CN115624971A - Amino resin supported palladium nano catalytic material, preparation method and method for removing selenate in water by reduction - Google Patents
Amino resin supported palladium nano catalytic material, preparation method and method for removing selenate in water by reduction Download PDFInfo
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- CN115624971A CN115624971A CN202211212071.9A CN202211212071A CN115624971A CN 115624971 A CN115624971 A CN 115624971A CN 202211212071 A CN202211212071 A CN 202211212071A CN 115624971 A CN115624971 A CN 115624971A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000000463 material Substances 0.000 title claims abstract description 94
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 81
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229920003180 amino resin Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 230000002829 reductive effect Effects 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 21
- 239000012279 sodium borohydride Substances 0.000 claims description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- -1 selenate ions Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 239000011669 selenium Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052711 selenium Inorganic materials 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229940082569 selenite Drugs 0.000 description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/106—Selenium compounds
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Thermal Sciences (AREA)
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Abstract
The invention discloses an amino resin supported palladium nano catalytic material, a preparation method and a method for removing selenate in water by reduction thereof, belonging to the technical field of wastewater treatment. The nano catalytic material matrix is chloromethylated polystyrene-divinylbenzene copolymer (namely chlorine ball), and the nano catalytic material is obtained by further grafting reductive amino group and loading nano zero-valent palladium. The steps of the invention for treating wastewater comprise: (1) filtering the selenate-containing wastewater, and adjusting the pH of the filtrate; (2) Passing the filtrate through an adsorption tower filled with an amino resin palladium-loaded nano catalytic material to obtain a purified water body; (3) When reaching the leakage point, the nanometer catalytic material is eluted and regenerated for recycling. The method combines the electron-donating effect of the reducing functional group and the reducing capability of the nano metal palladium catalytic hydrogenation to remove the selenate in the water, effectively improves the environmental adaptability and selectivity of the material to the removal of the selenate, and ensures that the concentration of the selenium in the effluent is stable and meets the emission standard.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an amino resin supported palladium nano catalytic material, a preparation method and a method for removing selenate in water by reduction.
Background
Selenium element is usually present in the form of selenate [ Se (VI) ] and selenite [ Se (IV) ] in high valence soluble state in the environmental water body. Generally speaking, selenite is easy to form stable inner core complexation adsorption removal with various metal oxides/hydroxides, while selenate is removed in a weakly-combined outer core complexation mode, and the removal effect of selenite is seriously interfered by other common coexisting ions (chloride ions, sulfate radicals, phosphate radicals, carbonate radicals and the like) in the environmental water body, pH and other factors, so that selenite is a key and difficult point for treating the selenium-polluted water body at present.
The method for treating the water body polluted by selenate is various, and can be generally divided into a physical method, a chemical method and other methods, and mainly comprises an ion exchange method, an adsorption method, a coprecipitation method, a chemical reduction method, a biological method and the like. The ion exchange method/adsorption method has poor selectivity to selenate and the removal rate is greatly influenced by water quality. The coprecipitation method needs to add a large amount of chemical agents to remove selenate, so that the economic cost is high and the sludge yield is high. The chemical reduction method generally uses ferrous iron compounds or zero-valent iron particles to reduce selenate, but iron and iron compounds are easy to passivate, so that the application development of the technology is limited. The biological method has the advantages that the strain has high sensitivity to temperature and related water conservancy conditions, and the removal effect is not easy to control. At present, the hydrogenation catalytic reduction of selenate is a simple and efficient removal method, and can reduce the selenate to a low valence state at normal temperature and normal pressure for removal. For hydrogenation catalytic reduction reaction, a supported noble metal catalyst is often adopted for catalytic reduction, and the method can fix nano metal particles on the surface of an adsorbent, so that the problems of active component loss, particle agglomeration, metal dissolution and the like are effectively solved, and reduced selenate can be adsorbed on the surface of a material for subsequent recovery treatment, and the method has very wide research prospect and significance.
By grafting the reductive functional group on the traditional porous repairing material framework and loading the catalytic noble metal, the synergistic effect of the reductive functional group and the catalytic noble metal can be realized, and the removal effect of pollutants is enhanced. According to research results, the nano palladium particles in the amino resin supported palladium nano catalytic material can receive electrons supplied by reducing amino groups to realize the function of hydrogenation catalytic reduction of selenate. The method not only effectively solves the problem of metal dissolution in the process of reducing selenate, but also can be recycled, is slightly influenced by environmental factors, and has practical application value. At present, no relevant amino resin supported palladium nano catalytic material, preparation method and method for reducing and removing selenate in water are adopted through literature retrieval.
Disclosure of Invention
The invention provides an amino resin supported palladium nano catalytic material, a preparation method and a method for removing selenate in water by reduction thereof, aiming at the problems of poor selective adsorption, easy metal poisoning, metal dissolution and the like of the traditional material. The method can realize the catalytic reduction removal of selenate in the water body in a wider pH value range under the condition that high-concentration competitive ions (chloride ions, sulfate radicals, phosphate radicals, carbonate radicals, nitrate radicals and the like) exist. After the reaction is finished, desorption regeneration can be carried out by sequentially adopting NaOH alkali liquor and sodium borohydride solution, so that the nano catalytic material can be recycled.
The invention adopts the following specific technical scheme:
the nanometer catalytic material comprises a matrix of chloromethylated polystyrene-divinylbenzene copolymer spheres, wherein the crosslinking degree is 6-10%, the particle size is distributed between 0.3-0.9 mm, the pore size is distributed between 5-80 nm, and ethylenediamine is used for grafting and modifying the copolymer spheres and loading nanometer zero-valent palladium, so that the framework of the copolymer spheres is grafted with reductive amino groups and loads the nanometer zero-valent palladium.
The preparation method of the amino resin supported palladium nano catalytic material comprises the following steps:
1) Performing Soxhlet extraction on chloromethylated polystyrene-divinylbenzene copolymer (i.e. chlorine spheres) by using ethanol to obtain 8-10 h, removing chemical substances and impurities remained on the surface of the resin, and then soaking the resin in N, N-Dimethylformamide (DMF) to fully swell the resin;
2) Placing the swelled chlorine ball matrix in the step 1) in an ethylenediamine/ethanol mixed solution, and carrying out a grafting reaction under a hydrothermal condition; then, soxhlet extraction is carried out on the mixture by ethanol for 6 to 10 h, and residual chemical reagents on the surface of the resin and in the pore channels are washed away to obtain amino resin;
3) Adding the amino resin obtained in the step 2) into a mixed solution of a palladium source and ethanol, and soaking under a hydrothermal condition to obtain an amino resin palladium-loaded nano catalytic material precursor;
4) Dropwise adding a sodium borohydride solution into the precursor of the amino resin palladium-loaded nano catalytic material obtained in the step 3) for reaction, reducing palladium element into nano zero-valent palladium, and then drying in vacuum to obtain the amino resin palladium-loaded nano catalytic material.
Further, in the step 2), the feeding solid-liquid ratio of the chlorine ball to the mixed solution of the ethylenediamine and the ethanol is 1 g: 15-50 mL, the volume ratio of the ethylenediamine to the ethanol in the mixed solution of the ethylenediamine and the ethanol is 1: 1-3: 1, the hydrothermal reaction temperature is 50-80 ℃, and the reaction time is 18-30 h.
Further, in the step 3), the ratio of the mass of the amino resin to the volume of the palladium source and ethanol mixed solution is 1 g: 30-50 mL, and the ratio of the mass of the amino resin to the addition amount of the palladium source in the mixed solution is 1 g: 0.2-1.5 mmol, preferably 1 g: 0.7 mmol; the soaking temperature under hydrothermal condition is 50-80 deg.C, and the soaking time is 30-60 min.
Further, in the step 4), the mass fraction of the sodium borohydride solution is 2.0-4.0-wt%, the solid-to-liquid ratio of the catalytic material precursor to the sodium borohydride solution is 1:30-80, the unit g/mL of the solid-to-liquid ratio is obtained, the reaction time is 1-2 h, after the reaction is finished, the solid is filtered out and vacuum dried, and the temperature of vacuum drying is 30-70 ℃.
Further, the loading of palladium on the nano catalytic material is 2.0-14.0 wt%.
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following steps:
(1) Adjusting the pH value of the water body containing selenate, and filtering to obtain filtrate;
(2) Filling the amino resin palladium-loaded nano catalytic material in an adsorption tower, and then enabling the filtrate obtained in the step (1) to pass through the adsorption tower filled with the amino resin palladium-loaded nano catalytic material to enable the selenate-containing water body to be fully contacted with the nano catalytic material to obtain a treated water body;
(3) When the treated water body reaches a leakage point, stopping running, and eluting and regenerating the saturated and ineffective nano catalytic material by sequentially adopting NaOH alkaline solution and sodium borohydride solution; and (3) repeatedly using the regenerated nano catalytic material in the adsorption process in the step (2).
The amino resin palladium-loaded nano catalytic material adopted by the invention is obtained by grafting an amino group on a chloromethylated polystyrene-divinylbenzene copolymer (namely, chlorine ball) framework and then loading palladium nano particles. The palladium nano-particles have active chemical properties and good acid and alkali resistance, and meanwhile, the surfaces of the palladium nano-particles can catalyze water molecules to generate reduced hydrogen, so that the palladium nano-particles have good reducing capacity, selenate in water can be reduced to a low valence state and adsorbed on the surfaces of resins, and reducing amino groups play a role in providing electrons for the palladium nano-particles. Compared with the zero-valent metal reduction material reported in the prior art, the nano catalytic material has stronger environmental adaptability, can be recycled for many times, and realizes selenium resource recovery. Meanwhile, the technical problem that hydrogen needs to be introduced as an electron donor in the conventional metal palladium catalysis technology is successfully solved through the reductive amino electron donating effect, so that the metal palladium catalysis technology is further developed in practical application.
Further, in the step (1), the pH value of the water body is adjusted to 3.0-11.0; the mass concentration of selenate in the water body is 0.2-50.0 mg/L (calculated by Se), and other coexisting anions in the water body are less than 500 times of the mass concentration of selenate ions.
Further, in the step (2), the temperature range of the filtrate which passes through the amino resin supported palladium nano catalytic material is 5-45 ℃, and the filtrate water body passes through the adsorption tower at the flow rate which is less than or equal to 20 catalytic material bed volumes per hour.
Further, in the step (3), the leakage point is that the mass concentration of selenate in the effluent exceeds 10 mug/L (calculated by Se).
Further, in the step (3), the mass fraction of the NaOH alkali liquor is 1.0-5.0 wt%, the mass fraction of the sodium borohydride solution is 1.0-3.0 wt%, elution regeneration is carried out at 10-60 ℃ at the flow rate of 1-5 resin bed volumes per hour, and the use amounts of the NaOH alkali liquor and the sodium borohydride solution are 5-20 catalytic material bed volumes;
further, the steps (2) and (3) adopt a single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption operation mode.
Compared with the prior art, the invention has the following beneficial effects:
(1) The amino resin supported palladium nano catalytic material adopted by the method is simultaneously used as a catalytic reduction and adsorption material to selectively remove selenate in water, and tests show that when the pH value of the water is 3.0-11.0 and high-concentration chloride ions, sulfate ions, carbonate ions, phosphate ions and nitrate ions coexist, the concentration of the selenate in the effluent can be well reduced from 0.2-50.0 mg/L to below 10 mug/L (calculated by Se);
(2) The amino resin palladium-loaded nano catalytic material adopted by the method has simple preparation conditions and stable effect, can be eluted and regenerated by NaOH alkali liquor and sodium borohydride solution in sequence after saturated adsorption, and has good reusability;
(3) According to the method, the amino resin palladium-loaded nano catalytic material is adopted, and the hydrogenation catalysis removal of selenate in the water body can be realized in a mode that the reductive amino group is supplied to nano palladium electrons, so that the operation condition is simple and convenient, and the practicability is high;
(4) The method adopts the form of loading palladium nano particles on amino resin, effectively avoids the problems of secondary pollution caused by the release of metal salt into water and spontaneous agglomeration of nano particles, and improves the catalytic activity of the palladium nano particles to the maximum extent.
Detailed Description
The invention is further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
The amino resin supported palladium nano catalytic material related in the following examples is prepared by the following specific steps:
(1) Performing Soxhlet extraction on a chloromethylated polystyrene-divinylbenzene copolymer (namely chlorine spheres purchased from Ningbo optical resin Co., ltd., the degree of crosslinking is about 8%, the particle size is distributed between 0.3-0.9 mm, and the pore size is distributed between 5-80 nm) by using ethanol to obtain 8 h, removing chemical substances and impurities remained on the surface of the resin, and then soaking the resin in a N, N-Dimethylformamide (DMF) solution (> 99.9%) to obtain 12 h so as to fully swell the resin;
(2) Placing the swelled chloromethylated bead matrix in an ethylenediamine/ethanol mixed solution (the solid-liquid adding ratio of the chloromethylated bead matrix to the mixed solution is 1 g: 20 mL, and the volume ratio of ethylenediamine to ethanol is 2: 1), and carrying out a grafting reaction at the temperature of 65 ℃ under a hydrothermal condition of 24 h; then, soxhlet extraction is carried out on the resin by using ethanol to obtain 8 h, and residual chemical reagents on the surface of the resin and in the pore channels are washed away to obtain amino resin;
(3) Adding the obtained amino resin into a mixed solution of palladium chloride and ethanol (the solid-to-liquid ratio of the amino resin to the mixed solution is 1 g: 50 mL; the ratio of the mass of the amino resin to the addition amount of the palladium chloride in the mixed solution is 1 g: 0.7 mmol), soaking for 30 min under the hydrothermal condition of 80 ℃ and evaporating ethanol to obtain an amino resin palladium-loaded nano catalytic material precursor;
(4) Dropwise adding 3.0 wt% sodium borohydride solution into the amino resin palladium-loaded nano catalytic material precursor for reaction, wherein the volume ratio of the mass of the nano catalytic material precursor to the sodium borohydride solution is 1 g: 50 mL, filtering, and carrying out vacuum drying on the filtered solid at 50 ℃ to obtain the amino resin palladium-loaded nano catalytic material.
Example 1
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following specific steps:
(1) Adjusting the pH value of the water body containing the selenate to 6.0, filtering to obtain filtrate, and putting 0.1 g amino resin palladium-loaded nano catalytic material into the solution; wherein the selenate has a concentration of 10.0 mg/L (Se) and a solution volume of 50 mL, and is placed in a constant temperature shaking table and shaken at 25 deg.C and 180 rpm for 48 h.
(2) After the reaction reaches the equilibrium, the solution supernatant is taken to determine the concentration of selenate, and the result is that the removal rate of selenate is about 99 percent (calculated by Se) after the reaction is balanced;
(3) Filtering out the reacted amino resin palladium-loaded nano catalytic material, adding 50 mL of 4.0 wt% NaOH alkali liquor, oscillating 24 h in a constant temperature shaking table at 25 ℃ and 180 rpm for desorption, then filtering out the NaOH alkali liquor, washing with pure water until the pH is neutral, adding 50 mL of 1.0 wt% sodium borohydride solution for catalytic material regeneration, and reacting for 20 min;
(4) And (4) repeating the steps (1), (2) and (3) to obtain the experimental result, wherein the removal rates of the selenate for the second time to the fifth time of repeated application of the catalytic material are respectively 99%,98%,98% and 97%. Therefore, the amino resin supported palladium nano catalytic material is determined to have good regeneration performance, and tests show that the regenerated nano catalytic material can be repeatedly utilized.
Example 2
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: and (2) controlling the temperature of the constant-temperature shaking table in the step (1) to be 5 +/-2 ℃, wherein the removal rate of the selenate is about 95%.
Example 3
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: controlling the temperature of the constant-temperature shaking table in the step (1) to be 45 +/-2 ℃, ensuring that the removal rate of selenate is more than 99 percent, and detecting that the content of the adsorbed solution is less than 10 mu g/L (calculated by Se).
Example 4
The same method as that of example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: and (2) in the step (1), the pH value of the water body containing the selenate is adjusted to 3.0, the removal rate of selenate is more than 99%, and the adsorbed solution is lower than 10 microgram/L (calculated by Se) through detection.
Example 5
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: in the step (1), the pH value of the water body containing selenate is adjusted to 11.0, and the removal rate of selenate is about 99%.
Example 6
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: setting the initial concentration of selenate in the step (1) to be 5.0 mg/L (calculated by Se), wherein the removal rate of selenate is more than 99%, and the concentration of selenate in the adsorbed solution is detected to be less than 10 mug/L (calculated by Se).
Example 8
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: step (1) was performed by adding 50 mmol/L Cl - (the cation combined with the anion is Na + As in the other examples), the removal rate of selenate was about 99%.
Example 9
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: adding 50 mmol/L NO in the step (1) 3 - The removal rate of selenate is about 99%.
Example 10
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: adding 50 mmol/L SO in the step (1) 4 2- The removal rate of selenate is about 99%.
Example 11
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: adding 50 mmol/L CO into the step (1) 3 2- The removal rate of selenate is about 99%.
Example 12
The same method as the example 1 is adopted to reduce and remove selenate in the water body, and the differences are that: adding 50 mmol/L PO into the step (1) 4 3- The removal rate of selenate is about 99%.
Example 13
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following specific steps:
(1) Adjusting the pH value of the selenate-containing water body (Se (VI) with the concentration of 0.2 mg/L) to 6.0, and filtering to obtain filtrate;
(2) 50 mL (about 25 g) amino resin supported palladium nano-catalysis material is loaded into a jacketed glass adsorption column (phi 32X 360 mm), the filtrate obtained in the step (1) is passed through the adsorption column filled with a nano-catalysis material bed layer at 25 +/-5 ℃ and the flow rate of 10 BV/h, the treatment capacity is about 1200 BV, and the concentration of the effluent Se (VI) is as low as below 10 mug/L;
(3) When reaching the leakage point (the concentration of Se (VI) in the effluent exceeds 10 mu g/L), the operation is stopped, 500 mL of 4.0 wt% NaOH alkali liquor and 500 mL of 1.0 wt% sodium borohydride solution are sequentially used for desorption and regeneration through the resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 5 BV/h, and the total regeneration rate of the nano catalytic material is more than 95%.
(4) The experimental results obtained by repeating steps (1), (2) and (3) were that the throughput of the second adsorption process (i.e., repeated use of the catalyst material) was approximately 1160 BV, the throughput of the third adsorption process was approximately 1158 BV and the throughput of the fourth adsorption process was approximately 1150 BV.
Example 14
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following specific steps:
(1) Adjusting the concentration of selenate-containing water (Se (VI) to 0.2 mg/L and Cl - 、SO 4 2- 、NO 3 - 、PO 4 3- And SiO 3 2- The concentration of (A) is 100.0 mg/L,100.0 mg/L,20.0 mg/L,10.0 mg/L and 5.0 mg/L respectively) the pH value is 6.0, and filtering is carried out to obtain filtrate;
(2) 50 mL (about 25 g) amino resin supported palladium nano-catalyst material is loaded into a jacketed glass adsorption column (phi 32X 360 mm), filtrate obtained in the step (1) is passed through a bed adsorption column filled with nano-catalyst material at 25 +/-5 ℃ and the flow rate of 10 BV/h, the treatment capacity is about 1170 BV, and the concentration of effluent Se (VI) is as low as below 10 mug/L;
(3) When reaching the leakage point (the concentration of Se (VI) in the effluent exceeds 10 mu g/L), the operation is stopped, 500 mL of 4.0 wt% NaOH alkali liquor and 500 mL of 1.0 wt% sodium borohydride solution are sequentially used for desorption and regeneration through the resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 5 BV/h, and the total regeneration rate of the nano catalytic material is more than 95%.
(4) The experimental results of repeating steps (1), (2) and (3) resulted in a secondary adsorption process throughput of about 1150 BV, a tertiary adsorption process throughput of about 1140 BV and a quartic adsorption process throughput of about 1140 BV.
Example 15
The same method as that of example 14 is adopted to carry out reduction removal of selenate in the water body, and the difference is that: in the step (2), the temperature of the filtrate passing through a bed layer filled with the amino resin supported palladium nano catalytic material is controlled to be 5 +/-2 ℃, the treatment capacity is about 1190 BV, and the concentration of the effluent Se (VI) is lower than 10 mu g/L.
Example 16
The same method as that of example 14 is adopted to carry out reduction removal of selenate in the water body, and the difference is that: in the step (2), the temperature of the filtrate passing through a bed layer filled with the amino resin supported palladium nano catalytic material is controlled to be 45 +/-2 ℃, the treatment capacity is about 1220 BV, and the concentration of the effluent Se (VI) is lower than 10 mu g/L.
Example 17
The same method as that of example 14 is adopted to carry out reduction removal of selenate in the water body, and the difference is that: in the step (1), the pH value of the selenate-containing water body is adjusted to 3.0, the adsorption effect is improved, the treatment capacity is about 1250 BV, and the concentration of the effluent Se (VI) is lower than 10 mu g/L.
Example 18
The same method as that of example 14 is adopted to carry out reduction removal of selenate in the water body, and the difference is that: in the step (1), the pH value of the water body containing the selenate is adjusted to 9.0, the adsorption effect is reduced, the treatment capacity is about 1130 BV, and the concentration of the effluent Se (VI) is lower than 10 mu g/L.
Example 19
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following specific steps:
(1) Adjusting the concentration of selenate-containing water (Se (VI) to 10.0 mg/L and Cl - 、SO 4 2- 、NO 3 - 、PO 4 3- And SiO 3 2- Respectively 200.0 mg/L,200.0 mg/L,50.0 mg/L,20.0 mg/L and 5.0 mg/L) pH value of 6.0, filtering to obtain filtrate;
(2) Loading 200 mL (about 100 g) amino resin supported palladium nano-catalytic material into a jacketed glass adsorption column (phi 32X 360 mm), passing the filtrate obtained in step (1) through the adsorption column filled with a nano-catalytic material bed at 25 +/-5 ℃ and at a flow rate of 10 BV/h, wherein the treatment capacity is about 850 BV, and the effluent Se (VI) concentration is lower than 10 mug/L;
(3) When reaching the leakage point (the concentration of Se (VI) in the effluent exceeds 10 mu g/L), the operation is stopped, 2000 mL of 4.0 wt% NaOH alkali liquor and 2000 mL of 1.0 wt% sodium borohydride solution are sequentially used for desorption and regeneration through the resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 5 BV/h, and the total regeneration rate of the nano catalytic material is more than 90%.
(4) The experimental results of repeating steps (1), (2) and (3) resulted in a secondary adsorption process throughput of approximately 795 BV, a tertiary adsorption process throughput of approximately 790 BV and a quartic adsorption process throughput of approximately 780 BV.
Example 20
A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material comprises the following specific steps:
(1) Adjusting the concentration of selenate-containing water (Se (VI) to 50.0 mg/L and Cl - 、SO 4 2- 、NO 3 - 、PO 4 3- And SiO 3 2- The concentration of (A) is 200.0 mg/L,200.0 mg/L,50.0 mg/L,20.0 mg/L and 5.0 mg/L respectively) the pH value is 6.0, and filtering is carried out to obtain filtrate;
(2) 500 mL (about 250 g) amino resin supported palladium nano-catalytic material is loaded into a jacketed glass adsorption column (phi 32X 360 mm), filtrate obtained in step (1) is passed through the adsorption column filled with nano-catalytic material bed layer at 25 +/-5 ℃ and flow rate of 10 BV/h, treatment capacity is about 645 BV, and effluent Se (VI) concentration is lower than 10 mug/L;
(3) When reaching the leakage point (the concentration of Se (VI) in the effluent exceeds 10 mu g/L), the operation is stopped, 5000 mL of 4.0 wt% NaOH alkali liquor and 5000 mL of 1.0 wt% sodium borohydride solution are sequentially used for desorption and regeneration through the resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 5 BV/h, and the total regeneration rate of the nano catalytic material is more than 95%.
(4) Repeating steps (1), (2) and (3) resulted in the experimental results of a secondary adsorption process throughput of about 630 BV, a tertiary adsorption process throughput of about 630 BV and a quartic adsorption process throughput of about 627 BV.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. An amino resin palladium-loaded nano catalytic material is characterized in that a matrix of the nano catalytic material is a chloromethylated polystyrene-divinylbenzene copolymer sphere, the crosslinking degree is 6-10%, the particle size is distributed between 0.3-0.9 mm, the pore size is distributed between 5-80 nm, the copolymer sphere is grafted and modified by ethylenediamine, nano zero-valent palladium is loaded, and the framework of the copolymer sphere is grafted with reductive amino groups and loaded with nano zero-valent palladium.
2. The amino resin supported palladium nanocatalysis material as recited in claim 1, wherein the loading of palladium on the nanocatalysis material is 2.0-14.0 wt%.
3. The preparation method of the amino resin supported palladium nano-catalytic material as claimed in claim 1, characterized by comprising the following steps:
1) Performing Soxhlet extraction on chloromethylated polystyrene-divinylbenzene copolymer (i.e. chlorine spheres) by using ethanol to obtain 8-10 h, removing chemical substances and impurities remained on the surface of the resin, and then soaking the resin in N, N-Dimethylformamide (DMF) to fully swell the resin;
2) Placing the swelled chlorine ball matrix in the step 1) in an ethylenediamine/ethanol mixed solution, and carrying out a grafting reaction under a hydrothermal condition; then, soxhlet extraction is carried out on the mixture by ethanol for 6 to 10 h, and residual chemical reagents on the surface of the resin and in the pore channels are washed away to obtain amino resin;
3) Adding the amino resin obtained in the step 2) into a mixed solution of a palladium source and ethanol, and soaking under a hydrothermal condition to obtain an amino resin palladium-loaded nano catalytic material precursor;
4) Dropwise adding a sodium borohydride solution into the precursor of the amino resin palladium-loaded nano catalytic material obtained in the step 3) for reaction, reducing palladium element into nano zero-valent palladium, and then drying in vacuum to obtain the amino resin palladium-loaded nano catalytic material.
4. The preparation method of the amino resin supported palladium nano-catalytic material as claimed in claim 3, wherein in the step 2), the feeding solid-liquid ratio of the chlorine spheres to the ethylenediamine/ethanol mixed solution is 1 g: 15-50 mL, the volume ratio of ethylenediamine to ethanol in the ethylenediamine/ethanol mixed solution is 1: 1-3: 1, the hydrothermal reaction temperature is 50-80 ℃, and the reaction time is 18-30 h.
5. The preparation method of the amino resin supported palladium nano-catalytic material according to claim 3, wherein in the step 3), the ratio of the mass of the amino resin to the volume of the palladium source and ethanol mixed solution is 1 g: 30-50 mL, and the ratio of the mass of the amino resin to the added amount of the palladium source in the mixed solution is 1 g: 0.2-1.5 mmol, preferably 1 g: 0.7 mmol; the soaking temperature under hydrothermal condition is 50-80 deg.C, and the soaking time is 30-60 min.
6. The preparation method of the amino resin supported palladium nano-catalytic material as claimed in claim 3, wherein in the step 4), the mass fraction of the sodium borohydride solution is 2.0-4.0 zxft 3238%, the solid-to-liquid ratio of the catalytic material precursor to the sodium borohydride solution is 1-80, the unit g/mL of the solid-to-liquid ratio is 1-2 h, the solid is filtered out after the reaction is finished and is dried in vacuum, and the temperature of the vacuum drying is 30-70 ℃.
7. A method for removing selenate in water by reduction of an amino resin supported palladium nano catalytic material is characterized by comprising the following steps:
(1) Adjusting the pH value of the water body containing selenate, and filtering to obtain filtrate;
(2) Filling the amino resin palladium-loaded nano catalytic material in an adsorption tower, and then enabling the filtrate obtained in the step (1) to pass through the adsorption tower filled with the amino resin palladium-loaded nano catalytic material to enable the selenate-containing water body to be fully contacted with the nano catalytic material to obtain a treated water body;
(3) When the treated water body reaches a leakage point, stopping running, and eluting and regenerating the saturated and failed nano catalytic material by sequentially adopting NaOH alkali liquor and sodium borohydride solution; and (3) repeatedly using the regenerated nano catalytic material in the adsorption process in the step (2).
8. The method for removing selenate in water by reduction of the nano catalytic material of palladium carried on amino resin as claimed in claim 7, wherein in the step (1), the pH value of the water body is adjusted to 3.0-11.0; the mass concentration of selenate in the water body is 0.2-50.0 mg/L (calculated by Se), and other coexisting anions in the water body are less than 500 times of the mass concentration of selenate ions.
9. The method for removing selenate in water by reduction of the amino resin supported palladium nano catalytic material as claimed in claim 7, wherein in the step (2), the treatment temperature of the filtrate passing through the amino resin supported palladium nano catalytic material is in the range of 5-45 ℃, and the filtrate water body passes through the adsorption tower at the flow rate of less than or equal to 20 catalytic material bed volumes per hour; in the step (3), the leakage point is that the mass concentration of selenate in the effluent exceeds 10 mug/L (calculated by Se).
10. The method for removing selenate in water by reduction of the amino resin supported palladium nano catalytic material as claimed in claim 7, wherein in the step (3), the mass fraction of the NaOH alkali solution is 1.0-5.0 wt%, the mass fraction of the sodium borohydride solution is 1.0-3.0 wt%, the elution regeneration is carried out at 10-60 ℃ and at the flow rate of 1-5 resin bed volumes per hour, and the dosages of the NaOH alkali solution and the sodium borohydride solution are 5-20 catalytic material bed volumes;
and (3) adopting a single-tower adsorption-desorption or multi-tower series-connection adsorption-single-tower desorption operation mode.
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| JP2016190221A (en) * | 2015-03-31 | 2016-11-10 | 国立大学法人九州大学 | Selenate reduction catalyst, production method of selenate reduction catalyst and reduction method of selenate solution |
| CN112774710A (en) * | 2020-12-18 | 2021-05-11 | 南京大学 | Method for reducing selenite through liquid-phase catalytic hydrogenation |
| CN113233536A (en) * | 2021-03-31 | 2021-08-10 | 浙江工业大学 | Method for directionally reducing nitrite in water body by using ethylenediamine resin-based zero-valent palladium nano composite material |
| CN115041152A (en) * | 2022-07-01 | 2022-09-13 | 浙江工业大学 | Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate radical in water |
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| JP2016190221A (en) * | 2015-03-31 | 2016-11-10 | 国立大学法人九州大学 | Selenate reduction catalyst, production method of selenate reduction catalyst and reduction method of selenate solution |
| CN112774710A (en) * | 2020-12-18 | 2021-05-11 | 南京大学 | Method for reducing selenite through liquid-phase catalytic hydrogenation |
| CN113233536A (en) * | 2021-03-31 | 2021-08-10 | 浙江工业大学 | Method for directionally reducing nitrite in water body by using ethylenediamine resin-based zero-valent palladium nano composite material |
| CN115041152A (en) * | 2022-07-01 | 2022-09-13 | 浙江工业大学 | Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate radical in water |
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