CN114804413A - Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof - Google Patents
Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a heavy metal wastewater treatment method, a treatment system and a preparation method of an adsorbent thereof, wherein the method comprises the following steps: removing Ag in wastewater by precipitation method using rough treatment device 2+ Adjusting the pH value to obtain a crude treatment solution; conveying the crude treatment liquid to an adsorption device, adsorbing heavy metal ions in the wastewater by an adsorbent in the adsorption device, and discharging the treatment liquid, wherein the adsorbent is a resin-supported humic acid modified nano zirconium dioxide compound; eluting heavy metal ions by adding a first eluent and a second eluent with selectivity into the adsorption device; and heavy metal ions can be stably adsorbed by recovering the heavy metal ions through the heavy metal ion recovery device. By passingAdsorbent and selective eluent capable of adsorbing Cr 3+ And Hg 2+ The Cr and the Hg in the wastewater can be directly separated and recovered by respectively eluting and recovering, so that the problem that a precipitation method is not beneficial to the subsequent recovery and utilization of the Cr and the Hg is solved.
Description
Technical Field
The invention relates to the field of laboratory sewage treatment, in particular to a heavy metal wastewater treatment method, a treatment system and a preparation method of an adsorbent thereof.
Background
Chemical Oxygen Demand (COD) is one of the important indexes for evaluating the quality of environmental water. At present, the standard test method in China is based on K 2 Cr 2 O 7 The oxidation method (HJ 828-2017) can generate high-concentration heavy metal waste liquid. Wherein, the concentrations of the heavy metals Cr and Hg with high toxicity are respectively as high as 270 mg/L and 1600 mg/L. Direct discharge of the COD test waste liquid causes environmental pollution, and thus it is necessary to treat it.
At present, the main precipitation method for treating COD test waste liquid is shown as figure 1. The method involves multi-step precipitation reaction, and NaCl, NaOH and Na are required to be added 2 CO 3 、Na 2 S、FeSO 4 And the like, and has the defects of complicated operation steps, high cost and the like. More importantly, the method cannot deeply remove Cr 3+ And the international sewage discharge standard is difficult to reach (GB 8978-. In addition, the precipitation method is disadvantageous for the subsequent recovery of Cr and Hg due to the formation of stable, poorly soluble substances. Therefore, an inexpensive treatment method capable of removing and recycling heavy metal ions in the waste liquid from the COD test needs to be developed.
Disclosure of Invention
Based on the method, the treatment system and the preparation method of the adsorbent, the heavy metal ions can be stably adsorbed, and the adsorbed Cr can be treated by selective eluent 3+ And Hg 2+ And the Cr and the Hg in the wastewater can be directly separated and recovered by respectively eluting, so that the problem that a precipitation method is not beneficial to the subsequent recovery and utilization of the Cr and the Hg is solved.
According to an aspect of the present invention, there is provided a method for treating heavy metal wastewater, comprising:
removing Ag in wastewater by precipitation method using rough treatment device 2+ Adjusting the pH value to obtain a crude treatment solution;
conveying the crude treatment liquid to an adsorption device, adsorbing heavy metal ions in the wastewater by an adsorbent in the adsorption device, and discharging the treatment liquid, wherein the adsorbent is a resin-supported humic acid modified nano zirconium dioxide compound;
eluting the heavy metal ions by adding a first eluent and a second eluent having selectivity into the adsorption device; and recovering the heavy metal ions by a heavy metal ion recovery device.
According to an embodiment of the present invention, the above precipitation method includes:
adding a precipitant to the crude treatment device by a dosing device, wherein the final concentration of the precipitant reaches 500-8000 mg/L.
According to an embodiment of the present invention, the pH of the crude treatment liquid is 2 to 8.
According to an embodiment of the present invention, the first eluent comprises 0.02 to 0.5mol/L nitric acid;
the second eluent comprises 0.1-1.5mol/L thiourea solution.
According to another aspect of the present invention, there is provided a heavy metal wastewater treatment system for implementing the above method, comprising:
the coarse treatment device is used for precipitating Ag in the wastewater 2+ And adjusting the pH of the wastewater to obtain the crude treatment liquid;
the adsorption device comprises a fixed bed containing the adsorbent and a liquid adding elution device;
the fixed bed for adsorbing the heavy metal ions in the crude treatment liquid and discharging the treatment liquid;
the liquid adding elution device is used for adding the first eluent and the second eluent into the fixed bed;
the heavy metal ion recovery device is arranged at the downstream of the adsorption device and used for separating and collecting the heavy metal ions.
According to an embodiment of the present invention, the rough processing apparatus includes:
the device comprises a precipitation separation unit and a pH adjusting unit, wherein the precipitation separation unit and the pH adjusting unit are both connected with the dosing device, and the dosing device is used for adding a precipitator for the precipitation separation unit or adding an adjusting agent for the pH adjusting unit.
According to an embodiment of the present invention, the heavy metal ion recovery device comprises Cr 3+ Ion recovery device and Hg 2+ An ion recovery device.
According to another aspect of the present invention, there is provided a method of preparing an adsorbent used in the above method, comprising:
dissolving sodium humate to obtain a sodium humate solution;
heating the resin-supported nano zirconium dioxide aqueous solution in a water bath, adding the sodium humate solution and ammonia water, and reacting for 5-24h to obtain a product precipitate;
cooling the product precipitate and washing to neutrality to obtain the adsorbent.
According to the embodiment of the present invention, the mass ratio of the sodium humate to the resin-supported nano zirconium dioxide is 1: 100.
According to an embodiment of the present invention, the ratio of the ammonia water to the sodium humate is: 10ml of ammonia water was added to 1g of the above humic acid sodium salt.
According to the technical scheme, the heavy metal wastewater treatment system, the treatment method and the preparation method of the adsorbent have the following beneficial effects:
1. according to the invention, the resin-supported humic acid modified nano zirconium dioxide compound is selected as the adsorbent, so that heavy metal ions can be stably adsorbed, and the adsorbed Cr can be adsorbed by selective eluent 3+ And Hg 2+ And the Cr and the Hg in the wastewater can be directly separated and recovered by respectively eluting, so that the problem that a precipitation method is not beneficial to the subsequent recovery and utilization of the Cr and the Hg is solved.
2. The invention selects the resin-supported humic acid modified nano zirconium dioxide compound as the adsorbent, has excellent physicochemical properties and adsorption performance, has a porous structure in the interior, can greatly increase the adsorption area, is beneficial to the adsorption of heavy metal ions, can be repeatedly utilized for multiple times, and has better economic benefit.
Drawings
FIG. 1 is a schematic flow diagram of a process for treating a COD test waste liquid by a precipitation method;
FIG. 2 is a schematic structural diagram of a heavy metal wastewater treatment system according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of the synthesis of an adsorbent according to an embodiment of the present invention;
FIG. 4 is an electron microscope image of the internal structure of the adsorbent according to the embodiment of the present invention;
FIG. 5 is a graph of zirconium ion release ratio versus pH for an adsorbent according to an embodiment of the present invention;
FIG. 6 shows Cr in accordance with an embodiment of the present invention 3+ And Hg 2+ Histogram of elution rates of (c);
figure 7 is a bar graph of the removal efficiency of heavy metal ions after multiple cycles of the adsorbent of an embodiment of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
FIG. 2 is a schematic structural diagram of a heavy metal wastewater treatment system according to an embodiment of the present invention.
As shown in fig. 2, according to an aspect of the present invention, there is provided a method for treating heavy metal wastewater, comprising:
the method comprises the following steps: removing Ag in wastewater by precipitation method using rough treatment device 2+ Adjusting the pH value to obtain a crude treatment solution;
step two: conveying the crude treatment liquid to an adsorption device, adsorbing heavy metal ions in the wastewater by an adsorbent in the adsorption device, and discharging the treatment liquid, wherein the adsorbent is a resin-supported humic acid modified nano zirconium dioxide compound (HA-HZO-201);
step three: eluting heavy metal ions by adding a first eluent and a second eluent with selectivity into the adsorption device; and recovering the heavy metal ions by a heavy metal ion recovery device.
The resin-supported humic acid modified nano zirconium dioxide compound is selected as the adsorbent, has excellent physicochemical properties and adsorption performance, has a porous structure in the interior, can greatly increase the adsorption area, is beneficial to the adsorption of heavy metal ions, can be repeatedly utilized for multiple times, and has better economic benefit.
By selecting the resin-supported humic acid modified nano zirconium dioxide compound as the adsorbent, heavy metal ions can be stably adsorbed, and the adsorbed Cr can be adsorbed by selective eluent 3+ And Hg 2+ And the Cr and the Hg in the wastewater can be directly separated and recovered by respectively eluting, so that the problem that a precipitation method is not beneficial to subsequent recovery and utilization of the Cr and the Hg is solved.
FIG. 1 is a schematic flow chart of a COD test waste liquid treated by a precipitation method.
As can be seen from FIGS. 1 to 2, by comparing the general precipitation method with the treatment method of heavy metal wastewater provided by the present invention, the COD test waste liquid treatment scheme based on the fixed bed continuous adsorption apparatus of the present invention has the advantages of high efficiency and simplicity. The invention can lead Cr to 3+ (136mg/L) and Hg 2+ (998mg/L) is respectively reduced to 0.28 and 0.02mg/L, and the sewage reaches the sewage discharge standard of China (GB 8978-. In addition, compared with a precipitation method, the method has the advantages of simple steps, no need of complicated operations such as precipitation, filtration and the like.
According to the embodiment of the invention, the adsorbent resin carries humic acid modified nano zirconium dioxide compound (HA-HZO-201) to Cr 3+ And Hg 2+ The saturated adsorption capacities of the adsorbent are respectively as high as 37.5 and 121.3 mg/g.
According to an embodiment of the present invention, in the first step, the precipitation method comprises:
adding a precipitator into the crude treatment device through a dosing device, wherein the final concentration of the precipitator reaches 500-8000 mg/L.
According to an embodiment of the present invention, in the first step, the precipitation method specifically includes:
NaCl is added into the precipitation separation unit through a medicine adding device, so that the final concentration is 500-8000 mg/L. Fully reacting for 10-120 min, and then filtering to obtain white precipitate AgCl.
According to an embodiment of the invention, in step one, the pH of the crude treatment liquid is 2 to 8.
According to an embodiment of the present invention, NaOH may be added to the crude treatment solution in step one to adjust the pH of the crude treatment solution.
According to an embodiment of the invention, in step three, the first eluent comprises 0.02-0.5mol/L nitric acid;
according to the embodiment of the present invention, in the third step, the first eluent is specifically used by the following steps: using 0.02-0.5mol/L nitric acid (HNO) 3 ) Performing first elution as eluent with total volume of 2-10BV to obtain Cr in heavy metal ion recovery unit 3+ 。
According to an embodiment of the present invention, in step three, the second eluent comprises 0.1-1.5mol/L thiourea solution;
according to the embodiment of the present invention, in the third step, the second eluent is specifically used by the following steps: adopting 0.1-1.5mol/L thiourea solution (HTU) as eluent to carry out secondary elution, wherein the total volume of the eluent is 2-10BV, and obtaining Hg in a heavy metal ion recovery device 2+ 。
FIG. 2 is a schematic structural diagram of a heavy metal wastewater treatment system according to an embodiment of the present invention.
As shown in fig. 2, according to another aspect of the present invention, there is provided a heavy metal wastewater treatment system for implementing the method, including:
a rough treatment device for precipitating Ag in the wastewater 2+ And adjusting the pH of the wastewater to obtain a crude treatment solution;
the adsorption device comprises a fixed bed containing an adsorbent and a liquid adding elution device;
the fixed bed is used for adsorbing heavy metal ions in the crude treatment liquid and discharging the treatment liquid;
the liquid adding elution device is used for adding a first eluent and a second eluent into the fixed bed;
and the heavy metal ion recovery device is arranged at the downstream of the adsorption device and is used for separating and collecting heavy metal ions.
By selecting the resin-supported humic acid modified nano zirconium dioxide compound as the adsorbent, heavy metal ions can be stably adsorbed, and the adsorbed Cr can be adsorbed by selective eluent 3+ And Hg 2+ And the Cr and the Hg in the wastewater can be directly separated and recovered by respectively eluting, so that the problem that a precipitation method is not beneficial to the subsequent recovery and utilization of the Cr and the Hg is solved.
According to an embodiment of the present invention, a rough processing apparatus includes:
the device comprises a precipitation separation unit and a pH adjusting unit, wherein the precipitation separation unit and the pH adjusting unit are both connected with a dosing device, and the dosing device is used for adding a precipitator for the precipitation separation unit or adding an adjusting agent for the pH adjusting unit.
According to the embodiment of the invention, the adsorption device is connected with the crude treatment device through a peristaltic pump, the crude treatment liquid can be conveyed into the adsorption device through the peristaltic pump, the flow rate of the peristaltic pump is constant between 5 ml/L and 50ml/L, and the total volume is 20 BV to 200 BV columns.
According to an embodiment of the present invention, the heavy metal ion recovery apparatus includes Cr 3+ Ion recovery device and Hg 2+ An ion recovery device.
According to the embodiment of the invention, the fixed bed can comprise a fixed bed group formed by connecting a plurality of fixed beds in series, the fixed bed part adopted in the application is the fixed bed group formed by 3 fixed beds, and the top of the No. 1 fixed bed and the tail part of the No. 3 fixed bed are respectively provided with a liquid adding elution device and a heavy metal ion recovery device.
FIG. 3 is a schematic diagram of the synthesis of an adsorbent according to an embodiment of the present invention.
As shown in fig. 3, according to another aspect of the present invention, there is provided a method of preparing an adsorbent used in the method, comprising:
step A: dissolving sodium humate to obtain a sodium humate solution;
and B: heating the resin-supported nano zirconium dioxide aqueous solution in a water bath, adding a sodium humate solution and ammonia water, and reacting for 5-24h to obtain a product precipitate;
and C: and cooling the product precipitate and cleaning to be neutral to obtain the adsorbent.
The resin-supported humic acid modified nano zirconium dioxide compound is selected as the adsorbent, has excellent physicochemical properties and adsorption performance, has a porous structure in the interior, can greatly increase the adsorption area, is beneficial to the adsorption of heavy metal ions, can be repeatedly utilized for multiple times, and has better economic benefit.
According to the embodiment of the invention, the step A specifically comprises the following steps:
0.1-1.0g of humic acid sodium salt (HA) is weighed into a 100mL glass bottle, 20-80mL of ultrapure water is added, and the glass bottle is placed into a shaking table to shake for 0.5-5 hours so as to be completely dissolved.
According to the embodiment of the present invention, step B specifically includes:
meanwhile, weighing 10-100g of resin-supported nano zirconium dioxide (HZO-201) into a three-neck flask, adding 50-300mL of ultrapure water, heating in a water bath to 40-100 ℃, rapidly adding a sodium humate solution dissolved by shaking and 2-20mL of ammonia water, and continuously keeping the temperature of 50-100 ℃ for reaction for 5-24h under stirring.
According to the embodiment of the invention, in the step B, the mass ratio of the sodium humate to the resin-supported nano zirconium dioxide is 1: 100.
According to the embodiment of the invention, in the step B, the adding ratio of the ammonia water to the sodium humate is as follows: 10ml of ammonia water was added per 1g of humic acid sodium salt.
According to an embodiment of the present invention, the concentration of ammonia water is 22-25%.
According to the embodiment of the invention, the heavy metal wastewater treatment system and the treatment method provided by the invention can be used for other metal ions, such as metal ions of Pb, Cu, Cd and the like.
Physical and chemical properties of the adsorbent are characterized in that:
1. characterization of the sorbent structure:
FIG. 4 is an electron microscope image of the internal structure of the adsorbent according to the embodiment of the present invention.
The structure of the resin-supported humic acid modified nano zirconium dioxide compound (HA-HZO-201) is characterized by an electron microscope, and the result is shown in figure 4.
As shown in FIG. 4, the interior of HA-HZO-201 is of a porous structure, so that the adsorption area can be greatly increased, and the adsorption of heavy metal ions is facilitated.
2. Adsorbent nitrogen adsorption test:
the resin-supported humic acid modified nano zirconium dioxide composite (HA-HZO-201) is subjected to a nitrogen adsorption test, and the physicochemical properties of the resin-supported humic acid modified nano zirconium dioxide composite are characterized by the nitrogen adsorption test, and the results are shown in Table 1.
TABLE 1 characterization of the physicochemical properties of HA-HZO-201.
As can be seen from Table 1, the specific surface area of the resin-supported humic acid modified nano zirconium dioxide composite (HA-HZO-201) prepared by the invention reaches 12.43m 2 Per g, pore volume up to 0.019cm 3 /g。
And Zr loading up to 12.2% and HA content up to 85.9C mg/g can further improve the heavy metal ion adsorption capacity.
3. Characterization of the adsorbent stability:
FIG. 5 is a graph of zirconium ion release ratio versus pH for an adsorbent of an example of the present invention.
Zirconium (Zr) dissolution in the resin-supported humic acid modified nano zirconium dioxide composite (HA-HZO-201) determines the durability and adsorption efficiency, so the release ratio of Zr is used for evaluating the stability of HA-HZO-201.
Since pH is an important factor affecting its stability. Therefore, the stability of HA-HZO-201 in solutions of different pH needs to be determined.
HA-HZO-201 was placed in solutions of different pH and shaken for 48 hours, and the supernatant was taken for quantitative determination of Zr, the results of which are shown in FIG. 5.
According to the results of FIG. 5, HA-HZO-201 hardly releases Zr ions in the solution with pH of 1-9, which proves that it HAs wide pH application range and high stability.
Sorbent performance testing:
1. and (3) testing the elution rate of heavy metal ions:
FIG. 6 shows Cr in accordance with an embodiment of the present invention 3+ And Hg 2+ Histogram of elution rate (c).
By using Cr adsorbed in HA-HZO-201 3+ And Hg 2+ Using 2-10BVHNO 3 (0.02-0.5mol/L) to obtain Cr 3+ . After the elution is finished, using HTU solution (0.1-1.5mol/L) of 2-10BV as eluent to carry out secondary elution to obtain Hg 2+ . Measurement of Cr 3+ And Hg 2+ Elution rates of eluted and recovered fractions, respectively.
As shown in FIG. 6, when HNO was used 3 When used as an eluent, Cr 3+ The elution rate of (2) is as high as 92.1%, and Hg 2+ The elution rate of (A) is only 1.2%, indicating that the step can specifically elute Cr 3+ . Completion of the above Cr 3+ After elution, the HTU is used as an eluent for desorption, and Hg can be completely eluted 2+ The elution rate is as high as 94.4%. Therefore, experiments prove that the method can enable Cr and Hg to be respectively recovered in an ionic state.
2. Testing of reproducibility of the adsorbent:
figure 7 is a bar graph of the removal efficiency of heavy metal ions after multiple cycles of the adsorbent of an embodiment of the present invention.
And (3) putting the eluted and regenerated HA-HZO-201 into the flow of the figure 1 again for recycling, measuring the concentration of heavy metal ions in discharged water, and calculating the removal efficiency.
As a result, Cr was obtained after 5 cycles as shown in FIG. 7 3+ And Hg 2+ The removal efficiency of the HA-HZO-201 is still not obviously reduced and is respectively as high as 86.0 percent and 89.7 percent, which proves the reusability of the HA-HZO-201.
Sorbent cost calculation:
and calculating the treatment cost of the COD test waste liquid according to the current price and the consumption of each article in the process. As a result, as shown in Table 2, the cost per 1 ton of the COD test waste liquid in this method was $ 302. According to literature reports, the cost of precipitation treatment is $ 600/ton (calculated according to the 2002 price). Even if the factor of inflation in the currency is not considered, the method for treating the COD test waste liquid can save nearly half of the cost and has certain economic benefit.
Table 2. treatment cost of the treatment method of heavy metal ions of the present invention.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for treating heavy metal wastewater comprises the following steps:
removing Ag in wastewater by precipitation method using rough treatment device 2+ Adjusting the pH value to obtain a crude treatment solution;
conveying the crude treatment liquid to an adsorption device, adsorbing heavy metal ions in the wastewater by an adsorbent in the adsorption device, and discharging the treatment liquid, wherein the adsorbent is a resin-supported humic acid modified nano zirconium dioxide compound;
eluting the heavy metal ions by adding a first eluent and a second eluent with selectivity into the adsorption device; and recovering the heavy metal ions by a heavy metal ion recovery device.
2. The method of claim 1, the precipitation method comprising:
adding a precipitating agent into the crude treatment device through a dosing device, wherein the final concentration of the precipitating agent reaches 500-8000 mg/L.
3. The method of claim 1, wherein the crude treatment fluid has a pH of 2 to 8.
4. The method of claim 1, the first eluent comprising 0.02-0.5mol/L nitric acid;
the second eluent comprises 0.1-1.5mol/L thiourea solution.
5. A heavy metal wastewater treatment system for implementing the method of any one of claims 1 to 4, comprising:
the coarse treatment device is used for precipitating Ag in the wastewater 2+ And adjusting the pH value of the wastewater to obtain the crude treatment liquid;
the adsorption device comprises a fixed bed containing the adsorbent and a liquid adding elution device;
the fixed bed is used for adsorbing the heavy metal ions in the crude treatment liquid and discharging the treatment liquid;
the liquid adding elution device is used for adding the first eluent and the second eluent into the fixed bed;
the heavy metal ion recovery device is arranged at the downstream of the adsorption device and used for separating and collecting the heavy metal ions.
6. The apparatus of claim 5, the rough processing means comprising:
the device comprises a precipitation separation unit and a pH adjusting unit, wherein the precipitation separation unit and the pH adjusting unit are both connected with a dosing device, and the dosing device is used for adding a precipitator for the precipitation separation unit or adding an adjusting agent for the pH adjusting unit.
7. The apparatus of claim 5, the heavy metal ion recovery device comprising Cr 3+ Ion recovery device and Hg 2+ An ion recovery device.
8. A process for preparing an adsorbent for use in the process of any one of claims 1 to 4, comprising:
dissolving sodium humate to obtain a sodium humate solution;
heating a resin-supported nano zirconium dioxide aqueous solution in a water bath, adding the sodium humate solution and ammonia water, and reacting for 5-24h to obtain a product precipitate;
and cooling the product precipitate and washing to be neutral to obtain the adsorbent.
9. The method of claim 8, wherein the mass ratio of the sodium salt of humic acid to the resin-supported nano zirconium dioxide is 1: 100.
10. The method of claim 8, wherein the ratio of the ammonia water to the sodium humate salt is: 10ml of ammonia water was added per 1g of the humic acid sodium salt.
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