing heads, the unit reactors are divided into an anode and a cathode, each unit reactor consists of a reticular electrode and a plate frame, the cathode reactor and the anode reactor are alternately and hermetically combined, an ionic membrane is arranged between the cathode reactor and the anode reactor, the reticular electrode is arranged at the longitudinal middle point of the plate frame, electrolyte flows through the reticular electrode, and the overlapping group number of the unit reactors is more than or equal to 10; preferably 12-16 grade; the electrode is a titanium tantalum-plated electrode. The reactor is characterized in that a polar plate is added into a single plate frame, and an ionic membrane structure is added between two plate frames, namely, the structure is as follows: an end enclosure I, a cathode plate I, an anode plate I, an ion membrane I … … I, an ion membrane I anode plate I, and an ion membrane I end enclosure. Unlike the structure of the conventional plate-and-frame electrochemical reactor, the conventional plate-and-frame structure: sealing head I plate frame I anode plate I sealing I ion membrane I sealing I cathode plate I plate frame … I head.
The sulfuric acid process titanium white electrolysis trivalent titanium process comprises the following steps:
(1) Acidolysis is carried out on the titanium concentrate/titanium slag and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Part of the titanium liquid flowing out of the reduction tank enters a cathode chamber of the multistage electrolytic tank, and part of the titanium liquid enters a hydrolysis reaction tank after being concentrated; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 140-170g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, dilute sulfuric acid is added into an anode; the current density is 200-400A/m 2, the operation is 48-72 hours, and the electrolytic level is more than or equal to 10 levels.
Preferably, the titanium liquid flowing out of the reduction tank is subjected to sedimentation and hot filtration to crystallize and separate and remove ferrous sulfate, and the titanium liquid part after fine filtration enters the electrolytic tank.
Preferably, the trivalent titanium solution in the step (2) has a Ti 3+ concentration of 130-150g/L calculated as titanium dioxide;
In the electrolytic process, dilute sulfuric acid is used as anode liquid, clarified titanium liquid is used as cathode liquid, a titanium tantalum plating electrode is used, two mediums are isolated by an ionic membrane, and tetravalent titanium in the titanium liquid is reduced. Dilute sulfuric acid is a strong electrolyte and readily soluble in water, ionizing in aqueous solution to form H + and HSO 4－, with a small amount of OH - ions. The clarified titanium liquid is mainly TiO 2+ and SO 4 2-. Before being electrified, various ions move freely in water; after being electrified, the ions which are freely moving change to directional movement under the action of an electric field. Positively charged TiO 2+ in solution moves toward the cathode and negatively charged OH - ions move toward the anode. At the cathode, the tetravalent titanium ions acquire electrons and are reduced to trivalent titanium ions; at the anode, the hydroxyl ions lose electrons to be oxidized to oxygen and are released from the anode.
The main reaction equation:
Anode main reaction: 4OH --4e＝＝O2↑+2H2 O
Cathode main reaction: tiO 2++2H++e＝＝Ti3++H2 O
Total electrolytic reaction: 4TiO 2++4OH-+8H+＝＝4Ti3++O2↑+6H2 O
The invention also discloses the titanium dioxide prepared by the method.
The beneficial effects of the invention are as follows:
(1) The reduction process of the invention does not need to add iron powder (scrap iron, iron sheet and the like) or sulfuric acid, thereby saving the cost of the reduction reaction. The cost of the consumed reduced iron powder is 200 yuan/ton of titanium white, and the comprehensive cost of the electrolytic trivalent titanium process is 95 yuan/ton of titanium white. The invention directly produces the trivalent titanium by using an electrolytic method, and does not need to add other reducing agents, thereby avoiding the influence of impurities in the reduced iron powder on the quality of the titanium white. The electrolytic process of the invention avoids the influence of local overheating of the titanium sulfate solution caused by reaction heat in the reduction process of the iron powder on the quality of the titanium white finished product.
(2) Through research experiments for many years, the applicant develops a multi-stage electrolytic structure special for reduction reaction, the structure adopts specific electrode materials, the number of electrode layers is strictly set, the device structure is simple, trivalent titanium liquid generated by electrolysis can be directly returned to an acidolysis tank for reduction reaction, the cost of the whole process is greatly reduced, the process flow is simplified, and the quality of titanium pigment is improved.
(3) The sulfuric acid process titanium dioxide enterprises aim to improve the product quality and the environmental protection of the process. By adopting the technical process, the high-quality titanium dioxide can be obtained by only adding a pipeline to be provided with a corresponding electrolysis device on the existing process for producing titanium dioxide by the sulfuric acid method without greatly changing the existing equipment, and the market competitiveness of the production of titanium dioxide by the sulfuric acid method is greatly improved.
Drawings
FIG. 1 is a process flow diagram for use with the present invention;
FIG. 2 is a schematic view of an electrolytic device according to the present invention.
Detailed Description
The following describes the invention in further detail with reference to examples:
Example 1
The preparation method of the titanium dioxide comprises the following steps:
(1) Acidolysis is carried out on titanium slag serving as a raw material and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Crystallizing and separating the titanium liquid flowing out of the reduction tank to remove ferrous sulfate through sedimentation and hot filtration, and concentrating part of the titanium liquid into a hydrolysis reaction tank after fine filtration; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 170g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, a titanium tantalum plating electrode is adopted as an electrode, and dilute sulfuric acid is added into an anode; the current density is 400A/m 2, the operation is carried out for 48 hours, and the number of the electrolytic unit reactor stages is 12;
(5) Concentrating, hydrolyzing, calcining, ball milling and post-treating by the prior art to finally obtain the titanium white powder with qualified quality.
Example 2
The preparation method of the titanium dioxide comprises the following steps:
(1) Acidolysis is carried out on titanium slag serving as a raw material and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Crystallizing and separating the titanium liquid flowing out of the reduction tank to remove ferrous sulfate through sedimentation and hot filtration, and concentrating part of the titanium liquid into a hydrolysis reaction tank after fine filtration; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 150g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, a titanium tantalum plating electrode is adopted as an electrode, and dilute sulfuric acid is added into an anode; the current density is 200A/m 2, the operation is carried out for 60 hours, and the number of the electrolytic unit reactor stages is 16;
(5) Concentrating, hydrolyzing, calcining, ball milling and post-treating by the prior art to finally obtain the titanium white powder with qualified quality.
Example 3
The preparation method of the titanium dioxide comprises the following steps:
(1) Acidolysis is carried out on titanium slag serving as a raw material and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Crystallizing and separating the titanium liquid flowing out of the reduction tank to remove ferrous sulfate through sedimentation and hot filtration, and concentrating part of the titanium liquid into a hydrolysis reaction tank after fine filtration; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 170g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, a titanium tantalum plating electrode is adopted as an electrode, and dilute sulfuric acid is added into an anode; the current density is 300A/m 2, the operation is carried out for 72 hours, and the number of the electrolytic unit reactor stages is 10;
(5) Concentrating, hydrolyzing, calcining, ball milling and post-treating by the prior art to finally obtain the titanium white powder with qualified quality.
Comparative example 1
The preparation method of the titanium dioxide comprises the following steps:
(1) Acidolysis is carried out on titanium slag serving as a raw material and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Crystallizing and separating the titanium liquid flowing out of the reduction tank to remove ferrous sulfate through sedimentation and hot filtration, and concentrating part of the titanium liquid into a hydrolysis reaction tank after fine filtration; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 170g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, a graphite electrode is adopted as an electrode, and dilute sulfuric acid is added into an anode; the current density is 300A/m 2, the operation is carried out for 72 hours, and the number of the electrolytic unit reactor stages is 10;
(5) Concentrating, hydrolyzing, calcining, ball milling and post-treating by the prior art to finally obtain the titanium white powder with qualified quality.
Comparative example 2
The preparation method of the titanium dioxide comprises the following steps:
(1) Acidolysis is carried out on titanium slag serving as a raw material and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank;
(3) Crystallizing and separating the titanium liquid flowing out of the reduction tank to remove ferrous sulfate through sedimentation and hot filtration, and concentrating part of the titanium liquid into a hydrolysis reaction tank after fine filtration; the concentration of Ti 4+ in the titanium liquid entering the multistage electrolytic tank is 170g/L based on titanium dioxide;
(4) The trivalent titanium solution generated after the electrolysis in the multistage electrolytic tank returns to the reduction tank to reduce the acidolysis titanium solution; in the multistage electrolytic reaction, a DSA titanium electrode is adopted as an anode, an active carbon electrode is adopted as a cathode, and dilute sulfuric acid is added into the anode; the current density is 300A/m 2, the operation is carried out for 72 hours, and the number of the electrolytic unit reactor stages is 10;
(5) Concentrating, hydrolyzing, calcining, ball milling and post-treating by the prior art to finally obtain the titanium white powder with qualified quality.
Comparative example 3 is a commercially available conventional titanium dioxide product without special treatment.
The resistivity of the titanium dioxide powder of the invention and the resistivity of the comparative example water extract are compared as follows.
TABLE 1
The improvement point of the invention is the improvement of the electrolytic process and the device and the whole process when preparing titanium pigment by the sulfuric acid method, and the process steps and structures which are well known in the art are not repeated here. The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed. And not as an attempt to limit the application of the doctrine of equivalents to the scope of the invention, any equivalents or modifications and variations would be covered by the claims.
Claims (1)
1. A sulfuric acid process titanium white electrolysis trivalent titanium process comprises the following steps:
(1) Acidolysis is carried out on the titanium concentrate/titanium slag and sulfuric acid in an acidolysis reaction tank to obtain acidolysis titanium solution;
(2) The acidolysis titanium solution flows into a reduction tank, and trivalent titanium solution obtained by electrolyzing the acidolysis titanium solution is added into the reduction tank; the trivalent titanium solution is calculated by titanium dioxide, and the Ti < 3+ > concentration is 130-150g/L;
(3) Part of the titanium liquid flowing out of the reduction tank enters a cathode chamber in a multistage electrolytic tank of the electrolytic device, and part of the titanium liquid enters a hydrolysis reaction tank after being concentrated; in the titanium liquid entering the multistage electrolytic tank of the electrolytic device, the concentration of Ti < 4+ > is 140-170g/L based on titanium dioxide;
(4) Returning the trivalent titanium solution generated after electrolysis to a reduction tank to reduce acidolysis titanium solution;
The electrolytic device is formed by overlapping unit reactors and combining the unit reactors in a pressurized sealing way, the outer sides of the first-stage unit reactor and the last-stage unit reactor are provided with sealing heads, the unit reactors are divided into an anode and a cathode, each unit reactor is composed of a reticular electrode and a plate frame, the reticular electrode is arranged at the longitudinal middle point of the plate frame, electrolyte flows through the reticular electrode, the cathode reactor and the anode reactor are alternately combined in a sealing way, and an ionic membrane is arranged between the cathode reactor and the anode reactor; the electrode is a titanium tantalum plating electrode; in the electrolytic process, dilute sulfuric acid is adopted as anode liquid, and clarified titanium liquid is adopted as cathode liquid; the current density is 200-400A/m2, the operation is 48-72 hours, and the number of overlapping groups of the unit reactors is 10-16 stages.
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| US4919772A (en) * | 1987-05-15 | 1990-04-24 | Rhone-Poulenc Chimie | Electrolytic cell/process for the reduction of titanium/iron solutions |
| CN1613776A (en) * | 2003-11-04 | 2005-05-11 | 谢亚汉 | Preparation for titanium pigment with sulfuric acid circulating use |
| CN103172115A (en) * | 2013-03-25 | 2013-06-26 | 山东东佳集团股份有限公司 | Method for removing ferric iron ion contained in metatitanic acid by adopting electrolytic reduction |
| CN103668302A (en) * | 2013-12-11 | 2014-03-26 | 中国科学院过程工程研究所 | Method for preparing high-concentration low-valent titanium aqueous solution through electrolytic reduction |
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| CN102515267B (en) * | 2011-11-03 | 2014-03-05 | 攀枝花鼎星钛业有限公司 | Production method of high-resistivity titanium dioxide |
| CN103553123B (en) * | 2013-10-18 | 2015-09-30 | 中国有色集团（广西）平桂飞碟股份有限公司 | The bleaching method of metatitanic acid in a kind of Titanium White Production By Sulfuric Acid Process |
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| US4919772A (en) * | 1987-05-15 | 1990-04-24 | Rhone-Poulenc Chimie | Electrolytic cell/process for the reduction of titanium/iron solutions |
| CN1613776A (en) * | 2003-11-04 | 2005-05-11 | 谢亚汉 | Preparation for titanium pigment with sulfuric acid circulating use |
| CN103172115A (en) * | 2013-03-25 | 2013-06-26 | 山东东佳集团股份有限公司 | Method for removing ferric iron ion contained in metatitanic acid by adopting electrolytic reduction |
| CN103668302A (en) * | 2013-12-11 | 2014-03-26 | 中国科学院过程工程研究所 | Method for preparing high-concentration low-valent titanium aqueous solution through electrolytic reduction |
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