CN109569725A - A kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst - Google Patents
A kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst Download PDFInfo
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- CN109569725A CN109569725A CN201811397504.6A CN201811397504A CN109569725A CN 109569725 A CN109569725 A CN 109569725A CN 201811397504 A CN201811397504 A CN 201811397504A CN 109569725 A CN109569725 A CN 109569725A
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- iron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000005389 magnetism Effects 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 87
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920001661 Chitosan Polymers 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000012692 Fe precursor Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000007605 air drying Methods 0.000 claims description 11
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical group O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 38
- 239000000975 dye Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004737 colorimetric analysis Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- -1 metals ion Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PEAGNRWWSMMRPZ-UHFFFAOYSA-L woodstain scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 PEAGNRWWSMMRPZ-UHFFFAOYSA-L 0.000 description 2
- NXPARLMCOXVMQH-UHFFFAOYSA-L C(C)(=O)[O-].[Cu+2].C(C)(=O)O.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Cu+2].C(C)(=O)O.C(C)(=O)[O-] NXPARLMCOXVMQH-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N Chloride-Acetic acid Natural products CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 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 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKPHXALLZGIJBL-UHFFFAOYSA-K chromium(3+);hydron;3-oxido-4-[(2-oxidonaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [H+].[H+].[H+].[Cr+3].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3[O-])=C([O-])C=C(S([O-])(=O)=O)C2=C1.C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3[O-])=C([O-])C=C(S([O-])(=O)=O)C2=C1 RKPHXALLZGIJBL-UHFFFAOYSA-K 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods of one-step method preparation magnetism Cu (I) microspherical catalyst.This method comprises: chitosan, divalent copper source, divalent source of iron are mixed with chitosan-copper-iron precursor solution, then the precursor solution is instilled in strong base solution and forms microballoon, solidified, taken out microballoon and be washed to neutrality, be crosslinked, wash, it is dry.This method is simple, low in cost, and the stability and catalyzing hydrogen peroxide degradation property of magnetic Cu (I) microspherical catalyst being prepared are higher than general copper and iron type Fenton catalyst.
Description
Technical field
The invention belongs to the preparation field of copper and iron bimetallic oxide, in particular to a kind of one-step method preparation magnetism Cu (I)
The method of microspherical catalyst.
Background technique
Compared with traditional monometallic ferrum-based catalyst, copper and iron bimetallic oxide can more efficiently activate peroxidating
The oxidants such as hydrogen, persulfate generate strong oxidizing property active material.Importantly, copper and iron bimetallic oxide is in neutrallty condition
Under still be able to keep higher catalytic activity, significantly widened the pH scope of application of type Fenton catalyst.However, such catalysis
Agent is mostly obtained using hydro-thermal method or high-temperature roasting method at present, and separates more difficulty after powdered catalyst use with water body,
Still have greatly improved space in terms of preparation method and separating property.
Chitosan is a kind of polysaccharide product by chitin after deacetylation, has stronger plasticity and stability,
And it is environmental-friendly, it is a kind of good catalyst carrier.Meanwhile there is-OH abundant and-NH in chitosan molecule2Side group is put down
The structure of Fu Jian can occur coordination with various metals ion and combine, and be not only able to as the formation of catalyst crystal seed
There is provided nucleation site, moreover it is possible to pass through the formation of confinement acting regulatory photocatalyst crystals.This two big advantage of chitosan material is melted
It closes, method easy to use prepares the chitosan particle of supported copper iron catalyst, can be obviously improved copper and iron bimetallic catalyst
Separating property and preparation efficiency.Many scholars research in recent years with Fe3O4The chitosan magnetic being prepared for magnetisable material is micro-
Ball, as adsorbent go water removal in pollutant see it is more.(Sun Yuexin, Wang Zhengping, Wang Hong wait a kind of magnetic crust of poly- to Sun Yuexin etc.
Application of the sugared microballoon in absorption trifluoroacetic acid: CN105536721A [P] .2016.) use lotion suspension polymerization with Fe3O4For magnetic
Property the chitosan magnetic micro-sphere that is prepared of substance be used to adsorb the trifluoroacetic acid radical ion in waste water, adsorption time is no less than
10h adsorbs the pH value 2.5~3.5 of environment.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of sides of one-step method preparation magnetism Cu (I) microspherical catalyst
Method, to solve in the prior art with Fe3O4The chitosan magnetic micro-sphere service efficiency being prepared for magnetisable material and its use
In the process the problem of the limitation of environmental factor.
A kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst of the invention, comprising:
Chitosan is dissolved in solvent, divalent copper source solution is added, stirring is added divalent source of iron solution, continues to stir, obtain
To chitosan-copper-iron precursor solution, which is added in strong base solution and forms microballoon, solidified, takes out microballoon water
It is washed till neutrality, is crosslinked, is washed, it is dry, magnetic Cu (I) microspherical catalyst is obtained, wherein mole of divalent copper source and divalent source of iron
Than for 1:1.8-5, the mass ratio of chitosan and divalent copper source is 1:0.5~1:2, and the ratio of chitosan and solvent is 10~50g:
1L。
The chitosan average molecular weight is 80~1,200,000, and deacetylation is 85~95%.
The solvent is acetic acid.
The divalent copper source is copper acetate dihydrate；Divalent source of iron is Iron dichloride tetrahydrate.
The solvent of the divalent copper source solution and divalent source of iron solution is acetic acid.
Divalent copper source molar concentration is about 0.05-0.1mol/L in the precursor solution, and divalent source of iron molar concentration is
0.1-0.3mol/L。
The stirring and the temperature for continuing to stir are room temperature, and the time is 60~120min.
The described presoma, which is added in strong base solution, to be added using syringe needle, and the diameter of syringe needle is 0.5 μm.
The speed that the described presoma is added in strong base solution is 1.0~2.5mL/min.
The strong base solution is the sodium hydroxide solution of 2~4mol/L.
The curing time be 12~for 24 hours.
The crosslinking are as follows: be crosslinked 12-24h at room temperature using crosslinking agent glutaraldehyde；Drying means is natural air drying.
A kind of magnetic Cu (I) microballoon of the method preparation of one-step method preparation magnetism Cu (I) microspherical catalyst of the invention is urged
Agent.
A kind of magnetic Cu (I) microballoon of the method preparation of one-step method preparation magnetism Cu (I) microspherical catalyst of the invention is urged
The application of agent.Including being used for sewage treatment.
The present invention selects Cu (II) and Fe (II) to be used as copper source and source of iron, and chitosan is added and is prepared as chitosan-copper-iron height
Molecular complex presoma, Fe (II) can restore the Cu (I) of Cu (II) to low price, and then partial oxidation is Fe (III) to Fe (II)
And it generates magnetic.Meanwhile also proper energy, the one-step method of the characteristics of not dissolving in alkali using chitosan and reproducibility carbohydrate prepare magnetic
After property microspherical catalyst, active component Cu (I) can maintain low price state in general environment.Not only significantly simplify tradition
The preparation method of iron copper type Fenton catalyst also significantly improves the catalyst separating property of such catalysis material.
The present invention considers the solubility of chitosan, and the concentration of chitosan controls between 10~50g/L in preparation process；
Due to chitosan monomer in chitosan-copper-iron complex and copper ion (Cu2+), iron ion (Fe2+) can be carried out with certain proportion
Coordination, therefore copper acetate-acetic acid solution concentration is 0.05-0.1mol/L in precursor solution, frerrous chloride-acetic acid solution is dense
Degree is 0.1-0.3mol/L, and the solubility of copper acetate and frerrous chloride all cannot be too high, and when copper acetate excessive concentration is easy to poly- with shell
Sugar forms colloid, and manufactured microspherical catalyst is too crisp frangible when frerrous chloride excessive concentration.Meanwhile copper acetate and frerrous chloride
Concentration can not be too low, Cu when concentration is too low2+With Fe2+Between redox reaction cannot go on smoothly, can also make major part
Chitosan cannot be with copper ion (Cu2+), iron ion (Fe2+) be coordinated, influence magnetic Cu (I) microspherical catalyst molding and
Catalytic activity.
The present invention is due to having-OH abundant and-NH in chitosan molecule2Side group, the structure of equatorial bond can be with
Copper, iron form chitosan-copper-iron complex, are not only able to provide nucleation site for the formation of catalyst crystal seed, moreover it is possible to pass through limit
The formation of domain acting regulatory photocatalyst crystals.
The present invention does not dissolve in alkali since chitosan is soluble in acid, and chitosan-copper-iron complex presoma is instilled hydrogen-oxygen
After changing sodium solution, more uniform magnetism Cu (I) microspherical catalyst of size can be formed by the effect of surface tension.
For the present invention since chitosan belongs to reproducibility carbohydrate, it is magnetic micro- that reducing property can make one-step method prepare
After sphere catalyst, active component Cu (I) can maintain low price state to improve catalytic activity in general environment.
Magnetic Cu (I) microspherical catalyst that the present invention is prepared is easy to operate when handling Organic Pollutants In Water,
Catalyst need to be only added directly in contaminant water, hydrogenperoxide steam generator is added, organic pollutant is completed in stirring at room temperature
Degradation, the amount that magnetism Cu (I) microspherical catalyst is added can be adjusted according to the concentration of practical pollutant.
Beneficial effect
(1) present invention completes at room temperature, nontoxic, harmless, does not generate secondary pollution；
(2) present invention is simple, low in cost, the stability of magnetic Cu (I) microspherical catalyst being prepared and is catalyzed
Hydrogen oxide degradation property is higher than general copper and iron type Fenton catalyst；
(3) magnetic Cu (I) microspherical catalyst that the present invention is prepared can be used for multiple types organic pollutant in water
Removal, including dyestuff, pesticide, antibiotic etc., and it is easy to operation；
(4) magnetic Cu (I) microspherical catalyst that is prepared of the present invention has magnetic well, can by externally-applied magnetic field into
Row Magneto separate；
(5) magnetic Cu (I) microspherical catalyst that the present invention is prepared, which is recycled for multiple times, can keep higher removal to imitate
Fruit.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph (edge cross-section) of magnetism Cu (I) microspherical catalyst in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (inner section) of magnetism Cu (I) microspherical catalyst in embodiment 1.
Fig. 3 is the outside drawing of magnetism Cu (I) microspherical catalyst in embodiment 1.
Fig. 4 is magnetism Cu (I) microspherical catalyst and Cu in embodiment 12O (inorganic compound crystal structural database #74-
No. 1230 substances) and Fe3O4The X-ray diffraction (XRD) of (inorganic compound crystal structural database #75-0033 substance)
Figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment agents useful for same is that analysis is pure, is used without further purification after purchase.
Embodiment 1
α-Chitosan powder 2g is weighed, is slowly added in the 250mL beaker equipped with 100mL acetic acid (mass fraction 1%),
It is stirred at room temperature, chitosan is completely dissolved after about 2h.Because copper acetate solubility is lower, therefore by 1.9963g copper acetate dihydrate
It is added in the beaker of 50mL acetic acid (mass fraction 1%), carries out ultrasonic dissolution, be slowly dropped into chitosan solution after being completely dissolved
In, 1h is stirred at room temperature.4.9703g Iron dichloride tetrahydrate is dissolved in the beaker of 10mL acetic acid (mass fraction 1%), it is complete
It is slowly dropped into after fully dissolved in chitosan copper solution, stirs 1h at room temperature, obtain chitosan-copper-iron complex precursor solution
(chloride containing ferrous iron 0.16mol/L contains copper acetate 0.06mol/L).It is with the speed of 1.0mL/min that presoma is molten using syringe pump
It is to form bead in 2mol/L sodium hydroxide solution that drop, which enters concentration, solidifies 12h.It takes out bead distillation and is washed to neutrality, set
In 95% ethanol solution of the 500mL containing 5% glutaraldehyde, cross-linking reaction 12h is carried out at room temperature.It takes out bead and uses ultrapure water
Cleaning several times, successively impregnates 15min in 10%, 50%, 100% ethyl alcohol, is placed in 100% ethyl alcohol and saves, and prepares
Magnetism Cu (I) microspherical catalyst is obtained, the used time is drawn off natural air drying.
Fig. 1 shows: magnetic (I) the microspherical catalyst edge Cu duct is wider, is suitble to pollutant from water phase into catalyst
Portion's migration；Internal gutter is smaller, so that surface area of catalytic material is larger, is suitble to the efficient degradation of pollutant.
Fig. 2 shows: being made of inside magnetic Cu (I) microspherical catalyst molecule, gap is uniform, is suitble to the height of pollutant
Effect degradation.
Fig. 3 shows: magnetic Cu (I) microspherical catalyst is brown spherical, and size and form is uniform.
Fig. 4 shows: according to database comparison result it is found that magnetism Cu (I) microspherical catalyst main component is cuprous oxide
(Cu2) and ferroso-ferric oxide (Fe O3O4)。
Magnetic Cu (I) microspherical catalyst that the present embodiment is obtained carries out sewage treatment:
Test one: selecting dyestuff contaminant acid red 73, acid blue 193 respectively, and antibiotic pollutant tetracycline, pesticide are dirty
Object Atrazine, chemical industry intermediate common parachlorophenol are contaminated as target contaminant, and volume is 100mL, and concentration is 20mg/
L.Catalysis material 0.2g manufactured in the present embodiment is added, the H that 0.2mL concentration is 30wt% is added dropwise2O2Solution, at room temperature
It stirs (500r/min) and reacts 30min, separate microballoon using magnet, the determination of aqueous solution pollutant concentration that takes that treated.Dyestuff
Pollutant concentration uses colorimetric method for determining, and tetracycline, Atrazine, parachlorophenol isoconcentration are surveyed using high performance liquid chromatography
It is fixed.Removal effect is as shown in table 1, and magnetic Cu (I) microspherical catalyst prepared using appropriate copper, iron ratio is to a variety of organic contaminations
The removal efficiency of object can reach 90% or more.
Table 1
Test two: taking magnetism Cu (I) microspherical catalyst 0.2g manufactured in the present embodiment, and being added separately to pH is 4,6,8,10
Volume be 100mL, concentration be 20mg/L AR73 dyestuff in, be added dropwise concentration be 30wt% 0.2mL H2O2Solution, in room
(500r/min) is stirred under the conditions of temperature and reacts 30min, is separated microballoon with magnet, is used colorimetric method for determining concentration.Removal effect is such as
Shown in table 2, magnetic Cu (I) microspherical catalyst prepared using appropriate copper, iron ratio is in acidity, faintly acid, alkalescent, alkaline item
Under part, 83.9% or more can reach to the removal rate of AR73 dyestuff.
Table 2
Test three: taking magnetism Cu (I) microspherical catalyst 0.2g manufactured in the present embodiment, and being added separately to volume is 100mL,
Concentration is in the AR73 dye solution of 20mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L, and dropwise addition concentration is 30wt%
0.2mL H2O2Solution stirs (500r/min) at room temperature and reacts 30min, separates microballoon with magnet, use colorimetric
Method measures concentration.Removal effect is as shown in table 3, magnetic Cu (I) microspherical catalyst prepared using appropriate copper, iron ratio,
It is wider to AR73 dye strength adaptation range, it can reach 85% or more removal rate between 20~200mg/L.
Table 3
Embodiment 2
The quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 is changed to 3.4792g, remaining with 1 phase of embodiment
Together, magnetic Cu (I) microspherical catalyst is prepared, the used time is drawn off natural air drying.
Embodiment 3
The quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 is changed to 3.9762g, remaining with 1 phase of embodiment
Together, magnetic Cu (I) microspherical catalyst is prepared, the used time is drawn off natural air drying.
Embodiment 4
It changes the quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 into 5.4673g, copper acetate is added in acetic acid,
For ultrasonic dissolution about 40min to blue solution, remaining is same as Example 1, obtains Cu (I)-Fe3O4@chitosan microball, used time
It is drawn off natural air drying.
Embodiment 5
The quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 is changed to 8.2838g, remaining with 1 phase of embodiment
Together, magnetic Cu (I) microspherical catalyst is prepared, the used time is drawn off natural air drying.
Comparative example 1
Iron dichloride tetrahydrate part related in embodiment 1 is deleted, remaining is constant, prepares the catalysis of Cu (II) microballoon
Agent, used time are drawn off natural air drying.
Comparative example 2
To be deleted related copper acetate part in embodiment 1, remaining is constant, prepare iron microspherical catalyst, the used time by its
Take out natural air drying.
Test four: embodiment 1, comparative example the 1-2 catalyst being prepared are tested, specifically: it is taken respectively by reality
Catalysis material 0.2g prepared by example 1, comparative example 1 and comparative example 2 is applied, the acidity that volume is 100mL, concentration is 20mg/L is added to
In red (C.I.Acid Red 73, hereinafter abbreviated as AR73) dyestuff, the concentration that 0.2mL is added dropwise is the H of 30wt%2O2Solution,
(500r/min) is stirred under room temperature, reacts 30min, microballoon is separated using magnet, with the concentration of colorimetric method for determining dyestuff.It goes
Division result is as shown in table 4, while magnetic Cu (I) microballoon for selecting copper acetate and frerrous chloride to prepare as source of iron and copper source
Catalyst has preferably catalytic performance compared with the microspherical catalyst of Single Iron component and single copper component, and catalytic activity is greater than
The superposition of one-component catalyst efficiency.Cuprous component in catalyst on the one hand being capable of peroxynitrite decomposition hydrogen generation strong oxidizing property
On the one hand substance can also promote the circulation in Fenton reaction between Fe (II) and Fe (III), play to cooperate with iron component and urge
Change the effect of oxidation stain object.
Table 4
Comparative example 3
The quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 is changed to 1.9881g, remaining with 1 phase of embodiment
Together, magnetic Cu (I) microspherical catalyst is prepared, the used time is drawn off natural air drying.
Comparative example 4
The quality 4.9703g of Iron dichloride tetrahydrate in embodiment 1 is changed to 9.6645g, remaining with 1 phase of embodiment
Together, magnetic Cu (I) microspherical catalyst is prepared, the used time is drawn off natural air drying.
Test five: embodiment 1-5 and comparative example the 3-4 catalyst being prepared are tested, specifically: it takes respectively
By
Embodiment 1-5 and comparative example 3-4 preparation catalysis material 0.2g, be added to volume be 100mL, concentration 20mg/L
AR73 dyestuff in, be added dropwise 0.2mL concentration be 30wt%H2O2Solution stirs (500r/min) at room temperature, reaction
30min separates microballoon using magnet, with the concentration of colorimetric method for determining dyestuff.The results are shown in Table 5 for removal, precursor solution
When middle copper content is 0.06mol/L, iron content (copper and iron ratio is 1:2~1:5) in 0.12~0.30mol/L is sub- in oxidation
The mole of iron is 0.01~0.0275mol, and magnetic Cu (I) the microspherical catalyst catalytic activity prepared is ideal.When
When frerrous chloride concentration is too low, Cu2+It can not be by the Fe of sufficient amount2+It is reduced to the Cu of lower valency+, lead to Fe in embryonic stem-like cells
(II) circulation between Fe (III) can not effectively enhance；When frerrous chloride excessive concentration, Cu+Play the role of also opposite
It is smaller.Therefore, copper, iron content and corresponding ratio are an important factor for determining catalyst activity in preparation process.
Table 5
Test six: magnetic Cu (I) microspherical catalyst 0.2g prepared by Example 1, being added separately to volume is 100mL,
Concentration is that the H for the 0.2mL that concentration is 30wt% is added dropwise in the AR73 dye solution of 20mg/L2O2Solution stirs at room temperature
(500r/min) reaction 30min is mixed, microballoon is separated with magnet, uses colorimetric method for determining concentration.Add again after waste water from dyestuff is colourless
Enter 73 dyestuff of AR of 2mL, 1g/L, is recycled 5 times, test method is same as above.The results are shown in Table 6: urging obtained by the present invention
Catalyst particles can still maintain 95% or more to the removal efficiency of dyestuff AR73 after being recycled 5 times.
Table 6
Comparative example 5
According to publication, (Sun Yuexin, Wang Zhengping, Wang Hong wait a kind of chitosan magnetic micro-sphere of in absorption trifluoroacetic acid
Application: CN105536721A [P] .2016.) using lotion suspension polymerization prepare Fe3O4Chitosan particle, specific steps packet
It includes: 0.5g Chitosan powder being dissolved in the acetic acid solution of 20mL 3%, the commercially available nanoscale ferroso-ferric oxide of 0.2g is added
In chitosan acetic acid solution, it is put into ultrasound 15min in supersonic wave cleaning machine, is uniformly mixed the two；Mixed solution is slowly added
Enter in the beaker equipped with 80mL atoleine and 6mL Span-80, is put into supersonic cleaning machine after ultrasound 15min, is stirred using machinery
It mixes and is stirred 30min at room temperature；The glutaraldehyde solution that 10mL volume fraction is 10% is then added, continues machine at 40 DEG C
Tool stirs 60min；The NaOH solution of 1mol/L is instilled in above-mentioned mixed liquor, adjusting pH is 9.0, and continued mechanical stirs at 70 DEG C
Mix 60min；Suspension is cooled to room temperature, magnet separation product is used；Products therefrom successively uses petroleum ether, acetone and ultrapure
Water sufficiently washs suction filtration, stand-by after vacuum drying.
Test seven: the magnetic microsphere catalyst 0.2g that respectively prepared by Example 1 and comparative example 5 is added separately to body
Product is 100mL, and concentration is to adjust pH value of solution=7, drop using the NaOH solution of 0.1mol/L in the AR73 dye solution of 20mg/L
Adding concentration is the H of the 0.2mL of 30wt%2O2Solution stirs (500r/min) at room temperature and reacts 30min, separated with magnet
Microballoon uses colorimetric method for determining concentration.The results are shown in Table 7 for removal, in neutral conditions, magnetic made from the embodiment of the present invention 1
Property chitosan particle to the removal rate of AR73 up to 95.8%, and use chitosan magnetic particle made from lotion suspension polymerization
Efficiency be only 59.7%.It can thus be seen that the addition of Cu (I) can effectively facilitate Fe3O4With H2O2Between class Fenton make
With so that still having preferable removal effect under dyestuff contaminant AR73 neutrallty condition.In addition, comparison lotion suspension polymerization,
The organic solvent that chitosan magnetic micro-sphere preparation method proposed by the present invention uses is obviously less, and preparation step is less, is grasping
Also there is apparent advantage in the property made.
Table 7
Claims (10)
1. a kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst, comprising:
Chitosan is dissolved in solvent, divalent copper source solution is added, stirring is added divalent source of iron solution, continues to stir, obtain shell
Then the precursor solution is added in strong base solution and forms microballoon by glycan-copper-iron precursor solution, solidify, and takes out microballoon water
It is washed till neutrality, is crosslinked, is washed, it is dry, magnetic Cu (I) microspherical catalyst is obtained, wherein mole of divalent copper source and divalent source of iron
Than for 1:1.8-5, the mass ratio of chitosan and divalent copper source is 1:0.5~1:2, and the ratio of chitosan and solvent is 10~50g:
1L。
2. taking off second the method according to claim 1, wherein the chitosan average molecular weight is 80~1,200,000
Acyl degree is 85~95%；Solvent is acetic acid.
3. the method according to claim 1, wherein the divalent copper source is copper acetate dihydrate；Divalent source of iron
For Iron dichloride tetrahydrate；The solvent of divalent copper source solution and divalent source of iron solution is acetic acid.
4. the method according to claim 1, wherein divalent copper source molar concentration is in the precursor solution
0.05-0.1mol/L, divalent source of iron molar concentration are 0.1-0.3mol/L.
5. the method according to claim 1, wherein it is described stirring and continue stirring temperature be room temperature, when
Between be 60~120min.
6. the method according to claim 1, wherein the speed in strong base solution is added in the described precursor solution
For 1.0~2.5mL/min；Strong base solution is the sodium hydroxide solution of 2~4mol/L.
7. the method according to claim 1, wherein the curing time be 12~for 24 hours.
8. the method according to claim 1, wherein the crosslinking are as follows: at room temperature using crosslinking agent glutaraldehyde
It is crosslinked 12-24h；Drying means is natural air drying.
9. a kind of magnetic Cu (I) microspherical catalyst of method preparation as described in claim 1.
10. a kind of application of magnetic Cu (I) microspherical catalyst of method preparation as described in claim 1.
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