CN110385132A - A kind of magnetic zeolite ozone oxidation catalyst and preparation method thereof - Google Patents
A kind of magnetic zeolite ozone oxidation catalyst and preparation method thereof Download PDFInfo
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- CN110385132A CN110385132A CN201910644452.6A CN201910644452A CN110385132A CN 110385132 A CN110385132 A CN 110385132A CN 201910644452 A CN201910644452 A CN 201910644452A CN 110385132 A CN110385132 A CN 110385132A
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- zeolite
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- ozone oxidation
- oxidation catalyst
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 144
- 239000010457 zeolite Substances 0.000 title claims abstract description 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 230000003647 oxidation Effects 0.000 title claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 56
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229940056319 ferrosoferric oxide Drugs 0.000 claims abstract description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 38
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 20
- -1 iron ion Chemical class 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 150000000703 Cerium Chemical class 0.000 claims description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006385 ozonation reaction Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000012901 Milli-Q water Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 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 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of magnetic zeolite ozone oxidation catalysts and preparation method thereof, belong to ozonation technology field.Magnetic zeolite ozone oxidation catalyst provided by the invention includes zeolite, ferroso-ferric oxide and active component, and the internal channel surfaces and outer surface of ferroso-ferric oxide and Active components distribution in zeolite, active component is cerium oxide.Ferroso-ferric oxide has been loaded in catalyst provided by the invention, so that catalyst has magnetism, used catalyst is effectively recycled using magnetic force, improves the rate of recovery of catalyst, in addition, magnetic zeolite ozone oxidation catalyst provided by the present invention has superior catalytic performance.Using magnetic zeolite ozone oxidation catalyst provided by the present invention, when the catalyst particle size is 200 mesh, the catalyst recovery yield after use is up to 99.4%, and partial size is the CeO that 200 purposes do not load ferroso-ferric oxide2The rate of recovery of/zeolite catalyst is only 79.5%.
Description
Technical field
The present invention relates to ozonation technology field more particularly to a kind of magnetic zeolite ozone oxidation catalyst and its preparations
Method.
Background technique
Catalytic ozonation technology is a kind of high-level oxidation technology developed on the basis of ozone oxidation, utilizes catalysis
The effect that agent is adsorbed, is catalyzed generates strong oxidizing property free radical, drops to efficiently solve organic matter during independent ozone oxidation
Solve incomplete problem.CeO2/ zeolite can be used as a kind of effective catalyst of catalysis ozone technology.In use, in order to
Obtain more reaction sites, it will usually select the CeO compared with small particle2/ zeolite catalyst such as selects partial size for 200 purposes
CeO2/ zeolite catalyst.However, compared with the CeO of small particle2/ zeolite catalyst, although having more reaction sites, catalytic efficiency
Height, but there is the problems such as separation and recovery of catalyst is difficult, loss is serious after the completion of reaction, easily cause secondary pollution.
Summary of the invention
The purpose of the present invention is to provide a kind of magnetic zeolite ozone oxidation catalyst and preparation method thereof, the present invention is provided
Magnetic zeolite ozone oxidation catalyst have be easily isolated, the advantage that the rate of recovery is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of magnetic zeolite ozone oxidation catalyst, including zeolite, ferroso-ferric oxide and active component,
The internal channel surfaces and outer surface of ferroso-ferric oxide and Active components distribution in zeolite, active component is cerium oxide.
Preferably, the zeolite is modified natural zeolite, and the preparation method of the modified natural zeolite includes the following steps:
Natural zeolite is successively impregnated in nitric acid solution and ammonium nitrate solution, modified natural zeolite is obtained.
Preferably, it is 1~8wt% that the cerium in the active component, which accounts for the percentage of zeolite,.
Preferably, it is 10~15wt% that the ferroso-ferric oxide, which accounts for the percentage of zeolite,.
The present invention also provides the preparation methods of magnetic zeolite ozone oxidation catalyst described in above-mentioned technical proposal, including such as
Lower step:
It disperses zeolite in the mixed solution of ferrous ion and iron ion, it is 9~11 that lye to pH value, which is added dropwise, is then passed through
Ageing, obtains magnetic zeolite；The molar ratio of the ferrous ion and iron ion is 1:2；
The magnetic zeolite is impregnated in the aqueous solution of cerium salt, is then successively dried and roasts, obtain magnetic
Property zeolite ozone oxidation catalyst.
Preferably, the concentration of the mixed solution ferrous ions of the ferrous ion and iron ion is 0.04~0.18mol/
The amount ratio of the mixed solution of L, zeolite and ferrous ion and iron ion is 1g:8~12mL.
Preferably, the temperature of the ageing is 60~80 DEG C, and the time is 2~3h.
Preferably, the concentration of cerium ion is 0.05~0.1mol/L in the aqueous solution of the cerium salt；The aqueous solution of cerium salt
PH value is 7~10；The amount ratio of magnetic zeolite and the aqueous solution of cerium salt is 25~35g:100mL.
Preferably, described be immersed under conditions of ultrasound carries out, and ultrasonic intensity is 40~70W/m2, the time of dipping is
5~7h.
Preferably, the roasting carries out in inert gas or stream of nitrogen gas；The temperature of roasting is 420~480 DEG C；Roasting
Time be 4~5h.
The present invention provides a kind of magnetic zeolite ozone oxidation catalyst, including zeolite, ferroso-ferric oxide and active component,
The internal channel surfaces and outer surface of ferroso-ferric oxide and Active components distribution in zeolite, active component is cerium oxide.The present invention
Ferroso-ferric oxide is loaded in the catalyst of offer, so that catalyst has magnetism, using magnetic force by used catalyst
It is effectively recycled, improves the rate of recovery of catalyst, in addition, magnetic zeolite ozone oxidation catalyst provided by the present invention
With superior catalytic performance.The experimental results showed that using magnetic zeolite ozone oxidation catalyst provided by the present invention, In
When the catalyst particle size is 200 mesh, the catalyst recovery yield after use is up to 99.4%, and partial size is that 200 purposes do not load
The CeO of ferroso-ferric oxide2The rate of recovery of/zeolite catalyst is only 79.5%.
Specific embodiment
The present invention provides a kind of magnetic zeolite ozone oxidation catalyst, including zeolite, ferroso-ferric oxide and active component,
The internal channel surfaces and outer surface of ferroso-ferric oxide and Active components distribution in zeolite, active component is cerium oxide.
In the present invention, the magnetic zeolite ozone oxidation catalyst includes zeolite；The zeolite is preferably modified natural
Zeolite；The preparation method of the modified natural zeolite preferably includes following steps: by natural zeolite successively in nitric acid solution and nitre
It is impregnated in acid ammonium solution, obtains modified natural zeolite.In the present invention, dipping can remove zeolite table in nitric acid solution
The impurity in face, dipping can play the role of cleaning and expand zeolite cavity in ammonium nitrate solution, and can finally obtain pore structure is
Mesoporous zeolite.
The present invention first impregnates natural zeolite in nitric acid solution.
In the present invention, the granularity of the natural zeolite is preferably 180~220 mesh, more preferably 200 mesh.
In the present invention, the concentration of the nitric acid solution is preferably 0.8~1.2mol/L, more preferably 1mol/L；Institute
Stating the time impregnated in nitric acid solution is preferably 3~5h, more preferably 4h；The natural zeolite and the amount ratio of nitric acid solution are excellent
It is selected as 1g:2.5~3.5mL.
After the completion of dipping in nitric acid solution, gained zeolite is preferably successively centrifuged and is washed by the present invention, then in nitre
It is impregnated in acid ammonium solution.In the present invention, the revolving speed of the centrifugation is preferably 2500~3500r/min, the time of centrifugation
Preferably 5~10min；The washing is preferably ultrapure water with washing lotion, and the number of the washing is preferably 2~3 times；The present invention couple
The mode of the washing is not particularly limited, using conventional mode of washing.
In the present invention, the concentration of the ammonium nitrate solution is preferably 0.08~0.12mol/L, more preferably 0.1mol/
L；The time impregnated in the ammonium nitrate solution is preferably 3~5h, more preferably 4h；The natural zeolite and nitric acid solution
Amount ratio is preferably 1g:2.5~3.5mL.
After the completion of dipping in the ammonium nitrate solution, gained zeolite is preferably successively centrifuged by the present invention, wash and
It is dry, obtain modified natural zeolite.In the present invention, the method for the centrifugation and washing carries out after dipping in nitric acid solution
Centrifugation it is identical with washing methods, details are not described herein；The temperature of the drying is preferably 100~110 DEG C, and the time is preferably 9
~12h.
In the present invention, stirring is preferably maintained in the dipping process.
In the present invention, the magnetic zeolite ozone oxidation catalyst includes ferroso-ferric oxide；The ferroso-ferric oxide accounts for
The percentage of zeolite is 10~15wt%, more preferably 12~14wt%.
In the present invention, the magnetic zeolite ozone oxidation catalyst includes active component, and the active component is oxidation
Cerium；The percentage that cerium in the active component accounts for zeolite is preferably 1~8wt%, more preferably 3~6wt%.
The present invention also provides the preparation methods of magnetic zeolite ozone oxidation catalyst described in above-mentioned technical proposal, including such as
Lower step:
It disperses zeolite in the mixed solution of ferrous ion and iron ion, it is 9~11 that lye to pH value, which is added dropwise, is then passed through
Ageing, obtains magnetic zeolite；The molar ratio of the ferrous ion and iron ion is 1:2；
The magnetic zeolite is impregnated in the aqueous solution of cerium salt, is then successively dried and roasts, obtain magnetic
Property zeolite ozone oxidation catalyst.
The present invention disperses zeolite in the mixed solution of ferrous ion and iron ion, and it is 9~11 that lye to pH value, which is added dropwise,
Then aged, obtain magnetic zeolite；The molar ratio of the ferrous ion and iron ion is 1:2.In the present invention, lye is added dropwise
Afterwards, ferrous ion and iron ion increasingly generate ferroso-ferric oxide, and solution colour gradually becomes black by orange red, in ageing process
The nucleus of ferroso-ferric oxide increases, and after aged, solution colour is remained unchanged.
In the present invention, the ferrous ion is preferably provided by ferrous salt, and the ferrous salt is preferably ferrous sulfate, chlorination
At least one of ferrous and ferrous nitrate；The iron ion is preferably provided by molysite, and the molysite is preferably ferric nitrate, sulfuric acid
At least one of iron and iron chloride；The concentration of the ferrous ion is preferably 0.04~0.18mol/L.
In the present invention, the amount ratio of the mixed solution of the zeolite and ferrous ion and iron ion be preferably 1g:8~
12mL。
In the present invention, the lye is preferably ammonium hydroxide or sodium hydrate aqueous solution；The ammonium hydroxide is preferably concentrated ammonia liquor, institute
The mass concentration for stating ammonium hydroxide is preferably 25~28%；The concentration of the sodium hydrate aqueous solution is preferably 0.2~0.4mol/L.
In the present invention, the speed of the dropwise addition is preferably 0.3~0.6mL/s.In the present invention, fast drop can be reduced
With the exposure duration of oxygen, to reduce the generation of by-product iron oxide.
In the present invention, after dropwise addition lye to pH value is 9~11, the present invention preferably stirs 15~25min, then heats to
Ageing required temperature is aged.In the present invention, 15~25min of stirring can prevent the reunion of ferriferrous oxide particles, mention
The uniformity of high product particle.
In the present invention, the temperature of the ageing is preferably 60~80 DEG C, and more preferably 70 DEG C, the time is preferably 2~3h,
More preferably 2h.In the present invention, the mode of the ageing is preferably stood.
After the completion of ageing, the present invention preferably filters ageing gained reaction solution, and filtering obtained solid is successively washed
And drying, obtain magnetic zeolite.
After obtaining magnetic zeolite, the present invention impregnates the magnetic zeolite in the aqueous solution of cerium salt, then successively
It is dried and roasts, obtain magnetic zeolite ozone oxidation catalyst.
In the present invention, the cerium salt is preferably at least one of cerous nitrate, cerium chloride and cerous sulfate, the cerium salt
The concentration of cerium ion is preferably 0.05~0.1mol/L in aqueous solution, more preferably 0.086mol/L；The aqueous solution of the cerium salt
PH value be preferably 7~10, more preferably 7~8, in the present invention, it is preferred to using ammonium hydroxide adjust cerium salt aqueous solution pH value,
The ammonium hydroxide is preferably concentrated ammonia liquor, and the mass concentration of the concentrated ammonia liquor is preferably 25~28%；The magnetic zeolite and cerium salt
The amount ratio of aqueous solution is preferably 25~35g:100mL.In the present invention, in above-mentioned pH value range, cerium ion can be made to be formed heavy
Shallow lake is adsorbed on magnetic zeolite.
In the present invention, the dipping preferably carries out under conditions of ultrasound, and the intensity of the ultrasound is preferably 40~
70W/m2；The time of the dipping is preferably 5~7h, more preferably 6h.
After the completion of dipping, the present invention is preferably filtered, and obtained solid is dried.
In the present invention, the temperature of the drying is preferably 55~70 DEG C, and more preferably 60 DEG C；The time of the drying is excellent
It is selected as 10~14h, more preferably 12h.
After the completion of drying, obtained solid is preferably cooled to room temperature by the present invention, after being ground, then is roasted, is obtained
Magnetic zeolite ozone oxidation catalyst.In the present invention, the granularity of the grinding products therefrom is preferably 180~220 mesh.This hair
It is bright that the grinding is not particularly limited, dry gained block product can be scatter.
In the present invention, the roasting is preferably carried out in inert gas or stream of nitrogen gas；The inert gas or nitrogen gas
The flow of stream is preferably 200~250mL/min；The temperature of the roasting is preferably 420~480 DEG C, and more preferably 450 DEG C；Institute
The time for stating roasting is preferably 4~5h, more preferably 4h；The heating rate for being warming up to roasting required temperature is preferably 4~6 DEG C/
Min, more preferably 5 DEG C/min.In the present invention, dehydration is played in roasting, while removing anion (such as nitrate ion)
Equal impurity, enhance the mechanical strength of catalyst；Slowly heating helps that active component is made to obtain better crystal form, improves catalyst
Activity.
Below with reference to embodiment to a kind of magnetic zeolite ozone oxidation catalyst provided by the invention and preparation method thereof into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) natural zeolite that 30g granularity is 200 mesh is added to the HNO that 90mL concentration is 1.0mol/L3It is stirred in solution
Then 4h is centrifuged 5min under 3000r/min revolving speed, by centrifugation obtained solid with milli-Q water 2 times；It is added into 90mL again
Concentration is the NH of 0.1mol/L4NO34h is stirred in solution, is then centrifuged 5min under the revolving speed of 3000r/min, by centrifugation gained
Solid is cooled to room temperature with dry 6h after milli-Q water 2 times, is put into 105 DEG C of baking ovens, is obtained modified natural zeolite；
(2) 3.60g FeSO is weighed respectively4·7H2O and 10.44g Fe (NO3)3·9H2O is dissolved in 300mL anaerobic water,
30g modified natural zeolite is taken to be placed in above-mentioned prepared solution, by concentrated ammonia liquor fast drop to outstanding under the conditions of being stirred at room temperature
In floating body system, 20min is stirred for after so that pH value is reached 11, then after 70 DEG C of waters bath with thermostatic control are aged 2h, filtering, then institute will be filtered
It obtains after solid washs 2 times and filters again, be placed in the dry 2h of 80 DEG C of drying boxes, obtain magnetic zeolite；
(3) 3.72g Ce (NO is weighed3)3·6H2O is added in the pure water of 100.0mL, compound concentration 0.086mol/L
Ce (NO3)3The above-mentioned magnetic zeolite of 30.0g is placed in one by solution, adjusts pH value to 7, in 60W/m using concentrated ammonia liquor2It is strong
Lower ultrasonic immersing 6h is spent, is taken out after being placed in 60 DEG C of baking ovens dry 12h, is cooled to room temperature rear grind into powder, is placed in tube furnace
In, in stream of nitrogen gas, 450 DEG C are warming up to the rate of 5 DEG C/min, the flow velocity of constant temperature calcining 4h, stream of nitrogen gas are
200.0mL/min；It is cooling after the completion of roasting, obtain magnetic zeolite ozone oxidation catalyst.
The ferroso-ferric oxide and cerium in magnetic zeolite ozone oxidation catalyst obtained by the present embodiment are analyzed through X-ray energy spectrometer
Content, obtain ferroso-ferric oxide and account for the percentages of modified zeolite to be 9.9wt%, cerium accounts for the mass percent meter of modified zeolite
For 3.7wt%.
Embodiment 2
(1) natural zeolite that 30g granularity is 200 mesh is added to the HNO that 90mL concentration is 1.0mol/L3It is stirred in solution
Then 4h is centrifuged 5min under 3000r/min revolving speed, by centrifugation obtained solid with milli-Q water 2 times；It is added into 90mL again
Concentration is the NH of 0.1mol/L4NO34h is stirred in solution, is then centrifuged 5min under the revolving speed of 3000r/min, by centrifugation gained
Solid is cooled to room temperature with dry 6h after milli-Q water 2 times, is put into 105 DEG C of baking ovens, is obtained modified natural zeolite；
(2) 5.33g FeSO is weighed respectively4·7H2O and 15.49g Fe (NO3)3·9H2O is dissolved in 300mL anaerobic water,
30g modified natural zeolite is taken to be placed in above-mentioned prepared solution, by concentrated ammonia liquor fast drop to outstanding under the conditions of being stirred at room temperature
In floating body system, 20min is stirred for after so that pH value is reached 11, then after 70 DEG C of waters bath with thermostatic control are aged 2h, filtering, then by obtained by
Solid filters again after washing 2 times, is placed in the dry 2h of 80 DEG C of drying boxes, obtains magnetic zeolite；
(3) 3.72g Ce (NO is weighed3)3·6H2O is added in the pure water of 100.0mL, compound concentration 0.086mol/L
Ce (NO3)3The above-mentioned magnetic zeolite of 30.0g is placed in one by solution, adjusts pH value to 7, in 60W/m using concentrated ammonia liquor2It is strong
Lower ultrasonic immersing 6h to be spent, dry 12h is placed in 60 DEG C of baking ovens, taking-up is ground to powder after being cooled to room temperature and is placed in tube furnace,
In stream of nitrogen gas, 450 DEG C, constant temperature calcining 4h are warming up to the rate of 5 DEG C/min, the flow velocity of stream of nitrogen gas is 200.0mL/
min；It is cooling after the completion of roasting, obtain magnetic zeolite ozone oxidation catalyst.
The ferroso-ferric oxide in magnetic zeolite ozone oxidation catalyst obtained by analysis the present embodiment is analyzed through X-ray energy spectrometer
With the load capacity of cerium, obtain ferroso-ferric oxide and account for the percentages of modified zeolite to be 14.8wt%, cerium accounts for the quality of modified zeolite
Percentages are 3.6wt%.
Embodiment 3
(1) natural zeolite that 30g granularity is 200 mesh is added to the HNO that 75mL concentration is 1.0mol/L3It is stirred in solution
Then 4h is centrifuged 5min under 3000r/min revolving speed, by centrifugation obtained solid with milli-Q water 2 times；It is added into 75mL again
Concentration is the NH of 0.1mol/L4NO34h is stirred in solution, is then centrifuged 5min under the revolving speed of 3000r/min, by centrifugation gained
Solid is cooled to room temperature with dry 6h after milli-Q water 2 times, is put into 105 DEG C of baking ovens, is obtained modified natural zeolite；
(2) 4.50g FeSO is weighed respectively4·7H2O and 13.09g Fe (NO3)3·9H2O is dissolved in 300mL anaerobic water,
30g modified natural zeolite is taken to be placed in above-mentioned prepared solution, by concentrated ammonia liquor fast drop to outstanding under the conditions of being stirred at room temperature
In floating body system, 20min is stirred for after so that pH value is reached 11, then after 70 DEG C of waters bath with thermostatic control are aged 2h, filtering, then by obtained by
Solid filters again after washing 3 times, is placed in the dry 2h of 80 DEG C of drying boxes, obtains magnetic zeolite；
(3) 3.72g Ce (NO is weighed3)3·6H2O is added in the pure water of 100.0mL, compound concentration 0.086mol/L
Ce (NO3)3The above-mentioned magnetic zeolite of 25.0g is placed in one by solution, adjusts pH value to 7, in 60W/m using concentrated ammonia liquor2It is strong
Lower ultrasonic immersing 6h to be spent, dry 12h is placed in 60 DEG C of baking ovens, taking-up is ground to powder after being cooled to room temperature and is placed in tube furnace,
In stream of nitrogen gas, 450 DEG C, constant temperature calcining 4h are warming up to the rate of 5 DEG C/min, the flow velocity of stream of nitrogen gas is 200.0mL/
min；It is cooling after the completion of roasting, obtain magnetic zeolite ozone oxidation catalyst.
The ferroso-ferric oxide and cerium in magnetic zeolite ozone oxidation catalyst obtained by the present embodiment are analyzed through X-ray energy spectrometer
Load capacity, obtain ferroso-ferric oxide and account for the mass percent of modified zeolite being calculated as 12.4wt%, cerium accounts for the quality of modified zeolite
Percentages are 3.5wt%.
Embodiment 4
(1) natural zeolite that 30g granularity is 200 mesh is added to the HNO that 90mL concentration is 1.0mol/L3It is stirred in solution
Then 4h is centrifuged 5min under 3000r/min revolving speed, by centrifugation obtained solid with milli-Q water 2 times；It is added into 90mL again
Concentration is the NH of 0.1mol/L4NO34h is stirred in solution, is then centrifuged 5min under the revolving speed of 3000r/min, by centrifugation gained
Solid is cooled to room temperature with dry 6h after milli-Q water 2 times, is put into 105 DEG C of baking ovens, is obtained modified natural zeolite；
(2) 1.8g FeSO is weighed respectively4·7H2O and 5.22gFe (NO3)3·9H2O is dissolved in 300mL anaerobic water, is taken
30g modified natural zeolite is placed in above-mentioned prepared solution, by concentrated ammonia liquor fast drop to suspension under the conditions of being stirred at room temperature
In system, 20min is stirred for after so that pH value is reached 11, then after 70 DEG C of waters bath with thermostatic control are aged 2h, filtering, then gained is solid
Body filters again after washing 2 times, is placed in the dry 2h of 80 DEG C of drying boxes, obtains magnetic zeolite；
(3) 3.72g Ce (NO is weighed3)3·6H2O is added separately in the pure water of 100.0mL, and compound concentration is
Ce (the NO of 0.086mol/L3)3The above-mentioned magnetic zeolite of 30.0g is placed in one by solution, adjusts pH value to 7, In using concentrated ammonia liquor
60W/m2Intensity under ultrasonic immersing 6h, be placed in 60 DEG C of baking ovens dry 12h, taking-up is ground to powder after being cooled to room temperature and is placed in
In tube furnace, in stream of nitrogen gas, 450 DEG C are warming up to the rate of 5 DEG C/min, the flow velocity of constant temperature calcining 4h, stream of nitrogen gas are
200.0mL/min；It is cooling after the completion of roasting, obtain magnetic zeolite ozone oxidation catalyst.
The ferroso-ferric oxide and cerium in magnetic zeolite ozone oxidation catalyst obtained by the present embodiment are analyzed through X-ray energy spectrometer
Load capacity, obtain ferroso-ferric oxide and account for the percentages of modified zeolite to be 5wt%, the percentages that cerium accounts for modified zeolite are
3.6wt%.
Comparative example 1
According to the method for embodiment 1, step (2) are omitted and prepares CeO2/ zeolite catalyst.
CeO obtained by this comparative example is analyzed through X-ray energy spectrometer2The load capacity of cerium, cerium account for modified zeolite in/zeolite catalyst
Percentages be 3.6wt%.
Application examples 1
Magnetic zeolite ozone oxidation catalyst prepared by Examples 1 to 4 is used to handle antibiotic pharmaceutical wastewater, it is used anti-
Raw element pharmacy waste water is the water outlet of certain pharmaceutical park antibiotic Sewage Treatment at Pharmaceutical Factory station biochemical treatment unit, and water quality is as follows: COD
For 258mgL-1, BOD5/ COD is 0.14, TOC 96.6mgL-1, pH value 7.5.
Specific treatment process is as follows:
The above-mentioned waste water of 1L is passed through to the reactor of ozone Oxidation Treatment, carries out catalytic ozonation processing；Magnetic zeolite is smelly
The dosage of oxygen oxidation catalyst is 1g, and the concentration of ozone is 50mg/L, flow 600mL/min in gas ozoniferous used,
The time of catalytic ozonation processing is 60min.After the completion of catalytic ozonation processing, magnet is placed on ozone Oxidation Treatment
Reactor bottom, magnetic zeolite ozone oxidation catalyst is adsorbed on reactor bottom, will treated that waste water is poured out, and it is right
Treated, and waste water quality carries out analysis test, and the results are shown in Table 1.
The recycling of magnetic zeolite ozone oxidation catalyst: 100mL deionized water and magnetic zeolite ozone are added into reactor
Oxidation catalyst mixes, and together pours into beaker, stays in beaker magnetic zeolite catalyst using magnet, liquid is fallen
Out, after washing 2 times repeatedly, it is placed in drying in 80 DEG C of baking ovens, is weighed after dry, catalyst recovery yield is calculated, as a result such as table 1
It is shown.
With 1 gained CeO of comparative example2/ zeolite catalyst is ozone catalytic oxidation catalyst, according to the method described above test comparison
1 gained catalyst of example is to the treatment effect of antibiotic pharmaceutical wastewater, and the results are shown in Table 1.
After the completion of processing, CeO is recycled with the following method2/ zeolite catalyst: by treated in reactor waste water with
CeO2/ zeolite catalyst is poured out together, and after quiescent setting 1h, supernatant liquid is poured out.Recycle deionized water by CeO2/ zeolite
After catalyst washs 2~3 times repeatedly, it is placed in drying in 80 DEG C of baking ovens, is weighed after dry, calculates catalyst recovery yield, as a result such as
Shown in table 1.
1 Examples 1 to 4 of table and 1 gained catalyst of comparative example after the treatment effect of antibiotic pharmaceutical wastewater and processing to urging
The rate of recovery of agent
Application examples 2
According to the method for application examples 1, ozone is carried out containing aniline waste water using embodiment 1 and 1 gained catalyst of comparative example and is urged
Change oxidation processes, the water quality containing aniline waste water is as follows: COD 568mgL-1, BOD5/ COD is 0.23, TOC 159mgL-1,
Concentration of aniline is 51.6mgL-1, pH 7.8, treatment effect is as shown in table 2.
After catalytic ozonation processing, after the aforementioned recovery method recycling use to magnetic zeolite ozonisation catalyst
Embodiment 1 catalyst, according to aforementioned to CeO2The recovery method of/zeolite catalyst recycles urging for the comparative example 1 after use
Agent calculates the rate of recovery, and the results are shown in Table 2.
The recycling of 2 embodiment 1 of table and 1 gained catalyst of comparative example to the treatment effect and processing rear catalyst of benzene-containing wastewater
Rate
By the data of Tables 1 and 2 it is found that the rate of recovery of magnetic zeolite ozone oxidation catalyst provided by the present invention is obvious
Higher than comparative example 1, illustrate that the stream of catalyst can be effectively reduced using magnetic zeolite ozone oxidation catalyst provided by the present invention
It loses, reduces secondary pollution.
In addition, after also knowing catalyst treatment antibiotic pharmaceutical wastewater obtained by Examples 1 to 4 by Tables 1 and 2, waste water
COD removal rate, TOC removal rate and BOD5/ COD is above comparative example 1, illustrates magnetic zeolite ozone oxidation provided by the present invention
Catalyst can not only reduce COD and TOC, while also improve the bio-degradable ability of waste water, i.e., provided by the present invention
Magnetic zeolite ozone oxidation catalyst has superior ozone oxidation catalytic performance.
In addition, 1 gained catalyst treatment of embodiment is containing after aniline waste water, COD removal rate, the aniline of gained waste water are removed
Rate, TOC removal rate and BOD5/ COD is above comparative example 1, illustrates that catalyst obtained by the present invention has excellent removal to aniline
Effect, can be used for handling various wastewater, and applicability is wide.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of magnetic zeolite ozone oxidation catalyst, which is characterized in that including zeolite, ferroso-ferric oxide and active component, four
The internal channel surfaces and outer surface of Fe 3 O and Active components distribution in zeolite, active component is cerium oxide.
2. magnetic zeolite ozone oxidation catalyst according to claim 1, which is characterized in that the zeolite is modified natural
Zeolite, the preparation method of the modified natural zeolite include the following steps: natural zeolite successively in nitric acid solution and ammonium nitrate
It is impregnated in solution, obtains modified natural zeolite.
3. magnetic zeolite ozone oxidation catalyst according to claim 1 or 2, which is characterized in that in the active component
Cerium account for zeolite percentage be 1~8wt%.
4. magnetic zeolite ozone oxidation catalyst according to claim 1 or 2, which is characterized in that the ferroso-ferric oxide
The percentage for accounting for zeolite is 10~15wt%.
5. the preparation method of any one of Claims 1 to 4 magnetic zeolite ozone oxidation catalyst, which is characterized in that including
Following steps:
It disperses zeolite in the mixed solution of ferrous ion and iron ion, it is 9~11 that lye to pH value, which is added dropwise, then through old
Change, obtains magnetic zeolite；The molar ratio of the ferrous ion and iron ion is 1:2；
The magnetic zeolite is impregnated in the aqueous solution of cerium salt, is then successively dried and roasts, obtain magnetic boiling
Stone ozone oxidation catalyst.
6. preparation method according to claim 5, which is characterized in that in the mixed solution of the ferrous ion and iron ion
The concentration of ferrous ion is that the amount ratio of the mixed solution of 0.04~0.18mol/L, zeolite and ferrous ion and iron ion is 1g:
8~12mL.
7. preparation method according to claim 5, which is characterized in that the temperature of the ageing is 60~80 DEG C, the time 2
~3h.
8. preparation method according to claim 5, which is characterized in that the concentration of cerium ion is in the aqueous solution of the cerium salt
0.05~0.1mol/L；The pH value of the aqueous solution of cerium salt is 7~10；The amount ratio of magnetic zeolite and the aqueous solution of cerium salt be 25~
35g:100mL。
9. preparation method according to claim 5, which is characterized in that described be immersed under conditions of ultrasound carries out, ultrasound
Intensity be 40~70W/m2, the time of dipping is 5~7h.
10. preparation method according to claim 5, which is characterized in that the roasting is in inert gas or stream of nitrogen gas
It carries out；The temperature of roasting is 420~480 DEG C；The time of roasting is 4~5h.
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