CN112591840A - Precipitation adsorption depth defluorination process for fluorine-containing water body - Google Patents
Precipitation adsorption depth defluorination process for fluorine-containing water body Download PDFInfo
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- CN112591840A CN112591840A CN202011353076.4A CN202011353076A CN112591840A CN 112591840 A CN112591840 A CN 112591840A CN 202011353076 A CN202011353076 A CN 202011353076A CN 112591840 A CN112591840 A CN 112591840A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 75
- 239000011737 fluorine Substances 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 26
- 238000001556 precipitation Methods 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 93
- 239000002351 wastewater Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 11
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 16
- -1 fluoride ions Chemical class 0.000 description 14
- 239000013522 chelant Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002699 waste material 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
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)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a precipitation adsorption deep defluorination process of a fluorine-containing water body, belonging to the technical field of fluorine-containing wastewater treatment. The method adopts the resin to carry out adsorption treatment on the fluorine-containing water body which is subjected to certain pretreatment, can effectively avoid the big problems caused by fluorine removal by a precipitation method or a chemical method, has the characteristics of safety, high efficiency, simple and convenient operation, convenient planning and application and the like, and has simple process flow, low treatment cost and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing wastewater treatment, and particularly relates to a novel precipitation adsorption deep fluorine removal process for a fluorine-containing water body.
Background
The waste water discharged by some industrial processes such as printing and dyeing, metallurgy, phosphate fertilizer production and electroplating and the like contains fluoride with different concentrations, wherein the fluorine content of some waste water is very high, generally at 100-3000mg/L, and the fluoride in the waste water needs to be effectively treated so as to be discharged or used after the fluoride is reduced to meet the corresponding national standard (lower than 10 mg/L).
There are many methods for treating fluoride in waste water, such as precipitation method, adsorption method, electrocoagulation method, electrodialysis method and reverse osmosis membrane method, but the concentration of the effluent after the above-mentioned method treatment is still above 20mg/L and can not reach the discharge standard. As a common precipitation method, Ca is added into water by adding chemicals such as lime, calcium chloride and the like2+And F-Calcium fluoride precipitate is generated, the concentration of fluoride ions in the wastewater can be reduced by adding a coagulant, and the Ca is increased2+Utilization ratio. But only calcium salt is used for treating the fluorine-containing wastewater to generate CaF2The precipitate will be encapsulated in Ca (OH)2The particle surface makes the precipitation process slow, the calcium salt utilization efficiency is lower, and the mass concentration of fluorine in the treated wastewater is generally above 20mg/L, and the wastewater can not be discharged after reaching the standard.
For example, chinese patent publication No. CN108996598A discloses a method for removing fluorine from wastewater by using a bifunctional metal chelate resin adsorbent, which comprises coordinating bifunctional chelate resin with high-valence metal ions to form metal chelate resin, and contacting the fluorine-containing waste liquid to be treated with the chelate resin sufficiently to obtain purified water after defluorination by utilizing the coordination of metal ions to fluorine ions. However, the method does not adjust the pH of the fluorine-containing wastewater, the existence of hydroxide ions under alkaline conditions causes deprotonation of metal oxides, electrostatic repulsion exists between the negatively charged metal oxides and fluorine ions, adsorption of the fluorine ions is inhibited, and the fluorine removal effect is influenced.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of unqualified defluorination effluent, high cost of defluorination adsorption and unsatisfactory effect in the prior art, the invention provides a precipitation adsorption deep defluorination process for fluorine-containing water body, which utilizes metal chelate resin to carry out deep treatment on the fluorine-containing wastewater after certain pretreatment, adjusts the pH of the water body to be proper before treatment, and further promotes the protonation of metal ions of the subsequent chelate resin, thereby enhancing the performance of adsorption defluorination.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a process for deeply removing fluorine by precipitation and adsorption of fluorine-containing water body comprises adsorbing fluorine-containing wastewater with resin; the resin is selected from metal chelating resin; before the fluorine-containing wastewater is subjected to resin adsorption treatment, the pH is adjusted to be weakly acidic.
Further, the fluoride ion concentration of the fluorine-containing wastewater is 8-12mg/L, the pH is adjusted to 5.0-6.5 before adsorption treatment, and the sum of the adding concentrations of the polyaluminium chloride and the polyferric chloride is within the range of 50-300 mg/L; it should be noted that, in principle, the sum of the adding concentrations of the polyaluminium chloride and the polyferric chloride is not less than 50mg/L, but is preferably within the range of 50-300mg/L in consideration of the actual investment cost and the corresponding national discharge standard.
Further, the metal chelating resin skeleton includes, but is not limited to, polystyrene-divinyl, polyacrylic acid, and the metal supported on the resin skeleton includes, but is not limited to, Zr, Al, Fe.
Further, the pH value of the fluorine-containing wastewater is adjusted by utilizing polyaluminium chloride and polyferric chloride, and the dosage of the polyaluminium chloride is not less than that of the polyferric chloride.
Further, the adding mass ratio of the polyaluminium chloride to the polyferric chloride is (1-9):1, preferably (2.33-9): 1.
Furthermore, the pH of the fluorine-containing wastewater is adjusted by adding polyaluminium chloride and then adding polyferric chloride at intervals of 5-10 min.
Further, the concrete steps during coagulating sedimentation treatment are as follows: s100, stirring the fluorine-containing wastewater, adding polyaluminium chloride under the stirring state, and adding polyferric chloride after the polyaluminium chloride is stabilized; and S200, continuing stirring for a certain time, and then settling to obtain water.
Further, the stirring speed in the S200 is 1/5-1/3 of the stirring speed in the S100.
Further, in the S100, the stirring speed is 150--1Stirring for 1-3 min;
in the step S200, the stirring speed is 40-50rmin-1And continuing stirring for 30-60min, stopping stirring, and settling for 10-30 min.
Further, in the adsorption treatment, the wastewater passes through the resin at a flow rate of 1-20 BV/h.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the deep defluorination process for the precipitation adsorption of the fluorine-containing water body, provided by the invention, the fluorine-containing wastewater needs to be adjusted to be weakly acidic before adsorption treatment, and then adsorption is carried out, so that the protonation of metal ions on the surface of the resin can be promoted, and the capture of fluorine ions and hydrogen fluoride by electrostatic attraction or electric double polarization is facilitated; compared with the adsorption defluorination under the alkaline condition, the defluorination effect can be improved, and the problem of generation of a large amount of solid waste in the alkaline defluorination process can be avoided; the existence of hydroxide ions under alkaline conditions leads to deprotonation of metal oxides, electrostatic repulsion exists between negatively charged metal oxides and fluorine ions, and adsorption of the fluorine ions is inhibited, so that defluorination adsorption needs to be carried out under a slightly acidic condition,
(2) the process for deeply removing fluorine by precipitation adsorption of the fluorine-containing water body provided by the invention creatively adopts the polyaluminium chloride and the polyferric chloride to adjust the pH value of the water body, the treated effluent is naturally weak acidic (the pH value is 5.0-6.5), and compared with the traditional method for adjusting the pH value of the water body by adding acid liquor into wastewater, the process has the following advantages:
firstly, as polyaluminum chloride and polyferric chloride have certain buffering performance, the accuracy of pH adjustment is easier to realize when the pH of a water body is adjusted, and the problem of difficult control in the process of adjusting strong acid and strong base is avoided;
secondly, in the traditional method of adding acid liquor (sulfuric acid, hydrochloric acid, acetic acid and the like) into the wastewater to adjust the pH of the water body, extra coexisting anions are introduced into the water body, so that the later adsorption and fluorine removal effects are interfered; in the invention, the pH value of the water body is creatively adjusted through the polyaluminium chloride and the polyferric chloride, and the polyaluminium chloride and the polyferric chloride have the effect of coagulating sedimentation, so that extra coexisting anions cannot be introduced into the water body, the adjusted effluent can be directly adsorbed, the protonation of metal ions of the chelate resin can be effectively promoted, the resin is prevented from being interfered by other coexisting anions, the better performance of adsorbing and removing fluorine is ensured, and the advantages of safety and high efficiency are achieved;
thirdly, in the invention, the pH of the water body is creatively adjusted through the polyaluminium chloride and the polyferric chloride, so that the pH of the water body can be adjusted, meanwhile, as the polyaluminium chloride and the polyferric chloride have the effect of coagulating sedimentation, partial fluorinions in the water body can be removed in advance through the coagulating sedimentation effect, and then the removal effect of the fluorinions is further improved through adsorption, thereby enhancing the defluorination performance.
(2) Through further research by the inventor, the polyferric chloride is utilized to adjust the water body, the floc formed by the polyferric chloride when the coagulation and bottom sedimentation effects are exerted is compact, the sedimentation speed is high, the strength is good, but the alumen ustum is small, the water is unclear, and the residual chroma is high; when the polyaluminium chloride is used for conditioning a water body, flocs generated by the polyaluminium chloride are slow, loose and slow in sedimentation when the polyaluminium chloride plays a role of coagulating and settling, but alumen ustum is large, and the residual chromaticity of effluent is low; therefore, the pH value of the water body needs to be adjusted simultaneously through the polyaluminium chloride and the polyferric chloride; the adding molar ratio of the polyaluminium chloride to the polyferric chloride is too small, which is not beneficial to the bridging of the coagulant and the exertion of the adsorption and electric neutralization effects, and the excessive adding molar ratio is not beneficial to the full utilization of the hydrolysis performance of the polyferric chloride coagulant to regulate and control the pH value of the wastewater;
therefore, if the precise regulation capability of the polyaluminium chloride and the polyferric chloride on the pH value of the water body and the best coagulation effect are both considered, the dosage of the polyaluminium chloride needs to be kept higher than that of the polyferric chloride, and the most preferable adding mass ratio of the polyaluminium chloride to the polyferric chloride is (3-9): 1.
(3) According to the resin adsorption deep defluorination process for the fluorine-containing water body, when the polyaluminium chloride and the polyferric chloride are used for adjusting the pH value of the fluorine-containing wastewater, the polyaluminium chloride and the polyferric chloride are required to be added at intervals of 1-2min, the pH value can be adjusted in the shortest time, the pH value of the water body is stable and balanced, and the phenomenon that the pH value is out of range in the resin adsorption treatment process is avoided.
Detailed Description
The invention is described in detail below with reference to specific exemplary embodiments. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description is to be construed as illustrative only and not restrictive, and any such modifications and variations are intended to be included within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When "mass, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction. "
The comprehensive water treatment cost is considered, the process is suitable for the deep adsorption treatment of the fluorine-containing wastewater, namely the deep treatment of the low-concentration fluorine-containing wastewater which is pretreated by calcification or other means and has a concentration which does not reach the discharge standard; but does not mean that the process is not suitable for adsorbing the wastewater containing fluorine with other concentrations, and the process is suitable for adsorbing the wastewater containing fluorine with any concentration regardless of the cost.
The resin can be NDA-F-A type resin, NDA-F-G type resin or NDA-F-C type resin in NDA-F series resin, is polystyrene-divinyl zirconium-loaded resin, is purchased from environmental protection science and technology limited in south Jiangsu province, and can also be purchased from other companies.
Example 1
In this embodiment, NDA-F-a type resin is adopted, polyaluminium chloride and polyferric chloride with different contents are respectively adopted, and fluorine-containing wastewater (wastewater is pretreated to a certain extent, and the fluorine ion concentration is lower than 20mg/L) with different fluorine ion concentrations and pH in the electronic industry is treated, and the specific treatment steps are as follows:
s100, at 200 r.min-1Firstly adding polyaluminium chloride at the stirring speed, and adding polyferric chloride for adjusting the pH value of the water body after 5 minutes; wherein the total adding concentration of the two is 100 mg/L;
s200, after reacting for 3min, reducing the stirring speed to 50 r.min-1Is followed byStirring for 30min, and stopping stirring and precipitating for 30 min;
and S300, introducing supernatant effluent after pH adjustment and precipitation into a resin adsorption column for adsorption, and allowing wastewater to pass through the resin at the flow rate of 1 BV/h.
The water quality of the water bodies before, during and after treatment in this example is shown in table 1.
TABLE 1 Water quality before, during and after treatment of each group of Water bodies in this example
The results show that when the dosage of the polyaluminium chloride is higher than that of the polyferric chloride under the condition of the same total dosage, the wastewater has better defluorination effect, and particularly, the dosage ratio of the polyaluminium chloride to the polyferric chloride is (2.3-9): 1, the concentration of the fluorine ions in the water adsorbed by the resin is lower.
Example 2
In this embodiment, NDA-F-a type resin is adopted, and different coagulants (different contents of polyaluminium chloride and polyferric chloride) are respectively adopted to treat the fluorine-containing wastewater (the wastewater is pretreated to a certain extent and the fluorine ion concentration is lower than 20mg/L) with different fluorine ion concentrations and pH in the chemical industry, and the specific treatment steps are as follows:
s100, at 200 r.min-1Firstly adding polyaluminium chloride at the stirring speed, and adding polyferric chloride for adjusting the pH value of the water body after 5 minutes; wherein the total adding concentration of the two is 100 mg/L;
s200, after reacting for 3min, reducing the stirring speed to 50 r.min-1
Continuing stirring for 30min, and then stopping stirring and precipitating for 30 min;
and S300, introducing supernatant effluent after pH adjustment and precipitation into a resin adsorption column for adsorption, and allowing wastewater to pass through the resin at the flow rate of 1 BV/h.
The water quality of the water bodies before, during and after treatment in this example is shown in table 2.
TABLE 2 Water quality before, during and after treatment of each group of Water bodies in this example
The results show that when the dosage of the polyaluminium chloride is higher than that of the polyferric chloride under the condition of the same total dosage, the wastewater has better defluorination effect, and particularly, the dosage ratio of the polyaluminium chloride to the polyferric chloride is (2.3-9): 1, the concentration of the fluorine ions in the water adsorbed by the resin is lower.
Comparative example 1
In the comparative example, the same resin as that in example 1 was used to treat fluorine-containing wastewater in the electronic industry (wastewater quality groups 1-2: fluorine ion concentration of 5.1mg/L, pH of 8.0; groups 3-4: fluorine ion concentration of 6.5mg/L, pH of 7.8), and no pH adjustment treatment was performed before resin adsorption, or the pH of the water before resin adsorption treatment was adjusted (to the same inlet water pH as that of resin adsorption of example 2/example 3 group 2) with a commercially available acid solution. The specific process flow is
The treatment conditions for the adsorption treatment with the resin were the same as in example 1.
The water quality of the treated medium water before and after the treatment in this comparative example is shown in Table 3.
TABLE 3 Water quality before, during and after treatment of each group of water bodies in this comparative example
The results show that the groups 1 and 3 show that the resin defluorination performance of the resin can be effectively enhanced by adjusting the pH value of the water body in advance through polyaluminium chloride and polyferric chloride and then performing resin adsorption before the resin adsorption treatment of the fluorine-containing wastewater is performed;
as can be seen from groups 2 and 3, compared with the traditional method for adjusting the pH of the water body by adding acid liquor (sulfuric acid, hydrochloric acid, acetic acid and the like) into the wastewater, the method can effectively enhance the defluorination performance of the resin by adjusting the pH of the water body through polyaluminium chloride and polyferric chloride and then performing resin adsorption, and not only plays a role in coagulating sedimentation due to the addition of the polyaluminium chloride and the polyferric chloride; and more particularly, because the polyaluminium chloride and the polyferric chloride have the effect of coagulating sedimentation, extra coexisting anions can not be introduced into the water body, the regulated effluent can be directly subjected to resin adsorption, the protonation of chelate resin metal ions can be promoted effectively, the resin is prevented from being interfered by other coexisting anions, and the better performance of resin adsorption and fluorine removal is ensured.
Comparative example 2
In the comparative example, the same resin as that in example 1 is adopted to treat fluorine-containing wastewater in the electronic industry (wastewater quality group 1-2: the concentration of fluorine ions is 9.8mg/L, the pH is 8.0; and wastewater quality group 3-4: the concentration of fluorine ions is 11.9mg/L, the pH is 7.8); the difference is that the total adding concentration of the polyaluminium chloride and the polyferric chloride is different from that of the example 1.
The concentration ratio of polyaluminum chloride to polyferric chloride, and the treatment conditions and parameters in each treatment step were the same as those in example 1.
The water quality of the medium water before and after the treatment in this comparative example is shown in Table 4.
TABLE 4 Water quality before, during and after treatment of each group of water bodies in this comparative example
The results show that when the total adding concentration of the polyaluminium chloride and the polyferric chloride is lower than 50mg/L, the pH value and the fluorine-containing concentration of effluent after coagulating sedimentation are high, and the fluorine removal effect of the resin is influenced. When the total adding concentration of the polyaluminium chloride and the polyferric chloride is higher than 300mg/L, compared with the data in the example 1, the concentration of the fluorine ions in the resin adsorbed water is almost the same, and the adding total amount of the polyaluminium chloride and the polyferric chloride coagulant is determined to be 50-300mg/L in consideration of the actual investment cost and the corresponding national discharge standard.
Claims (10)
1. A process for deeply removing fluorine by precipitation and adsorption of fluorine-containing water body is characterized by comprising the following steps: adsorbing the fluorine-containing wastewater by using an adsorbent; the adsorbent is selected from metal chelating resin; and before the fluorine-containing wastewater is subjected to adsorption treatment, the pH is adjusted to be weakly acidic.
2. The deep defluorination process by precipitation and adsorption of fluorine-containing water body according to claim 1, which is characterized in that: the fluorine ion concentration of the fluorine-containing wastewater is 8-12mg/L, and the pH is adjusted to 5.0-6.5 before the adsorption treatment.
3. The deep defluorination process by precipitation and adsorption of fluorine-containing water body according to claim 1, which is characterized in that: the metal chelating resin skeleton comprises, but is not limited to, polystyrene-divinyl and polyacrylic acid, and the metal loaded on the resin skeleton comprises, but is not limited to, Zr, Al and Fe.
4. The deep defluorination process by precipitation adsorption of fluorine-containing water body according to any one of claims 1 to 3, characterized in that: and (2) regulating the pH value of the fluorine-containing wastewater by utilizing polyaluminium chloride and polyferric chloride, wherein the dosage of the polyaluminium chloride is not lower than that of the polyferric chloride, and the sum of the adding concentrations of the polyaluminium chloride and the polyferric chloride is not lower than 50 mg/L.
5. The deep defluorination process by precipitation and adsorption of fluorine-containing water body according to claim 4, which is characterized in that: the adding mass ratio of the polyaluminium chloride to the polyferric chloride is (1-9) to 1.
6. The deep defluorination process by precipitation and adsorption of fluorine-containing water body according to claim 5, which is characterized in that: when the pH value of the fluorine-containing wastewater is adjusted, polyaluminium chloride is added firstly, and then polyferric chloride is added, wherein the interval time is 5-10 min.
7. The deep defluorination process by precipitation and adsorption of fluorine-containing water body according to claim 6, which is characterized in that: the concrete steps during coagulating sedimentation treatment are as follows:
s100, stirring the fluorine-containing wastewater, adding polyaluminium chloride under the stirring state, and adding polyferric chloride after a period of time;
and S200, continuing stirring for a certain time, and then settling to obtain water.
8. The deep fluorine removal process of claim 7, wherein the stirring rate in S200 is 1/5-1/3 of the stirring rate in S100.
9. The deep fluorine removal process by precipitation adsorption of fluorine-containing water as claimed in claim 8, wherein in S100, the stirring rate is 150-200 r-min-1Stirring for 1-3 min;
in the step S200, the stirring speed is 40-50rmin-1And continuing stirring for 30-60min, stopping stirring, and settling for 10-30 min.
10. The deep defluorination process by precipitation adsorption of fluorine-containing water body according to claim 8, wherein the wastewater passes through the adsorbent at a flow rate of 1-20BV/h during the adsorption treatment.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001005710A1 (en) * | 1999-07-17 | 2001-01-25 | Dyneon Gmbh & Co. Kg | Method for recovering fluorinated emulsifiers from aqueous phases |
| CN109574177A (en) * | 2018-12-29 | 2019-04-05 | 北京中持净水材料技术有限公司 | A kind of high-effective defluorination compound drug |
| CN110104733A (en) * | 2019-06-20 | 2019-08-09 | 湖南中金岭南康盟环保科技有限公司 | A kind of processing method of fluoride waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001005710A1 (en) * | 1999-07-17 | 2001-01-25 | Dyneon Gmbh & Co. Kg | Method for recovering fluorinated emulsifiers from aqueous phases |
| CN109574177A (en) * | 2018-12-29 | 2019-04-05 | 北京中持净水材料技术有限公司 | A kind of high-effective defluorination compound drug |
| CN110104733A (en) * | 2019-06-20 | 2019-08-09 | 湖南中金岭南康盟环保科技有限公司 | A kind of processing method of fluoride waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282435A (en) * | 2023-04-10 | 2023-06-23 | 济南大学 | Coagulation cooperative adsorption precipitation method for synchronously reducing turbidity and middle-low concentration fluorine by inorganic fluorine removal and turbidity removal agent |
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