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
- Publication number
- CN114804413A CN114804413A CN202210396901.1A CN202210396901A CN114804413A CN 114804413 A CN114804413 A CN 114804413A CN 202210396901 A CN202210396901 A CN 202210396901A CN 114804413 A CN114804413 A CN 114804413A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- adsorbent
- wastewater
- eluent
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 65
- 239000003463 adsorbent Substances 0.000 title claims abstract description 43
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000001179 sorption measurement Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000003480 eluent Substances 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 32
- 238000011084 recovery Methods 0.000 claims abstract description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004021 humic acid Substances 0.000 claims abstract description 17
- -1 zirconium dioxide compound Chemical class 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 23
- 238000010828 elution Methods 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- HMGUIQPKFUZDPV-UHFFFAOYSA-L disodium;bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C2C=CC1C(C(=O)[O-])C2C([O-])=O HMGUIQPKFUZDPV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 15
- 239000002699 waste material Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210396901.1A CN114804413A (en) | 2022-04-15 | 2022-04-15 | Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210396901.1A CN114804413A (en) | 2022-04-15 | 2022-04-15 | Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114804413A true CN114804413A (en) | 2022-07-29 |
Family
ID=82537306
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210396901.1A Pending CN114804413A (en) | 2022-04-15 | 2022-04-15 | Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114804413A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5630785A (en) * | 1995-03-15 | 1997-05-20 | Hydromex Inc. | Process for the treatment of waste products |
CN103467645A (en) * | 2013-08-30 | 2013-12-25 | 南京大学 | Organic pollution resistance ion exchange resin, and preparation method and application of resin |
CN106944005A (en) * | 2017-04-27 | 2017-07-14 | 南京大学 | A kind of depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application |
CN108218038A (en) * | 2018-01-31 | 2018-06-29 | 南京大学 | A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water |
US20190287691A1 (en) * | 2016-09-29 | 2019-09-19 | The Regents Of The University Of California | Separation of metal ions by liquid-liquid extraction |
CN112897743A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Gradient adsorption and recovery method for heavy metals in wastewater based on magnetic titanium-containing mineral/humic acid composite adsorption material |
-
2022
- 2022-04-15 CN CN202210396901.1A patent/CN114804413A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5630785A (en) * | 1995-03-15 | 1997-05-20 | Hydromex Inc. | Process for the treatment of waste products |
CN103467645A (en) * | 2013-08-30 | 2013-12-25 | 南京大学 | Organic pollution resistance ion exchange resin, and preparation method and application of resin |
US20190287691A1 (en) * | 2016-09-29 | 2019-09-19 | The Regents Of The University Of California | Separation of metal ions by liquid-liquid extraction |
CN106944005A (en) * | 2017-04-27 | 2017-07-14 | 南京大学 | A kind of depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application |
CN108218038A (en) * | 2018-01-31 | 2018-06-29 | 南京大学 | A kind of method of resin adsorption desorption-diffusion dialysis processing heavy metal-containing waste water |
CN112897743A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Gradient adsorption and recovery method for heavy metals in wastewater based on magnetic titanium-containing mineral/humic acid composite adsorption material |
Non-Patent Citations (1)
Title |
---|
郝立腾: "负载型纳米材料的重金属吸附功能强化修饰及其在水处理过程中释放研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Xu et al. | PAN/PVDF chelating membrane for simultaneous removal of heavy metal and organic pollutants from mimic industrial wastewater | |
Shao et al. | Recovery of nickel from aqueous solutions by complexation-ultrafiltration process with sodium polyacrylate and polyethylenimine | |
JP3883491B2 (en) | Method for producing lithium concentrate from aqueous solution containing lithium | |
TWI594950B (en) | A process, method and plant for recovering scandium | |
RU2674272C2 (en) | Method of extracting gold | |
JPH0222123A (en) | Fractionation of rare earth metal mixture by ion exchange | |
CN113941318A (en) | Preparation method and application of MOF-polymer adsorption material | |
CN111019147A (en) | Metal organic framework adsorbent, one-step preparation method and application thereof | |
US5601722A (en) | Method for the preparation of an ion exchanger for cesium ions and method for the regeneration thereof | |
WO2021169483A1 (en) | Device and method for removing heavy metal ions in photovoltaic waste liquid | |
Ting-Chia et al. | Selective separation of nickel and copper from a complexing solution by a cation-exchange membrane | |
CN114804413A (en) | Heavy metal wastewater treatment method, treatment system and preparation method of adsorbent thereof | |
CN113088699B (en) | Method for gold adsorption reduction recovery and strong acid recycling in waste circuit board pickle liquor | |
WO2023097923A1 (en) | Low-cost reducing agent for selective precipitation of noble metal ions | |
CN115927852A (en) | Method for recovering gold, silver and copper from sulfur concentrate calcine washing waste liquid | |
CN113105647B (en) | Application of Cu-MOF | |
JP4169640B2 (en) | Method for recovering precious metals in solution | |
Ricoux et al. | A selective dynamic sorption-filtration process for separation of Pd (II) ions using an aminophosphine oxide polymer | |
CN110643818B (en) | Method for recovering nickel from electroplating wastewater | |
AU2008283739B2 (en) | Enrichment process for a PGM-metals containing stream | |
Hubicki et al. | Studies of the selective removal of microquantities of platinum (IV) ions from model chloride solutions onto ion exchangers containing functional tertiary amine and polyamine groups | |
CN110578063B (en) | Method for separating and extracting palladium by using polystyrene-benzoxazole thioether resin | |
JPS6153117A (en) | Recovery of noble metal element | |
JP2006526491A (en) | Extraction method of resin and non-ferrous metal | |
CN113702572A (en) | Experimental method for treating uranium-bearing mine water by using iron-carrying charcoal |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220729 |
|
RJ01 | Rejection of invention patent application after publication |