CN113213607B - Multi-effect defluorination medicament and preparation method and application thereof - Google Patents
Multi-effect defluorination medicament and preparation method and application thereof Download PDFInfo
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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
- C02F1/52—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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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Abstract
The invention relates to the technical field of fluorine-containing wastewater treatment, in particular to a multi-effect fluorine removal medicament and a preparation method and application thereof. The multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 3-10 parts of polymeric aluminum ferric salt and Al 2 O 3 8 to 15 portions of oxidant, 2 to 10 portions of acetate, 3 to 6 portions of dimethyl diallyl ammonium chloride, 0.5 to 1.5 portions of iminodiacetic acid, 1 to 3 portions of iminodiacetic acid and 2 to 3 portions of aluminum chlorohydroxide. The defluorination medicament can ensure that the concentration of fluorine ions in the treated water is less than or equal to 1.0mg, can meet the requirement of surface water III specified in GB3838-2002 surface water environmental quality standard, has the functions of defluorination, denitrification, dephosphorization and COD removal, has stable removal effect, can realize higher removal rate under lower addition amount, has less addition amount, generates less sludge in the treatment process, is easier to treat the sludge and has low comprehensive cost.
Description
Technical Field
The invention relates to the technical field of fluorine-containing wastewater treatment, in particular to a multi-effect fluorine removal medicament and a preparation method and application thereof.
Background
Fluorine is one of essential trace elements for human body, the trace fluorine has the functions of promoting the growth and development of children and preventing decayed teeth, and the daily fluoride intake of an adult is generally 1.0-1.5 mg/L. Scientific research finds that fluorine has strong affinity to calcium and phosphorus in human body, can destroy normal metabolism of calcium and phosphorus in the body, and can inhibit the activity of certain enzymes, thereby triggering a series of actions including: dental fluorosis, kidney, liver and brain damage, immunologic dysfunction, pulmonary edema, pulmonary hemorrhage, children intelligence decline, etc. Thus, excessive intake can be a health hazard. The emission limit of the fluorine ion concentration is 1.0mg/L as specified in GB 5749-2006 sanitary Standard for Drinking Water. In GB8978-2002 Integrated wastewater discharge Standard, the concentration of fluoride ions in the primary discharge standard is 10mg/L, and the special discharge limit value in the pollutant discharge standards of the other battery industries, inorganic chemical industries, aluminum industries and copper nickel cobalt industries is required to be lower than 2mg/L. And GB3838-2002 'surface water environment quality standard' stipulates that the maximum allowable content of fluorine ions in surface water I, surface water II and surface water III is 1.0mg/L, and the maximum allowable content of fluoride in surface IV and V water is 1.5mg/L.
At present, the treatment method of the fluorine-containing wastewater mainly comprises an adsorption method and a precipitation method. The adsorption method is generally carried out by loading an adsorbent into a packed column and adopting a dynamic adsorption mode, and common adsorbents for removing fluorine mainly comprise activated alumina, bone charcoal, zeolite, bentonite, activated carbon, hydroxyapatite and the like. However, the adsorption method has a problem that the adsorbent is difficult to regenerate at a treatment capacity. The precipitation method mainly comprises a chemical precipitation method and a coagulating precipitation method, wherein the chemical precipitation method mainly utilizes calcium fluoride precipitation generated by calcium ions and negative ions in lime or carbide slag to remove fluorine ions, and the coagulating precipitation method utilizes a coagulant to form positively charged colloidal particles in water to adsorb the fluorine ions in the water, so that the colloidal particles form flocculent precipitates, and the aim of removing fluorine is fulfilled. The chemical precipitation method has the advantages of convenient treatment, low cost and the like, but has the defects of huge equipment, difficult standard reaching of treated effluent, slow sediment sedimentation, difficult dehydration and the like. The existing coagulating sedimentation method adopts a single coagulant, and has the problems of large adding amount, high sludge yield and the like. Moreover, the existing coagulation sedimentation method can less meet the requirement of the surface water environmental quality standard.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a multi-effect defluorination medicament which can enable the discharged wastewater to meet the requirements of surface water III.
The second purpose of the invention is to provide a preparation method of the multi-effect defluorinating medicament, which has simple operation and mild conditions.
The third purpose of the invention is to provide the application of the multi-effect fluorine removal agent in the treatment of the fluorine-containing wastewater.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the multi-effect defluorination medicament comprises the following components in parts by weight:
polyaluminium salts with Al 2 O 3 3-10 parts of polymeric aluminum ferric salt as Al 2 O 3 8 to 15 portions of oxidant, 2 to 10 portions of acetate, 3 to 6 portions of dimethyl diallyl ammonium chloride, 0.5 to 1.5 portions of iminodiacetic acid, 1 to 3 portions of iminodiacetic acid and 2 to 3 portions of aluminum chlorohydroxide.
In a specific embodiment of the invention, the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4-10 parts of polymeric aluminum ferric salt and Al 2 O 3 9 to 14 portions, 3 to 10 portions of oxidant, 3.4 to 6 portions of acetate, 0.8 to 1.2 portions of poly dimethyl diallyl ammonium chloride, 1.5 to 2.5 portions of iminodiacetic acid and 2.2 to 2.6 portions of aluminum chlorohydroxide.
In a specific embodiment of the invention, the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 Calculated by 3.8 to 4.2 portions, polymeric aluminum ferric salt and Al 2 O 3 8.8 to 9.2 portions of oxidant, 2.8 to 3.2 portions of acetate, 3.4 to 3.6 portions of poly dimethyl diallyl ammonium chloride, 0.8 to 1.0 portion of iminodiacetic acid, 1.8 to 2.2 portions of iminodiacetic acid and 2.2 to 2.5 portions of aluminum chlorohydroxide; or the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.2 to 8.6 portions of polymeric aluminum ferric salt and Al 2 O 3 11 to 14 portions, 9.5 to 10 portions of oxidant, 5.5 to 6 portions of acetate, 0.8 to 1.0 portion of poly dimethyl diallyl ammonium chloride, 1.8 to 2.2 portions of iminodiacetic acid and 2.2 to 2.5 portions of aluminum chlorohydroxide.
In a particular embodiment of the invention, the polyaluminium salt comprises any one or more of polyaluminium chloride, polyaluminium sulphate and polyaluminium silicate.
In a particular embodiment of the invention, the polyaluminium iron salt comprises any one or more of polyaluminium iron chloride, polyaluminium iron sulfate and polyaluminium iron silicate.
In a particular embodiment of the invention, the oxidizing agent comprises either or both of potassium ferrate and potassium permanganate.
In a particular embodiment of the invention, the acetate salt comprises any one or more of sodium acetate, potassium acetate, aluminum acetate, calcium acetate and magnesium acetate.
In a specific embodiment of the invention, the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4 portions of polymeric aluminum ferric salt calculated as Al 2 O 3 9 portions, 3 portions of oxidant, 3.48 to 3.6 portions of acetate, 0.9 portion of polydimethyldiallylammonium chloride, 1.8 portions of iminodiacetic acid and 2.3 to 2.4 portions of aluminum chlorohydroxide.
In a specific embodiment of the invention, the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.4 parts of polymeric aluminum ferric salt calculated as Al 2 O 3 13.8 parts, 9.8 parts of an oxidant, 5.9-6 parts of acetate, 0.9 part of polydimethyldiallylammonium chloride, 1.8 parts of iminodiacetic acid and 2.3-2.4 parts of aluminum chlorohydrol.
In a specific embodiment of the invention, the multi-effect defluorinating agent is a liquid agent.
In a specific embodiment of the present invention, in the liquid medicine, the polyaluminium salt is Al 2 O 3 The calculated mass fraction is 2-10%.
The invention also provides a preparation method of the multi-effect defluorination medicament, which comprises the following steps:
mixing the components in proportion.
In a specific embodiment of the invention, after mixing the components in a ratio, water is added to obtain a liquid medicament.
In another embodiment of the present invention, the preparation method comprises the steps of:
uniformly mixing polymeric aluminum ferric salt and aqueous solution containing polymeric aluminum salt, adding an oxidant, aluminum chlorohydrate, polydimethyldiallyl ammonium chloride, iminodiacetic acid and acetate, and uniformly mixing. Further, the oxidant, the aluminum chlorohydrol, the poly dimethyl diallyl ammonium chloride, the iminodiacetic acid and the acetate are sequentially added.
In actual practice, the polyaluminium salt may be prepared in advance as a solution, or a liquid polyaluminium salt may be purchased and used as it is.
In a specific embodiment of the present invention, the preparation method comprises the steps of:
mixing polymeric aluminum ferric salt and aqueous solution containing polymeric aluminum salt, and stirring at the rotating speed of 200 +/-50 r/min for 2-5 min; then adding an oxidant, and stirring for 5-10 min at the rotating speed of 250 +/-20 r/min; then adding aluminum chlorohydrate, and stirring at the rotating speed of 200 +/-50 r/min for 4-5 min; then adding poly dimethyl diallyl ammonium chloride, and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min; adding iminodiacetic acid, and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min; then adding acetate, and stirring at the rotating speed of 300 +/-50 r/min for 5-10 min.
In a specific embodiment of the present invention, the method further comprises: detecting the pH value of the mixed system; if the pH is between 3 and 5, the rest of the operations are not carried out, and if the pH is not between 3 and 5, the pH is adjusted to between 3 and 5. In the actual operation, a proper amount of conventional acid-base regulation is adopted.
In actual operation, polymeric aluminum ferric salt, oxidant, aluminum chlorohydroxide, poly dimethyl diallyl ammonium chloride, iminodiacetic acid and acetate can be added in respective pure forms, can also be prepared into corresponding aqueous solution forms, can also be directly purchased corresponding solution and added according to the calculation of a compounding ratio.
The invention also provides application of the multi-effect defluorination medicament in treating the wastewater containing fluorine.
In a specific embodiment of the present invention, the multi-effect defluorinating agent is used in a biochemical treatment unit of a sewage treatment plant.
In a specific embodiment of the invention, the adding point of the multi-effect fluorine removal agent is the front end of the biochemical treatment unit.
In a specific embodiment of the invention, the multi-effect fluorine removal agent is added in an amount of 100-2000 ppm, preferably 400-600 ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The defluorination medicament has good defluorination effect, can ensure that the concentration of fluorine ions in the treated water is less than or equal to 1.0mg and is lower than the primary discharge standard specified in GB8978-2002 'comprehensive wastewater discharge standard', and can meet the requirements of surface water III specified in GB3838-2002 'surface water environmental quality standard'; the defluorination agent has the functions of defluorination, denitrification, dephosphorization and COD removal, has stable defluorination effect, can realize higher removal rate under lower dosage, has less dosage, generates less sludge in the treatment process, is easy to treat the sludge and has low comprehensive cost;
(2) The defluorination medicament can be widely applied to the treatment of the fluorine-containing wastewater of the municipal sewage treatment plant, and solves the problem that the fluorine of the current sewage treatment plant exceeds the standard on the basis of the prior treatment process;
(3) The defluorination medicament has a pH buffering effect, can stabilize the pH of a water body in the using process, and cannot cause the pH of the water body to be greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a treatment process and an addition site of a sewage treatment plant according to Experimental example 1 of the present invention;
FIG. 2 is a process flow diagram and dosing sites of a sewage treatment plant according to Experimental example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present 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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The multi-effect defluorinating medicament comprises the following components in parts by weight:
polyaluminium salts with Al 2 O 3 3-10 parts of polymeric aluminum ferric salt and Al 2 O 3 8 to 15 portions of oxidant, 2 to 10 portions of acetate, 3 to 6 portions of dimethyl diallyl ammonium chloride, 0.5 to 1.5 portions of iminodiacetic acid, 1 to 3 portions of iminodiacetic acid and 2 to 3 portions of aluminum chlorohydroxide.
The defluorination agent provided by the invention can efficiently remove fluoride, has the functions of denitrification, dephosphorization and COD removal, and is safe and low in cost. The fluorine-removing agent can ensure that the fluorine content in the treated discharged wastewater reaches the requirements of surface water III specified in GB3838-2002 surface water environmental quality standard.
The defluorinating agent has multiple action mechanisms, such as complexation, agglomeration, adsorption and the like, and has good stability and good precipitability, and the problem of re-release of fluorine ions does not exist.
In addition, the defluorination medicament system has a pH buffering effect, can stabilize the pH of the water body in the using process, and cannot cause the pH of the water body to be greatly reduced in the medicament using process.
As in various embodiments, the polyaluminum salt is present in an amount of Al in the multi-effect fluorine removal medicament 2 O 3 In amounts of 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.; polymeric aluminum ferric salt is used in an amount of Al 2 O 3 In amounts of 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, etc.; the oxidizing agent may be used in an amount of 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, etc.; the amount of acetate salt may be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, etc.; the polydimethyldiallylammonium chloride can be used in amounts of 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, and the like; the iminodiacetic acid may be used in an amount of 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 partsParts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, etc.; the aluminum chlorohydrate may be used in an amount of 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3 parts, etc.
Wherein the polyaluminium salt is Al 2 O 3 3-10 parts by weight are as follows: polyaluminium salt in an amount of Al as an effective substance 2 O 3 The amount of (B) is 3-10 parts; polymerizing aluminoferrite with Al 2 O 3 The 8-15 parts are as follows: the dosage of polymeric aluminum ferric salt and the effective substance Al 2 O 3 The amount of (B) is 8-15 parts.
In a specific embodiment of the invention, the multi-effect fluorine removal medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4 to 10 portions of polymeric aluminum ferric salt and Al 2 O 3 9 to 14 portions, 3 to 10 portions of oxidant, 3.4 to 6 portions of acetate, 0.8 to 1.2 portions of poly dimethyl diallyl ammonium chloride, 1.5 to 2.5 portions of iminodiacetic acid and 2.2 to 2.6 portions of aluminum chlorohydroxide.
In a specific embodiment of the invention, the multi-effect fluorine removal medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 3.8-4.2 parts of polyaluminum ferric salt as Al 2 O 3 8.8 to 9.2 portions of oxidant, 2.8 to 3.2 portions of acetate, 3.4 to 3.6 portions of polydimethyldiallyl ammonium chloride, 1.8 to 1.0 portion of iminodiacetic acid, 1.8 to 2.2 portions of iminodiacetic acid and 2.2 to 2.5 portions of aluminum chlorohydroxide; or the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.2 to 8.6 portions of polymeric aluminum ferric salt and Al 2 O 3 11 to 14 portions, 9.5 to 10 portions of oxidant, 5.5 to 6 portions of acetate, 0.8 to 1.0 portion of poly dimethyl diallyl ammonium chloride, 1.8 to 2.2 portions of iminodiacetic acid and 2.2 to 2.5 portions of aluminum chlorohydroxide.
In a specific embodiment of the present invention, the polyaluminium salt comprises any one or more of polyaluminium chloride, polyaluminium sulfate and polyaluminium silicate, preferably polyaluminium chloride or polyaluminium sulfate.
In a specific embodiment of the present invention, the aluminum polychloride has a salinity of 70 to 85%. The basicity of the polyaluminium sulfate is 50-55%.
In practice, the polyaluminum chloride can be added in liquid form, for example, commercially available technical-grade liquid polyaluminum chloride is used, wherein the effective substance content is Al 2 O 3 The weight percentage is more than or equal to 10 percent, such as 10 percent or 12 percent, the Fe content is 0.1 to 0.5 percent, and the basicity is 80 percent.
In a particular embodiment of the invention, the polyaluminium iron salt comprises any one or more of polyaluminium iron chloride, polyaluminium iron sulfate and polyaluminium iron silicate.
In practice, solid commercial industrial grade polyaluminum ferric chloride, polyaluminum ferric sulfate, and polyaluminum ferric silicate can be used, wherein the content of the effective substance of the polyaluminum ferric chloride is Al 2 O 3 30-32 wt% of Fe 2 O 3 3 to 5 percent of the weight; the content of the polymeric aluminum ferric sulfate effective substance is Al 2 O 3 Less than or equal to 33 percent by weight of Fe 2 O 3 Less than or equal to 12 percent by weight; the content of the polymeric aluminum ferric silicate effective substance is Al 2 O 3 36 to 46 percent of the total weight.
In particular embodiments of the invention, the oxidizing agent comprises either or both of potassium ferrate and potassium permanganate.
In practice, commercial industrial-grade potassium ferrate aqueous solutions can be used, in which the mass content of active substances is 30% to 35%, for example 30%. Commercial solid potassium permanganate may also be used.
In a particular embodiment of the invention, the acetate salt comprises any one or more of sodium acetate, potassium acetate, aluminum acetate, calcium acetate and magnesium acetate.
In actual operation, commercial industrial grade acetate solid can be adopted, wherein the content of the effective substance is 58-99%.
In actual operation, a commercial industrial grade poly dimethyl diallyl ammonium chloride solution can be adopted, and the content of effective substances is 45-50%. Can adopt the industrial grade iminodiacetic acid solid, effective substance on the marketThe content is 90-95%. Commercially available technical grade aluminum chlorohydrate solution can be adopted, and the content of effective substances is Al 2 O 3 The weight is more than or equal to 23 percent, and the basicity is 75 to 83 percent.
The dosage is calculated according to the content of effective substances in each industrial grade component without special description; the industrial-grade components are adopted, so that the production cost can be further reduced.
In a specific embodiment of the invention, the multi-effect fluorine removal medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4 portions of polymeric aluminum ferric salt calculated as Al 2 O 3 9 portions, 3 portions of oxidant, 3.48 to 3.6 portions of acetate, 0.9 portion of polydimethyldiallylammonium chloride, 1.8 portions of iminodiacetic acid and 2.3 to 2.4 portions of aluminum chlorohydroxide.
In a specific embodiment of the invention, the multi-effect defluorination medicament comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.4 parts of polymeric aluminum ferric salt calculated as Al 2 O 3 13.8 parts, 9.8 parts of an oxidant, 5.9-6 parts of acetate, 0.9 part of polydimethyldiallylammonium chloride, 1.8 parts of iminodiacetic acid and 2.3-2.4 parts of aluminum chlorohydrol.
In a specific embodiment of the invention, the multi-effect defluorinating agent is a liquid agent.
In a specific embodiment of the present invention, in the liquid medicine, the polyaluminium salt is Al 2 O 3 The calculated mass fraction is 2-10%. In practical operation, the mass fraction of the solute in the liquid medicament can be adjusted according to practical requirements.
The invention also provides a preparation method of the multi-effect defluorination medicament, which comprises the following steps:
mixing the components in proportion.
In a specific embodiment of the present invention, after mixing the components in proportion, water is added to obtain a liquid medicament.
In another embodiment of the present invention, the preparation method comprises the steps of:
uniformly mixing polymeric aluminum ferric salt and aqueous solution containing polymeric aluminum salt, adding an oxidant, aluminum chlorohydrate, polydimethyldiallyl ammonium chloride, iminodiacetic acid and acetate, and uniformly mixing. Further, the oxidant, the aluminum chlorohydrate, the polydimethyldiallyl ammonium chloride, the iminodiacetic acid and the acetate are sequentially added.
In actual practice, the polyaluminium salt may be prepared in advance as a solution, or a liquid polyaluminium salt may be purchased and used as it is.
In a specific embodiment of the present invention, the preparation method comprises the steps of:
mixing polymeric aluminum ferric salt and aqueous solution containing polymeric aluminum salt, and stirring at the rotating speed of 200 +/-50 r/min for 2-5 min; then adding an oxidant, and stirring for 5-10 min at the rotating speed of 250 +/-20 r/min; then adding aluminum chlorohydrate, and stirring at the rotating speed of 200 +/-50 r/min for 4-5 min; then adding poly dimethyl diallyl ammonium chloride, and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min; adding iminodiacetic acid, and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min; then adding acetate, and stirring at the rotating speed of 300 +/-50 r/min for 5-10 min.
In a specific embodiment of the present invention, the method further comprises: detecting the pH value of the mixed system; if the pH is between 3 and 5, the rest of the operations are not carried out, and if the pH is not between 3 and 5, the pH is adjusted to between 3 and 5. In the actual operation, a proper amount of conventional acid-base regulation is adopted.
In actual operation, polymeric aluminum ferric salt, oxidant, aluminum chlorohydroxide, poly dimethyl diallyl ammonium chloride, iminodiacetic acid and acetate can be added in respective pure forms, can also be prepared into corresponding aqueous solution forms, can also be directly purchased corresponding solution and added according to the calculation of a compounding ratio.
The invention also provides application of the multi-effect defluorinating medicament in treating fluorine-containing wastewater.
In a specific embodiment of the present invention, the multi-effect defluorinating agent is used in a biochemical treatment unit of a sewage treatment plant.
In a specific embodiment of the invention, the adding point of the multi-effect fluorine removal agent is the front end of the biochemical treatment unit.
The fluorine removing agent is arranged at the front end of a biochemical treatment process for sewage treatment, fluoride is gradually reduced along with the addition of the fluorine removing agent, and when the fluorine removing agent enters a biochemical treatment unit, microorganisms can utilize agent components to remove nitrogen and COD, so that phosphorus in water quality is further reduced in the treatment process.
The purposes of defluorination, denitrification, dephosphorization and COD removal are realized through the mechanical stirring, the biochemical treatment unit and the precipitation unit by adding the defluorination agent into the fluorine-containing wastewater at the front end of the biochemical treatment unit, and the device has the advantages of simple dosing, multiple effects, safe use, low cost and the like.
In a specific embodiment of the invention, the multi-effect fluorine removal agent is added in an amount of 100-2000 ppm, preferably 400-600 ppm.
In a specific embodiment of the invention, the pH value of the multi-effect defluorination medicament is applicable to be in a range of 6-9. In the process of using the multi-effect fluorine removal medicament, the pH value of a system is regulated and controlled to be between 6 and 9.
Some of the reagent information used in the following examples may be as follows:
polyaluminum chloride: commercial industrial grade, liquid state, effective substance content is Al 2 O 3 10 or 12 percent by weight, 0.1 to 0.5 percent by weight of Fe and 80 percent of basicity;
polyaluminum chloride: commercial industrial grade, solid state, active substance content is Al 2 O 3 29% by weight;
polymeric aluminum sulfate: commercial industrial grade, solid state, active substance content is Al 2 O 3 30% by weight and 50% basicity;
polyaluminum ferric chloride: commercial industrial grade, in solid form, with Al as active substance 2 O 3 30% by weight of Fe 2 O 3 3 to 5 percent of the weight;
polymeric aluminum ferric sulfate: commercial industrial grade, in solid form, with Al as active substance 2 O 3 33% by weight or less (actually about 30%) as Fe 2 O 3 Less than or equal to 12 percent by weight;
polymeric siliconAcid aluminum iron: commercial industrial grade, in solid form, with Al as active substance 2 O 3 36-46% by weight (practically about 46%);
potassium ferrate: the product is in a commercial industrial grade, is in a liquid state, and has an effective substance content of 30 percent;
potassium permanganate: the product is commercially available in industrial grade, is in a solid state, and has an effective substance content of 98%;
sodium acetate: the product is sold in the market, the form is solid, and the content of effective substances is 58-60%;
aluminum acetate: the product is commercially available industrial grade, is in a solid state, and has an effective substance content of 98.5%;
calcium acetate: the product is commercially available industrial grade, is in a solid state, and has an effective substance content of 99%;
polydimethyldiallylammonium chloride: the product is commercially available in industrial grade, is in liquid state, and has an effective substance content of 45%;
iminodiacetic acid: the product is commercially available in industrial grade, is in a solid state, and has an effective substance content of 90%;
aluminum chlorohydrate: commercial industrial grade, liquid state, effective substance content is Al 2 O 3 The weight is more than or equal to 23 percent, and the basicity is 75 to 83 percent;
aluminum chlorohydrate: commercial industrial grade, in solid form, with Al as active substance 2 O 3 Is > 46% (actually about 50%) by weight.
Example 1
The embodiment provides a multi-effect fluorine removal medicament, which comprises the following components in parts by weight:
polyaluminium chloride and Al 2 O 3 4 portions of polymeric aluminum ferric salt calculated as Al 2 O 3 9 parts, 3 parts of potassium ferrate, 3.6 parts of sodium acetate, 0.9 part of polydimethyldiallylammonium chloride, 1.8 parts of iminodiacetic acid, 2.3 parts of aluminum chlorohydroxide and 17 parts of water. Wherein the polyaluminum ferric salt comprises polyaluminum ferric sulfate and polyaluminum ferric chloride.
The multi-effect defluorination medicament can be prepared by adopting industrial raw materials, and the preparation method of the multi-effect defluorination medicament comprises the following steps:
(a) Weighing industrial-grade liquid polyaluminum chloride (Al) according to weight percentage 2 O 3 10% by weight), 40% by weight, 15% by weight of industrial solid polymeric aluminum ferric chloride, 15% by weight of industrial solid polymeric aluminum ferric sulfate, 10% by weight of industrial liquid potassium ferrate, 6% by weight of industrial solid sodium acetate, 2% by weight of industrial liquid polydimethyldiallyl ammonium chloride, 2% by weight of industrial solid iminodiacetic acid, and 10% by weight of industrial liquid aluminum chlorohydrate;
(b) Adding polymeric aluminum ferric chloride and polymeric aluminum ferric sulfate into polymeric aluminum chloride according to the proportion, and mechanically stirring to uniformly mix the polymeric aluminum ferric chloride and the polymeric aluminum ferric sulfate, wherein the stirring speed is 200 +/-50 r/min, and the stirring time is 2-5 min;
(c) Adding potassium ferrate and water into the material obtained in the step (b) according to the proportion, and stirring at the rotating speed of 250 +/-20 r/min for 5-10 min to uniformly mix the materials;
(d) Adding aluminium chlorohydrate into the material obtained in the step (c), and stirring at the rotating speed of 200 +/-50 r/min for 4-5 min to uniformly mix the materials;
(e) Adding poly dimethyl diallyl ammonium chloride into the material obtained in the step (d), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the materials;
(f) Adding iminodiacetic acid into the material obtained in the step (e), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the iminodiacetic acid and the material;
(g) Adding sodium acetate into the material obtained in the step (f), and stirring at the rotating speed of 300 +/-50 r/min for 5-10 min to uniformly mix the materials; adjusting the pH value of the solution to be between 3.3 and 3.4.
Example 2
This example refers to the multi-effect defluorinating agent of example 1 and its preparation method, with the only differences:
the defluorination medicament comprises the following components in parts by weight:
polyaluminium chloride with Al 2 O 3 3 portions of polymeric aluminum ferric salt as Al 2 O 3 8 parts of potassium ferrate, 2 parts of sodium acetate, 0.5 part of polydimethyldiallyl ammonium chloride, 1 part of iminodiacetic acid, 2 parts of aluminum chlorohydroxide and 20 parts of water. Wherein the polymeric aluminum ferric salt is polymeric aluminum ferric sulfate.
The multi-effect defluorination medicament is prepared according to the preparation method of the example 1 by calculating and weighing the corresponding industrial-grade raw materials according to the dosage of the effective components.
Example 3
This example refers to the multi-effect fluorine removing agent of example 1 and the preparation method thereof, except that:
the defluorination medicament comprises the following components in parts by weight:
polyaluminium chloride with Al 2 O 3 10 portions of polymeric aluminum ferric salt as Al 2 O 3 The paint comprises 15 parts of potassium ferrate, 6 parts of sodium acetate, 1.5 parts of polydimethyldiallylammonium chloride, 3 parts of iminodiacetic acid, 3 parts of aluminum chlorohydrate and 18 parts of water. Wherein the polymeric aluminum ferric salt is polymeric aluminum ferric sulfate.
The multi-effect defluorination medicament is prepared according to the preparation method of the example 1 by calculating and weighing the corresponding industrial-grade raw materials according to the dosage of the effective components.
Example 4
The embodiment provides a multi-effect fluorine removal medicament, which comprises the following components in parts by weight:
polyaluminium salts with Al 2 O 3 8.4 parts by weight of polymeric aluminum ferric silicate and Al 2 O 3 The weight portions of the components are 13.8 portions, 9.8 portions of potassium permanganate, 2.95 portions of aluminum acetate, 2.97 portions of calcium acetate, 0.9 portion of polydimethyldiallyl ammonium chloride, 1.8 portions of iminodiacetic acid, 2.3 portions of aluminum chlorohydrate and 29 portions of water. Wherein the polyaluminium salt comprises polyaluminium chloride and polyaluminium sulfate.
The multi-effect defluorination medicament can be prepared by adopting industrial raw materials, and the preparation method of the multi-effect defluorination medicament comprises the following steps:
(a) Weighing 20 percent of industrial-grade liquid polyaluminium sulfate and 20 percent of industrial-grade polyaluminium chloride (Al) according to weight percentage 2 O 3 12 percent by weight), 20 percent by weight, 30 percent by weight of industrial solid polymeric ferric aluminum silicate, 10 percent by weight of industrial solid potassium permanganate, 3 percent by weight of industrial solid aluminum acetate, 3 percent by weight of industrial solid calcium acetate, 2 percent by weight of industrial liquid polydimethyldiallyl ammonium chloride and 2 percent by weight of industrial solid iminodiacetic acid10% of industrial-grade liquid aluminum chlorohydrate;
(b) Adding polyaluminium sulfate and polyaluminum ferric silicate into polyaluminum chloride according to the proportion, and mechanically stirring to uniformly mix the polyaluminum sulfate and the polyaluminum ferric silicate at the stirring speed of 200 +/-50 r/min for 2-5 min;
(c) Adding potassium permanganate into the material obtained in the step (b) according to the proportion, and stirring at the rotating speed of 250 +/-20 r/min for 5-10 min to uniformly mix the potassium permanganate and the material;
(d) Adding aluminium chlorohydrate into the material obtained in the step (c), and stirring at the rotating speed of 200 +/-50 r/min for 4-5 min to uniformly mix the materials;
(e) Adding poly dimethyl diallyl ammonium chloride into the material obtained in the step (d), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the materials;
(f) Adding iminodiacetic acid into the material obtained in the step (e), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the iminodiacetic acid and the material;
(g) Adding sodium acetate into the material obtained in the step (f), and stirring at the rotating speed of 300 +/-50 r/min for 5-10 min to uniformly mix the materials; adjusting the pH value of the solution to be between 3.3 and 3.4.
Example 5
The embodiment provides a multi-effect fluorine removal medicament, which comprises the following components in parts by weight:
polyaluminium chloride with Al 2 O 3 3.19 parts of polymeric aluminum ferric salt calculated as Al 2 O 3 8.1 parts of potassium ferrate, 2.2 parts of sodium acetate, 1 part of polydimethyldiallylammonium chloride, 2 parts of iminodiacetic acid and aluminum chlorohydroxide in Al 2 O 3 1.84 parts and 50 parts of water.
The preparation method of the multi-effect defluorinating agent comprises the following steps:
(a) Weighing industrial solid polyaluminium chloride (Al) according to weight percentage 2 O 3 29 percent by weight), 27 percent by weight of industrial-grade solid polyaluminum ferric chloride, 2.2 percent by weight of industrial-grade solid potassium ferrate, 3 percent by weight of industrial-grade solid sodium acetate, 1 percent by weight of industrial-grade liquid poly dimethyl diallyl ammonium chloride, 2 percent by weight of industrial-grade solid iminodiacetic acid, 4 percent by weight of industrial-grade solid aluminum chlorohydroxide and water50％；
(b) Putting water into a mixer with stirring, adding solid polyaluminium chloride and solid polyaluminium ferric chloride into the water according to the mixture ratio, and mechanically stirring to uniformly mix the materials, wherein the stirring speed is 200 +/-50 r/min, and the stirring time is 2-5 min;
(c) Adding solid potassium ferrate into the material obtained in the step (b) according to the proportion, and stirring at the rotating speed of 250 +/-20 r/min for 5-10 min to uniformly mix the solid potassium ferrate and the material;
(d) Adding solid aluminum chlorohydrate into the material obtained in the step (c), and stirring at the rotating speed of 200 +/-50 r/min for 4-5 min to uniformly mix the materials;
(e) Adding poly dimethyl diallyl ammonium chloride into the material obtained in the step (d), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the materials;
(f) Adding iminodiacetic acid into the material obtained in the step (e), and stirring at the rotating speed of 300 +/-50 r/min for 5-20 min to uniformly mix the iminodiacetic acid and the material;
(g) Adding sodium acetate into the material obtained in the step (f), and stirring at the rotating speed of 300 +/-50 r/min for 5-10 min to uniformly mix the materials; adjusting the pH value of the solution to be between 3.3 and 3.4.
Comparative example 1
Comparative example 1 the multi-effect defluorinating agent and the preparation method thereof according to example 1 provide an agent with the difference that: the medicament does not contain iminodiacetic acid.
The corresponding industrial grade raw materials are calculated and weighed according to the dosage of each effective component, and the corresponding medicament is prepared according to the preparation method of the example 1.
Comparative example 2
Comparative example 2 the multi-effect defluorinating agent and the preparation method thereof according to example 1 provide an agent with the difference that: the medicament does not contain aluminum chlorohydrate.
The corresponding industrial grade raw materials are calculated and weighed according to the dosage of each effective component, and the corresponding medicament is prepared according to the preparation method of the example 1.
Comparative example 3
Comparative example 3 the multi-effect defluorinating agent and the preparation method thereof according to example 1 provide an agent with the difference that: the medicament does not contain sodium acetate.
The corresponding industrial grade raw materials are calculated and weighed according to the dosage of each effective component, and the corresponding medicament is prepared according to the preparation method of the example 1.
Comparative example 4
Comparative example 4 the multi-effect fluorine removing agent and the preparation method thereof of reference example 1 provided an agent except that:
the medicament comprises the following components in parts by weight:
polyaluminium chloride with Al 2 O 3 Calculated by 12 parts, polymeric aluminum ferric salt as Al 2 O 3 9 parts of potassium ferrate 12 parts, 5 parts of sodium acetate, 2 parts of polydimethyldiallyl ammonium chloride, 5 parts of iminodiacetic acid, 4 parts of aluminum chlorohydrate and 8 parts of water. Wherein, the polymeric aluminum ferric salt comprises polymeric aluminum ferric sulfate and polymeric aluminum ferric chloride (the mixture ratio is the same as that of the embodiment 1).
The raw materials of the corresponding industrial grade are calculated and weighed according to the dosage of the effective components, and the corresponding medicament is prepared according to the preparation method of the example 1.
Comparative example 5
A fluorine-removing agent prepared according to the formulation and method described in example 1 of CN 109574177A.
Experimental example 1
In order to compare and illustrate the effect difference of different fluorine removal medicaments, the medicaments of the examples 1-5 and the comparative examples 1-5 are applied to the treatment of the fluorine-containing wastewater of a certain sewage treatment plant by the same method, the addition point positions are shown in figure 1, the addition amount is 600ppm (the medicaments are added by adopting a diaphragm metering pump), and the pH value of the wastewater is controlled to be between 6.9 and 7.0 in the treatment process. The water quality before and after treatment is shown in Table 1. Wherein, the water quality detection sampling point before treatment and the water quality detection sampling point after treatment are respectively shown in figure 1.
TABLE 1 comparison of water quality before and after treatment of wastewater with different agents
Experimental example 2
In order to compare and illustrate the effect difference of different fluorine removal medicaments, the medicaments of examples 1-5 and comparative examples 1-5 are applied to the treatment of the fluorine-containing wastewater of a certain municipal sewage treatment plant according to the same method, the adding point is shown in figure 2, the adding amount is 400ppm (adding by adopting a diaphragm metering pump), and the pH value of the wastewater is controlled between 7.0 and 7.1 in the treatment process. The water quality before and after treatment is shown in Table 2. Wherein, the water quality detection sampling point before treatment and the water quality detection sampling point after treatment are respectively shown in figure 2.
TABLE 2 comparison of water quality before and after treatment of wastewater with different agents
As is clear from the effluent water qualities in tables 1 and 2, the fluorine removing agent of the present invention can efficiently remove fluoride (as F) - Measured), can assist in denitrification, dephosphorization and COD removal.
The multi-effect defluorinating agent can lead the fluoride in the discharged wastewater to meet the requirements of surface water III specified in GB3838-2002 'surface water environmental quality standard'. The defluorination compound medicament has excellent treatment effect, has the functions of denitrification, dephosphorization and COD removal, has stable result, and can be widely applied to the treatment of the fluorine-containing wastewater of the municipal sewage treatment plant.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (14)
1. The multi-effect defluorination medicament is characterized by comprising the following components in parts by weight:
polyaluminium salts with Al 2 O 3 3-10 parts of polymeric aluminum ferric salt as Al 2 O 3 8 to 15 portions of oxidant, 2 to 10 portions of acetate, 3 to 6 portions of dimethyl diallyl ammonium chloride, 0.5 to 1.5 portions of iminodiacetic acid, 1 to 3 portions of iminodiacetic acid and 2 to 3 portions of aluminum chlorohydroxide;
the oxidant comprises any one or two of potassium ferrate and potassium permanganate;
the acetate comprises any one or more of sodium acetate, potassium acetate and aluminum acetate.
2. The multi-effect fluorine removal agent as claimed in claim 1, which comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4-10 parts of polymeric aluminum ferric salt and Al 2 O 3 9 to 14 portions, 3 to 10 portions of oxidant, 3.4 to 6 portions of acetate, 0.8 to 1.2 portions of poly dimethyl diallyl ammonium chloride, 1.5 to 2.5 portions of iminodiacetic acid and 2.2 to 2.6 portions of aluminum chlorohydroxide.
3. The multi-effect fluorine removal agent as claimed in claim 1, which comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 Calculated by 3.8 to 4.2 portions, polymeric aluminum ferric salt and Al 2 O 3 8.8 to 9.2 portions of oxidant, 2.8 to 3.2 portions of acetate, 3.4 to 3.6 portions of poly-dimethyl diallyl ammonium chloride, 0.8 to 1.0 portion of iminodiacetic acid, 1.8 to 2.2 portions of iminodiacetic acid2.2 to 2.5 portions of aluminum chlorohydrate;
or the composition comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.2 to 8.6 portions of polymeric aluminum ferric salt and Al 2 O 3 11 to 14 portions, 9.5 to 10 portions of oxidant, 5.5 to 6 portions of acetate, 0.8 to 1.0 portion of poly dimethyl diallyl ammonium chloride, 1.8 to 2.2 portions of iminodiacetic acid and 2.2 to 2.5 portions of aluminum chlorohydroxide.
4. The multi-effect fluorine-removing agent as claimed in claim 1, wherein the polyaluminium salt comprises any one or more of polyaluminium chloride, polyaluminium sulfate and polyaluminium silicate.
5. The multi-effect defluorinating agent of claim 1, wherein the polyaluminum ferric salt comprises any one or more of polyaluminum ferric chloride, polyaluminum ferric sulfate, and polyaluminum ferric silicate.
6. The multi-effect fluorine removal agent as claimed in claim 1, which comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 4 portions of polymeric aluminum ferric salt calculated as Al 2 O 3 9 parts, 3 parts of an oxidant, 3.48-3.6 parts of acetate, 0.9 part of polydimethyldiallylammonium chloride, 1.8 parts of iminodiacetic acid and 2.3-2.4 parts of aluminum chlorohydroxide;
or the composition comprises the following components in parts by weight: polyaluminium salts with Al 2 O 3 8.4 parts of polymeric aluminum ferric salt calculated as Al 2 O 3 13.8 parts, 9.8 parts of an oxidant, 5.9-6 parts of acetate, 0.9 part of polydimethyldiallylammonium chloride, 1.8 parts of iminodiacetic acid and 2.3-2.4 parts of aluminum chlorohydrol.
7. The multipurpose defluorinating agent of claim 1, wherein the multipurpose defluorinating agent is a liquid agent.
8. The multi-effect fluorine-removing agent according to claim 7, wherein the fluorine-removing agent is selected from the group consisting ofIn the liquid medicine, the polyaluminium salt is Al 2 O 3 The calculated mass fraction is 2-10%.
9. The method for preparing the multi-effect defluorinating agent of any one of claims 1-8, comprising the steps of:
mixing the components in proportion.
10. The method for preparing the multi-effect defluorinating agent according to claim 9, wherein the polymeric aluminum ferric salt is mixed with the polymeric aluminum salt, and then the oxidant, the chlorohydroxyaluminum, the polydimethyldiallylammonium chloride, the iminodiacetic acid and the acetate are added and mixed uniformly.
11. The method for preparing multiple effect fluorine removal agents of claim 9 further comprising, after the mixing, detecting and/or adjusting the pH to make the pH of the mixed materials between 3 and 5.
12. Use of the multi-effect fluorine removal agent of any one of claims 1 to 8 for treating wastewater containing fluorine.
13. The use according to claim 12, wherein the multi-effect fluorine-removing agent is used in a biochemical treatment unit of a sewage treatment plant.
14. The use according to claim 12, wherein the point of addition of the multi-effect fluorine removal agent is the front end of a biochemical treatment unit.
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