CN113087207A - Method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation - Google Patents

Method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation Download PDF

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CN113087207A
CN113087207A CN202110373510.3A CN202110373510A CN113087207A CN 113087207 A CN113087207 A CN 113087207A CN 202110373510 A CN202110373510 A CN 202110373510A CN 113087207 A CN113087207 A CN 113087207A
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magnesium oxide
porous magnesium
ferrous metal
beneficiation wastewater
porous
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CN113087207B (en
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陆帅帅
张彩娥
闫平科
王儒
高玉娟
白阳
崔万顺
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Shandong University of Technology
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Abstract

The invention belongs to the technical field of beneficiation wastewater purification, and particularly relates to a method for purifying nonferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation. Taking non-ferrous metal beneficiation wastewater, adjusting the temperature and the pH, adding plant polysaccharide to regulate and control prepared porous magnesium oxide, and oscillating and adsorbing to obtain wastewater turbid liquid; filtering the waste water suspension to obtain purified water and a filter cake, adding water into the filter cake for dispersing, and adding an oxidant for degradation to obtain a degraded suspension; filtering the degraded suspension, putting the filter cake into an ammonium salt solution, and leaching under the heating and stirring conditions to obtain a high-purity magnesium salt leaching solution and a heavy metal ion hydroxide precipitate; adjusting the pH value of the leachate, adding plant polysaccharide and carbonate, crystallizing, filtering and drying to obtain a porous magnesium oxide precursor, and calcining the porous magnesium oxide precursor to obtain regenerated porous magnesium oxide. The method provided by the invention realizes synchronous removal of the sulfydryl collecting agent and heavy metal ions through co-adsorption, and the porous magnesium oxide can be recycled.

Description

Method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation
Technical Field
The invention belongs to the technical field of beneficiation wastewater purification, and particularly relates to a method for purifying nonferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation.
Background
The discharge amount of beneficiation wastewater in China is huge, which accounts for about one tenth of the total amount of industrial wastewater every year in China, and the discharge amount of the beneficiation wastewater of non-ferrous metals only reaches more than 560 million tons/day. The sulfydryl collecting agents such as xanthate and black powder remained in the nonferrous metal beneficiation wastewater have the characteristics of high pollution and high toxicity, and the remained Cu2+、Pb2+、Zn2+The heavy metal ions have accumulative property, irreversibility and continuous pollution property, and have great harm to an ecosystem. When the beneficiation wastewater is recycled, the residual sulfydryl collecting agent and Cu2+、Pb2+、Zn2+The heavy metal ions can reduce the selectivity of flotation operation, deteriorate product indexes, and key harmful components (a mercapto collecting agent and heavy metal ions) of the nonferrous metal beneficiation wastewater must be effectively purified, which is also an inevitable requirement for building green mines.
The prior common treatment methods for purifying the nonferrous metal mineral separation wastewater comprise a flocculation precipitation method, a chemical oxidation method, an adsorption purification method and the like. Wherein, the adsorption method is a process for removing various pollutants in the wastewater simultaneously by utilizing the physical adsorption and the chemical adsorption performance of the solid adsorbent. The adsorption method has the advantages of good effect and simple process for treating organic pollutants or heavy metal ions in the wastewater. Common adsorbents include activated carbon, graphene, carbon nanotubes, polymeric resins, zeolites, modified diatomaceous earth, bentonite, and the like. However, for the non-ferrous metal beneficiation wastewater, the problems of large adsorbent dosage, difficult regeneration and high cost still exist at present.
The porous magnesium oxide is an important porous mineral material, has high specific surface area, rich pore channels, good appearance and a large number of active sites, and is widely used as a catalyst, an antibacterial agent, an adsorbent and the like. The porous magnesium oxide is prepared by adopting soluble magnesium salt, low-grade magnesite and brine as magnesium sources, and has the characteristics of low cost and high added value of products. The precursor thermal decomposition method is a commonly used method for synthesizing porous magnesium oxide, and utilizes the release of H in the thermal decomposition process of the precursor2O and CO2Creating the principle of a large pore structure. Common crystal form regulating agents for preparing the porous magnesium oxide precursor comprise SDS (sodium dodecyl sulfate), CTAB (cetyl trimethyl ammonium bromide), SDBS (sodium dodecyl benzene sulfonate), PEG (polyethylene glycol), P123 and the like. Plant polysaccharide is ubiquitous in natural plant, and a large molecular compound composed of a plurality of same or different monosaccharides through alpha-glycosidic bonds or beta-glycosidic bonds participates in various life activities in organisms, and is widely applied to the industries of food, medicine, chemical industry, papermaking, building, ceramics, daily chemicals, petroleum, printing and dyeing and the like. However, no relevant report is found for regulating and controlling the crystallization process of the porous magnesium oxide precursor by adopting the plant polysaccharide.
In conclusion, the plant polysaccharide is used for regulating and controlling the crystallization process and the calcination pore-forming process of the porous magnesium oxide precursor, and the porous magnesium oxide is used as an adsorbent, so that the method has great practical value and wide application prospect in the purification treatment of the non-ferrous metal beneficiation wastewater.
Disclosure of Invention
The purpose of the invention is: provides a method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide recycling preparation. The method can efficiently remove the key harmful components such as the sulfydryl collecting agent, the heavy metal ions and the like in the nonferrous metal beneficiation wastewater, and simultaneously realize the regeneration preparation and the use of the porous magnesium oxide.
The invention relates to a method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide recycling preparation, which comprises the following steps:
(1) adsorption reaction
Taking a non-ferrous metal beneficiation wastewater solution, adjusting the temperature and the pH of the solution, adding porous magnesium oxide prepared by regulating and controlling plant polysaccharide into non-ferrous metal beneficiation wastewater as an adsorbent, and oscillating at constant temperature to obtain a wastewater suspension;
(2) oxidative degradation
Filtering the wastewater suspension obtained in the step (1), wherein the filtrate is purified water, dispersing a filter cake in the water, stirring, adjusting the pH value of the obtained suspension, and adding an oxidant for oxidative degradation to obtain a degraded suspension;
(3) ammonium salt leaching
Filtering the degradation suspension obtained in the step (2), combining the filtrate with the purified water obtained in the step (2), and putting the filter cake into an ammonium salt solution for leaching to obtain a high-purity magnesium salt leaching solution and a heavy metal ion hydroxide precipitate;
(4) regeneration of porous magnesium oxide
And (3) adjusting the pH value of the high-purity magnesium salt leaching solution obtained in the step (3) to 6-9, adding plant polysaccharide and carbonate for crystallization, filtering the obtained crystal, washing with water, drying to obtain a porous magnesium oxide precursor, and finally calcining the porous magnesium oxide precursor to obtain regenerated porous magnesium oxide which is continuously used for adsorption purification of non-ferrous metal beneficiation wastewater.
Wherein:
in the non-ferrous metal beneficiation wastewater in the step (1), key harmful impurities are residual mercapto collecting agents and heavy metal ions, wherein the concentration of the mercapto collecting agents is 5-200 mg/L, and the concentration of the heavy metal ions is 0.1-50 mg/L. The sulfydryl collecting agent is one or more of ethyl xanthate, butyl xanthate, isoamyl xanthate, butylammonium nigricans or aniline nigricans, and the heavy metal ions are Cu2+、Pb2+Or Zn2+One or more of (a).
The plant polysaccharide used in step (1) is the same as that used in step (4).
Adjusting the temperature of the non-ferrous metal beneficiation wastewater solution in the step (1) to be 25-50 ℃, and adjusting the pH to be 6-9; the dosage of the porous magnesium oxide prepared by regulating and controlling the plant polysaccharide is 0.1-10 g/L, and the constant-temperature oscillation is carried out for 60-180 min.
And (3) dispersing the filter cake in water according to the mass ratio of 0.5-2: 10 in the step (2), stirring for 5-10 min, and adjusting the pH of the obtained suspension to 6-8.
And (3) the oxidant in the step (2) is one or more of sodium hypochlorite, hydrogen peroxide or sodium persulfate, and the dosage of the oxidant is 1.5-3 times of the mass of the mercapto collector in the non-ferrous metal beneficiation wastewater.
The oxidative degradation time in the step (2) is 120-300 min.
The solid-liquid ratio of the filter cake and the ammonium salt solution in the step (3) is 20-100 g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 2-6: 1, and the ammonium salt is one or more of ammonium chloride, ammonium sulfate or ammonium nitrate.
The leaching temperature in the step (3) is 75-95 ℃, the stirring speed is 50-200 r/min, and the leaching time is 60-180 min.
The crystallization temperature in the step (4) is 40-75 ℃, and the time is 60-120 min.
The number of washing times in the step (4) is 3.
Drying at 40-60 ℃ in the step (4) to obtain a porous magnesium oxide precursor, and calcining the porous magnesium oxide precursor at 450-550 ℃ for 0.1-1 h to obtain regenerated porous magnesium oxide.
The plant polysaccharide in the step (4) is one or more of carboxymethyl starch, carboxymethyl cellulose or guar gum, the using amount of the plant polysaccharide is 0.5-2.5% of the mass of the magnesium salt in the high-purity magnesium salt leaching solution, the carbonate is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate, and the molar ratio of the carbonate to the magnesium salt in the high-purity magnesium salt leaching solution is 1-2.5: 1.
In the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of the sulfydryl collecting agent is 0.1-3.0 mg/L, and the content of heavy metal ions is 0.005-0.50 mg/L.
As a preferred technical scheme, the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation comprises the following steps:
(1) adsorption reaction
Taking a non-ferrous metal beneficiation wastewater solution, adjusting the temperature of the wastewater solution to 25-50 ℃, adjusting the pH to 6-9, adding porous magnesium oxide prepared by regulating and controlling plant polysaccharide as an adsorbent, wherein the adding amount of the porous magnesium oxide is 0.1-10 g/L, adding the porous magnesium oxide into the non-ferrous metal beneficiation wastewater, and oscillating at a constant temperature for 60-180 min to obtain a wastewater suspension;
(2) oxidative degradation
Filtering the wastewater suspension obtained in the step (1), wherein the filtrate is purified water, the filter cake is dispersed in the water according to the mass ratio of (0.5-2) to (10), stirring for 5-10 min, adjusting the pH value of the suspension to be 6-8, and then adding an oxidant to oxidize for 120-300 min to obtain a degraded suspension;
(3) ammonium salt leaching
Filtering the degradation turbid liquid obtained in the step (2), combining the filtrate with the purified water obtained in the step (2), putting the filter cake into an ammonium salt solution, heating to 75-95 ℃, stirring at a speed of 50-200 r/min, and leaching for 60-180 min to obtain a high-purity magnesium salt leaching liquid and a heavy metal ion hydroxide precipitate;
(4) regeneration of porous magnesium oxide
And (3) adjusting the pH value of the leachate obtained in the step (4) to 6-9, adding plant polysaccharide and carbonate, carrying out crystallization reaction for 60-120 min at the reaction temperature of 40-75 ℃, filtering the obtained crystal, washing the crystal with water for three times, drying the crystal at the temperature of 40-60 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at the temperature of 450-550 ℃ for 0.1-1 h to obtain regenerated porous magnesium oxide, and continuously using the regenerated porous magnesium oxide for adsorption purification of the nonferrous metal beneficiation wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cyclic preparation can efficiently remove the key harmful components such as the sulfydryl collecting agent, the heavy metal ions and the like in the non-ferrous metal beneficiation wastewater, simultaneously realize the regeneration preparation and the use of the porous magnesium oxide, reduce the adsorption treatment cost and realize the application of the porous magnesium oxide in the purification treatment of the non-ferrous metal beneficiation wastewater.
(2) According to the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cyclic preparation, the porous magnesium oxide is selected as the adsorbent of the non-ferrous metal beneficiation wastewater, the low-price soluble magnesium salt and carbonate are used as raw materials, the method has the characteristic of wide source, the preparation process is simple, the temperature condition of the precursor crystallization reaction is mild, the crystal growth process is easy to regulate and control, the dosage of the crystal form regulating agent plant polysaccharide is small, the cost is low, the product yield is high, and the stability is good.
(3) The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cyclic preparation selects the plant polysaccharide to regulate the structural process and the calcination pore-forming process of the porous magnesium oxide precursor, the prepared porous magnesium oxide has a multi-stage pore structure, contains a large number of micropores, mesopores and macropores, has good adsorption performance, can realize the synchronous removal of the small-size heavy metal ions and the large-size sulfydryl collecting agent through co-adsorption, has the removal rate of two key harmful components of more than 90 percent, fills the blank of preparing the porous magnesium oxide by taking the plant polysaccharide as the crystal form regulating agent, and has huge practical value and wide application prospect in the purification treatment of the non-ferrous metal beneficiation wastewater.
(4) According to the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cyclic preparation, the porous magnesium oxide after the non-ferrous metal beneficiation wastewater is purified can be converted into the high-purity magnesium salt by the ammonium salt leaching method, the high-purity magnesium salt is induced by the plant polysaccharide crystal form regulating agent to prepare the precursor again, the porous magnesium oxide is obtained after calcination, the regeneration of the porous magnesium oxide is realized, the porous magnesium oxide is applied to the adsorption and purification of the non-ferrous metal beneficiation wastewater again, and after the porous magnesium oxide is prepared in a cyclic mode for many times, the removal rate of the sulfydryl collecting agent and the heavy metal ions by the porous.
(5) According to the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cyclic preparation, the porous magnesium oxide is less in dosage, the adsorption efficiency is high, only the adsorption process needs to be carried out on a wastewater treatment site, the three processes of oxidative degradation, ammonium salt leaching and regeneration of the recovered porous magnesium oxide after adsorption and purification can be separately and intensively treated, the operation is simple, and the method is suitable for popularization and application.
(6) According to the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide cycle preparation, the heavy metal ions can be precipitated and recovered while the mercapto collecting agent is adsorbed and degraded, and the economic benefit is improved.
Drawings
FIG. 1 is a process flow diagram according to the present invention;
FIG. 2 is a graph showing the pore size distribution of porous magnesium oxide according to example 1 of the present invention;
FIG. 3 is a pore size distribution diagram of the porous magnesium oxide according to comparative example 1 of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
The process flow diagram of the method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the examples 1 to 4 is shown as the attached figure 1.
Example 1
The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the embodiment 1 comprises the following steps:
(1) collecting radix Polygoni Ciliinerve and Cu2+、Pb2+、Zn2+Heavy metal ion non-ferrous metal beneficiation wastewater solution, the concentration of butyl xanthate is 11.78mg/L, and Cu is2+The concentration is 0.18mg/L, Pb2+The concentration is 2.4mg/L, Zn2+The concentration was 4.1 mg/L. Adjusting the temperature of the wastewater solution to 25 ℃, adjusting the pH to 7, adding 0.5g/L porous magnesium oxide serving as an adsorbent, prepared by regulating and controlling carboxymethyl cellulose, into the non-ferrous metal beneficiation wastewater, and oscillating at constant temperature for 60min to obtain a wastewater suspension.
(2) Filtering the obtained wastewater suspension, wherein the filtrate is purified water, dispersing a filter cake in water according to the mass ratio of 2:10, stirring for 5min, adjusting the pH of the suspension to 7, adding sodium hypochlorite with the content of 1.5 times of the content of the butyl xanthate, and oxidizing for 120min to obtain the degraded suspension.
(3) And (3) filtering the degraded suspension, combining the filtrate with the purified water obtained in the step (2), putting the filter cake into an ammonium chloride solution, wherein the solid-to-liquid ratio of the filter cake to the ammonium chloride solution is 30g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 2:1, heating to 75 ℃, stirring at the speed of 80r/min, and leaching for 60min to obtain a high-purity magnesium salt leaching solution and precipitates of copper hydroxide, lead hydroxide and zinc hydroxide.
(4) Adjusting the pH value of the magnesium chloride leachate to 7, adding carboxymethyl cellulose accounting for 1% of the mass of magnesium chloride in the leachate, and adding the mixture with the magnesium chloride in a molar ratio of 1.5:1, crystallizing and reacting for 60min at the reaction temperature of 60 ℃, filtering the obtained crystals, washing the crystals with water for three times, drying the crystals at the temperature of 60 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at the temperature of 450 ℃ for 0.2h to obtain regenerated porous magnesium oxide, wherein the pore diameter characteristics of the regenerated porous magnesium oxide are shown in figure 2, the regenerated porous magnesium oxide prepared in a circulating way simultaneously contains a large number of micropores, mesopores and macropores, and can synchronously adsorb butyl xanthate and Cu again2+、Pb2+、Zn2 +Heavy metal ions.
In the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of butyl xanthate is 0.37mg/L, the content of heavy metal copper is 0.006mg/L, the content of heavy metal lead is 0.014mg/L, and the content of heavy metal zinc is 0.023 mg/L.
Comparative example 1
The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the comparative example 1 comprises the following steps:
(1) collecting radix Polygoni Ciliinerve and Cu2+、Pb2+、Zn2+Heavy metal ion non-ferrous metal beneficiation wastewater solution, the concentration of butyl xanthate is 11.78mg/L, and Cu is2+The concentration is 0.18mg/L, Pb2+The concentration is 2.4mg/L, Zn2+The concentration was 4.1 mg/L. Adjusting the temperature of the wastewater solution to 25 ℃, adjusting the pH to 7, adding porous magnesium oxide prepared by PEG regulation and control as an adsorbent, wherein the adding amount of the porous magnesium oxide is 0.5g/L, adding the porous magnesium oxide into the non-ferrous metal beneficiation wastewater, and oscillating at constant temperature for 60min to obtain a wastewater suspension.
(2) Filtering the obtained wastewater suspension, wherein the filtrate is purified water, dispersing a filter cake in water according to the mass ratio of 2:10, stirring for 5min, adjusting the pH of the suspension to 7, adding sodium hypochlorite with the content of 1.5 times of the content of the butyl xanthate, and oxidizing for 120min to obtain the degraded suspension.
(3) And (3) filtering the degraded suspension, combining the filtrate with the purified water obtained in the step (2), putting the filter cake into an ammonium chloride solution, wherein the solid-to-liquid ratio of the filter cake to the ammonium chloride solution is 30g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 2:1, heating to 75 ℃, stirring at the speed of 80r/min, and leaching for 60min to obtain a high-purity magnesium salt leaching solution and precipitates of copper hydroxide, lead hydroxide and zinc hydroxide.
(4) Adjusting the pH value of the magnesium chloride leachate to 8, adding PEG accounting for 1% of the mass of magnesium chloride in the leachate, and adding the mixture of the PEG and the magnesium chloride in a molar ratio of 1.5:1 for 60min at 50 ℃, filtering the obtained crystal, washing the crystal with water for three times, drying the crystal at 60 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at 500 ℃ for 0.4h to obtain regenerated porous magnesium oxide, wherein the pore diameter of the regenerated porous magnesium oxide is characterized as shown in figure 3, and the porous magnesium oxide prepared in a circulating manner only contains micropores and a small amount of mesopores and does not contain macropores.
After the non-ferrous metal beneficiation wastewater is treated by the porous magnesium oxide prepared in the comparative example 1, the content of the butyl xanthate is 3.87mg/L, the content of heavy metal copper is 0.056mg/L, the content of heavy metal lead is 0.726mg/L, the content of heavy metal zinc is 1.239mg/L, and the removal rate is lower than 90%. The removal rate of butyl xanthate and heavy metals of copper, lead and zinc is less than 70 percent, so that the butyl xanthate and the heavy metals of copper, lead and zinc cannot be used for re-adsorption.
Example 2
The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the embodiment 2 comprises the following steps:
(1) taking the mixture containing the ammonium nitrate and Pb2+And Zn2+The concentration of the ammonium nitrate black powder in the heavy metal ion non-ferrous metal beneficiation wastewater solution is 18.3mg/L, Pb2+The concentration is 2.7mg/L, Zn2+The concentration was 3.6 mg/L. Adjusting the temperature of the wastewater solution to 30 ℃, adjusting the pH to 8, taking porous magnesium oxide prepared by carboxymethyl starch regulation as an adsorbent, adding the porous magnesium oxide with the adding amount of 1g/L into the non-ferrous metal mineral separation wastewater, and oscillating at constant temperature for 80min to obtain a wastewater suspension.
(2) Filtering the obtained wastewater suspension, wherein the filtrate is purified water, dispersing a filter cake in the water according to the mass ratio of 1.5:10, stirring for 6min, adjusting the pH of the suspension to 7.5, adding sodium persulfate with 2 times of the content of the ammonium butyrate black drugs, and oxidizing for 200min to obtain the degraded suspension.
(3) And (3) filtering the degraded suspension, combining the filtrate with the purified water obtained in the step (2), putting the filter cake into an ammonium sulfate solution, wherein the solid-to-liquid ratio of the filter cake to the ammonium sulfate solution is 50g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 2.5:1, heating to 80 ℃, stirring at a speed of 100r/min, and leaching for 80min to obtain a high-purity magnesium salt leaching solution and precipitates of lead hydroxide and zinc hydroxide.
(4) Adjusting the pH value of the magnesium sulfate leaching solution to 8, adding carboxymethyl starch accounting for 1.5 percent of the mass of magnesium sulfate in the leaching solution, and adding a mixture of the carboxymethyl starch and the magnesium sulfate in a molar ratio of 2:1, crystallizing for 80min at 55 ℃, filtering the obtained crystal, washing with water for three times, drying at 50 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at 480 ℃ for 0.25h to obtain regenerated porous magnesium oxide which simultaneously contains a large number of micropores, mesopores and macropores and can adsorb the ammonium butyrate black drug and Pb again2+、Zn2+Heavy metal ions.
In the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of the ammonium nitrate black powder is 1.29mg/L, the content of heavy metal lead is 0.011mg/L, and the content of heavy metal zinc is 0.039 mg/L.
Example 3
The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the embodiment 3 comprises the following steps:
(1) collecting crude drug containing isoamyl xanthate and Cu2+、Pb2+、Zn2+Heavy metal ion non-ferrous metal beneficiation wastewater solution, isoamyl xanthate concentration is 24.7mg/L, Cu2+The concentration is 2.9mg/L, Pb2+The concentration is 5.7mg/L, Zn2+The concentration was 13.2 mg/L. Adjusting the temperature of the wastewater solution to 35 ℃, adjusting the pH value to 8.5, adding porous magnesium oxide prepared by guar gum regulation and control as an adsorbent, wherein the adding amount of the porous magnesium oxide is 2.5g/L, into the non-ferrous metal beneficiation wastewater, and oscillating at constant temperature for 140min to obtain a wastewater suspension.
(2) Filtering the obtained wastewater suspension, wherein the filtrate is purified water, dispersing a filter cake in water according to the mass ratio of 1.8:10, stirring for 6min, adjusting the pH of the suspension to 7, adding hydrogen peroxide with 2.5 times of the content of isoamyl xanthate, and oxidizing for 240min to obtain the degraded suspension.
(3) And (3) filtering the degraded suspension, combining the filtrate with the purified water obtained in the step (2), putting the filter cake into an ammonium nitrate solution, wherein the solid-to-liquid ratio of the filter cake to the ammonium nitrate solution is 40g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 3.5:1, heating to 80 ℃, stirring at the speed of 120r/min, and leaching for 60min to obtain a high-purity magnesium salt leaching solution and precipitates of copper hydroxide, lead hydroxide and zinc hydroxide.
(4) Adjusting the pH value of the magnesium nitrate leaching solution to 7, adding guar gum accounting for 0.5% of the mass of the magnesium nitrate in the leaching solution, and adding a mixture of guar gum and the magnesium nitrate according to a molar ratio of 2.5:1, crystallizing and reacting for 120min at 55 ℃, filtering the obtained crystals, washing the crystals with water for three times, drying the crystals at 50 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at 550 ℃ for 0.1h to obtain regenerated porous magnesium oxide which simultaneously contains a large number of micropores, mesopores and macropores and can synchronously adsorb isoamyl xanthate and Cu again2+、Pb2+、Zn2+Heavy metal ions.
In the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of isoamyl xanthate is 2.12mg/L, the content of heavy metal copper is 0.013mg/L, the content of heavy metal lead is 0.024mg/L, and the content of heavy metal zinc is 0.162 mg/L.
Example 4
The method for purifying the non-ferrous metal beneficiation wastewater based on the porous magnesium oxide recycling preparation in the embodiment 4 comprises the following steps:
(1) taking the mixture containing ethyl xanthate, aniline black powder and Cu2+、Pb2+、Zn2+The concentration of ethyl xanthate in the non-ferrous metal beneficiation wastewater solution of heavy metal ions is 3mg/L, the concentration of aniline nigre is 13.9mg/L, and Cu is2+The concentration is 1.2mg/L, Pb2+The concentration is 3mg/L, Zn2 +The concentration was 16 mg/L. Adjusting the temperature of the wastewater solution to 45 ℃ and the pH value of the wastewater solution to 9 in any ratioAnd (3) taking porous magnesium oxide prepared by regulating and controlling the mixed carboxymethyl cellulose and guar gum as an adsorbent, adding the porous magnesium oxide with the addition amount of 5g/L into the non-ferrous metal beneficiation wastewater, and oscillating at constant temperature for 180min to obtain a wastewater suspension.
(2) Filtering the obtained wastewater suspension, wherein the filtrate is purified water, dispersing a filter cake in water according to the mass ratio of 1.5:10, stirring for 10min, adjusting the pH value of the suspension to 8, adding sodium hypochlorite and sodium persulfate which are 3 times of the total content of the ethyl xanthate and the aniline nigricans, and oxidizing for 100min to obtain the degraded suspension.
(3) And (3) filtering the degraded suspension, combining the filtrate with the purified water obtained in the step (2), putting the filter cake into ammonium salt solution compounded by ammonium chloride and ammonium sulfate in a ratio of 1:1, wherein the solid-to-liquid ratio of the filter cake to the ammonium salt solution is 60g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 4:1, heating to 90 ℃, stirring at a speed of 90r/min, and leaching for 90min to obtain high-purity magnesium salt leachate and precipitates of copper hydroxide, lead hydroxide and zinc hydroxide.
(4) Adjusting the pH value of the leachate containing magnesium chloride and magnesium sulfate to 7, adding carboxymethyl cellulose and guar gum which account for 0.7 percent of the total mass of the magnesium chloride and the magnesium sulfate in the leachate, and adding the mixture, wherein the molar ratio of the mixture to the magnesium chloride to the magnesium sulfate is 1.5:1, crystallizing for 90min at 65 ℃, filtering the obtained crystal, washing with water for three times, drying at 60 ℃ to obtain a porous magnesium oxide precursor, calcining the porous magnesium oxide precursor at 550 ℃ for 0.1h to obtain regenerated porous magnesium oxide simultaneously containing a large number of micropores, mesopores and macropores and capable of synchronously adsorbing ethyl xanthate, aniline nigride and Cu again2+、Pb2+、Zn2+Heavy metal ions.
In the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of ethyl xanthate is 0.176mg/L, the content of aniline nigride is 0.478mg/L, the content of heavy metal copper is 0.009mg/L, the content of heavy metal lead is 0.017mg/L, and the content of heavy metal zinc is 0.059 mg/L.
Example 5
(1) Taking the mixture containing ethyl xanthate, aniline black powder and Cu2+、Pb2+、Zn2+Non-ferrous metal beneficiation waste of heavy metal ionsThe concentration of ethyl xanthate in the aqueous solution is 1.833mg/L, the concentration of aniline black is 5.716mg/L, and the concentration of Cu in the aqueous solution is2+The concentration is 0.647mg/L, Pb2+The concentration is 2.138mg/L, Zn2+The concentration was 5.4 mg/L. The temperature of the waste water solution was adjusted to 40 ℃ and the pH was 8.5.
(2) The regenerated porous magnesium oxide obtained in example 1 was used as an adsorbent, which contained a large number of micropores, mesopores and macropores. The adding amount of the porous magnesium oxide is 2g/L, and the porous magnesium oxide is added into the non-ferrous metal mineral processing wastewater to carry out adsorption test and cycle preparation test for 20 times.
(3) And (3) the porous magnesium oxide recycled and regenerated in the 20 th time is applied to the non-ferrous metal beneficiation wastewater again, and the obtained purified water after the non-ferrous metal beneficiation wastewater is treated has the content of ethyl xanthate of 0.084mg/L, aniline xanthate of 0.231mg/L, heavy metal copper of 0.017mg/L, heavy metal lead of 0.017mg/L and heavy metal zinc of 0.072 mg/L. The removal rate of the regenerated porous magnesium oxide to the sulfydryl collecting agent and the heavy metal ions is still larger than 90%, and the fact that the regenerated porous magnesium oxide prepared by multiple cycles still keeps high adsorption performance and is excellent in adsorption and purification effects is verified.

Claims (10)

1. A method for purifying non-ferrous metal beneficiation wastewater based on porous magnesium oxide cyclic preparation is characterized by comprising the following steps: the method comprises the following steps:
(1) adsorption reaction
Taking a non-ferrous metal beneficiation wastewater solution, adjusting the temperature and the pH of the solution, adding porous magnesium oxide prepared by regulating and controlling plant polysaccharide into non-ferrous metal beneficiation wastewater as an adsorbent, and oscillating at constant temperature to obtain a wastewater suspension;
(2) oxidative degradation
Filtering the wastewater suspension obtained in the step (1), wherein the filtrate is purified water, dispersing a filter cake in the water, stirring, adjusting the pH value of the obtained suspension, and adding an oxidant for oxidative degradation to obtain a degraded suspension;
(3) ammonium salt leaching
Filtering the degradation suspension obtained in the step (2), combining the filtrate with the purified water obtained in the step (2), and putting the filter cake into an ammonium salt solution for leaching to obtain a high-purity magnesium salt leaching solution and a heavy metal ion hydroxide precipitate;
(4) regeneration of porous magnesium oxide
And (3) adjusting the pH value of the high-purity magnesium salt leaching solution obtained in the step (3) to 6-9, adding plant polysaccharide and carbonate for crystallization, filtering the obtained crystal, washing with water, drying to obtain a porous magnesium oxide precursor, and finally calcining the porous magnesium oxide precursor to obtain regenerated porous magnesium oxide which is continuously used for adsorption purification of non-ferrous metal beneficiation wastewater.
2. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: harmful impurities in the non-ferrous metal beneficiation wastewater obtained in the step (1) are residual sulfydryl collecting agents and heavy metal ions, wherein the concentration of the sulfydryl collecting agents is 5-200 mg/L, and the concentration of the heavy metal ions is 0.1-50 mg/L;
the sulfydryl collecting agent is one or more of ethyl xanthate, butyl xanthate, isoamyl xanthate, butylammonium nigricans or aniline nigricans, and the heavy metal ions are Cu2+、Pb2+Or Zn2+One or more of; the plant polysaccharide adopted in the step (1) is the same as that adopted in the step (4);
adjusting the temperature of the non-ferrous metal beneficiation wastewater solution in the step (1) to be 25-50 ℃, and adjusting the pH to be 6-9; the dosage of the porous magnesium oxide prepared by regulating and controlling the plant polysaccharide is 0.1-10 g/L, and the constant-temperature oscillation is carried out for 60-180 min.
3. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: and (3) dispersing the filter cake in water according to the mass ratio of 0.5-2: 10 in the step (2), stirring for 5-10 min, and adjusting the pH of the obtained suspension to 6-8.
4. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: the oxidant in the step (2) is one or more of sodium hypochlorite, hydrogen peroxide or sodium persulfate, and the dosage of the oxidant is 1.5-3 times of the mass of the mercapto collector in the non-ferrous metal beneficiation wastewater; the time of oxidative degradation is 120-300 min.
5. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: the solid-liquid ratio of the filter cake and the ammonium salt solution in the step (3) is 20-100 g/L, the molar ratio of ammonium ions to magnesium oxide in the filter cake is 2-6: 1, and the ammonium salt is one or more of ammonium chloride, ammonium sulfate or ammonium nitrate;
the leaching temperature in the step (3) is 75-95 ℃, the stirring speed is 50-200 r/min, and the leaching time is 60-180 min.
6. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: the crystallization temperature in the step (4) is 40-75 ℃, and the time is 60-120 min; the number of washes was 3.
7. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: drying at 40-60 ℃ in the step (4) to obtain a porous magnesium oxide precursor, and calcining the porous magnesium oxide precursor at 450-550 ℃ for 0.1-1 h to obtain regenerated porous magnesium oxide.
8. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: the plant polysaccharide in the step (4) is one or more of carboxymethyl starch, carboxymethyl cellulose or guar gum, and the dosage of the plant polysaccharide is 0.5-2.5% of the mass of the magnesium salt in the high-purity magnesium salt leaching solution.
9. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: the carbonate in the step (4) is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate, and the molar ratio of the carbonate to the magnesium salt in the high-purity magnesium salt leaching solution is 1-2.5: 1.
10. The method for purifying the non-ferrous metal beneficiation wastewater prepared based on the porous magnesium oxide circulation according to the claim 1, characterized in that: in the purified water obtained after the non-ferrous metal beneficiation wastewater is treated, the content of the sulfydryl collecting agent is 0.1-3.0 mg/L, and the content of heavy metal ions is 0.005-0.50 mg/L.
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