CN111498960A - Defluorination medicament and application thereof - Google Patents
Defluorination medicament and application thereof Download PDFInfo
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- CN111498960A CN111498960A CN202010261374.4A CN202010261374A CN111498960A CN 111498960 A CN111498960 A CN 111498960A CN 202010261374 A CN202010261374 A CN 202010261374A CN 111498960 A CN111498960 A CN 111498960A
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- fluorine
- defluorination
- containing wastewater
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- removing agent
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular 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
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a defluorination medicament, which comprises the following components in percentage by weight: 30-40% of desulfurized sludge, 10-20% of ferrous sulfate heptahydrate, 10-20% of polymeric ferric sulfate, 3-5% of coagulant aid, 10-30% of lanthanum chloride and 5-15% of lanthanum nitrate. When in use, the defluorination agent is dissolved in deionized water to prepare a defluorination agent solution, and the defluorination agent solution prepared in the step S1 is added into the fluorine-containing wastewater. When the fluorine-containing wastewater is treated, the method has the advantages of high fluorine removal speed and good fluorine removal effect, and is suitable for industrial wastewater.
Description
Technical Field
The invention relates to the technical field of fluorine removal agents, in particular to a fluorine removal agent and application thereof.
Background
In addition, the quality standard of IV and V types of surface water bodies requires that the fluoride standard is less than or equal to 1.5 mg/L, and steel enterprises which force the wastewater to be discharged into surface water bodies further control the discharge concentration of the wastewater fluoride.
The prior method for treating the fluorine-containing wastewater mainly comprises an adsorption method, an electrocoagulation method, a reverse osmosis method, an ion exchange method, a chemical precipitation method, a coagulation sedimentation method and the like. Each of these treatments has its advantages and disadvantages, ion exchange is generally more expensive, and removal of fluoride from the regenerated desorption solution is still required to concentrate it. The reverse osmosis method has complex device and high requirement on the quality of inlet water, and calcium fluoride is easy to block a membrane component of the membrane. The electrocoagulation method is easy to generate polarization, has large power consumption, generates competition in a solution system, has very high requirements on the quality of a polar plate and has few adopted materials. The chemical precipitation method for treating the fluorine-containing wastewater has the advantages of simple process operation, less equipment investment and stable fluorine removal effect, and is the most widely applied method for treating the fluorine-containing wastewater at present.
The traditional calcium salt precipitation method mainly comprises the steps of adding calcium oxide (CaO) and carbide slag (Ca (OH) into waste water2) Calcium chloride (CaCl)2) Iso-calcium salt, reacting with fluoride ion in waste water to generate CaF2And (4) precipitating. However, CaO or Ca (OH) alone is used2Treating the fluorine-containing wastewater to generate CaF2The precipitate is very fine and difficult to settle, and fine precipitate particles can be adsorbed on Ca (OH)2On the surface of the particles, the utilization efficiency of calcium salt is low, the solubility is increased because the precipitation process is very slow due to fine precipitation, the concentration of residual fluoride in water is high, and the concentration of fluoride ions can only be reduced to about 15 mg/L and cannot reach the national emission standard of 10 mg/L.
Aluminum salt is added into the defluorinating agent of a patent product, and mainly forms a ligand with fluoride, so that the fluoride disappears temporarily during detection, and the fluoride in the wastewater is not reduced actually. In addition, excessive aluminum salt is needed to control drinking water, and the aluminum salt in the water has high probability of easily causing senile dementia.
The traditional advanced treatment methods comprise an alumina adsorption method, an aluminum-loaded ion resin exchange method, a reverse osmosis method and the like, but the investment cost and the operation cost are generally high, the requirements on the quality of inlet water are strict, the regeneration, the backwashing and the like are frequent and complicated, and the method is only suitable for drinking water and is not suitable for industrial wastewater. Therefore, research and development of a novel deep fluorine removal agent for improving the removal effect of the fluorine ions in the wastewater to meet the increasingly strict emission standards are urgently needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a fluorine removal medicament and application thereof, and the fluorine removal medicament has the advantages of high fluorine removal speed and good fluorine removal effect when used for treating fluorine-containing wastewater, and is suitable for industrial wastewater.
The technical purpose of the invention is realized by the following technical scheme: a defluorination medicament comprises the following components in percentage by weight: 30-40% of desulfurized sludge, 10-20% of ferrous sulfate heptahydrate, 10-20% of polymeric ferric sulfate, 3-5% of coagulant aid, 10-30% of lanthanum chloride and 5-15% of lanthanum nitrate.
In one embodiment, the desulfurized sludge contains 50% of water, 10% of calcium salt and 40% of magnesium salt.
In one embodiment, the defluorinating agent is prepared by uniformly mixing the components.
The invention also includes the application of a defluorination agent, which comprises:
s1: dissolving the defluorination agent in deionized water to prepare defluorination agent solution with the mass fraction of 10 wt%;
s2, adjusting the pH of the fluorine-containing wastewater to 7-9 by using alkali liquor, adding the defluorinating agent solution prepared in the step S1 into the fluorine-containing wastewater, wherein 2mg of the defluorinating agent solution is added into 1L of the fluorine-containing wastewater, stirring for 2 minutes, adding 3 drops of polyacrylamide, continuing stirring for 1 minute, standing and settling for 5 minutes, and taking the supernatant to measure the fluoride content.
In one embodiment, the molecular weight of the polyacrylamide in step S2 is 1800 ten thousand.
In one embodiment, the fluorine ion concentration of the fluorine-containing wastewater in the step S2 is less than or equal to 50 mg/L.
In one embodiment, the supernatant in step S2 is measured for fluoride ion concentration by using a spectrophotometer, and the fluoride ion concentration is measured by ion selective electrode method (GB/T7484-1987) with pHSJ-3F as an instrument.
In conclusion, the invention has the following beneficial effects:
1. the invention obtains the defluorinating agent by selecting proper components and optimizing the proportion of the components, when the defluorinating agent is used for treating low-concentration fluorine-containing wastewater (less than or equal to 50 mg/L), the defluorinating agent can ensure that the removal rate of fluorine ions reaches more than 90 percent after stirring reaction for 5min, and has high defluorinating speed and good defluorinating effect.
2. The desulfurized sludge (industrial solid waste and sintered flue gas wet-process desulfurized sludge) in the defluorination agent is mainly subjected to primary precipitation by using calcium salt in the sludge, the magnesium salt in the sludge is used for adsorption, and the ferric salt (polymeric ferric sulfate and ferrous iron) plays a role in adsorption and flocculation, so that the floc structure is changed, the density of the floc is improved, the pH range of floc sedimentation is increased, better sedimentation efficiency is obtained, and the method is equivalent to the treatment of waste by waste.
3. The lanthanum salt in the defluorination medicament can be used as a generated lanthanum fluoride crystal to provide a carrier for the formation of other calcium fluoride precipitates of fluoride, so that fluorine ions in a water body are induced to be combined with other components (ferric salt) to form precipitate flocs to be separated out, the precipitate flocs are promoted to grow, the rapid generation and sedimentation of fluorine-containing precipitates are facilitated, and the removal rate and the removal effect of the fluorine ions are improved.
4. The existence of the coagulant aid activated silicic acid in the defluorination medicament can eliminate the electrostatic repulsion among all flocculation components, is beneficial to enlarging fine and loose floccules formed in a water body so as to quickly settle, and improves the removal efficiency of fluorinion.
5. The method takes the desulfurized sludge as a raw material, and takes the coking wastewater with the fluoride content of 40 mg/L test or the turbid circulating water of a converter in a steel mill as the basis, the fluoride content after primary treatment is less than 5 mg/L, the treatment cost per ton of water is 4 yuan, the fluoride content after secondary chemical treatment is less than 2 mg/L, and the treatment cost per ton of water is 5 yuan.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
It should be noted that all the directional terms such as "upper" and "lower" referred to herein are used with respect to the view of the drawings, and are only for convenience of description, and should not be construed as limiting the technical solution.
Example 1:
the defluorination medicament consists of the following components in percentage by mass: 40% of desulfurized sludge, 20% of ferrous sulfate heptahydrate, 10% of polymeric ferric sulfate, 3% of activated silicic acid, 15% of lanthanum chloride and 12% of lanthanum nitrate.
Uniformly mixing the components (the desulfurized sludge is the solid waste of a steel mill, and the rest are commercial products) according to the formula ratio to prepare the efficient defluorination medicament;
referring to fig. 1, phenol-cyanogen wastewater is taken from a steel mill as fluorine-containing wastewater to be treated, wherein the pH of the fluorine-containing wastewater to be treated is 7.80, the concentration of fluorine ions is 36 mg/L, and the prepared fluorine-containing wastewater is treated by using a prepared fluorine-removing agent SGDF1 to examine the fluorine-removing effect of the fluorine-removing agent, and the specific steps are as follows:
(1) dissolving 1mg of prepared defluorination agent in deionized water to prepare a solution with the mass fraction of 10 wt%; preparing 3 parts of the solution;
(2) adding 1L fluorine-containing wastewater to be treated into 3 beakers, adjusting the pH of a water body to 6-9 by using slaked lime milk, then adding 1.8, 2.0 and 2.2 parts of the solution prepared in the step (1) into each of the 3 beakers, stirring for reaction for 5min, adding 3 drops of PAM solution, standing and settling for 5min, taking a supernatant, and detecting the concentration of fluorine ions by using a spectrophotometer, wherein the detection method of the concentration of the fluorine ions refers to an ion selective electrode method (GB/T7484-1987), the instrument is pHSJ-3F, and the results of the content of the fluoride are 3.27 mg/L, 3.14 mg/L and 2.79 mg/L.
Example 2:
the defluorination medicament consists of the following components in percentage by mass: 40% of desulfurized sludge, 20% of ferrous sulfate heptahydrate, 10% of polymeric ferric sulfate, 3% of activated silicic acid, 20% of lanthanum chloride and 7% of lanthanum nitrate.
Uniformly mixing all the components (all commercial products) in the formula amount to prepare a defluorination medicament;
continuous casting turbid circulating water is taken from a certain steel mill as fluorine-containing wastewater to be treated, wherein the pH value of the fluorine-containing wastewater to be treated is 7.90, the concentration of fluorine ions is 45 mg/L, the fluorine-containing wastewater to be treated is treated by adopting the prepared defluorination medicament SGDF1 so as to investigate the defluorination effect of the defluorination medicament, and the specific steps are as follows:
(1) dissolving 1mg of prepared defluorination agent in deionized water to prepare a solution with the mass fraction of 10 wt%; preparing 1 part of the solution;
(2) adding 1L fluorine-containing wastewater to be treated into 3 beakers, adjusting the pH of a water body to 6-9 by using slaked lime milk, then adding 2.0, 2.2 and 2.4 parts of the solution prepared in the step (1) into each of the 3 beakers, stirring for reaction for 5min, adding 3 drops of PAM solution, standing and settling for 5min, taking a supernatant, and detecting the concentration of fluorine ions by using a spectrophotometer, wherein the detection method of the concentration of the fluorine ions refers to an ion selective electrode method (GB/T7484-1987), the instrument is pHSJ-3F, and the results of the content of fluoride are 3.86 mg/L, 3.71 mg/L and 3.42 mg/L respectively.
(3) And (3) adjusting the pH value of the water body to 6.5-7 by using slaked lime milk after the sample in the step (2) is re-stirred, then adding 0.5, 0.6 and 0.7 part of the solution prepared in the step (1) into 3 beakers respectively, stirring and reacting for 5min, adding 3 drops of PAM solution, standing and settling for 5min, taking the supernatant, and detecting the concentration of fluorine ions by using a spectrophotometer according to an ion selective electrode method (GB/T7484-1987), wherein the instrument is pHSJ-3F, and the results of the fluoride content are 1.96 mg/L, 1.36 mg/L and 1.32 mg/L respectively.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. The defluorination medicament is characterized by comprising the following components in percentage by weight: 30-40% of desulfurized sludge, 10-20% of ferrous sulfate heptahydrate, 10-20% of polymeric ferric sulfate, 3-5% of coagulant aid, 10-30% of lanthanum chloride and 5-15% of lanthanum nitrate.
2. The defluorination agent according to claim 1, wherein said desulfurized sludge has a water content of 50%, a calcium salt content of 10% and a magnesium salt content of 40%.
3. The fluorine-removing agent according to claim 1, wherein the fluorine-removing agent is prepared by uniformly mixing the components.
4. Use of a fluorine-removing agent according to claim 1, comprising:
s1: dissolving the defluorination agent in deionized water to prepare defluorination agent solution with the mass fraction of 10 wt%;
s2, adjusting the pH of the fluorine-containing wastewater to 7-9 by using alkali liquor, adding the defluorinating agent solution prepared in the step S1 into the fluorine-containing wastewater, wherein 2mg of the defluorinating agent solution is added into 1L of the fluorine-containing wastewater, stirring for 2 minutes, adding 3 drops of polyacrylamide, continuing stirring for 1 minute, standing and settling for 5 minutes, and taking the supernatant to measure the fluoride content.
5. The use of the fluorine-removing agent according to claim 4, wherein the molecular weight of the polyacrylamide in the step S2 is 1800 ten thousand.
6. The use of the fluorine-removing agent as set forth in claim 4, wherein the fluorine ion concentration of the fluorine-containing wastewater in the step S2 is less than or equal to 50 mg/L.
7. The use of a fluorine-removing agent as claimed in claim 4, wherein the supernatant in step S2 is subjected to a spectrophotometric measurement of the fluoride ion concentration according to ion selective electrode method (GB/T7484-1987) with pHSJ-3F.
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| CN202010261374.4A CN111498960A (en) | 2020-04-03 | 2020-04-03 | Defluorination medicament and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057331A (en) * | 2021-11-08 | 2022-02-18 | 上海天汉环境资源有限公司 | Method and treatment system for removing fluorine pollution in incineration waste gas washing water |
| CN114853109A (en) * | 2022-07-07 | 2022-08-05 | 湖南大学 | Deep defluorination medicament and preparation method and use method thereof |
| CN115745115A (en) * | 2022-10-31 | 2023-03-07 | 深圳信息职业技术学院 | Polymeric lanthanum silicate flocculant, and preparation method and application thereof |
| CN115745113A (en) * | 2023-01-05 | 2023-03-07 | 河北协同水处理技术有限公司 | Coking wastewater defluorinating agent and application thereof |
| CN115872507A (en) * | 2022-12-28 | 2023-03-31 | 广州沃索环境科技有限公司 | Fluorine removal agent for wastewater of pop can and preparation method and use method thereof |
| CN116534963A (en) * | 2023-01-13 | 2023-08-04 | 兰州华星高科技开发有限公司 | Fluorine removing agent for acidic high-fluorine wastewater and use method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057331A (en) * | 2021-11-08 | 2022-02-18 | 上海天汉环境资源有限公司 | Method and treatment system for removing fluorine pollution in incineration waste gas washing water |
| CN114057331B (en) * | 2021-11-08 | 2023-10-03 | 上海天汉环境资源有限公司 | Method and treatment system for removing fluorine pollution in incineration waste gas washing water |
| CN114853109A (en) * | 2022-07-07 | 2022-08-05 | 湖南大学 | Deep defluorination medicament and preparation method and use method thereof |
| CN115745115A (en) * | 2022-10-31 | 2023-03-07 | 深圳信息职业技术学院 | Polymeric lanthanum silicate flocculant, and preparation method and application thereof |
| CN115872507A (en) * | 2022-12-28 | 2023-03-31 | 广州沃索环境科技有限公司 | Fluorine removal agent for wastewater of pop can and preparation method and use method thereof |
| CN115745113A (en) * | 2023-01-05 | 2023-03-07 | 河北协同水处理技术有限公司 | Coking wastewater defluorinating agent and application thereof |
| CN115745113B (en) * | 2023-01-05 | 2023-04-07 | 河北协同水处理技术有限公司 | Coking wastewater defluorinating agent and application thereof |
| CN116534963A (en) * | 2023-01-13 | 2023-08-04 | 兰州华星高科技开发有限公司 | Fluorine removing agent for acidic high-fluorine wastewater and use method thereof |
| CN116534963B (en) * | 2023-01-13 | 2024-04-09 | 兰州华星高科技开发有限公司 | Fluorine removing agent for acidic high-fluorine wastewater and use method thereof |
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