CN114515566A - Application of functional protein ferric oxide composite material in oxidation complex-breaking complex-state heavy metal - Google Patents
Application of functional protein ferric oxide composite material in oxidation complex-breaking complex-state heavy metal Download PDFInfo
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- CN114515566A CN114515566A CN202210057338.5A CN202210057338A CN114515566A CN 114515566 A CN114515566 A CN 114515566A CN 202210057338 A CN202210057338 A CN 202210057338A CN 114515566 A CN114515566 A CN 114515566A
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- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 84
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 84
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 51
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002657 fibrous material Substances 0.000 claims description 19
- 102000008192 Lactoglobulins Human genes 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 230000010355 oscillation Effects 0.000 claims description 12
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 11
- 229940098773 bovine serum albumin Drugs 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 102000016943 Muramidase Human genes 0.000 claims description 10
- 108010014251 Muramidase Proteins 0.000 claims description 10
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims description 10
- 239000011133 lead Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 230000002860 competitive effect Effects 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 101001008231 Bos taurus Beta-lactoglobulin Proteins 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229960000274 lysozyme Drugs 0.000 claims 1
- 235000010335 lysozyme Nutrition 0.000 claims 1
- 239000004325 lysozyme Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000033558 biomineral tissue development Effects 0.000 abstract description 13
- 239000013110 organic ligand Substances 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 16
- 108010060630 Lactoglobulins Proteins 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000009713 electroplating Methods 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 9
- 229960001484 edetic acid Drugs 0.000 description 9
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 125000003275 alpha amino acid group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 2
- -1 nitrate ions Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 102000001049 Amyloid Human genes 0.000 description 1
- 108010094108 Amyloid Proteins 0.000 description 1
- 102000009091 Amyloidogenic Proteins Human genes 0.000 description 1
- 108010048112 Amyloidogenic Proteins Proteins 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/28028—Particles immobilised within fibres or filaments
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/58—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
An application of a functional protein ferric oxide composite material in oxidation complex breaking of heavy metals belongs to the technical field of environmental sewage treatment. The invention provides a method for preparing a functional protein ferric oxide composite material in oxidation-decomplexation complex heavy metalApplication is carried out. Also provided is an application method thereof, comprising: (1) preparing a functional protein ferric oxide composite material; (2) controlling the temperature and pH of the water polluted by the complex heavy metal, and adding H2O2And a functional protein iron oxide composite. The invention still has high-efficiency selective removal capability on complex heavy metals, the removal efficiency of the invention on metal ions in various complex heavy metals is up to more than 95%, the mineralization rate of organic ligands can be up to more than 70%, and the environmental protection benefit is obvious.
Description
Technical Field
The invention belongs to the technical field of environmental sewage treatment, and particularly relates to an application of a functional protein ferric oxide composite material in oxidation, breaking of a complex state heavy metal.
Background
Heavy metal pollution of water bodies becomes a global environmental problem, and the human health and ecological balance are seriously threatened. However, in typical heavy metal pollution industries such as electroplating, metallurgy and tanning, a large amount of complexing agents such as citric acid, oxalic acid and Ethylene Diamine Tetraacetic Acid (EDTA) are used, heavy metal ions are easy to chelate with the complexing agents to form complex heavy metals, and a typical organic ligand-heavy metal composite pollution system is shown. At present, common heavy metal treatment methods in water bodies include a chemical precipitation method, an adsorption method, a membrane separation method and the like, but compared with heavy metal ions, the complex heavy metal pollutants have higher stability and toxicity and stronger migration capacity, so that the ideal removal effect is difficult to achieve by the conventional water treatment technology. Therefore, the development of a treatment method aiming at the complex heavy metal has important environmental significance.
The advanced oxidation technology utilizes active free radicals with strong oxidizing property to efficiently catalyze and degrade water pollutants, can be used as an excellent choice for decomplexing complex-state heavy metals, and is very representative of Fenton catalytic reaction. The nano material has great application potential in the field of Fenton catalysis due to the high activity property brought by the large specific surface area and the nano size. The functional protein amyloid fiber is used as a novel biomass material, and the high length-diameter ratio and the abundant surface amino acid functional groups of the functional protein amyloid fiber can play a good role in promoting catalytic oxidation. Early researches find that the amyloid fiber has good catalytic effect on organic pollutants in a water body, but no relevant report is found on the removal of complex-state heavy metals by breaking the complex.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide the application of the functional protein ferric oxide composite material in oxidizing and breaking the complex-state heavy metal. The invention takes beta-lactoglobulin and other various functional protein amyloid fibers as a supporting layer as a cocatalyst, takes ferric oxide as a catalyst, and the prepared functional protein ferric oxide composite material can perform catalytic reaction under acidic, especially neutral conditions, can efficiently remove complex heavy metals in water by synergistically utilizing heterogeneous Fenton-like reaction and adsorption, and provides a new way for deep purification of the complex heavy metals.
In order to achieve the purpose, the invention adopts the following technical scheme:
the functional protein ferric oxide composite material is applied to oxidation, decomplexing and complexing heavy metals.
The application method of the functional protein ferric oxide composite material in oxidation complex breaking of heavy metal is characterized by comprising the following steps:
(1) preparing a functional protein ferric oxide composite material;
(2) controlling the temperature of the water polluted by the complex heavy metal to be 15-55 ℃, controlling the pH to be 2.0-7.0, and adding H2O2And the functional protein ferric oxide composite material prepared in the step (1).
The application method is characterized in that the preparation method of the functional protein iron oxide composite material in the step (1) comprises the following steps:
(a) weighing functional protein with the mass fraction of 2-10%, dissolving the functional protein in water, adjusting the pH value, and placing the functional protein in a water bath at the temperature of 85-105 ℃ to stir and react for 6-12 hours to obtain an amyloid fiber material;
(b) weighing ferric iron salt, putting into the amyloid fiber material obtained in the step (a), dissolving by vortex oscillation, and adjusting pH to obtain the functional protein ferric oxide composite material.
The application method is characterized in that the functional protein in the step (a) comprises lysozyme protein, bovine serum albumin or beta-lactoglobulin, the pH is adjusted to 2.0-4.0, the diameter of the amyloid fiber material is 3-5nm, and the length of the amyloid fiber material is 2-15 microns.
The application method is characterized in that the mass ratio of the ferric iron salt to the amyloid fiber material in the step (b) is 4-10: 1, and the pH is adjusted to 2.0-7.0.
The application method is characterized in that the ferric salt in the step (b) comprises FeCl3.·6H2O、Fe2(SO4)3Or Fe (NO)3)3。
The application method is characterized in that the complexed heavy metal in the step (2) comprises an organic-heavy metal complex formed by heavy metal ions and organic chelating ligands, preferably the heavy metal ions comprise copper, nickel and lead, and the organic chelating ligands comprise citric acid, oxalic acid and ethylenediamine tetraacetic acid.
The application method is characterized in that the concentration of the complex-state heavy metal in the water polluted by the complex-state heavy metal in the step (2) is 1-50 mg/L, at least one competitive ion exists in the water polluted by the complex-state heavy metal, and the concentration of the competitive ion is 0-100 molar times of that of the complex-state heavy metal.
The application method is characterized in that the competitive ions comprise anions, cations and natural organic matters, preferably the anions comprise sulfate ions, chloride ions and nitrate ions, and preferably the cations comprise calcium ions, magnesium ions and sodium ions.
The application method is characterized in that H in the step (2)2O2Is 30% wt, H2O2The volume ratio of the functional protein iron oxide composite material to the functional protein iron oxide composite material is 1: 10-25. Forming a heterogeneous Fenton catalytic system. Through the synergistic effect of oxidation, decomplexing, adsorption and the like of the composite catalyst, the discharged water of the heavy metal is lower than the heavy metal ion discharge limit value specified in the electroplating pollutant discharge standard (GB21900-2008), and the environmental protection benefit is obvious.
The amyloid protein fiber is 2-15 mu m in length and 3-5nm in diameter, has an ultra-long length-diameter ratio (>1000), an ultra-large specific surface area and unique functional groups such as rich amino groups and carboxyl groups, can provide a large number of loading sites, and easily forms a high-activity iron oxide catalyst with sub-5 nm. The charged structure constructed by the amino acid residue chain specific to the protein amyloid fiber is beneficial to obtaining the high-dispersion nano-scale iron oxide catalyst through simple chemical deposition.
The functional protein ferric oxide composite material utilizes amyloid fiber as a cocatalyst, realizes the redox cycle process of interface Fe (III)/Fe (II), and strengthens the removal capability of the composite catalyst to complex heavy metals in water. The functional protein amyloid fiber has abundant amino acid functional groups and charged disulfide bond structures on the surface, and can show extremely high adsorption activity and selectivity on complex heavy metals, so that the deep purification capability on the complex heavy metals is enhanced by the synergistic Fenton catalytic action. Under the condition of protein fiber limited domain, can excite H2O2Strong oxidizing free radicals such as singlet oxygen are generated, and the high-density protein fiber cross-linked structure obviously improves the catalytic oxidation capacity of the reaction system to complex heavy metals.
Compared with the prior art, the invention has the following beneficial effects:
the amyloid fiber raw material is easy to obtain and environment-friendly, and the amyloid fiber structure can be formed by simple heat treatment reaction of functional protein. In addition, the invention still has high-efficiency selective removal capability on complex heavy metals under the existence conditions of conventional competitive anion sulfate ions, chloride ions, nitrate ions, cation calcium ions, magnesium ions, sodium ions, natural organic matters and the like. The inventor researches and discovers that the removal efficiency of the complex metal ion removing agent on metal ions in various complex heavy metals is up to more than 95%, the mineralization rate of an organic ligand is up to more than 70%, and the environmental protection benefit is obvious. The high-density protein fiber cross-linked structure is utilized to form high-activity iron hydroxide with sub-5 nm in situ, and the synergistic effect of the amyloid fiber co-catalysis characteristic and the strong oxidizing property of the iron hydroxide is utilized to enhance the removal capability of the catalyst on complex heavy metals in water.
Drawings
FIG. 1 is a transmission electron micrograph of β -lactoglobulin amyloid fibrils of example 1;
FIG. 2 is an atomic force microscope topography of beta-lactoglobulin amyloid fibers of example 1;
FIG. 3 shows Cu in the functional protein ferric oxide composite material for catalyzing and degrading copper citrate wastewater in example 12+The removal rate;
FIG. 4 shows the mineralization rate of organic matters in the wastewater from the catalytic degradation of copper citrate by the functional protein-iron oxide composite material of example 1.
Detailed Description
Example 1:
accurately weighing 2g of beta-lactoglobulin, dissolving in 100mL of water, adjusting the pH value of the solution to 2.0, and then placing the solution in a water bath at 85 ℃ to react for 6 hours under stirring to obtain the beta-lactoglobulin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 microns (shown in figures 1 and 2). Subsequently, 2g FeCl was weighed3·6H2And (3) placing the O into 10mL of the protein fiber solution, carrying out vortex oscillation and dissolution, and adjusting the pH of the solution to 2.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the copper citrate sewage is controlled to be 15 ℃, the pH of the reaction solution is adjusted to be 2.0, the concentration of the copper citrate solution is 1mg/L, and 0.5mLH is added2O2In the 5mL functional protein ferric oxide composite material, the copper ion removal rate is close to 100% (as shown in figure 3), the organic ligand mineralization rate is close to 80% (as shown in figure 4), and the effluent is lower than the copper ion limit (0.5mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 2:
accurately weighing 10g of beta-lactoglobulin, dissolving the beta-lactoglobulin in 100mL of water, adjusting the pH value of the solution to 3.0, and then placing the solution in a water bath at 95 ℃ for stirring and reacting for 10 hours to obtain the beta-lactoglobulin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 mu m. Subsequently, 2g Fe (NO) was weighed3)3And (3) placing the mixture into 25mL of the protein fiber solution, performing vortex oscillation and dissolution, and adjusting the pH value of the solution to 5.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the nickel citrate sewage is controlled to be 30 ℃, the pH of the reaction solution is adjusted to be 5.0, the concentration of the nickel citrate solution is 10mg/L, and 0.5mLH is added2O210mL of the functional protein ferric oxide composite material has the nickel ion removal rate of 98 percent and the organic ligand mineralization rate of 79 percent, and the effluent is lower than the nickel ion limit value (0.5mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 3:
accurately weighing 2g of lysozyme protein, dissolving the lysozyme protein into 100mL of water, adjusting the pH value of the solution to 4.0, and then placing the solution in a water bath at 105 ℃ for stirring and reacting for 12 hours to obtain the lysozyme protein amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 mu m. Subsequently, 2g of Fe was weighed2(SO4)3And (3) placing the mixture into 10mL of the protein fiber solution, performing vortex oscillation and dissolution, and adjusting the pH value of the solution to 7.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the lead oxalate sewage is controlled to be 55 ℃, the pH of a reaction solution is adjusted to be 7.0, the concentration of the lead oxalate solution is 50mg/L, and 0.5mLH is added2O212.5mL of the functional protein ferric oxide composite material has the lead ion removal rate of 97.6 percent and the organic ligand mineralization rate of 76.9 percent, and the effluent is lower than the lead ion limit value (0.2mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 4:
accurately weighing 10g of bovine serum albumin, dissolving the bovine serum albumin in 100mL of water, adjusting the pH value of the solution to 4.0, and then placing the solution in a water bath at 105 ℃ to react for 6 hours under stirring to obtain the bovine serum albumin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 microns. Subsequently, 2g FeCl was weighed3·6H2And (3) placing the O into 20mL of the protein fiber solution, carrying out vortex oscillation and dissolution, and adjusting the pH of the solution to 7.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of EDTA copper sewage is controlled to be 55 ℃, the pH of the reaction solution is adjusted to be 2.0, the concentration of the EDTA copper solution is 50mg/L, and 0.5mLH is added2O25mL of the functional protein ferric oxide composite material has the copper ion removal rate of 96.8 percent and the organic ligand mineralization rate of 77.5 percent, and the effluent is lower than the effluent water specified in the electroplating pollutant discharge standard (GB21900-The copper ion limit of (2) (0.5 mg/L).
Example 5:
accurately weighing 5g of bovine serum albumin, dissolving the bovine serum albumin in 100mL of water, adjusting the pH value of the solution to 3.0, and then placing the solution in a water bath at 85 ℃ for stirring and reacting for 6 hours to obtain the bovine serum albumin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 microns. Subsequently, 2g of Fe was weighed2(SO4)3And (3) placing the mixture into 10mL of the protein fiber solution, performing vortex oscillation and dissolution, and adjusting the pH value of the solution to 7.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the lead oxalate sewage is controlled to be 15 ℃, the pH of a reaction solution is adjusted to be 7.0, the concentration of the lead oxalate solution is 1mg/L, and 0.5mLH is added2O212.5mL of the functional protein ferric oxide composite material has the lead ion removal rate of 99.3 percent and the organic ligand mineralization rate of 79.5 percent, and the effluent is lower than the lead ion limit value (0.2mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 6:
accurately weighing 5g of beta-lactoglobulin, dissolving the beta-lactoglobulin in 100mL of water, adjusting the pH value of the solution to 2.0, and then placing the solution in a water bath at 105 ℃ for stirring and reacting for 6 hours to obtain the beta-lactoglobulin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 microns. Subsequently, 2g Fe (NO) was weighed3)3And (3) placing the mixture into 25mL of the protein fiber solution, performing vortex oscillation and dissolution, and adjusting the pH value of the solution to 7.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of EDTA nickel sewage is controlled to be 15 ℃, the pH of a reaction solution is adjusted to be 7.0, the concentration of the EDTA nickel solution is 1mg/L, and 0.5mLH is added2O212.5mL of the functional protein ferric oxide composite material has the lead ion removal rate of 98 percent and the organic ligand mineralization rate of 78.3 percent, and the effluent is lower than the nickel ion limit value (0.5mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 7:
accurately weighing 10g of lysozyme protein, dissolving into 100mL of water, adjusting the pH value of the solution to 4.0Then placing the mixture into a water bath at 85 ℃ to be stirred and react for 12 hours, thus obtaining the lysozyme protein amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 mu m. Subsequently, 2g FeCl was weighed3·6H2And (3) placing the O into 15mL of the protein fiber solution, carrying out vortex oscillation and dissolution, and adjusting the pH of the solution to 4.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the lead citrate sewage is controlled to be 55 ℃, the pH of the reaction solution is adjusted to be 2.0, the concentration of the lead citrate solution is 50mg/L, and 0.5mLH is added2O25mL of the functional protein ferric oxide composite material has the lead ion removal rate of 99 percent and the organic ligand mineralization rate of 77 percent, and the effluent is lower than the lead ion limit value (0.2mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Example 8:
accurately weighing 2g of beta-lactoglobulin, dissolving the beta-lactoglobulin in 100mL of water, adjusting the pH value of the solution to 2.0, and then placing the solution in a water bath at 100 ℃ for stirring and reacting for 12 hours to obtain the beta-lactoglobulin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 mu m. Subsequently, 2g of Fe was weighed2(SO4)3And (3) placing the fiber into 10mL of the protein fiber solution, performing vortex oscillation and dissolution, and adjusting the pH value of the solution to 5.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of EDTA lead sewage is controlled to be 15 ℃, the pH of a reaction solution is adjusted to be 2.0, the concentration of the EDTA lead solution is 20mg/L, and 0.5mLH is added2O2And the removal rate of lead ions of the 10mL functional protein ferric oxide composite material is 96.6 percent, the mineralization rate of the organic ligand is 74 percent, and the effluent is lower than the limit value (0.2mg/L) of the lead ions specified in the discharge standard of electroplating pollutants (GB 21900-2008).
Example 9:
accurately weighing 10g of bovine serum albumin, dissolving the bovine serum albumin in 100mL of water, adjusting the pH value of the solution to 3.0, and then placing the solution in a water bath at 90 ℃ to react for 12 hours under stirring to obtain the bovine serum albumin amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 microns. Subsequently, 2g Fe (NO) was weighed3)3Is placed at 25And (4) dissolving the mL of protein fiber solution in vortex oscillation, and adjusting the pH value of the solution to 7.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of nickel oxalate sewage is controlled to be 55 ℃, the pH of a reaction solution is adjusted to be 7.0, the concentration of the nickel oxalate solution is 10mg/L, and 0.5mLH is added2O212.5mL of the functional protein ferric oxide composite material has the nickel ion removal rate of 95.8 percent and the organic ligand mineralization rate of 78 percent, and the effluent is lower than the nickel ion limit value (0.5mg/L) specified in the discharge standard of electroplating pollutants (GB 21900-2008).
Example 10:
accurately weighing 10g of lysozyme protein, dissolving the lysozyme protein into 100mL of water, adjusting the pH value of the solution to 4.0, and then placing the solution in a water bath at 105 ℃ for stirring and reacting for 6 hours to obtain the lysozyme protein amyloid fiber material with the diameter of about 3-5nm and the length of about 2-15 mu m. Subsequently, 2g FeCl was weighed3·6H2And (3) placing the O into 10mL of the protein fiber solution, carrying out vortex oscillation and dissolution, and adjusting the pH of the solution to 4.0 to obtain the functional protein ferric oxide composite material.
The prepared functional protein ferric oxide composite material is used as a catalyst, the temperature of the copper citrate sewage is controlled to be 15 ℃, the pH of the reaction solution is adjusted to be 2.0, the concentration of the copper citrate solution is 50mg/L, and 0.5mLH is added2O210mL of the functional protein ferric oxide composite material has the copper ion removal rate of 97 percent and the organic ligand mineralization rate of 80 percent, and the effluent is lower than the copper ion limit value (0.5mg/L) specified in the electroplating pollutant discharge standard (GB 21900-2008).
Claims (10)
1. The functional protein ferric oxide composite material is applied to oxidation complex breaking heavy metal.
2. The application method of the functional protein ferric oxide composite material in the oxidation complex-breaking complex-state heavy metal is characterized by comprising the following steps:
(1) preparing a functional protein ferric oxide composite material;
(2) controlling the temperature of water polluted by complex heavy metalsControlling the pH value to be 2.0-7.0 at 15-55 ℃, and adding H2O2And the functional protein ferric oxide composite material prepared in the step (1).
3. The method of claim 2, wherein the step (1) of preparing the functional protein iron oxide composite material comprises the steps of:
(a) weighing functional protein with the mass fraction of 2-10%, dissolving the functional protein in water, adjusting the pH value, and placing the functional protein in a water bath at the temperature of 85-105 ℃ to stir and react for 6-12 hours to obtain an amyloid fiber material;
(b) weighing ferric iron salt, putting into the amyloid fiber material obtained in the step (a), dissolving by vortex oscillation, and adjusting the pH value to obtain the functional protein ferric oxide composite material.
4. The method according to claim 3, wherein the functional protein in step (a) comprises lysozyme, bovine serum albumin or beta-lactoglobulin, the pH is adjusted to 2.0-4.0, and the amyloid fiber material has a diameter of 3-5nm and a length of 2-15 μm.
5. The use according to claim 3, wherein the mass ratio of the ferric salt to the amyloid fiber material in step (b) is 4-10: 1, and the pH is adjusted to 2.0-7.0.
6. The use of claim 3, wherein said ferric salt of step (b) comprises FeCl3.·6H2O、Fe2(SO4)3Or Fe (NO)3)3。
7. The method of claim 2, wherein the complexed heavy metal in step (2) comprises an organo-heavy metal complex of a heavy metal ion and an organic chelating ligand, preferably the heavy metal ion comprises copper, nickel, lead, preferably the organic chelating ligand comprises citric acid, oxalic acid, ethylenediaminetetraacetic acid.
8. The application method as claimed in claim 2, wherein the concentration of the heavy metal in the complexed state in the water polluted by the heavy metal in the complexed state in the step (2) is 1-50 mg/L, at least one competitive ion exists in the water polluted by the heavy metal in the complexed state, and the concentration of the competitive ion is 0-100 times of the concentration of the heavy metal in the complexed state.
9. The method of claim 8, wherein the competitive ions comprise anions, cations, natural organics, preferably wherein the anions comprise sulfate, chloride, nitrate, preferably wherein the cations comprise calcium, magnesium, sodium.
10. The method of claim 2, wherein H is the same as H in step (2)2O2Is 30% wt, H2O2The volume ratio of the functional protein iron oxide composite material to the functional protein iron oxide composite material is 1: 10-25.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040134857A1 (en) * | 1998-05-14 | 2004-07-15 | The Arizona Board Of Regents | Contaminant adsorption and oxidation via the fenton reaction |
| EP1674157A1 (en) * | 2004-12-22 | 2006-06-28 | Technische Universiteit Delft | Decomplexing metallic cations from metallo-organic compounds |
| AU2008322276A1 (en) * | 2007-11-12 | 2009-05-22 | Technion Research And Development Foundation Ltd. | Method for adsorption of phosphate contaminants from water solutions and its recovery |
| CN106495377A (en) * | 2016-11-16 | 2017-03-15 | 安徽工程大学 | A kind of processing method of complexation nickel waste water |
| CN106927547A (en) * | 2017-04-05 | 2017-07-07 | 同济大学 | A kind of method that magnetic iron-based material reduction contact break removes complex state heavy metal |
| CN207243638U (en) * | 2017-08-03 | 2018-04-17 | 苏州中晟环境修复股份有限公司 | Based on fenton methods processing Treatment of Industrial Park of Plating complexing sewage treatment equipment |
| CN109939643A (en) * | 2019-04-09 | 2019-06-28 | 西安工业大学 | α-Fe2O3Adulterate the preparation method and applications of charcoal |
| CN110342628A (en) * | 2019-06-13 | 2019-10-18 | 南京工业大学 | A kind of processing method that copper waste water is complexed |
| CN112675910A (en) * | 2021-01-11 | 2021-04-20 | 燕山大学 | Amyloid fiber ferric hydroxide heterogeneous Fenton catalyst and preparation method and application thereof |
| CN113562877A (en) * | 2021-07-26 | 2021-10-29 | 中南大学 | Treatment method of EDTA-Ni-containing wastewater |
-
2022
- 2022-01-18 CN CN202210057338.5A patent/CN114515566A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040134857A1 (en) * | 1998-05-14 | 2004-07-15 | The Arizona Board Of Regents | Contaminant adsorption and oxidation via the fenton reaction |
| EP1674157A1 (en) * | 2004-12-22 | 2006-06-28 | Technische Universiteit Delft | Decomplexing metallic cations from metallo-organic compounds |
| AU2008322276A1 (en) * | 2007-11-12 | 2009-05-22 | Technion Research And Development Foundation Ltd. | Method for adsorption of phosphate contaminants from water solutions and its recovery |
| CN106495377A (en) * | 2016-11-16 | 2017-03-15 | 安徽工程大学 | A kind of processing method of complexation nickel waste water |
| CN106927547A (en) * | 2017-04-05 | 2017-07-07 | 同济大学 | A kind of method that magnetic iron-based material reduction contact break removes complex state heavy metal |
| CN207243638U (en) * | 2017-08-03 | 2018-04-17 | 苏州中晟环境修复股份有限公司 | Based on fenton methods processing Treatment of Industrial Park of Plating complexing sewage treatment equipment |
| CN109939643A (en) * | 2019-04-09 | 2019-06-28 | 西安工业大学 | α-Fe2O3Adulterate the preparation method and applications of charcoal |
| CN110342628A (en) * | 2019-06-13 | 2019-10-18 | 南京工业大学 | A kind of processing method that copper waste water is complexed |
| CN112675910A (en) * | 2021-01-11 | 2021-04-20 | 燕山大学 | Amyloid fiber ferric hydroxide heterogeneous Fenton catalyst and preparation method and application thereof |
| CN113562877A (en) * | 2021-07-26 | 2021-10-29 | 中南大学 | Treatment method of EDTA-Ni-containing wastewater |
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