CN111302470A - Defluorination precipitator, preparation method thereof and method for defluorination of waste acid and wastewater by using defluorination precipitator - Google Patents
Defluorination precipitator, preparation method thereof and method for defluorination of waste acid and wastewater by using defluorination precipitator Download PDFInfo
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- CN111302470A CN111302470A CN202010159181.8A CN202010159181A CN111302470A CN 111302470 A CN111302470 A CN 111302470A CN 202010159181 A CN202010159181 A CN 202010159181A CN 111302470 A CN111302470 A CN 111302470A
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention relates to a defluorination precipitator, a preparation method thereof and a method for defluorination of waste acid and wastewater by using the defluorination precipitator, belonging to the technical field of wastewater and waste liquid treatment and recycling. The defluorination precipitator provided by the invention comprises the following components in a molar ratio of 0.01: 1-100: 1 and thiourea. The silicon atom and imino group in the defluorination precipitator respectively provide 'nucleophilic substitution' and 'ionic bonding' reaction sites which are acted with fluorinion, hydrophobic fluorine-containing precipitate is generated through hydrolysis and polycondensation reaction, and solution is separated out, so that the concentration of fluoride in the waste acid water is reduced to be below 10mg/L, the reaction process is not interfered by coexisting ions in the waste acid water, and the defluorination capability with high selectivity is realized. The fluorine-containing precipitate generated after fluorine removal is reduced by more than 96% compared with the conventional fluorine removal method, and the fluorine-containing precipitate and the purified waste acid and wastewater can be recycled.
Description
Technical Field
The invention relates to a defluorination precipitator, a preparation method thereof and a method for defluorination of waste acid and wastewater by using the defluorination precipitator, belonging to the technical field of wastewater and waste liquid treatment and recycling.
Background
The waste acid water mainly comes from the industries of non-ferrous metal smelting, sulfur concentrate acid making and the like and contains sulfuric acid with higher concentration(50-200g/L) and fluoride (200-3000 mg/L). Aiming at the method for removing fluorine in waste acid wastewater, the industry commonly adopts a lime milk neutralization method, namely, lime milk is added into the wastewater to lead fluorine ions to be CaF2And (3) precipitating to remove, and adding auxiliary agents such as iron salt and flocculating agent in order to remove fluoride ions up to the standard and accelerate precipitation. However, the strong acid solution contains 50-180g/L sulfate ions which consume a large amount of calcium ions, and if the defluorination efficiency is ensured, the use amount of lime milk needs to be further increased; meanwhile, the addition of a large amount of lime milk can cause the generation of a large amount of gypsum residues, thereby greatly increasing the difficulty of solid-liquid separation, and according to the real investigation, each cubic meter treated by the lime milk contains 50g/L H2SO4The waste water of (2) will produce 50-100Kg of gypsum slag, which contains not only fluorine but also zinc, lead, arsenic, iron, copper and other heavy metal ions of different concentration levels, belonging to dangerous solid waste, and still requiring enterprises to invest high cost to safely dispose the waste water, and if the disposal is improper, there is a risk of secondary pollution. In addition, the lime milk neutralization defluorination method causes that valuable resources can not be recycled, thereby causing the waste of resources.
Other defluorination methods, such as adsorption, ion exchange, reverse osmosis, etc., are only suitable for removal of low fluoride (<10mg/L) at pH values near neutral conditions (5-8) in drinking or surface water, and are not suitable for effective removal of fluoride from wastewater with strong acidity, higher fluoride concentrations (>100mg/L) and complex composition.
So far, no technology for removing fluoride in waste acid and wastewater can solve the defects of large generation amount of dangerous solid waste, slow sedimentation, difficult dehydration, incapability of recycling useful resources and the like of the existing fluorine removal method.
Disclosure of Invention
The invention aims to solve the technical problems in the background art and provides a defluorination precipitator, a preparation method thereof and a method for defluorination of waste acid and wastewater by using the defluorination precipitator.
The technical scheme for solving the technical problems is as follows: a defluorination precipitating agent, which comprises a molar ratio of 0.01: 1-100: 1 and thiourea.
The defluorination precipitator provided by the invention has the beneficial effects that:
the silicon atom and imino contained in the defluorination precipitator provided by the invention respectively provide 'nucleophilic substitution' and 'ionic bonding' reaction sites which are obligatory to fluorine ions, generate fluorine-containing precipitates through hydrolysis and polycondensation reactions, and separate out a solution. The defluorination process is basically not interfered by coexisting ions in the waste acid water, and the fluoride in the waste acid water can be directly removed to be below 10mg/L without acidity adjustment, so that the high selectivity and high efficiency removal of the fluoride in the waste acid water are realized.
Because the defluorination precipitator provided by the invention has a certain number of hydrophobic groups, the generated fluorine-containing precipitate has certain hydrophobicity, and the solid-liquid separation is easy to carry out. The agent only generates precipitation reaction with fluorine ions in the waste acid water, the generated fluorine-containing precipitation amount is very small, and compared with the precipitation amount generated by using a conventional neutralization precipitation method, the reduction amount is more than 96%.
In addition, the separated fluorine-containing precipitate is another novel material with higher purity, and can be recycled as a resource. The waste acid and waste water after defluorination can be returned to the production process again for utilization. Therefore, the defluorination precipitate can overcome the defects of a large amount of dangerous solid wastes generated after the prior waste acid wastewater is treated, difficult dehydration and incapability of recycling useful resources, and the whole defluorination process using the defluorination precipitate almost has no wastes, thereby not only saving the production cost for enterprises, but also generating excellent economic and social benefits by recycling valuable components.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the oxygen-containing organosilicon compound comprises any one or more of methyl triacetoxysilane, methoxy trichlorosilane, dimethoxy dichlorosilane, phenyl trichlorosilane, methoxy silane, ethoxy silane, methylsilicol, butadienyl triethoxysilane, potassium methylsilicol, vinyl triethoxysilane and gamma-aminopropyl triethoxysilane.
The invention also provides the following technical scheme for solving the technical problems: a method for preparing the defluorination precipitating agent comprises the following steps: taking an oxygen-containing organic silicon compound and thiourea as raw materials, taking ammonium sulfate as a catalyst, and reacting at 50-300 ℃ for 10min-72h to obtain the defluorination precipitator.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the molar ratio of the ammonium sulfate to the oxygen-containing organosilicon compound is 0.1: 1-10: 1.
the invention also provides the following technical scheme for solving the technical problems: the application of the defluorination precipitator in the defluorination of waste acid water, metallurgical waste liquid and/or metallurgical liquid in the metallurgical industry is provided.
The invention also provides the following technical scheme for solving the technical problems: a method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
adding a defluorination precipitator into the waste acid water, mixing and reacting at 0-100 ℃ for 10min-24h to generate hydrophobic fluorine-containing precipitate, namely, removing fluorine ions by a precipitation method, separating the hydrophobic fluorine-containing precipitate from the waste acid water, respectively recovering the hydrophobic fluorine-containing precipitate and the purified waste acid water, and performing resource utilization.
The method for removing fluorine from the waste acid wastewater by using the fluorine removal precipitator has the beneficial effects that:
the method for removing fluorine from the waste acid water by the fluorine removal precipitator enables fluorine ions in the waste acid water to generate hydrophobic fluorine-containing precipitate and separate out solution, and the reaction process is not interfered by coexisting ions in the waste acid water and has high selective fluorine removal capability. The fluorine-containing precipitate generated after fluorine removal is reduced by more than 96% compared with the conventional fluorine removal method, and the fluorine-containing precipitate and the purified waste acid and wastewater can be recycled.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the molar ratio of the fluorine-removing precipitator to fluorine ions in the waste acid wastewater is 0.01: 1-100: 1.
further, the mixing reaction mode comprises mechanical stirring, magnetic stirring or rotary mixing.
Further, the separation mode comprises plate-type filter pressing, membrane separation, sand filtration, centrifugation or suction filtration.
Further, the hydrophobic fluorine-containing precipitate can be used as a waterproof agent, a retarder and/or a binding agent for building materials; and evaporating and concentrating the purified waste acid and waste water to prepare high-concentration acid which can be reused in an acid leaching process.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of a defluorination precipitator comprises the following steps:
0.2mol of methyltriacetoxysilane and 0.1mol of thiourea are used as raw materials, 0.02mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed and reacted for 5 hours at 170 ℃, and the defluorination precipitator is obtained and is sealed and stored for standby.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
500mL of 50g/L H2SO4And adding 1g of defluorination precipitator into the polluted acid wastewater of 1000mg/L of fluoride ions, magnetically stirring for 2 hours at the temperature of 60 ℃, separating the fluoride-containing precipitate from the polluted acid wastewater by suction filtration, measuring the concentration of the fluoride ions in the treated polluted acid wastewater to be 9mg/L by using an ion selective electrode method, measuring the dry weight of the fluoride-containing precipitate to be 1.4g and the concentration of sulfuric acid to be 50g/L, dissolving the recovered fluoride-containing precipitate in alkali, using the dissolved precipitate as a concrete waterproofing agent, and recycling the purified polluted acid wastewater to an acid leaching process.
Example 2
A preparation method of a defluorination precipitator comprises the following steps:
taking 0.2mol of vinyl triethoxysilane and 0.2mol of thiourea as raw materials, taking 0.02mol of ammonium sulfate as a catalyst, uniformly mixing, reacting at 180 ℃ for 4h to obtain the defluorination precipitator, and sealing and storing for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
1L of 100g/L H2SO4And 2000mg/L of fluoride ion waste water, adding 4g of defluorination precipitator, magnetically stirring for 2 hours at 60 ℃, separating the fluoride-containing precipitate from the waste water by sand filtration, measuring the concentration of fluoride ions in the treated waste water by an ion selective electrode method to be 10mg/L, the dry weight of the fluoride-containing precipitate to be 5.9g, the concentration of sulfuric acid to be 100g/L, dissolving the recovered fluoride-containing precipitate in alkali to be used as a concrete waterproofing agent, and reusing the purified waste water to an acid leaching process.
Example 3
A preparation method of a defluorination precipitator comprises the following steps:
2mol of gamma-aminopropyltriethoxysilane and 1mol of thiourea are used as raw materials, 0.5mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed and react for 4 hours at 180 ℃, and then the defluorination precipitator is obtained and is sealed and stored for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
1L of 100g/L H2SO4And sewage acid wastewater containing 3000mg/L fluorine ions, adding 6g of fluorine removal precipitator, magnetically stirring for 2h at 60 ℃, separating fluorine-containing precipitate from the sewage acid wastewater through sand filtration, measuring the concentration of the fluorine ions in the treated sewage acid wastewater to be 10mg/L by using an ion selective electrode method, measuring the dry weight of the fluorine-containing precipitate to be 8.9g, measuring the concentration of sulfuric acid to be 100g/L, dissolving the recovered fluorine-containing precipitate in alkali, using the dissolved precipitate as a cement retarder, and recycling the purified sewage acid wastewater to an acid leaching process.
Example 4
A preparation method of a defluorination precipitator comprises the following steps:
3mol of methoxysilane and 2mol of thiourea are used as raw materials, 1mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed, and then the mixture reacts for 4 hours at 180 ℃ to obtain the defluorination precipitator, and the defluorination precipitator is sealed and stored for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
taking 1L of 150g/L H2SO4And 1000mg/L of fluoride ion, adding 1g of defluorination precipitator,and magnetically stirring for 1 hour at the temperature of 80 ℃, performing suction filtration separation on the fluorine-containing precipitate from the waste acid wastewater, measuring the concentration of fluorine ions in the treated waste acid wastewater to be 10mg/L by using an ion selective electrode method, wherein the dry weight of the fluorine-containing precipitate is 1.9g, the concentration of sulfuric acid is 150g/L, dissolving the recovered fluorine-containing precipitate in alkali, using the dissolved precipitate as a concrete waterproofing agent, and recycling the purified waste acid wastewater to an acid leaching process.
Example 5
A preparation method of a defluorination precipitator comprises the following steps:
uniformly mixing 2mol of butadiene triethoxy silane and 2mol of thiourea as raw materials and 0.5mol of ammonium sulfate as a catalyst, reacting for 3 hours at 190 ℃ to obtain the defluorination precipitator, and sealing and storing for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
taking 1L of 200g/L H2SO4And adding 3g of defluorination precipitator into the polluted acid wastewater of 3000mg/L of fluoride ions, magnetically stirring for 2 hours at 60 ℃, separating the fluoride-containing precipitate from the polluted acid wastewater through sand filtration, measuring the concentration of the fluoride ions in the treated polluted acid wastewater to be 9mg/L by using an ion selective electrode method, measuring the dry weight of the fluoride-containing precipitate to be 5.9g, measuring the concentration of sulfuric acid to be 200g/L, dissolving the recovered fluoride-containing precipitate in alkali, using the dissolved precipitate as a concrete waterproofing agent, and recycling the purified polluted acid wastewater to an acid leaching process.
Example 6
A preparation method of a defluorination precipitator comprises the following steps:
5mol of methyl silicon potassium alkoxide and 2mol of thiourea are used as raw materials, 1mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed, and then the mixture reacts for 3 hours at the temperature of 200 ℃ to obtain the defluorination precipitator, and the defluorination precipitator is sealed and stored for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
taking 5L of 200g/L H2SO4Adding 10g of defluorination precipitator into the sewage acid wastewater containing 2000mg/L of fluorinion, magnetically stirring the sewage acid wastewater at 80 ℃ for 30min, separating the fluorine-containing precipitate from the sewage acid wastewater through suction filtration, and measuring the concentration of the fluorinion in the treated sewage acid wastewater to be 10mg/L by using an ion selective electrode method, wherein the concentration of the fluorinion is the concentration of the fluorine-containing precipitateThe dry weight of the fluorine precipitate is 19.9g, the concentration of sulfuric acid is 200g/L, the recovered fluorine-containing precipitate is used as a cement retarder after being dissolved in alkali, and the purified waste acid and waste water is reused in an acid leaching process.
Example 7
A preparation method of a defluorination precipitator comprises the following steps:
1mol of vinyl triethoxysilane and 1mol of thiourea are used as raw materials, 0.1mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed and react for 6 hours at 180 ℃, and then the defluorination precipitator is obtained and is sealed and stored for standby.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
taking 5L of 100g/L H2SO4And adding 5g of defluorination precipitator into the polluted acid wastewater of 1000mg/L of fluoride ions, magnetically stirring for 3 hours at the temperature of 60 ℃, separating the fluoride-containing precipitate from the polluted acid wastewater through sand filtration, measuring the concentration of the fluoride ions in the treated polluted acid wastewater to be 6mg/L by using an ion selective electrode method, measuring the dry weight of the fluoride-containing precipitate to be 9.8g, measuring the concentration of sulfuric acid to be 100g/L, dissolving the recovered fluoride-containing precipitate in alkali, using the dissolved precipitate as a concrete waterproofing agent, and recycling the purified polluted acid wastewater to an acid leaching process.
Example 8
A preparation method of a defluorination precipitator comprises the following steps:
2mol of methoxytrichlorosilane and 1mol of thiourea are taken as raw materials, 0.2mol of ammonium sulfate is taken as a catalyst, the materials are uniformly mixed and react for 9 hours at 160 ℃, and then the defluorination precipitator is obtained and is sealed and stored for standby.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
taking 10L of 200g/L H2SO4And 1000mg/L of fluoride ion waste water, adding 10g of defluorination precipitator, mechanically stirring for 1h at 70 ℃, separating the fluoride-containing precipitate from the waste water by plate-type filter pressing, measuring the fluoride ion concentration in the treated waste water to be 8mg/L by an ion selective electrode method, measuring the dry weight of the fluoride-containing precipitate to be 19.7g and the sulfuric acid concentration to be 200g/L, dissolving the recovered fluoride-containing precipitate in alkali to be used as a concrete waterproofing agent, and recycling the purified waste water to an acid leaching process.
Example 9
A preparation method of a defluorination precipitator comprises the following steps:
uniformly mixing 20mol of gamma-aminopropyltriethoxysilane and 10mol of thiourea serving as raw materials and 2mol of ammonium sulfate serving as a catalyst, reacting at 180 ℃ for 6 hours to obtain the defluorination precipitator, and sealing and storing for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
100L of 100g/L H2SO4And 2000mg/L of fluoride ion waste water, adding 200g of defluorination precipitator, mechanically stirring for 1h at 80 ℃, separating the fluoride-containing precipitate from the waste water by plate-type filter pressing, measuring the fluoride ion concentration in the treated waste water by an ion selective electrode method to be 10mg/L, the dry weight of the fluoride-containing precipitate to be 400g, the sulfuric acid concentration to be 100g/L, dissolving the recovered fluoride-containing precipitate in alkali to be used as a cement retarder, and recycling the purified waste water to the acid leaching process.
Example 10
A preparation method of a defluorination precipitator comprises the following steps:
20mol of gamma-aminopropyltriethoxysilane and 5mol of thiourea are used as raw materials, 4mol of ammonium sulfate is used as a catalyst, the raw materials are uniformly mixed and react for 2 hours at 200 ℃, and then the defluorination precipitator is obtained and is sealed and stored for later use.
A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator comprises the following steps:
100L of 100g/L H2SO4Adding 150g of defluorination precipitator into the sewage acid wastewater containing 2000mg/L of fluoride ions, mechanically stirring for 2h at 60 ℃, separating the fluoride-containing precipitate from the sewage acid wastewater through plate-type filter pressing, measuring the concentration of the fluoride ions in the treated sewage acid wastewater to be 10mg/L by using an ion selective electrode method, measuring the dry weight of the fluoride-containing precipitate to be 348g and the concentration of sulfuric acid to be 100g/L, dissolving the recovered fluoride-containing precipitate in alkali to be used as a concrete waterproofing agent, and recycling the purified sewage acid wastewater to an acid leaching process.
Comparative example 1
A method for removing fluorine from waste acid wastewater by using lime milk comprises the following steps:
1L of 100g/L H2SO4Adding 56g of lime emulsion into sewage acid wastewater containing 3000mg/L of fluoride ions, magnetically stirring for 2 hours, carrying out suction filtration separation on the fluoride-containing precipitate from the sewage acid wastewater, measuring the concentration of the fluoride ions in the treated sewage acid wastewater to be 20mg/L by using an ion selective electrode method, wherein the dry weight of the fluoride-containing precipitate is 155g, and the pH of the treated sewage acid wastewater is close to neutral without recycling value.
According to the conditions of the examples 1 to 10, the invention is seen from small-scale (0.5-10L) tests in laboratories or 100L semi-industrial tests with enlarged scale, the concentration of the fluorine ions in the purified waste acid water is less than or equal to 10mg/L, the generation amount of the fluorine-containing precipitate is basically the sum of the addition amount of the fluorine removal precipitator and the mass of the fluorine ions, the fluorine removal precipitator is basically not remained in the purified waste acid water, and the concentration of the fluorine-removed waste acid water is basically kept unchanged, so that the invention has recycling value.
In contrast, in the comparative example 1, a fluorine removal test is carried out by adopting a conventional lime neutralization method, the adding amount of lime milk is up to 56g, the concentration of fluorine ions in the treated waste acid water is 20mg/L, 155g of fluorine-containing gypsum slag is generated after the lime milk reacts with a large amount of sulfate radicals, and the reuse of valuable components cannot be realized. Under the same conditions, the dosage of the fluorine removal agent used in the embodiment 3 of the invention is only 6g, and only 8.9g of fluorine-containing precipitate is generated after the reaction, so that the partial fluorine-containing precipitate and the purified waste acid and wastewater can be recycled.
The comparative experiment shows that the creativity and the defluorination principle of the defluorination precipitator overcome the defects that the generation amount of dangerous solid wastes is extremely large and useful resources cannot be recovered after the existing waste acid wastewater is treated, and almost no wastes are generated in the whole defluorination process using the defluorination precipitator, so that the defluorination precipitator not only can save the production cost for enterprises, but also can generate excellent economic and social benefits, and has great advantages and application prospects.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A defluorination precipitating agent is characterized by comprising the following components in a molar ratio of 0.01: 1-100: 1 and thiourea.
2. A defluorination precipitating agent according to claim 1, wherein said oxygen containing organosilicon compound comprises any one or more of methyltriacetoxysilane, methoxytrichlorosilane, dimethoxydichlorosilane, phenyltrichlorosilane, methoxysilane, ethoxysilane, methylsilicol, butadienyltriethoxysilane, potassium methylsilicol, vinyltriethoxysilane and γ -aminopropyltriethoxysilane.
3. A method of preparing a defluorination precipitating agent as defined in any one of claims 1 or 2, comprising: taking an oxygen-containing organic silicon compound and thiourea as raw materials, taking ammonium sulfate as a catalyst, and reacting at 50-300 ℃ for 10min-72h to obtain the defluorination precipitator.
4. The production method according to claim 3, characterized in that the molar ratio of the ammonium sulfate to the oxygen-containing organosilicon compound is 0.1: 1-10: 1.
5. use of the defluorination precipitating agent according to any one of the claims 1 or 2 in defluorination of waste acid water, waste metallurgical liquid and/or metallurgical liquid in the metallurgical industry.
6. A method for removing fluorine from waste acid wastewater by using the fluorine removal precipitator in any one of claims 1 or 2, comprising:
adding a defluorination precipitator into the waste acid water, mixing and reacting for 10min-24h at 0-100 ℃, generating hydrophobic fluorine-containing precipitate, separating the hydrophobic fluorine-containing precipitate from the waste acid water, and respectively recovering the hydrophobic fluorine-containing precipitate and the purified waste acid water for resource utilization.
7. The method according to claim 6, wherein the molar ratio of the defluorination precipitating agent to the fluoride ions in the waste acid water is 0.01: 1-100: 1.
8. the method of claim 6, wherein the mixing reaction means comprises mechanical stirring, magnetic stirring, or rotational mixing.
9. The method of claim 6, wherein the separation means comprises plate press filtration, membrane separation, sand filtration, centrifugation, or suction filtration.
10. The method of claim 6, wherein the hydrophobic fluorine-containing precipitate is capable of acting as a water repellent, retarder and/or adhesive for building materials; and evaporating and concentrating the purified waste acid and waste water to prepare high-concentration acid which can be reused in an acid leaching process.
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| CN112755972A (en) * | 2020-11-19 | 2021-05-07 | 江苏海普功能材料有限公司 | Preparation of silicon-based resin and application of silicon-based resin as defluorination adsorbent |
| CN113501573A (en) * | 2021-07-08 | 2021-10-15 | 中国科学院生态环境研究中心 | Hydrogen sulfide sustained release agent under acidic solution condition and preparation method and application thereof |
| CN114835232A (en) * | 2022-05-23 | 2022-08-02 | 中国科学院生态环境研究中心 | Defluorination agent for waste acid wastewater, application and defluorination method |
| CN115837270A (en) * | 2022-11-03 | 2023-03-24 | 皇甫鑫 | Defluorination adsorbent, preparation method thereof and defluorination method of acidic wastewater |
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| CN112755972A (en) * | 2020-11-19 | 2021-05-07 | 江苏海普功能材料有限公司 | Preparation of silicon-based resin and application of silicon-based resin as defluorination adsorbent |
| CN112755972B (en) * | 2020-11-19 | 2023-06-27 | 江苏海普功能材料有限公司 | Preparation of silicon-based resin and application of silicon-based resin as defluorination adsorbent |
| CN113501573A (en) * | 2021-07-08 | 2021-10-15 | 中国科学院生态环境研究中心 | Hydrogen sulfide sustained release agent under acidic solution condition and preparation method and application thereof |
| CN113501573B (en) * | 2021-07-08 | 2022-04-19 | 中国科学院生态环境研究中心 | Hydrogen sulfide sustained release agent under acidic solution condition and preparation method and application thereof |
| CN114835232A (en) * | 2022-05-23 | 2022-08-02 | 中国科学院生态环境研究中心 | Defluorination agent for waste acid wastewater, application and defluorination method |
| CN115837270A (en) * | 2022-11-03 | 2023-03-24 | 皇甫鑫 | Defluorination adsorbent, preparation method thereof and defluorination method of acidic wastewater |
| CN115837270B (en) * | 2022-11-03 | 2024-05-10 | 皇甫鑫 | Defluorination adsorbent, preparation method thereof and method for defluorination of acidic wastewater |
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