CN117069226A - Preparation method of pH-controllable fluorine removal agent and application of pH-controllable fluorine removal agent in fluorine-containing sewage treatment - Google Patents
Preparation method of pH-controllable fluorine removal agent and application of pH-controllable fluorine removal agent in fluorine-containing sewage treatment Download PDFInfo
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- 239000011737 fluorine Substances 0.000 title claims abstract description 91
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 91
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 72
- 239000010865 sewage Substances 0.000 title claims abstract description 55
- 238000011282 treatment Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 96
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001509 sodium citrate Substances 0.000 claims abstract description 32
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 25
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 10
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims 2
- 239000005077 polysulfide Substances 0.000 claims 2
- 150000008117 polysulfides Polymers 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 5
- 230000015271 coagulation Effects 0.000 abstract description 4
- 238000005345 coagulation Methods 0.000 abstract description 4
- 238000005096 rolling process Methods 0.000 abstract description 3
- 238000010408 sweeping Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 66
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The patent discloses a preparation method of a pH-controllable fluorine removal agent and application of the pH-controllable fluorine removal agent in fluorine-containing sewage treatment, and belongs to the technical field of sewage treatment. The fluorine removing agent is prepared from raw materials such as sodium silicate, polymeric aluminum ferric diacid, citric acid, sodium citrate and the like, and can play roles in inorganic mixed coagulation and sedimentation, and also has the functions of net capturing and rolling sweeping of a polymeric flocculant, so that fluorine can be removed efficiently, and the concentration of fluoride in sewage finally reaches the sewage emission standard. The fluorine removing agent prepared by the invention has less dosage, does not need to add liquid alkali/acid to adjust the pH of sewage, saves the dosage and cost of the fluorine removing agent and the liquid alkali/acid, and reduces the fluorine removing operation cost.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method of a fluorine removal agent and application of the fluorine removal agent in fluorine-containing sewage treatment.
Background
Fluorine-containing sewage is inevitably generated in the production process of industries such as aluminum electrorefining, thermal power generation, photovoltaic and the like. Wherein, sanitary standard of drinking water (GB 5749-2006) requires fluoride concentration not to be higher than 1 mg/L; the quality standard of surface water environment (GB 3838-2002) requires that the concentration of fluoride is not higher than 1 mg/L, and the concentration of fluoride is not higher than 1.5 mg/L for IV and V; meanwhile, the world health organization and European Union food sanitation also issue corresponding regulations to limit the fluoride or fluoride ion content in water (not higher than 1.5 mg/L), so that further reduction of fluoride content in industrial wastewater and domestic sewage is very necessary.
In practical engineering, the method of chemical precipitation, coagulating sedimentation, adsorption and the like is more applied to the treatment of fluorine-containing sewage, wherein the calcium salt chemical precipitation method is convenient to treat and has the widest application, and is mainly used for the first stage of fluorine removal. Calcium salt chemical precipitation method is mainly to add calcium salt (CaO, caCl) into sewage 2 、Ca(OH) 2 Etc.), to generate CaF 2 Precipitation to remove fluoride, but CaF 2 It is difficult to treat the wastewater to reach the standard (research on treating industrial fluorine-containing wastewater by precipitation-adsorption combined process, liu Xu) because the wastewater has certain solubility (about 7-8 mg/L) in water. At present, calcium salt chemical precipitation is generally adopted as primary treatment, and is matched with a coagulating sedimentation method for deeply removing fluoride, wherein the coagulating sedimentation method is to add a fluorine removing agent into fluorine-containing sewage, and form a complex with the fluoride under the actions of adsorption bridging, rolling sweeping and the like, so that precipitate is generated and discharged.
The fluoride concentration fluctuation of the effluent of the traditional defluorinating agent is large, the effect is unstable, the pertinence is poor in the aspect of treating low-concentration fluoride, and fluoride removal is generally carried out at the tail end of sewage treatment (other indexes except fluoride are qualified), and the effluent is discharged after treatment. The pH of the effluent is affected by adding the fluorine removing agent, which means that in the final flow of sewage treatment, not only is the fluoride qualified for effluent, but also potential requirements are put on pH indexes (the effluent reaches 6-9). Therefore, developing a fluorine removal agent for ensuring that fluoride and pH effluent in sewage can reach the standard stably aiming at low-fluorine sewage is a problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a fluorine removal agent, and the fluorine removal agent is used for treating low-fluorine sewage, and has the advantages of good effect, high fluorine removal rate, capability of reaching emission standards and the like, and the pH of the sewage is not required to be regulated, so that the addition amount of liquid alkali/acid is saved, the running cost of enterprises is reduced, and the benefit of the enterprises is improved.
The technical idea of the invention is as follows: firstly, taking a fluorine-containing sewage water sample at the tail end of sewage treatment to detect the pH value, preparing a fluorine-removing agent with lower pH value if the sewage pH value is relatively higher, and preparing a fluorine-removing agent with higher pH value if the sewage pH value is relatively lower, wherein the fluorine-removing agent is added into the fluorine-containing sewage to achieve the condition of the optimal pH value (6-7) of the coagulation reaction (see Table 1 in detail), improving the reaction rate, saving the consumption of the fluorine-removing agent, and the mass ratio of fluorine-removing agent components under different sewage pH values is shown in Table 2.
TABLE 1 technical idea of the invention
TABLE 2 fluorine scavenger component mass ratio at different sewage pH
In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a defluorinating agent, which is prepared from the following components in parts by mass: 0.57-2.88 parts of sodium silicate, 0.34-1.72 parts of acid, 58-90 parts of polymeric aluminum ferric diacid, 0.22-0.31 part of citric acid, 0.02-0.12 part of sodium citrate and 8.74-37.09 parts of deionized water.
According to the technical thought of the invention, the pH value of the fluorine-containing sewage at the tail end of sewage treatment is detected, and the fluorine removal agent with corresponding pH value is prepared according to the detection result.
(1) When the pH value of the sewage is measured to be 6-7, the fluorine removing agent provided by the invention comprises the following raw materials in parts by mass: 2.15-2.88 parts of sodium silicate, 1.28-1.72 parts of acid, 58-68 parts of polymeric aluminum ferric sulfate, 0.31 part of citric acid, 0.02 part of sodium citrate and 28.22-37.09 parts of deionized water.
(2) When the pH value of the sewage is measured to be 7-8, the fluorine removing agent provided by the invention comprises the following raw materials in parts by mass: 1.36-2.16 parts of sodium silicate, 0.82-1.29 parts of acid, 68-79 parts of polymeric aluminum ferric diacid, 0.25 part of citric acid, 0.09 part of sodium citrate and 18.48-28.24 parts of deionized water.
(3) When the pH value of the sewage is measured to be 8-9, the fluorine removing agent provided by the invention comprises the following raw materials in parts by mass: 0.57-1.36 parts of sodium silicate, 0.34-0.82 parts of acid, 79-90 parts of polymeric aluminum ferric sulfate, 0.22 parts of citric acid, 0.12 parts of sodium citrate and 8.74-18.49 parts of deionized water.
Wherein the acid in the (1), the (2) and the (3) comprises any one of hydrochloric acid, sulfuric acid and nitric acid, and the polymeric aluminum ferric diacid component comprises polyaluminium sulfate chloride and polyaluminium sulfate chloride.
Meanwhile, the invention provides a preparation method of the fluorine removing agent (1), which comprises the following steps: (1) slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to 3-4, and standing and activating for 3-6 hours to obtain a solution A; (2) adding polymeric aluminum ferric diacid into the solution A, wherein the ratio of the polymeric aluminum ferric diacid to the solution A is (1.45-2.26) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B; (3) at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 13.29:1, and regulating the pH value to be about 4 to obtain a solution C; (4) and adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent (1).
Meanwhile, the invention provides a preparation method of the fluorine removing agent described in the above (2), which comprises the following steps: (1) slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to 2-3, and standing and activating for 3-6 hours to obtain a solution A; (2) adding polymeric aluminum ferric diacid into the solution A, wherein the ratio of the polymeric aluminum ferric diacid to the solution A is (2.26-4.16) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B; (3) at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 2.78:1, and regulating the pH value to be about 3.5 to obtain a solution C; (4) and adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent (2).
Meanwhile, the invention provides a preparation method of the fluorine removing agent described in the above (3), which comprises the following steps: (1) slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to be 1-2, and standing and activating for 3-6 hours to obtain a solution A; (2) adding polymeric aluminum ferric diacid into the solution A according to the proportion of (4.16-11.25) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B; (3) at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 1.83:1, and regulating the pH value to be about 3 to obtain a solution C; (4) and adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent (3).
Finally, the use method of the fluorine removing agent prepared by adopting the invention comprises the following steps: adding a corresponding defluorinating agent into the fluorine-containing sewage at the tail end of sewage treatment, stirring, reacting for 10-20 min, adding polyacrylamide, standing and settling for 10-30 min, and enabling the supernatant to meet the drainage requirement of fluoride.
Wherein the concentration of the polyacrylamide is 1 per mill, and the adding volume ratio of the polyacrylamide to the sewage is 200:1.
The defluorinating agent mainly takes sodium silicate, polymeric aluminum ferric sulfate, citric acid and sodium citrate as raw materials. The polymeric silicic acid synthesized by taking sodium silicate as a raw material has various space structures and good adsorption bridging capability, polymeric silicic acid reacts with polymeric aluminum ferric diacid to generate polymeric aluminum ferric silicate diacid, the adsorption electric neutralization and adsorption bridging capability is enhanced, and the flocculation effect is good; the polyaluminum ferric diacid is prepared by introducing proper amount of synergist SO4 based on polyaluminum chloride and polyferric chloride 2- The novel high-efficiency flocculant composed of inorganic high-molecular polymers of polyaluminium sulfate chloride and ferric sulfate chloride is formed, the advantages of an aluminum salt system and an iron salt flocculant are integrated, and compared with the traditional flocculant, the novel high-efficiency flocculant can improve the treatment efficiency, has small dosage and reduces the water treatment cost; and citric acid and sodium citrate are used as pH buffer solution, so that the pH can be maintained relatively stable under a certain dilution condition, and meanwhile, most of divalent and trivalent metal ions can be chelated by the citric acid and the sodium citrate, so that the interference of metal on fluoride removal is weakened, and the defluorination effect is remarkable.
The invention has the beneficial effects that: 1. the invention relates to an inorganic high polymer defluorinating agent which has the functions of inorganic mixed coagulation and sedimentation and the net capturing and rolling sweeping of a high polymer flocculant, and can efficiently remove fluorine, so that the concentration of fluoride (fluoride ions) finally reaches the sewage discharge standard, the consumption of the defluorinating agent is small, the sludge production amount is small, the operation is simple, the follow-up work is less, and the operation of a sewage treatment system is more stable.
2. The pH adjustment range of the fluorine removing agent obtained by the preparation method is larger and controllable, the pH of the fluorine removing agent can be adjusted in a targeted manner according to the pH of sewage, so that the fluorine removing agent can obtain the optimal pH (6-7) of a coagulation reaction when the sewage is added, the reaction rate is accelerated, and the fluorine removing effect is obvious; in the running process, the adding amount of the fluorine removing agent is small, the pH value of the sewage is not required to be adjusted by adding liquid alkali/acid, the consumption and the cost of the fluorine removing agent and the liquid alkali/acid are saved, and the running cost of fluorine removal is reduced.
Detailed Description
For further explanation of the technical solution of the present invention, the following description is given with reference to specific embodiments, not all of which are listed, and all other embodiments that can be obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Example 1
And (3) detecting that the pH value of fluorine-containing sewage 500 mL of a certain photovoltaic enterprise is 6.15, the fluoride concentration is 3.19 mg/L, and the fluoride concentration of the effluent is required to meet the V-type requirement (not higher than 1.5 mg/L) of the surface water environment quality standard (GB 3838-2002).
The fluoride removal agent of the invention is adopted to remove fluoride, and the fluoride removal agent of the embodiment 1 comprises the following components in parts by mass: 2.87 parts of sodium silicate, 1.71 parts of hydrochloric acid, 58 parts of polymeric aluminum ferric sulfate, 0.31 part of citric acid, 0.02 part of sodium citrate and 37.09 parts of deionized water.
The preparation method comprises the following steps: (1) Slowly adding 0.3 mol/L sodium silicate solution into 50% acid solution, continuously stirring, adjusting pH to 4, standing and activating to 3 h to obtain solution A; (2) Adding polymeric aluminum ferric diacid into the solution A, fully and uniformly stirring, and standing for 2 h to obtain a solution B; (3) At room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, and regulating the pH value to be 4 to obtain a solution C; (4) And adding the solution C into the solution B, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
The using method is as follows: adding the 0.2 mL fluorine removing agent into sewage, stirring, reacting for 10 min, adding 2.5 mL polyacrylamide with the concentration of 1%o, standing and settling for 10 min, taking supernatant to measure the concentration of the fluoride to be 0.86 mg/L, and discharging the fluoride reaching the standard with the concentration of not higher than 1.5 mg/L.
Example 2
And (3) detecting that the pH value of fluorine-containing sewage 500 mL of a certain photovoltaic enterprise is 7.46, the fluoride concentration is 4.22 mg/L, and the fluoride concentration of the effluent is required to meet the V-type requirement (not higher than 1.5 mg/L) of the surface water environment quality standard (GB 3838-2002).
The fluoride removal agent of the invention is adopted to remove fluoride, and the fluoride removal agent of the embodiment 2 comprises the following components in parts by mass: 2.15 parts of sodium silicate, 1.29 parts of hydrochloric acid, 68 parts of polymeric aluminum ferric sulfate, 0.25 part of citric acid, 0.09 part of sodium citrate and 28.22 parts of deionized water.
The preparation method comprises the following steps: (1) Slowly adding 0.3 mol/L sodium silicate solution into 50% acid solution, continuously stirring, adjusting pH to 3, standing and activating to 4 h to obtain solution A; (2) Adding polymeric aluminum ferric diacid into the solution A, fully and uniformly stirring, and standing for 3 h to obtain a solution B; (3) At room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, and regulating the pH value to 3.5 to obtain a solution C; (4) And adding the solution C into the solution B, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
The using method is as follows: adding the 0.3 mL fluorine removing agent into sewage, stirring, reacting for 15 min, adding 2.5 mL polyacrylamide with the concentration of 1%o, standing and settling for 15 min, taking supernatant to measure the concentration of the fluoride to be 0.96 mg/L, and discharging the fluoride reaching the standard with the concentration of not higher than 1.5 mg/L.
Example 3
And (3) taking the fluorine-containing sewage 500 mL of a certain power plant, and detecting that the pH value of the fluorine-containing sewage is 8.05, the fluoride concentration is 5.60 mg/L, and the fluoride concentration of the effluent is required to meet the V-type requirement (not higher than 1.5 mg/L) of the surface water environment quality standard (GB 3838-2002).
The fluoride removal agent of the invention is adopted to remove fluoride, and the fluoride removal agent of the embodiment 3 comprises the following components in parts by mass: 1.36 parts of sodium silicate, 0.82 part of hydrochloric acid, 80.66 parts of polymeric aluminum ferric sulfate, 0.22 part of citric acid, 0.12 part of sodium citrate and 16.82 parts of deionized water.
The preparation method comprises the following steps: (1) Slowly adding 0.3 mol/L sodium silicate solution into 50% acid solution with volume fraction, stirring, adjusting pH to 2.0, standing and activating 5. 5 h to obtain solution A; (2) Adding polymeric aluminum ferric diacid into the solution A, fully and uniformly stirring, and standing for 3 h to obtain a solution B; (3) At room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, and regulating the pH value to 3.0 to obtain a solution C; (4) And adding the solution C into the solution B, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
The using method is as follows: adding the 0.5 mL fluorine removing agent into sewage, stirring, reacting for 20 min, adding 2.5 mL polyacrylamide with the concentration of 1%o, standing and settling for 15 min, taking supernatant to measure the concentration of the fluoride to be 0.92 mg/L, and discharging the fluoride reaching the standard with the concentration of not higher than 1.5 mg/L.
Example 4
And (3) taking the fluorine-containing sewage 500 mL of a certain power plant, and detecting that the pH value of the fluorine-containing sewage is 8.95, the fluoride concentration of the fluorine-containing sewage is 8.74 mg/L, and the fluoride concentration of the effluent is required to meet the V-type requirement (not higher than 1.5 mg/L) of the surface water environment quality standard (GB 3838-2002).
The fluoride removal agent of the invention is adopted to remove fluoride, and the fluoride removal agent of the embodiment 4 comprises the following components in parts by mass: 0.57 part of sodium silicate, 0.36 part of hydrochloric acid, 89.99 parts of polymeric aluminum ferric sulfate, 0.22 part of citric acid, 0.12 part of sodium citrate and 8.74 parts of deionized water.
The preparation method comprises the following steps: (1) Slowly adding 0.3 mol/L sodium silicate solution into 50% acid solution with volume fraction, stirring, adjusting pH to 1.0, standing and activating 6 h to obtain solution A; (2) Adding polymeric aluminum ferric diacid into the solution A, fully and uniformly stirring, and standing for 4 h to obtain a solution B; (3) At room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, and regulating the pH value to 3.0 to obtain a solution C; (4) And adding the solution C into the solution B, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
The using method is as follows: adding the 0.75 mL fluorine removing agent into sewage, stirring, reacting for 10 min, adding 2.5 mL polyacrylamide with the concentration of 1%o, standing and settling for 30 min, taking supernatant to measure the concentration of fluoride to be 1.02 mg/L, and discharging the fluoride reaching the standard with the concentration of not higher than 1.5 mg/L.
Claims (12)
1. The pH-controllable fluorine removing agent is characterized by comprising the following preparation raw materials in parts by mass: 0.57-2.88 parts of sodium silicate, 0.34-1.72 parts of acid, 58-90 parts of polymeric aluminum ferric diacid, 0.22-0.31 part of citric acid, 0.02-0.12 part of sodium citrate and 8.74-37.09 parts of deionized water.
2. The fluorine removal agent of claim 1, which is dynamically prepared based on the pH of fluorine-containing wastewater.
3. The fluorine removal agent according to claim 1 or 2, wherein when the pH of fluorine-containing sewage is 6-7, the raw materials for preparation are as follows in parts by mass: 2.15-2.88 parts of sodium silicate, 1.28-1.72 parts of acid, 58-68 parts of polymeric aluminum ferric sulfate, 0.31 part of citric acid, 0.02 part of sodium citrate and 28.22-37.09 parts of deionized water.
4. The fluorine removal agent according to claim 1 or 2, wherein when the pH of fluorine-containing sewage is 7-8, the raw materials for preparation are as follows in parts by mass: 1.36-2.16 parts of sodium silicate, 0.82-1.29 parts of acid, 68-79 parts of polymeric aluminum ferric diacid, 0.25 part of citric acid, 0.09 part of sodium citrate and 18.48-28.24 parts of deionized water.
5. The fluorine removal agent according to claim 1 or 2, wherein when the pH of fluorine-containing sewage is 8-9, the raw materials for preparation are as follows in parts by mass: 0.57-1.36 parts of sodium silicate, 0.34-0.82 parts of acid, 79-90 parts of polymeric aluminum ferric sulfate, 0.22 parts of citric acid, 0.12 parts of sodium citrate and 8.74-18.49 parts of deionized water.
6. The fluorine removing agent according to claim 1 to 5, wherein the acid comprises any one of hydrochloric acid, sulfuric acid and nitric acid.
7. The fluorine removal agent as defined in claims 1-5, wherein the polymeric aluminum ferric diacid component comprises polyaluminum chloride polysulfide, polyaluminum ferric chloride polysulfide.
8. The method for producing a fluorine scavenger according to any of claims 1, 2, 3, 6, 7, comprising the steps of:
s1, slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to 3-4, and standing and activating for 3-6 hours to obtain a solution A;
s2, adding polymeric aluminum ferric diacid into the solution A, wherein the ratio of the polymeric aluminum ferric diacid to the solution A is (1.45-2.26) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B;
s3, at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 13.29:1, and regulating the pH value to be about 4 to obtain a solution C;
and S4, adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
9. The method for producing a fluorine scavenger according to any of claims 1, 2, 4, 6, 7, comprising the steps of:
s1, slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to 2-3, and standing and activating for 3-6 hours to obtain a solution A;
s2, adding polymeric aluminum ferric diacid into the solution A, wherein the ratio of the polymeric aluminum ferric diacid to the solution A is (2.26-4.16) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B;
s3, at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 2.78:1, and regulating the pH value to be about 3.5 to obtain a solution C;
and S4, adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
10. The method for producing a fluorine scavenger according to any of claims 1, 2, 5, 6, 7, comprising the steps of:
s1, slowly adding 0.3 mol/L sodium silicate solution into an acid solution with the volume fraction of 50%, continuously stirring, adjusting the pH value to be 1-2, and standing and activating for 3-6 hours to obtain a solution A;
s2, adding polymeric aluminum ferric diacid into the solution A, wherein the ratio of the polymeric aluminum ferric diacid to the solution A is (4.16-11.25) 1, fully and uniformly stirring, and standing for 2-4 hours to obtain a solution B;
s3, at room temperature, dissolving citric acid and sodium citrate in deionized water, uniformly stirring, wherein the ratio of the citric acid to the sodium citrate is 1.83:1, and regulating the pH value to be about 3 to obtain a solution C;
and S4, adding the solution C into the solution B, wherein the ratio of the solution C to the solution B is 1:49, uniformly mixing, and fully stirring to obtain the fluorine removing agent.
11. The application of the pH-controllable fluorine removal agent in fluorine-containing sewage treatment is characterized by comprising the following steps: adding the fluorine removing agent in the method for removing fluorine from the wastewater, stirring, reacting for 10-20 min, adding polyacrylamide, standing and settling for 10-30 min, and enabling supernatant fluid to meet the drainage requirement of fluoride.
12. The use of a pH-controllable fluorine-removing agent according to claim 11 in the treatment of fluorine-containing wastewater, wherein the mass fraction of polyacrylamide is 1%o, and the ratio of polyacrylamide to wastewater is 200:1 by volume.
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