CN111591959A - Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide - Google Patents
Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide Download PDFInfo
- Publication number
- CN111591959A CN111591959A CN201910130599.3A CN201910130599A CN111591959A CN 111591959 A CN111591959 A CN 111591959A CN 201910130599 A CN201910130599 A CN 201910130599A CN 111591959 A CN111591959 A CN 111591959A
- Authority
- CN
- China
- Prior art keywords
- hydrochloric acid
- titanium dioxide
- tiocl
- bacl
- acidolysis
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for co-producing barium chloride and ceramic titanium dioxide (TiO)2) In particular by means of a catalyst containing TiOCl2Performing acidolysis reaction on the hydrochloric acid byproduct of titanium dioxide and witherite, and introducing Ba in the witherite ore and metal elements such as impurities Fe, Ca, Mg and the like into the solution in the form of chloride; soluble TiOCl in hydrochloric acid2The concentration of free hydrochloric acid decreases with the progress of the acidolysis reaction, and the hydrolysis reaction proceeds to precipitate TiO2The hydrochloric acid as the by-product of hydrolysis is used to supplement the hydrochloric acid consumed by acidolysis reaction of witherite. Separating siliceous acid insoluble substance in witherite ore and TiOCl in hydrochloric acid as by-product of titanium dioxide produced by chlorination process2Hydrolyzed TiO2Washing and drying to obtain a ceramic titanium dioxide finished product; adding Ba (OH) into acidolysis solution2And H2C2O4Neutralizing twice to remove Fe, Ca, Mg and other impurity elements, flash evaporating to concentrate, freezing to crystallize and separate hydrated BaCl2.2H2Washing and drying the O to obtain BaCl2And (5) finishing.
Description
Technical Field
The invention relates to a production method for co-producing barium chloride and ceramic titanium dioxide, belonging to the field of inorganic chemical industry. In particular by using a composition containing TiOCl2The hydrochloric acid byproduct of titanium dioxide produced by the chlorination process is subjected to acidolysis reaction with the witherite ore, and the silicon dioxide acid insoluble substance and TiOCl in the hydrochloric acid byproduct are separated2Hydrolysate TiO of2Washing and drying twice to obtain a ceramic titanium dioxide product; the acidolysis is purified and the impurities are removed, and then the freezing crystallization, the washing and the drying are carried out to obtain the BaCl2And (5) producing the product.
Background
In the production process of titanium dioxide by a chlorination method, the tail gas acid-washing waste acid of the chlorination process has two types: one is HCl with a hydrochloric acid concentration of about 20% and contains TiOCl2The concentration is about 10.2 percent; another is HCl, TiOCl, with a hydrochloric acid concentration of about 28%2The concentration is about 1.2%. In the use of such compositions containing TiOCl2Hydrochloric acid of impurities, TiOCl2Hydrolysis reaction can be carried out to separate out TiO along with the reduction of the concentration of free hydrochloric acid2This hydrolytically precipitated fine TiO particle2The impurities exist in the reaction system as solid phase, so that the application field of the hydrochloric acid is greatly limited.
Researchers develop a method for coating titanium dioxide by using hydrochloric acid as a byproduct of titanium chloride white, and the method is used for washing and recovering the tail gas of chlorination to contain TiOCl2The crude hydrochloric acid as a coating agent is used for coating the titanium dioxide by adopting an inorganic and organic composite coating process, so that the hydrophilicity, chalking resistance, decoloring power and color retention of the titanium dioxide can be improved, but TiOCl in hydrochloric acid2The hydrolysis is not complete in the process, the hydrochloric acid is not fully utilized, the process only uses the hydrochloric acid once, and the titanium chloride resource is not effectively utilized.
And the method is characterized in that acid tail gas generated in the chlorination method production process directly passes through a water washing tower, and the tail gas after water washing passes through an alkali washing tower and then is discharged after reaching the standard. Adding alkalinity to acidic waste water generated in the washing processSubstance, pH adjustment to TiOCl in solution2In hydrolysis to form TiO2Insoluble substances, filtering the solution, and recycling filter residues. The method enables TiOCl through simple neutralization2Hydrolyzed to TiO2Becomes solid waste, the solution obtains low-value chloride salt, and the resource utilization of the chloride salt with higher value is not realized.
In addition, carbon monoxide in the chlorination tail gas is used as a heat source, and the chlorination tail gas is pickled to obtain the product containing TiOCl2The method for obtaining high-purity hydrogen chloride by desorption of by-product hydrochloric acid. Although the method can be used for desorbing and recovering the hydrochloric acid in the hydrochloric acid to obtain the hydrogen chloride with higher quality, the TiOCl in the hydrochloric acid can be recovered2TiO separated from water in hydrochloric acid desorption process2But becomes solid waste, and the resource utilization of the solid waste cannot be realized.
Other methods for preparing TiO by using waste gas of titanium dioxide produced by chlorination process2And a HCl solution, introducing the chlorination waste gas generated in the production process of the chlorination-process titanium dioxide into an acid washing tower, and spraying 18-22% dilute hydrochloric acid to enable TiCl contained in the waste gas to be sprayed4Absorption, TiCl in hydrochloric acid solution4Hydrolysis reaction in water to generate TiOCl2And HCl, passing through a two-stage membrane filtration system, and generating the chlorinated waste gas containing TiOCl2Separating the hydrochloric acid solution to obtain hydrochloric acid solution and TiOCl2TiO formed by hydrolysis2. This method uses membrane filtration to separate TiOCl2And HCl, which is less efficient and less economical.
Therefore, in order to efficiently utilize TiOCl contained in the production process of titanium dioxide by chlorination process2The invention combines the production process of hydrochloric acid method barium chloride, and uses hydrochloric acid to carry out acidolysis on the witherite ore to ensure that metal elements such as Ba, Fe, Ca, Mg and the like in the witherite ore generate soluble chloride, and TiOCl in the hydrochloric acid2Hydrolysis reaction occurs to precipitate hydrated TiO as the concentration of free hydrochloric acid decreases with the progress of acidolysis reaction2The hydrochloric acid as the by-product of hydrolysis is used to supplement the hydrochloric acid consumed by acidolysis reaction of witherite. Separating siliceous acid insoluble substance in witherite ore and TiOCl in hydrochloric acid as by-product of titanium dioxide produced by chlorination process2Ti produced by hydrolysisO2Washing and drying to obtain a ceramic titanium dioxide finished product; adding Ba (OH) to the acid hydrolysis solution from which insoluble matter has been separated2Neutralizing to remove impurity elements such as Fe, Ca, Mg, etc. in the form of hydroxide (pH value is controlled to be above 12.5), and adding controlled amount of H into the filtrate2C2O4And activated carbon to further remove calcium impurities in the BaCl, and after twice impurity removal and purification2Adjusting pH value of the solution to 7 with hydrochloric acid, performing flash evaporation concentration, and then performing freeze crystallization to separate hydrated BaCl2.2H2Washing and drying the O to obtain BaCl2And (4) returning the crystallization filtrate to a primary neutralization process for recycling.
The main chemical reaction equation in the acidolysis process of witherite is as follows:
BaCO3+2HCl=BaCl2+ H2O+CO2
MgCO3+2HCl=MgCl2+H2O+CO2
CaCO3+2HCl=CaCl2+ H2O+CO2
FeO+2HCl= FeCl2+2H2O
Fe2O3+6HCl=2FeCl3+3H2O
TiOCl2hydrolysis to produce TiO2The chemical reaction equation of (a) is:
TiOCl2+H2O=TiO2↓+2HCl。
disclosure of Invention
The invention aims to utilize a catalyst containing TiOCl2The hydrochloric acid byproduct of titanium dioxide produced by the chlorination process is subjected to acidolysis reaction with the witherite ore, and the silicon dioxide acid insoluble substance and TiOCl in the hydrochloric acid byproduct are separated2Hydrolysate TiO of2Washing and drying twice to obtain a ceramic titanium dioxide product; the acidolysis is purified and the impurities are removed, and then the freezing crystallization, the washing and the drying are carried out to obtain the BaCl2And (5) producing the product.
The invention relies on the acidification of witherite with hydrochloric acid to prepare BaCl2Production method of the ore containing siliconAcid insoluble substance and TiOCl in hydrochloric acid byproduct of titanium dioxide produced by chlorination process2TiO produced by hydrolysis2As a ceramic titanium dioxide byproduct, the same BaCl is obtained2And (5) producing the product. The method has the advantages that the titanium element in the hydrochloric acid byproduct of titanium dioxide produced by the chlorination process is utilized with high added value, the chlorine element is fully utilized, the defect of low utilization efficiency of the titanium element and the chlorine element in the existing method is overcome, and the high-efficiency resource utilization of the hydrochloric acid byproduct of titanium dioxide produced by the chlorination process is effectively realized.
The purpose of the invention is realized as follows:
measuring a certain amount of TiOCl2Adding the byproduct hydrochloric acid of titanium white chloride into an acidolysis reaction kettle, simultaneously adding a certain amount of treated witherite slurry according to a certain acid-ore ratio, and closing a feed valve of the acidolysis reaction kettle. And (3) introducing steam into a jacket of the acidolysis reaction kettle for heating, keeping the acidolysis temperature at 85 +/-5 ℃, and starting stirring to ensure that the carbonate and the metal oxide in the witherite ore are fully contacted with hydrochloric acid for reaction. TiOCl in hydrochloric acid during acidolysis reaction2Hydrolysis reaction occurs to precipitate hydrated TiO as the concentration of free hydrochloric acid decreases during the acidolysis reaction2The hydrochloric acid as the by-product of hydrolysis is used to supplement the hydrochloric acid consumed by acidolysis reaction of witherite. After the reaction is finished, filtering the reactant, separating insoluble solids, washing and drying to obtain ceramic titanium dioxide which can be used in the ceramic industry; the solution containing metal chloride is sent to a primary neutralization reaction kettle, the temperature is kept to be not lower than 85 ℃, and Ba (OH) is added into the solution2Controlling the pH value of the solution to be more than 12.5, filtering and separating insoluble solid phase after the reaction is finished, sending the filtrate to a secondary neutralization reaction kettle, and sequentially adding H2C2O4Filtering, flash evaporating to concentrate, cooling to crystallize, washing and drying to obtain BaCl2And (5) finishing.
The invention has the beneficial effects that: by using a catalyst containing TiOCl2The chlorination titanium dioxide byproduct hydrochloric acid performs acidolysis reaction on witherite, and TiOCl is utilized2The hydrochloric acid byproduct of the hydrolysis reaction is used for supplementing the hydrochloric acid consumed by the acidolysis reaction of the witherite, and the hydrochloric acid is generated by hydrolysisOf TiO 22Filtering and separating the heavy stone ore and acid insoluble substances containing silicon, and then treating to obtain ceramic titanium dioxide; removing impurities and purifying the acidolysis filtrate, crystallizing and separating out barium chloride, washing and drying to obtain BaCl2And (5) finishing. The whole process realizes full resource utilization of the titanium element and the chlorine element in the raw materials, and greatly improves the economy of the process.
Drawings
FIG. 1 is a schematic view of a process flow of co-production of barium chloride and ceramic titanium white by hydrochloric acid as a byproduct of titanium dioxide by a chlorination process.
Detailed Description
The present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
The first embodiment is as follows: 100g of Dukushi (BaCO) from Chongqing mining company368.26%) and 100g of washing water, together with 200g of water containing 10.2% TiOCl2The hydrochloric acid (the concentration of free hydrochloric acid is 21.2%) as the byproduct of titanium dioxide by the chlorination method is put into an acidolysis reaction kettle, and the reaction is carried out for 2.5 hours under the condition of controlling the temperature to be 85 +/-5 ℃. Filtering the acidolysis mixture after the acidolysis reaction is finished, separating acid insoluble substances in the acidolysis mixture, and washing and drying the acid insoluble substances to obtain 32.47g of ceramic titanium dioxide finished products; heating the filtrate in a primary neutralization reaction kettle to above 80 ℃, and adding Ba (OH)2Controlling the pH value of the solution to be not less than 12.5, stirring the solution for reaction for 2 hours, filtering the solution to separate out solid phase substances, transferring the filtrate into a secondary neutralization reaction kettle, and sequentially adding H into the secondary neutralization reaction kettle2C2O4Mixing with activated carbon, stirring at 80 deg.C or lower for 2 hr, filtering, regulating pH to 7 with 31% hydrochloric acid, flash evaporating, concentrating, cooling with-5 deg.C saline water for crystallization, and separating BaCl2.2H2O crystal is washed and dried to BaCl258.46g of finished product.
Example two: 200g of witherite (BaCO) from Shaanxi certain mining company355.48%) and 100g of washing water, together with 500g of 10.2% TiOCl2Adding hydrochloric acid (concentration of free hydrochloric acid is 21.2%) as by-product of titanium dioxide by chlorination processAdding the mixture into an acidolysis reaction kettle, and stirring and reacting for 2.5 hours under the condition of controlling the temperature to be 85 +/-5 ℃. Filtering the acidolysis mixture after the acidolysis reaction is finished, separating acid insoluble substances in the acidolysis mixture, and washing and drying the acid insoluble substances to obtain 80.44g of ceramic titanium dioxide finished products; heating the filtrate in a primary neutralization reaction kettle to above 80 ℃, and adding Ba (OH)2Controlling the pH value of the solution to be not less than 12.5, stirring the solution for reaction for 2 hours, filtering the solution to separate out solid phase substances, transferring the filtrate into a secondary neutralization reaction kettle, and sequentially adding H into the secondary neutralization reaction kettle2C2O4Mixing with activated carbon, stirring at 80 deg.C or lower for 2 hr, filtering, regulating pH to 7 with 31% hydrochloric acid, flash evaporating, concentrating, cooling with-5 deg.C saline water for crystallization, and separating BaCl2.2H2O crystal is washed and dried to BaCl294.85g of finished product.
Claims (7)
1. A method for coproducing barium chloride and ceramic titanium dioxide is characterized in that the titanium dioxide containing TiOCl is utilized2The hydrochloric acid byproduct of titanium dioxide produced by chlorination process and witherite ore are subjected to acidolysis reaction, and the acid insoluble substance containing silicon and TiOCl in ore removal are filtered and separated2Washing and drying the hydrolysate to obtain a ceramic titanium dioxide finished product; removing impurities from acidolysis solution to obtain purified BaCl2Freezing and crystallizing the solution to separate BaCl2.2H2O, washing and drying to obtain BaCl2And (5) finishing.
2. The method as claimed in claim 1, wherein the hydrochloric acid used for the acidolysis of witherite is TiOCl-containing hydrochloric acid2The by-product hydrochloric acid of titanium dioxide produced by the chlorination process.
3. The method according to claim 1, wherein the acidolysis reaction temperature of the witherite ore is 85 ± 5 ℃.
4. The method as claimed in claim 1, wherein Ba (OH) is used for purifying the acidolysis solution2Removing iron, magnesium and most calcium by chemical precipitation (pH value is controlled to be above 12.5), and recycling H2C2O4The method for removing calcium by combining chemical precipitation and physical adsorption of activated carbon, wherein the temperature of two precipitation reactions is not lower than 80 ℃.
5. The method of claim 1, wherein the purified BaCl is purified of impurities2The solution was adjusted to pH 7 using hydrochloric acid.
6. The method of claim 1, wherein the BaCl is present in the sample2.2H2And the washing water of O is used as the primary washing water of the insoluble substances in the acidolysis reaction, the condensed water obtained by flash evaporation is used as the secondary washing water, and the two washing waters are returned to the witherite ore treatment procedure to be used as the water required for preparing ore pulp for recycling.
7. The process according to claim 1, characterized in that the BaCl is isolated by freeze crystallization2.2H2And returning the residual liquid of O to the primary neutralization and impurity removal process for recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910130599.3A CN111591959A (en) | 2019-02-21 | 2019-02-21 | Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910130599.3A CN111591959A (en) | 2019-02-21 | 2019-02-21 | Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111591959A true CN111591959A (en) | 2020-08-28 |
Family
ID=72179300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910130599.3A Pending CN111591959A (en) | 2019-02-21 | 2019-02-21 | Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111591959A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109437A (en) * | 2022-07-12 | 2022-09-27 | 龙佰禄丰钛业有限公司 | Preparation method of composite titanium dioxide |
| CN115820001A (en) * | 2022-11-28 | 2023-03-21 | 攀钢集团研究院有限公司 | Method for coating titanium dioxide by using hydrochloric acid as chlorination by-product |
-
2019
- 2019-02-21 CN CN201910130599.3A patent/CN111591959A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109437A (en) * | 2022-07-12 | 2022-09-27 | 龙佰禄丰钛业有限公司 | Preparation method of composite titanium dioxide |
| CN115820001A (en) * | 2022-11-28 | 2023-03-21 | 攀钢集团研究院有限公司 | Method for coating titanium dioxide by using hydrochloric acid as chlorination by-product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2756763C (en) | Process for simultaneous production of potassium sulphate, ammonium sulfate, magnesium hydroxide and/or magnesium oxide from kainite mixed salt and ammonia | |
| US3350292A (en) | Utilization of saline water | |
| SU1519528A3 (en) | Method of producing magnesium oxide from magnesite | |
| US3980753A (en) | Industrial process of preparing magnesia of high purity | |
| US4119698A (en) | Reclamation treatment of red mud | |
| CN111591959A (en) | Method for co-producing barium chloride and ceramic titanium white by-product hydrochloric acid of chlorination-process titanium dioxide | |
| JP5202514B2 (en) | Carbonate group-containing magnesium hydroxide particles and method for producing the same | |
| CN104591234A (en) | Process for preparing light magnesium carbonate from industrial magnesium hydroxide | |
| US4210626A (en) | Manufacture of magnesium carbonate and calcium sulphate from brine mud | |
| US4100254A (en) | Industrial process of preparing magnesia of high purity | |
| CN109019680A (en) | A kind of Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid production titanium dioxide method | |
| US3676067A (en) | Production of fresh water,brine and magnesium hydroxide | |
| MX2012000137A (en) | Process for production of commercial quality potassium nitrate from polyhalite. | |
| FR2629072A1 (en) | PROCESS FOR PRODUCING HYDRATED ZIRCONIUM OXIDE FROM GRANULAR CRYSTALLIZED ZIRCONIUM OXIDE | |
| PL185259B1 (en) | Method of precipitating calcium carbonate | |
| KR20000068137A (en) | PROCESS FOR PRODUCING ANHYDROUS MgCl2 | |
| RU2702572C1 (en) | Method of producing iron-containing coagulant from production wastes | |
| RU2690820C1 (en) | Method of producing magnesium and calcium chloride crystal-dydrates from industrial wastes | |
| US2216402A (en) | Method of producing pure magnesium compounds | |
| US20070009423A1 (en) | Apparatus and Methods For Producing Calcium Chloride, and Compositions and Products Made Therefrom | |
| JPS5860616A (en) | Preparation of high purity magnesium oxide | |
| CN114291955B (en) | Method for jointly utilizing iron pigment wastewater and reduced titanium tail gas | |
| CN108585006A (en) | A kind of method that in aluminium ash treatment process prepared by activity dissolution and raw material | |
| US3819803A (en) | Method of preparing magnesium hydroxide | |
| RU2312065C1 (en) | Method of production of the chemically deposited chalk |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200828 |
|
| WD01 | Invention patent application deemed withdrawn after publication |