CN115231685B - Method for removing heavy metal nickel ions in wastewater by oxidation/adsorption method - Google Patents
Method for removing heavy metal nickel ions in wastewater by oxidation/adsorption method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 78
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 36
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 34
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 159
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 239000003463 adsorbent Substances 0.000 claims abstract description 42
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 abstract description 52
- 239000010865 sewage Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 17
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000010841 municipal wastewater Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method, belonging to the technical field of electroplating wastewater heavy metal ion removal; in the invention, firstly, a hydrothermal method is adopted to prepare the nano sodium titanate whisker (Na 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, then using oxidation adsorption technique, using only small amount of Ca (ClO) 2 And a small amount of adsorbent, and the nickel-containing industrial electroplating wastewater is subjected to oxidation adsorption treatment to obtain Ni 2+ The concentration is lower than 0.05mg/L, and reaches the national urban sewage discharge standard.
Description
Technical Field
The invention belongs to the technical field of heavy metal ion removal, and particularly relates to a method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method.
Background
The existing method for removing heavy metal ions in electroplating wastewater mainly comprises a chemical precipitation method, an electrochemical method and an adsorption method. The chemical precipitation method is to add a certain amount of precipitant such as NaOH, flocculant, etc. into industrial electroplating wastewater containing nickel, and make the precipitant and Ni in the wastewater under proper pH value and temperature 2+ Forming insoluble precipitate, and removing Ni by flocculation, sedimentation, filtration, etc 2+ . However, in the actual industrial electroplating wastewater, due to complex ligands such as hydrocyanic acid radical, citric acid radical, tartaric acid radical and the like and Ni 2+ The combination is firm, and the sodium hydroxide or the ferric flocculant and the like are difficult to lead Ni to be difficult 2+ And settling. Industrial treatment of nickel-containing electroplating wastewater by alkali and flocculant, and Ni in treated water 2+ The content is about 1-2mg/L, which is far higher than the national municipal sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L and is higher than the total nickel discharge limit value Ni of the electroplating enterprise wastewater 2+ ≤0.1mg/L。
The electrochemical method is to electrolyze the pollutant in the waste water to remove, and the electrochemical method comprises the steps of respectively carrying out reduction and oxidation reactions on a cathode and an anode, and containing Ni in industrial electroplating waste water containing nickel 2+ The reduction deposition is carried out on the surface of the cathode, but the cost of electrochemical treatment of nickel-containing electroplating wastewater is high, and domestic and foreign electroplating wastewater treatment enterprises do not adopt the method. The adsorption method uses solid matter with strong adsorption capacity, large specific surface area and good stability, and uses active groups (carboxyl, carbonyl, hydroxyl, etc.) and Ni existing in the molecular structure of adsorption material 2+ Forming chemical bond or electrostatic adsorption to make Ni 2+ Can be effectively adsorbed on the adsorbent material, and then the Ni is recovered by desorption 2+ . Ni in high-concentration electroplating wastewater can be treated and recycled by adsorption method 2+ And recovering the nickel salt. But Ni in the treated nickel-containing wastewater 2+ The content is up to tens of milligrams per liter, and the wastewater discharge standard specified by the state is not met, and secondary treatment is needed.
Titanate nanowhiskers have high surface basicity and can form strong bonding with metal ions, but the surface basicity groups of the titanate nanowhiskers are bonded with metal Ni 2+ Is still insufficient to overcome the binding capacity of hydrogen cyanide, citrate, tartrate and the like with Ni 2+ Is complex and abstracts Ni 2+ . If the oxidation technology is only adopted to oxidize the hydrogen cyanide, the citrate and the tartrate in the nickel-containing electroplating wastewater, the formed oxidation product containing polyhydroxy and multi-carboxyl functional groups still has the same properties as Ni 2+ Is unable to make Ni 2 + A precipitate was generated. Therefore, there is a need to find a suitable method for removing Ni from electroplating wastewater 2+ Removing the waste water and reaching the national urban sewage discharge standard.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method. In the invention, firstly, a hydrothermal method is adopted to prepare the nano sodium titanate whisker (Na 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, then useOxidation adsorption technology using only small amounts of Ca (ClO) 2 And a small amount of adsorbent, and the nickel-containing industrial electroplating wastewater is subjected to oxidation adsorption treatment to obtain Ni 2+ The concentration is lower than 0.05mg/L, and reaches the national urban sewage discharge standard.
The invention provides a method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method, which specifically comprises the following steps:
(1) Preparation of nano sodium titanate whisker adsorbent:
dispersing meta-titanic acid in deionized water, regulating the pH value, adding sodium hydroxide aqueous solution, stirring and mixing uniformly, performing hydrothermal reaction at 120-175 ℃, filtering, washing and drying after the reaction is finished to obtain sodium titanate whisker adsorbent;
(2) Removing heavy metal nickel ions in wastewater by an oxidation/adsorption method:
adding an oxidant and a sodium titanate whisker adsorbent into nickel-containing wastewater, performing oxidation adsorption, performing centrifugal separation after the oxidation adsorption is finished, and measuring Ni in the adsorption liquid by using an inductively coupled plasma emission spectrometer 2+ Concentration.
Further, in the step (1), the molar ratio of the sodium hydroxide to the metatitanic acid is 8:1-6:1.
Further, in the step (1), the pH value is adjusted to 2-3.
Further, in the step (1), the prepared sodium titanate whisker adsorbent has a layered structure and is in a rod shape, the diameter distribution is 280-950nm, and the average diameter is 530nm; the length distribution is 1.8-17.2 μm and the average length is 4.93 μm.
Further, in the step (1), the hydrothermal reaction time is 72-96 hours.
Further, in the step (2), the concentration range of nickel in the nickel-containing wastewater is 0.28-1.13 mg/L.
Further, in the step (2), the dosage ratio of the oxidant to the nickel-containing wastewater is 6.25-50 g/1L.
Further, in the step (2), the mass ratio of the oxidant to the sodium titanate whisker adsorbent is 31.25-500:1.
Further, the oxidant is Ca (ClO) 2 。
Further, in the step (2), the time of the oxidation adsorption is 0.3 to 4 hours.
Compared with the prior art, the invention has the beneficial effects that:
at present, the pure oxidation mode of NaClO (effective chlorine content 10%) is adopted to degrade nickel ions in industry, and 0.2-0.4m of NaClO is added into each cubic meter of electroplating wastewater 3 NaClO still does not reach the national urban sewage discharge standard (Ni 2+ Less than or equal to 0.05 mg/L). The patent adopts the oxidation adsorption technology for the first time, and only uses a small amount of Ca (ClO) 2 And a small amount of adsorbent, and the nickel-containing industrial electroplating wastewater is subjected to oxidation adsorption treatment to obtain Ni 2+ The concentration is lower than 0.05mg/L, and reaches the national urban sewage discharge standard. NaClO has a price of about 600 yuan/ton, ca (ClO) 2 The price is about 1000 yuan/ton, the preparation cost of titanate crystal is about 5000 yuan/ton, and a large amount of NaClO is added in industry to degrade heavy metal Ni 2+ Compared with the method, the cost is reduced, and the requirement of removing nickel metal ions in the electroplating wastewater is met.
The invention effectively solves the problem of removing Ni in stable nickel-containing complex in industrial electroplating wastewater 2+ The bottleneck problem of the treatment of nickel-containing industrial electroplating wastewater after treatment reaches the national municipal wastewater Ni 2+ Emission standards. The invention prepares the layered nano sodium titanate whisker (Na) by adopting a hydrothermal method 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, average diameter and length distribution of sodium titanate whisker are 280-950nm and 1.8-17.2 μm respectively. The preparation process of the adsorbent is environment-friendly, only generates a small amount of waste alkali liquor, and can be safely discharged after being regulated to be neutral by acid. The invention also adopts the calcium hypochlorite with environmental protection and high safety and stability as the oxidant, and utilizes the calcium hypochlorite to oxidize the hydrocyanic acid radical, the citric acid radical, the tartaric acid radical and the like in the nickel-containing electroplating wastewater to weaken the rest Ni 2+ At the same time, sodium titanate whisker is added, and Ni is used for the complexing ability 2+ Adsorbing on the surface of the alloy to enable Ni in electroplating wastewater 2+ Separated from the wastewater.
Drawings
Fig. 1 shows XRD spectrum (a) and SEM spectrum (b) of nano sodium titanate whisker adsorbent.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1: preparation of nano sodium titanate whisker adsorbent
45g of meta-titanic acid was dispersed in 100mL of deionized water and the pH of the suspension was adjusted to 2 with concentrated hydrochloric acid under stirring. Then, 100mL of an aqueous solution of sodium hydroxide (15 mol/L) was added to the above suspension, and stirred at room temperature for 2 hours. The suspension was added to a polytetrafluoroethylene-lined autoclave and reacted at 175℃for 96 hours. The prepared sodium titanate whisker sample was washed to neutrality with deionized water and then dried at 100 ℃ for 12h.
As can be seen from the XRD spectrum of the nano sodium titanate whisker adsorbent shown in FIG. 1, the XRD spectrum of the titanate sample shows peaks appearing at the 2 theta values of 17.9, 24.8, 26.8, 29.3, 35.02, 37.7, 47.4 and 48.3 degrees, corresponding to the (4 0-2), (1 1 0), (3 1 0), (8 0-2), (1 1 3), (10 0-1), (8 0-6) and (0 2 0) crystal planes of Na0.98H1.02Ti4O9. 1.9H2O, respectively, na 0.98 H 1.02 Ti 4 O 9 ·1.9H 2 The PDF standard chart card (JCPDS 38-0021) of O is consistent, which shows that we successfully prepare the nano sodium titanate whisker adsorbent.
In the graph, b is an SEM spectrogram of the nano sodium titanate whisker adsorbent, and the nano sodium titanate whisker adsorbent is in a rod-shaped structure and a lamellar form, wherein the diameter and length distribution of the nano sodium titanate whisker is 280-950nm and 1.8-17.2 mu m respectively, and the average diameter and length are 530nm and 4.93 mu m respectively.
Example 2: removal of heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ 400mL of industrial electroplating wastewater containing nickel with the concentration of 0.51mg/L is added with 40mg of nano sodium titanate whisker adsorbent prepared in example 1 and 2.5g of calcium hypochlorite, the adsorbent is respectively adsorbed for 0.3h, 2h and 4h at 25 ℃, after centrifugal separation, the Ni in the adsorbed liquid is measured by an inductively coupled plasma emission spectrometer 2+ Concentration.
By measurement of oxygenNi after 0.3h of chemical adsorption 2+ The concentration of (C) is 0.04858mg/L, and Ni is oxidized and adsorbed for 2 hours 2+ The concentration of (C) is 0.04801mg/L, and Ni is oxidized and adsorbed for 4 hours 2+ The concentration of (C) is 0.04655mg/L, which indicates that the treated nickel-containing industrial electroplating wastewater reaches the Ni in the national municipal wastewater 2+ Emission standards.
Example 3: removal of heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ 400mL of industrial electroplating wastewater containing nickel with the concentration of 1.13mg/L is added with 40mg of nano sodium titanate whisker adsorbent prepared in example 1 and 10g of calcium hypochlorite, and the adsorbent is respectively adsorbed for 0.3h, 2h and 4h at 25 ℃, and after centrifugal separation, the Ni in the adsorbed liquid is measured by an inductively coupled plasma emission spectrometer 2+ Concentration.
After 0.3h of oxidation adsorption, ni is measured 2+ The concentration of (C) is 0.04437mg/L, and Ni is oxidized and adsorbed for 2 hours 2+ The concentration of (C) is 0.04102mg/L, and Ni is oxidized and adsorbed for 4 hours 2+ The concentration of (C) is 0.04032mg/L, which indicates that the treated nickel-containing industrial electroplating wastewater reaches the Ni in the national municipal wastewater 2+ Emission standards.
Example 4: removal of heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ 400mL of industrial electroplating wastewater containing nickel with the concentration of 1.13mg/L is added with 40mg of nano sodium titanate whisker adsorbent prepared in example 1 and 20g of calcium hypochlorite, and the adsorbent is respectively adsorbed for 0.3h, 2h and 4h at 25 ℃, and after centrifugal separation, the Ni in the adsorbed liquid is measured by an inductively coupled plasma emission spectrometer 2+ Concentration.
After 0.3h of oxidation adsorption, ni is measured 2+ The concentration of (C) is 0.04037mg/L, and Ni is oxidized and adsorbed for 2 hours 2+ The concentration of (C) is 0.03645mg/L, and Ni is oxidized and adsorbed for 4 hours 2+ The concentration of (C) is 0.03521mg/L, which indicates that the treated nickel-containing industrial electroplating wastewater reaches the Ni in the national municipal wastewater 2+ Emission standards.
Example 5: performance investigation of removal of heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method under different conditions
In this example, the influence on the capacity of oxidizing and adsorbing to remove heavy metal nickel ions in the nickel electroplating wastewater under the condition of adding calcium hypochlorite and nano sodium titanate whisker adsorbents with different contents is discussed respectively.
(1) Effect of different contents of calcium hypochlorite on the ability of oxidizing adsorption to remove heavy metal nickel ions in nickel electroplating wastewater:
the method for removing heavy metal nickel ions in the nickel electroplating wastewater by the oxidation/adsorption method is as shown in example 2, with the following modifications: the added calcium hypochlorite is 0g, 2.5g, 5g and 10g respectively, and the initial concentration of Ni in the industrial electroplating wastewater containing nickel is 0.28mg/L.
Adsorbing at 25deg.C for 0.3h, 2h, and 4h respectively, centrifuging, and measuring Ni in the adsorbed liquid by inductively coupled plasma emission spectrometer 2+ Concentration of Ni measured 2+ The concentrations are shown in Table 1.
TABLE 1 concentration of heavy Metal Nickel ions in Nickel electroplating wastewater after Oxidation adsorption at calcium hypochlorite of different contents
Table 1 shows the concentration of heavy metal nickel ions in the electroplating wastewater after oxidation adsorption under different calcium hypochlorite contents, and it can be seen from the table that only the adsorbent is added, and Ni in the electroplating wastewater 2+ The concentration is basically unchanged, and the calcium hypochlorite oxidant and the nano sodium titanate adsorbent are added to oxidize and adsorb the nickel-containing electroplating wastewater, when the calcium hypochlorite addition amount is 2.5g, the nickel is added to the electroplating wastewater 2+ The concentration reaches the national urban sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L, ni is added along with the increase of the addition amount of the oxidant 2+ The concentration is lower and lower.
(2) Influence of nano sodium titanate whisker adsorbents with different contents on capacity of oxidizing and adsorbing to remove heavy metal nickel ions in nickel electroplating wastewater:
the method for removing heavy metal nickel ions in the nickel electroplating wastewater by the oxidation/adsorption method is as shown in example 2, with the following modifications: the added calcium hypochlorite was 5g, and the added amounts of the nano sodium titanate whisker adsorbents prepared in example 1 were 40mg, 60mg and 80mg, respectively, and the initial concentration of Ni in the nickel-containing industrial electroplating wastewater was 0.51mg/L.
Adsorbing at 25deg.C for 0.3h, 2h, and 4h respectively, centrifuging, and measuring Ni in the adsorbed liquid by inductively coupled plasma emission spectrometer 2+ Concentration of Ni measured 2+ The concentrations are shown in table 2.
TABLE 2 concentration of heavy Metal Nickel ions in Nickel electroplating wastewater after Oxidation adsorption with Nano sodium titanate whisker adsorbents of different contents
Table 2 shows the concentration of heavy metal nickel ions in the electroplating wastewater after oxidation adsorption by the nano sodium titanate whisker adsorbents with different contents, and it can be seen from the table that the nano sodium titanate adsorbent is simultaneously added under the condition that the amount of the calcium hypochlorite oxidant added is unchanged by 5g, and the Ni in the electroplating wastewater is increased along with the increase of the adsorbent amount 2+ The concentration is also smaller and smaller, and the concentration reaches the national urban sewage discharge standard Ni 2+ ≤0.05mg/L。
(3) Effect of different contents of calcium hypochlorite on the capacity of removing heavy metal nickel ions in high-concentration nickel-containing electroplating wastewater by oxidation adsorption:
the method for removing heavy metal nickel ions in the nickel electroplating wastewater by the oxidation/adsorption method is as shown in example 3 and example 4:
adsorbing at 25deg.C for 0.3h, 2h, and 4h respectively, centrifuging, and measuring Ni in the adsorbed liquid by inductively coupled plasma emission spectrometer 2+ Concentration of Ni measured 2+ The concentrations are shown in Table 3.
TABLE 3 removal of heavy Metal Nickel ion concentration from high concentration Nickel-containing electroplating wastewater by calcium hypochlorite adsorption with different content
Table 3 shows the contents of hypochlorous acidAs can be seen from the table, the concentration of heavy metal nickel ions in the electroplating wastewater containing high concentration nickel is removed by the calcium carbonate through oxidation adsorption, the amount of the oxidant in the electroplating wastewater containing higher concentration nickel is increased, and Ni in the electroplating wastewater 2+ The concentration is smaller and smaller, and reaches the national urban sewage discharge standard Ni 2+ ≤0.05mg/L。
In conclusion, the calcium hypochlorite oxidant and the nano titanate adsorbent are added simultaneously, and Ni is added along with the increase of the oxidant amount and the adsorbent amount 2+ The concentration is lower and lower, and reaches the national urban sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L, both the oxidant and the adsorbent are indispensible, and play an important role in the oxidation adsorption process for removing nickel ions.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (7)
1. A method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method, which is characterized by comprising the following steps:
(1) Preparation of nano sodium titanate whisker adsorbent:
dispersing meta-titanic acid in deionized water, regulating the pH value, adding sodium hydroxide aqueous solution, stirring and mixing uniformly, performing hydrothermal reaction at 120-175 ℃, filtering, washing and drying after the reaction is finished to obtain a sodium titanate whisker adsorbent;
the prepared sodium titanate whisker adsorbent has a layered structure and is in a rod shape, the diameter distribution is 280-950nm, and the average diameter is 530nm; the length distribution is 1.8-17.2 μm, and the average length is 4.93 μm;
(2) Removing heavy metal nickel ions in wastewater by an oxidation/adsorption method:
adding an oxidant and a sodium titanate whisker adsorbent into nickel-containing wastewater, performing oxidation adsorption, performing centrifugal separation after the oxidation adsorption is finished, and measuring Ni in the adsorption liquid by using an inductively coupled plasma emission spectrometer 2+ Concentration;
in the step (2), the mass ratio of the oxidant to the sodium titanate whisker adsorbent is 31.25-500:1, and the oxidant is Ca (ClO) 2 。
2. The method for removing heavy metal nickel ions from wastewater by oxidation/adsorption according to claim 1, wherein in the step (1), the molar ratio of sodium hydroxide to metatitanic acid is 8:1-6:1.
3. The method for removing heavy metal nickel ions from wastewater by oxidation/adsorption according to claim 1, wherein in step (1), the pH is adjusted to 2-3.
4. The method for removing heavy metal nickel ions from wastewater by oxidation/adsorption according to claim 1, wherein in the step (1), the hydrothermal reaction time is 72-96 hours.
5. The method for removing heavy metal nickel ions from wastewater by an oxidation/adsorption method according to claim 1, wherein in the step (2), the nickel-containing wastewater has a nickel-containing concentration ranging from 0.28 to 1.13mg/L.
6. The method for removing heavy metal nickel ions from wastewater by an oxidation/adsorption method according to claim 1, wherein in the step (2), the dosage ratio of the oxidizing agent to the nickel-containing wastewater is 6.25-50 g/1L.
7. The method for removing heavy metal nickel ions from wastewater by using an oxidation/adsorption method according to claim 1, wherein in the step (2), the time of oxidation and adsorption is 0.3-4 hours.
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