CN112973618B - Layered metal sulfide adsorbent, preparation method thereof and method for selectively enriching lead ions from heavy metal wastewater - Google Patents
Layered metal sulfide adsorbent, preparation method thereof and method for selectively enriching lead ions from heavy metal wastewater Download PDFInfo
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Abstract
The invention relates to a layered metal sulfide adsorbent, a preparation method thereof and a method for selectively enriching lead ions from heavy metal wastewater, wherein the adsorbent is prepared by mixing anhydrous K2CO3And mixing Zn, Sn and S with ultrapure water, performing ultrasonic dispersion uniformly, then placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, heating the reaction temperature of the reaction kettle to 200 ℃, reacting for 25 hours at 200 ℃, cooling, cleaning residual reactants, performing vacuum drying at 80 ℃ for 8 hours, and sieving with a 100-mesh sieve to obtain the product. The prepared layered metal sulfide adsorbent has excellent adsorption capacity and good selectivity, and when the adsorbent is used for treating heavy metal wastewater, the adsorption capacity of the adsorbent on lead ions is up to 300-500 mg/g; the invention can also desorb the adsorbent for adsorbing lead ions to enrich lead, and the recovery rate is up to more than 94%. Therefore, the invention provides a cheap and efficient method for recovering lead element in heavy metal wastewater and deeply treating the wastewater.
Description
Technical Field
The invention belongs to the technology of treating lead ion-containing wastewater and recovering other valuable elements in the mining and smelting industries of non-ferrous metal mines, and particularly relates to a layered metal sulfide adsorbent, a preparation method thereof and a method for selectively enriching lead ions from heavy metal wastewater.
Background
Lead (Pb), lead alloy and its compound are used in the fields of accumulator, machine construction, shipbuilding and radiation protection. The widespread use of lead-containing products accelerates the concentration of lead in the atmosphere, soil, water and food chain, thereby increasing global environmental risks. Among these, water for mining, mineral processing, metallurgy and battery industries is a major source of lead-containing wastewater. Lead is a toxic heavy metal element commonly found in human tissues and organs. Even at low doses, lead is highly carcinogenic and can damage the bone, hematopoiesis, digestion, cardiovascular system, skeletal muscle, glands, liver, kidneys, immune system, and nervous system. Therefore, selective separation of lead pollution in wastewater is an urgent task of environmental remediation and separation science.
For decades, various methods have been developed to remove lead ions, such as chemical precipitation, ion exchange, adsorption, membrane filtration, electrochemical methods, flotation, etc. The methods play an important role in the treatment of heavy metal wastewater, but still have the defects of low recovery rate, long separation time, high toxicity, high price, secondary pollution, poor treatment effect on low-concentration wastewater and the like. Although many important research results are obtained, the development of wastewater treatment technology and process with excellent performance such as high efficiency, rapidness, safety, low price, environmental protection and the like is still urgent. It is known that the composition of environmental wastewater is very complex, and under extreme conditions such as strong acid, the adsorbent not only loses adsorption performance and capacity, but also has reduced selectivity. Therefore, the problems of reducing the cost, improving the stability of the adsorbent under extreme conditions, increasing the adsorption capacity and improving the adsorption selectivity are urgently needed to be solved in the practical application of the adsorbent.
Adsorption is considered to be one of the most promising techniques for the removal of heavy metals, dyes and radionuclides, based on physical or chemical adsorption principles. The method has obvious effect of removing pollutants which are difficult to degrade, and has the advantages of strong selectivity, good adsorption effect, low energy consumption, simple operation, cheap and easily obtained raw materials and the like, thereby having unique advantages in enriching and recovering heavy metal lead ions.
For the above reasons, the present application has been made.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a layered metal sulfide adsorbent, a preparation method thereof and a method for selectively enriching lead ions from heavy metal wastewater.
In order to realize the purpose, the invention firstly puts the needed raw materials into a hydro-thermal synthesis reaction kettle, reacts at high temperature, then cleans the obtained product until the supernatant is clear, and screens the product after vacuum drying to obtain the layered metal sulfide. The invention takes the obtained layered metal sulfide as an adsorbent to adsorb and recover lead ions from the wastewater containing heavy metal ions. The method can efficiently recover valuable lead elements in the heavy metal wastewater, and reduces the harm of lead ions to the water environment, thereby providing a cheap and efficient method for recovering the valuable elements in the heavy metal wastewater and deeply treating the wastewater.
One of the above objects of the present invention is achieved by the following technical solutions:
a preparation method of a layered metal sulfide adsorbent specifically comprises the following steps:
mixing anhydrous potassium carbonate (K)2CO3) Mixing zinc (Zn) powder, tin (Sn) powder and sulfur (S) powder, then adding a proper amount of ultrapure water, ultrasonically dispersing uniformly, transferring the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing, raising the reaction temperature of the reaction kettle to 200 ℃, and carrying out constant-temperature reaction for 25 hours at the temperature of 200 ℃; and finally, washing, vacuum drying and sieving the obtained product to obtain the layered metal sulfide adsorbent.
Further, according to the technical scheme, the use amount ratio of the anhydrous potassium carbonate, the zinc powder, the tin powder, the sulfur powder and the ultrapure water is 3.35 parts by mass: 0.788 parts by mass: 2.854 parts by mass: 3.874 parts by mass: 2 parts by volume, wherein: the mass part and the volume part are as follows: ml is used as a reference.
Further, according to the technical scheme, the washing is specifically that the washing is alternately and repeatedly carried out by using absolute ethyl alcohol and ultrapure water until the supernatant is clear, and the purpose of the washing is to wash the residual reactant.
Further, in the above technical scheme, the temperature of the vacuum drying is preferably 80 ℃, and the time of the vacuum drying is preferably 8 h.
Further, in the above technical solution, the size of the sieve opening of the molecular sieve used for sieving is preferably 100 meshes.
The second purpose of the invention is to provide the layered metal sulfide adsorbent with the molecular formula of K prepared by the method1.87Zn0.13Sn6.4S12.67The layered metal sulfide adsorbent is of a layered nano structure and does not contain bulk components, K ions exist between layers, and a-S-structure exists in a framework, so that the layered metal sulfide adsorbent has good affinity for heavy metals. In addition, the layered metal sulfide adsorbent synthesized by the invention has no functional group, so that the layered metal sulfide adsorbent is extremely strong in adaptability to a system.
The third purpose of the invention is to provide the application of the layered metal sulfide adsorbent prepared by the method in selective enrichment of lead ions from heavy metal wastewater.
The fourth purpose of the invention is to provide a method for selectively enriching lead ions from heavy metal wastewater by using the layered metal sulfide adsorbent, which comprises the following steps:
(1) keeping the pH value of the heavy metal wastewater at 1.0-6.0;
(2) the obtained adsorbent was mixed in an amount of 0.4 mg: adding 1L of the heavy metal ions into the wastewater obtained in the step (1), uniformly stirring, and then oscillating and adsorbing at constant temperature for 0.5-25 h at normal temperature to make the heavy metal ions in the wastewater adsorbed on the surface of the adsorbent;
(3) and after adsorption, standing the wastewater for 30-60 min, discharging clear liquid, recovering the adsorbent adsorbed with the heavy metal ions, and performing oscillation desorption by using a dilute acid solution.
Further, in the technical scheme, the concentration of the heavy metal wastewater in the step (1) is preferably 25-250 mg/L.
Further, in the above technical solution, the pH value of the heavy metal wastewater in the step (1) is preferably about 5.2, for example, may be 5 to 5.5, because when the pH is greater than this value, some ions in the wastewater start to precipitate.
Further, in the above technical scheme, the normal temperature in the step (2) is a natural room temperature condition in four seasons, no additional cooling or heating treatment is performed, and the normal temperature is generally controlled to be 10-30 ℃, preferably 15-25 ℃.
Further, in the above technical solution, the oscillation adsorption time in the step (2) is preferably 4 hours.
Further, in the technical scheme, the adsorption capacity of the layered metal sulfide adsorbent in the step (2) on lead ions is 1 mg/g-522.34 mg/g.
Further, in the above technical solution, the dilute acid solution in the step (3) is preferably a dilute nitric acid solution with a concentration of 1 mol/L.
Further, in the above technical solution, the time for the oscillating desorption in the step (3) is preferably 12 hours.
The invention takes the synthesized layered metal sulfide as an adsorbent, a functional group (-S-) on the surface of the adsorbent can be coordinated with lead ions, and K between layers+Can exchange with lead ions, thereby leading the lead ions to be efficiently enriched.
Compared with the prior art, the layered metal sulfide adsorbent, the preparation method thereof and the method for selectively enriching lead ions from heavy metal wastewater have the following advantages and beneficial effects:
(1) the adsorbent prepared by the invention has two effects on lead adsorption, namely chemical bonding and ion exchange, and is used for wastewater treatment, wherein the adsorption capacity of the adsorbent on heavy metal lead ions is up to 300-500 mg/g; and the adsorbent can be desorbed by a simple acid treatment method, so that the lead is efficiently recovered, and the recovery rate is up to 95%.
(2) The adsorbent prepared by the invention has good adsorption capacity at different temperatures and pH values, and the adsorption capacity can still reach about 310mg/L even under the strong acid condition that the pH value is 1; the adsorption capacity at room temperature is about 430mg/L, and the adsorption capacity is up to 522.34mg/g as the temperature rises and the adsorption capacity rises rapidly.
(3) The adsorbent prepared by the invention has yellow color before adsorption, and the color is changed into black after adsorption of lead ions. The rapid color change reaction can provide a new detection method for rapid detection of lead ions.
(4) The adsorbent prepared by the invention has stable property, no toxicity and no harm; and starting materials therefor, e.g. anhydrous K2CO3Zn, Sn, S and the like are cheap and easily obtained, and the preparation method and the adsorption method are simple, rapid and efficient, and have good application prospects in the aspect of treatment of heavy metal wastewater.
(5) The adsorbent synthesized by the invention has a layered structure and does not contain any block material. When it is Pb2+When the ions act with the adsorbent, the specific surface area is larger, the contact probability is higher, and the adsorption is more facilitated.
(6) The layered metal sulfide adsorbent prepared by the invention can be used for recovering valuable elements in high-low concentration wastewater generated in the non-ferrous metal mining and smelting processes and providing a new way for advanced treatment of the wastewater.
Drawings
FIG. 1 is a scanning electron microscopy topography of a layered metal sulfide prepared in example 1 of the present invention;
FIG. 2 is a comparison graph of the color change of the layered metal sulfide adsorbent before and after adsorption in example 2 of the present invention;
FIG. 3 is a graph showing the effect of the layered metal sulfide adsorbent on the adsorption capacity of heavy metal lead ions under different initial ion concentrations in example 2 of the present invention;
FIG. 4 is a graph showing the effect of layered metal sulfide adsorbents on the adsorption capacity of heavy metal lead ions at different pH's in example 3 of the present invention;
FIG. 5 is a graph showing the effect of the layered metal sulfide adsorbent on the capacity of adsorption of heavy metal lead ions under different adsorption time conditions in example 4 of the present invention;
FIG. 6 is a graph showing the effect of layered metal sulfide adsorbents on the adsorption capacity for heavy metal lead ions at different adsorption temperatures in example 5 of the present invention;
FIG. 7 is a graph comparing the adsorption effect on lead ions in the presence of different competitive ions for inventive example 6.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.
The layered metal sulfide adsorbent is prepared by mixing anhydrous K2CO3Mixing Zn, Sn and S with ultrapure water, stirring, ultrasonically dispersing uniformly, and then placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene liningHeating the reaction temperature of the reaction kettle to 200 ℃, reacting for 25h at 200 ℃, cooling, cleaning residual reactants, drying for 8h at 80 ℃ in vacuum, and sieving with a 100-mesh sieve to obtain the product. The prepared layered metal sulfide adsorbent has excellent adsorption capacity and good selectivity, and when the adsorbent is used for treating heavy metal wastewater, the adsorption capacity of the adsorbent on lead ions is up to 300-500 mg/g; the invention can also desorb the adsorbent for adsorbing lead ions to enrich lead, and the recovery rate is up to more than 94%. Therefore, the invention provides a cheap and efficient method for recovering lead element in heavy metal wastewater and deeply treating the wastewater.
Example 1
The preparation method of the layered metal sulfide adsorbent of the embodiment comprises the following steps:
(1) 3.35g of anhydrous potassium carbonate, 0.788g of zinc powder, 2.854g of tin powder and 3.874g of sulfur powder are uniformly mixed, then 2ml of ultrapure water is added, the mixture is uniformly stirred and subjected to ultrasonic treatment for 10 minutes, the obtained mixture is transferred to a 100ml hydrothermal synthesis reaction kettle, the reaction kettle is sealed, the reaction temperature of the reaction kettle is raised to 200 ℃, and the reaction is carried out for 25 hours at a constant temperature of 200 ℃.
(2) And (2) cooling the product obtained in the step (1) to room temperature, alternately and repeatedly washing the product with absolute ethyl alcohol and ultrapure water until the supernatant is colorless, and then drying the obtained precipitate for 8 hours in vacuum at the temperature of 80 ℃. And finally, screening the obtained product by a 100-mesh screen to obtain the final product.
The molecular formula of the layered metal sulfide adsorbent prepared in the example is K1.87Zn0.13Sn6.4S12.67The shape of the scanning electron microscope is shown in FIG. 1, and it can be seen that the shape of the adsorbent is laminar and does not contain bulk components.
In the methods for enriching lead ions from heavy metal solutions described in the following embodiments 2 to 7, all the adsorbents used are layered metal sulfide adsorbents prepared by the method of embodiment 1.
In examples 2 to 6 described below, the reagents used for preparing the lead ion solutions were all lead nitrate, and the pH values of the lead ion solutions were about 5.2 when dissolved in water, so that in examples 2 and 4 to 6, the pH values of the lead ion solutions prepared were all about 5.2 without artificially adjusting the pH values of the lead ion solutions.
Example 2
The method for enriching lead ions from a heavy metal solution by using the layered metal sulfide adsorbent comprises the following steps:
(1) taking a plurality of 30mL transparent sample bottles, and respectively preparing a lead ion solution with the pH value of 5.2, wherein: the initial concentration of lead ions in the lead ion solution is 0.025g/L, 0.05g/L, 0.10g/L, 0.15g/L, 0.20g/L and 0.25g/L in sequence; the influence of the initial concentration of lead ions on the adsorption effect was investigated.
(2) The layered metal sulfide adsorbent obtained in example 1 was prepared in the following manner of 0.4 mg: adding 1L of the lead ions into the sample bottles filled with the lead ion solutions with different initial concentrations in the step (1) respectively, uniformly stirring, and then adsorbing for 4 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 25 ℃ to enable the lead ions in the solutions to be adsorbed on the surface of the adsorbent;
(3) and after adsorption, standing the obtained mixed solution, discharging supernatant, carrying out oscillation desorption on the adsorbent adsorbed with the lead ions by using dilute nitric acid with the concentration of 1mol/L for 12 hours, and finally, naturally drying the adsorbent and storing the adsorbent at room temperature.
The colors of the adsorbent before and after adsorption in this example are shown in fig. 2, and it can be seen that the layered metal sulfide before adsorption is yellow, and the color of the adsorbent after adsorption of lead ions is changed to black, indicating that lead ions and the layered metal sulfide generate new compounds. The rapid color change reaction can provide a new detection method for rapid detection of lead ions.
Taking a certain amount of clear liquid obtained in the step (3), measuring the concentration of lead ions in the clear liquid by using ICP-OES of a laboratory, and calculating the adsorption capacity of the lead ions, wherein the adsorption capacity of the layered metal sulfide adsorbent under different initial lead ion concentrations is shown in figure 3. As can be seen from fig. 3, the adsorption capacity of the layered metal sulfide to lead ions increases as the initial concentration of lead ions increases. When the initial concentration of lead ions was 0.025g/L, the adsorption capacity of the layered metal sulfide was 120 mg/g. The adsorption capacity of the layered metal sulfide gradually increases as the initial concentration of lead ions increases. When the initial concentration of lead ions is 0.15g/L, the adsorption capacity of the adsorbent is as high as 430 mg/g.
Example 3
The method for enriching lead ions from heavy metal solution by using the layered metal sulfide adsorbent comprises the following steps:
(1) taking a plurality of 30mL transparent sample bottles, and respectively preparing lead ion solutions with pH values of 1.0, 2.0, 3.0, 4.0, 5.0 and 6.0, wherein: the initial concentration of the lead ion solution is 0.15 g/L;
(2) the layered metal sulfide adsorbent obtained in example 1 was prepared in a weight ratio of 0.4 mg: adding 1L of the lead ions into the sample bottles filled with the lead ion solutions with different pH values in the step (1) respectively, uniformly stirring, and adsorbing for 4 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 25 ℃ to make the lead ions in the solutions adsorbed on the surface of the adsorbent;
(3) and after adsorption, standing the obtained mixed solution, discharging supernatant, carrying out oscillation desorption on the adsorbent adsorbed with the lead ions by using nitric acid with the mass concentration of 1mol/L for 12 hours, and finally, naturally drying the adsorbent and storing the adsorbent at room temperature.
Taking a certain amount of clear liquid obtained in the step (3), measuring the concentration of lead ions in the clear liquid by using ICP-OES of a laboratory, and calculating the adsorption capacity of the lead ions, wherein the adsorption capacity of the adsorbent under different pH conditions is shown in figure 4.
As can be seen from fig. 4, the adsorption capacity of the layered metal sulfide to lead ions increases with increasing pH. The pH is increased from 1.0 to 6.0, and the adsorption capacity of the adsorbent to lead ions is increased from 309.72mg/g to 452.32 mg/g.
Example 4
The method for enriching lead ions from a heavy metal solution by using the layered metal sulfide adsorbent comprises the following steps:
(1) taking a plurality of 30mL transparent sample bottles, and respectively preparing lead ion solutions with pH values of about 5.2, wherein: the initial concentration of the lead ion solution is 0.15 g/L;
(2) the layered metal sulfide adsorbent obtained in example 1 was prepared in the following manner of 0.4 mg: adding 1L of the lead ion solution into each sample bottle filled with the lead ion solution in the step (1) respectively, stirring uniformly, adsorbing in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 25 ℃, and adjusting the adsorption time to be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 12h and 24h respectively to enable the lead ions in the solution to be adsorbed on the surface of an adsorbent;
(3) and after adsorption, standing the obtained mixed solution, discharging supernatant, carrying out oscillation desorption on the adsorbent adsorbed with lead ions by using dilute nitric acid with the concentration of 1mol/L for 12 hours, and finally, naturally drying and storing at room temperature.
Taking a certain amount of clear liquid obtained in the step (3), measuring the concentration of lead ions in the clear liquid by using ICP-OES of a laboratory, and calculating the adsorption capacity of the lead ions, wherein the adsorption capacity of the adsorbent under different adsorption time conditions is shown in figure 5.
As can be seen from fig. 5, the adsorption capacity of the layered metal sulfide adsorbent for lead ions increases with the adsorption time. When the adsorption time is increased from 0.5h to 4h, the adsorption capacity of the layered metal sulfide adsorbent to lead ions is increased from 219.16mg/g to 426.96 mg/g. And the adsorption time is continuously increased to 24h, the adsorption capacity is not obviously changed, and the optimal time of the layered metal sulfide adsorbent for adsorbing the lead ions is 4 h.
Example 5
The method for enriching lead ions from a heavy metal solution by using the layered metal sulfide adsorbent comprises the following steps:
(1) taking a plurality of 30mL conical flasks, and respectively preparing lead ion solutions with the pH value of about 5.2, wherein: the initial concentration of the lead ion solution is 0.15 g/L;
(2) the layered metal sulfide adsorbent obtained in example 1 was prepared in the following manner of 0.4 mg: adding 1L of the solution into each sample bottle filled with the lead ion solution in the step (1) respectively, stirring uniformly, and adsorbing for 4 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the conditions of 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ respectively to enable the lead ions in the solution to be adsorbed on the surface of an adsorbent;
(3) and after adsorption, standing the obtained mixed solution, discharging supernatant, carrying out oscillation desorption on the adsorbent adsorbed with lead ions by using dilute nitric acid with the concentration of 1mol/L for 12 hours, and finally, naturally drying and storing at room temperature.
Taking a certain amount of the clear liquid obtained in the step (3), measuring the concentration of lead ions in the clear liquid by using ICP-OES of a laboratory, and calculating the adsorption capacity of the lead ions, wherein the adsorption capacity of the adsorbent under different adsorption temperature conditions is shown in figure 6.
As can be seen from fig. 6, the adsorption capacity of the layered metal sulfide adsorbent for lead ions increases with increasing temperature. When the temperature is increased from 25 ℃ to 70 ℃, the adsorption capacity of the layered metal sulfide to lead ions is increased from 428.56mg/g to 522.34 mg/g.
Example 6
A method for enriching lead from a heavy metal solution using a layered metal sulfide adsorbent, the method comprising the steps of:
taking a plurality of 30mL transparent sample bottles, wherein each sample bottle is a mixed heavy metal ion solution consisting of two different heavy metal ions, and the pH value of the mixed heavy metal ion solution is about 5.2; wherein:
the sample bottle 1 is filled with a mixed heavy metal ion solution 1 consisting of lead ions and cadmium ions, the initial concentration of the lead ions in the mixed heavy metal ion solution 1 is 0.15g/L, and the initial concentration of the cadmium ions is 0.168 g/L;
the sample bottle 2 is filled with a mixed heavy metal ion solution 2 consisting of lead ions and cobalt ions, the initial concentration of the lead ions in the mixed heavy metal ion solution 2 is 0.15g/L, and the initial concentration of the cobalt ions is 0.167 g/L;
the sample bottle 3 is filled with a mixed heavy metal ion solution 3 consisting of lead ions and aluminum ions, the initial concentration of the lead ions in the mixed heavy metal ion solution 3 is 0.15g/L, and the initial concentration of the aluminum ions is 0.158 g/L;
a mixed heavy metal ion solution 4 consisting of lead ions and manganese (II) ions is arranged in the sample bottle 4, the initial concentration of the lead ions in the mixed heavy metal ion solution 4 is 0.15g/L, and the initial concentration of the manganese (II) ions is 0.213 g/L;
the sample bottle 5 is filled with a mixed heavy metal ion solution 5 consisting of lead ions and calcium ions, wherein the initial concentration of the lead ions in the mixed heavy metal ion solution 5 is 0.15g/L, and the initial concentration of the calcium ions in the mixed heavy metal ion solution 5 is 0.14 g/L.
(2) The layered metal sulfide adsorbent prepared in example 1 was prepared in the following manner, respectively, in an amount of 0.4 mg: adding 1L of the solution into each sample bottle filled with the lead ion solution in the step (1) respectively, stirring uniformly, and adsorbing for 4 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 25 ℃ to enable lead ions in the solution to be adsorbed on the surface of an adsorbent;
(3) and after adsorption, standing the obtained mixed solution, discharging supernatant, carrying out oscillation desorption on the adsorbent adsorbed with lead ions by using dilute nitric acid with the concentration of 1mol/L for 12 hours, and finally, naturally drying and storing at room temperature.
Taking a certain amount of clear liquid obtained in the step (3), measuring the concentrations of lead ions, cadmium ions, cobalt ions, aluminum ions, manganese (II) ions and calcium ions in the clear liquid by using ICP-OES of a laboratory, calculating the adsorption capacity of each ion, and showing the influence of different ions on the adsorption capacity of the lead ions in the presence of different ions as shown in figure 7.
As can be seen from FIG. 7, the lead ion adsorption capacity of the layered metal sulfide adsorbent is very good even in the presence of other heavy metal ions. This also shows that the layered metal sulfide adsorbent synthesized by the invention has good selectivity to lead ions. Has good competitive adsorption capacity even in the presence of other heavy metal ions and stearic acid ions, so the layered metal sulfide adsorbent synthesized by the invention still has Pb-tolerant function even in complex water environment2+Has good recovery effect and stability.
Example 7
The desorption method of the layered metal sulfide adsorbent after lead ions are enriched comprises the following steps:
the adsorbent samples adsorbed in example 2 were each subjected to ultra-pure adsorptionWater and 1mol/L diluted HNO3The solution was subjected to desorption experiments as follows:
two 0.5g samples of the adsorbent of example 2 were taken and placed in excess ultrapure water and 1mol/L dilute HNO3The solution was magnetically stirred at room temperature for 12 h.
Experiments have shown that the desorption rate by ultrapure water is about 11%, while 1mol/L HNO is used3The resolution of the solution is close to 95%, and the Pb of the supernatant is measured after desorption2+The concentration was about 410 mg/L.
Claims (7)
1. A preparation method of a layered metal sulfide adsorbent for selectively enriching lead ions from heavy metal wastewater is characterized by comprising the following steps: the method comprises the following steps:
mixing anhydrous potassium carbonate, zinc powder, tin powder and sulfur powder according to a ratio, adding a proper amount of ultrapure water, ultrasonically dispersing uniformly, transferring the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing, raising the reaction temperature of the reaction kettle to 200 ℃, and carrying out constant-temperature reaction for 25 hours at the temperature of 200 ℃; finally, washing, vacuum drying and sieving the obtained product to obtain the layered metal sulfide adsorbent; wherein:
the using amount ratio of the anhydrous potassium carbonate, the zinc powder, the tin powder, the sulfur powder and the ultrapure water is 3.35 parts by mass: 0.788 parts by mass: 2.854 parts by mass: 3.874 parts by mass: 2 parts by volume, wherein: the mass part and the volume part are as follows: ml is taken as a benchmark;
the layered metal sulfide adsorbent is of a layered nano structure, K ions exist between layers, a-S-structure exists in a framework, and the molecular formula of the adsorbent is K1.87Zn0.13Sn6.4S12.67。
2. The method of claim 1, wherein: the method for selectively enriching lead ions from heavy metal wastewater by using the layered metal sulfide adsorbent comprises the following steps:
(1) keeping the pH value of the heavy metal wastewater at 1.0-6.0;
(2) the obtained adsorbent was mixed in an amount of 0.4 mg: adding 1L of the heavy metal ions into the wastewater obtained in the step (1), uniformly stirring, and then oscillating and adsorbing at constant temperature for 0.5-25 h at normal temperature to make the heavy metal ions in the wastewater adsorbed on the surface of the adsorbent;
(3) and after adsorption, standing the wastewater for 30-60 min, discharging clear liquid, recovering the adsorbent adsorbed with the heavy metal ions, and performing oscillation desorption by using a dilute acid solution.
3. The method of claim 2, wherein: the concentration of the heavy metal wastewater in the step (1) is 25-250 mg/L.
4. The method of claim 2, wherein: and (2) the pH value of the heavy metal wastewater in the step (1) is 5-5.5.
5. The method of claim 2, wherein: and (3) oscillating the adsorption time in the step (2) to be 4 h.
6. The method of claim 2, wherein: the adsorption capacity of the layered metal sulfide material on lead ions in the step (2) is 300-500 mg/g.
7. The method of claim 2, wherein: and (4) in the step (3), the dilute acid solution is a dilute nitric acid solution with the concentration of 1 mol/L.
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