CN117602690B - Nonferrous metal mine flotation wastewater treatment agent and preparation method thereof - Google Patents
Nonferrous metal mine flotation wastewater treatment agent and preparation method thereof Download PDFInfo
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- CN117602690B CN117602690B CN202410090385.9A CN202410090385A CN117602690B CN 117602690 B CN117602690 B CN 117602690B CN 202410090385 A CN202410090385 A CN 202410090385A CN 117602690 B CN117602690 B CN 117602690B
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- 238000005188 flotation Methods 0.000 title claims abstract description 49
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 238000001035 drying Methods 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 40
- 238000001914 filtration Methods 0.000 claims abstract description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010992 reflux Methods 0.000 claims abstract description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000011162 core material Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000003944 tolyl group Chemical group 0.000 claims 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- 239000012991 xanthate Substances 0.000 abstract description 19
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 xanthate anions Chemical class 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention discloses a nonferrous metal mine flotation wastewater treatment agent and a preparation method thereof. The preparation method of the nonferrous metal mine flotation wastewater treatment agent comprises the following steps of: adding the coating material into a solvent, performing ultrasonic treatment, adding chloropropyl triethoxysilane, refluxing, filtering, washing and drying to obtain a modified coating material; and (2) adding the modified coating material into a solvent, performing ultrasonic treatment, adding pancreatic alkali and triethylamine, refluxing, filtering, washing and drying to obtain the nonferrous metal mine flotation wastewater treatment agent. According to the invention, the nonferrous metal mine flotation wastewater treatment agent with good heavy metal ion and xanthate removal performance is prepared by synthesizing the coating material with large specific surface area and high Cu element content and grafting pancreatic alkali with rich nitrogen content in a synergistic manner.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a nonferrous metal mine flotation wastewater treatment agent and a preparation method thereof.
Background
The development of mineral resources creates great economic benefits and brings certain influence to the environment. Among them, beneficiation wastewater is a main factor causing deterioration of mine environment. The residual chemical agent and heavy metal ions contained in the wastewater are one of the most important factors causing harm to the environment in the beneficiation wastewater, and are also difficult to effectively treat the wastewater.
Xanthate in flotation wastewater is used as a flotation agent which is most widely applied in mineral separation, causes great damage to the environment, is a great obstacle for green mine construction, and can exist in water for a long time, so that the xanthate is difficult to remove, and has long-term influence on the environment and human health. In the prior art, when the xanthate is degraded during wastewater treatment, synchronous removal of heavy metal ions is less involved, and the removal efficiency is required to be improved. Therefore, the development of the adsorbent which is low in cost, easy to separate and high in efficiency can remove xanthate and heavy metal ions in flotation wastewater.
Disclosure of Invention
The invention aims to provide a nonferrous metal mine flotation wastewater treatment agent and a preparation method thereof, which are used for solving the technical problems that the flotation wastewater treatment efficiency is low and xanthate and heavy metal ions cannot be synchronously removed in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a nonferrous metal mine flotation wastewater treatment agent, which comprises the following steps:
adding the coating material into a solvent, performing ultrasonic treatment, adding chloropropyl triethoxysilane, refluxing, filtering, washing and drying to obtain a modified coating material;
in the above process, the surface hydroxyl groups or surface oxygen (=o) of the coating material react and graft with silanol groups hydrolyzed by chloropropyl triethoxysilane.
And (2) adding the modified coating material into a solvent, performing ultrasonic treatment, adding pancreatic alkali and triethylamine, refluxing, filtering, washing and drying to obtain the nonferrous metal mine flotation wastewater treatment agent.
In the process, the chlorine atoms on the surface of the modified coating material and primary amino groups of pancreatic alkali undergo nucleophilic substitution reaction to generate the treating agent.
The structural formula of the nonferrous metal mine flotation wastewater treatment agent is as follows:
preferably, the preparation method of the coating material comprises the following steps:
s1, mgCl of 20-40L and 0.5mol/L is added 2 ·6H 2 Heating O solution to 40-60deg.C in water bath, adding 10-20L sodium alginate solution 10g/L, stirring at 100-300r/min for 10-30min, and adding 20-40L NH 1mol/L 4 HCO 3 Reacting the solution for 2-4h, filtering, washing the filter residue with water for 3-5 times, and finally drying at 40-60 ℃ for 12-36h to obtain a core material;
s2 dispersing 50-100g core material in 2-4L ethanol, adding 0.6-1.2L Cu (NO) 0.5mol/L 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 2-4h at the temperature of 30-50 ℃ and the rotating speed of 100-200r/min, filtering, washing filter residues with water for 3-5 times, drying for 5-7h at the temperature of 30-50 ℃, and finally carrying out heat treatment for 1-2h at the temperature of 100-140 ℃ to obtain the coating material.
In the process, hydrated magnesium carbonate is used as a core material, and a copper-based coating material is prepared by a surface substitution method; firstly, generating basic copper nitrate through surface substitution, and then obtaining the composite coating material of copper oxide and hydrated magnesium carbonate through pyrolysis.
Preferably, in the step (1), the dosage ratio of the coating material, the solvent and the chloropropyl triethoxysilane is (25-50) g (1-2) L (0.1-0.2) L.
Preferably, in the step (1), the solvent is a 90wt% toluene aqueous solution; ultrasonic treatment conditions: the ultrasonic treatment frequency is 20-100KHz, and the ultrasonic treatment time is 10-20min.
Preferably, in the step (1), the reflux conditions are as follows: the reflux temperature is 100-140 ℃ and the reflux time is 12-36h; the washing method comprises the following steps: alternately washing the filter residue with ethanol and deionized water for 3-5 times; drying conditions: the drying temperature is 40-60deg.C, and the drying time is 6-18h.
Preferably, in the step (2), the dosage ratio of the modified coating material, the solvent, the pancreatic alkali and the triethylamine is (15-30) g (0.4-0.8) L (4-8) g (0.045-0.09) L.
Preferably, in the step (2), the solvent is a 90wt% toluene aqueous solution; the ultrasonic treatment time is 15-25min; reflux conditions: the reflux temperature is 100-140 ℃ and the reflux time is 36-54h; the washing method comprises the following steps: washing the filter residue with ethanol for 3-5 times; drying conditions: the drying temperature is 40-60deg.C, and the drying time is 24-48 hr.
The nonferrous metal mine flotation wastewater treatment agent is prepared by adopting the preparation method of the nonferrous metal mine flotation wastewater treatment agent.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, the novel large-particle-size coating material is prepared by a hydrothermal crystallization-surface displacement method, basic copper nitrate is decomposed in the heat treatment process, nitrate is released in a gas form to form a plurality of cavities and copper oxide is generated, so that the coating material has larger specific surface area, higher Cu element content and higher isoelectric point, more active sites are provided, bivalent copper ions serve as active sites of a treating agent to attract xanthate anions to the surface of the treating agent, oxidation products of Cu (I) ions and xanthate anions are generated, xanthate is further oxidized to generate polysulfide and sulfate, and the coating material has good adsorption performance and faster adsorption efficiency on xanthate.
2. The grafted pancreatic alkali in the treating agent has good adsorption characteristics on metal ions and xanthate due to the rich nitrogen content, the noncovalent interaction between heavy metal ions and the surface of an electron-rich pi system (such as benzene, ethylene and acetylene) also enhances the adsorptivity of the treating agent to heavy metal, and meanwhile, the heavy metal ions are coupled with imino groups and nitrogen in purine rings, so that the treating agent has good effect of removing the heavy metal, and meanwhile, the action of sulfur ions and heavy metal generated in the xanthate treatment process generates precipitation, so that the removing efficiency of the heavy metal is synergistically improved; the large-size structure of the wastewater treated by the treating agent is kept complete, which is beneficial to the subsequent solid-liquid separation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation process of the nonferrous metal mine flotation wastewater treatment agent;
FIG. 2 is a graph of the effect of different doses of treatment agent according to the invention on the treatment of flotation wastewater;
FIG. 3 is a graph showing the effect of the treatment agent of the present invention and the comparative treatment agent on wastewater treatment.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The substances and sources involved in the following examples and comparative examples are shown in Table 1:
TABLE 1
Example 1 this example discloses a method for preparing a coating material comprising the steps of:
s1 MgCl of 30L and 0.5mol/L 2 ·6H 2 Heating O solution to 50deg.C in water bath, adding 15L alginic acid 10g/LSodium solution is stirred for 15min at a speed of 200r/min, and then 30L of NH and 1mol/L of NH are added 4 HCO 3 Reacting the solution for 3 hours, filtering, washing filter residues for 4 times, and finally drying at 50 ℃ for 24 hours to obtain a core material;
s2 dispersing 75g core material in 3L ethanol, adding 0.9L and 0.5mol/L Cu (NO) 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 3 hours at the temperature of 40 ℃ and the rotating speed of 150r/min, filtering, washing filter residues with water for 4 times, drying for 6 hours at the temperature of 40 ℃, and finally carrying out heat treatment for 1.5 hours at the temperature of 120 ℃ to obtain the coating material.
Example 2 this example discloses a method for preparing a coating material comprising the steps of:
s1, 20L of MgCl of 0.5mol/L 2 ·6H 2 Heating O solution to 60deg.C in water bath, adding 10L sodium alginate solution at a concentration of 10g/L, stirring at a rotation speed of 300r/min for 10min, and adding NH at a concentration of 40L and 1mol/L 4 HCO 3 Reacting the solution for 2 hours, filtering, washing filter residues for 5 times, and finally drying at 40 ℃ for 36 hours to obtain a core material;
s2 dispersing 50g core material in 4L ethanol, adding 0.6L and 0.5mol/L Cu (NO) 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 4 hours at the temperature of 50 ℃ and the rotating speed of 100r/min, filtering, washing filter residues with water for 3 times, drying for 5 hours at the temperature of 50 ℃, and finally carrying out heat treatment for 1 hour at the temperature of 140 ℃ to obtain the coating material.
Example 3 this example discloses a method for preparing a clad material comprising the steps of:
s1, 20L of MgCl of 0.5mol/L 2 ·6H 2 Heating O solution to 40deg.C in water bath, adding 20L sodium alginate solution 10g/L, stirring at 100r/min for 30min, and adding NH 20L 1mol/L 4 HCO 3 Reacting the solution for 4 hours, filtering, washing filter residues for 3 times, and finally drying at 60 ℃ for 12 hours to obtain a core material;
s2 dispersing 100g core material in 2L ethanol, adding 1.2L Cu (NO) 0.5mol/L 3 ) 2 ·3H 2 O solution, then at 30 ℃ and 200r/minAnd (3) carrying out water bath reaction for 2 hours, filtering, washing filter residues with water for 5 times, drying at 30 ℃ for 7 hours, and finally carrying out heat treatment at 100 ℃ for 2 hours to obtain the coating material.
Example 4 this example discloses a method for preparing a coating material comprising the steps of:
s1 MgCl 25L and 0.5mol/L 2 ·6H 2 Heating O solution to 46 ℃ in water bath, adding 18L of sodium alginate solution with the concentration of 10g/L, stirring for 25min at the rotating speed of 150r/min, and adding 35L of NH with the concentration of 1mol/L 4 HCO 3 Reacting the solution for 2.5h, filtering, washing filter residues for 4 times, and finally drying at 56 ℃ for 15h to obtain a core material;
s2 dispersing 60g core material in 3.5L ethanol, adding 0.7L and 0.5mol/L Cu (NO) 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 3.5h at the temperature of 35 ℃ and the rotating speed of 180r/min, filtering, washing filter residues with water for 4 times, drying at 45 ℃ for 7h, and finally carrying out heat treatment at 110 ℃ for 2h to obtain the coating material.
Example 5 this example discloses a method for preparing a coating material comprising the steps of:
s1 MgCl of 32L and 0.5mol/L 2 ·6H 2 Heating O solution to 50deg.C in water bath, adding 12L sodium alginate solution 10g/L, stirring at 230r/min for 11min, and adding NH 30L 1mol/L 4 HCO 3 Reacting the solution for 2.2h, filtering, washing filter residues for 5 times, and finally drying at 50 ℃ for 30h to obtain a core material;
s2 dispersing 88g core material in 4L ethanol, adding 1.1L Cu (NO) 0.5mol/L 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 3.5h at the temperature of 32 ℃ and the rotating speed of 180r/min, filtering, washing filter residues with water for 3 times, drying for 5.2h at the temperature of 35 ℃, and finally carrying out heat treatment for 1.7h at the temperature of 100 ℃ to obtain the coating material.
Example 6 referring to fig. 1, the present embodiment discloses a method for preparing a non-ferrous metal mine flotation wastewater treatment agent, comprising the following steps:
step (1), adding 37.5g of the coating material prepared in the embodiment 1 into 1.5L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment at the frequency of 60KHz for 15min, adding 0.15L of chloropropyl triethoxysilane, refluxing for 24h at 120 ℃, filtering, alternately washing for 4 times with ethanol and deionized water, and drying for 12h at 50 ℃ to obtain a modified coating material;
and (2) adding 22g of modified coating material into 0.6L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment for 15min, adding 6g of pancreatic alkali and 0.07L of triethylamine, refluxing at 120 ℃ for 48h, filtering, washing with ethanol for 4 times, and drying at 50 ℃ for 36h to obtain the nonferrous metal mine flotation wastewater treatment agent.
Example 7 referring to fig. 1, the present example discloses a method for preparing a non-ferrous metal mine flotation wastewater treatment agent, comprising the following steps:
step (1) adding 50g of the coating material prepared in the example 2 into 1L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment at the frequency of 100KHz for 10min, adding 0.2L of chloropropyl triethoxysilane, refluxing at 100 ℃ for 36h, filtering, alternately washing with ethanol and deionized water for 3 times, and drying at 60 ℃ for 6h to obtain a modified coating material;
and (2) adding 30g of modified coating material into 0.4L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment for 20min, adding 4g of pancreatic alkali and 0.09L of triethylamine, refluxing at 100 ℃ for 54h, filtering, washing with ethanol for 3 times, and drying at 60 ℃ for 24h to obtain the nonferrous metal mine flotation wastewater treatment agent.
Example 8 referring to fig. 1, the present example discloses a method for preparing a non-ferrous metal mine flotation wastewater treatment agent, comprising the following steps:
step (1) adding 25g of the coating material of the embodiment 3 into 2L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment for 20min at the frequency of 20KHz, adding 0.1L of chloropropyl triethoxysilane, refluxing for 12h at 140 ℃, filtering, alternately washing for 5 times by using ethanol and deionized water, and drying for 18h at 40 ℃ to obtain a modified coating material;
15g of the modified coating material in the step (2) is added into 0.8L of 90wt% toluene aqueous solution, ultrasonic treatment is carried out for 10min, 8g of pancreatic alkali and 0.045L of triethylamine are added, reflux is carried out for 36h at 140 ℃, filtration is carried out, ethanol is used for washing 5 times, and drying is carried out for 48h at 40 ℃ to obtain the nonferrous metal mine flotation wastewater treatment agent.
Example 9 referring to fig. 1, the present embodiment discloses a method for preparing a non-ferrous metal mine flotation wastewater treatment agent, comprising the following steps:
step (1), adding 30g of the coating material of the example 4 into 1.2L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment at the frequency of 30KHz for 18min, adding 0.18L of chloropropyl triethoxysilane, refluxing for 15h at 110 ℃, filtering, alternately washing with ethanol and deionized water for 5 times, and drying at 60 ℃ for 10h to obtain a modified coating material;
28g of modified coating material is added into 0.5L of 90wt% toluene aqueous solution, ultrasonic treatment is carried out for 16min, 7g of pancreatic alkali and 0.05L of triethylamine are added, reflux is carried out for 40h at 130 ℃, filtration is carried out, ethanol is used for washing 3 times, and drying is carried out for 45h at 55 ℃, thus obtaining the nonferrous metal mine flotation wastewater treatment agent.
Example 10 referring to fig. 1, the present example discloses a method for preparing a non-ferrous metal mine flotation wastewater treatment agent, comprising the following steps:
step (1), adding 45g of the coating material of the embodiment 5 into 1.4L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment at the frequency of 70KHz for 12min, adding 0.13L of chloropropyl triethoxysilane, refluxing at 130 ℃ for 29h, filtering, alternately washing with ethanol and deionized water for 5 times, and drying at 45 ℃ for 15h to obtain a modified coating material;
and (2) adding 25g of modified coating material into 0.7L of 90wt% toluene aqueous solution, carrying out ultrasonic treatment for 12min, adding 5g of pancreatic alkali and 0.08L of triethylamine, refluxing at 110 ℃ for 50h, filtering, washing with ethanol for 5 times, and drying at 45 ℃ for 28h to obtain the nonferrous metal mine flotation wastewater treatment agent.
Comparative example 1 in the step (1) of preparing a non-ferrous metal mine flotation wastewater treatment agent of comparative example 1, the added coating material prepared in example 1 was not subjected to heat treatment, and other conditions were not changed, and the prepared coating material was specifically as follows:
s1 MgCl of 30L and 0.5mol/L 2 ·6H 2 Heating O solution to 50 in water bathAdding 15L of sodium alginate solution at a concentration of 10g/L, stirring at a rotation speed of 200r/min for 15min, and adding 30L of NH at a concentration of 1mol/L 4 HCO 3 Reacting the solution for 3 hours, filtering, washing filter residues for 4 times, and finally drying at 50 ℃ for 24 hours to obtain a core material;
s2 dispersing 75g core material in 3L ethanol, adding 0.9L and 0.5mol/L Cu (NO) 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 3 hours at the temperature of 40 ℃ and the rotating speed of 150r/min, filtering, washing filter residues with water for 4 times, and drying at the temperature of 40 ℃ for 6 hours to obtain the coating material.
Comparative example 2 compared with example 6, comparative example 2 does not have the step (2) of adding pancreatic alkali in the process of preparing the nonferrous metal mine flotation wastewater treatment agent, namely the modified coating material obtained in the step (1) is the final nonferrous metal mine flotation wastewater treatment agent, and other conditions are unchanged.
Experimental example the content of each component of the flotation wastewater: the content of xanthate is 11-34mg/L, the content of heavy metal lead is 0.3-19mg/L, the content of heavy metal zinc is 5-19mg/L, and the content of heavy metal cadmium is 0.2-19mg/L.
The nonferrous metal mine flotation wastewater treatment agents of examples 6-10 and comparative examples 1-2 were used to treat the flotation wastewater, specifically as follows:
under normal temperature, 0.5g, 1g, 1.5g, 2.0g and 3.0g of the nonferrous metal mine flotation wastewater treatment agent prepared in the example 6 are respectively added into 1L of flotation wastewater, stirred at the rotating speed of 200r/min for 60min, respectively collecting supernatant fluid for analysis, wherein the component is A, B, C, D, E, and the residual xanthate in the suspension is measured by using an ultraviolet-visible spectrophotometer with the wavelength of 301nm, and N is adopted 2 An adsorption-desorption analyzer (NOVA win m, quantachrome, usa) measures the surface area of the treatment agent, total pore volume.
The removal rate of xanthate and heavy metal ions in the flotation wastewater is analyzed, and the test results are shown in table 2 and fig. 2:
TABLE 2
Under normal temperature, 1.5g of nonferrous metal mine flotation wastewater treatment agents prepared in examples 6-10 and comparative examples 1-2 are respectively added into 1L of flotation wastewater, stirred for 60min at a rotating speed of 200r/min, respectively taking supernatant for analysis, wherein the group is a, b, c, d, e, f, g, the removal rate of xanthate and heavy metal ions in the flotation wastewater is tested, and the test results are shown in Table 3 and FIG. 3:
TABLE 3 Table 3
From the test results in tables 2 and 3, the nonferrous metal mine flotation wastewater treatment agent prepared in example 6 of the present invention has good xanthate and heavy metal ion treatment effects. As can be seen from the comparison of the comparative example 1 and the example 6, the coating material of the invention is not subjected to heat treatment, and the specific surface area of the final treating agent and the higher Cu element content can be increased, so that the treating effect of the treating agent on xanthate and heavy metal ions can be improved; as can be seen from the comparison of the comparative example 2 and the example 6, the addition of pancreatic alkali in the invention can increase the functional group of the treating agent and can better improve the treating effect of the treating agent on xanthate and heavy metal ions.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The preparation method of the nonferrous metal mine flotation wastewater treatment agent is characterized by comprising the following steps of:
adding the coating material into a solvent, performing ultrasonic treatment, adding chloropropyl triethoxysilane, refluxing, filtering, washing and drying to obtain a modified coating material;
adding the modified coating material into a solvent, performing ultrasonic treatment, adding pancreatic alkali and triethylamine, refluxing, filtering, washing and drying to obtain the nonferrous metal mine flotation wastewater treatment agent;
the preparation method of the coating material comprises the following steps:
s1, mgCl of 20-40L and 0.5mol/L is added 2 ·6H 2 Heating O solution to 40-60deg.C in water bath, adding 10-20L sodium alginate solution 10g/L, stirring at 100-300r/min for 10-30min, and adding 20-40L NH 1mol/L 4 HCO 3 Reacting the solution for 2-4h, filtering, washing the filter residue with water for 3-5 times, and finally drying at 40-60 ℃ for 12-36h to obtain a core material;
s2 dispersing 50-100g core material in 2-4L ethanol, adding 0.6-1.2L Cu (NO) 0.5mol/L 3 ) 2 ·3H 2 O solution, then carrying out water bath reaction for 2-4h at the temperature of 30-50 ℃ and the rotating speed of 100-200r/min, filtering, washing filter residues with water for 3-5 times, drying for 5-7h at the temperature of 30-50 ℃, and finally carrying out heat treatment for 1-2h at the temperature of 100-140 ℃ to obtain the coating material.
2. The method for preparing a non-ferrous metal mine flotation wastewater treatment agent according to claim 1, wherein in the step (1), the dosage ratio of the coating material, the solvent and the chloropropyl triethoxysilane is (25-50) g (1-2) L (0.1-0.2) L.
3. The method for preparing a nonferrous metal mine flotation wastewater treatment agent according to claim 1, wherein in the step (1), the solvent is a toluene aqueous solution of 90 wt%; ultrasonic treatment conditions: the ultrasonic treatment frequency is 20-100KHz, and the ultrasonic treatment time is 10-20min.
4. The method for preparing a nonferrous metal mine flotation wastewater treatment agent according to claim 1, wherein in the step (1), the reflux condition is as follows: the reflux temperature is 100-140 ℃ and the reflux time is 12-36h; the washing method comprises the following steps: alternately washing the filter residue with ethanol and deionized water for 3-5 times; drying conditions: the drying temperature is 40-60deg.C, and the drying time is 6-18h.
5. The method for preparing a non-ferrous metal mine flotation wastewater treatment agent according to claim 1, wherein in the step (2), the dosage ratio of the modified coating material, the solvent, the pancreatic alkali and the triethylamine is (15-30) g (0.4-0.8) L (4-8) g (0.045-0.09) L.
6. The method for preparing a nonferrous metal mine flotation wastewater treatment agent according to claim 1, wherein in the step (2), the solvent is a toluene aqueous solution of 90 wt%; the ultrasonic treatment time is 15-25min; reflux conditions: the reflux temperature is 100-140 ℃ and the reflux time is 36-54h; the washing method comprises the following steps: washing the filter residue with ethanol for 3-5 times; drying conditions: the drying temperature is 40-60deg.C, and the drying time is 24-48 hr.
7. A nonferrous metal mine flotation wastewater treatment agent prepared by the method of any one of claims 1-6.
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| WO2008045599A2 (en) * | 2006-06-16 | 2008-04-17 | World Minerals, Inc. | Heavy metal adsorbent material, processes of making same, and methods of separating heavy metals from fluids |
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| CN113087207A (en) * | 2021-04-07 | 2021-07-09 | 山东理工大学 | Method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation |
| WO2022165989A1 (en) * | 2021-02-05 | 2022-08-11 | 南方科技大学 | Mxene material having organic chelating functional groups grafted on surface and preparation method therefor |
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| WO2008045599A2 (en) * | 2006-06-16 | 2008-04-17 | World Minerals, Inc. | Heavy metal adsorbent material, processes of making same, and methods of separating heavy metals from fluids |
| KR20130015013A (en) * | 2013-01-14 | 2013-02-12 | 한국화학연구원 | Porous organic-inorganic hybrid materials, method for preparing thereof, adsorbant comprising them and application thereof |
| CN105948201A (en) * | 2016-06-08 | 2016-09-21 | 江西元再生资源有限公司 | Preparation method of beneficiation wastewater metal trapping agent |
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| WO2022165989A1 (en) * | 2021-02-05 | 2022-08-11 | 南方科技大学 | Mxene material having organic chelating functional groups grafted on surface and preparation method therefor |
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