CN115231540A - Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process - Google Patents
Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process Download PDFInfo
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- CN115231540A CN115231540A CN202210940367.6A CN202210940367A CN115231540A CN 115231540 A CN115231540 A CN 115231540A CN 202210940367 A CN202210940367 A CN 202210940367A CN 115231540 A CN115231540 A CN 115231540A
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- titanium
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- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention relates to the technical field of titanium dioxide waste acid recovery, in particular to a method for preparing titanium phosphate from waste acid generated in the production of titanium dioxide by a chlorination process. The method can utilize Ti in the byproduct waste acid to prepare and synthesize the titanium phosphate, thereby improving the utilization rate of the byproduct and saving the production cost; the preparation method has the advantages of simple operation, high product generation speed and high reaction yield, and the recovery rate of Ti in the titanium dioxide waste acid can reach 95%; the titanium phosphate obtained by the invention has less impurities, high quality and good crystal form; the hydrochloric acid without titanium can be used for preparing phosphoric acid by a hydrochloric acid method, and the resource utilization rate is improved by recycling.
Description
Technical Field
The invention relates to the technical field of titanium dioxide waste acid recovery, in particular to a method for preparing titanium phosphate from by-product waste acid generated in titanium dioxide production by a chlorination process.
Background
The titanium phosphate as a novel inorganic chemical product has the advantages of no toxicity, strong covering power, strong cohesive force, strong ultraviolet reflection capability, heat resistance, flame retardance and the like, and can be used as a flame retardant, an antirust agent, a ceramic cosolvent and a glass hardener; has the advantages of high temperature resistance, radiation resistance and the like, is particularly suitable for the paint industry, and is used as a nontoxic antirust anticorrosive pigment; has good thermal stability and mechanical strength, can be used as a catalyst, an ion exchange material and a proton conduction material, and has wide application.
At present, the production process of titanium dioxide mainly comprises two process routes of a sulfuric acid method and a chlorination method.
Titanium phosphate can be prepared by using titanium white waste acid and phosphoric acid as main raw materials. For example, CN201710654554.7 discloses a method for preparing titanium phosphate from titanium white waste acid, wherein the titanium white waste acid is waste acid generated in the process of preparing titanium dioxide by a sulfuric acid method. The industrial production method of titanium dioxide mainly comprises a sulfuric acid method and a hydrochloric acid method, and combined production indicates that in the process of producing titanium dioxide by a chlorination method, 0.2-0.3 t of waste acid with the concentration of about 36% is produced every 1t of titanium dioxide is produced, the waste acid contains a main component of HCl and also contains partial impurities, wherein the content of Ti is 1-2 wt%, the waste acid is not ideal to be recycled by utilizing the prior art, and Ti is not effectively utilized, so that resource waste is caused, and the economic benefit is not high.
Disclosure of Invention
Aiming at the problems of Ti waste and the like in waste acid in the prior art, the invention provides a method for preparing titanium phosphate from titanium dioxide byproduct waste acid produced by a chlorination method, which can utilize Ti in the byproduct waste acid to prepare synthetic titanium phosphate and improve the utilization rate of byproducts.
The invention provides a method for preparing titanium phosphate from by-product waste acid generated in the production of titanium dioxide by a chlorination process, which is used for synthesizing and preparing titanium phosphate by taking titanium white waste acid and dilute phosphoric acid as raw materials, and the titanium white waste acid is waste hydrochloric acid generated in the production of titanium dioxide by the chlorination process.
Furthermore, the dilute phosphoric acid is prepared by carrying out acidolysis, pretreatment and extraction on the powdered rock phosphate by hydrochloric acid, and the unconcentrated dilute phosphoric acid prepared by a hydrochloric acid method is used as a raw material, so that the energy consumption is reduced.
Further, the method specifically comprises the following steps:
(1) Adding dilute phosphoric acid into the heated titanium white waste acid, stirring, and naturally cooling to obtain a sol;
(2) Filtering the sol and pickling to obtain a filter cake;
(3) Washing and bleaching the filter cake to obtain colloid;
(4) Washing and drying the colloid to obtain filter residue;
(5) And calcining the filter residue to obtain a finished product of the titanium phosphate.
Further, in the step (1), the weight concentration of the dilute phosphoric acid is 6-10%, the temperature of the heated titanium white waste acid is 85-100 ℃, and the molar ratio of the dilute phosphoric acid to the titanium salt in the titanium white waste acid is 1.1-1:1.
Further, in the step (2), one or more of dilute hydrochloric acid, dilute phosphoric acid and dilute sulfuric acid is used for acid washing.
Furthermore, the weight concentration of the acid for pickling is 3 to 10 percent.
Further, in the step (3), desalted water is used for washing, and bleaching agent is used for bleaching.
Further, the bleaching agent is a trivalent titanium salt solution.
Further, in the step (5), the calcining temperature is 600-1000 ℃.
The mechanism of the invention is that phosphoric acid is selected as a reactant and is mixed with TiCl in titanium dioxide waste acid 4 The main reaction process is as follows: 2TiCl 4 +2H 3 PO 4 +H 2 O→2TiO 2 ·P 2 O 5 +8HCl of 2TiO 2 ·P 2 O 5 The preparation method is simple and convenient, and the final product is washed and then calcined to obtain the titanium phosphate with better crystal form.
The invention has the beneficial effects that:
(1) The method can utilize Ti in the byproduct waste acid to prepare and synthesize the titanium phosphate, thereby improving the utilization rate of the byproduct and saving the production cost;
(2) The preparation method has the advantages of simple operation, high product generation speed and high reaction yield, and the recovery rate of Ti in the titanium dioxide waste acid can reach 95%;
(3) The titanium phosphate obtained by the invention has less impurities, high quality and good crystal form;
(4) The hydrochloric acid without titanium can be used for preparing phosphoric acid by a hydrochloric acid method, and the resource utilization rate is improved by recycling.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The dilute phosphoric acid adopted in the following examples is prepared by carrying out acidolysis, pretreatment and extraction on ground phosphate rock by hydrochloric acid, and is not concentrated.
Example 1
Weighing titanium dioxide waste acid, adding the titanium dioxide waste acid into a five-neck flask, heating the mixture to 85 ℃ by using a heating sleeve, pumping a dilute phosphoric acid solution with the mass concentration of 6wt% by using a peristaltic pump, and pumping the dilute phosphoric acid solution and the TiCl of the dilute phosphoric acid and the titanium dioxide waste acid within 5 minutes 4 The mass ratio is 1:1, the mixture is fully mixed and stirred, the stirring time is 10 minutes, then the mixture is naturally cooled to room temperature, the mixture is filtered, 200ml of dilute sulfuric acid with the concentration of 3wt% is used for carrying out acid cleaning on a filter cake, 200ml of desalted water is used for washing after the acid cleaning, then trivalent titanium solution is used for bleaching, 200ml of desalted water is used for washing for 1 time after the bleaching is finished, then the titanium content in the filtrate is analyzed, and the filter residue is placed into a constant-temperature oven for heat preservation for 2 hours at the temperature of 105 ℃; and finally, grinding the dried filter residue, putting the ground filter residue into a crucible, and calcining the filter residue for 2 hours at the calcining temperature of 600 ℃ to obtain the titanium phosphate product.
The analysis showed that the filtrate contained 0.0039% of titanium and the removal rate of titanium was about 98.75%, and the calcined sample was analyzed by X-ray to show that it was titanium phosphate in large amount and had a small amount of impurities.
Example 2
Weighing titanium white waste acid, adding the titanium white waste acid into a five-neck flask, heating the mixture to 90 ℃ by using a heating sleeve, pumping a 7wt% dilute phosphoric acid solution by using a peristaltic pump, pumping the dilute phosphoric acid solution in 30 minutes, and mixing the dilute phosphoric acid solution and TiCl of the titanium white waste acid 4 The mass ratio of the components is 1.1, the mixture is fully mixed and stirred, the stirring time is 30 minutes, the mixture is naturally cooled to room temperature, the mixture is filtered, 200ml of dilute hydrochloric acid with the concentration of 10wt% is used for carrying out acid cleaning on a filter cake, 200ml of desalted water is used for washing, then trivalent titanium solution is used for bleaching, 1000ml of desalted water is used for washing for 5 times after bleaching is finished, then the titanium content in the filtrate is analyzed, and filter residue is placed into a constant temperature oven 105 ℃ for heat preservation for 2 hours; finally, grinding the dried filter residue, placing the ground filter residue into a crucible for calcination at the temperature of 800 ℃ for 2 hours to obtain the titanium phosphate product.
After analysis, the content of titanium in the filtrate was 0.0001%, the removal rate of titanium was about 99.98%, and the calcined samples were analyzed by X-ray to be titanium phosphate and had no impurity peak.
Example 3
Weighing titanium dioxide waste acid, adding the titanium dioxide waste acid into a five-neck flask, heating the mixture to 90 ℃ by using a heating sleeve, pumping a dilute phosphoric acid solution with the mass concentration of 7wt% by using a peristaltic pump, and pumping the dilute phosphoric acid solution and TiCl of the titanium dioxide waste acid within 20 minutes 4 The mass ratio of the components is 1.1, the mixture is fully mixed and stirred, the stirring time is 10 minutes, then the mixture is cooled to room temperature and filtered, 200ml of dilute phosphoric acid with the concentration of 4wt% is used for carrying out acid washing on a filter cake, 200ml of desalted water is used for washing, then trivalent titanium solution is used for bleaching, 600ml of desalted water is used for washing for 3 times after bleaching is finished, then the titanium content in the filtrate is analyzed, and filter residue is placed into a constant temperature oven for heat preservation for 2 hours at the temperature of 105 ℃; and finally, grinding the dried filter residue, putting the ground filter residue into a crucible, and calcining the filter residue for 2 hours at the calcining temperature of 1000 ℃ to obtain the titanium phosphate product.
After analysis, the content of titanium in the filtrate was 0.0061%, the removal rate of titanium was about 99.05%, and the calcined samples were all titanium phosphate and had no impurity peak, as determined by X-ray analysis.
Example 4
Weighing titanium dioxide waste acid, adding the titanium dioxide waste acid into a five-neck flask, heating the mixture to 100 ℃ by using a heating sleeve, pumping a dilute phosphoric acid solution with the mass concentration of 10wt% by using a peristaltic pump, and pumping the dilute phosphoric acid solution and the TiCl of the dilute phosphoric acid and the titanium dioxide waste acid within 30 minutes 4 The mass ratio of the components is 1.05; and finally, grinding the dried filter residue, putting the ground filter residue into a crucible, and calcining the filter residue for 2 hours at the calcining temperature of 1000 ℃ to obtain the titanium phosphate product.
After analysis, the content of titanium in the filtrate was 0.0001%, the removal rate of titanium was about 99.98%, and the calcined samples were analyzed by X-ray to be titanium phosphate without impurity peak.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (9)
1. A method for preparing titanium phosphate from waste acid which is a byproduct in titanium dioxide production by a chlorination method is characterized in that titanium phosphate is synthesized and prepared by taking titanium white waste acid and dilute phosphoric acid as raw materials, and the titanium white waste acid is waste hydrochloric acid which is a byproduct in titanium dioxide production by the chlorination method.
2. The method for preparing titanium phosphate from the byproduct waste acid generated in the production of titanium dioxide by the chlorination process as claimed in claim 1, wherein the dilute phosphoric acid is prepared from powdered rock phosphate by acid hydrolysis with hydrochloric acid, pretreatment and extraction.
3. The method for preparing titanium phosphate from the byproduct waste acid generated in the production of titanium dioxide by the chlorination process according to claim 1, which is characterized by comprising the following steps:
(1) Adding diluted phosphoric acid into the heated titanium white waste acid, stirring, and naturally cooling to obtain a sol;
(2) Filtering the sol and pickling to obtain a filter cake;
(3) Washing and bleaching the filter cake to obtain colloid;
(4) Washing and drying the colloid to obtain filter residue;
(5) And calcining the filter residue to obtain a finished product of the titanium phosphate.
4. The method for preparing titanium phosphate from the by-product waste acid generated in the production of titanium dioxide by the chlorination process according to claim 3, wherein in the step (1), the weight concentration of the dilute phosphoric acid is 6-10%, the temperature of the heated titanium white waste acid is 85-100 ℃, and the molar ratio of the dilute phosphoric acid to the titanium salt in the titanium white waste acid is 1.1-1:1.
5. The method for preparing titanium phosphate from the by-product waste acid generated in the production of titanium dioxide by the chlorination process according to claim 3, wherein one or more of dilute hydrochloric acid, dilute phosphoric acid and dilute sulfuric acid is used for acid washing in the step (2).
6. The method for preparing titanium phosphate from the byproduct waste acid generated in the production of titanium dioxide by the chlorination process according to claim 5, wherein the acid used for pickling has a weight concentration of 3-10%.
7. The method for preparing titanium phosphate from the by-product waste acid generated in the production of titanium dioxide by the chlorination process according to claim 3, wherein in the step (3), desalted water is used for washing, and a bleaching agent is used for bleaching.
8. The method for preparing titanium phosphate from the byproduct waste acid generated in the production of titanium dioxide by the chlorination process according to claim 7, wherein the bleaching agent is a trivalent titanium salt solution.
9. The method for preparing titanium phosphate from the by-product waste acid generated in the production of titanium dioxide by the chlorination process according to claim 3, wherein in the step (5), the calcining temperature is 600-1000 ℃.
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| CN202210940367.6A CN115231540A (en) | 2022-08-05 | 2022-08-05 | Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process |
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| CN202210940367.6A CN115231540A (en) | 2022-08-05 | 2022-08-05 | Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215709A (en) * | 1994-01-31 | 1995-08-15 | Nippon Paint Co Ltd | Production of titanium phosphate amorphous particle |
| US20100111818A1 (en) * | 2008-10-29 | 2010-05-06 | Haydock Frederick J | Removal of contaminants from by-product hydrochloric acid |
| CN102442656A (en) * | 2010-10-14 | 2012-05-09 | 上海澎博钛白粉有限公司 | Method for producing titanium phosphate fire retardant with titanium white waste acid |
| CN102701153A (en) * | 2011-12-30 | 2012-10-03 | 锦州钛业有限公司 | Treatment method for titanium dioxide process waste acid generated by molten salt chlorination process |
| CN110436420A (en) * | 2019-09-06 | 2019-11-12 | 攀枝花学院 | The purifying process of titanium dioxide waste acid by sulfuric acid process |
| CN112978805A (en) * | 2021-01-26 | 2021-06-18 | 北京科技大学 | Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid |
| CN115959642A (en) * | 2022-10-29 | 2023-04-14 | 宜宾天原科创设计有限公司 | Method for utilizing hydrochloric acid byproduct of titanium dioxide chloride |
-
2022
- 2022-08-05 CN CN202210940367.6A patent/CN115231540A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215709A (en) * | 1994-01-31 | 1995-08-15 | Nippon Paint Co Ltd | Production of titanium phosphate amorphous particle |
| US20100111818A1 (en) * | 2008-10-29 | 2010-05-06 | Haydock Frederick J | Removal of contaminants from by-product hydrochloric acid |
| CN102442656A (en) * | 2010-10-14 | 2012-05-09 | 上海澎博钛白粉有限公司 | Method for producing titanium phosphate fire retardant with titanium white waste acid |
| CN102701153A (en) * | 2011-12-30 | 2012-10-03 | 锦州钛业有限公司 | Treatment method for titanium dioxide process waste acid generated by molten salt chlorination process |
| CN110436420A (en) * | 2019-09-06 | 2019-11-12 | 攀枝花学院 | The purifying process of titanium dioxide waste acid by sulfuric acid process |
| CN112978805A (en) * | 2021-01-26 | 2021-06-18 | 北京科技大学 | Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid |
| CN115959642A (en) * | 2022-10-29 | 2023-04-14 | 宜宾天原科创设计有限公司 | Method for utilizing hydrochloric acid byproduct of titanium dioxide chloride |
Non-Patent Citations (2)
| Title |
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| "钛白废酸中钛资源的萃取及磷酸钛的制备研究", 造纸装备及材料, vol. 51, no. 203, pages 51 - 53 * |
| 鲍树涛;: "钛白废酸高效高值利用工业实践", 硫酸工业, no. 06 * |
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