CN114735781A - Method for removing fluorine in neutral or weakly acidic solution - Google Patents
Method for removing fluorine in neutral or weakly acidic solution Download PDFInfo
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- CN114735781A CN114735781A CN202210444894.8A CN202210444894A CN114735781A CN 114735781 A CN114735781 A CN 114735781A CN 202210444894 A CN202210444894 A CN 202210444894A CN 114735781 A CN114735781 A CN 114735781A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Inorganic Chemistry (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for removing fluorine from a neutral or weakly acidic solution, which comprises the following steps: adding zirconium oxychloride and titanium dioxide into a concentrated sulfuric acid solution, dissolving the zirconium oxychloride and the titanium dioxide by using the concentrated sulfuric acid, then adding ammonia water to adjust the pH value of the mixed solution to 10-11 to obtain a titanium-zirconium composite precipitate, washing the precipitate by using deionized water, roasting the washed precipitate, grinding the roasted product to below 325 meshes for later use at the roasting temperature of 400-700 ℃, thus completing the preparation of the defluorinating agent for the titanium-zirconium composite, adding the ground titanium-zirconium composite into the solution, adjusting the pH value to be neutral or weakly acidic, heating the solution to about 30 ℃, and removing oil and fluorine in the solution by using the titanium-zirconium composite.
Description
Technical Field
The invention belongs to the field of fluorine removal agents, and particularly relates to a method for removing fluorine in a neutral or weakly acidic solution.
Background
Removal of fluorine from solution is a big problem facing many industries. For example, in the direct smelting technology of low-grade zinc oxide ore, the leaching and accumulation of impurity fluorine seriously harm the subsequent purification and electrolysis process. After the fluorine content is too high, the cathode zinc stripping is difficult, the electrode consumption is increased, the anode is corroded, the service life is prolonged, and therefore the requirement for fluorine in zinc sulfate electrolyte at home and abroad is less than 50mg/L.
For example, the number of lithium batteries used has been increased in multiples in recent years, and the number of obsolete lithium batteries has been increased synchronously. Lithium batteries contain rare metals such as cobalt nickel lithium. If the waste water is not recycled, not only resources are wasted, but also the environment is polluted. In the process of purifying and separating valuable elements in the lithium ion battery, fluorine in the electrolyte enters the leaching solution along with leaching, so that the fluorine content in subsequent products is high. Fluorine in the lithium ion battery enters solution along with various metals in a leaching process, so that equipment corrosion is accelerated, fluorine enters stripping solution in an extraction section and is continuously enriched and circulated, and fluorine enters products in an extraction process, so that the product quality is influenced. Therefore, the battery powder leachate is required to be subjected to a defluorination treatment so as to avoid the above problems.
There are several main ways of removing fluorine currently in use: the method 1 adopts calcium salt, aluminum salt, magnesium salt and the like, other ions can be substituted in the defluorination process, the requirement on the pH value is strict, the operation difficulty is high, the adsorption efficiency is slow, the use amount is large, and the cost is high. 2, the method of adsorption removal is adopted, and the existing adsorbent includes polymeric materials and adsorbents such as iron-titanium composite. However, the existing adsorbents are expensive, need frequent regeneration and are not suitable for industrial popularization and use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for removing fluorine from a neutral or weakly acidic solution, which can quickly adsorb organic matters and fluorine ions in the solution, has strong adsorption capacity and can be repeatedly utilized.
In order to achieve the above object, the present invention is achieved by the following means.
A preparation method of a fluorine removal agent comprises the following steps:
step 1) adding 10-30 parts of zirconium oxychloride and 70-90 parts of titanium dioxide into 100-500 parts of concentrated sulfuric acid solution, stirring for 5-20 hours, and dissolving the zirconium oxychloride and the titanium dioxide by using concentrated sulfuric acid;
step 2) adding ammonia water into the mixed solution obtained in the step 1) under the stirring state to adjust the pH value of the mixed solution to 10-11, and carrying out coprecipitation reaction on the solution after adding the ammonia water to obtain a titanium-zirconium composite precipitate;
step 3) washing the precipitate obtained in the step 2) with deionized water;
and 4) roasting the washed precipitate at the roasting temperature of 400-700 ℃, and grinding the roasted product to below 325 meshes to form the fluorine removal agent for later use.
The invention protects another technical scheme that: the method for removing fluorine in neutral or weakly acidic solution by using the fluorine removing agent comprises the following steps:
step a) adjusting the solution to be subjected to fluorine removal to be neutral or weakly acidic, and then adding a fluorine removal agent into the solution, wherein 10-100g of fluorine removal agent is added into each liter of solution;
and b) adding the solution, heating to about 25-35 ℃, and removing oil and fluorine in the solution by using a fluorine removing agent.
Further, the fluorine removing agent used in the step 6) is heated to 60-100 ℃ in hot water to remove oil and fluorine adsorbed on the fluorine removing agent, and then the fluorine removing agent is washed by using the removing water, and the washed fluorine removing agent can be recycled.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for removing fluorine in the solution adopts an adsorption mode to remove fluorine ions in the solution, does not bring other additional ions, does not cause secondary pollution to the solution, can be used in various occasions, and does not influence the subsequent process.
2. The titanium-zirconium coprecipitate has good stability and strong adsorption capacity after being sintered, can reduce TOC in the solution from 1000mg/L to 20mg/L and reduce fluorine in the solution to 2g/L, and greatly improves the fluorine removal effect compared with the existing high-molecular fluorine removal agent and other metal compounds.
3. The preparation process and the use process of the defluorinating agent are simple and easy to control, and the used titanium-zirconium mixture can be recycled through simple recovery treatment, so that the use cost of enterprises is greatly reduced.
Detailed Description
The present invention is described in further detail below by way of specific examples.
Example one
A method for removing fluorine from a neutral or weakly acidic solution, comprising the steps of:
step 1) adding 15 parts of zirconium oxychloride and 75 parts of titanium dioxide into 200 parts of concentrated sulfuric acid solution, stirring for 10 hours, and dissolving the zirconium oxychloride and the titanium dioxide by using concentrated sulfuric acid;
step 2) adding ammonia water into the mixed solution obtained in the step 1) under the stirring state to adjust the pH value of the mixed solution to 10.5, and carrying out coprecipitation reaction on the solution after adding the ammonia water to obtain a titanium-zirconium composite precipitate;
step 3) washing the precipitate obtained in the step 2) with deionized water;
step 4) roasting the washed precipitate at 500 ℃, and grinding the roasted product to below 325 meshes for later use;
step 5) adjusting the solution to be subjected to fluorine removal to be neutral or weakly acidic, then adding the product ground in the step 4) into the solution, and adding 40g of the product into each liter of the solution;
and 6) adding the solution to about 30 ℃, and removing oil and fluorine in the solution by using a titanium-zirconium compound.
Example two
A method for removing fluorine from a neutral or weakly acidic solution, comprising the steps of:
step 1) adding 20 parts of zirconium oxychloride and 80 parts of titanium dioxide into 300 parts of concentrated sulfuric acid solution, stirring for 12 hours, and dissolving the zirconium oxychloride and the titanium dioxide by using concentrated sulfuric acid;
step 2) adding ammonia water into the mixed solution obtained in the step 1) under the stirring state to adjust the pH value of the mixed solution to 10.5, and carrying out coprecipitation reaction on the solution after adding the ammonia water to obtain a titanium-zirconium composite precipitate;
step 3) washing the precipitate obtained in the step 2) with deionized water;
step 4) roasting the washed precipitate at 600 ℃, and grinding the roasted product to below 325 meshes for later use;
step 5) adjusting the solution to be subjected to fluorine removal to be neutral or weakly acidic, then adding the product ground in the step 4) into the solution, and adding 50g of the product into each liter of the solution;
and 6) adding the solution to about 28 ℃, and removing oil and fluorine in the solution by using a titanium-zirconium compound.
EXAMPLE III
A method for removing fluorine from a neutral or weakly acidic solution, comprising the steps of:
step 1) adding 25 parts of zirconium oxychloride and 85 parts of titanium dioxide into 400 parts of concentrated sulfuric acid solution, stirring for 15 hours, and dissolving the zirconium oxychloride and the titanium dioxide by using concentrated sulfuric acid;
step 2) adding ammonia water into the mixed solution obtained in the step 1) under the stirring state to adjust the pH value of the mixed solution to 11, and carrying out coprecipitation reaction on the solution after adding the ammonia water to obtain a titanium-zirconium composite precipitate;
step 3) washing the precipitate obtained in the step 2) with deionized water;
step 4) roasting the washed precipitate at 600 ℃, and grinding the roasted product to below 325 meshes for later use;
step 5) adjusting the solution to be subjected to fluorine removal to be neutral or weakly acidic, then adding the product ground in the step 4) into the solution, and adding 40g of the product into each liter of the solution;
and 6) adding the solution to about 30 ℃, and removing oil and fluorine in the solution by using a titanium-zirconium compound.
The titanium-zirconium compound prepared in the three embodiments can efficiently adsorb fluorine and TOC in a neutral or weakly acidic solution, after adsorption is completed, the titanium-zirconium compound is filtered and taken out, and then is heated in hot water to 60-100 ℃ to remove oil and fluorine adsorbed on the titanium-zirconium compound, then the titanium-zirconium compound is washed by using the deionized water, and the washed titanium-zirconium compound can be recycled.
The defluorination method has high efficiency, strong adsorption capacity, repeated utilization for many times and low cost, and is very suitable for industrial application.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A preparation method of a defluorinating agent is characterized by comprising the following steps: the method comprises the following steps:
step 1) adding 10-30 parts of zirconium oxychloride and 70-90 parts of titanium dioxide into 100-500 parts of concentrated sulfuric acid solution, stirring for 5-20 hours, and dissolving the zirconium oxychloride and the titanium dioxide by using concentrated sulfuric acid;
step 2) adding ammonia water into the mixed solution obtained in the step 1) under the stirring state to adjust the pH value of the mixed solution to 10-11, and carrying out coprecipitation reaction on the solution after adding the ammonia water to obtain a titanium-zirconium composite precipitate;
step 3) washing the precipitate obtained in the step 2) with deionized water;
and 4) roasting the washed precipitate at the roasting temperature of 400-700 ℃, and grinding the roasted product to below 325 meshes to form the fluorine removal agent for later use.
2. A method for removing fluorine in a neutral or weakly acidic solution by using the fluorine removing agent of claim 1, characterized in that: the method comprises the following steps:
step a) adjusting the solution to be subjected to fluorine removal to be neutral or weakly acidic, and then adding a fluorine removal agent into the solution, wherein 10-100g of fluorine removal agent is added into each liter of solution;
step b) heating the solution to about 25-35 ℃, and removing oil and fluorine in the solution by using a fluorine removing agent.
3. A method as claimed in claim 2 for removing fluorine from a neutral or weakly acidic solution, wherein: heating the defluorinating agent used in the step b) in hot water to 60-100 ℃, removing oil and fluorine adsorbed on the defluorinating agent, and then washing the defluorinating agent by using the deionized water, wherein the defluorinating agent can be recycled after washing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210444894.8A CN114735781A (en) | 2022-04-26 | 2022-04-26 | Method for removing fluorine in neutral or weakly acidic solution |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210444894.8A CN114735781A (en) | 2022-04-26 | 2022-04-26 | Method for removing fluorine in neutral or weakly acidic solution |
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| CN114735781A true CN114735781A (en) | 2022-07-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
| CN108126714A (en) * | 2017-12-21 | 2018-06-08 | 大连智讯科技有限公司 | A kind of low temperature preparation method of titanium system solid super-strong acid |
| CN109876763A (en) * | 2019-03-15 | 2019-06-14 | 西安工程大学 | A kind of preparation method of zirconium dioxide/titanium dioxide composite adsorbing material |
| WO2019143264A1 (en) * | 2018-01-18 | 2019-07-25 | Общество С Ограниченной Ответственностью "Объединенная Компания Русал Инженерно -Технологический Центр" | Method of producing scandium oxide from scandium-containing concentrates |
| CN113694874A (en) * | 2021-09-02 | 2021-11-26 | 南京大学 | Titanium-zirconium adsorbent and preparation method and application thereof |
-
2022
- 2022-04-26 CN CN202210444894.8A patent/CN114735781A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
| CN108126714A (en) * | 2017-12-21 | 2018-06-08 | 大连智讯科技有限公司 | A kind of low temperature preparation method of titanium system solid super-strong acid |
| WO2019143264A1 (en) * | 2018-01-18 | 2019-07-25 | Общество С Ограниченной Ответственностью "Объединенная Компания Русал Инженерно -Технологический Центр" | Method of producing scandium oxide from scandium-containing concentrates |
| CN109876763A (en) * | 2019-03-15 | 2019-06-14 | 西安工程大学 | A kind of preparation method of zirconium dioxide/titanium dioxide composite adsorbing material |
| CN113694874A (en) * | 2021-09-02 | 2021-11-26 | 南京大学 | Titanium-zirconium adsorbent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马宏瑞;马秀;郭颖艳;: "Zr、Al、Ti复合氧化物的制备及其对EDTA-Cr的吸附性能研究", 化工新型材料, no. 12, pages 98 - 100 * |
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