CN115231685A - 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 82
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 38
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 37
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 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 49
- 239000003463 adsorbent Substances 0.000 claims abstract description 45
- 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
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 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 50
- 239000010865 sewage Substances 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 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 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium 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
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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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- 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
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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
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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
- 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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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 nano sodium titanate whisker (Na) 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, then using an oxidative adsorption technique, using only a small amount of Ca (ClO) 2 And a small amount of adsorbent are oxidized and adsorbed to obtain the nickel-containing industrial electroplating wasteNi in water 2+ The concentration is lower than 0.05mg/L, and the urban sewage discharge standard specified by the state is reached.
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 chemistryPrecipitation, electrochemical and adsorption. The chemical precipitation method is to add a certain amount of precipitant, such as NaOH, flocculant, etc., into the nickel-containing industrial electroplating wastewater, and to make the precipitant and Ni in the wastewater at a proper pH value and temperature 2+ Forming insoluble precipitate, and removing Ni by flocculation, sedimentation and filtration 2+ . However, in the actual industrial electroplating wastewater, complex ligands such as hydrocyanic acid radical, citric acid radical, tartaric acid radical and the like and Ni 2+ Firm bonding, and difficult Ni formation by sodium hydroxide or polyferric flocculant 2+ And precipitating. The nickel-containing electroplating wastewater is treated by alkali and flocculant in industry, and Ni is contained in the treated water 2+ The content is about 1-2mg/L and is far higher than national urban sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L and is also higher than the total nickel discharge limit Ni of the wastewater of electroplating enterprises 2+ ≤0.1mg/L。
The electrochemical method is to remove pollutants in the wastewater by electrolyzing, and specifically comprises the steps of respectively carrying out reduction and oxidation reactions on a cathode and an anode, and Ni in the nickel-containing industrial electroplating wastewater 2+ The reduction deposition is carried out on the surface of the cathode, but the cost for electrochemically treating the nickel-containing electroplating wastewater is high, and the method is not adopted by domestic and foreign electroplating wastewater treatment enterprises. The adsorption method is to utilize solid matter with strong adsorption capacity, large specific surface area and good stability, and to rely on active groups (carboxyl, carbonyl, hydroxyl and the like) and Ni existing in the molecular structure of the adsorption material 2+ Form chemical bond or electrostatic adsorption to make Ni 2+ Can be effectively adsorbed on an adsorbent material and then Ni is recovered by desorption 2+ . Adsorption method for treating and recovering Ni in high-concentration electroplating wastewater 2+ And recovering the nickel salt. But Ni in the treated nickel-containing wastewater 2+ The content of the waste water reaches dozens of milligrams per liter, the waste water can not reach the national wastewater discharge standard, and secondary treatment is needed.
The titanate nano whisker has high surface alkalinity and can form strong bonding with metal ions, but the surface alkaline group and metal Ni 2+ The binding capacity of (2) is still insufficient to overcome the combination of hydrocyanic acid, citrate, tartrate, etc. with Ni 2+ By complexation of Ni 2+ . If the oxidation technology is only adopted to oxidize the hydrocyanic acid radical, the citric acid radical and the tartaric acid radical in the nickel-containing electroplating wastewater, the formed oxidation product containing polyhydroxy and polycarboxyl functional groups still has the Ni and the Ni 2+ Bonding ability of Ni not to 2 + A precipitate is generated. Therefore, it is necessary to find a suitable method for removing Ni from the plating wastewater 2+ Removing the waste water to reach 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 nano sodium titanate whisker (Na) 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, then using an oxidative adsorption technique, using only a small amount of Ca (ClO) 2 Ni in the nickel-containing industrial electroplating wastewater after being oxidized and adsorbed with a small amount of adsorbent 2+ The concentration is lower than 0.05mg/L, and the urban sewage discharge standard specified by the state is reached.
The invention provides a method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method, which comprises the following steps:
(1) Preparing a nano sodium titanate whisker adsorbent:
dispersing metatitanic acid in deionized water, adjusting the pH value, then adding a sodium hydroxide aqueous solution, stirring and mixing uniformly, carrying out hydrothermal reaction at 120-175 ℃, filtering, washing and drying after the reaction is finished, thus obtaining a sodium titanate whisker adsorbent;
(2) Removing heavy metal nickel ions in the wastewater by an oxidation/adsorption method:
adding oxidant and sodium titanate whisker adsorbent into nickel-containing wastewater for oxidation adsorption, centrifugally separating after the oxidation adsorption is finished, and measuring Ni in adsorbed liquid by using an inductively coupled plasma emission spectrometer 2+ And (4) concentration.
Further, in the step (1), the molar ratio of the sodium hydroxide to the metatitanic acid is 8.
Further, in the step (1), the pH value is adjusted to 2-3.
Further, in the step (1), the prepared sodium titanate whisker adsorbent is of a layered structure and is rod-shaped, the diameter distribution is 280-950nm, and the average diameter is 530nm; the length distribution was 1.8-17.2 μm, and the average length was 4.93. Mu.m.
Furthermore, in the step (1), the hydrothermal reaction time is 72-96h.
Furthermore, in the step (2), the concentration of nickel in the nickel-containing wastewater ranges from 0.28mg/L to 1.13mg/L.
Furthermore, in the step (2), the dosage ratio of the oxidant to the nickel-containing wastewater is 6.25-50g.
Furthermore, in the step (2), the mass ratio of the oxidant to the sodium titanate whisker adsorbent is 31.25-500.
Further, the oxidant is Ca (ClO) 2 。
Furthermore, in the step (2), the time of oxidation adsorption is 0.3-4 h.
Compared with the prior art, the invention has the beneficial effects that:
at present, the nickel ions are degraded in the industry by adopting a pure oxidation mode of NaClO (effective chlorine content of 10 percent), and 0.2 to 0.4m is added into per cubic meter of electroplating wastewater 3 NaClO still can not meet 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 a small amount of Ca (ClO) is used 2 Ni in the nickel-containing industrial electroplating wastewater after being oxidized and adsorbed with a small amount of adsorbent 2+ The concentration is lower than 0.05mg/L, and reaches the national urban sewage discharge standard. The NaClO price is about 600 yuan/ton, ca (ClO) 2 The price is about 1000 yuan/ton, the cost of preparing 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 prior art, the method has the advantages that 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 the stable nickel-containing complex in the industrial electroplating wastewater 2+ The treatment bottleneck problem of (1) can ensure that the treated nickel-containing industrial electroplating wastewater reaches Ni in town sewage specified by the state 2+ And (4) emission standard. The invention adopts a hydrothermal method to prepare the nano titanium with a layered structureSodium acid whisker (Na) 0.98 H 1.02 Ti 4 O 9 ·9H 2 O) adsorbent, and sodium titanate whisker with average diameter and length distribution of 280-950nm and 1.8-17.2 μm, respectively. The preparation process of the adsorbent is green and environment-friendly, only a small amount of waste alkali liquor is generated, and the adsorbent can be safely discharged after being adjusted to be neutral by using acid. The invention also adopts environment-friendly, safe and high-stability calcium hypochlorite as an oxidant, utilizes the calcium hypochlorite to oxidize hydrocyanic acid radicals, citric acid radicals, tartaric acid radicals and the like in the nickel-containing electroplating wastewater, and weakens the rest Ni 2+ The sodium titanate whisker is added into the solution through Ni 2+ Adsorbed on the surface of the plating solution to make Ni in the electroplating wastewater 2+ Separated from the wastewater.
Drawings
Fig. 1 is an XRD spectrum (a) and an SEM spectrum (b) of the nano sodium titanate whisker adsorbent.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, to which, however, the scope of the invention is not limited.
Example 1: preparation of nano sodium titanate whisker adsorbent
45g of metatitanic acid are dispersed in 100mL of deionized water and the pH of the suspension is adjusted to 2 with concentrated hydrochloric acid with 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 teflon-lined autoclave and reacted at 175 ℃ for 96h. The prepared sodium titanate whisker sample is washed to be neutral by deionized water and then dried for 12 hours at 100 ℃.
FIG. 1 a is an XRD spectrum of the sodium titanate whisker adsorbent, and it can be seen from the graph that the XRD spectrum of the titanate sample shows peaks appearing at 2 theta values of 17.9, 24.8, 26.8, 29.3, 35.02, 37.7, 47.4 and 48.3 degrees corresponding to (4 0-2), (1 1 0), (3 1 0), (8 0-2), (1 3), (10 0-1), (8 0-6) and (0 2 0) crystal planes of Na0.98H1.02Ti4O9.19H2O, respectively, and then Na is present in the crystal planes 0.98 H 1.02 Ti 4 O 9 ·1.9H 2 The PDF standard graphic card (JCPDS 38-0021) of O is consistent, which shows that the nano sodium titanate whisker adsorbent is successfully prepared.
In the figure b is SEM spectrogram of the nano sodium titanate whisker adsorbent, and as can be seen from the figure, the nano sodium titanate whisker has a rod-shaped structure and a layered shape, the diameter and the length distribution of the nano sodium titanate whisker are respectively 280-950nm and 1.8-17.2 mu m, and the average diameter and the length of the nano sodium titanate whisker are respectively 530nm and 4.93 mu m.
Example 2: method for removing heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ Adding 40mg of the nano sodium titanate whisker adsorbent prepared in example 1 and 2.5g of calcium hypochlorite into 400mL of nickel-containing industrial electroplating wastewater with the concentration of 0.51mg/L, adsorbing for 0.3h, 2h and 4h at 25 ℃, respectively, centrifugally separating the adsorbent, and measuring Ni in the adsorbed liquid by using an inductively coupled plasma emission spectrometer 2+ And (4) concentration.
Measured, ni is absorbed by oxidation for 0.3h 2+ Has a concentration of 0.04858mg/L, and Ni is oxidized and adsorbed for 2h 2+ Has a concentration of 0.04801mg/L, and Ni is oxidized and adsorbed for 4 hours 2+ The concentration of (A) is 0.04655mg/L, which shows that the treated nickel-containing industrial electroplating wastewater reaches Ni in town sewage regulated by the state 2+ And (4) emission standard.
Example 3: method for removing heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ Adding 40mg of the nano sodium titanate whisker adsorbent prepared in example 1 and 10g of calcium hypochlorite into 400mL of nickel-containing industrial electroplating wastewater with the concentration of 1.13mg/L, adsorbing for 0.3h, 2h and 4h at 25 ℃, respectively, centrifugally separating the adsorbent, and measuring Ni in the adsorbed liquid by using an inductively coupled plasma emission spectrometer 2+ And (4) concentration.
Measured, ni is absorbed after 0.3h by oxidation 2+ Has a concentration of 0.04437mg/L, and Ni is oxidized and adsorbed for 2h 2+ Has a concentration of 0.04102mg/L, ni after 4h of oxidation adsorption 2+ The concentration of (A) is 0.04032mg/L, which shows that the treated nickel-containing industrial electroplating wastewater reaches Ni in town sewage regulated by the state 2+ And (4) emission standard.
Example 4: method for removing heavy metal nickel ions in nickel electroplating wastewater by oxidation/adsorption method
To Ni 2+ 400mL nickel-containing industrial electricity with concentration of 1.13mg/L40mg of the sodium titanate whisker adsorbent prepared in example 1 and 20g of calcium hypochlorite were added to the plating wastewater, and the adsorbent was adsorbed at 25 ℃ for 0.3h, 2h and 4h, respectively, and after centrifugal separation, ni in the adsorbed liquid was measured by inductively coupled plasma emission spectrometer 2+ And (4) concentration.
Measured, ni is absorbed by oxidation for 0.3h 2+ Has a concentration of 0.04037mg/L, ni after 2h of oxidative adsorption 2+ Has a concentration of 0.03645mg/L, and Ni is oxidized and adsorbed for 4 hours 2+ The concentration of (A) is 0.03521mg/L, which shows that the treated nickel-containing industrial electroplating wastewater reaches Ni in town sewage regulated by the state 2+ And (4) emission standard.
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 of the addition of different amounts of calcium hypochlorite and nano sodium titanate whisker adsorbents on the ability of removing heavy metal nickel ions in nickel electroplating wastewater by oxidative adsorption was examined.
(1) The calcium hypochlorite with different contents has the influence on the capability of removing heavy metal nickel ions in the nickel electroplating wastewater through oxidation and adsorption:
the method for removing the heavy metal nickel ions in the nickel electroplating wastewater by the oxidation/adsorption method is shown in example 2, and only changes are made as follows: the added calcium hypochlorite is 0g, 2.5g, 5g and 10g respectively, and the initial concentration of Ni in the nickel-containing industrial electroplating wastewater is 0.28mg/L.
Adsorbing at 25 deg.C for 0.3h, 2h, 4h, centrifuging to separate adsorbent, and measuring Ni in the adsorbed liquid with inductively coupled plasma emission spectrometer 2+ Concentration, measured Ni 2+ The concentrations are shown in Table 1.
TABLE 1 concentration of heavy metal nickel ions in the nickel-electroplating wastewater after oxidative adsorption under different contents of calcium hypochlorite
Table 1 shows the concentrations of heavy metal nickel ions in the nickel electroplating wastewater after oxidative adsorption under different contents of calcium hypochloriteOnly adding an adsorbent and Ni in the electroplating wastewater 2+ The concentration is basically unchanged, the calcium hypochlorite oxidant and the nano sodium titanate adsorbent are added to carry out oxidation adsorption on the electroplating nickel-containing wastewater, and when the addition amount of the calcium hypochlorite is 2.5g, the post-Ni in the electroplating wastewater 2+ The concentration of the Ni reaches the national regulation town sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L, ni along with the increase of the addition of the oxidant 2+ The concentration becomes lower and lower.
(2) The influence of the nano sodium titanate whisker adsorbents with different contents on the capability of removing heavy metal nickel ions in the nickel electroplating wastewater by oxidation adsorption is as follows:
the method for removing heavy metal nickel ions in the nickel electroplating wastewater by the oxidation/adsorption method is shown in example 2, and only changes are made as follows: the added calcium hypochlorite is 5g respectively, the added amount of the nano sodium titanate whisker adsorbent prepared in example 1 is 40mg, 60mg and 80mg respectively, and the initial concentration of Ni in the nickel-containing industrial electroplating wastewater is 0.51mg/L.
Adsorbing at 25 deg.C for 0.3h, 2h, 4h, centrifuging to separate adsorbent, and measuring Ni in the adsorbed liquid with inductively coupled plasma emission spectrometer 2+ Concentration, measured Ni 2+ The concentrations are shown in Table 2.
TABLE 2 concentration of heavy metal nickel ion in the nickel electroplating wastewater after oxidation adsorption under different content of nano sodium titanate whisker adsorbent
Table 2 shows the concentration of heavy metal nickel ions in the nickel electroplating wastewater after oxidation and adsorption under the condition of different contents of nano sodium titanate whisker adsorbents, and it can be seen from the table that under the condition that the amount of 5g of calcium hypochlorite is added and the amount of the calcium hypochlorite is not changed, the nano sodium titanate adsorbents are added simultaneously, and along with the increase of the amount of the adsorbents, ni in the nickel electroplating wastewater 2+ The concentration is also getting smaller and all reach the national urban sewage discharge standard Ni 2+ ≤0.05mg/L。
(3) The calcium hypochlorite with different contents has the influence on the capability of removing the heavy metal nickel ions in the electroplating wastewater containing high-concentration nickel through oxidation and adsorption:
the method for removing heavy metal nickel ions in the nickel electroplating wastewater by an oxidation/adsorption method is shown in example 3 and example 4:
adsorbing at 25 deg.C for 0.3h, 2h, 4h, centrifuging to separate adsorbent, and measuring Ni in the adsorbed liquid with inductively coupled plasma emission spectrometer 2+ Concentration, measured Ni 2+ The concentrations are shown in Table 3.
TABLE 3 concentration of heavy metal nickel ion in electroplating wastewater containing high concentration nickel by oxidation adsorption with different content of calcium hypochlorite
Table 3 shows that the concentration of nickel ions in electroplating wastewater containing high concentration nickel removed by oxidation adsorption with calcium hypochlorite of different contents increases the amount of the oxidizing agent in the electroplating wastewater containing high concentration nickel, and Ni in the electroplating wastewater 2+ The concentration is reduced and reaches the national urban sewage discharge standard Ni 2+ ≤0.05mg/L。
In conclusion, when the calcium hypochlorite oxidant and the nano titanate adsorbent are added simultaneously, ni is added along with the increase of the oxidant amount and the adsorbent amount 2+ The concentration is lower and reaches the national urban sewage discharge standard Ni 2+ Less than or equal to 0.05mg/L, and the oxidant and the adsorbent are both indispensable and play an important role in the oxidation adsorption process of removing nickel ions.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method for removing heavy metal nickel ions in wastewater by an oxidation/adsorption method is characterized by comprising the following steps:
(1) Preparing a nano sodium titanate whisker adsorbent:
dispersing metatitanic acid in deionized water, adjusting the pH value, then adding a sodium hydroxide aqueous solution, stirring and mixing uniformly, carrying out hydrothermal reaction at 120-175 ℃, and after the reaction is finished, filtering, washing and drying to obtain a sodium titanate whisker adsorbent;
(2) Removing heavy metal nickel ions in the wastewater by an oxidation/adsorption method:
adding oxidant and sodium titanate whisker adsorbent into nickel-containing wastewater for oxidation adsorption, centrifugally separating after the oxidation adsorption is finished, and measuring Ni in adsorbed liquid by using an inductively coupled plasma emission spectrometer 2+ And (4) concentration.
2. The oxidation/adsorption method for removing heavy metal nickel ions in wastewater according to claim 1, wherein in the step (1), the molar ratio of sodium hydroxide to metatitanic acid is 8.
3. The oxidation/adsorption method for removing nickel ions as a heavy metal in wastewater according to claim 1, wherein the pH value is adjusted to 2-3 in step (1).
4. The oxidation/adsorption method for removing heavy metal nickel ions in wastewater according to claim 1, wherein in the step (1), the prepared sodium titanate whisker adsorbent has a layered structure and 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. Mu.m.
5. The oxidation/adsorption method for removing nickel ions as a heavy metal in wastewater according to claim 1, wherein in the step (1), the hydrothermal reaction time is 72-96h.
6. The oxidation/adsorption method for removing nickel ions as a heavy metal in wastewater according to claim 1, wherein in the step (2), the concentration of nickel in the nickel-containing wastewater is in the range of 0.28 to 1.13mg/L.
7. The oxidation/adsorption method for removing heavy metal nickel ions in wastewater according to claim 1, wherein in the step (2), the dosage ratio of the oxidant to the wastewater containing nickel is 6.25-50g.
8. The oxidation/adsorption method for removing nickel ions as a heavy metal in wastewater according to claim 1, wherein in the step (2), the mass ratio of the oxidizing agent to the sodium titanate whisker adsorbent is 31.25-500.
9. The oxidation/adsorption method for removing nickel ions as a heavy metal from wastewater according to claim 1, wherein the oxidant is Ca (ClO) 2 。
10. The oxidation/adsorption method for removing nickel ions as a heavy metal in wastewater according to claim 1, wherein in the step (2), the oxidation and adsorption time is 0.3-4 h.
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