CN113526639A - Compound fluorine removal agent and fluorine removal method for fluorine-containing wastewater - Google Patents
Compound fluorine removal agent and fluorine removal method for fluorine-containing wastewater Download PDFInfo
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- CN113526639A CN113526639A CN202110973794.XA CN202110973794A CN113526639A CN 113526639 A CN113526639 A CN 113526639A CN 202110973794 A CN202110973794 A CN 202110973794A CN 113526639 A CN113526639 A CN 113526639A
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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
- C02F1/28—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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
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- 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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Abstract
The invention provides a compound fluorine removal agent and a fluorine removal method for fluorine-containing wastewater, belonging to the technical field of wastewater fluorine removal. The compound defluorinating agent provided by the invention comprises 20-70 wt% of a trivalent metal source, 10-30 wt% of a calcium source, 10-30 wt% of a magnesium source and 10-20 wt% of a hydrogen phosphate, wherein the trivalent metal source comprises an aluminum source and/or an iron source. Under the combined action of an aluminum source and/or an iron source, a calcium source, a magnesium source and hydrogen phosphate, fluoride generated by fluoride ions in the fluorine-containing wastewater can be accelerated to rapidly grow and separate out in a form of precipitation flocs, the precipitation time of the fluoride ions is effectively shortened, and the removal rate of the fluoride ions is more than 99%. Furthermore, fluorine ion adsorption is combined for deep fluorine removal, so that the total removal rate of fluorine ions in the fluorine-containing wastewater is improved to more than 99.9%, and the fluorine removal effect is obvious; furthermore, the fluorine ion adsorption can be regenerated in a simple and low-cost manner, and the cyclic utilization of the fluorine ion adsorption can be realized.
Description
Technical Field
The invention relates to the technical field of wastewater fluorine removal, in particular to a compound fluorine removal agent and a fluorine-containing wastewater fluorine removal method.
Background
The method for treating the fluorine-containing industrial 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. The treatment methods have the advantages and the disadvantages, wherein the ion exchange method has higher cost, strict requirements on the quality of wastewater and complex regeneration operation; the electrocoagulation method and the reverse osmosis method have the disadvantages of complex devices, expensive equipment, high power consumption and high operation level requirement, so the electrocoagulation method and the reverse osmosis method are rarely adopted; the chemical precipitation method for treating the fluorine-containing wastewater has simple process and reasonable and controllable cost, 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 calcium hydroxide (Ca (OH) into wastewater2) Calcium chloride (CaCl)2) Calcium salt reacts with fluoride ions in the wastewater to generate CaF2Precipitation, however, the fluoride solubility of the fluorine-containing wastewater treated by the method is high, and the precipitation process is slow.
Disclosure of Invention
In view of the above, the present invention provides a compound fluorine removal agent and a fluorine removal method for fluorine-containing wastewater, and the compound fluorine removal agent provided by the present invention can achieve rapid fluorine removal for fluorine-containing wastewater and has a high fluorine removal rate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a compound defluorinating agent which comprises 20-70 wt% of a trivalent metal source, 10-30 wt% of a calcium source, 10-30 wt% of a magnesium source and 10-20 wt% of hydrogen phosphate;
the trivalent metal source comprises an aluminum source and/or an iron source.
Preferably, the aluminium source comprises an aluminium salt and/or an aluminium oxide;
the aluminum salt comprises at least one of aluminum sulfate, aluminum chloride, sodium metaaluminate, potassium metaaluminate, polyaluminum sulfate, aluminum nitrate, polyaluminum chloride and polyaluminum ferric chloride;
the aluminum oxide comprises a polymeric alumina.
Preferably, the iron source is an iron salt;
the ferric salt comprises at least one of ferric sulfate, ferric trichloride, polymeric ferric sulfate, ferric nitrate and polymeric ferric chloride.
Preferably, the calcium source comprises at least one of calcium salt, calcium oxide and calcium hydroxide;
the calcium salt includes at least one of calcium chloride, calcium sulfate, calcium nitrate, and calcium carbonate.
Preferably, the magnesium source comprises at least one of magnesium salt, magnesium oxide and magnesium hydroxide;
the magnesium salt includes at least one of magnesium chloride, magnesium sulfate, magnesium nitrate, and magnesium carbonate.
Preferably, the hydrogen phosphate salt comprises disodium hydrogen phosphate and/or sodium dihydrogen phosphate.
Preferably, the compound fluorine removal agent further comprises a fluorine ion adsorbent;
the fluoride ion adsorbent comprises at least one of activated carbon, bone charcoal, ion exchange resin, activated zeolite and activated hydroxyapatite.
The invention provides a fluorine removal method of fluorine-containing wastewater, which comprises the following steps: adding a compound defluorination agent into the fluorine-containing wastewater to carry out fluorine ion precipitation to obtain the defluorination wastewater;
the compound fluorine removal agent is the compound fluorine removal agent in the technical scheme.
Preferably, the mass ratio of the compound fluorine removal agent to fluorine ions in the fluorine-containing wastewater is 1-20: 1.
preferably, after the fluorine ions are precipitated, the method further comprises the step of adsorbing the fluorine ions in the fluorine-removing wastewater by using a fluorine ion adsorbent to obtain deep fluorine-removing wastewater;
the fluorine ion adsorbent is the fluorine ion adsorbent in the compound fluorine removal agent in the technical scheme.
The invention provides a compound defluorinating agent which comprises 20-70 wt% of a trivalent metal source, 10-30 wt% of a calcium source, 10-30 wt% of a magnesium source and 10-20 wt% of hydrogen phosphate; the trivalent metal source comprises an aluminum source and/or an iron source. In the invention, under the combined action of the aluminum source and/or the iron source, the calcium source, the magnesium source and the hydrogen phosphate, the fluoride generated by the fluoride ions in the fluorine-containing wastewater can be accelerated to rapidly grow and separate out in the form of precipitation flocs, the precipitation time of the fluoride ions is effectively shortened, and the removal rate of the fluoride ions is more than 99%.
Furthermore, the fluorine ion adsorbent can further remove fluorine ions in low-concentration fluorine-containing wastewater (the concentration of the fluorine ions is less than 50mg/L) to realize deep fluorine removal on the fluorine-containing wastewater, and the effluent index completely meets the requirement of national sanitary Standard for Drinking Water GB5749-2006 issued by the ministry of health; furthermore, the fluorine ion adsorption can be regenerated in a simple and low-cost manner, and the cyclic utilization of the fluorine ion adsorption can be realized.
The invention provides a fluorine removal method of fluorine-containing wastewater, which comprises the following steps: adding a compound defluorination agent into the fluorine-containing wastewater to carry out fluorine ion precipitation to obtain the defluorination wastewater; the compound fluorine removal agent is the compound fluorine removal agent in the technical scheme. According to the defluorination method provided by the invention, the fluoride generated by the fluorine ions in the fluorine-containing wastewater is accelerated to rapidly grow and separate out in a form of precipitation floc by using the compound defluorination agent, so that the precipitation time of the fluorine ions is effectively shortened, and the removal rate of the fluorine ions is more than 99%. Furthermore, fluorine ion adsorption is added for deep fluorine removal, so that the total removal rate of fluorine ions in the fluorine-containing wastewater is improved to more than 99.9%, and the fluorine removal effect is obvious. Moreover, the traditional defluorinating agent is mainly calcium-based defluorination, and the pH value of the wastewater needs to be adjusted to be alkaline or alkalescent before use; the compound defluorinating agent provided by the invention simultaneously contains a calcium source, a magnesium source, hydrogen phosphate, an aluminum source and/or an iron source, does not need to adjust the pH value of the fluorine-containing wastewater, is simple to operate, and can realize large-scale and deep defluorination of the fluorine-containing wastewater.
Detailed Description
The invention provides a compound defluorinating agent which comprises 20-70 wt% of a trivalent metal source, 10-30 wt% of a calcium source, 10-30 wt% of a magnesium source and 10-20 wt% of hydrogen phosphate; the trivalent metal source comprises an aluminum source and/or an iron source.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The complex defluorinating agent (namely the complex precipitation defluorinating agent) provided by the invention comprises 20-70 wt% of trivalent metal source, preferably 30-60 wt%, and more preferably 40-50 wt%; the trivalent metal source comprises an aluminum source and/or an iron source. In the present invention, the aluminum source preferably comprises an aluminum salt and/or an aluminum oxide; the aluminum salt preferably includes at least one of aluminum sulfate, aluminum chloride, sodium metaaluminate, potassium metaaluminate, polyaluminum sulfate, aluminum nitrate, polyaluminum chloride, and polyaluminum ferric chloride; the aluminum oxide preferably comprises a polymeric alumina. In the present invention, the iron source is preferably an iron salt; the iron salt preferably comprises at least one of ferric sulfate, ferric trichloride, polymeric ferric sulfate, ferric nitrate, and polymeric ferric chloride.
The compound defluorinating agent provided by the invention comprises 10-30 wt% of a calcium source, preferably 15-25 wt%, and more preferably 20 wt%. In the present invention, the calcium source preferably includes at least one of calcium salt, calcium oxide and calcium hydroxide; the calcium salt preferably includes at least one of calcium chloride, calcium sulfate, calcium nitrate, and calcium carbonate.
The compound fluorine removal agent provided by the invention comprises 10-30 wt% of a magnesium source, preferably 15-25 wt%, and more preferably 20 wt%. In the present invention, the magnesium source preferably includes at least one of a magnesium salt, magnesium oxide, and magnesium hydroxide; the magnesium salt preferably includes at least one of magnesium chloride, magnesium sulfate, magnesium nitrate, and magnesium carbonate.
The compound fluorine removal agent provided by the invention comprises 10-20 wt% of hydrogen phosphate, preferably 12-18 wt%, and more preferably 15 wt%. In the present invention, the hydrogen phosphate preferably includes disodium hydrogen phosphate and/or sodium dihydrogen phosphate.
In the present invention, the complex fluorine removal agent preferably further comprises a fluorine ion adsorbent; the fluoride ion adsorbent preferably comprises activated carbon, bone charcoal, ion exchange resin, activated zeolite and activated phosphorus hydroxideAt least one member selected from the group consisting of apatites. In the present invention, the ion exchange resin preferably includes a macroporous basic styrene-based anion exchange resin or a macroporous basic acrylic anion exchange resin; the macroporous basic styrene anion exchange resin comprises macroporous strong-base styrene anion exchange resin or macroporous weak-base styrene anion exchange resin; the macroporous basic acrylic acid series anion exchange resin comprises macroporous strong-base acrylic acid series anion exchange resin or macroporous weak-base acrylic acid series anion exchange resin. In the invention, the aperture of the activated carbon is preferably 30-50 nm, and more preferably 30-40 nm; the specific surface area of the activated carbon is preferably 800-1200 m2A concentration of 1000 to 1100m is more preferable2(ii)/g; the activated zeolite is preferably obtained by activating zeolite by using an activating agent, and the activating agent preferably comprises one or more of hydrochloric acid, sulfuric acid, sodium chloride and ammonium chloride; the zeolite preferably comprises one or more of clinoptilolite, mordenite, chabazite, erionite, phillipsite and analcime; the activation mode preferably comprises high-temperature roasting, acid treatment and salt-alkali treatment; the high-temperature roasting temperature is preferably 350-580 ℃, and more preferably 400-500 ℃; the acid treatment preferably comprises hydrochloric acid treatment or sulfuric acid treatment; the salt-alkali treatment preferably employs a salt comprising sodium chloride and/or ammonium chloride, and the alkali preferably comprises sodium hydroxide and/or potassium hydroxide. In the present invention, the shape of the active hydroxyapatite preferably includes a sphere, a cylinder or a powder type; the particle size of the active hydroxyapatite is preferably 200-500 nm, and more preferably 300-400 nm; the active hydroxyapatite has the advantages of low operation cost, high defluorination efficiency, high adsorption capacity, no harmful ion dissolution and the like, is suitable for defluorination requirements of different water qualities, does not need to adjust the pH value of fluorine-containing wastewater in the use process, and is simple and convenient to operate; the source of the active hydroxyapatite in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
The invention provides a fluorine removal method of fluorine-containing wastewater, which comprises the following steps: adding a compound defluorination agent into the fluorine-containing wastewater to carry out fluorine ion precipitation to obtain the defluorination wastewater; the compound fluorine removal agent is the compound fluorine removal agent in the technical scheme.
In the invention, the fluorine-containing wastewater is preferably high-fluorine wastewater, and the concentration of fluorine ions in the fluorine-containing wastewater is preferably more than 2500 mg/L; the source of the fluorine-containing wastewater is not particularly limited, and the fluorine-containing wastewater known by the person skilled in the art can be adopted; in an embodiment of the present invention, the fluorine-containing wastewater is preferably fluorine-containing wastewater generated from an element manufacturing plant or fluorine-containing wastewater generated from a metal smelting plant. In the invention, the mass ratio of the compound fluorine removal agent to fluorine ions in the fluorine-containing wastewater is preferably 1-20: 1, more preferably 2 to 10: 1, more preferably 3 to 5: 1. in the invention, the fluoride ion precipitation is preferably carried out under stirring, and the stirring time is preferably 10-150 min, preferably 30-100 min, and further preferably 40-60 min; the stirring speed in the present invention is not particularly limited, and a stirring speed known to those skilled in the art may be used. In the present invention, the fluoride ion concentration in the fluorine removal wastewater is preferably <25 mg/L.
In the invention, after the fluorine ions are precipitated, a fluorine ion adsorbent is used for adsorbing the fluorine ions in the defluorination wastewater to obtain deep defluorination wastewater; the fluorine ion adsorbent is the fluorine ion adsorbent in the compound fluorine removal agent in the technical scheme.
In the present invention, the adsorption means preferably includes static adsorption or dynamic adsorption. In the present invention, the static adsorption preferably comprises static adsorption by stirring and mixing a fluoride ion adsorbent with the defluorination wastewater. In the invention, the stirring and mixing time is preferably 10-150 min, preferably 30-100 min, and more preferably 40-60 min; the stirring and mixing speed of the present invention is not particularly limited, and a stirring and mixing speed known to those skilled in the art may be used. In the present invention, the mass of the fluoride ion adsorbent is preferably 2 to 10 times, and more preferably 3 to 5 times, the mass of the fluoride ions in the fluorine-containing wastewater. In the invention, the concentration of fluorine ions in the deep defluorination wastewater is preferably less than 1.5 mg/L.
In the present invention, after the static adsorption, the system after the static adsorption is preferably filtered to obtain a recovered fluoride ion adsorbent, and the recovered fluoride ion adsorbent is preferably regenerated to recycle the obtained regenerated fluoride ion adsorbent. In the present invention, the method of the regeneration is preferably determined according to the kind of the fluoride ion adsorbent. In the present invention, the activated carbon is preferably regenerated by high-temperature calcination; the high-temperature roasting temperature is preferably 200-450 ℃, more preferably 300-400 ℃, and further preferably 300-350 ℃; the high-temperature roasting time is preferably 60-240 min, and more preferably 90-180 min. In the invention, the bone charcoal is preferably regenerated by soaking with NaOH solution and then washing with water to be neutral; the concentration of the NaOH solution is preferably 3-15 wt%, and more preferably 5 wt%; the soaking time is preferably 1-5 hours, and more preferably 2-4 hours. In the present invention, the ion exchange resin is preferably regenerated by soaking in a NaCl solution and then washing with water to remove NaCl; the concentration of the NaCl solution is preferably 5-20 wt%, and more preferably 10 wt%; the soaking time is preferably 1-5 hours, and more preferably 2-3 hours. In the invention, the activated zeolite is preferably regenerated by soaking with a NaCl solution, then soaking with a NaCl-NaOH mixed solution, and washing with water to be neutral; the concentration of the NaCl solution is preferably 2-15 wt%, more preferably 5-10 wt%, and the soaking time of the NaCl solution is preferably 0.5-2.5 h, more preferably 1 h; the concentration of NaCl in the NaCl-NaOH mixed solution is preferably 2-15 wt%, more preferably 5 wt%, the concentration of NaOH is preferably 5-20 wt%, more preferably 10 wt%, and the soaking time of the NaCl-NaOH mixed solution is preferably 5-15 h, more preferably 10-12 h. In the invention, the regeneration mode of the active hydroxyapatite is preferably to soak the active hydroxyapatite by using NaOH solution and wash the active hydroxyapatite to be neutral; the concentration of the NaOH solution is preferably 1-10 wt%, and more preferably 5 wt%; the soaking time is preferably 5-10 hours, and more preferably 7-8 hours.
In the present invention, the dynamic adsorption preferably comprises subjecting the defluorination waste water to dynamic adsorption through an adsorption column filled with a fluoride ion adsorbent. In the present invention, the loading volume of the fluoride ion adsorbent in the adsorption column is 55% to 90%, more preferably 60% to 80% of the volume of the adsorption column. In the invention, the contact time of the unit volume of the defluorination waste water and the fluorine ion adsorption is preferably 0.5-10 min, and more preferably 5-8 min. In the invention, the concentration of fluorine ions in the deep defluorination wastewater is preferably less than 1.5 mg/L.
After the dynamic adsorption, the invention preferably takes out the fluorine ion adsorbent in the adsorption column and then regenerates the fluorine ion adsorbent, and the obtained regenerated fluorine ion adsorbent is recycled. In the present invention, the method of regenerating the fluorine ion adsorbent is preferably determined according to the kind of fluorine ion adsorption. In the invention, the regeneration mode of the activated carbon is preferably high-temperature roasting; the high-temperature roasting temperature is preferably 200-450 ℃, more preferably 300-400 ℃, and further preferably 300-350 ℃; the high-temperature roasting time is preferably 60-240 min, and more preferably 90-180 min. In the invention, the regeneration mode of the bone charcoal is preferably that NaOH solution is used for backwashing the adsorption column and then the adsorption column is washed to be neutral; the concentration of the NaOH solution is preferably 3-15 wt%, and more preferably 5 wt%; the volume of the NaOH solution is 1-5 times of the filling volume of the bone charcoal, and more preferably 3-4 times; the backwashing time is preferably 30-150 min, and more preferably 50-100 min. In the invention, the regeneration mode of the ion exchange resin is preferably to carry out backwashing on the adsorption column by using a NaCl solution; the concentration of the NaCl solution is preferably 5-20 wt%, and more preferably 10 wt%; the volume of the NaCl solution is preferably 2-8 times of the filling volume of the ion exchange resin, and more preferably 3-5 times; the backwashing time is preferably 30-150 min, and more preferably 50-100 min. In the invention, the regeneration mode of the activated zeolite is preferably to carry out backwashing on the adsorption column by using a NaCl-NaOH mixed solution; the concentration of NaCl in the NaCl-NaOH mixed solution is preferably 2-15 wt%, more preferably 5 wt%, and the concentration of NaOH is preferably 5-20 wt%, more preferably 10 wt%; the volume of the NaCl-NaOH mixed solution is preferably 1-8 times of the filling volume of the activated zeolite, and more preferably 3-5 times; the backwashing time is preferably 30-150 min, and more preferably 50-100 min. In the invention, the regeneration mode of the active hydroxyapatite is preferably to back wash the adsorption column by using NaOH solution; the concentration of the NaOH solution is preferably 5-10 wt%, and more preferably 7-8 wt%; the volume of the NaOH solution is preferably 1-10 times of the filling volume of the zeolite; the backwashing time is preferably 30-150 min, and more preferably 50-100 min.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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
The fluorine-containing wastewater generated in a certain electronic element production workshop has fluorine ion concentration of 3125mg/L, and for entering a sewage treatment plant for biochemical treatment, the fluorine ion concentration needs to be less than 6.0 mg/L.
(1) A primary fluorine removal stage: adding a compound precipitation defluorinating agent into the fluorine-containing wastewater, stirring for 60min, and filtering to remove the precipitate to obtain defluorinating wastewater; wherein the compound precipitation defluorinating agent is a trivalent metallic iron source (FeCl)3·6H2O)35 wt%, calcium source (CaCl)2)35 wt% magnesium source (MgCl)2)15 wt% and hydrogen phosphate (Na)2HPO4)15 wt%, the mass ratio of the compound precipitation fluorine removal agent to fluorine ions in the fluorine-containing wastewater is 5:1, the concentration of the fluorine ions in the fluorine-containing wastewater is 24.3mg/L, and the removal rate of the fluorine ions is 99.22%;
(2) and (3) deep fluorine removal stage: adding active hydroxyapatite into the defluorination wastewater, stirring for 30min, filtering and recovering the hydroxyapatite to obtain deep defluorination wastewater; the mass of the hydroxyapatite is 0.5 percent of the mass of the defluorination wastewater, the concentration of the fluorinion in the deep defluorination wastewater is 1.1mg/L, the removal rate of the fluorinion is 95.47 percent, and the requirement of biochemical treatment of a sewage treatment plant on the concentration of the fluorinion is met.
(3) Regeneration of hydroxyapatite adsorbent: soaking the hydroxyapatite in 2.5 wt% NaOH solution for 5.5h, and washing the hydroxyapatite until the hydroxyapatite is neutral to obtain a regenerated hydroxyapatite adsorbent;
and (3) deeply removing fluorine from the fluorine-removing wastewater by using the regenerated hydroxyapatite adsorbent according to the method in the step (2), wherein the removal rate of the fluorine ions in the deep fluorine removal stage is 94.91%.
Example 2
The fluorine-containing wastewater generated by a certain metal smelting plant has the fluorine ion concentration of 2736mg/L, and is recycled after fluorine removal, and the fluorine ion concentration is required to be less than 4.5 mg/L.
(1) A primary fluorine removal stage: adding a compound precipitation defluorinating agent into the fluorine-containing wastewater, stirring for 45min, and filtering to remove the precipitate to obtain defluorinating wastewater; wherein the compound precipitation defluorinating agent is a trivalent metal aluminum source (AlCl)3)30 wt% of calcium source (CaCl)2)20 wt% magnesium source (MgCl)2)35 wt% and hydrogen phosphate (NaH)2PO4), the mass ratio of the compound precipitation fluorine removal agent to the fluorine ions in the fluorine-containing wastewater is 3.5:1, the concentration of the fluorine ions in the fluorine-containing wastewater is 26.7mg/L, and the removal rate of the fluorine ions is 99.02 percent;
(2) and (3) deep fluorine removal stage: filling weak-base styrene anion exchange resin (320 type) as dynamic adsorption filler into an adsorption column, and performing dynamic adsorption on the defluorination wastewater through the adsorption column to obtain deep defluorination wastewater; wherein the filling volume of the styrene-based alkaline anion exchange resin is 70 percent of the volume of the adsorption column, the contact time of the defluorination wastewater and the adsorbent in the adsorption column is 3.5min, the concentration of the fluorine ions in the deep defluorination wastewater is 2.4mg/L, the removal rate of the fluorine ions is 91.01 percent, and the requirement of wastewater reuse on the concentration of the fluorine ions is met.
(3) Ion exchange resin regeneration: carrying out backwashing on a NaCl solution with the concentration of 10 wt%, wherein the volume of the NaCl solution is 2-8 times of the filling volume of the ion exchange resin, and the backwashing time is 30min, so as to obtain the regenerated styrene-based alkaline anion exchange resin adsorbent;
and (3) deeply removing fluorine from the fluorine-removing wastewater by using the regenerated styrene-based alkaline anion exchange resin adsorbent according to the method in the step (2), wherein the average removal rate of fluorine ions in the deep fluorine removal stage is 90.92%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The compound defluorinating agent is characterized by comprising 20-70 wt% of a trivalent metal source, 10-30 wt% of a calcium source, 10-30 wt% of a magnesium source and 10-20 wt% of hydrogen phosphate;
the trivalent metal source comprises an aluminum source and/or an iron source.
2. The compound fluorine removal agent of claim 1, wherein the aluminum source comprises an aluminum salt and/or an aluminum oxide;
the aluminum salt comprises at least one of aluminum sulfate, aluminum chloride, sodium metaaluminate, potassium metaaluminate, polyaluminum sulfate, aluminum nitrate, polyaluminum chloride and polyaluminum ferric chloride;
the aluminum oxide comprises a polymeric alumina.
3. The compound defluorinating agent as set forth in claim 1, wherein the iron source is an iron salt;
the ferric salt comprises at least one of ferric sulfate, ferric trichloride, polymeric ferric sulfate, ferric nitrate and polymeric ferric chloride.
4. The built-up defluorinating agent of claim 1, wherein the calcium source comprises at least one of a calcium salt, calcium oxide, and calcium hydroxide;
the calcium salt includes at least one of calcium chloride, calcium sulfate, calcium nitrate, and calcium carbonate.
5. The built-up defluorinating agent of claim 1, wherein the magnesium source comprises at least one of magnesium salts, magnesium oxide, and magnesium hydroxide;
the magnesium salt includes at least one of magnesium chloride, magnesium sulfate, magnesium nitrate, and magnesium carbonate.
6. The built-up defluorinating agent of claim 1, wherein the hydrogen phosphate salt comprises disodium hydrogen phosphate and/or sodium dihydrogen phosphate.
7. The compound fluorine removal agent according to any one of claims 1 to 6, further comprising a fluorine ion adsorbent;
the fluoride ion adsorbent comprises at least one of activated carbon, bone charcoal, ion exchange resin, activated zeolite and activated hydroxyapatite.
8. A fluorine removal method for fluorine-containing wastewater is characterized by comprising the following steps: adding a compound defluorination agent into the fluorine-containing wastewater to carry out fluorine ion precipitation to obtain the defluorination wastewater;
the compound fluorine removal agent is the compound fluorine removal agent as defined in any one of claims 1 to 6.
9. The method for removing fluorine according to claim 8, wherein the mass ratio of the compound fluorine removal agent to the fluorine ions in the fluorine-containing wastewater is 1-20: 1.
10. the method for removing fluorine according to claim 8 or 9, wherein after the fluorine ion precipitation, further comprising adsorbing fluorine ions in the fluorine removal wastewater by using a fluorine ion adsorbent to obtain deep fluorine removal wastewater;
the fluoride ion adsorbent is the fluoride ion adsorbent in the compound fluorine removal agent of claim 7.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772762A (en) * | 2021-10-26 | 2021-12-10 | 中煤科工集团杭州研究院有限公司 | Aluminum-based compound defluorinating agent and preparation method thereof |
| CN114605018A (en) * | 2022-02-04 | 2022-06-10 | 重庆大学 | Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recycling salt |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113772762A (en) * | 2021-10-26 | 2021-12-10 | 中煤科工集团杭州研究院有限公司 | Aluminum-based compound defluorinating agent and preparation method thereof |
| CN113772762B (en) * | 2021-10-26 | 2023-02-21 | 中煤科工集团杭州研究院有限公司 | Aluminum-based compound defluorinating agent and preparation method thereof |
| CN116354368A (en) * | 2021-12-28 | 2023-06-30 | 江苏国泰超威新材料有限公司 | Fluorine removal purification method of fluorine-containing salt |
| CN114605018A (en) * | 2022-02-04 | 2022-06-10 | 重庆大学 | Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recycling salt |
| CN114605018B (en) * | 2022-02-04 | 2024-02-02 | 重庆大学 | Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt |
| CN115893535A (en) * | 2022-08-08 | 2023-04-04 | 广西博世科环保科技股份有限公司 | Efficient fluorine removal agent applied to waste lithium battery recovery and synthesis method thereof |
| CN116177702A (en) * | 2022-12-28 | 2023-05-30 | 明金阳 | Medicament suitable for fluorine-containing wastewater treatment in semiconductor industry |
| CN116640342A (en) * | 2023-05-05 | 2023-08-25 | 宁波聚久全塑料制品有限公司 | PP, PE composite material with low oil permeability and preparation method and application thereof |
| CN116640342B (en) * | 2023-05-05 | 2024-03-26 | 宁波聚久全塑料制品有限公司 | PP, PE composite material with low oil permeability and preparation method and application thereof |
| CN117699938A (en) * | 2023-12-15 | 2024-03-15 | 苏州苏沃特环境科技股份有限公司 | Low-concentration fluorine-containing wastewater inorganic composite defluorination medicament and application thereof |
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