CN109019680A - A kind of Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid production titanium dioxide method - Google Patents
A kind of Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid production titanium dioxide method Download PDFInfo
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- CN109019680A CN109019680A CN201811234160.7A CN201811234160A CN109019680A CN 109019680 A CN109019680 A CN 109019680A CN 201811234160 A CN201811234160 A CN 201811234160A CN 109019680 A CN109019680 A CN 109019680A
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- hydrochloric acid
- titanium dioxide
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- 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
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Abstract
The present invention relates to a kind of methods of titanium dioxide, specifically using containing TiOCl2Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid and ilmenite concentrate carry out acidolysis reaction, after separation removes the acid non-soluble substances such as silica therein, it is hydrolyzed acidolysis titanium liquid to obtain titanium dioxide crude product, titanium dioxide finished product is obtained after titanium dioxide crude product is washed and post-processed again, and the frerrous chloride crystal of high-quality can be then made in hydrolyzate after recrystallization.
Description
Technical field
The present invention relates to a kind of methods of titanium dioxide, belong to titanium chemical field.Specifically using containing TiOCl2's
Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid and ilmenite concentrate carry out acidolysis reaction, after separation removes the acid non-soluble substances such as silica therein,
Acidolysis titanium liquid is hydrolyzed to obtain titanium dioxide crude product, then obtains titanium white after titanium dioxide crude product is washed and post-processed
Powder finished product.Belong to titanium chemical field.
Background technique
In the production process of Titanium Dioxide Produced by Chloride Procedure, there are two types of the tail gas acid-washing waste acids of chloride process: it is dense that one is hydrochloric acid
The HCl of degree about 20%, wherein containing TiOCl2Concentration is 10.2% or so；Another kind is the HCl that concentration of hydrochloric acid is about 28%,
TiOCl2Concentration is 1.2% or so.Containing TiOCl using this2When the hydrochloric acid of impurity, TiOCl2It can be with free hydrochloric acid concentration
It reduces and hydrolysis occurs, TiO is precipitated2, the fine grained TiO of this hydrolysis precipitation2It is present in reaction system as solid phase impurity
In, cause the application field of this hydrochloric acid to be very restricted.
There is researcher to develop a kind of method that titanium white chloride by-product hydrochloric acid is used for titanium dioxide coating, this method by pair
Chlorinated exhaust washing recycling contains TiOCl2Crude salt acid as coating agent by using inorganic and organic composite coating process
Coating is carried out to titanium dioxide, hydrophily, resistance to chalking, reducing power and the colour retention of titanium dioxide can be improved, but in hydrochloric acid
TiOCl2It hydrolyzes not fully, and hydrochloric acid and is underutilized in the process, this process is only to use hydrochloric acid
Once, titanium chlorine resource therein is not utilized effectively.
There are also researchers to disclose waste hydrochloric acid produced by chlorination elution tail gas process in a kind of production of Titanium Dioxide Produced by Chloride Procedure
The acid tail gas generated in chloridising production process is directly passed through water scrubber by method of comprehensive utilization, this method, the tail after washing
Gas passes through caustic wash tower again, then qualified discharge.Alkaline matter is added in the acid waste water generated into water-washing process, adjusts its pH
Make the TiOCl in solution2TiO is generated in hydrolysis2Solution is then filtered by insoluble matter, and filter residue recycles.This method is logical
Cross simple neutralize so that TiOCl2It is hydrolyzed to TiO2Become solid waste, solution obtains the chlorate of low value, without real
Now there is the resource utilization of higher-value to it.
In addition, chlorinated exhaust pickling is contained there are also using the carbon monoxide in chlorinated exhaust as heat source
TiOCl2The de- analysis of the by-product hydrochloric acid method that obtains high-purity hydrogen chloride.Although this method can obtain the de- analysis recycling of hydrochloric acid therein
The hydrogen chloride of higher quality, but TiOCl therein2The TiO of precipitation is hydrolyzed during hydrochloric acid de- analysis2But at solid waste, not
It is able to achieve the resource utilization to it.
There is also prepare TiO using Titanium Dioxide Produced by Chloride Procedure exhaust gas2And the method for HCl solution, this method is by chloridising titanium
Chlorination exhaust gas in white powder production process is passed through pickling tower, the TiCl that will be contained in exhaust gas by spraying 18 ~ 22% dilute hydrochloric acid4It inhales
It receives, TiCl in hydrochloric acid solution4It meets water and hydrolysis occurs, generate TiOCl2And HCl is given up chlorination by two-stage membrane filtration system
What gas generated contains TiOCl2Hydrochloric acid solution separated, obtain hydrochloric acid solution and TiOCl2Hydrolyze the TiO generated2.This method
It is filtered using film by TiOCl2It is separated with HCl, efficiency is lower to cause its econmics comparison poor.
Therefore, contain TiOCl using by-product in Titanium Dioxide Produced by Chloride Procedure production process to be efficient2Hydrochloric acid, the present invention combine
The production process of hydrochloric acid method titanium dioxide allows the gold such as iron oxide therein, calcium oxide, magnesia using hydrochloric acidolysis ilmenite concentrate
While belonging to oxide generation chlorate, the titanium oxide in ilmenite concentrate mutually can also be reacted with hydrochloric acid generates TiOCl2, it is incorporated in
The TiOCl originally contained in this titanium chloride white powder by-product hydrochloric acid2, by hydrolyzing it as TiO2Crude product, crude product warp are located later
Titanium dioxide finished product is obtained after reason.Mother liquor containing iron chloride salt and hydrochloric acid after hydrolysis then passes through evaporation and concentration and obtains frerrous chloride
Saturated solution, then it is crystallized in 10 ~ 15 DEG C of mixture of ice and water below, frerrous chloride crystal is precipitated, it is made after recrystallization
Obtain the frerrous chloride crystal of high-quality；Steam containing hydrogen chloride, which is condensed into after hydrochloric acid, then returns to ilmenite concentrate acidolysis system circulation benefit
With.
Main chemical reactions equation in ilmenite concentrate acid hemolysis process are as follows:
FeO·TiO2+4HCl= FeCl2+ TiOCl2+2H2O
Fe2O3·TiO2+8HCl=2FeCl3+TiOCl2+4H2O
MgO·TiO2+4HCl=MgCl2+TiOCl2+2H2O
CaO·TiO2+4HCl=CaCl2+TiOCl2+2H2O
TiOCl2Hydrolysis generates TiO2Chemical equation are as follows:
TiOCl2+H2O=TiO2↓+2HCl 。
Summary of the invention
It is an object of the invention to utilize to contain TiOCl2Titanium white chloride by-product hydrochloric acid acidolysis ilmenite concentrate generation be rich in
TiOCl2Acidolysis titanium liquid, and then hydrolyze and further work-up obtain titanium dioxide finished product.The present invention allows Titanium Dioxide Produced by Chloride Procedure pair
Produce the TiOCl contained originally in hydrochloric acid2With the TiOCl obtained after hydrochloric acid and ilmenite concentrate acidolysis2It is integrated, and is eventually become
Titanium dioxide finished product, makes the titanium elements in titanium white chloride by-product hydrochloric acid obtain high value added utilization, and chlorine element also achieves sufficiently
Utilization, overcome in existing method to the disadvantage of its titanium elements and the lower deficiency of chlorine element utilization efficiency, effectively realize
The high-efficiency resource recycling of Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid.
The object of the present invention is achieved like this:
It measures a certain amount of containing TiOCl2Titanium white chloride by-product hydrochloric acid be added in acidolysis reaction kettle, while according to certain acid
Mine handles ilmenite concentrate than the quantitative dehydration and drying that passes through is added, and closes the inlet valve of acidolysis reaction kettle.Toward the folder of acidolysis reaction kettle
Be passed through steam in set to be heated, keep acidolysis temperature at 85 ~ 95 DEG C, and open stirring, make the metal oxide of ilmenite concentrate with
Hydrochloric acid, which comes into full contact with, to be reacted.During acidolysis reaction, the condensation hydrochloric acid that subsequent flash distillation hydrolyzing process generates is supplemented
In acidolysis reaction kettle, the acidity of reaction system is maintained.After reaction, reactant is filtered, separation insoluble solids are residual
After slag, titanium liquid is obtained.
The titanium liquid for having separated acid non-soluble substance is heated to 105 ~ 115 DEG C by graphite heat exchanger, is then delivered to flash tank
Carry out flash distillation hydrolysis.In this course, the TiOCl in titanium liquid2It is TiO as acid concentration reduces hydrolysis and is precipitated2Insoluble matter, can
The metal chlorination salt FeCl of dissolubility2、FeCl3、MgCl2、CaCl2Deng then still remaining in solution；Then hydrolysate is divided
From to TiO2Insoluble matter after washing again to its according to existing titanium dioxide postprocessing working procedures processing after obtain titanium dioxide at
Product；Hydrating solution can be worth the higher frerrous chloride crystal of quality after being recrystallized.
The beneficial effects of the present invention are: containing TiOCl by utilizing2Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid to ilmenite concentrate into
Row acidolysis reaction, the TiOCl generated using acidolysis reaction2And integrate original TiOCl in hydrochloric acid2It is set adequately to utilize,
Soluble metal chlorination salt then passes through the frerrous chloride crystal that recrystallization is made as high-quality, and entire technical process is in raw material
Titanium elements and chlorine element realize sufficient resource utilization, substantially increase the economy of the technical process.
Detailed description of the invention
Fig. 1 is the flow diagram that titanium white chloride by-product hydrochloric acid of the present invention produces titanium dioxide.
Specific embodiment
The present invention is described in further detail below with reference to embodiment, but protection scope of the present invention is not only limited in
These examples.
Embodiment one: it is 7:1 according to sour mine ratio, 700g is contained to 10.2% TiOCl2Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid
100g ilmenite concentrate (the TiO of (free hydrochloric acid concentration is 21.2%) and the production of Panzhihua company246.5%、FeO2+Fe2O348.2%)
It puts into acidolysis reaction kettle, it, will be subsequent during acidolysis reaction controlled at being stirred to react 3 hours under the conditions of 90 ± 2 DEG C
The condensation hydrochloric acid that flash distillation hydrolysis is collected is complemented in acidolysis reaction kettle, and the free hydrochloric acid concentration of its acid hydrolysis solution is kept to be not less than
150g/L.Acidolysis mixture is filtered after acidolysis reaction, separates acid non-soluble substance therein, then acid hydrolysis solution is heated
To 110 ± 2 DEG C, enters and carry out flash distillation hydrolysis in flash tank.After free acid concentration is lower than 100g/L in hydrolyzate, hydrolysis is anti-
It should terminate, be filtered washing drying, obtain 80.7gTiO2Crude product, then it is post-processed obtain titanium dioxide at
Product.
Embodiment two: it is 6:1 according to sour mine ratio, 600g is contained to 10.2% TiOCl2Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid
100g ilmenite concentrate (the TiO of (free hydrochloric acid concentration is 21.2%) and the production of Hainan company248.1%、FeO2+Fe2O349.3%) it throws
Enter into acidolysis reaction kettle, controlled at being stirred to react 3 hours under the conditions of 90 ± 2 DEG C, by subsequent sudden strain of a muscle during acidolysis reaction
It steams the condensation hydrochloric acid that hydrolysis is collected to be complemented in acidolysis reaction kettle, keeps the free hydrochloric acid concentration of its acid hydrolysis solution not less than 150g/
L.Acidolysis mixture is filtered after acidolysis reaction, acid non-soluble substance therein is separated, 110 then is heated to acid hydrolysis solution
It ± 2 DEG C, enters and carries out flash distillation hydrolysis in flash tank.After free acid concentration is lower than 100g/L in hydrolyzate, hydrolysis knot
Beam is filtered washing drying, obtains 78.7gTiO2Then crude product post-processes it to obtain titanium dioxide finished product.
Claims (5)
1. a kind of production method of titanium dioxide, it is characterised in that using containing TiOCl2Titanium chloride white powder by-product hydrochloric acid to titanium
Concentrate carries out acidolysis reaction, and the acidolysis titanium liquid after isolating acid non-soluble substance is under conditions of free hydrochloric acid concentration is not less than 150g/L
It carries out flash distillation water solution and obtains TiO2Crude product is filtered, washed, calcines and post-processes TiO2Rutile type titanium white is obtained after crude product.
2. according to the method described in claim 1, it is characterized in that being 85 ~ 95 DEG C to the acidolysis reaction temperature of ilmenite concentrate.
3. according to the method described in claim 1, it is characterized in that ilmenite concentrate carry out acidolysis reaction hydrochloric acid be containing
TiOCl2Titanium Dioxide Produced by Chloride Procedure by-product hydrochloric acid.
4. according to the method described in claim 1, it is characterized in that the hydrolysis of titanium liquid is carried out in the solution containing frerrous chloride
's.
5. according to the method described in claim 1, it is characterized in that it is 100 ~ 150g/ that the hydrolysis of titanium liquid, which is in free hydrochloric acid concentration,
It is carried out under conditions of L.
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Cited By (3)
| 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 |
| CN115974166A (en) * | 2022-12-08 | 2023-04-18 | 攀枝花全瑞实业有限公司 | Method for preparing high-chloride-ion pure ferrous chloride solution in industrial production of titanium dioxide by hydrochloric acid method |
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Cited By (3)
| 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 |
| CN115974166A (en) * | 2022-12-08 | 2023-04-18 | 攀枝花全瑞实业有限公司 | Method for preparing high-chloride-ion pure ferrous chloride solution in industrial production of titanium dioxide by hydrochloric acid method |
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Application publication date: 20181218 |