CN112694213A - Method for removing metal ions in wastewater - Google Patents
Method for removing metal ions in wastewater Download PDFInfo
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- CN112694213A CN112694213A CN202110039001.7A CN202110039001A CN112694213A CN 112694213 A CN112694213 A CN 112694213A CN 202110039001 A CN202110039001 A CN 202110039001A CN 112694213 A CN112694213 A CN 112694213A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 100
- 238000001179 sorption measurement Methods 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims description 150
- 238000003795 desorption Methods 0.000 claims description 56
- 239000002019 doping agent Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 239000004327 boric acid Substances 0.000 claims description 23
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000007710 freezing Methods 0.000 claims description 18
- 230000008014 freezing Effects 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 10
- 229960002089 ferrous chloride Drugs 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- 229940072056 alginate Drugs 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 239000003463 adsorbent Substances 0.000 description 26
- 239000011259 mixed solution Substances 0.000 description 26
- 235000010338 boric acid Nutrition 0.000 description 21
- 229960001484 edetic acid Drugs 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- 238000003760 magnetic stirring Methods 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000011324 bead Substances 0.000 description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 10
- 239000000661 sodium alginate Substances 0.000 description 10
- 235000010413 sodium alginate Nutrition 0.000 description 10
- 229940005550 sodium alginate Drugs 0.000 description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000000728 ammonium alginate Substances 0.000 description 6
- 235000010407 ammonium alginate Nutrition 0.000 description 6
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- FBBUUPWITNHCTH-UHFFFAOYSA-M [Cl-].[Ca+2].OB(O)[O-] Chemical compound [Cl-].[Ca+2].OB(O)[O-] FBBUUPWITNHCTH-UHFFFAOYSA-M 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 4
- 235000019691 monocalcium phosphate Nutrition 0.000 description 4
- 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 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZTDUXQYGFKBQBH-UHFFFAOYSA-L calcium boric acid hydrogen phosphate Chemical compound P(=O)([O-])([O-])O.B(O)(O)O.[Ca+2] ZTDUXQYGFKBQBH-UHFFFAOYSA-L 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- OACTUMJBTUXLRY-UHFFFAOYSA-M dicalcium borate chloride Chemical compound [Cl-].[Ca++].[Ca++].[O-]B([O-])[O-] OACTUMJBTUXLRY-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- MOTIHDAUKXSVQY-UHFFFAOYSA-N B([O-])([O-])O.C(O)(O)=O.[Ca+2] Chemical compound B([O-])([O-])O.C(O)(O)=O.[Ca+2] MOTIHDAUKXSVQY-UHFFFAOYSA-N 0.000 description 1
- SWLGHJDGALBJEQ-UHFFFAOYSA-L C([O-])([O-])=O.B(O)(O)O.[Ca+2] Chemical compound C([O-])([O-])=O.B(O)(O)O.[Ca+2] SWLGHJDGALBJEQ-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XBTKKSQDZDPDMD-UHFFFAOYSA-L P(=O)(O)(O)[O-].[Ca+2].B(O)(O)O.P(=O)(O)(O)[O-] Chemical compound P(=O)(O)(O)[O-].[Ca+2].B(O)(O)O.P(=O)(O)(O)[O-] XBTKKSQDZDPDMD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
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
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/28047—Gels
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for removing metal ions in wastewater, which is characterized in that a magnetic gel ball adsorption material is added into the wastewater at an addition ratio of 1-5g/L and is mixed and vibrated for 2-6 h or the magnetic gel ball adsorption material is filled into an adsorption column according to a column height-diameter ratio (6-10):1, and the wastewater flows through the adsorption column at a flow rate of 0.6-1L/h, so that the metal ions in the wastewater are removed, the pollution of the metal ions to a water body is reduced, a new way is provided for solving the problem of water pollution, and the method is a pollutant treatment material with practical application prospect. The magnetic gel ball adsorption material has the advantages of low price and easy obtainment of synthetic raw materials, mature preparation process, low requirement on reaction conditions, simple and easy processing method, and easy separation and recovery.
Description
Technical Field
The invention belongs to the field of material preparation and environmental science and technology, and particularly relates to a method for removing metal ions in wastewater.
Background
Water pollution has become one of the serious environmental problems. The metal ions in water greatly damage the survival of animals, plants and human beings. The high toxicity, non-degradability and bioaccumulation of metal ions seriously threaten human health. How to effectively treat metal ions in wastewater is a troublesome problem. The adsorption method has the advantages of simple treatment method, low requirement on treatment conditions and low cost, and is widely concerned by people. The adsorbent material is critical to the performance of the adsorption treatment and it directly affects the treatment effect and quality. The traditional adsorbing material has low treatment efficiency, poor treatment quality, difficult separation of the adsorbing material and high use cost. Therefore, it is necessary to develop an adsorption material for removing metal ions from wastewater, which is environmentally friendly, has high treatment efficiency, and is easy to separate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for removing metal ions in wastewater, the prepared magnetic gel ball adsorption material can efficiently remove the metal ions in the wastewater, is easy to separate from the wastewater after adsorption is completed, has good stability, can be recycled, and can meet the requirement of actually treating the metal ions in the wastewater.
In order to achieve the purpose, the invention provides the following technical scheme: a method for removing metal ions in wastewater comprises the following steps:
s1, adjusting the pH value of the waste water to 4-6 at the temperature of 30-50 ℃;
s2, preparing a magnetic gel ball adsorbing material;
s3, adding the magnetic gel ball adsorbing material into the wastewater at an addition ratio of 1-5g/L, mixing and oscillating for 2-6 h, or filling the magnetic gel ball adsorbing material into an adsorption column according to a column height-diameter ratio (6-10):1, and allowing the wastewater to flow through the adsorption column at a flow rate of 0.6-1L/h to obtain a treatment solution for removing metal ions.
Further, step S2 specifically includes the following steps:
1) mixing deionized water, ferrous chloride tetrahydrate, ferric chloride hexahydrate, 25% ammonia water by mass fraction and humate to prepare a magnetic dopant, and preparing the magnetic dopant into a magnetic dopant aqueous dispersion;
2) uniformly mixing a polyvinyl alcohol solution and an alginate solution to obtain a first precursor, adding a dopant water dispersion into the first precursor, and uniformly mixing to obtain a second precursor;
3) preparing a saturated boric acid soluble calcium salt solution from a soluble calcium salt solution and a boric acid solution in a mass ratio of 1:1, dropwise adding a second precursor into the saturated boric acid soluble calcium salt solution, uniformly stirring, carrying out curing crosslinking, and filtering to obtain a third precursor;
4) and washing the third precursor, repeatedly freezing and unfreezing the third precursor under the same condition to obtain a fourth precursor, and freeze-drying the fourth precursor to obtain the magnetic gel ball adsorption material.
Further, the mass ratio of polyvinyl alcohol, alginate, magnetic dopant, boric acid and soluble calcium salt in the magnetic gel ball adsorption material is (1-2): (0.3-0.6): (0.1-0.5): (5-8): (4-6).
Further, in step S1, a 0.1mol/L NaOH solution and a 0.1mol/L HCl solution are used to adjust the pH of the wastewater.
Further, in step S3, the magnetic gel bead-adsorbing material is separated by an external magnetic field.
Further, the magnetic gel ball adsorption material which has adsorbed the metal ions is mixed with a desorption agent for desorption treatment, the pH of the magnetic gel ball adsorption material is adjusted to be neutral after desorption, and the magnetic gel ball adsorption material is dried and recovered.
Further, the desorption agent is an EDTA solution with the concentration of 0.1mol/L, the solid-to-liquid ratio of the magnetic gel ball adsorption material for adsorbing metal ions to the desorption agent is 1:10, the mixing is performed by shaking mixing, the shaking speed is 120r/min, the solution temperature of the desorption agent is 30-50 ℃, the desorption treatment time is 2-4 h, and the pH value of the desorption agent is neutral by water washing and soaking the magnetic gel ball adsorption material; the drying temperature is 40-60 ℃.
Further, the concentration of the remaining metal ions in the treatment solution and the concentration of the metal ions in the desorbent were detected by an atomic absorption spectrometer.
Compared with the prior art, the invention has at least the following beneficial effects:
the method for removing the metal ions in the wastewater provided by the invention is characterized in that the magnetic gel ball adsorption material and the wastewater are mixed or the magnetic gel ball adsorption material is used for adsorbing the metal ions in the wastewater through an adsorption column, the magnetic gel ball adsorption material has high removal efficiency, the temperature of the wastewater is kept between 30 and 50 ℃ during adsorption, the adsorption efficiency of the magnetic adsorption material is improved, the adsorption rate of the gel ball adsorption material on the metal ions can be improved while lower energy consumption is consumed, the pollution of the metal ions on a water body is reduced, a new way is provided for solving the problem of water pollution, and the method is a pollutant treatment material with practical application prospect.
The adding ratio of the magnetic adsorbing material in the wastewater is 1-5g/L, and when the adding ratio of the magnetic adsorbing material is larger, the removing rate of the metal particles in the wastewater is higher; or filling the magnetic adsorbing material into an adsorption column with the column height-diameter ratio (6-10):1, wherein the higher the height-diameter ratio of the adsorption column, the slower the flow speed of the wastewater, the longer the time for the wastewater to flow through the adsorption column, and the higher the removal rate of the metal particles in the wastewater.
The magnetic gel ball adsorbing material has the advantages of low price and easy obtainment of synthetic raw materials, mature preparation process, low requirement on reaction conditions and simple and easy processing method, and can be easily separated from wastewater and easily separated and recycled under the condition of an external magnetic field due to the magnetism of the magnetic gel ball adsorbing material.
The separated magnetic gel ball adsorption material can remove metal ions in EDTA (ethylene diamine tetraacetic acid) solution, and the magnetic gel ball adsorption material for removing the metal ions can be recycled, so that the requirement of actually removing the metal ions in the wastewater can be met.
Drawings
FIG. 1 is a FT-IR chart of the magnetic gel bead adsorbent of example 2 before and after adsorbing Pb (II);
FIG. 2 is an XRD pattern of the magnetic gel bead adsorbent of example 2 before and after adsorbing Pb (II);
FIG. 3 is SEM images of the magnetic gel ball adsorbing material before and after adsorbing Pb (II) in example 2, wherein (a) - (e) are SEM images of different magnifications before the magnetic gel ball adsorbing material adsorbs Pb (II), and (f) - (l) are SEM images of different magnifications after the magnetic gel ball adsorbing material adsorbs Pb (II);
FIG. 4 is a TGA-DTG graph before and after the magnetic adsorbent adsorbs Pb (II) in example 2;
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1:
preparing a magnetic gel ball adsorbing material:
50g of deionized water is heated to 85 ℃, 1g of ferrous chloride tetrahydrate and 2.5g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. And then adding 5g of 25% ammonia water and 0.5g of potassium humate into the mixed solution, continuously stirring for 1h, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 3 times, and vacuum drying at 40 deg.C for 8 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% sodium alginate solution, 1% magnetic dopant water dispersion solution, 5% boric acid solution and 4% calcium chloride solution. Mixing a 5% boric acid solution and a 4% calcium chloride solution according to the mass ratio of 1:1 to prepare a calcium borate chloride solution.
Uniformly mixing 10g of 10% polyvinyl alcohol solution and 10g of 3% sodium alginate solution at 40 ℃ under mechanical stirring at the rotating speed of 120r/min, adding 10g of 1% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 2h, dripping the mixed solution into a calcium borate-chloride solution with magnetic stirring, solidifying and crosslinking for 12h under magnetic stirring after dripping the mixed solution, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol for 3 times respectively, freezing for 12h at-4 ℃, then unfreezing for 12h at room temperature, and freezing and unfreezing for 4 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Pb (ii):
the pH of the Pb (II) -containing wastewater was adjusted to 4 with 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature was controlled at 30 ℃. Subsequently, the magnetic gel ball adsorbing material was mixed with Pb (II) wastewater at an addition ratio of 1g/L, and then the mixture was shaken for 2 hours. Then, the adsorbed treatment solution is subjected to a magnetic field application condition to separate the magnetic gel bead adsorbent from the treatment solution. The concentration of the remaining Pb (II) in the treatment solution was measured by an atomic absorption spectrometer, and the adsorbed amount was 312.43mg/g and the removal rate was 91.34% by calculation based on formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 30 ℃, the desorption treatment time is 2 hours, the concentration of Pb (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount 275.62mg/g and the desorption rate 81.72 are respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
Example 2:
preparing a magnetic gel ball adsorbing material:
after 75g of deionized water was heated to 90 ℃, 1.5g of ferrous chloride tetrahydrate and 3.8g of ferric chloride hexahydrate were added to the deionized water, and stirred and mixed uniformly. Then 7.5g of 25% ammonia water and 0.75g of potassium humate are added into the mixed solution, the mixture is continuously stirred for 2 hours, the heating is stopped, the mixture is cooled to the room temperature, and black precipitate is obtained by filtration. Washing the black precipitate with water and ethanol for 4 times, and vacuum drying at 50 deg.C for 10 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% sodium alginate solution, 3% magnetic dopant water dispersion solution, 6.5% boric acid solution and 5% calcium chloride solution. Then, a 6.5% boric acid solution and a 5% calcium chloride solution were mixed at a mass ratio of 1:1 to prepare a calcium borate chloride solution.
Mixing 15g of 10% polyvinyl alcohol solution and 15g of 3% sodium alginate solution uniformly at 50 ℃ under mechanical stirring at the rotating speed of 130 r/min. And then adding 10g of 3% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 3h, dropwise adding the mixed solution into a calcium borate-chloride solution with magnetic stirring, dropwise adding the mixed solution, curing and crosslinking for 9h under magnetic stirring, filtering and separating to obtain magnetic gel sphere particles, flushing the magnetic gel sphere particles with water and ethanol for 4 times respectively, freezing for 9h at-7 ℃, then unfreezing for 9h at room temperature, and freezing and unfreezing for 3 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Pb (ii):
the pH of the Pb (II) -containing wastewater was adjusted to 5 with 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature was controlled at 40 ℃. Subsequently, the magnetic gel bead-adsorbing material was mixed with the Pb (II) wastewater at an addition ratio of 3g/L, and the mixture was shaken for 4 hours. Then, the adsorbed treatment solution is subjected to a magnetic field application condition to separate the magnetic gel bead adsorbent from the treatment solution. The treatment liquid was examined for the concentration of the remaining Pb (II) in the solution by an atomic absorption spectrometer, and the adsorbed amount was 339.38mg/g and the removal rate was 93.25% by calculation based on the formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 40 ℃, the desorption treatment time is 4 hours, the concentration of Pb (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount 287.64mg/g and the desorption rate 85.26% are respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 50 ℃ for use in subsequent processing.
Example 3:
preparing a magnetic gel ball adsorbing material:
100g of deionized water is heated to 95 ℃, 2g of ferrous chloride tetrahydrate and 5.2g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. And adding 10g of 25% ammonia water and 1g of potassium humate into the mixed solution, continuously stirring for 3 hours, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 5 times, and vacuum drying at 60 deg.C for 12h to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% sodium alginate solution, 5% magnetic dopant water dispersion solution, 8% boric acid solution and 6% calcium chloride solution. Then, 8% boric acid solution and 6% calcium chloride are mixed according to the mass ratio of 1:1 to prepare calcium borate chloride solution.
20g of 10 percent polyvinyl alcohol solution and 20g of 3 percent sodium alginate solution are mixed evenly under the mechanical stirring at the temperature of 60 ℃ and the rotating speed of 150 r/min. And then adding 10g of 5% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 4h, dropwise adding the mixed solution into a boric acid and calcium chloride solution with magnetic stirring, solidifying and crosslinking for 6h under the magnetic stirring, filtering and separating to obtain magnetic gel ball particles, flushing the magnetic gel ball particles with water and ethanol for 5 times respectively, freezing for 6h at-10 ℃, then unfreezing for 6h at room temperature, and freezing and unfreezing for 2 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Pb (ii):
the pH of the Pb (II) -containing wastewater was adjusted to 4 with 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature was controlled at 30 ℃. Then, the magnetic gel ball adsorbing material is filled into a column according to the ratio of the height to the diameter of the column being 6:1, and Pb (II) wastewater flows through the column at the flow rate of 0.6L/h. Subsequently, the treatment liquid was examined for the concentration of the remaining Pb (II) in the solution by an atomic absorption spectrometer, and the adsorbed amount was 285.76mg/g and the removal rate was 81.72% by calculation based on the formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the suction at time tThe attached amount; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 40 ℃, the desorption treatment time is 3 hours, the concentration of Pb (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount is 251.46mg/g and the desorption rate is 79.62% respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
Example 4:
preparing a magnetic gel ball adsorbing material:
50g of deionized water is heated to 85 ℃, 1g of ferrous chloride tetrahydrate and 2.5g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. And then adding 5g of 25% ammonia water and 0.5g of sodium humate into the mixed solution, continuously stirring for 1h, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 3 times, and vacuum drying at 40 deg.C for 8 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% ammonium alginate solution, 1% magnetic dopant water dispersion solution, 5% boric acid solution and 4% calcium bicarbonate solution. Then, a 5% boric acid solution and a 4% calcium bicarbonate solution were mixed in a mass ratio of 1:1 to prepare a calcium bicarbonate borate solution.
10g of 10% polyvinyl alcohol solution and 10g of 3% ammonium alginate solution are mixed uniformly at 40 ℃ under mechanical stirring at a speed of 120 r/min. And then adding 10g of 1% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 2h, dropwise adding the mixed solution into a calcium hydrogen borate carbonate solution with magnetic stirring, solidifying and crosslinking for 12h under magnetic stirring, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol for 3 times, freezing for 12h at-4 ℃, then unfreezing for 12h at room temperature, and freezing and unfreezing for 4 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Pb (ii):
the pH of the Pb (II) -containing wastewater was adjusted to 5 with 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature was controlled at 40 ℃. Then, the magnetic gel ball adsorbing material is filled into a column according to the ratio of the height to the diameter of the column being 8:1, and Pb (II) wastewater flows through the column at the flow rate of 0.8L/h. Subsequently, the treatment liquid was examined for the concentration of the remaining Pb (II) in the solution by an atomic absorption spectrometer, and the adsorbed amount was 261.42mg/g and the removal rate was 76.61% by calculation based on the formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 50 ℃, and the desorption treatment time is 4 hours, the concentration of Pb (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount is 237.82mg/g and the desorption rate is 77.62 percent respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
Example 5:
preparing a magnetic gel ball adsorbing material:
after 75g of deionized water was heated to 90 ℃, 1.5g of ferrous chloride tetrahydrate and 3.8g of ferric chloride hexahydrate were added to the deionized water, and stirred and mixed uniformly. Then 7.5g of 25% ammonia water and 0.75g of sodium humate are added into the mixed solution, the mixture is continuously stirred for 2 hours, the heating is stopped, the mixture is cooled to the room temperature, and black precipitate is obtained by filtration. Washing the black precipitate with water and ethanol for 4 times, and vacuum drying at 50 deg.C for 10 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% ammonium alginate solution, 3% magnetic dopant water dispersion solution, 6.5% boric acid solution and 5% calcium dihydrogen phosphate solution. Then, a 6.5% boric acid solution and a 5% monocalcium phosphate solution were mixed in a mass ratio of 1:1 to prepare a monocalcium borate phosphate solution.
Mixing 15g of 10% polyvinyl alcohol solution and 15g of 3% ammonium alginate solution at 50 ℃ and under mechanical stirring at the rotation speed of 130 r/min. And then adding 10g of 3% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 3h, dropwise adding the mixed solution into a boric acid calcium dihydrogen phosphate solution with magnetic stirring, solidifying and crosslinking for 9h under the magnetic stirring, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol for 4 times, freezing for 9h at-7 ℃, then unfreezing for 9h at room temperature, and freezing and unfreezing for 3 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Cu (ii):
the pH value of the obtained wastewater containing Cu (II) is adjusted to 5 by using 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature is controlled at 40 ℃. Subsequently, the magnetic gel ball adsorbing material was mixed with the Cu (II) wastewater at an addition ratio of 3g/L, and then the mixture was shaken for 4 hours. Then, the adsorbed treatment solution is subjected to a magnetic field application condition to separate the magnetic gel bead adsorbent from the treatment solution. The concentration of the remaining Cu (II) in the treatment solution was measured by an atomic absorption spectrometer, and the adsorption amount was 253.21mg/g and the removal rate was 87.53% by calculation based on formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 40 ℃, the desorption treatment time is 2 hours, the concentration of Cu (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount is 167.24mg/g and the desorption rate is 79.28% respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
Example 6:
preparing a magnetic gel ball adsorbing material:
100g of deionized water is heated to 95 ℃, 2g of ferrous chloride tetrahydrate and 5.2g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. And adding 10g of 25% ammonia water and 1g of sodium humate into the mixed solution, continuously stirring for 3 hours, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 5 times, and vacuum drying at 60 deg.C for 12h to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% ammonium alginate solution, 5% magnetic dopant water dispersion solution, 8% boric acid solution and 6% calcium dihydrogen phosphate solution. Then, the 8% boric acid solution and the 6% monocalcium phosphate solution were mixed in a mass ratio of 1:1 to prepare a monocalcium borate phosphate solution.
20g of 10% polyvinyl alcohol solution and 20g of 3% ammonium alginate solution are mixed uniformly at 60 ℃ under mechanical stirring at a speed of 150 r/min. And then adding 10g of 5% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 4h, dropwise adding the mixed solution into a calcium dihydrogen borate phosphate solution with magnetic stirring, solidifying and crosslinking for 6h under magnetic stirring, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol for 5 times, freezing for 6h at-10 ℃, then unfreezing for 6h at room temperature, and freezing and unfreezing for 2 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Cu (ii):
the pH value of the obtained wastewater containing Cu (II) is adjusted to 6 by using 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature is controlled at 50 ℃. Subsequently, the magnetic gel ball adsorbing material was mixed with the Cu (II) wastewater at an addition ratio of 5g/L, and the mixture was shaken for 6 hours. Then, the adsorbed treatment solution is subjected to a magnetic field application condition to separate the magnetic gel bead adsorbent from the treatment solution. The concentration of the remaining Cu (II) in the treatment solution was measured by an atomic absorption spectrometer, and the adsorption amount was 229.62mg/g and the removal rate was 85.62% by calculation based on formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 50 ℃, the desorption treatment time is 4 hours, the concentration of Cu (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount 157.67mg/g and the desorption rate 77.82 are respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 60 ℃ for use in subsequent processing.
Example 7:
preparing a magnetic gel ball adsorbing material:
80g of deionized water is heated to 90 ℃, 1.5g of ferrous chloride tetrahydrate and 3.5g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. Then adding 10g of 25% ammonia water and 0.7g of potassium humate into the mixed solution, continuously stirring for 2h, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 3 times respectively, and vacuum drying at 50 deg.C for 10 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% sodium alginate solution, 3% magnetic dopant water dispersion solution, 8% boric acid solution and 6% soluble calcium salt solution. Then, 8% boric acid solution and 6% calcium chloride solution are mixed according to the mass ratio of 1:1 to prepare calcium borate-calcium chloride solution.
Mixing 15g of 10% polyvinyl alcohol solution and 15g of 3% sodium alginate solution at 50 ℃ and under the condition of mechanical stirring at the rotating speed of 130 r/min. Adding 10g of 3% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 3h, dropwise adding the mixed solution into boric acid soluble calcium salt solution with magnetic stirring, solidifying and crosslinking for 9h under magnetic stirring, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol respectively for 3 times, freezing for 6h at-4 ℃, then unfreezing for 6h at room temperature, and freezing and unfreezing for 3 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Cu (ii):
the pH value of the obtained wastewater containing Cu (II) is adjusted to 4 by using 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature is controlled at 30 ℃. Then, the magnetic gel ball adsorbing material is filled into a column according to the ratio of the height to the diameter of the column being 8:1, and Cu (II) wastewater flows through the column at the flow rate of 0.8L/h. Subsequently, the treatment liquid was examined for the concentration of Cu (II) remaining in the solution by an atomic absorption spectrometer, and the adsorbed amount was 234.61mg/g and the removal rate was 85.32% by calculation based on formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) are the metal ion concentrations of the solution at the initial time, time t and equilibrium, respectively; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 40 ℃, the desorption treatment time is 3 hours, the concentration of Cu (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount is 146.28mg/g and the desorption rate is 74.31% are respectively calculated according to the formulas (1) and (2). And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
Example 8:
preparing a magnetic gel ball adsorbing material:
80g of deionized water is heated to 90 ℃, 1.5g of ferrous chloride tetrahydrate and 3.5g of ferric chloride hexahydrate are added into the deionized water, and the mixture is stirred and mixed uniformly. Then adding 10g of 25% ammonia water and 0.7g of potassium humate into the mixed solution, continuously stirring for 2h, stopping heating, cooling to room temperature, and filtering to obtain black precipitate. Washing the black precipitate with water and ethanol for 3 times respectively, and vacuum drying at 50 deg.C for 10 hr to obtain the magnetic dopant.
Respectively preparing 10% polyvinyl alcohol solution, 3% sodium alginate solution, 3% magnetic dopant water dispersion solution, 8% boric acid solution and 6% soluble calcium salt solution. Then, 8% boric acid solution and 6% calcium chloride solution are mixed according to the mass ratio of 1:1 to prepare calcium borate-calcium chloride solution.
Mixing 15g of 10% polyvinyl alcohol solution and 15g of 3% sodium alginate solution at 50 ℃ and under the condition of mechanical stirring at the rotating speed of 130 r/min. Adding 10g of 3% magnetic dopant aqueous dispersion into the mixed solution, continuously stirring for 3h, dropwise adding the mixed solution into boric acid soluble calcium salt solution with magnetic stirring, solidifying and crosslinking for 9h under magnetic stirring, filtering and separating to obtain magnetic gel ball particles, washing the magnetic gel ball particles with water and ethanol respectively for 3 times, freezing for 6h at-4 ℃, then unfreezing for 6h at room temperature, and freezing and unfreezing for 3 times under the same conditions and operation. And then freeze-drying in a freeze dryer to obtain the magnetic gel ball adsorbing material.
Treatment of heavy metal ions Cu (ii):
the pH value of the obtained wastewater containing Cu (II) is adjusted to 5 by using 0.1mol/L NaOH and 0.1mol/L HCl solution, and the water temperature is controlled at 40 ℃. Then, the magnetic gel ball adsorbing material is filled into a column according to the ratio of the height to the diameter of the column being 10:1, and Cu (II) wastewater flows through the column at the flow rate of 1L/h. Subsequently, the treatment liquid was examined for the concentration of Cu (II) remaining in the solution by an atomic absorption spectrometer, and the adsorbed amount was 197.56mg/g and the removal rate was 76.24% by calculation based on formulas (1) and (2), respectively.
Wherein Qt(μ g/g) is the amount adsorbed at time t; r is the removal rate; c0，CtAnd Ce(μ g/L) of the solution at the initial time, time t and equilibrium, respectivelyThe concentration of metal ions; v (L) is the volume of the solution; m (g) is the mass of the adsorbent.
0.1mol/L EDTA (ethylene diamine tetraacetic acid) solution is used as a desorption agent, an adsorption material is added according to the solid-to-liquid ratio of 1:10 for mixing, after the oscillation speed is 120r/min, the solution temperature is 50 ℃, the desorption treatment time is 4 hours, the concentration of Cu (II) in the desorption agent is detected by an atomic absorption spectrometer, and the desorption amount is 167.52mg/g and the desorption rate is 67.62 percent according to the formula (1) and the formula (2) respectively. And washing and soaking the desorbed adsorption material with water until the pH value is neutral. The adsorbent material was then dried at 40 ℃ for use in subsequent processing.
The magnetic gel ball adsorbing material can also adsorb various metal ions such as Co (II), Ni (II), Zn (II) and the like in wastewater, and has excellent adsorption performance and high-efficiency removal rate.
FIG. 1 is a FT-IR chart showing the results of adsorption of Pb (II) by the magnetic gel bead adsorbent in example 2. As shown in FIG. 1, after adsorbing Pb (II) on the magnetic gel bead adsorbent, the concentration of Pb (II) was 3470cm-1Move to 3450cm-1Here, this may be due to-OH (or-NH) in the gel beads2) There may be electrostatic interactions between the group and Pb (ii). At 1640cm-1The absorption peak at (A) is shifted to 1650cm-1Here, this is probably due to stretching vibration of C ═ O groups (carboxylic acids), suggesting that these groups may interact with Pb (ii). This observed spectral change is similar to other reported heavy metal adsorption spectral changes.
FIG. 2 is an XRD pattern of the magnetic gel beads before and after adsorbing Pb (II) in example 2. Compared with the XRD pattern before the magnetic gel spheres adsorb Pb (II), a plurality of sharp and narrow peaks appear in the diffraction pattern of the gel spheres-Pb (II) when the 2 theta is 19.85 degrees, 22.85 degrees, 32.34 degrees and 38.16 degrees after the adsorption of the Pb (II). This indicates that the gel beads have successfully bound Pb (II).
FIG. 3 is SEM images of the magnetic gel ball adsorbing material before and after adsorbing Pb (II) in example 2, wherein (a) to (e) are SEM images of different magnifications before the magnetic gel ball adsorbing material adsorbs Pb (II), and (f) to (l) are SEM images of different magnifications after the magnetic gel ball adsorbing material adsorbs Pb (II), and compared with the SEM images before the magnetic gel ball adsorbing Pb (II), the surface of the gel ball after adsorbing Pb (II) shows a denser morphology without cracks, which is significantly different from the surface of the gel ball before adsorbing, and further, it can be seen that many irregular particles mainly generated by Pb (II) deposition are attached to the rough surface of the gel ball.
FIG. 4 is a TGA-DTG graph before and after the magnetic gel beads adsorb Pb (II) in example 2. Compared with a TGA-DTG graph before the magnetic gel ball adsorbs Pb (II), the thermal decomposition process after the magnetic gel ball adsorbs the Pb (II) mainly comprises two stages, which is probably different from the magnetic gel ball before adsorption due to the chelation of the magnetic gel ball and the Pb (II), and shows that the magnetic gel ball has the adsorption performance on metal ions.
Claims (8)
1. A method for removing metal ions in wastewater is characterized by comprising the following steps:
s1, preparing a magnetic gel ball adsorbing material;
s2, adjusting the pH value of the waste water to 4-6 at the temperature of 30-50 ℃;
s3, adding the magnetic gel ball adsorbing material into the wastewater obtained in the step S1 at an addition ratio of 1-5g/L, mixing and oscillating for 2-6 h, or filling the magnetic gel ball adsorbing material into an adsorption column according to a column height-diameter ratio (6-10):1, and allowing the wastewater to flow through the adsorption column at a flow rate of 0.6-1L/h to obtain a treatment solution for removing metal ions.
2. The method for removing metal ions in wastewater according to claim 1, wherein the step S1 comprises the following steps:
1) mixing deionized water, ferrous chloride tetrahydrate, ferric chloride hexahydrate, 25% ammonia water by mass fraction and humate to prepare a magnetic dopant, and preparing the magnetic dopant into a magnetic dopant aqueous dispersion;
2) uniformly mixing a polyvinyl alcohol solution and an alginate solution to obtain a first precursor, adding a dopant water dispersion into the first precursor, and uniformly mixing to obtain a second precursor;
3) preparing a saturated boric acid soluble calcium salt solution from a soluble calcium salt solution and a boric acid solution in a mass ratio of 1:1, dropwise adding a second precursor into the saturated boric acid soluble calcium salt solution, uniformly stirring, carrying out curing crosslinking, and filtering to obtain a third precursor;
4) and washing the third precursor, repeatedly freezing and unfreezing the third precursor under the same condition to obtain a fourth precursor, and freeze-drying the fourth precursor to obtain the magnetic gel ball adsorption material.
3. The method for removing the metal ions in the wastewater as claimed in claim 2, wherein the mass ratio of the polyvinyl alcohol, the alginate, the magnetic doping agent, the boric acid and the soluble calcium salt in the magnetic gel ball adsorbing material is (1-2): (0.3-0.6): (0.1-0.5): (5-8): (4-6).
4. The method of claim 1, wherein in step S2, the pH of the wastewater is adjusted by using 0.1mol/L NaOH solution and 0.1mol/L HCl solution.
5. The method of claim 1, wherein in step S3, the magnetic gel ball adsorbing material is separated by an external magnetic field.
6. The method according to claim 1, wherein the magnetic gel ball adsorption material having adsorbed the metal ions is mixed with a desorption agent to perform desorption treatment, the pH of the magnetic gel ball adsorption material is adjusted to be neutral after desorption, and the magnetic gel ball adsorption material is dried and recovered.
7. The method for removing the metal ions in the wastewater according to claim 6, wherein the desorption agent is an EDTA solution with a concentration of 0.1mol/L, the solid-to-liquid ratio of the magnetic gel ball adsorption material for adsorbing the metal ions to the desorption agent is 1:10, the mixing is performed by shaking and mixing, the shaking speed is 120r/min, the solution temperature of the desorption agent is 30-50 ℃, the desorption treatment time is 2-4 h, and the pH value of the desorption agent is neutral by washing and soaking the magnetic gel ball adsorption material with water; the drying temperature is 40-60 ℃.
8. The method for removing metal ions from wastewater as claimed in claim 7, wherein the concentration of the metal ions remaining in the treatment solution and the concentration of the metal ions in the desorbent are detected by an atomic absorption spectrometer.
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| CN115301204A (en) * | 2022-09-02 | 2022-11-08 | 浙江大学 | Residual sludge alginate magnetic nano-phosphorus adsorbent and preparation method thereof |
| CN115301204B (en) * | 2022-09-02 | 2024-01-02 | 浙江大学 | Residual sludge alginate magnetic nano phosphorus adsorbent and preparation method thereof |
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