CN110205442B - Preparation method of artificial fluorite ball - Google Patents
Preparation method of artificial fluorite ball Download PDFInfo
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- CN110205442B CN110205442B CN201910455457.4A CN201910455457A CN110205442B CN 110205442 B CN110205442 B CN 110205442B CN 201910455457 A CN201910455457 A CN 201910455457A CN 110205442 B CN110205442 B CN 110205442B
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- fluorite
- precipitate
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
Abstract
The invention discloses a preparation method of an artificial fluorite ball, which comprises the following steps: 1) filtering: collecting fluorine-containing wastewater, filtering, concentrating the filtrate, and controlling the fluorine concentration to be more than 1 g/L; 2) precipitation: adding excessive calcium compound into the concentrated solution, then dropwise adding a mixed solution of dilute hydrochloric acid and aluminum chloride, filtering and collecting the precipitate; 3) acidification: dripping dilute hydrochloric acid into the precipitate, filtering and collecting the precipitate; 4) preparing mud: adding composite fiber powder and pure water into the precipitate, and stirring into paste; 5) pressing: pressing the paste, and performing cold air cooling; 6) drying: firstly, microwave drying is carried out, and then heating drying is carried out; 7) sintering: sintering fluorite balls at low temperature and high pressure; 8) cooling: cooling the fluorite balls by air cooling, and grinding and polishing to obtain artificial fluorite balls; the artificial fluorite ball is extracted by using the fluorine-containing wastewater, so that the fluorine content in the wastewater is reduced, the wastewater pollution is avoided, the consumption of natural fluorite is reduced, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of preparation of fluorite balls, and particularly relates to a preparation method of artificial fluorite balls.
Background
The fluorite has the characteristics of reducing the melting point of refractory substances in the smelting process of special steel, stainless steel, iron alloy and other metals, promoting the flow of furnace slag and well separating the slag from the metals, is used as a fluxing agent in the smelting processes of special steel, iron alloy production, iron melting process and nonferrous metals, and is widely used for desulfurization, dephosphorization, metal forgeability, tensile strength and the like. The general required grade of fluorite ore for smelting is CaF2The content of the lump ore is more than or equal to 70 wt%, but the lump ore is limited by resources, the lump ore of the fluorite with medium and high grade is increasingly tense, the cost is greatly increased, the fluorite raw ore blocks and powder of oxides such as low grade, high FeO, MnO and the like are numerous, particularly, the tailings of the fluorite with low grade and high impurities generated by mineral separation which is symbiotic with non-ferrous metal ores are accumulated like mountains, do not go out of roads, waste resources and pollute the environment, and how to dispose the wastes, an effective recycling method is provided to become a problem which is extremely concerned by society.
In order to effectively solve the problem, firstly, the low-grade fluorite blocks and powder tailings are subjected to flotation to improve the grade to CaF2The content of the fluorite is more than or equal to 80 wt%, then the high-grade fluorite flotation powder after flotation is properly agglomerated so as to be used for metal smelting, and a reasonable method for preparing the fluorite balls needs to be found so as to ensure that the prepared fluorite balls have higher grade and higher strength and can be used for smelting special steel, stainless steel, blast furnaces and non-ferrous metals.
Disclosure of Invention
The invention aims to overcome the defects, and the technical problem to be solved is to provide the heavy-duty automobile brake pad, which is added with inorganic fibers to fully play a role of reinforcing a framework and reduce the phenomena of cracks and crazing in the processing and use of the brake pad; the powder of rubber and resin is added to improve the toughness of the brake pad, and the tungsten phenolic resin is added to improve the thermal stability of the whole braking process. And adding a small amount of antirust agent or zinc powder to control the rusting of the materials.
In order to realize the purpose of the invention, the adopted technical scheme is as follows: a preparation method of artificial fluorite balls specifically comprises the following steps:
1) filtering: collecting wastewater containing fluoride ions, filtering to remove insoluble substances, and concentrating the filtrate in a concentration tank to control the concentration of the fluoride ions to be more than 1 g/L;
2) precipitation: adding excessive calcium compound into the concentrated fluorine-containing wastewater, fully stirring, dropwise adding a mixed solution of dilute hydrochloric acid with the concentration of 1-2% and aluminum chloride, controlling the pH value of the fluorine-containing wastewater to be 6.5-7.5, fully stirring, filtering, collecting precipitate, and washing the precipitate with pure water for 2-3 times;
3) acidification: adding 1-2% dilute hydrochloric acid into the collected precipitate, stirring thoroughly, stopping adding dilute hydrochloric acid when the quality of the precipitate is not changed, filtering, collecting the precipitate, washing the precipitate with pure water for 2-3 times, and collecting the filtrate for reuse in step 2;
4) preparing mud: adding composite fiber powder into the collected precipitate, mixing completely, adding pure water, stirring completely to obtain paste with water content of 30-50%;
5) pressing: transferring the prepared paste into a spherical particle pressing machine for pressing, controlling the pressing temperature to be 20-50 ℃, and carrying out air cooling on the fluorite balls obtained by pressing in cold air at the temperature of 10-30 ℃;
6) drying: arranging the air-dried fluorite spheres, and then placing the arranged fluorite spheres in a microwave drying oven, wherein the frequency of the microwave drying oven is set to be 300MHz-3GHz, and the microwave drying is carried out for 10-30 min;
then placing the fluorite balls in a hot oven, setting the temperature in the oven to be 30-60 ℃, and drying for 2-5h to obtain dried fluorite balls;
starting a hot oven exhaust fan at intervals of 1h every time, exhausting the damp and hot air in the oven, and raising the temperature and drying again;
7) sintering: arranging fluorite balls, placing the fluorite balls in a sintering furnace at the temperature of 100-300 ℃, controlling the pressure in the sintering furnace to be 2-5MPa, and sintering at low temperature and high pressure for 3-5 h;
8) cooling: and cooling the fluorite ball by air cooling, controlling the cooling rate to be 3-5 ℃/min, and grinding and polishing the fluorite ball after cooling to the room temperature to obtain the artificial fluorite ball.
Preferably, the calcium compound is calcium carbonate, calcium oxide, calcium hydroxide, a mixture of calcium carbonate and calcium oxide, a mixture of calcium carbonate and calcium hydroxide or a mixture of calcium oxide and calcium hydroxide; calcium carbonate, calcium oxide or calcium hydroxide and the like react with fluoride ions under an acidic condition to obtain calcium fluoride precipitate.
Preferably, the proportion of the dilute hydrochloric acid to the aluminum chloride in the step 2 of the preparation method of the artificial fluorite balls is 3-5: 1; adding aluminum ions for hydrolysis to obtain an aluminum hydroxide adsorbent, performing sedimentation adsorption on the obtained calcium fluoride to accelerate liquid-solid separation, and adding aluminum hydroxide into the fluorite balls to improve the hardness of the fluorite balls.
Preferably, in the step 4 of the preparation method of the artificial fluorite ball, the composite fiber powder is a mixture of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder, and various minerals are added to further improve the heat resistance and the wear resistance of the fluorite ball and improve the texture of the fluorite ball.
Preferably, the adding proportion of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder in the composite fiber powder is 1-2:1-3:1:1: 1.
Preferably, the addition ratio of the calcium fluoride precipitate to the composite fiber powder is 3-8: 1.
Preferably, the content of calcium fluoride in the fluorite spheres is 70% or more.
Preferably, the diameter of the fluorite ball is 1-5 cm.
The invention has the beneficial effects that: the artificial fluorite ball prepared by the invention takes calcium fluoride as a main component, and is added with a plurality of mineral elements, so that the thermal stability, the wear resistance and the hardness of the artificial fluorite ball are improved, in the sedimentation process of the calcium fluoride, aluminum ions are added to improve the sedimentation rate of the calcium fluoride, the added aluminum ions further supplement the heat resistance and the stability of the artificial fluorite ball, and the most initial precipitate is treated by acidification, so that the content of unstable compounds in the artificial fluorite ball is reduced, and the artificial fluorite ball is prevented from cracking; adopt fluoride waste water to refine calcium fluoride, greatly reduced the fluorinion content in the waste water, avoided waste water pollution, also reduced the consumption of natural fluorite, reduced manufacturing cost.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
A preparation method of artificial fluorite balls is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
1) filtering: collecting wastewater containing fluoride ions, filtering to remove insoluble substances, and concentrating the filtrate in a concentration tank to control the concentration of the fluoride ions to be more than 1 g/L;
2) precipitation: adding excessive calcium compound into the concentrated fluorine-containing wastewater, dropwise adding a mixed solution of dilute hydrochloric acid with the concentration of 2% and aluminum chloride after fully stirring, controlling the pH value of the fluorine-containing wastewater to be 6.5-7.5, filtering after fully stirring, collecting precipitate, and washing the precipitate with pure water for 2-3 times;
3) acidification: adding 1% dilute hydrochloric acid into the collected precipitate, stirring thoroughly, stopping adding dilute hydrochloric acid when the quality of the precipitate does not change any more, filtering, collecting the precipitate, washing the precipitate with pure water for 2-3 times, collecting the filtrate, and applying the filtrate in step 2;
4) preparing mud: adding composite fiber powder into the collected precipitate, fully and uniformly mixing, adding pure water, and fully stirring to form a paste with the water content of 40%;
5) pressing: the prepared paste is transferred into a spherical particle pressing machine for pressing, the pressing temperature is controlled to be 30 ℃, and the fluorite balls obtained by pressing are air-cooled in cold air at the temperature of 15 ℃;
6) drying: arranging the air-dried fluorite spheres, and then placing the arranged fluorite spheres in a microwave drying oven, wherein the frequency of the microwave drying oven is set to be 1000MHz, and the microwave drying is carried out for 15 min;
then placing the fluorite balls in a hot oven, setting the temperature in the oven to be 40 ℃, and drying for 3 hours to obtain dried fluorite balls;
starting a hot oven exhaust fan at intervals of 1h every time, exhausting the damp and hot air in the oven, and raising the temperature and drying again;
7) sintering: arranging fluorite balls, placing the fluorite balls in a sintering furnace at 200 ℃, controlling the pressure in the sintering furnace to be 3MPa, and sintering at low temperature and high pressure for 4 hours;
8) cooling: and cooling the fluorite ball by air cooling, controlling the cooling rate to be 4 ℃/min, and grinding and polishing the fluorite ball after cooling to the room temperature to obtain the artificial fluorite ball.
Further, the calcium compound is calcium carbonate, calcium oxide, calcium hydroxide, a mixture of calcium carbonate and calcium oxide, a mixture of calcium carbonate and calcium hydroxide, or a mixture of calcium oxide and calcium hydroxide.
Further, the proportion of the dilute hydrochloric acid to the aluminum chloride in the step 2 of the preparation method of the artificial fluorite ball is 4: 1.
Further, in the preparation method of the artificial fluorite ball, in the step 4, the composite fiber powder is a mixture of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder.
Furthermore, the adding proportion of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder in the composite fiber powder is 2:1:1:1: 1.
Further, the addition ratio of the calcium fluoride precipitate to the composite fiber powder is 5: 1.
Further, the content of calcium fluoride in the fluorite balls is more than or equal to 70 percent.
Further, the particle diameter of the fluorite ball is 2-4 cm.
Example 2
A preparation method of artificial fluorite balls is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
1) filtering: collecting wastewater containing fluoride ions, filtering to remove insoluble substances, and concentrating the filtrate in a concentration tank to control the concentration of the fluoride ions to be more than 1 g/L;
2) precipitation: adding excessive calcium compound into the concentrated fluorine-containing wastewater, dropwise adding a mixed solution of dilute hydrochloric acid with the concentration of 1% and aluminum chloride after fully stirring, controlling the pH value of the fluorine-containing wastewater to be 6.5-7.0, filtering after fully stirring, collecting precipitate, and washing the precipitate with pure water for 2-3 times;
3) acidification: adding 1% dilute hydrochloric acid into the collected precipitate, stirring thoroughly, stopping adding dilute hydrochloric acid when the quality of the precipitate does not change any more, filtering, collecting the precipitate, washing the precipitate with pure water for 2-3 times, collecting the filtrate, and applying the filtrate in step 2;
4) preparing mud: adding composite fiber powder into the collected precipitate, fully and uniformly mixing, adding pure water, and fully stirring to form a paste with the water content of 50%;
5) pressing: transferring the prepared paste into a spherical particle pressing machine for pressing, controlling the pressing temperature to be 20 ℃, and carrying out air cooling on the fluorite balls obtained by pressing in cold air at the temperature of 10 ℃;
6) drying: arranging the air-dried fluorite spheres, and then placing the arranged fluorite spheres in a microwave drying oven, wherein the frequency of the microwave drying oven is set to be 300MHz, and the microwave drying is carried out for 30 min;
then placing the fluorite balls in a hot oven, setting the temperature in the oven to be 30 ℃, and drying for 5 hours to obtain dried fluorite balls;
starting a hot oven exhaust fan at intervals of 1h every time, exhausting the damp and hot air in the oven, and raising the temperature and drying again;
7) sintering: arranging fluorite balls, placing the fluorite balls in a sintering furnace at 100 ℃, controlling the pressure in the sintering furnace to be 5MPa, and sintering at low temperature and high pressure for 5 hours;
8) cooling: and cooling the fluorite ball by air cooling, controlling the cooling rate to be 3 ℃/min, and grinding and polishing the fluorite ball after cooling to the room temperature to obtain the artificial fluorite ball.
Further, the calcium compound is calcium carbonate, calcium oxide, calcium hydroxide, a mixture of calcium carbonate and calcium oxide, a mixture of calcium carbonate and calcium hydroxide, or a mixture of calcium oxide and calcium hydroxide.
Further, the proportion of the dilute hydrochloric acid to the aluminum chloride in the step 2 of the preparation method of the artificial fluorite ball is 3: 1.
Further, in the preparation method of the artificial fluorite ball, in the step 4, the composite fiber powder is a mixture of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder.
Furthermore, the adding proportion of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder in the composite fiber powder is 1:1:1:1: 1.
Further, the addition ratio of the calcium fluoride precipitate to the composite fiber powder is 3: 1.
Further, the content of calcium fluoride in the fluorite balls is more than or equal to 70 percent.
Further, the particle diameter of the fluorite ball is 1-3 cm.
Example 3
A preparation method of artificial fluorite balls is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
1) filtering: collecting wastewater containing fluoride ions, filtering to remove insoluble substances, and concentrating the filtrate in a concentration tank to control the concentration of the fluoride ions to be more than 1 g/L;
2) precipitation: adding excessive calcium compound into the concentrated fluorine-containing wastewater, dropwise adding a mixed solution of dilute hydrochloric acid with the concentration of 2% and aluminum chloride after fully stirring, controlling the pH value of the fluorine-containing wastewater to be 7.0-7.5, filtering after fully stirring, collecting precipitate, and washing the precipitate with pure water for 2-3 times;
3) acidification: adding dilute hydrochloric acid with the concentration of 2% into the collected precipitate, fully stirring, stopping adding the dilute hydrochloric acid when the quality of the precipitate does not change any more, filtering, collecting the precipitate, washing the precipitate for 2-3 times by using pure water, and collecting filtrate for applying to the step 2;
4) preparing mud: adding composite fiber powder into the collected precipitate, fully and uniformly mixing, adding pure water, and fully stirring to form a paste with the water content of 50%;
5) pressing: the prepared paste is transferred into a spherical particle pressing machine for pressing, the pressing temperature is controlled to be 50 ℃, and the fluorite balls obtained by pressing are air-cooled in cold air at the temperature of 30 ℃;
6) drying: arranging the air-dried fluorite spheres, and then placing the arranged fluorite spheres in a microwave drying oven, wherein the frequency of the microwave drying oven is set to be 3GHz, and the microwave drying is carried out for 10 min;
then placing the fluorite balls in a hot oven, setting the temperature in the oven to be 60 ℃, and drying for 2 hours to obtain dried fluorite balls;
starting a hot oven exhaust fan at intervals of 1h every time, exhausting the damp and hot air in the oven, and raising the temperature and drying again;
7) sintering: arranging fluorite balls, placing the fluorite balls in a sintering furnace at 300 ℃, controlling the pressure in the sintering furnace to be 2MPa, and sintering at low temperature and high pressure for 3 hours;
8) cooling: and cooling the fluorite ball by air cooling, controlling the cooling rate to be 5 ℃/min, and grinding and polishing the fluorite ball after cooling to the room temperature to obtain the artificial fluorite ball.
Further, the calcium compound is calcium carbonate, calcium oxide, calcium hydroxide, a mixture of calcium carbonate and calcium oxide, a mixture of calcium carbonate and calcium hydroxide, or a mixture of calcium oxide and calcium hydroxide.
Further, the proportion ratio of the dilute hydrochloric acid to the aluminum chloride in the step 2 of the preparation method of the artificial fluorite ball is 5: 1.
Further, in the preparation method of the artificial fluorite ball, in the step 4, the composite fiber powder is a mixture of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder.
Furthermore, the adding proportion of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder in the composite fiber powder is 2:3:1:1:1: 1.
Further, the addition ratio of the calcium fluoride precipitate to the composite fiber powder is 8: 1.
Further, the content of calcium fluoride in the fluorite balls is more than or equal to 70 percent.
Further, the particle diameter of the fluorite ball is 2-5 cm.
According to the artificial fluorite ball prepared by the invention, calcium fluoride is used as a main component, and a plurality of mineral elements are added, so that the thermal stability, the wear resistance and the hardness of the artificial fluorite ball are improved, in the sedimentation process of the calcium fluoride, aluminum ions are added to improve the sedimentation rate of the calcium fluoride, the added aluminum ions further supplement the heat resistance and the stability of the artificial fluorite ball, and the most initial sediment is treated by acidification, so that the content of unstable compounds in the artificial fluorite ball is reduced, and the artificial fluorite ball is prevented from cracking; adopt fluoride waste water to refine calcium fluoride, greatly reduced the fluorinion content in the waste water, avoided waste water pollution, also reduced the consumption of natural fluorite, reduced manufacturing cost.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of artificial fluorite balls is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
1) filtering: collecting wastewater containing fluoride ions, filtering to remove insoluble substances, and concentrating the filtrate in a concentration tank to control the concentration of the fluoride ions to be more than 1 g/L;
2) precipitation: adding excessive calcium compound into the concentrated fluorine-containing wastewater, fully stirring, dropwise adding a mixed solution of dilute hydrochloric acid with the concentration of 1-2% and aluminum chloride, controlling the pH value of the fluorine-containing wastewater to be 6.5-7.5, fully stirring, filtering, collecting precipitate, and washing the precipitate with pure water for 2-3 times;
3) acidification: adding 1-2% dilute hydrochloric acid into the collected precipitate, stirring thoroughly, stopping adding dilute hydrochloric acid when the quality of the precipitate is not changed, filtering, collecting the precipitate, washing the precipitate with pure water for 2-3 times, and collecting the filtrate for reuse in step 2;
4) preparing mud: adding composite fiber powder into the collected precipitate, mixing completely, adding pure water, stirring completely to obtain paste with water content of 30-50%;
the composite fiber powder is a mixture of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder;
5) pressing: transferring the prepared paste into a spherical particle pressing machine for pressing, controlling the pressing temperature to be 20-50 ℃, and carrying out air cooling on the fluorite balls obtained by pressing in cold air at the temperature of 10-30 ℃;
6) drying: arranging the air-dried fluorite spheres, and then placing the arranged fluorite spheres in a microwave drying oven, wherein the frequency of the microwave drying oven is set to be 300MHz-3GHz, and the microwave drying is carried out for 10-30 min;
then placing the fluorite balls in a hot oven, setting the temperature in the oven to be 30-60 ℃, and drying for 2-5h to obtain dried fluorite balls;
starting a hot oven exhaust fan at intervals of 1h every time, exhausting the damp and hot air in the oven, and raising the temperature and drying again;
7) sintering: arranging fluorite balls, placing the fluorite balls in a sintering furnace at the temperature of 100-300 ℃, controlling the pressure in the sintering furnace to be 2-5MPa, and sintering at low temperature and high pressure for 3-5 h;
8) cooling: and cooling the fluorite ball by air cooling, controlling the cooling rate to be 3-5 ℃/min, and grinding and polishing the fluorite ball after cooling to the room temperature to obtain the artificial fluorite ball.
2. The method of claim 1, wherein the method comprises the steps of: the calcium compound is calcium carbonate, calcium oxide, calcium hydroxide, a mixture of calcium carbonate and calcium oxide, a mixture of calcium carbonate and calcium hydroxide or a mixture of calcium oxide and calcium hydroxide.
3. The method of claim 1, wherein the method comprises the steps of: in the preparation method of the artificial fluorite ball, the proportion ratio of the dilute hydrochloric acid to the aluminum chloride in the step 2 is 3-5: 1.
4. The method of claim 1, wherein the method comprises the steps of: the adding proportion of fluorite flotation powder, fluorite mineral powder, mineral composite fiber powder, glass fiber powder, ceramic fiber powder and silicate fiber powder in the composite fiber powder is 1-2:1-3:1:1: 1.
5. The method of claim 1, wherein the method comprises the steps of: the adding ratio of the calcium fluoride precipitate to the composite fiber powder is 3-8: 1.
6. The method of claim 5, wherein the method comprises the steps of: the content of calcium fluoride in the fluorite balls is more than or equal to 70 percent.
7. The method for preparing artificial fluorite pellets as set forth in any one of claims 1 to 6, wherein: the diameter of the fluorite ball particles is 1-5 cm.
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| CN103232053A (en) * | 2013-05-17 | 2013-08-07 | 北方民族大学 | Method for producing calcium fluoride by bottom sludge generated during treatment of industrial fluoride-containing wastewater |
| CN105905933A (en) * | 2016-06-23 | 2016-08-31 | 昆山阳澄蓝谷环境研究所有限公司 | Process for preparing high-purity artificial fluorite by recovering fluoride-containing wastewater |
| CN106986368A (en) * | 2017-03-13 | 2017-07-28 | 李德寿 | A kind of preparation method of artificial Fluorite pellet |
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2019
- 2019-05-29 CN CN201910455457.4A patent/CN110205442B/en active Active
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| JPH054090A (en) * | 1991-06-27 | 1993-01-14 | Hitachi Plant Eng & Constr Co Ltd | Treatment of fluorine-containing organic waste water |
| CN101492192A (en) * | 2009-02-26 | 2009-07-29 | 杭州诚洁环保有限公司 | Coagulating agent for treating wastewater containing fluorine and use process thereof |
| CN102899486A (en) * | 2012-11-05 | 2013-01-30 | 内蒙古科技大学 | Method for leaching bastnaesite-containing rare-earth ore concentrates in complexing mode and preparing kryocide |
| CN103232053A (en) * | 2013-05-17 | 2013-08-07 | 北方民族大学 | Method for producing calcium fluoride by bottom sludge generated during treatment of industrial fluoride-containing wastewater |
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