CN112299518B - Preparation method and application of magnesium-iron-manganese-based efficient wastewater treatment agent - Google Patents
Preparation method and application of magnesium-iron-manganese-based efficient wastewater treatment agent Download PDFInfo
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Abstract
The invention discloses a magnesium-iron-manganese-based efficient wastewater treatment agent which is a poly-ferric-magnesium-manganese chloride aggregate, wherein tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate are adsorbed or inserted into the poly-ferric-magnesium-manganese chloride aggregate. The invention also discloses a preparation method and application of the magnesium-iron-manganese-based efficient wastewater treatment agent. The preparation process is simple, the preparation raw materials are easy to obtain, and the prepared wastewater treatment agent can treat organic pollutants in the waste liquid and can also treat inorganic pollutants efficiently. The wastewater treatment agent prepared by the invention has high-efficiency adsorbability and strong oxidizing property. The wastewater treatment agent prepared by the invention can efficiently remove 99% of pollutants such as COD, total phosphorus, ammonia nitrogen, lead and the like in the wastewater.
Description
Technical Field
The invention relates to the field of new material technology research and development, and particularly relates to a preparation method and application of a magnesium-iron-manganese-based efficient wastewater treatment agent.
Background
A ferro-manganese bimetallic oxide (Fe-Mn Binary Oxides) is one of the most common ferro-manganese-based adsorption catalytic materials in the field of wastewater treatment. The iron-manganese double-metal oxide has a loose structure, a large specific surface area and rich hydroxyl groups on the surface, and can adsorb heavy metal ions in a water body through electrostatic adsorption and coordination. However, the adsorption capacity of the iron-manganese bimetallic oxide is small, and the adsorbed heavy metal pollutants are easy to be desorbed from the adsorption material by environmental disturbance, so that the removal rate of the heavy metal pollutants in the water body is low. In order to provide the ferro-manganese bimetallic oxide with both stable structure and oxidation, the manganese used in the ferro-manganese material is typically tetravalent manganese. However, for organic pollution, ammonia nitrogen pollutants and phosphorus pollutants in the waste liquid, the treatment target is difficult to realize by singly using the ferro-manganese bimetallic oxide. The common ferro-manganese bimetallic oxide used as a catalyst needs to be matched with other strong oxidizers to treat waste liquid containing organic, ammonia nitrogen and phosphorus pollutants. The method not only increases the operation steps of the adsorption or waste liquid evolution link, but also introduces other anions into the water body.
Therefore, in summary, it is the core type and key for developing new ferrimanganic materials to enhance the adsorptivity and oxidizability of traditional ferrimanganic materials to dispose waste liquid containing various high-concentration pollutants.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a magnesium-iron-manganese-based high-efficiency wastewater treatment agent which is a poly-ferric-magnesium-manganese chloride aggregate and has a special structure, and generated tetravalent manganese oxides, potassium ferrate, potassium permanganate and potassium permanganate are adsorbed on the surface of the poly-ferric-magnesium-manganese chloride aggregate or are inserted in the poly-ferric-magnesium-manganese chloride aggregate; the layered magnesium iron manganese hydroxide intercalated by the chloride ions is subjected to hydrolytic polymerization under the action of hydroxyl radicals and oxygen radicals to generate a poly-ferric magnesium manganese chloride aggregate.
The invention also aims to solve the technical problem of providing a preparation method of the magnesium-iron-manganese-based efficient wastewater treatment agent which is simple in preparation process and easy in preparation raw material obtaining.
The invention finally aims to solve the technical problem of providing the application of the magnesium-iron-manganese-based efficient wastewater treatment agent in the treatment of landfill leachate.
In order to solve the technical problem, the invention adopts the following technical scheme: the magnesium-iron-manganese-based efficient wastewater treatment agent is a poly-ferric-magnesium-manganese chloride aggregate, and tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate are adsorbed or inserted into the poly-ferric-magnesium-manganese chloride aggregate.
The polyferric chloride magnesium manganese oxide aggregate is prepared by carrying out hydrolytic polymerization on layered magnesium iron manganese oxide intercalated by chloride ions under the action of hydroxyl radicals and oxygen radicals, wherein the layered magnesium iron manganese oxide intercalated by the chloride ions is the layered magnesium iron manganese oxide intercalated by the chloride ions generated by divalent magnesium ions, trivalent iron ions and trivalent manganese ions in a potassium hydroxide aqueous solution and a magnesium iron manganese activating solution.
The invention also discloses a preparation method of the magnesium-iron-manganese-based efficient wastewater treatment agent, which comprises the following steps: respectively weighing magnesium chloride, manganese chloride and ferric chloride, mixing and dissolving into water to prepare a magnesium chloride, ferric chloride and manganese solution; performing low-temperature plasma irradiation on the magnesium iron manganese chloride solution to obtain a magnesium iron manganese activation solution, mixing a potassium hydroxide aqueous solution with the magnesium iron manganese activation solution, and uniformly stirring to obtain magnesium iron manganese activation precipitation slurry; and (3) carrying out low-temperature plasma irradiation on the magnesium-iron-manganese activated precipitation slurry to obtain magnesium-iron-manganese base treatment mixed slurry, curing the magnesium-iron-manganese base treatment mixed slurry, drying, and grinding into powder to obtain the magnesium-iron-manganese base efficient wastewater treatment agent.
Wherein the molar ratio of the magnesium chloride to the manganese chloride to the ferric chloride is 5-15: 1-3: 10.
Wherein the total concentration of magnesium ions, iron ions and manganese ions in the magnesium chloride ferro-manganese solution is 1-10M.
Wherein the concentration of the potassium hydroxide aqueous solution is 2-10M.
Wherein the molar ratio of the potassium hydroxide aqueous solution to the ferric chloride is 4-10: 1.
Wherein the action voltage of the low-temperature plasma is 10-50 kV, the exposed atmosphere in the low-temperature plasma reactor is air, and the low-temperature plasma is irradiated for 0.5-1.5 hours.
Wherein the curing temperature is 30-90 ℃, the curing time is 12-48 hours, and the drying temperature is 50-150 ℃.
The invention also comprises the application of the magnesium-iron-manganese-based high-efficiency wastewater treatment agent in the treatment of domestic garbage leachate.
The reaction mechanism is as follows: in the process of low-temperature plasma irradiation on the magnesium chloride iron manganese solution, oxygen in the air and evaporated water vapor are ionized and dissociated in a discharge channel generated by a high-voltage electrode to generate hydroxyl radicals, oxygen radicals, hydrogen radicals and hydrated electrons. The hydroxyl radical and the oxygen radical can oxidize ferric iron, bivalent manganese and chloride ions to generate high-valence iron, tetravalent manganese oxide, hexavalent manganese, heptavalent manganese, hypochlorite, chlorate, perchlorate and the like. Hypochlorite, chlorate and perchlorate can further promote the generation of strengthened high-valence iron, tetravalent manganese oxide, hexavalent manganese and heptavalent manganese. Meanwhile, hypochlorite, chlorate and perchlorate can also absorb hydrogen free radicals and hydrated electrons, and the reductive influence of the hydrogen free radicals and the hydrated electrons is eliminated. Mixing the potassium hydroxide aqueous solution with the magnesium-iron-manganese activating solution, and generating the layered magnesium-iron-manganese hydroxide with chloride ion intercalation by the potassium hydroxide, divalent magnesium ions, trivalent iron ions and a small amount of trivalent manganese ions in the stirring process. The potassium hydroxide reacts with high-valence iron, hexavalent manganese and heptavalent manganese to generate potassium ferrate, potassium manganate and potassium permanganate. Tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate are adsorbed on the surface of the magnesium-iron-manganese hydroxide and are inserted among the layers of the magnesium-iron-manganese hydroxide. The magnesium-iron-manganese activated precipitation slurry is subjected to low-temperature plasma irradiation, and hydroxyl radicals and oxygen radicals can further enhance the generation of potassium permanganate and potassium ferrate, and can also enable the layered magnesium-iron-manganese hydroxide to undergo hydrolytic polymerization to generate a poly-ferric magnesium-manganese chloride aggregate. Under the action of plasma impact, the poly (ferric magnesium manganese chloride) aggregate is fully mixed with tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate, and the tetravalent manganese oxide, the potassium ferrate, the potassium manganate and the potassium permanganate are adsorbed on the poly (ferric magnesium manganese chloride) aggregate or are inserted in the poly (ferric magnesium manganese chloride) aggregate. In the process of treating the waste liquid, the poly-ferric magnesium manganese chloride aggregate can quickly adsorb pollutants in a water body, the quaternary manganese oxide, the potassium ferrate, the potassium manganate and the potassium permanganate adsorbed in the poly-ferric magnesium manganese chloride aggregate or inserted in the poly-ferric magnesium manganese chloride aggregate can oxidize ammonia nitrogen into nitrate, the organic matters are quickly oxidized and decomposed, and the generated ferric iron and low-valence manganese can further strengthen the adsorption of phosphorus and heavy metal pollutants.
Has the advantages that: the wastewater treatment agent prepared by the invention is a poly-ferric-magnesium-manganese chloride aggregate, and has a special structure, and the structure is adsorbed on the surface of the poly-ferric-magnesium-manganese chloride aggregate through tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate or is inserted in the poly-ferric-magnesium-manganese chloride aggregate. The preparation process is simple, the preparation raw materials are easy to obtain, and the prepared wastewater treatment agent can treat organic pollutants in the waste liquid and can also treat inorganic pollutants efficiently. The wastewater treatment agent prepared by the invention has high-efficiency adsorbability and strong oxidizing property. The wastewater treatment agent prepared by the invention can efficiently remove 99% of pollutants such as COD, total phosphorus, ammonia nitrogen, lead and the like in the wastewater.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
Sampling and basic property explanation of the domestic garbage leachate: the garbage leachate for the test is taken from a domestic garbage landfill in a Changchan lake town of normal maturity. The COD mass concentration of the urban domestic garbage percolate of the batch is 1237mg/L, the total phosphorus concentration is 286mg/L, the ammonia nitrogen concentration is 1034mg/L, and the lead ion concentration is 1.83 mg/L.
Example 1 Effect of molar ratio of magnesium chloride, manganese chloride and ferric chloride on the Performance of a Mg-Fe-Mn-based high-efficiency wastewater treatment agent prepared
Magnesium chloride, manganese chloride and ferric chloride are respectively weighed according to the molar ratio of 2.5:1:10, 3.5:1:10, 4.5:1:10, 5:0.5:10, 5:0.7:10, 5:0.9:10, 5:1:10, 10:1:10, 15:1:10, 5:2:10, 10:2:10, 15:2:10, 5:3:10, 10:3:10, 15:3:10, 15.5:3:10, 16.5:3:10, 17.5:3:10, 15:3.5:10, 15:4:10 and 15:4.5:10, and are dissolved in water to prepare 21 groups of magnesium chloride, manganese chloride and ferric chloride manganese chloride solutions with the total concentration of the ferric chloride being 1M. And (3) carrying out low-temperature plasma irradiation on the 21 groups of magnesium chloride, iron and manganese solutions for 0.5 hour to obtain 21 groups of magnesium, iron and manganese activation solutions, wherein the action voltage of the low-temperature plasma is 10kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to the ferric chloride of 4:1, and then dissolving the potassium hydroxide into water to obtain a 2M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium-ferrum-manganese activation solution, and uniformly stirring to obtain 21 groups of magnesium-ferrum-manganese activation precipitation slurry. And (3) carrying out low-temperature plasma irradiation on the 21 groups of magnesium-iron-manganese activated precipitation slurry for 0.5 hour to obtain 21 groups of magnesium-iron-manganese based treatment mixed slurry, wherein the action voltage of the low-temperature plasma is 10kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Curing 21 groups of magnesium-iron-manganese-based treatment mixed slurry at the temperature of 30 ℃ for 12 hours, then drying at the temperature of 50 ℃, and grinding into powder to obtain 21 groups of magnesium-iron-manganese-based efficient wastewater treatment agents.
And (3) adsorption test: respectively putting 10g of 21 groups of prepared magnesium-iron-manganese-based efficient wastewater treatment agents into 1L of household garbage leachate, stirring at the rotating speed of 60rmp for 30min, centrifuging at the rotating speed of 5000rpm, and carrying out solid-liquid separation. And detecting the concentrations of different pollutants in the separated liquid and calculating the removal rate, wherein the specific detection and calculation are as follows.
COD concentration detection and COD removal rate calculation: the Chemical Oxygen Demand (COD) concentration of the leachate is measured according to the national standard bichromate method for measuring the chemical oxygen demand of water (GB 11914-. The COD removal rate was calculated according to the formula (1), wherein R COD As the removal rate of COD, c 0 And c t The COD concentration (mg/L) of the domestic garbage percolate before and after treatment is respectively.
And (3) detecting the concentration of total phosphorus and calculating the removal rate of the total phosphorus: the total phosphorus concentration of the leachate is measured according to the standard continuous flow-ammonium molybdate spectrophotometry for measuring phosphate and total phosphorus in water (HJ 670-2013). Total phosphorus removalThe division ratio is calculated according to the formula (2), wherein R TP As a total phosphorus removal rate, c TPO And c TPt The total phosphorus concentration (mg/L) of the domestic garbage leachate before and after treatment is respectively.
Ammonia nitrogen concentration detection and ammonia nitrogen removal rate calculation: the concentration of the leachate ammonia nitrogen is measured according to salicylic acid spectrophotometry for measuring water ammonia nitrogen (HJ 536-2009). The ammonia nitrogen removal rate is calculated according to formula (3), wherein R N For ammonia nitrogen removal, c N0 And c Nt The concentration (mg/L) of ammonia nitrogen before and after the treatment of the domestic garbage leachate is respectively.
Detecting the concentration of lead ions and calculating the removal rate: the lead ion concentration in the leachate was measured by inductively coupled plasma emission spectrometry (HJ 776-2015) for determination of 32 elements in water quality. The lead ion removal rate was calculated according to the formula (4) wherein R Pb As lead ion removal rate, c Pb0 And c Pbt The lead ion concentrations (mg/L) of the domestic garbage leachate before and after treatment are respectively.
The results of the removal rates of COD, total phosphorus, ammonia nitrogen and lead ions are shown in the table 1.
TABLE 1 magnesium chloride, manganese chloride, iron chloride molar ratio the prepared Mg-Fe-Mn based high efficiency wastewater treatment agent performance impact
As can be seen from table 1, when the molar ratio of magnesium chloride, manganese chloride and ferric chloride is less than 5:1:10 (as shown in table 1, when the molar ratio of magnesium chloride, manganese chloride and ferric chloride is 5:0.9:10, 5:0.7:10, 5:0.5:10, 4.5:1:10, 3.5:1:10, 2.5:1:10 and lower ratios not listed in table 1), the amount of magnesium chloride and manganese chloride is less, and the amount of tetravalent manganese oxide, potassium manganate and potassium permanganate and polymerized iron magnesium manganese chloride aggregates generated under the action of low-temperature plasma is less, so that the removal rates of pollutants COD, total phosphorus, ammonia nitrogen and lead ions in leachate are all remarkably reduced as the molar ratio of magnesium chloride, manganese chloride and ferric chloride is reduced. When the molar ratio of magnesium chloride, manganese chloride and ferric chloride is 5-15: 1-3: 10 (as shown in table 1, when the molar ratio of magnesium chloride, manganese chloride and ferric chloride is 5:1:10, 10:1:10, 15:1:10, 5:2:10, 10:2:10, 15:2:10, 5:3:10, 10:3:10 and 15:3: 10), the hydroxyl radical and the oxygen radical can oxidize ferric iron, divalent manganese and chloride ions to generate high-valence iron, manganese tetravalent oxide, hexavalent manganese, heptavalent manganese, hypochlorite, chlorate, perchlorate and the like. Hypochlorite, chlorate and perchlorate can further promote the generation of high-valence iron, tetravalent manganese oxide, hexavalent manganese and heptavalent manganese. The layered magnesium iron manganese hydroxide is hydrolyzed and polymerized to generate a poly iron magnesium manganese chloride aggregate. Under the action of plasma impact, the poly (ferric magnesium manganese chloride) aggregate is fully mixed with tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate, and the tetravalent manganese oxide, the potassium ferrate, the potassium manganate and the potassium permanganate are adsorbed on the poly (ferric magnesium manganese chloride) aggregate or are inserted in the poly (ferric magnesium manganese chloride) aggregate. And the COD removal rate of the final leachate pollutants is more than 92%, the total phosphorus removal rate is more than 94%, the ammonia nitrogen removal rate is more than 91%, and the lead ion removal rate is more than 92%. When the molar ratio of magnesium chloride, manganese chloride and ferric chloride is more than 15:3:10 (as shown in table 1, the molar ratio of magnesium chloride, manganese chloride and ferric chloride is 15.5:3:10, 16.5:3:10, 17.5:3:10, 15:3.5:10, 15:4:10 and 15:4.5:10 and higher ratios not listed in table 1), the formation of layered magnesium iron manganese hydroxide and polymerized iron magnesium manganese chloride aggregate is reduced due to excessive magnesium chloride and manganese chloride, and the removal rate of pollutants such as leachate, total phosphorus, ammonia nitrogen and Chemical Oxygen Demand (COD) and lead ions is remarkably reduced along with further increase of the molar ratio of magnesium chloride, manganese chloride and ferric chloride. Comprehensively, the benefits and the cost are combined, and when the molar ratio of magnesium chloride to manganese chloride to ferric chloride is 5-15: 1-3: 10, the performance of the prepared magnesium-iron-manganese-based efficient wastewater treatment agent is improved.
Example 2 Effect of molar ratio of Potassium hydroxide to ferric chloride on Performance of Mg-Fe-Mn based high efficiency wastewater treatment agent
Respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of the magnesium chloride to the manganese chloride to the ferric chloride of 15:3:10, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of the magnesium chloride, the manganese chloride and the ferric chloride of 5.5M. And (3) carrying out low-temperature plasma irradiation on the magnesium chloride, iron and manganese chloride solution for 1 hour to obtain the magnesium, iron and manganese chloride activating solution, wherein the action voltage of the low-temperature plasma is 30kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 1:1, 2:1, 3:1, 4:1, 7:1, 10:1, 11:1, 12:1 and 13:1 respectively, and dissolving the potassium hydroxide into water to obtain nine groups of 6M potassium hydroxide aqueous solutions. Respectively mixing the potassium hydroxide aqueous solution with the magnesium-ferrum-manganese activation solution, and uniformly stirring to obtain nine groups of magnesium-ferrum-manganese activation precipitation slurries. And (3) carrying out low-temperature plasma irradiation on the nine groups of magnesium-iron-manganese activated precipitation slurry for 1 hour to obtain nine groups of magnesium-iron-manganese based treatment mixed slurry, wherein the action voltage of the low-temperature plasma is 30kV, and the atmosphere exposed in the low-temperature plasma reactor is air. And curing the nine groups of magnesium-iron-manganese-based treatment mixed slurry at the temperature of 60 ℃ for 30 hours, then drying at the temperature of 100 ℃, and grinding into powder to obtain nine groups of magnesium-iron-manganese-based efficient wastewater treatment agents.
The adsorption test, the COD concentration detection and the calculation of the COD removal rate, the total phosphorus concentration detection and the calculation of the total phosphorus removal rate, the ammonia nitrogen concentration detection and the ammonia nitrogen removal rate, and the lead ion concentration detection and the calculation of the removal rate are the same as those in the embodiment 1.
The results of the removal rates of COD, total phosphorus, ammonia nitrogen and lead ions are shown in Table 2.
Table 2 influence of molar ratio of potassium hydroxide to ferric chloride on performance of magnesium-iron-manganese-based efficient wastewater treatment agent prepared
As can be seen from table 2, when the molar ratio of potassium hydroxide to ferric chloride is less than 4:1 (as shown in table 2, the molar ratio of potassium hydroxide to ferric chloride is 3:1, 2:1, 1:1, and is lower than the ratio not listed in table 2), potassium hydroxide is less, and the generated lamellar mgfe-mn hydroxide and polymeric mgfe-mn chloride aggregates are less, so that the removal rates of the leachate pollutants COD, total phosphorus, ammonia nitrogen, and lead ions are all significantly reduced as the molar ratio of potassium hydroxide to ferric chloride is reduced. When the molar ratio of potassium hydroxide to ferric chloride is 4-10: 1 (as shown in table 2, the molar ratio of potassium hydroxide to ferric chloride is 4:1, 7:1, 10: 1), mixing the potassium hydroxide aqueous solution with the magnesium-iron-manganese activating solution, and generating the chloride ion intercalated layered magnesium-iron-manganese hydroxide by the potassium hydroxide, the divalent magnesium ions, the trivalent iron ions and a small amount of trivalent manganese ions during stirring. The potassium hydroxide reacts with the high-valence iron, the hexavalent manganese and the heptavalent manganese to generate potassium ferrate, potassium manganate and potassium permanganate. Tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate are adsorbed on the surface of the magnesium-iron-manganese hydroxide and are inserted among the layers of the magnesium-iron-manganese hydroxide. The magnesium iron manganese activation precipitation slurry is irradiated by low-temperature plasma, and hydroxyl radicals and oxygen radicals can further enhance the generation of potassium permanganate and potassium ferrate and can also lead layered magnesium iron manganese hydroxide to generate hydrolytic polymerization to generate a poly-ferric magnesium manganese chloride aggregate. Under the action of plasma impact, the poly (ferric magnesium manganese chloride) aggregate is fully mixed with tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate, and the tetravalent manganese oxide, the potassium ferrate, the potassium manganate and the potassium permanganate are adsorbed on the poly (ferric magnesium manganese chloride) aggregate or are inserted in the poly (ferric magnesium manganese chloride) aggregate. And finally, the COD removal rate of the leachate pollutants is more than 96%, the total phosphorus removal rate is more than 96%, the ammonia nitrogen removal rate is more than 95%, and the lead ion removal rate is more than 95%. When the molar ratio of potassium hydroxide to ferric chloride is greater than 10:1 (as shown in table 2, the molar ratio of potassium hydroxide to ferric chloride is 11:1, 12:1, 13:1 and higher ratios not listed in table 2), the potassium hydroxide is excessive, the oxidation potential of oxygen radicals and hydroxyl radicals is reduced during the low-temperature plasma treatment process, the oxidation efficiency is reduced, the production of potassium permanganate and potassium ferrate is reduced, the hydrolysis polymerization efficiency of the layered magnesium iron manganese hydroxide is reduced, and the removal rates of leachate pollutants COD, total phosphorus, ammonia nitrogen and lead ions are all significantly reduced as the molar ratio of potassium hydroxide to ferric chloride is further increased. Comprehensively, the benefits and the cost are combined, and when the molar ratio of potassium hydroxide to ferric chloride is equal to 4-10: 1, the performance of the prepared Mg-Fe-Mn-based efficient wastewater treatment agent is improved.
Example 3 Effect of the Low-temperature plasma irradiation time of Mg-Fe-Mn activated precipitation slurry on the Performance of the prepared Mg-Fe-Mn based high-efficiency wastewater treatment agent
Respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of 15:3:10 of magnesium chloride, manganese chloride and ferric chloride, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of 10M of magnesium chloride, manganese chloride and ferric chloride. And (3) carrying out low-temperature plasma irradiation on the magnesium chloride ferro-manganese solution for 1.5 hours to obtain the magnesium-ferro-manganese activating solution, wherein the action voltage of the low-temperature plasma is 50kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 10:1, and dissolving the potassium hydroxide into water to obtain a 10M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium-iron-manganese activation solution, and uniformly stirring to obtain the magnesium-iron-manganese activation precipitation slurry. And respectively carrying out low-temperature plasma irradiation on the nine groups of magnesium-iron-manganese activated precipitation slurry for 0.25 hour, 0.35 hour, 0.45 hour, 0.5 hour, 1 hour, 1.5 hours, 1.55 hours, 1.65 hours and 1.75 hours to obtain nine groups of magnesium-iron-manganese based treatment mixed slurry, wherein the low-temperature plasma action voltage is 50kV, and the atmosphere exposed in a low-temperature plasma reactor is air. And curing the nine groups of magnesium-iron-manganese-based treatment mixed slurry at the temperature of 90 ℃ for 48 hours, then drying at the temperature of 150 ℃, and grinding into powder to obtain nine groups of magnesium-iron-manganese-based efficient wastewater treatment agents.
The adsorption test, COD concentration detection and COD removal rate calculation, total phosphorus concentration detection and total phosphorus removal rate calculation, ammonia nitrogen concentration detection and ammonia nitrogen removal rate calculation, and lead ion concentration detection and removal rate calculation are the same as those in example 1.
The results of the removal rates of COD, total phosphorus, ammonia nitrogen and lead ions are shown in the table 3.
TABLE 3 influence of the low-temperature plasma irradiation time of the Mg-Fe-Mn activated precipitation slurry on the performance of the prepared Mg-Fe-Mn based high-efficiency wastewater treatment agent
As can be seen from table 3, when the low-temperature plasma irradiation time of the mgfe-mn activated precipitation slurry is less than 0.5 hour (the low-temperature plasma irradiation time of the mgfe-mn activated precipitation slurry is 0.45 hour, 0.35 hour, 0.25 hour, and lower values not listed in table 3), the hydrolysis polymerization of the layered mgfe-mn hydroxide occurs insufficiently, and the generated polyferric-mg-mn chloride aggregates are less, so that the removal rates of the leachate pollutants COD, total phosphorus, ammonia nitrogen, and lead ions are all significantly reduced as the low-temperature plasma irradiation time of the mgfe-mn activated precipitation slurry is reduced. When the irradiation time of the low-temperature plasma of the magnesium-iron-manganese activated precipitation slurry is equal to 0.5-1.5 hours (the irradiation time of the low-temperature plasma of the magnesium-iron-manganese activated precipitation slurry is equal to 0.5 hour, 1 hour and 1.5 hours), the low-temperature plasma irradiation is carried out on the magnesium-iron-manganese activated precipitation slurry, and hydroxyl radicals and oxygen radicals can not only further enhance the generation of potassium permanganate and potassium ferrate, but also enable the layered magnesium-iron-manganese hydroxide to undergo hydrolytic polymerization to generate a polymerized iron-magnesium-manganese chloride aggregate. Under the action of plasma impact, the poly (ferric magnesium manganese chloride) aggregate is fully mixed with tetravalent manganese oxide, potassium ferrate, potassium manganate and potassium permanganate, and the tetravalent manganese oxide, the potassium ferrate, the potassium manganate and the potassium permanganate are adsorbed on the poly (ferric magnesium manganese chloride) aggregate or are inserted in the poly (ferric magnesium manganese chloride) aggregate. And finally, the COD removal rate of the leachate pollutants is more than 96%, the total phosphorus removal rate is more than 97%, the ammonia nitrogen removal rate is more than 96%, and the lead ion removal rate is more than 96%. When the irradiation time of the low-temperature plasma of the magnesium-iron-manganese activated precipitation slurry is longer than 1.5 hours (the irradiation time of the low-temperature plasma of the magnesium-iron-manganese activated precipitation slurry is 1.55 hours, 1.65 hours and 1.75 hours and higher values which are not listed in table 3), the plasma irradiation time is too long, and excessive ferric iron in the magnesium-iron-manganese activated precipitation slurry is converted into high-valent iron, so that the generated poly-ferric-magnesium-manganese chloride aggregate is reduced, and the removal rates of pollutants COD, total phosphorus, ammonia nitrogen and lead ions of leachate are all remarkably reduced along with the further increase of the irradiation time of the low-temperature plasma of the magnesium-iron-manganese activated precipitation slurry. Comprehensively, the benefits and the cost are combined, and when the low-temperature plasma irradiation time of the magnesium-iron-manganese activated precipitation slurry is equal to 0.5-1.5 hours, the performance of the prepared magnesium-iron-manganese based efficient wastewater treatment agent is improved most beneficially.
Comparison of performances of Mg-Fe-Mn-based efficient wastewater treatment agent prepared by different comparison methods
The method comprises the following steps: respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of 15:3:10 of magnesium chloride, manganese chloride and ferric chloride, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of 10M of magnesium chloride, manganese chloride and ferric chloride. And (3) carrying out low-temperature plasma irradiation on the magnesium chloride ferro-manganese solution for 1.5 hours to obtain the magnesium-ferro-manganese activating solution, wherein the action voltage of the low-temperature plasma is 50kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 10:1, and dissolving the potassium hydroxide into water to obtain a 10M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium-iron-manganese activation solution, and uniformly stirring to obtain the magnesium-iron-manganese activation precipitation slurry. And (3) irradiating the magnesium-iron-manganese activated precipitation slurry by using low-temperature plasma for 1.5 hours to obtain the magnesium-iron-manganese base treatment mixed slurry, wherein the action voltage of the low-temperature plasma is 50kV, and the atmosphere exposed in the low-temperature plasma reactor is air. And (3) curing the magnesium-iron-manganese-based treatment mixed slurry at the temperature of 90 ℃ for 48 hours, then drying at the temperature of 150 ℃, and grinding into powder to obtain the magnesium-iron-manganese-based efficient wastewater treatment agent.
Comparative method 1: respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of the magnesium chloride to the manganese chloride to the ferric chloride of 15:3:10, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of the magnesium chloride, the manganese chloride and the ferric chloride of 10M. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 10:1, and dissolving the potassium hydroxide into water to obtain a 10M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium, iron and manganese chloride solution, and uniformly stirring to obtain the magnesium, iron and manganese precipitation slurry. And (3) carrying out low-temperature plasma irradiation on the magnesium-iron-manganese precipitation slurry for 1.5 hours to obtain magnesium-iron-manganese activated mixed slurry, wherein the action voltage of the low-temperature plasma is 50kV, and the atmosphere exposed in the low-temperature plasma reactor is air. And (3) curing the magnesium-iron-manganese activated mixed slurry at the temperature of 90 ℃ for 48 hours, then drying at the temperature of 150 ℃, and grinding into powder to obtain the magnesium-iron-manganese based efficient wastewater treatment agent.
Comparative method 2: respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of the magnesium chloride to the manganese chloride to the ferric chloride of 15:3:10, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of the magnesium chloride, the manganese chloride and the ferric chloride of 10M. And (3) carrying out low-temperature plasma irradiation on the magnesium chloride iron manganese solution for 1.5 hours to obtain the magnesium iron manganese activating solution, wherein the action voltage of the low-temperature plasma is 50kV, and the atmosphere exposed in the low-temperature plasma reactor is air. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 10:1, and dissolving the potassium hydroxide into water to obtain a 10M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium-iron-manganese activation solution, and uniformly stirring to obtain the magnesium-iron-manganese activation precipitation slurry. And (3) curing the magnesium-iron-manganese activation precipitation slurry at the temperature of 90 ℃ for 48 hours, then drying at the temperature of 150 ℃, and grinding into powder to obtain the magnesium-iron-manganese based efficient wastewater treatment agent.
Comparative method 3: respectively weighing magnesium chloride, manganese chloride and ferric chloride according to the molar ratio of the magnesium chloride to the manganese chloride to the ferric chloride of 15:3:10, mixing, dissolving in water, and preparing a magnesium chloride, iron and manganese chloride solution with the total concentration of the magnesium chloride, the manganese chloride and the ferric chloride of 10M. Weighing potassium hydroxide according to the molar ratio of the potassium hydroxide to ferric chloride of 10:1, and dissolving the potassium hydroxide into water to obtain a 10M potassium hydroxide aqueous solution. And mixing the potassium hydroxide aqueous solution with the magnesium iron manganese chloride solution, and uniformly stirring to obtain the magnesium iron manganese precipitation slurry. And (3) curing the magnesium-iron-manganese precipitation slurry at the temperature of 90 ℃ for 48 hours, then drying at the temperature of 150 ℃, and grinding into powder to obtain the magnesium-iron-manganese based efficient wastewater treatment agent.
The adsorption test, the COD concentration detection and the calculation of the COD removal rate, the total phosphorus concentration detection and the calculation of the total phosphorus removal rate, the ammonia nitrogen concentration detection and the ammonia nitrogen removal rate, and the lead ion concentration detection and the calculation of the removal rate are the same as those in the embodiment 1.
The results of removal rates of COD, total phosphorus, ammonia nitrogen and lead ions are shown in Table 4.
TABLE 4 comparison of performance of Mg-Fe-Mn based high efficiency wastewater treatment agent prepared by different comparison methods
| Different comparison methods | R COD | R TP | R N | R Pb |
| The method of the invention | 99.26％ | 99.47％ | 99.18％ | 99.06％ |
| Comparative method 1 | 45.62％ | 50.24％ | 48.13％ | 53.73％ |
| Comparative method 2 | 42.95％ | 43.72％ | 46.39％ | 40.95％ |
| Comparative method 3 | 23.45％ | 31.96％ | 28.27％ | 22.18％ |
As can be seen from Table 4, the removal rates of COD, total phosphorus, ammonia nitrogen and lead ions of the wastewater treatment agent prepared by the method are higher than the sum of corresponding values of the wastewater treatment agents prepared by the comparative methods 1 and 2. Compared with the wastewater treatment agent prepared by the method 3, the removal rate of COD, total phosphorus, ammonia nitrogen and lead ions is the lowest among the four methods.
Claims (3)
1. A preparation method of a magnesium-iron-manganese-based efficient wastewater treatment agent is characterized by comprising the following steps: respectively weighing magnesium chloride, manganese chloride and ferric chloride, mixing and dissolving into water to prepare a magnesium chloride-ferric-manganese chloride solution; performing low-temperature plasma irradiation on the magnesium iron manganese chloride solution to obtain a magnesium iron manganese activation solution, mixing a potassium hydroxide aqueous solution with the magnesium iron manganese activation solution, and uniformly stirring to obtain magnesium iron manganese activation precipitation slurry; performing low-temperature plasma irradiation on the magnesium-iron-manganese activated precipitation slurry to obtain magnesium-iron-manganese based treatment mixed slurry, curing the magnesium-iron-manganese based treatment mixed slurry, drying, and grinding into powder to obtain the magnesium-iron-manganese based efficient wastewater treatment agent, wherein the molar ratio of magnesium chloride, manganese chloride and iron chloride is 5-15: 1-3: 10, the total concentration of magnesium ions, iron ions and manganese ions in the magnesium-iron-manganese chloride solution is 1-10M, the molar ratio of potassium hydroxide aqueous solution and iron chloride is 4-10: 1, the action voltage of the low-temperature plasma is 10-50 kV, the exposed atmosphere in the low-temperature plasma reactor is air, and the low-temperature plasma irradiation is performed for 0.5-1.5 hours.
2. The preparation method of the Mg-Fe-Mn based efficient wastewater treatment agent according to claim 1, wherein the concentration of the potassium hydroxide aqueous solution is 2-10M.
3. The preparation method of the Mg-Fe-Mn based efficient wastewater treatment agent according to claim 1, wherein the curing temperature is 30-90 ℃, the curing time is 12-48 hours, and the drying temperature is 50-150 ℃.
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