CN105776498B - The method that magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation removes antineoplastic in water removal - Google Patents
The method that magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation removes antineoplastic in water removal Download PDFInfo
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- CN105776498B CN105776498B CN201610126608.8A CN201610126608A CN105776498B CN 105776498 B CN105776498 B CN 105776498B CN 201610126608 A CN201610126608 A CN 201610126608A CN 105776498 B CN105776498 B CN 105776498B
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- order mesoporous
- nickel ferrite
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- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000000118 anti-neoplastic effect Effects 0.000 title claims abstract description 17
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000005389 magnetism Effects 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000005273 aeration Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 41
- CMSMOCZEIVJLDB-UHFFFAOYSA-N Cyclophosphamide Chemical compound ClCCN(CCCl)P1(=O)NCCCO1 CMSMOCZEIVJLDB-UHFFFAOYSA-N 0.000 claims description 40
- 229960004397 cyclophosphamide Drugs 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 2
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 206010028980 Neoplasm Diseases 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 229940034982 antineoplastic agent Drugs 0.000 description 2
- 239000002246 antineoplastic agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000708 MFe2O4 Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002651 drug therapy Methods 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- VKFOYDLMKRBPND-UHFFFAOYSA-N iron;oxonickel Chemical compound [Fe].[Ni]=O VKFOYDLMKRBPND-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000816 toxic dose Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of method for removing antineoplastic in water removal using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation, operating procedure is as follows: (1) the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation；(2) solution of a certain concentration containing antineoplastic is prepared；(3) magnetic order mesoporous nickel ferrite based magnetic loaded is added, certain time is mixed to reach adsorption equilibrium；(4) ozone is passed through by sand core aeration head；(5) by the magnetic order mesoporous nickel ferrite based magnetic loaded of externally-applied magnetic field separation, a kind of method for efficiently removing antineoplastic in water removal using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation can be completed.The order mesoporous nickel ferrite based magnetic loaded of magnetism of the invention not only has extremely strong catalytic performance to ozone (removal rate of antineoplastic is higher than 95%), and have the advantages such as easy to operate, catalyst is recyclable, nickel ion dissolution concentration is low, the efficient removal of various persistent organic pollutants suitable for water.
Description
Technical field
The invention belongs to water treatment fields, and in particular to a kind of efficient using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation
The method for removing antineoplastic in water removal.
Background technique
With the aggravation of environmental pollution and aging of population, cancer morbidity improves year by year.World Health Organization's prediction,
The year two thousand twenty whole world cancer morbidity will increase by 50%, will increase by 15,000,000 people every year.One of main means as treatment of cancer,
Antineoplastic is used widely in drug therapy.Antineoplastic can be useless by body discharges, production and hospital's use process
The different approaches such as abandoning enter water environment.Currently, trace antineoplastic is detected in surface water in the world.Although earth's surface
The concentrations of antineoplastic are lower than toxic concentration threshold value in water, but its residence time is long, not degradable, there is accumulative and migration
Property, the health hazards such as teratogenesis, carcinogenic and mutagenesis can be generated at low concentrations.In addition, most of antineoplastics have heredity
Toxicity, cytotoxicity and genotoxicity.Waterworks routine handling technology of water supply " coagulation-precipitating-filtering-disinfection " and tradition
Advanced Treatment of Drinking Water such as absorption, ozone oxidation and UF membrane to the removal effects of most of antineoplastics and pay no attention to
Think.Therefore, it needs to seek the pollution problem that efficient, economic control method solves antineoplastic in water environment.
Heterogeneous catalysis ozonation technology is the persistent organic pollutants oxidation removal hot spot skill with application prospect
Art promotes ozone to decompose the hydroxyl radical free radical (OH) for generating high oxidation activity in water using solid material as catalyst, with
Realize the efficient removal of organic pollutants.As emerging magnetic material, spinel type ferrite MFe2O4(M=Mn2+、Ni2+、
Zn2+And Cu2+Deng) favor in heterogeneous catalysis ozone field by researchers.Catalysis of the spinel type ferrite to ozone
Performance and the activity of M transition metal ions and the quantity of catalyst surface hydroxyl are closely related.In addition, in reaction solution
O2-/O2And catalyst surface M2+/M3+Inversion equilibrium ensure that OH continues efficiently to generate.Although spinel type ferrite exists
Show good stability and reuse in use process, but small (usually less than 10 m of the specific surface area of catalyst2·g-1), and serious particle agglomeration is further reduced the touch opportunity with organic pollutant in the solution, reduces catalytic efficiency.Cause
This, developing highly efficient, stable heterogeneous ozone catalyst becomes the project in water process with engineering application value.
In recent years, ordered mesoporous metal oxide is widely paid close attention in catalytic field.Ordered mesoporous metal oxide
Have high specific surface area and three-dimensional open-framework abundant, lattice defect and Lacking oxygen can be formed in catalyst surface,
To generate a large amount of active oxygen.In addition, high-specific surface area provides a large amount of active points for organic pollutant, be conducive to
Adsorption of Organic is in catalyst surface, and then the active specy being generated is aoxidized；Regular orderly open duct, ruler
Very little adjustable aperture provides the path of mass transfer for catalysis reaction, is conducive to the expansion of organic pollutant and its oxidation product
It dissipates.However, ordered mesoporous metal oxide application during there are reclaimer operations it is cumbersome, at high cost the problems such as, limit
They are further applied.As can preparing order mesoporous ferrite, then while can guaranteeing convenient catalyst recycling, it is brilliant to solve point
The problems such as stone-type ferrite low specific surface area and particle agglomeration, develops its catalytic activity highly efficient to ozone, this is being controlled
Persistent organic pollutants, the research field of guarantee water environment safety will be completely new a trial and breakthrough in water.
Summary of the invention
It is relatively low it is an object of the invention to solve existing spinel-type ferrous acid nickel catalytic efficiency during catalytic ozonation
The problem of, it develops and a kind of efficiently removes high toxicity in water removal, difficult to degrade anti-swollen using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation
The method of tumor medicine.
The technical solution adopted by the present invention to solve the technical problems is:
The method for removing antineoplastic in water removal using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation, the method is by following
Step carries out:
(1) the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O be dissolved in 10 mL methanol (Ni:
Fe molar ratio is 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, heats 12 in 50 DEG C
h；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, rise
Warm speed is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred to the round-bottomed flask for filling 2 M NaOH solutions
Interior, 24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, dry in 70 DEG C of vacuum
It is dry to obtain black solid, it is stored after this solid is fully ground stand-by；
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step 2 and fills ring phosphorus
In the reactor of amide solution, by 30 min of magnetic stirrer, to reach adsorption equilibrium, the magnetism is order mesoporous
The dosage of nickel ferrite based magnetic loaded is 0.1-1.0 g/L；
(4) it is passed through ozone, is reacted:
Prepare ozone with pure oxygen, be passed through by sand core aeration head from reactor bottom, keep 15 ~ 45 DEG C of reaction temperature and
PH reacts 5 ~ 30 min under conditions of being 3 ~ 11, realizes the efficient removal of water cyclophosphamide；
(5) recycling of magnetic order mesoporous nickel ferrite based magnetic loaded is realized by externally-applied magnetic field: magnetic orderly using externally-applied magnetic field recycling
Mesoporous nickel ferrite based magnetic loaded, resulting magnetism order mesoporous nickel ferrite based magnetic loaded ethyl alcohol and deionized water are cleaned 3 times repeatedly and are done in 70 DEG C of vacuum
The order mesoporous nickel ferrite based magnetic loaded of magnetism that is dry, being recycled.
The concentration of step (2) cyclophosphamide is 1-10 mg/L.
Ozone flow velocity 0.1-1.0 L/min in the step (4).
The principle of the invention: the specific surface area of spinel-type ferrous acid nickel (usually less than 10 m less than normal at present2/ g), and reacting
It is prone to particle agglomeration in liquid, seriously inhibits the performance of its catalytic performance.And magnetic orderly Jie of the present invention
Hole nickel ferrite based magnetic loaded has huge specific surface area (up to 218 m2/ g) and three dimensional pore structures abundant (hole appearance up to 0.48 m2/
G), can efficiently solve spinel-type ferrous acid nickel there are the problem of, to give full play to nickel ferrite based magnetic loaded to the catalytic activity of ozone.It is high
Specific surface area provides a large amount of active points for cyclophosphamide, is conducive to cyclophosphamide and is adsorbed on catalyst surface, and then is produced
Raw OH is aoxidized；Regular orderly open duct, size adjustable aperture be that catalysis reacts and provides mass transfer
Path is conducive to the diffusion of organic pollutant and its oxidation product.More importantly high-specific surface area and hole knot abundant
Structure makes magnetic order mesoporous nickel ferrite based magnetic loaded have surface hydroxyl abundant, generates OH to be greatly promoted ozone and decompose, substantially
Improve the removal of water cyclophosphamide.
Beneficial effects of the present invention are as follows:
The order mesoporous nickel ferrite based magnetic loaded of magnetism of the invention has extremely strong catalytic activity to ozone；
The order mesoporous nickel ferrite based magnetic loaded of magnetism of the invention can be recycled after using to be recycled, and operating cost is reduced；
Operation of the present invention is simple, it is easy to accomplish；
The method applied in the present invention nickel ion dissolution concentration is extremely low, and environmental pollution is minimum；
The present invention can be effectively removed water cyclophosphamide, and removal rate is up to 95% or more.
The present invention can be used for persistent organic pollutants in water removal, such as cyclophosphamide.
Detailed description of the invention
Fig. 1 is the removal situation of cyclophosphamide under different working conditions；
Fig. 2 is influence of the reuse number to order mesoporous nickel ferrite based magnetic loaded catalytic ozonation removal cyclophosphamide effect.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, technical scheme of the present invention will be further explained in detail.
Technical solution of the present invention is not limited to specific implementation method exemplified below, further includes times between each specific embodiment
Meaning combination.
Specific embodiment 1: a kind of in present embodiment efficiently gone using magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation
The method of antineoplastic, sequentially includes the following steps: in water removal
(1) the magnetic order mesoporous NiFe of preparation2O4:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O be dissolved in 10 mL methanol (Ni:
Fe molar ratio is 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, heats 12 in 50 DEG C
h；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, rise
Warm speed is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred to the round-bottomed flask for filling 2 M NaOH solutions
Interior, 24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, dry in 70 DEG C of vacuum
It is dry to obtain black solid, it is stored after this solid is fully ground stand-by；
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor, the ring phosphinylidyne
The concentration of amine is 1-5 mg/L, and liquor capacity is 500mL in reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step (2) and fills ring phosphorus
In the reactor of amide solution, by 5 ~ 30 min of magnetic stirrer, to reach adsorption equilibrium.
The dosage of the order mesoporous nickel ferrite based magnetic loaded of magnetism described in step (3) is 0.1-0.5 g/L；
(4) it is passed through ozone, is reacted: ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, is protected
Hold react 30min under conditions of 25 DEG C of reaction temperature and pH are 7, it can be achieved that water cyclophosphamide efficient removal；
Ozone flow velocity 0.1-0.5 L/min described in step (4)；
(5) recycling of magnetic order mesoporous nickel ferrite based magnetic loaded is realized by externally-applied magnetic field: magnetic orderly using externally-applied magnetic field recycling
Mesoporous nickel ferrite based magnetic loaded, resulting magnetism order mesoporous nickel ferrite based magnetic loaded ethyl alcohol and deionized water are cleaned 3 times repeatedly and are done in 70 DEG C of vacuum
The order mesoporous nickel ferrite based magnetic loaded of magnetism that is dry, being recycled.
Specific embodiment 2: the present embodiment is different from the first embodiment in that target contaminant ring in step 2
The concentration of phosphamide is 5 ~ 10 mg/L, other steps are same as the specific embodiment one；
Specific embodiment 3: one of present embodiment and specific embodiment one to two difference are: magnetic in step 3
Property order mesoporous nickel ferrite based magnetic loaded dosage be 0.5-1.0 g/L, other steps are identical as one of specific embodiment one to two；
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: smelly in step 4
Oxygen flow velocity 0.5-1.0 L/min, other steps are identical as one of specific embodiment one to three；
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: anti-in step 4
Answering temperature is 15,35 and 45 DEG C, other steps are identical as one of specific embodiment one to four；
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: anti-in step 4
Answering pH value of solution is 3,5,9 and 11, other steps are identical as one of specific embodiment one to five；
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 4
The order mesoporous iron oxygen nickel of magnetism added is the order mesoporous nickel ferrite based magnetic loaded of magnetism recycled in step 5 by externally-applied magnetic field, other steps
Suddenly identical as one of specific embodiment one to six；
In order to verify beneficial effects of the present invention, following experiment has been carried out:
Experiment one: magnetic order mesoporous nickel ferrite based magnetic loaded tests the absorption property of cyclophosphamide, carries out by the following method:
One, the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O be dissolved in 10 mL methanol (Ni:
Fe molar ratio is 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, heats 12 in 50 DEG C
h；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, rise
Warm speed is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred to the round-bottomed flask for filling 2 M NaOH solutions
Interior, 24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, dry in 70 DEG C of vacuum
It is dry to obtain black solid, it is stored after this solid is fully ground stand-by.
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；The ring phosphinylidyne
The concentration of amine is 5 mg/L；Liquor capacity is 500mL in reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step 2 and fills ring phosphorus
In the reactor of amide solution, by 30 min of magnetic stirrer, to reach adsorption equilibrium；The magnetism is order mesoporous
The dosage of nickel ferrite based magnetic loaded is 0.5 g/L；
Complete the absorption property experiment for individually adding magnetic order mesoporous nickel ferrite based magnetic loaded to cyclophosphamide.
Experiment two: the performance test of independent ozone oxidation cyclophosphamide carries out by the following method:
(1) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；
The concentration of cyclophosphamide as described in step (1) is 5 mg/L；
Liquor capacity is 500mL in reactor in step (1)；
(2) it is passed through ozone, is reacted: ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, is protected
It holds under conditions of 25 DEG C of reaction temperature and pH are 7 and reacts 30 min.
0.5 L/min of ozone flow velocity described in step (2), that is, the performance for completing independent ozone oxidation cyclophosphamide are real
It tests.
Experiment three: the performance test of spinel-type ferrous acid nickel O3 catalytic oxidation cyclophosphamide carries out by the following method:
(1) spinel-type ferrous acid nickel is prepared:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O is dissolved in 10 mL deionized waters
In (Ni:Fe molar ratio be 1:2)；
2. 47.056 g sodium citrates are dissolved in 20 mL deionized waters, it is thoroughly mixed uniform (Ni:Fe: lemon
Acid group=1:2:8)；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, adds in 90 DEG C of water-baths
Heat obtains gel；
4. by step, 3. gained gel 5 h of calcination at 800 DEG C, heating rate are 1 DEG C/min；5. by step 4. gained
Solid is cooled to room temperature, and polished storage is stand-by；
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；
The concentration of cyclophosphamide described in step (2) is 5 mg/L；Liquor capacity is 500mL in reactor；
(3) it adds spinel-type ferrous acid nickel: spinel-type ferrous acid nickel being added in step 3 and fills cyclophosphamide solution
Reactor in, by 30 min of magnetic stirrer, to reach adsorption equilibrium, the spinel-type ferrous acid nickel is added
Amount is 0.5 g/L；
(4) it is passed through ozone, is reacted: ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, is protected
It holds under conditions of 25 DEG C of reaction temperature and pH are 7 and reacts 30 min, 0.5 L/min of ozone flow velocity completes point
The performance test of spar type nickel ferrite based magnetic loaded O3 catalytic oxidation cyclophosphamide.
Experiment four: the performance test of magnetic order mesoporous nickel ferrite based magnetic loaded O3 catalytic oxidation cyclophosphamide, by the following method into
Row:
(1) the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O be dissolved in 10 mL methanol (Ni:
Fe molar ratio is 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, heats 12 in 50 DEG C
h；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, rise
Warm speed is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred to the round-bottomed flask for filling 2 M NaOH solutions
Interior, 24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, dry in 70 DEG C of vacuum
It is dry to obtain black solid, it is stored after this solid is fully ground stand-by；
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；The ring phosphinylidyne
The concentration of amine is 5 mg/L；Liquor capacity is 500mL in reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step 2 and fills ring phosphorus
In the reactor of amide solution, by 30 min of magnetic stirrer, to reach adsorption equilibrium, the magnetism is order mesoporous
The dosage of nickel ferrite based magnetic loaded is 0.5 g/L；
(4) it is passed through ozone, is reacted: ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, is protected
It holds under conditions of 25 DEG C of reaction temperature and pH are 7 and reacts 30 min, 0.5 L/min of ozone flow velocity.Complete magnetic
The performance test of the order mesoporous nickel ferrite based magnetic loaded O3 catalytic oxidation cyclophosphamide of property.
Experiment five: the influence experiment to magnetic order mesoporous nickel ferrite based magnetic loaded catalytic performance is repeatedly used, by the following method
It carries out:
(1) the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O be dissolved in 10 mL methanol (Ni:
Fe molar ratio is 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, heats 12 in 50 DEG C
h；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, rise
Warm speed is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred to the round-bottomed flask for filling 2 M NaOH solutions
Interior, 24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, dry in 70 DEG C of vacuum
It is dry to obtain black solid, it is stored after this solid is fully ground stand-by.
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；The ring phosphinylidyne
The concentration of amine is 5 mg/L；Liquor capacity is 500mL in reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step 2 and fills ring phosphorus
In the reactor of amide solution, by 30 min of magnetic stirrer, to reach adsorption equilibrium, the magnetism is order mesoporous
The dosage of nickel ferrite based magnetic loaded is 0.5 g/L；
(4) it is passed through ozone, is reacted: ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, is protected
It holds under conditions of 25 DEG C of reaction temperature and pH are 7 and reacts 30 min, 0.5 L/min of ozone flow velocity；
(5) recycling of magnetic order mesoporous nickel ferrite based magnetic loaded is realized by externally-applied magnetic field: magnetic orderly using externally-applied magnetic field recycling
Mesoporous nickel ferrite based magnetic loaded, resulting magnetism order mesoporous nickel ferrite based magnetic loaded ethyl alcohol and deionized water are cleaned 3 times repeatedly and are done in 70 DEG C of vacuum
The order mesoporous nickel ferrite based magnetic loaded of magnetism that is dry, being recycled is completed and is repeatedly used to magnetic order mesoporous nickel ferrite based magnetic loaded catalysis
The influence of performance is tested.
The removal situation of cyclophosphamide is as shown in Figure 1, reuse number urges order mesoporous nickel ferrite based magnetic loaded under different working conditions
The influence for changing ozonisation removal cyclophosphamide effect is as shown in Figure 2:
Fig. 1 shows the removal situations of cyclophosphamide under different working conditions.As shown, order mesoporous nickel ferrite based magnetic loaded is to ring phosphorus
The removal effect of amide is limited, is only 5.28% in 30 minutes；The ring phosphorus of removal 44.43% is only capable of in independent ozone oxidation 30 minutes
Amide.And when nickel ferrite based magnetic loaded and ozone are combined, the removal effect of water cyclophosphamide is significant.When using spinel-type ferrous acid nickel with it is smelly
When oxygen is combined, 61.8% cyclophosphamide is removed in 30 minutes；And when order mesoporous nickel ferrite based magnetic loaded and ozone are combined, 30 minutes
Interior cyclophosphamide is almost completely removed (97.4%).Fig. 2 indicates that reuse number removes order mesoporous nickel ferrite based magnetic loaded catalytic ozonation
The influence of cyclophosphamide effect.As shown, catalysis ozone is to cyclophosphamide after order mesoporous nickel ferrite based magnetic loaded continuous reuse 5 times
Removal rate be still higher than 95%, show the reuse of exceptional.It can be seen that order mesoporous nickel ferrite based magnetic loaded catalysis ozone oxygen
Chemical industry skill has the advantages that efficient, green, economic, the removal of persistent organic pollutants suitable for water.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (1)
1. the method that magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation removes antineoplastic in water removal, which is characterized in that the method
It sequentially includes the following steps:
(1) the magnetic order mesoporous nickel ferrite based magnetic loaded of preparation:
1. by 5.816 g Ni (NO3)2·6H2O and 16.16 g Fe (NO3)3·9H2O is dissolved in 10 mL methanol that (Ni:Fe rubs
You are than being 1:2)；
2. 1 g KIT-6 is put into the polytetrafluoroethylcontainer container for filling 20 mL n-hexanes, it is sufficiently stirred；
3. 1. solution is added dropwise 2. in solution, it is formed by after 4 h are sufficiently stirred in mixed solution, in 50 DEG C of 12 h of heating；
4. 3. obtained solid 5 h of calcination at 250 DEG C, heating rate are 1 DEG C/min to step；
5. 4. obtained solid repeated impregnations are primary for step, i.e., repeatedly step 1. 2. 3. after, 5 h of calcination at 800 DEG C, heating speed
Degree is 1 DEG C/min；
6. by step, 5. obtained solid is cooled to room temperature, polished to be transferred in the round-bottomed flask for filling 2 M NaOH solutions,
24 h of return stirring is centrifuged recycling after removing removing template under 50 DEG C of water bath conditions；
7. by step, 6. obtained solid is cleaned to pH=7 with ethyl alcohol and deionized water repeatedly respectively, is dried in vacuo in 70 DEG C
To black solid, stored after this solid is fully ground stand-by；
(2) raw water of the prescribed concentration containing cyclophosphamide is prepared, the solution of preparation is poured into reactor；
(3) it adds magnetic order mesoporous nickel ferrite based magnetic loaded: magnetic order mesoporous nickel ferrite based magnetic loaded being added in step 2 and fills cyclophosphamide
In the reactor of solution, by 30 min of magnetic stirrer, to reach adsorption equilibrium, the order mesoporous ferrous acid of magnetism
The dosage of nickel is 0.1-1.0 g/L；
(4) it is passed through ozone, is reacted:
Ozone is prepared with pure oxygen, is passed through by sand core aeration head from reactor bottom, 15 ~ 45 DEG C of reaction temperature is kept and pH is
5 ~ 30 min are reacted under conditions of 3 ~ 11, realize the efficient removal of water cyclophosphamide；
(5) recycling of magnetic order mesoporous nickel ferrite based magnetic loaded is realized by externally-applied magnetic field: magnetic order mesoporous using externally-applied magnetic field recycling
Nickel ferrite based magnetic loaded, resulting magnetism order mesoporous nickel ferrite based magnetic loaded ethyl alcohol and deionized water are cleaned 3 times repeatedly and are dried in vacuo in 70 DEG C,
The order mesoporous nickel ferrite based magnetic loaded of magnetism recycled；
The concentration of step (2) cyclophosphamide is 1-10 mg/L；
Ozone flow velocity 0.1-1.0 L/min in the step (4).
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