CN114920287A - Method for preparing titanyl sulfate by continuous acidolysis of ilmenite - Google Patents
Method for preparing titanyl sulfate by continuous acidolysis of ilmenite Download PDFInfo
- Publication number
- CN114920287A CN114920287A CN202210791289.8A CN202210791289A CN114920287A CN 114920287 A CN114920287 A CN 114920287A CN 202210791289 A CN202210791289 A CN 202210791289A CN 114920287 A CN114920287 A CN 114920287A
- Authority
- CN
- China
- Prior art keywords
- acidolysis
- ilmenite
- reactor
- sulfuric acid
- acidolysis reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/008—Titanium- and titanyl sulfate
-
- 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
Abstract
A method for preparing titanyl sulfate by continuous acidolysis of ilmenite is characterized by comprising the following steps: adopting ilmenite and 55-60% sulfuric acid, and carrying out continuous acidolysis in five serial acidolysis reactors, wherein the mass ratio of pure sulfuric acid in the 55-60% sulfuric acid to ilmenite is 1.55-1.65: 1; and (3) conveying the reaction mixture into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 500 ml.
Description
Technical Field
The invention relates to a method for preparing titanyl sulfate by continuous acidolysis of ilmenite.
Background
The first step in the production of titania from a titaniferous concentrate is the production of a titaniferous solution, i.e. an attempt is made to convert the useful components of the concentrate into a soluble state, or a state that is readily reactive, or to break down the concentrate into simpler compounds, which are then made into a titaniferous solution to be separated from various impurities. This measure is known as the breakdown of the concentrate. The decomposition of ilmenite can be carried out by either a pyrogenic process, i.e. a dry process, by a high-temperature reaction or by a water process, i.e. a wet process, by a low-temperature reaction. In industrial production, wet process is the main process, and the sulfuric acid process which is industrialized in 1916 is adopted.
From the history of the sulfuric acid process, five methods have appeared: liquid phase processes, solid phase processes, two phase processes, pressurized processes and continuous processes. The first three are divided mainly according to the concentration of the sulfuric acid participating in the reaction and the state of the final reaction product. The latter two are distinguished by process characteristics.
The liquid phase method uses 55-65% sulfuric acid, and the whole reaction is carried out in a liquid phase to directly obtain a titanium liquid. The two-phase method decomposes ilmenite by using 65-80% sulfuric acid, the ilmenite and the sulfuric acid are mixed and heated, and precipitates are separated out in the main reaction; the obtained product is pasty and is added with water for leaching to generate a suspension solution.
The pressurization method has the advantages that dilute sulfuric acid with the concentration of 20-50% can be used as a reactant, but high-pressure resistant equipment is required, and the reaction temperature is between 180 ℃ and 300 ℃. Most of the selected ores are titanium-rich materials and high-titanium slag which are easily dissolved in sulfuric acid and are obtained after ilmenite is pretreated. The product is a solid phase. The pressure method and the continuous method have not been widely adopted due to the difficulty of processes, equipment, material selection and the like.
The solid phase method adopts concentrated sulfuric acid, the reaction temperature is high, the reaction degree is violent, and the obtained product is a solid phase substance. The method has the advantages of low acid consumption, low energy consumption, rapid reaction, high ilmenite decomposition rate, high equipment production strength, low acid ratio of the obtained titaniferous solution and easy titanium solution hydrolysis, so the method becomes the traditional acidolysis method in the current production. The solid phase method generally combines titanium materials (ilmenite rock ore and placer ore, titanium slag) with concentrated sulfuric acid (90-96% H) 2 SO 4 ) And (4) acid hydrolysis. At this time, the reaction is exothermic and violent, a large amount of sulfur-containing gas is emitted, and the amount of waste acid is large.
The present invention proposes a new sulfuric acid process which makes it possible to eliminate the abovementioned drawbacks. The method provided by the patent comprises the steps of adopting ilmenite and sulfuric acid with the concentration of 55-60% to carry out continuous acidolysis in five series acidolysis reactors, wherein the operating temperature of the first acidolysis reactor is 135-140 ℃, the operating temperature of the second acidolysis reactor is 105-110 ℃, the operating temperature of the third acidolysis reactor is 95-100 ℃, the operating temperature of the fourth acidolysis reactor is 85-90 ℃, and the operating temperature of the fifth acidolysis reactor is 80-85 ℃;
the retention time of the first acidolysis reactor is 1-2 hours, the retention time of the second acidolysis reactor is 1-2 hours, the retention time of the third acidolysis reactor is 2-3 hours, the retention time of the fourth acidolysis reactor is 3-4 hours, and the retention time of the fifth acidolysis reactor is 4-5 hours;
the mass ratio of pure sulfuric acid in the sulfuric acid with the concentration of 55-60% to ilmenite is 1.55-1.65: 1;
and (3) conveying the reaction mixture into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 500 ml.
Disclosure of Invention
A method for preparing titanyl sulfate by continuous acidolysis of ilmenite is characterized by comprising the following steps: ilmenite and sulfuric acid with the concentration of 55-60 percent are adopted to carry out continuous acidolysis in five acidolysis reactors connected in series, the operating temperature of the first acidolysis reactor is 135-140 ℃, the operating temperature of the second acidolysis reactor is 105-110 ℃, the operating temperature of the third acidolysis reactor is 95-100 ℃, the operating temperature of the fourth acidolysis reactor is 85-90 ℃, and the operating temperature of the fifth acidolysis reactor is 80-85 ℃;
the retention time of the first acidolysis reactor is 1-2 hours, the retention time of the second acidolysis reactor is 1-2 hours, the retention time of the third acidolysis reactor is 2-3 hours, the retention time of the fourth acidolysis reactor is 3-4 hours, and the retention time of the fifth acidolysis reactor is 4-5 hours;
the mass ratio of pure sulfuric acid to ilmenite in the sulfuric acid with the concentration of 55-60% is 1.55-1.65: 1;
and (3) conveying the reaction mixture into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 500 ml.
Method for determining stability of titanium liquid
The stability of the titanium liquid is expressed in terms of the volume of water required for diluting the titanium liquid with distilled water at a prescribed temperature per ml until just before turbidity occurs.
Sucking lmL into a 500mL conical flask, adding distilled water at (25 + -1) deg.C, adding 100mL three times, adding 25mL each time, shaking for 15 s after each time, standing for 45 s, and adding water until turbidity appears if no turbidity appears. The volume of water consumed is the stability.
Stability = volume of water/volume of sample.
Detailed Description
Example 1
Performing continuous acidolysis in five acidolysis reactors connected in series, stirring with compressed air, heating with steam and controlling temperature, simultaneously adding ilmenite and 55% sulfuric acid into the first acidolysis reactor, wherein the ilmenite adding amount is 5140kg/hr, the 55% sulfuric acid adding amount is 14400kg/hr, and the first acidolysis reactor has a volume of 10m 3 At 135 deg.C, second acid hydrolysis reactorThe volume is 20m 3 The temperature is 110 ℃, and the volume of the third acidolysis reactor is 30m 3 The temperature is 100 ℃, and the volume of the fourth acidolysis reactor is 40m 3 The temperature is 85 ℃, and the volume of the fifth acidolysis reactor is 50m 3 The temperature was 85 ℃.
And (4) sending the titanium sulfate into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 550 ml.
Example 2
Continuously carrying out acidolysis in five acidolysis reactors with different volumes connected in series, stirring with compressed air, heating with steam and controlling temperature, simultaneously adding ilmenite and 60% sulfuric acid into a first acidolysis reactor, wherein the ilmenite adding amount is 5140kg/hr, the 60% sulfuric acid adding amount is 14100kg/hr, and the first acidolysis reactor has a volume of 15m 3 The temperature is 140 ℃, and the volume of the second acidolysis reactor is 18m 3 The temperature is 110 ℃, and the volume of the third acidolysis reactor is 30m 3 The temperature is 95 ℃, and the volume of the fourth acidolysis reactor is 30m 3 The temperature is 85 ℃, and the volume of the fifth acidolysis reactor is 40m 3 The temperature was 80 ℃.
And (4) sending the titanium sulfate into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 535 ml.
Example 3
Continuously carrying out acidolysis in five acidolysis reactors with different volumes connected in series, stirring with compressed air, heating with steam and controlling temperature, simultaneously adding ilmenite and 58% sulfuric acid into a first acidolysis reactor, wherein the addition amount of ilmenite is 5140kg/hr, the addition amount of 58% sulfuric acid is 14200kg/hr, and the volume of the first acidolysis reactor is 10m 3 The temperature is 138 ℃, and the volume of the second acidolysis reactor is 20m 3 The temperature is 107 ℃, and the volume of the third acidolysis reactor is 25m 3 The temperature is 98 ℃, and the volume of the fourth acidolysis reactor is 38m 3 The temperature is 88 ℃, and the volume of the fifth acidolysis reactor is 45m 3 The temperature was 82 ℃.
And (4) sending the titanium sulfate into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 544 ml.
Example 4
Continuously carrying out acidolysis in five acidolysis reactors with different volumes connected in series, stirring with compressed air, heating with steam and controlling temperature, simultaneously adding ilmenite and 56% sulfuric acid into a first acidolysis reactor, wherein the ilmenite adding amount is kg/hr, the 56% sulfuric acid adding amount is 14600kg/hr, and the first acidolysis reactor has a volume of 20m 3 The temperature is 136 ℃, and the volume of the second acidolysis reactor is 20m 3 The temperature is 106 ℃, and the volume of the third acidolysis reactor is 25m 3 The temperature is 96 ℃, and the volume of the fourth acidolysis reactor is 30m 3 The temperature is 87 ℃, and the volume of the fifth acidolysis reactor is 45m 3 The temperature was 81 ℃.
And (4) sending the titanium sulfate into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 560 ml.
Claims (1)
1. A method for preparing titanyl sulfate by continuous acidolysis of ilmenite is characterized by comprising the following steps: ilmenite and sulfuric acid with the concentration of 55-60 percent are adopted to carry out continuous acidolysis in five acidolysis reactors connected in series, the operating temperature of the first acidolysis reactor is 135-140 ℃, the operating temperature of the second acidolysis reactor is 105-110 ℃, the operating temperature of the third acidolysis reactor is 95-100 ℃, the operating temperature of the fourth acidolysis reactor is 85-90 ℃, and the operating temperature of the fifth acidolysis reactor is 80-85 ℃;
the residence time of the first acidolysis reactor is 1-2 hours, the residence time of the second acidolysis reactor is 1-2 hours, the residence time of the third acidolysis reactor is 2-3 hours, the residence time of the fourth acidolysis reactor is 3-4 hours, and the residence time of the fifth acidolysis reactor is 4-5 hours;
the mass ratio of pure sulfuric acid to ilmenite in the sulfuric acid with the concentration of 55-60% is 1.55-1.65: 1;
and (3) conveying the reaction mixture into a separator from the fifth acidolysis reactor, and separating all unreacted ilmenite to obtain a titanyl sulfate solution, wherein the stability of the titanyl sulfate solution is more than 500 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791289.8A CN114920287A (en) | 2022-07-07 | 2022-07-07 | Method for preparing titanyl sulfate by continuous acidolysis of ilmenite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791289.8A CN114920287A (en) | 2022-07-07 | 2022-07-07 | Method for preparing titanyl sulfate by continuous acidolysis of ilmenite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114920287A true CN114920287A (en) | 2022-08-19 |
Family
ID=82815910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210791289.8A Pending CN114920287A (en) | 2022-07-07 | 2022-07-07 | Method for preparing titanyl sulfate by continuous acidolysis of ilmenite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114920287A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288416A (en) * | 1979-08-10 | 1981-09-08 | Nl Industries, Inc. | Process for manufacturing titanium compounds |
| CN102502811A (en) * | 2011-11-07 | 2012-06-20 | 云浮市惠沄钛白有限公司 | Continuous acidolysis method for preparing titanium white with sulfuric acid process |
| CN103482696A (en) * | 2013-09-02 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method and device for preparing titanium solution from fluidized acidolysis titanium-containing material |
| CN114084903A (en) * | 2021-12-20 | 2022-02-25 | 攀钢集团重庆钛业有限公司 | Continuous acidolysis method for titanium concentrate |
-
2022
- 2022-07-07 CN CN202210791289.8A patent/CN114920287A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288416A (en) * | 1979-08-10 | 1981-09-08 | Nl Industries, Inc. | Process for manufacturing titanium compounds |
| CN102502811A (en) * | 2011-11-07 | 2012-06-20 | 云浮市惠沄钛白有限公司 | Continuous acidolysis method for preparing titanium white with sulfuric acid process |
| CN103482696A (en) * | 2013-09-02 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method and device for preparing titanium solution from fluidized acidolysis titanium-containing material |
| CN114084903A (en) * | 2021-12-20 | 2022-02-25 | 攀钢集团重庆钛业有限公司 | Continuous acidolysis method for titanium concentrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018000404A1 (en) | Method for preparing taurine | |
| CN105836767B (en) | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium | |
| CN102911086B (en) | Preparation method of trifluoro methanesulfonic anhydride | |
| CN112645290B (en) | Continuous production system and production method of potassium monopersulfate composite salt | |
| CN106276820A (en) | A kind of be raw material production high purity tellurium with coarse tellurium powder technique | |
| CN102816093B (en) | Method for producing dimethyl disulfide by using methyl mercaptan oxidation method | |
| CN106278875B (en) | A kind of production method of isooctyl acid | |
| CN110114304B (en) | Process for producing sulfur tetrafluoride | |
| CN110483473B (en) | Method for preparing 1, 3-propane sultone | |
| CN109761238B (en) | Method for recovering sodium fluosilicate and phosphoric acid by using fluorine-containing and phosphorus-containing waste liquid | |
| CN107556214A (en) | A kind of preparation method of paracyanobenzoic acid | |
| CN104710351B (en) | A kind of continuous preparation method of vitamin B6 | |
| CN102897804A (en) | Method for preparing lithium carbonate directly from lithium chloride and carbon dioxide | |
| CN114920287A (en) | Method for preparing titanyl sulfate by continuous acidolysis of ilmenite | |
| KR101952060B1 (en) | Method for preparing furan-2,5-dicarboxylic acid (FDCA) from solid salt | |
| CN108558700A (en) | A kind of synthetic method of 1,2- pentanediols | |
| CN106865513B (en) | A kind of preparation method of hydrazine hydrate | |
| CN111233644A (en) | Synthesis and extraction method of adamantanone | |
| CN106044730A (en) | Method for producing wet-process phosphoric acid from high-grade phosphate ore | |
| CN102718197A (en) | Preparation method of sodium azide | |
| CN103145181B (en) | Three-phase fluidized continuous reaction device for preparing rutile by hydrochloric acid leaching method | |
| CN101993423A (en) | Method for producing epoxy chloropropane | |
| CN100999456A (en) | Preparation method of perfluoro caprylic acid | |
| CN112592262A (en) | Preparation method of adamantanone | |
| CN111233651A (en) | Method for recovering and preparing L (+) -2, 3-dihydroxysuccinic acid from polybara production wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |