CN112264031A - Method for purifying galvanizing waste liquid and preparing zinc-iron catalytic material - Google Patents
Method for purifying galvanizing waste liquid and preparing zinc-iron catalytic material Download PDFInfo
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Abstract
The invention discloses a method for purifying galvanizing waste liquid and preparing a zinc-iron catalytic material, which comprises the following steps: (1) mixing and stirring the galvanizing waste liquid and a sodium hydroxide aqueous solution to obtain zinc-iron slurry; (2) mixing expanded perlite and zinc-iron slurry, stirring, and irradiating by low-temperature plasma to obtain zinc-iron catalytic slurry; (3) centrifuging the zinc-iron catalytic slurry to obtain a waste liquid purifying solution and zinc-iron catalytic precipitation; and drying and grinding the zinc-iron catalytic precipitate to obtain the zinc-iron catalytic material. The method has simple process, can realize the purification of the galvanizing waste liquid, and can also synchronously prepare the zinc-iron catalytic material; the method can remove 99% of zinc, iron, lead, copper and nickel in the galvanizing waste liquid to the maximum, the prepared zinc-iron catalytic material can be suitable for a water body environment with the pH value of 1-13, and 97% of diclofenac sodium can be removed to the maximum in a non-illumination environment.
Description
Technical Field
The invention relates to a method for purifying galvanizing waste liquid and preparing a zinc-iron catalytic material, belonging to the field of waste water purification and new material research and development.
Background
In the steel industry, steel components are typically pickled prior to being galvanized. At present, iron and steel enterprises generally select hydrochloric acid as an acid cleaning medium. A large amount of galvanizing pickling waste liquid is easily generated in the pickling process, belongs to dangerous waste, and contains toxic and harmful substances such as iron, zinc, copper, nickel, lead and the like. At present, over 500 electric iron tower plants in China generate dozens of thousand tons of acid liquor waste liquid every year. For the disposal of the galvanizing waste liquid, a limestone neutralization method is most commonly used. The limestone neutralization method is simple in process, but the high content of iron and zinc in the waste liquid cannot be recycled, and the generated precipitate still belongs to dangerous waste and still needs to be subjected to advanced treatment. In recent years, practitioners have developed new technologies for disposing of the zinc plating waste liquid, including membrane separation, direct roasting, and concentration processes. The methods can recover partial components in the galvanizing waste liquid to a certain extent, but all have some technical defect limitations. For example, high concentration waste streams from concentration processes still require advanced treatment. The membrane separation method has the problems of high requirement on the material of the membrane material, easy blockage of the membrane material, difficult replacement of the filter membrane and the like. The direct roasting method has the problems of easy generation of gaseous metal chloride pollutants and poor waste liquid purification effect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for purifying zinc-plating waste liquid and preparing a zinc-iron catalytic material, which can realize the purification of the zinc-plating waste liquid and can fully recycle effective components in the waste liquid.
The technical scheme is as follows: the invention discloses a method for purifying zinc plating waste liquid and preparing a zinc-iron catalytic material, which comprises the following steps:
(1) mixing and stirring the galvanizing waste liquid and a sodium hydroxide aqueous solution to obtain zinc-iron slurry;
(2) mixing expanded perlite and zinc-iron slurry, stirring, and irradiating by low-temperature plasma to obtain zinc-iron catalytic slurry;
(3) centrifuging the zinc-iron catalytic slurry to obtain a waste liquid purifying solution and zinc-iron catalytic precipitation; and drying and grinding the zinc-iron catalytic precipitate to obtain the zinc-iron catalytic material.
Preferentially, in the step (1), when the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is 0.5-1.5: 1, the sodium hydroxide reacts with most of metal ions in the zinc plating waste liquid to generate hydroxide precipitates, oxygen radicals are favorable for dehydrogenating the metal hydroxides in the low-temperature plasma irradiation process, and finally, the purification of the zinc plating waste liquid and the preparation of a zinc-iron catalytic material are favorable.
Preferably, in the step (2), the mass ratio of the expanded perlite powder to the zinc-iron slurry is 2.5-12.5: 100. The low-temperature plasma irradiation voltage is 5-50 kV. The low-temperature plasma irradiation time is 2-6 h. The stirring speed is 60-360 rpm. The low-temperature plasma irradiation atmosphere is oxygen. So be provided with and do benefit to expanded perlite powder and zinc-iron slurry and mix the back, the free heavy metal ion that does not deposit in the adsorbable galvanizing waste liquid of surface hydroxyl of expanded perlite powder and promote adsorbed heavy metal ion and hydroxyl further combine, also be favorable to low temperature plasma to shine the in-process, oxygen takes place ionization, dissociation in the passageway that discharges, generates the oxygen free radical. And is also beneficial to the combination of oxygen free radicals and heavy metal ions to induce the generation of heavy metal oxides.
Preferably, in the step (3), the centrifugation speed is 3000-12000 rpm. The drying temperature of the zinc-iron catalytic precipitation is 50-150 ℃. The device is beneficial to effectively separating the waste liquid purifying liquid from the zinc-iron catalytic precipitation and is also beneficial to drying the zinc-iron catalytic precipitation.
The reaction mechanism is as follows: mixing a sodium hydroxide aqueous solution with the galvanizing waste liquid, and reacting the sodium hydroxide with most metal ions (target elements) in the galvanizing waste liquid to generate hydroxide precipitates; after the expanded perlite powder is mixed with the zinc-iron slurry, the surface hydroxyl of the expanded perlite powder can adsorb free heavy metal ions which are not precipitated in the galvanizing waste liquid and promote the adsorbed heavy metal ions to be further combined with hydroxide radicals; in the low-temperature plasma irradiation process, oxygen is ionized and dissociated in the discharge channel to generate oxygen radicals, the oxygen radicals can increase the surface activity of the expanded perlite powder and improve the surface hydroxyl loading capacity of the expanded perlite powder, the expanded perlite powder with the improved surface activity can strengthen the adsorption of free heavy metal ions, and meanwhile, the oxygen radicals can also combine the heavy metal ions with the oxygen to induce the generation of heavy metal oxides; with the lapse of the low-temperature plasma irradiation time, the oxygen radicals may further dehydrogenate the metal hydroxide to convert into a binary metal oxide. Because the zinc and iron ion content in the galvanizing waste liquid is far higher than that of other heavy metal ions, the metal hydroxide is mainly converted into a zinc-iron binary oxide catalytic material doped with lead, copper and nickel under the full action of oxygen radicals.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the method has simple process, can realize the purification of the galvanizing waste liquid, and can also synchronously prepare the zinc-iron catalytic material; the method can remove 99% of zinc, iron, lead, copper and nickel in the galvanizing waste liquid to the maximum, the prepared zinc-iron catalytic material can be suitable for a water body environment with the pH value of 1-13, and 97% of diclofenac sodium can be removed to the maximum in a non-illumination environment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1 volume ratio of sodium hydroxide aqueous solution to galvanizing waste liquid to effect of purifying zinc waste liquid and performance of prepared zinc-iron catalytic material
Sodium hydroxide was weighed and dissolved in water to prepare a 0.5M aqueous solution of sodium hydroxide. Respectively mixing the sodium hydroxide aqueous solution and the zinc plating waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid of 0.25:1, 0.35:1, 0.45:1, 0.5:1, 1:1, 1.5:1, 1.6:1, 1.8:1 and 2.0:1, and stirring for 0.5 hour to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 10 minutes to obtain expanded perlite powder. Respectively weighing the expanded perlite powder and the zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 2.5:100, mixing, stirring, and carrying out low-temperature plasma irradiation for 2 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 60rpm, the low-temperature plasma action voltage is 5kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 3000 rpm. And drying the zinc-iron catalytic precipitate at 50 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Sodium dichlorophenolate removal test: according to the solid/liquid ratio of the prepared zinc-iron catalytic material to the water containing the diclofenac sodium of 15g:1L, the zinc-iron catalytic material is put into the water with the initial pH value of 1 and containing 50mM diclofenac sodium, stirred for 60min under the dark environment and the rotating speed of 120rpm, and subjected to solid-liquid separation.
And (3) measuring the concentration of the diclofenac sodium in the water body: the concentration of the diclofenac sodium in the water body is determined by referring to a method of detecting diclofenac sodium in water environment by an LC-MS/MS method.
Calculating the removal rate of the diclofenac sodium in the water body: the removal rate of sodium dichlorophenolate in the water body is calculated according to the following equation (1), wherein RdIs the removal rate of sodium dichlorophenolate, cd0And cdtThe concentrations of diclofenac sodium in the solution before and after the adsorption experiment are shown respectively.
And (3) measuring the concentration of a target element in the galvanizing waste liquid: the concentration of five target elements of zinc, copper, lead, iron and nickel in the galvanizing waste liquid is measured according to the inductively coupled plasma emission spectrometry for measuring 32 elements in water (HJ 776-.
Calculating the removal rate of the target elements in the galvanizing waste liquid: the removal rate of the target element in the zinc plating waste liquid is calculated according to the following equation (2), wherein RsIs the removal rate of the target element S (the target element S represents zinc, copper, lead, nickel and iron), cs0And cstThe concentrations of the target element S in the solution before and after the adsorption experiment are respectively shown. The test results are shown in Table 1.
TABLE 1 volume ratio of sodium hydroxide aqueous solution to zinc plating waste liquid for purifying zinc plating waste liquid and influence of prepared zinc-iron catalytic material on performance
As can be seen from table 1, when the volume ratio of the aqueous sodium hydroxide solution to the waste zinc plating solution is less than 0.5:1 (as shown in table 1, when the volume ratio of the aqueous sodium hydroxide solution to the waste zinc plating solution is 0.45:1, 0.35:1, 0.25:1, and lower ratios not listed in table 1), the hydroxide ions are less, the hydroxide precipitate formation amount is less, and the binary metal oxide formation amount is less, so that the removal rates of zinc, iron, copper, lead, and nickel in the waste zinc plating solution and the removal rate of sodium dichlorophenate in the water body are both significantly reduced as the volume ratio of the aqueous sodium hydroxide solution to the waste zinc plating solution is reduced. When the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is equal to 0.5-1.5: 1 (as shown in table 1, when the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is 0.5:1, 1:1, 1.5: 1), mixing the sodium hydroxide aqueous solution with the zinc plating waste liquid, and reacting the sodium hydroxide with most of metal ions in the zinc plating waste liquid to generate hydroxide precipitate. With the lapse of the low-temperature plasma irradiation time, the oxygen radicals may further dehydrogenate the metal hydroxide to convert into a binary metal oxide. Finally, the removal rate of zinc in the galvanizing waste liquid is more than 86%, the removal rate of iron is more than 85%, the removal rate of copper is more than 91%, the removal rate of lead is more than 92%, the removal rate of nickel is more than 90%, and the removal rate of diclofenac sodium in the water body is more than 82%. When the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is greater than 1.5:1 (as shown in table 1, when the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is 1.6:1, 1.8:1, 2.0:1 and higher ratios not listed in table 1), too many hydroxide ions are generated, the oxidation potential of oxygen is reduced, the generation amounts of heavy metal oxides and binary metal oxides are reduced, and the removal rates of zinc, iron, copper, lead and nickel in the zinc plating waste liquid and the removal rate of sodium dichlorophenolate in a water body are obviously reduced along with the further increase of the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid. Therefore, in summary, the benefits and the cost are combined, and when the volume ratio of the sodium hydroxide aqueous solution to the zinc plating waste liquid is equal to 0.5-1.5: 1, the purification of the zinc plating waste liquid and the preparation of the zinc-iron catalytic material are most facilitated.
Example 2 quality ratio of expanded perlite powder and zinc-iron slurry to effect of purifying waste galvanizing solution and performance of prepared zinc-iron catalytic material
Sodium hydroxide was weighed and dissolved in water to prepare a 2.75M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1 hour to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 20 minutes to obtain expanded perlite powder. Respectively weighing expanded perlite powder and zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 1:100, 1.5:100, 2:100, 2.5:100, 7.5:100, 12.5:100, 13:100, 14:100 and 15:100, mixing, stirring and carrying out low-temperature plasma irradiation for 4 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 210rpm, the low-temperature plasma action voltage is 27.5kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 7500 rpm. And drying the zinc-iron catalytic precipitate at 100 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Sodium dichlorophenolate removal test: according to the solid/liquid ratio of the prepared zinc-iron catalytic material to the water containing the diclofenac sodium of 15g:1L, the zinc-iron catalytic material is put into the water with the initial pH of 7 and containing 50mM diclofenac sodium, stirred for 60min under the dark environment and the rotating speed of 120rpm, and subjected to solid-liquid separation.
The concentration determination of sodium dichlorophenolate in the water body, the calculation of the removal rate of sodium dichlorophenolate in the water body, the concentration determination of the target element in the galvanizing waste liquid and the calculation of the removal rate of the target element in the galvanizing waste liquid are the same as those in the embodiment 1.
TABLE 2 Mass ratio of expanded perlite powder to zinc-iron slurry influences on the purification effect of the waste liquid from galvanizing and the performance of the prepared zinc-iron catalytic material
As can be seen from table 2, when the mass ratio of the expanded perlite powder to the zinc-iron slurry is less than 2.5:100 (as shown in table 2, when the mass ratio of the expanded perlite powder to the zinc-iron slurry is 2:100, 1.5:100, 1:100 and lower ratios not listed in table 2), the amount of the expanded perlite powder is less, the adsorption amount of the free heavy metal ions and the precipitation conversion efficiency in the galvanizing waste liquid are reduced, and the removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenate in the water body are all significantly reduced as the mass ratio of the expanded perlite powder to the zinc-iron slurry is reduced. When the mass ratio of the expanded perlite powder to the zinc-iron slurry is equal to 2.5-12.5: 100 (as shown in table 2, when the mass ratio of the expanded perlite powder to the zinc-iron slurry is 2.5:100, 7.5:100, or 12.5: 100), after the expanded perlite powder is mixed with the zinc-iron slurry, the surface hydroxyl groups of the expanded perlite powder can absorb the free heavy metal ions which are not precipitated in the zinc plating waste liquid and promote the further combination of the absorbed heavy metal ions and hydroxyl groups. The oxygen free radicals can increase the surface activity of the expanded perlite powder and improve the surface hydroxyl loading capacity of the expanded perlite powder. The expanded perlite powder with improved surface activity can strengthen the adsorption of free heavy metal ions. Finally, the zinc removal rate of the galvanizing waste liquid is more than 91%, the iron removal rate is more than 90%, the copper removal rate is more than 94%, the lead removal rate is more than 95%, the nickel removal rate is more than 95%, and the sodium dichlorophenolate removal rate of the water body is more than 89%. When the mass ratio of the expanded perlite powder to the zinc-iron slurry is greater than 12.5:100 (as shown in table 2, when the mass ratio of the expanded perlite powder to the zinc-iron slurry is 13:100, 14:100, 15:100 and higher ratios not listed in table 2), the expanded perlite powder is too much, and too much oxygen radicals are consumed by the expanded perlite powder, so that the generation amounts of heavy metal oxides and binary metal oxides are reduced, and the removal rates of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenate in the water body are remarkably reduced along with the further increase of the mass ratio of the expanded perlite powder to the zinc-iron slurry. Therefore, in summary, the benefits and the cost are combined, and when the mass ratio of the expanded perlite powder to the zinc-iron slurry is 2.5-12.5: 100, the method is most beneficial to purifying the galvanizing waste liquid and preparing the zinc-iron catalytic material.
Example 3 Effect of Low temperature plasma action Voltage on Zinc plating waste liquid purification Effect and Performance of prepared Zinc-iron catalytic Material
Sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 30 minutes to obtain expanded perlite powder. Weighing the expanded perlite powder and the zinc-iron slurry respectively according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 12.5:100, mixing, stirring and carrying out low-temperature plasma irradiation for 6 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the low-temperature plasma action voltage is respectively 2.5kV, 3.5kV, 4.5kV, 5kV, 27.5kV, 50kV, 52kV, 55kV and 60kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Sodium dichlorophenolate removal test: according to the solid/liquid ratio of the prepared zinc-iron catalytic material to the water containing the diclofenac sodium of 15g:1L, the zinc-iron catalytic material is put into the water with the initial pH of 13 and containing 50mM diclofenac sodium, stirred for 60min under the dark environment and the rotating speed of 120rpm, and subjected to solid-liquid separation.
The concentration determination of sodium dichlorophenolate in the water body, the calculation of the removal rate of sodium dichlorophenolate in the water body, the concentration determination of the target element in the galvanizing waste liquid and the calculation of the removal rate of the target element in the galvanizing waste liquid are the same as those in the embodiment 1.
TABLE 3 influence of low-temperature plasma action voltage on the purification effect of zinc-plating waste liquid and the performance of the prepared zinc-iron catalytic material
As can be seen from table 3, when the low-temperature plasma applied voltage is less than 5kV (as shown in table 3, when the low-temperature plasma applied voltage is 4.5kV, 3.5kV, 2.5kV and lower values not listed in table 3), oxygen radicals generated during the low-temperature plasma irradiation process are less, the surface activity of the expanded perlite powder is not significantly improved, and the generation amounts of heavy metal oxides and binary metal oxides are reduced, so that the removal rates of zinc, iron, copper, lead, and nickel in the zinc plating waste liquid and the removal rate of sodium dichlorophenate in the water body are all significantly reduced along with the reduction of the low-temperature plasma applied voltage. When the low-temperature plasma applied voltage is 5 to 50kV (as shown in table 3, the low-temperature plasma applied voltage is 5kV, 27.5kV, or 50 kV), oxygen is ionized and dissociated in the discharge channel during the low-temperature plasma irradiation process, and oxygen radicals are generated. The oxygen free radicals can increase the surface activity of the expanded perlite powder and improve the surface hydroxyl loading capacity of the expanded perlite powder. Meanwhile, the oxygen free radicals can also combine heavy metal ions with oxygen to induce the generation of heavy metal oxides. With the lapse of the low-temperature plasma irradiation time, the oxygen radicals may further dehydrogenate the metal hydroxide to convert into a binary metal oxide. Finally, the zinc removal rate, the iron removal rate, the copper removal rate, the lead removal rate, the nickel removal rate and the sodium dichlorophenolate removal rate in the galvanizing waste liquid are respectively greater than 95%, 97%, 98% and 94%. When the low-temperature plasma action voltage is more than 50kV (as shown in Table 3, when the low-temperature plasma action voltage is 52kV, 55kV and 60kV and higher values which are not listed in Table 3), the removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenolate in the water body are not obviously changed along with the further increase of the low-temperature plasma action voltage. Therefore, in summary, the benefit and the cost are combined, and when the low-temperature plasma action voltage is equal to 5-50 kV, the method is most beneficial to the purification of the galvanizing waste liquid and the preparation of the zinc-iron catalytic material.
Example 4 influence of Low-temperature plasma irradiation time on the purification effect of zinc plating waste liquid and the performance of the prepared zinc-iron catalytic material
Sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 30 minutes to obtain expanded perlite powder. Respectively weighing the expanded perlite powder and the zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 12.5:100, mixing, stirring, and respectively carrying out low-temperature plasma irradiation for 1 hour, 1.5 hours, 1.8 hours, 2 hours, 4 hours, 6 hours, 6.5 hours, 7 hours and 8 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the low-temperature plasma action voltage is 50kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
The sodium dichlorophenolate removal test was the same as in example 2. The concentration determination of sodium dichlorophenolate in the water body, the calculation of the removal rate of sodium dichlorophenolate in the water body, the concentration determination of the target element in the galvanizing waste liquid and the calculation of the removal rate of the target element in the galvanizing waste liquid are the same as those in the embodiment 1.
TABLE 4 influence of low-temperature plasma irradiation time on the purification effect of zinc-plating waste liquid and the performance of the prepared zinc-iron catalytic material
As can be seen from table 4, when the low-temperature plasma irradiation time is less than 2 hours (as shown in table 4, the low-temperature plasma irradiation time is 1.8 hours, 1.5 hours, 1 hour, and lower values not listed in table 4), the low-temperature plasma irradiation time is too short, the generated oxygen radicals are less, the surface activity of the expanded perlite powder is not significantly improved, and the amount of the binary metal oxide generated is reduced, so that the removal rate of zinc, iron, copper, lead, and nickel in the zinc plating waste liquid and the removal rate of sodium dichlorophenolate in the water body are significantly reduced as the low-temperature plasma irradiation time is reduced. When the low-temperature plasma irradiation time is 2-6 hours (as shown in table 4, the low-temperature plasma irradiation time is 2 hours, 4 hours, and 6 hours), in the low-temperature plasma irradiation process, oxygen is ionized and dissociated in the discharge channel to generate oxygen radicals, and the oxygen radicals can increase the surface activity of the expanded perlite powder, improve the surface hydroxyl loading capacity of the expanded perlite powder, enhance the adsorption of free heavy metal ions by the expanded perlite powder with improved surface activity, and simultaneously, the oxygen radicals can combine the heavy metal ions with oxygen to induce the generation of heavy metal oxides; with the lapse of the low-temperature plasma irradiation time, the oxygen radicals may further dehydrogenate the metal hydroxide to convert into a binary metal oxide. Because the zinc and iron ion content in the galvanizing waste liquid is far higher than that of other heavy metal ions, the metal hydroxide is mainly converted into a zinc-iron binary oxide catalytic material doped with lead, copper and nickel under the full action of oxygen radicals. Finally, the removal rate of zinc in the galvanizing waste liquid is greater than 93%, the removal rate of iron is greater than 92%, the removal rate of copper is greater than 95%, the removal rate of lead is greater than 96%, the removal rate of nickel is greater than 97%, and the removal rate of diclofenac sodium in the water body is greater than 93%. When the low-temperature plasma irradiation time is longer than 6 hours (as shown in table 4, the low-temperature plasma irradiation time is 2 hours, 4 hours, 6 hours and higher values not listed in table 4), the low-temperature plasma irradiation time is too long, and shock waves and microwaves released in the low-temperature plasma action process enable lead, copper and nickel doped zinc-iron binary oxides to be dissolved back, so that the purification effect of the galvanizing waste liquid is reduced, and the removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenate in the water body are reduced along with the further increase and change of the low-temperature plasma irradiation time. Therefore, in summary, the benefit and the cost are combined, and when the low-temperature plasma irradiation time is equal to 2-6 hours, the method is most beneficial to the purification of the galvanizing waste liquid and the preparation of the zinc-iron catalytic material.
Comparative example 1 influence of different low-temperature plasma action atmospheres on purification effect of galvanizing waste liquid and performance of prepared zinc-iron catalytic material
Sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 30 minutes to obtain expanded perlite powder. Respectively weighing the expanded perlite powder and the zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 12.5:100, mixing, stirring, and performing low-temperature plasma irradiation for 6 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the low-temperature plasma action voltage is 50kV, and the low-temperature plasma action atmospheres are respectively oxygen, air, nitrogen and argon. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
The sodium dichlorophenolate removal test was the same as in example 2. The concentration determination of sodium dichlorophenolate in the water body, the calculation of the removal rate of sodium dichlorophenolate in the water body, the concentration determination of the target element in the galvanizing waste liquid and the calculation of the removal rate of the target element in the galvanizing waste liquid are the same as those in the embodiment 1.
TABLE 5 influence of different low-temperature plasma action atmospheres on the purification effect of the zinc plating waste liquid and the performance of the prepared zinc-iron catalytic material
As can be seen from Table 5, the removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenolate in the water body, which are realized by taking oxygen as the low-temperature plasma action atmosphere, are far higher than the removal effect realized by taking air, nitrogen and argon as the low-temperature plasma action atmosphere.
Comparative example 2 different comparative processes affect the purification effect of the galvanizing waste liquid and the performance of the prepared zinc-iron catalytic material
The treatment process of the invention comprises the following steps: sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 30 minutes to obtain expanded perlite powder. Respectively weighing the expanded perlite powder and the zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 12.5:100, mixing, stirring, and performing low-temperature plasma irradiation for 6 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the low-temperature plasma action voltage is 50kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Comparative process 1: sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And (3) carrying out low-temperature plasma irradiation on the zinc-iron slurry for 6 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the acting voltage of the low-temperature plasma is 50kV, and the acting atmosphere of the low-temperature plasma is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Comparative process 2: respectively weighing the expanded perlite powder and the galvanizing waste liquid according to the mass ratio of the expanded perlite powder to the galvanizing waste liquid of 12.5:100, mixing, stirring and carrying out low-temperature plasma irradiation for 6 hours to obtain the zinc-iron catalytic slurry, wherein the stirring speed is 360rpm, the low-temperature plasma action voltage is 50kV, and the low-temperature plasma action atmosphere is oxygen. And centrifuging the zinc-iron catalytic material slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron catalytic precipitate at 150 ℃, and grinding into powder to obtain the zinc-iron catalytic material.
Comparative process 3: sodium hydroxide was weighed and dissolved in water to prepare a 5M aqueous solution of sodium hydroxide. And mixing the sodium hydroxide aqueous solution with the galvanizing waste liquid according to the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid of 1.5:1, and stirring for 1.5 hours to obtain the zinc-iron slurry. And weighing the expanded perlite, and grinding for 30 minutes to obtain expanded perlite powder. Respectively weighing the expanded perlite powder and the zinc-iron slurry according to the mass ratio of the expanded perlite powder to the zinc-iron slurry of 12.5:100, mixing, stirring for 6 hours, and then centrifuging the mixed slurry to obtain waste liquid purified liquid and zinc-iron precipitate, wherein the centrifugation speed is 12000 rpm. And drying the zinc-iron precipitate at 150 ℃, and grinding the zinc-iron precipitate into powder to obtain the zinc-iron catalytic material.
The sodium dichlorophenolate removal test was the same as in example 2. The concentration determination of sodium dichlorophenolate in the water body, the calculation of the removal rate of sodium dichlorophenolate in the water body, the concentration determination of the target element in the galvanizing waste liquid and the calculation of the removal rate of the target element in the galvanizing waste liquid are the same as those in the embodiment 1.
TABLE 6 influence of different comparative processes on the purification effect of the waste zinc plating solution and the performance of the prepared zinc-iron catalytic material
As can be seen from Table 6, the removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenolate in the water body, which are realized by the treatment process of the invention, are much higher than the removal effects realized by the comparative processes 1, 2 and 3. The removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenolate in the water body, which are realized by the treatment process, are higher than the sum of the removal rates of zinc, iron, copper, lead and nickel and the removal rate of sodium dichlorophenolate in the water body, which are realized by the comparison process 1 and the comparison process 2. The removal rate of zinc, iron, copper, lead and nickel in the galvanizing waste liquid and the removal rate of sodium dichlorophenolate in the water body, which are realized by the treatment process, are higher than the sum of the removal rates of zinc, iron, copper, lead and nickel and the removal rate of sodium dichlorophenolate in the water body, which are realized by the comparison process 2 and the comparison process 3.
Claims (9)
1. A method for purifying galvanizing waste liquid and preparing zinc-iron catalytic material is characterized by comprising the following steps:
(1) mixing and stirring the galvanizing waste liquid and a sodium hydroxide aqueous solution to obtain zinc-iron slurry;
(2) mixing expanded perlite and zinc-iron slurry, stirring, and irradiating by low-temperature plasma to obtain zinc-iron catalytic slurry;
(3) and centrifuging the zinc-iron catalytic slurry to obtain waste liquid purified liquid and zinc-iron catalytic precipitate, wherein the zinc-iron catalytic precipitate is dried and ground to obtain the zinc-iron catalytic material.
2. The method of claim 1, wherein: in the step (1), the volume ratio of the sodium hydroxide aqueous solution to the galvanizing waste liquid is 0.5-1.5: 1.
3. The method of claim 1, wherein: in the step (2), the mass ratio of the expanded perlite powder to the zinc-iron slurry is 2.5-12.5: 100.
4. The method of claim 1, wherein: in the step (2), the voltage of the low-temperature plasma irradiation is 5-50 kV.
5. The method of claim 1, wherein: in the step (2), the low-temperature plasma irradiation time is 2-6 h.
6. The method of claim 1, wherein: in the step (2), the stirring speed is 60-360 rpm.
7. The method of claim 1, wherein: in the step (2), the atmosphere of the low-temperature plasma irradiation is oxygen.
8. The method of claim 1, wherein: in the step (3), the centrifugal speed is 3000-12000 rpm.
9. The method of claim 1, wherein: in the step (3), the drying temperature of the zinc-iron catalytic precipitation is 50-150 ℃.
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