CN109999818A - A kind of activation persulfate Magnetic solid phases catalyst and the preparation method and application thereof - Google Patents
A kind of activation persulfate Magnetic solid phases catalyst and the preparation method and application thereof Download PDFInfo
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- CN109999818A CN109999818A CN201910326352.9A CN201910326352A CN109999818A CN 109999818 A CN109999818 A CN 109999818A CN 201910326352 A CN201910326352 A CN 201910326352A CN 109999818 A CN109999818 A CN 109999818A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 230000004913 activation Effects 0.000 title claims abstract description 24
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 21
- 239000007790 solid phase Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000004246 zinc acetate Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 28
- 229940106691 bisphenol a Drugs 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 241000238370 Sepia Species 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 5
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229960002036 phenytoin Drugs 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 238000006731 degradation reaction Methods 0.000 abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 3
- 238000005049 combustion synthesis Methods 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 19
- 235000019394 potassium persulphate Nutrition 0.000 description 19
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- -1 hydroxyl radical free radical Chemical class 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003918 potentiometric titration Methods 0.000 description 5
- 239000012901 Milli-Q water Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical class CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- PHCDZUPEIPGYOG-UHFFFAOYSA-N [Fe].[Co].[Zn] Chemical compound [Fe].[Co].[Zn] PHCDZUPEIPGYOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100001239 persistent pollutant Toxicity 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
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- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
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- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The present invention provides a kind of activation persulfate Magnetic solid phases catalyst and its preparation method and application, the method of the present invention is using citric acid as chelating agent, zinc acetate, cobalt acetate, ferric nitrate pass through colloidal sol combustion synthesis final catalyst respectively as zinc source, cobalt source and source of iron.The advantage of the method for the present invention using acetate as zinc source, cobalt source and source of iron is its metal cation and coordinating group is easier to carry out special shape bridging with citric acid and complexing is reunited, facilitate crystal form and crystal size growth control, and the formation of colloidal sol does not need the organic solvents such as ethylene glycol as thickener, method more simple economy.Catalyst of the invention is high to the degradation efficiency and degradation rate of organic pollutant, and performance is stablized, and recycling effect is good, is a kind of magnetic solid catalyst of tool, convenient for being separated from the water.
Description
Technical field
The present invention relates to catalyst preparations and applied technical field, and in particular to a kind of activation persulfate Magnetic solid phases are urged
Agent and the preparation method and application thereof.
Background technique
In recent years, a large amount of persistent organic pollutants have been discharged in mankind's activity into environment, such as pharmaceutical compound, agriculture
Medicine, surfactant and dyestuff etc. not only result in water resources crisis, also directly threaten human health.Traditional is physico
It learns and biologic treating technique can not often effectively remove these persistent pollutants.
Potentiometric titrations (SO is generated based on activation persulfate4 -) high-level oxidation technology (SR-AOPs) be in recent years
Come the new technology of the processing persistent organic pollutants to grow up, especially repaired in the underground water and soil of organic pollutant pollution
Success on multiple, make it arrives extensive concern and research.SR-AOPs technology has oxidant stability and dissolubility good, wider
The pH scope of application, the advantages that oxidability is strong.SO4 -In water there are the service life is long, SO can be greatly improved4 -With it is organic
Pollutant touch opportunity, conducive to the degradation and mineralising of organic pollutant.
The method of activation persulfate includes heat treatment, ultraviolet radioactive, microwave treatment and transition metal ion catalyst at present
The methods of activation.Wherein the three kinds of technologies in front need external energy, and its device systems is complicated, with high costs.Transition metal
Ionic catalysis activation method reaction condition is mild, easy to operate, but the metal ion introduced needs further after the completion of reaction
Removal processing, had both increased technique operation cost, and had also increased the risk of toxicity of water outlet.The hair of heterogeneous activation persulfate technology
Exhibition overcomes some critical issues of homogeneous technology, for example no longer introduces free metal ion to water body, realize catalyst and
Active component separation.But the solid catalyst developed at present is limited by contact area in water and is moved by reaction system electronics
It moves and cycle rate influences, catalytic efficiency is mostly relatively low lower and has certain selectivity, it is difficult to meet actual demand.It receives
Rice catalyst can increase the degrees of exposure of specific surface area and active sites, promote catalytic activity, be separated by solid-liquid separation it can be difficult to realizing.
Summary of the invention
A kind of activation persulfate magnetism is provided it is an object of the invention to overcome the shortcomings of the prior art place
Solid-phase catalyst and its preparation method and application.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of activation persulfate Magnetic solid phases catalyst
Preparation method, the described method comprises the following steps:
(1) zinc acetate, cobalt acetate, ferric nitrate are dissolved in nitric acid solution and are mixed, obtain mixed solution A, the acetic acid
The dosage of zinc, cobalt acetate, ferric nitrate are as follows: the molal quantity ratio of Zn, Co, Fe element is 1:2-x:x, wherein 0 ﹤ x ﹤ 2；
(2) citric acid is added into mixed solution A, it is in sepia colloidal sol that solution is heated with stirring at 60-100 DEG C,
In, the molal quantity ratio of the citric acid and Zn element is (2-9): 1；
(3) the sepia colloidal sol is heated to 100-220 DEG C in air, is kept for 6-15 hours, obtains solid matter；
(4) it roasts, is kept for 2-20 hours at 400-1000 DEG C after the solid matter grinding obtained step (3)；
(5) by the solid natural cooling after roasting, successively with dry after inorganic acid and water washing.
The method of the present invention is using citric acid as chelating agent, zinc acetate (Zn (CH3COO)2), cobalt acetate (Co (CH3COO)2)、
Ferric nitrate (Fe (NO3)3) respectively as zinc source, cobalt source and source of iron, pass through colloidal sol combustion synthesis final catalyst.Side of the present invention
The advantage of method using acetate as zinc source, cobalt source and source of iron is that its metal cation and coordinating group are easier to carry out spy with citric acid
Different form bridging and complexing are reunited, and crystal form and crystal size growth control are facilitated.In addition, the formation of colloidal sol is not required in the present invention
Want the organic solvents such as ethylene glycol as thickener, method more simple economy.
Preferably, the dosage of the zinc acetate, cobalt acetate, ferric nitrate are as follows: x=1.4.
Preferably, the molal quantity ratio of the citric acid and Zn element is 6:1
Preferably, solution is heated with stirring in step (2) at 90 DEG C in sepia colloidal sol, the time of agitating and heating is 4-
6 hours.
It is highly preferred that be heated with stirring to solution in step (2) at 90 DEG C in sepia colloidal sol, the time of agitating and heating is
5 hours.
Preferably, the sepia colloidal sol is heated to 170 DEG C in step (3) in air, is kept for 12 hours.
Preferably, the maturing temperature in step (4) is 600 DEG C, and calcining time is 6 hours.
Preferably, the heating rate heated in step (3) is less than 20 DEG C/min.
It is highly preferred that the heating rate heated in step (3) is 10 DEG C/min.
Preferably, the heating rate roasted in step (4) is 5-10 DEG C/min.
Preferably, the mass fraction of the nitric acid solution is 3%-13.7%.
It is highly preferred that the mass fraction of the nitric acid solution is 5.8%.
Preferably, inorganic acid described in step (5) is hydrochloric acid solution, and the pH of hydrochloric acid solution is 2-3.
It is highly preferred that the pH value of the hydrochloric acid solution is 2.45.
Preferably, the method for inorganic acid and water washing the following steps are included: weigh 0.5g roasting after solid in beaker,
The hydrochloric acid solution that 100mL pH value is 2-3 is added, is centrifuged after agitator treating 20min, in triplicate；It uses milli-Q water 2 times again
After dry.
Preferably, in step (5), dry temperature is 50-100 DEG C after washing.
It is highly preferred that dry temperature is 70 DEG C after washing in step (5).
Preferably, speed of agitator is 200-400r/min, centrifugal rotational speed 8000-10000r/ when washing in step (5)
min。
Preferably, speed of agitator is 300r/min, centrifugal rotational speed 10000r/min when washing in step (5).
The present invention also provides a kind of activation persulfate Magnetic solid phases catalysis that any of the above-described method is prepared
Agent.
The catalyst is three metal oxide (ZnFe of zinc-iron cobaltxCo2-xO4), the catalyst is the solid powder of sepia
End is magnetic, and can be adsorbed on ferromagnetic material easily, and the specific surface area of catalyst is big, dispersion degree in water is high, catalysis effect
Rate is high, it is good to be easy to separation of solid and liquid, stability in water, can still keep higher catalytic activity through being repeated several times after degradation.
The present invention also provides a kind of application of catalyst described above in degradation organic pollutants.
The present invention also provides a kind of method of organic pollutants of degrading, be added into water catalyst described above and
Persulfate is uniformly mixed.
Above-mentioned activation persulfate Magnetic solid phases catalyst (ZnFexCo2-xO4) with persulfate (PMS) be combined when can produce
Raw hydroxyl radical free radical (HO) and SO4 -, catalyst itself has magnetism, is easily recycled.Catalytic degradation of the present invention is living
Property and efficiency are apparently higher than conventional multiphase Fenton catalyst.
Preferably, the organic pollutant includes bisphenol-A, phenytoinum naticum, 2-chlorophenol, 2,4- dichlorphenoxyacetic acid, rhodamine
B, at least one of methylene blue.
The beneficial effects of the present invention are: the present invention provides a kind of activation persulfate Magnetic solid phases catalyst and its systems
Preparation Method and application, using citric acid as chelating agent, the advantage using acetate as zinc source, cobalt source and source of iron is the method for the present invention
Its metal cation and coordinating group are easier to carry out special shape bridging with citric acid and complexing is reunited, and facilitates crystal form and crystal
Size growth control, and the formation of colloidal sol does not need the organic solvents such as ethylene glycol as thickener in the present invention, method is simpler
It is economical.Activation persulfate Magnetic solid phases catalyst prepared by the present invention has the advantage that
(1) catalyst of the invention requires the reaction condition of system low, at room temperature to persistent organic pollutants
Removal efficiency and rate are all very high；
(2) catalyst of the invention is the irregular block structure with conglomerate's phase nanoaperture, and specific surface area is huge,
With the easy contact to pollutant and PMS；
(3) catalyst of the invention has good stability during removing removal organic polluter；
(4) catalyst of the invention is magnetic retention, can be recycled easily with magnetic material, convenient for recycling；
(5) catalyst of the invention can promote the migration of electronics Rapid Circulation using pollutant as system electronic donor.
Detailed description of the invention
Fig. 1 is the activation persulfate Magnetic solid phases catalyst (ZnFe of preparation of the embodiment of the present inventionxCo2-xO4) SEM and
TEM electron microscope.
Fig. 2 is the activation persulfate Magnetic solid phases catalyst (ZnFe of preparation of the embodiment of the present inventionxCo2-xO4) HRTEM
Figure.
Fig. 3 be TEMPO of the embodiment of the present invention capture differential responses system in differential responses time singlet oxygen (1O2) EPR
Wave spectrogram
Fig. 4 is that DMPO of the embodiment of the present invention captures hydroxyl radical free radical (HO) and potentiometric titrations in differential responses system
(SO4 -) EPR wave spectrogram.
Fig. 5 is the degradation effect figure of the embodiment of the present invention and comparative example to bisphenol-A.
Fig. 6 is that the activation persulfate Magnetic solid phases catalyst of preparation of the embodiment of the present invention imitates the degradation of organic pollutant
Fruit figure.
Fig. 7 is the recycling of the activation persulfate Magnetic solid phases catalyst degradation bisphenol-A of preparation of the embodiment of the present invention
Degradation effect figure.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of preparation method of activation persulfate Magnetic solid phases catalyst as the embodiment of the present invention, the method packet
Include following steps:
(1) by 2.195g Zn (CH3COO)2·2H2O、1.494g Co(CH3COO)2·4H2O、5.656g Fe(NO)3·
9H2O is dissolved in the nitric acid solution of mass fraction 5.8% and mixes, and obtains mixed solution A；
(2) 11.526g citric acid is added in mixed solution A, stirring 10min to solid all dissolves, then in 90 DEG C
Lower stirring 5h obtains sepia colloidal sol until solution is in sepia sol form；
(3) sepia colloidal sol obtained in step (2) is transferred in ceramic crucible, is put into baking oven, dried at 170 DEG C
Dry, heating rate is 10 DEG C/min, the solid matter after being dried；
(4) it is put into Muffle furnace after being fully ground solid matter obtained in step (3) to roast at 600 DEG C, heating speed
Rate is 5 DEG C/min, keeps 6h；
(5) become powdered after the solid natural cooling after roasting, salt of the powder pH after cooling for 2.45 will be roasted
Acid elution 3 times, then with after milli-Q water 2 times, dried at 70 DEG C, it grinds, obtains activation persulfate Magnetic solid phases catalysis
Agent (ZnFexCo2-xO4)；
Wherein, the method for inorganic acid and water washing the following steps are included: weigh 0.5g roasting after solid in beaker, add
Enter the hydrochloric acid solution that 100mL pH value is 2.45, is centrifuged after agitator treating 20min, in triplicate；After using milli-Q water 2 times again
Dry, dry temperature is 70 DEG C after washing, and speed of agitator is 300r/min, centrifugal rotational speed 10000r/min when washing.
The result of product characterizes:
1, TEM and SEM: Fig. 1 is the ZnFe being prepared in embodimentxCo2-xO4TEM figure and SEM figure.It can from Fig. 1
To find out, ZnFexCo2-xO4Spherical in nanometer of uniform size, particle size is 20~50nm.Figure it is seen that
ZnFexCo2-xO4Nanosphere has clearly lattice fringe, and lattice width is respectively 0.205,0.291,0.254nm, illustrates the material
Crystallinity it is good, have apparent crystal structure.
2, catalytic performance
A group: the ZnFe that embodiment 1 is prepared is added in waterxCo2-xO4, potassium peroxydisulfate (PMS) and bisphenol-A (BPA),
After 2,2,6,6- tetramethyl piperidine oxides (TEMPO) are added, investigation TEMPO capture singlet oxygen (1O2) EPR wave spectrogram.
B group: the ZnFe that embodiment 1 is prepared is added in waterxCo2-xO4, potassium peroxydisulfate, be added TEMPO after, investigate
TEMPO capture singlet oxygen (1O2) EPR wave spectrogram.
C group: being added potassium peroxydisulfate in water, after TEMPO is added, investigation TEMPO capture singlet oxygen (1O2) EPR wave spectrum
Figure.
D group: the ZnFe that embodiment 1 is prepared is added in waterxCo2-xO4, potassium peroxydisulfate and bisphenol-A, dimethyl is added
After pyridine N-oxides (DMPO), DMPO capture hydroxyl radical free radical (HO) and potentiometric titrations (SO are investigated4 -) EPR wave
Spectrogram.
E group: the ZnFe that embodiment 1 is prepared is added in waterxCo2-xO4, potassium peroxydisulfate, be added DMPO after, investigate
DMPO captures hydroxyl radical free radical (HO) and potentiometric titrations (SO4 -) EPR wave spectrogram.
F group: being added potassium peroxydisulfate in water, after DMPO is added, investigates DMPO capture hydroxyl radical free radical (HO) and sulfuric acid
Root free radical (SO4 -) EPR wave spectrogram.
Fig. 3 be TEMPO capture differential responses system in differential responses time singlet oxygen (1O2) EPR wave spectrogram, Fig. 4 is
DMPO captures hydroxyl radical free radical (HO) and potentiometric titrations (SO in differential responses system4 -) EPR wave spectrogram.From figure
As can be seen that in ZnFexCo2-xO4/PMS/H2O and ZnFexCo2-xO4Have in/PMS/BPA reaction system apparent HO,
SO4 -And1O2Epr signal, illustrate ZnFexCo2-xO4There is very strong activation capacity to PMS.In ZnFexCo2-xO4/PMS/BPA
In system, the intensity of three kinds of Free Radical Signals is obviously stronger than that ZnFexCo2-xO4/PMS/H2O system, wherein1O2Signal strength
It is ZnFexCo2-xO4/PMS/H22.8 times in O system, HO and SO4 -Signal strength be ZnFexCo2-xO4/PMS/H2O body
3.1 times in system.Illustrate that the addition of pollutant BPA has been obviously promoted the generation of above-mentioned three kinds of free radicals in system, shows to pollute
Object directly can provide electronics for system, and catalyst of the present invention is to the further decomposition of pollutant and mineralising important in inhibiting.
Embodiment 2
A kind of method of degradation organic pollutants as the embodiment of the present invention, the described method comprises the following steps:
(1) into the bisphenol-A solution of 100mL 10mg/L, the catalyst that 0.1g embodiment 1 is prepared, constant temperature 25 is added
DEG C, continuously stirring 10min makes to reach adsorption equilibrium between pollutant and catalyst；
(2) 0.307g (1mmol) potassium peroxydisulfate is added, mixes；
(3) it reacts 30 minutes.
Sample detection bisphenol A concentration in different time points.
Embodiment 3
A kind of method of degradation organic pollutants as the embodiment of the present invention, the present embodiment and embodiment 1 are only
One difference are as follows: organic pollutant is 2-chlorophenol (2-CP).
Embodiment 4
A kind of method of degradation organic pollutants as the embodiment of the present invention, the present embodiment and embodiment 1 are only
One difference are as follows: organic pollutant is methylene blue (MB).
Embodiment 5
A kind of method of degradation organic pollutants as the embodiment of the present invention, the described method comprises the following steps:
(1) into the bisphenol-A solution of 100mL 10mg/L, the catalyst that 0.1g embodiment 1 is prepared, constant temperature 25 is added
DEG C, continuously stirring 10min makes to reach adsorption equilibrium between pollutant and catalyst；
(2) 0.307g (1mmol) potassium peroxydisulfate is added, mixes.
(3) it separates after the catalyst in solution is filtered with milli-Q water and dries after reacting 30 minutes；
(4) step (1), (2), (3) are repeated.
Comparative example 1
A kind of method of degradation organic pollutants as comparative example of the present invention, the described method comprises the following steps:
(1) into the bisphenol-A solution of 100mL 10mg/L, the catalyst that 0.1g embodiment 1 is prepared, constant temperature 25 is added
DEG C, continuously stirring 10min makes to reach adsorption equilibrium between pollutant and catalyst；
(2) it reacts 30 minutes.
Sample detection bisphenol A concentration in different time points.
Comparative example 2
A kind of method of degradation organic pollutants as comparative example of the present invention, the described method comprises the following steps:
(1) into the bisphenol-A solution of 100mL 10mg/L, 0.307g potassium peroxydisulfate is added, 25 DEG C of constant temperature, continuously stirs
10min makes to reach adsorption equilibrium between pollutant and catalyst；
(2) it reacts 30 minutes.
Sample detection bisphenol A concentration in different time points.
Experimental result:
As shown in figure 5, being embodiment 2, comparative example 1, the degradation results of comparative example 2.Comparative example 1 and comparative example 2 are to BPA's
Degradation effect is respectively less than 8%, and the degradation effect of embodiment 2 is obvious, and the removal rate of BPA is 83% when reacting 10min, illustrates to implement
The activation persulfate Magnetic solid phases catalyst (ZnFe that example 1 is preparedxCo2-xO4) mixed with persulfate after to organic contamination
Object just has good degradation effect.
As shown in fig. 6, the degradation results of respectively embodiment 2, embodiment 3, embodiment 4.Persulfate and ZnFexCo2- xO4High to the degradation rate of bisphenol-A, 2-chlorophenol, methylene blue, degradation rate is fast, and reaction starts the removal of 3 kinds of pollutants when 5min
Rate is above 60%, and the removal rate of 3 kinds of pollutants reaches 90% or more when reacting 10min.
As shown in fig. 7, being the degradation results of embodiment 5.ZnFe in four repetition testsxCo2-xO4Show higher urge
Change activity, ZnFe in the 4th repetition testxCo2-xO485% is still higher than to the removal rate of BPA, illustrates ZnFexCo2-xO4Anti-
Having good stability in system is answered, it is reusable.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method for activating persulfate Magnetic solid phases catalyst, which is characterized in that the method includes following steps
It is rapid:
(1) zinc acetate, cobalt acetate, ferric nitrate are dissolved in nitric acid solution and are mixed, obtain mixed solution A, the zinc acetate, vinegar
The dosage of sour cobalt, ferric nitrate are as follows: the molal quantity ratio of Zn, Co, Fe element is 1:2-x:x, wherein 0 ﹤ x ﹤ 2；
(2) citric acid is added into mixed solution A, solution is heated with stirring at 60-100 DEG C in sepia colloidal sol, wherein institute
The molal quantity ratio for stating citric acid and Zn element is (2-9): 1；
(3) the sepia colloidal sol is heated to 100-220 DEG C in air, is kept for 6-15 hours, obtains solid matter；
(4) it roasts, is kept for 2-20 hours at 400-1000 DEG C after the solid matter grinding obtained step (3)；
(5) by the solid natural cooling after roasting, successively with dry after inorganic acid and water washing.
2. the method according to claim 1, wherein the dosage of the zinc acetate, cobalt acetate, ferric nitrate are as follows: x=
1.4。
3. the method according to claim 1, wherein solution is heated with stirring in step (2) at 90 DEG C in palm fibre
Brown colloidal sol, the time of agitating and heating are 4-6 hours.
4. the method according to claim 1, wherein the sepia colloidal sol is added in air in step (3)
Heat is kept for 12 hours to 170 DEG C.
5. the method according to claim 1, wherein maturing temperature in step (4) is 600 DEG C, calcining time
It is 6 hours.
6. the method according to claim 1, wherein the heating rate heated in step (3) is less than 20 DEG C/min,
The heating rate roasted in step (4) is 5-10 DEG C/min, and inorganic acid described in step (5) is hydrochloric acid solution, hydrochloric acid solution
PH is 2-3.
7. the method according to claim 1, wherein the mass fraction of nitric acid solution described in step (1) is
3%-13.7%.
8. a kind of activation persulfate Magnetic solid phases catalyst that method as claimed in claim 1 is prepared.
9. a kind of method for organic pollutants of degrading, catalyst and persulfuric acid as claimed in claim 8 are added into water
Salt is uniformly mixed.
10. according to the method described in claim 9, it is characterized in that, the organic pollutant includes bisphenol-A, phenytoinum naticum, 2- chlorine
At least one of phenol, 2,4 dichlorophenoxyacetic acid, rhodamine B, methylene blue.
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