Method for deeply removing fluorine from high-salinity wastewater

Abstract

The invention discloses a method for deeply removing fluorine from high-salinity wastewater, and belongs to the technical field of wastewater treatment of glass, electroplating, semiconductor processing, aluminum manufacturing and the like. According to the present invention, the amino acetic acid resin is adopted to load the metal ions to form the novel metal ion ligand resin, the deep fluorine removal is performed in the high salt environment, the fluorine removal effect is excellent, and the fluorine removal effect is 1.4 times higher than the fluorine removal effect of the salt-free system, such that the salt promotion effect is represented, and the fluorine ions in the high salt environment can be efficiently removed; meanwhile, the difficulty that the fluorine removal performance of a traditional adsorbent in a high-salt and low-fluorine environment has different degrees of inhibition and the anti-ion interference performance is poor, namely the salt negative effect is overcome, the fluorine removal difficulty of the adsorbent in a high-salt solution is greatly reduced, and the high practical application value is achieved.

Description

Technical Field

[0001] The invention belongs to the field of wastewater treatment technology for glass, electroplating, semiconductor processing, aluminum manufacturing, etc., and specifically relates to a method for deep defluorination in high-salt wastewater. Background Art

[0002] In industrial production, fluorine and its compounds are widely used in coke and glass production, electroplating etching, electronic material component production, steel and aluminum production, metal etching, and fertilizer production, generating a large amount of fluorine-containing waste liquid. These fluorine-containing wastewater systems not only contain high-concentration fluorides, but also coexist with a large amount of inorganic metal ions such as chlorides and sulfates, and are high-salt complex solutions. Literature reports show that the existence of the "salt effect" increases the solubility of insoluble substances, and the growth of microorganisms in high-salt systems is inhibited. At the same time, fluorine may exist in various forms, and the high-concentration coexisting salt ions compete with fluoride ions for reaction sites, which significantly increases the difficulty of removing fluoride from high-salt solutions.

[0003] At present, the treatment of fluoride-containing wastewater in industry mainly includes two-stage defluoridation. The first-stage defluoridation is mainly achieved by chemical precipitation by adding lime / calcium salt. Under normal dosage, the fluoride content of wastewater can only be reduced to about 10-20 mg / L by this method; the second-stage defluoridation is mainly achieved by adding calcium chloride, PAC and PAM to strengthen chemical coagulation and adsorption. Under normal dosage, the fluoride content of wastewater can only be reduced to about 5-10 mg / L by this method, which cannot meet the latest requirements (fluoride ≤1.5-5 mg / L). Therefore, in order to meet the minimum requirements for fluoride content, a deep defluoridation process must be introduced.

[0004] At present, the reported fluoride removal technologies mainly include coprecipitation, membrane separation, electrodialysis, ion exchange, adsorption, etc. Among them, adsorption has been regarded as an environmentally friendly and efficient fluoride removal technology due to its simple operation, low cost, and high fluoride removal efficiency. Various adsorbents have been developed for removing fluoride from aqueous solutions, such as anion exchange resins, zirconium oxide, activated alumina, magnetic iron oxide, magnesium oxide, magnesium-aluminum layered double hydroxides (LDHs) and metal organic frameworks (MOFs).

[0005] Pan synthesized nano-hydrated zirconium oxide (HZO-201) to treat 10 mg / L fluoride-containing wastewater, and the defluorination effect decreased by 75% under the condition of high concentration of salt ion interference (500 mg / L) (Environ. Sci. Technol, 47 (2013) 9347-9354); Cai used nano-layered hydroxide to impregnate polystyrene anion resin to obtain LALDH-201, and treated 20 mg / L fluoride-containing wastewater. Under the condition of salt ion interference (40 mg / L), the defluorination effect decreased by 50% (Water Res, 102 (2016) 109-116); the Mg-Al-LDH adsorbent synthesized by Gao inhibited 30% of 10 mg / L fluoride ions under salt ion interference conditions (J. Mater. Chem. A, 2 (2014) 2119-2128); the fumaric acid anchored zirconium hydroxide chitosan hydrogel beads synthesized by Zhang treated 40 mg / L fluoride ion solution and the defluorination effect decreased by 50% under salt ion interference conditions (Adv. Funct. Mater. 2023, 33, 2213999).

[0006] The above adsorbents have different degrees of inhibition in the defluorination performance in a high-salt and low-fluorine environment, and their anti-ion interference performance is poor, that is, the "salt negative" effect. Therefore, providing an adsorbent that can deeply remove fluorine in high-salt wastewater has become an urgent problem to be solved. Summary of the invention

[0007] The purpose of the present invention is to propose a method for deep defluorination in high-salt wastewater, using acidic resin to load metal ions to prepare a metal ion ligand resin adsorbent, which can achieve better defluorination effect under higher salt concentrations.

[0008] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0009] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0010] (1) preparing a metal ion ligand resin adsorbent;

[0011] (2) adding the metal ion ligand resin adsorbent prepared in step (1) into saline-containing fluoride-containing wastewater for adsorption; in the saline wastewater, F - The concentration of SO4 is not less than 10mg / L; 2- The concentration is 0.05~0.1M.

[0012] Furthermore, in step (1), the metal ion in the metal ion ligand resin adsorbent is selected from one of zirconium ion, copper ion, iron ion, lanthanum ion and aluminum ion.

[0013] Furthermore, in the step (1), the resin in the metal ion ligand resin adsorbent is selected from one of IRC-748, D463, D467 and D001.

[0014] Furthermore, the loading amount of metal ions in the metal ion ligand resin adsorbent does not exceed 10 mM / g.

[0015] Furthermore, in the step (1), the method for preparing the metal ligand resin adsorbent is: adding the acidic resin to the metal salt solution for loading, and after the reaction is completed, filtering and drying to obtain the metal ion ligand resin adsorbent.

[0016] Furthermore, the metal salt solution is selected from one of zirconium oxychloride solution, copper sulfate solution, ferric chloride solution, aluminum chloride solution and lanthanum chloride solution.

[0017] Furthermore, the concentration of the metal salt solution is 1-20 mM.

[0018] Furthermore, in the step (2), a metal ion ligand resin adsorbent is added to the saline-containing and fluoride-containing wastewater for adsorption, and the addition amount of the metal ion ligand resin adsorbent is 0.5 to 1 g / L; and the adsorption time is 12 to 24 hours.

[0019] Furthermore, in the step (2), a metal ion ligand resin adsorbent is added to the saline-containing and fluoride-containing wastewater for adsorption, and the addition amount of the metal ion ligand resin adsorbent is 0.5 g / L; and the adsorption time is 24 h.

[0020] Furthermore, in the step (2), in the salt-containing wastewater, SO4 2- The concentration is 0.05M.

[0021] Compared with the prior art, the advantages of the present invention are as follows:

[0022] 1) Compared with the prior art, various defluorination adsorbents will have different degrees of inhibition in a high-salt environment, that is, they will be "salt negative" and have poor anti-ion interference performance; the present invention uses aminoacetic acid resin IRC-748 to be used for high-salt defluorination after pre-loading metal ions, and will have a "salt-promoting" effect under the coexistence of sulfate.

[0023] 2) The novel metal ion ligand resin prepared in the present invention has a 1.4-fold increase in fluoride removal efficiency under the coexistence of high-concentration sulfate (the concentration is 100 times that of F-), and can deeply remove fluoride-containing wastewater in a high-salt environment.

[0024] 3) The four resins disclosed in the present invention can be used for defluorination after being loaded with iron, lanthanum, zirconium and aluminum metal ions. They all show a "salt-promoting" effect under the condition of 0.05M Na2SO4 solution. Under the same conditions, aminoacetic acid resin IRC-748 loaded with Zr 4+ and Al 3+ The fluoride removal effect is most significantly improved after treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a diagram showing the defluorination effect of aminoacetic acid resin IRC-748 loaded with different concentrations of zirconium ions under different sulfate conditions;

[0026] Figure 2 This is a diagram showing the defluorination effect of aminoacetic acid resin IRC-748 loaded with different metal ions in the presence of sulfate;

[0027] Figure 3 This is a graph showing the defluorination effect of a new zirconium ligand resin (748-Zr) and an alkaline ion exchange resin (PAMD, D213) in the presence of sulfate;

[0028] Figure 4 This is a graph showing the defluorination effect of the new zirconium ligand resin (748-Zr) and the acidic resin loaded with zirconium ions (D463-Zr, D467-Zr, D001-Zr) in the presence of sulfate;

[0029] Figure 5 The new zirconium ligand resin (748-Zr) and the zirconium ligand resin preloaded with 0.05M sulfate (748-Zr-SO4 2- ) Fluoride removal effect diagram in the presence of sulfate;

[0030] Figure 6 The adsorption of fluoride ions by LALDH-201 at 298K is interfered by the competition of anions; wherein the adsorbent dosage is 0.50 g / L; the initial F - The concentration is 20 mg / L; the adsorption time is 24 h.

[0031] Figure 7 The existing literature reports that the adsorption of fluoride ions by HZO-201 and D201 at 298K and pH 7.0±0.2 is affected by the coexistence of Cl - 、NO3 - 、SO4 2- 、HCO3 - The effect diagram of adsorbent was 1.0 g / L and the initial fluorine concentration was 10 mg / L. DETAILED DESCRIPTION

[0032] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with specific embodiments.

[0033] In the following examples, F - The concentration test method is as follows: take 20 ml of the solution after adsorption equilibrium, filter it with a 0.22 μm filter head, add 10 ml of total ionic strength adjustment buffer (TISAB), and finally dilute it to 50 ml and transfer it to a 100 ml polyethylene beaker to measure the F in the solution using a fluoride ion meter. - concentration.

[0034] The preparation method of total ionic strength adjustment buffer (TISAB) is as follows: weigh 58g sodium chloride, 10g sodium citrate, measure 50ml acetic acid, add 500ml water to dissolve, after dissolution, add 135ml 5M sodium hydroxide solution, adjust the solution pH to 5.2, and dilute to 1L with water.

[0035] In the following examples, the test method for the metal ion loading concentration is: taking appropriate amounts of metal ion solutions before and after adsorption, diluting, measuring using an inductively coupled plasma atomic emission spectrometer (ICP-OES), and obtaining the metal loading by calculation.

[0036] Example 1

[0037] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0038] 1. Preparation of zirconium ligand resin (748-Zr): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a zirconium oxychloride solution with a molar concentration of 5 mM for loading, shake for 12 hours, filter, and dry at 60°C overnight to obtain a new zirconium ligand resin 748-Zr with a zirconium ion loading of 1.1 mM / g.

[0039] 2. Use zirconium ligand resin (748-Zr) to adsorb fluoride ions. The steps are as follows:

[0040] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution and 10mg / LF - +0.1M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0041] (2) 748-Zr was added to the solution prepared in step (1) for adsorption (dosage: 0.5 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0042] Example 2

[0043] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0044] 1. Preparation of zirconium ligand resin (748-Zr): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a zirconium oxychloride solution with a molar concentration of 10 mM for loading, shake for 12 hours, filter, and dry at 60°C overnight to obtain a new zirconium ligand resin 748-Zr with a zirconium ion loading of 4.9 mM / g.

[0045] 2. Use zirconium ligand resin (748-Zr) to adsorb fluoride ions. The steps are as follows:

[0046] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution and 10mg / LF - +0.1M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0047] (2) 748-Zr was added to the solution prepared in step (1) for adsorption (dosage: 0.5 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0048] Example 3

[0049] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0050] 1. Preparation of zirconium ligand resin (748-Zr): aminoacetic acid resin IRC-748 (dosage: 1 g / L) was added to a zirconium oxychloride solution with a molar concentration of 20 mM for loading, shaken for 12 hours, filtered, and dried at 60°C overnight to obtain a novel zirconium ligand resin 748-Zr. The loading amount of zirconium ions was 6.5 mM / g.

[0051] 2. Use zirconium ligand resin (748-Zr) to adsorb fluoride ions. The steps are as follows:

[0052] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution and 10mg / LF - +0.1M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0053] (2) 748-Zr was added to the solution prepared in step (1) for adsorption (dosage: 0.5 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0054] Example 4

[0055] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0056] 1. Preparation of zirconium ligand resin (748-Zr): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a zirconium oxychloride solution with a molar concentration of 1 mM for loading, shake for 12 hours, filter, and dry at 60°C overnight to obtain a new zirconium ligand resin 748-Zr with a zirconium ion loading of 0.3 mM / g.

[0057] 2. Use zirconium ligand resin (748-Zr) to adsorb fluoride ions. The steps are as follows:

[0058] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution and 10mg / LF - +0.1M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0059] (2) 748-Zr was added to the solution prepared in step (1) for adsorption (dosage: 0.5 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0060] The defluorination effects of 748-Zr loaded with different zirconium ion concentrations under different sulfate conditions in Examples 1 to 4 are as follows: Figure 1As shown in the figure, with the increase of zirconium ion concentration, the defluorination effect of 748-Zr gradually improved. When the zirconium content was 10mM, the load reached saturation. When it continued to increase to 20mM, the defluorination effect did not show a significant improvement. - Compared with the solution, the fluoride removal effect was improved in the presence of 0.05M and 0.1M Na2SO4 solutions, which is the "salt-promoted" effect. The improvement was most obvious under the 0.05M Na2SO4 solution condition, and the fluoride removal effect could be increased by 1 times. The 0.1M condition also promoted fluoride removal, but the improvement was slightly lower than that under the 0.05M condition.

[0061] Example 5

[0062] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0063] 1. Preparation of zirconium ligand resin (748-Zr): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a zirconium oxychloride solution with a molar concentration of 10 mM for loading, shake for 12 hours, filter, and dry at 60°C overnight to obtain zirconium ligand resin 748-Zr, with a zirconium ion loading amount of 4.9 mM / g.

[0064] 2. Use zirconium ligand resin (748-Zr) to adsorb fluoride ions. The steps are as follows:

[0065] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0066] (2) 748-Zr was added to the solution prepared in step (1) for adsorption (dosage was 1 g / L), and the mixture was shaken for 24 h. When the adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0067] Example 6

[0068] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0069] 1. Preparation of copper ligand resin (748-Cu): aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) is added to a copper sulfate solution with a molar concentration of 10 mM for loading, shaken for 12 hours, filtered, and dried at 60°C overnight to obtain copper ligand resin 748-Cu, with a copper ion loading capacity of 5.3 mM / g.

[0070] 2. Use copper ligand resin (748-Cu) to adsorb fluoride ions. The steps are as follows:

[0071] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0072] (2) 748-Cu was added to the solution prepared in step (1) for adsorption (dosage: 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0073] Example 7

[0074] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0075] 1. Preparation of iron ligand resin (748-Fe): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a 10 mM ferric chloride solution for loading, shake for 12 h, filter, and dry at 60 ° C overnight to obtain iron ligand resin 748-Fe, with an iron ion loading capacity of 4.4 mM / g.

[0076] 2. Use iron ligand resin (748-Fe) to adsorb fluoride ions. The steps are as follows:

[0077] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0078] (2) 748-Fe was added to the solution prepared in step (1) for adsorption (dosage: 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0079] Example 8

[0080] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0081] 1. Preparation of lanthanum ligand resin (748-La): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a lanthanum chloride solution with a molar concentration of 10 mM for loading, shake for 12 hours, filter, and dry at 60°C overnight to obtain lanthanum ligand resin 748-La, with a lanthanum ion loading amount of 3.6 mM / g.

[0082] 2. Use lanthanum ligand resin (748-La) to adsorb fluoride ions. The steps are as follows:

[0083] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0084] (2) 748-La was added to the solution prepared in step (1) for adsorption (dosage was 1 g / L), and the mixture was shaken for 24 h. When the adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0085] Example 9

[0086] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0087] 1. Preparation of aluminum ligand resin (748-Al): Add aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) to a 10 mM aluminum chloride solution for loading, shake for 12 h, filter, and dry at 60 ° C overnight to obtain aluminum ligand resin 748-Al, with an aluminum ion loading of 4.5 mM / g.

[0088] 2. Use aluminum ligand resin (748-Al) to adsorb fluoride ions. The steps are as follows:

[0089] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution, 10mg / LF - +0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0090] (2) 748-Al was added to the solution prepared in step (1) for adsorption (dosage: 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0091] The defluorination effects of aminoacetic acid resin IRC-748 loaded with different metals in Examples 5 to 9 are as follows: Figure 2 As shown, IRC-748 is loaded with Fe 3+ ,La 3+ 、Zr 4+ 、Al 3+ These four metal ions all showed a "salt-promoting" effect in 0.05M Na2SO4 solution, among which Zr 4+ and Al 3+ The fluorine removal effect is most significant; Cu loading 2+ It has almost no effect on fluoride removal.

[0092] Example 10

[0093] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0094] 1. The preparation of zirconium ligand resin (748-Zr) is the same as in Example 2; the zirconium ion loading is 4.9 mM / g.

[0095] 2. Use zirconium ligand resin (748-Zr) to remove fluorine from high salt, the steps are as follows:

[0096] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF - +0.05M Na2SO4 solution, adjust pH to 7 using sodium hydroxide and hydrochloric acid solution.

[0097] (2) 748-Zr (zirconium ion loading of 4.9 mM / g) was added to the solution prepared in step (1) for adsorption (dosage of 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0098] Embodiment 11

[0099] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0100] 1. Preparation of zirconium ligand resin (D463-Zr): Add resin D463 (dosage amount is 1 g / L) to zirconium oxychloride solution (molar concentration is 10 mM) for loading, oscillate for 12 hours, filter, and dry at 60°C overnight to obtain a new zirconium ligand resin D463-Zr with a zirconium ion loading of 2.5 mM / g.

[0101] 2. Use zirconium ligand resin (D463-Zr) to remove fluorine from high salt. The steps are as follows:

[0102] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF - +0.05M Na2SO4 solution, adjust pH to 7 using sodium hydroxide and hydrochloric acid solution.

[0103] (2) D463-Zr (zirconium ion loading of 2.5 mM / g) was added to the solution prepared in step (1) for adsorption (dosage of 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0104] Example 12

[0105] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0106] 1. Preparation of zirconium ligand resin (D467-Zr): Add resin D467 (dosage of 1 g / L) to zirconium oxychloride solution (molar concentration of 10 mM) for loading, oscillate for 12 hours, filter, and dry at 60°C overnight to obtain a new zirconium ligand resin D467-Zr with a zirconium ion loading of 1.9 mM / g.

[0107] 2. Use zirconium ligand resin (D467-Zr) to remove fluorine from high salt. The steps are as follows:

[0108] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF - +0.05M Na2SO4 solution, adjust pH to 7 using sodium hydroxide and hydrochloric acid solution.

[0109] (2) D467-Zr (zirconium ion loading of 1.9 mM / g) was added to the solution prepared in step (1) for adsorption (dosage of 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0110] Embodiment 13

[0111] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0112] 1. Preparation of zirconium ligand resin (D001-Zr): Add resin D001 (dosage of 1 g / L) to zirconium oxychloride solution (molar concentration of 10 mM) for loading, oscillate for 12 h, filter, and dry at 60 ° C overnight to obtain a new zirconium ligand resin D001-Zr with a zirconium ion loading of 1.1 mM / g.

[0113] 2. Use zirconium ligand resin (D001-Zr) to remove fluorine from high salt. The steps are as follows:

[0114] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF - +0.05M Na2SO4 solution, adjust pH to 7 using sodium hydroxide and hydrochloric acid solution.

[0115] (2) D001-Zr (zirconium ion loading of 1.1 mM / g) was added to the solution prepared in step (1) for adsorption (dosage of 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0116] In Examples 10 to 13, the defluorination effect is as follows Figure 4 As shown in the figure, it can be seen that these four acidic resins can be used for fluorine removal after loading zirconium ions, and all show a "salt-promoted" effect, but 748-Zr has the most obvious improvement under the same conditions, and the best fluorine removal effect under high salt conditions.

[0117] Embodiment 14

[0118] A method for deep defluorination in high-salinity wastewater, comprising the following steps:

[0119] 1. Pre-soak the zirconium ligand resin 748-Zr (zirconium ion loading 4.9 mM / g) with sulfate, the steps are as follows:

[0120] (1) Aminoacetic acid resin IRC-748 (dosage amount is 1 g / L) is added to zirconium oxychloride solution (molar concentration is 10 mM) for loading, shaken for 12 hours, filtered, and dried at 60°C overnight to obtain a new zirconium ligand resin 748-Zr (zirconium ion loading amount is 4.9 mM / g).

[0121] (2) The above 748-Zr (dosage: 1 g / L) was added to a 0.05 M Na2SO4 solution for soaking, shaken for 12 h, filtered, and dried at 60° C. overnight to obtain a novel zirconium ligand resin 748-Zr-SO4 soaked in sulfate 2- .

[0122] 2. A new zirconium ligand resin (748-Zr-SO4 2- ) for high salt defluoridation:

[0123] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF - +0.05M Na2SO4 solution, adjust pH to 7 using sodium hydroxide and hydrochloric acid solution.

[0124] (2) The new zirconium ligand resin (748-Zr-SO4 2- ) was added to the solution prepared in (1) for adsorption (dosage was 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0125] Figure 5 The new zirconium ligand resin 748-Zr (zirconium ion loading is 4.9 mM / g) and the zirconium ligand resin 748-Zr-SO4 treated by sulfate immersion 2- (Zirconium ion loading is 4.9mM / g) The defluorination effect in single-component fluoride ion and high-salt fluoride ion systems, respectively, can be seen from the figure, the zirconium ligand resin 748-Zr-SO4 treated with sulfate ion immersion 2- The fluoride removal effect of 748-Zr was similar to that of 748-Zr without sulfate ion immersion treatment, and there was no improvement. 2- When removing fluoride ion solution containing sulfate, the defluorination effect is significantly improved compared with the single-component fluoride ion case. This shows that whether 748-Zr is treated with sulfate or not, it can effectively remove fluoride ions in high-salinity fluoride ion wastewater.

[0126] Comparative Example 1

[0127] Use alkaline ion exchange resin (PAMD is an acrylic resin grafted with triethylenetetramine, patent number ZL201310108031.4, D213 is a commercially available quaternary ammonium salt type styrene resin) to remove fluorine from high salt:

[0128] (1) Prepare 500 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution; mix the fluoride ion stock solution, Na2SO4 stock solution and deionized water to prepare 10 mg / L fluoride ion stock solution and 1 M Na2SO4 stock solution. - Solution and 10mg / LF -+0.05M Na2SO4 solution, adjusted to pH 7 using sodium hydroxide and hydrochloric acid solution;

[0129] (2) PAMD and D213 were added to the solution prepared in step (1) for adsorption (dosage of 1 g / L), and oscillated for 24 h. When adsorption equilibrium was reached, the F content in the solution was measured. - concentration.

[0130] Figure 3 The defluorination effect of 748-Zr (zirconium ion loading of 4.9 mM / g) prepared in Example 2 of the present invention and the alkaline ion exchange resins PAMD and D213 is shown in the figure. Although the alkaline ion exchange resins (PAMD and D213) have no significant difference in the defluorination performance under the condition of single F - The defluorination effect is better under solution conditions, but the defluorination efficiency is close to zero under 0.05M Na2SO4 solution conditions.

[0131] Comparative Example 2

[0132] The defluorination materials reported in the existing literature, commercial polystyrene anion exchange resins loaded with hydrated zirconium oxide and impregnated with Li / Al double hydroxide, D201, HZO-201 and LALDH-201 (Environ. Sci. Technol, 47 (2013) 9347-9354; Water Res, 102 (2016) 109-116) were used for high-salt defluorination under the coexistence of sulfate. The method was the same as that of Comparative Example 1.

[0133] Figure 6 , Figure 7 The ion interference of the defluorination materials (D201, HZO-201 and LALDH-201) reported in the literature is shown in the figure below. Figure 7 It can be seen that the fluorine removal efficiency of the two materials D201 and HZO-201 gradually decreases with the increase of sulfate concentration, and the inhibition is more obvious; the new zirconium ligand resin 748-Zr of the present invention shows a "salt-promoted" effect under high sulfate concentration conditions (converted to 4800 mg / L and 9600 mg / L), and the fluorine removal efficiency is increased by 1.4 times, which is more suitable for fluorine-containing wastewater containing high concentration of sulfate.

[0134] Combination Figure 1 , 2, 3, 4 and 5 show that after aminoacetic acid resin IRC-748 is loaded with zirconium ions, a "salt-promoted" effect will occur in the removal of fluorine in the presence of sulfate, and the effect is best among different resins and loaded with different metal ions; IRC-748 tends to be saturated when loaded with zirconium ions at 10mM, and the fluorine removal efficiency does not increase significantly when the zirconium ion concentration is further increased; the "salt-promoted" effect is most obvious under the conditions of 0.05M Na2SO4 solution, and the fluorine removal efficiency is increased by 1.4 times. Under the conditions of 0.1M Na2SO4 solution, the "salt-promoted" effect slows down.

[0135] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for deep defluorination in high-salinity wastewater, characterized in that: Here are the steps: (1) preparing a metal ion ligand resin adsorbent; (2) adding the metal ion ligand resin adsorbent prepared in step (1) into saline-containing fluoride-containing wastewater for adsorption; in the saline wastewater, F - The concentration of SO4 is not less than 10mg / L; 2- The concentration is 0.05~0.1M.

2. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: In the step (1), the metal ion in the metal ion ligand resin adsorbent is selected from one of zirconium ion, copper ion, iron ion, lanthanum ion and aluminum ion.

3. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: In the step (1), the resin in the metal ion ligand resin adsorbent is selected from one of IRC-748, D463, D467 and D001.

4. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: The loading amount of metal ions in the metal ion ligand resin adsorbent does not exceed 10 mM / g.

5. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: In the step (1), the method for preparing the metal ligand resin adsorbent is: adding an acidic resin into a metal salt solution for loading, and after the reaction is completed, filtering and drying to obtain the metal ion ligand resin adsorbent.

6. The method for deep defluorination in high-salinity wastewater according to claim 5, characterized in that: The metal salt solution is selected from one of zirconium oxychloride solution, copper sulfate solution, ferric chloride solution, aluminum chloride solution and lanthanum chloride solution.

7. The method for deep defluorination in high-salinity wastewater according to any one of claims 5 or 6, characterized in that: The concentration of the metal salt solution is 1-20 mM.

8. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: In the step (2), a metal ion ligand resin adsorbent is added to the saline-containing and fluoride-containing wastewater for adsorption, and the addition amount of the metal ion ligand resin adsorbent is 0.5 to 1 g / L; and the adsorption time is 12 to 24 hours.

9. The method for deep defluorination in high-salinity wastewater according to claim 8, characterized in that: In the step (2), a metal ion ligand resin adsorbent is added to the saline-containing and fluoride-containing wastewater for adsorption, and the addition amount of the metal ion ligand resin adsorbent is 0.5 g / L; and the adsorption time is 24 hours.

10. The method for deep defluorination in high-salinity wastewater according to claim 1, characterized in that: In the step (2), SO4 2- The concentration is 0.05M.

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