CN105854821A - Porous magnetic spherical material with sewage purification function and preparation method thereof - Google Patents
Porous magnetic spherical material with sewage purification function and preparation method thereof Download PDFInfo
- Publication number
- CN105854821A CN105854821A CN201610243110.XA CN201610243110A CN105854821A CN 105854821 A CN105854821 A CN 105854821A CN 201610243110 A CN201610243110 A CN 201610243110A CN 105854821 A CN105854821 A CN 105854821A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- porous
- porous magnetic
- nano
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000010865 sewage Substances 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002689 soil Substances 0.000 claims abstract description 32
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 20
- 239000000356 contaminant Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000006249 magnetic particle Substances 0.000 claims description 62
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 8
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 239000010840 domestic wastewater Substances 0.000 abstract 1
- 238000004043 dyeing Methods 0.000 abstract 1
- 238000009713 electroplating Methods 0.000 abstract 1
- 238000007885 magnetic separation Methods 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000007639 printing Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000010918 textile wastewater Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005406 washing Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000002122 magnetic nanoparticle Substances 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 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 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000005484 gravity Effects 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
- 239000005416 organic matter Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000011640 ferrous citrate Substances 0.000 description 1
- 235000019850 ferrous citrate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- 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
- B01J20/28054—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 surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Soil Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a porous magnetic spherical material with a sewage and contaminated soil purification function and a preparation method thereof. The material can be used for removing contaminants in papermaking wastewater, textile wastewater, printing and dyeing wastewater, electroplating wastewater, rubber industry wastewater, domestic wastewater and the like, soil contaminated by the sewage, wastewater containing organic contaminants or heavy metal contaminants or containing the organic contaminants and the heavy metal contaminants, and the contaminated soil. By the adoption of the nano-technology, a nano functional material and a natural polymer material are compounded, and preparation of the multifunctional magnetic porous spherical material is completed through metal particle marks and chemical crosslinking reactions. The material can degrade the organic contaminants and the heavy metal contaminants in the wastewater and the contaminated soil, recovery, regeneration and reuse can be achieved through magnetic separation, spherical materials of different scales can be obtained through adjustment of the preparation process, and the design of the treatment process of the wastewater and the contaminated soil is more flexible and efficient.
Description
Technical field
The present invention relates to a kind of porous magnetic spheroidal material with sewage and contaminated soil purification function and preparation method thereof, belong to
Technical field of function materials.Porous magnetic spheroidal material provided by the present invention can be widely applied in waste water and contaminated soil organic
Pollutant and the removal of heavy metal contaminants.
Background technology
Water pollutes and soil pollution is that the huge environmental pollution quickly increasing with China's rapid economic development and population and producing is asked
Topic.China's year quantity of wastewater effluent nearly hundred billion tons at present, owing to sewage disposal technology is difficult to meet sewage discharge demand, through tens
The accumulation in year, main water source in a large number, nationwide is heavily polluted, and also has a large amount of soil by sewage severe contamination simultaneously.China
Sewage mainly has two sources: trade effluent and sanitary sewage.Major pollutants in sewage include organic pollutants and heavy metal
Pollutant.Sewage disposal process typically can only select suitably to process individually for organic pollution or heavy metal contaminants
Method and technique, if not only needing to process organic pollution but also need to process heavy metal contaminants, be then usually taken two or more step
Suddenly, simultaneously need to apply two or more to process raw material, not only process technique and affect the factor complexity for the treatment of effect, and cost
High.Such as generally organic pollution takes biological sludge process to carry out biodegradable, and heavy metal contaminants then needs to take absorption
Or flocculation sediment mode is removed.China's sewage source is extensive, and in sewage, pollutant composition complexity, contains the most simultaneously and have
Organic pollutants and heavy metal contaminants, the most traditional process technique and process raw material remove organic pollution and heavy metal at the same time
Pollutant aspect still suffers from great difficulty, particularly removes the pollutant difficulty in contaminated soil bigger.
Summary of the invention
It is an object of the invention to provide a kind of porous magnetic spheroidal material with sewage and contaminated soil purification function.
Another object of the present invention is to provide the system of a kind of porous magnetic spheroidal material with sewage and contaminated soil purification function
Preparation Method.
The technical solution used in the present invention is:
A kind of porous magnetic spheroidal material, this porous magnetic spheroidal material is the spherical crosslinking shell being coated with nano-composne magnetic particle
Glycan porous material, described nano-composne magnetic particle is nanoscale TiO2Layer is coated with nanometer Fe3O4。
Further, the porosity of above-mentioned porous magnetic spheroidal material is 30%～75%.
Further, in above-mentioned porous magnetic spheroidal material, the content of nano-composne magnetic particle is mass percent 1%～55%.
Further, above-mentioned nanoscale TiO2The thickness of layer is 5～50nm.
The preparation method of porous magnetic spheroidal material described above, comprises the following steps:
1) preparation of nano-composne magnetic particle: by nanometer Fe3O4Magnetic particle is scattered in the aqueous isopropanol of metatitanic acid four fourth fat,
Nanoscale TiO is obtained through Magneto separate after arrest reaction 2～72h2Layer is coated with nanometer Fe3O4Nano-composne magnetic particle；
2) preparation of porous magnetic spheroidal material: by molten at shitosan acetic acid for the nano-composne magnetic even particulate dispersion of upper step gained
In liquid, ultrasonic disperse, the mixture after dispersion is added dropwise to CuSO4Solution solidifies, crosses leaching filter residue；
After filter residue and drying, in redisperse to glutaraldehyde water solution, process 3～6h in 70～90 DEG C, cross leaching filter residue, by filter residue
In copper ion remove with acid solution, washes clean, be redispersed in water, regulation pH value be neutral, mistake leaching filter residue,
I.e. obtain porous magnetic ball shape material after drying.
Further, above-mentioned steps 1) described nanometer Fe3O4The mass ratio of magnetic particle and metatitanic acid four fourth fat is (0.15～6): 1.
Further, above-mentioned steps 1) described metatitanic acid four fourth fat aqueous isopropanol in the mass concentration of metatitanic acid four fourth fat be
0.1～5%w/w.
Further, above-mentioned steps 2) described in the mass ratio of shitosan and nano-composne magnetic particle be (1.2～19): 1.
The porous magnetic spheroidal material described above application in sewage and contaminated soil purify.
Further, above-mentioned sewage and contaminated soil purify the removal including organic pollutants and/or heavy metal contaminants.
The invention has the beneficial effects as follows:
1) the porous magnetic spheroidal material with sewage and contaminated soil purification function of the present invention is a kind of nano compound stephanoporate
Material, includes the Fe of a size of 50～500 nanometers inside this porous material3O4Magnetic particle, due to depositing of magnetic material
In the method that can take Magneto separate, material after processing is separated and recovered, make material process for separating and recovering be simplified, special
It not that the separation after processing for polluted soil facilitates feasible especially.This Fe3O4Magnetic particle surface is 5～50nm by thickness
TiO2It is coated with, it is possible to play the effect of organic pollution in sewage and contaminated soil of decomposing.Cross-linked chitosan is as porous material
Matrix, in preparation process of the present invention, make substantial amounts of-NH in shitosan2Functional group obtains good preservation, has more excellent
Remove sewage and the function of Heavy Metals in Contaminated Soils pollutant.The present invention there is sewage and contaminated soil purification function is many
Hole magnetic spheroidal material is the complex of several functions, can not only the function of organic pollution in degrading waste water and contaminated soil,
And adsorption and enrichment sewage and the effect of Heavy Metals in Contaminated Soils pollutant can be played, the mode of Magneto separate can also be used simultaneously
Material after using simply reclaims.
2) the porous magnetic spheroidal material with sewage and contaminated soil purification function of the present invention can make waste water and contaminated soil clean
In change, organic pollution and heavy metal contaminants are removed simultaneously, and method is simple and convenient, settle at one go.The pollutant purification of the present invention
The porous magnetic spheroidal material of function can also reclaim after a procedure by the way of Magneto separate, and acidified process will be adsorbed
Heavy metal contaminants separate after, repeated multiple times application, after being applied multiple times, matrix cross-linked chitosan material can drop naturally
Solving, the magnetic particle in porous magnetic spheroidal material can also be reclaimed by Magneto separate and continue to apply to porous magnetic spheroidal material
Preparation.
3) the size adjustable wide ranges of the porous magnetic spheroidal material with sewage and contaminated soil purification function of the present invention, according to
Different technique for applying requirement, it is possible to be prepared as undersized spheroidal material, it is also possible to be prepared as larger-size spheroidal material.
Various sizes of spheroidal material can also be used in mixed way, and meets water and soil earth greatly and processes the design requirement of technique.Application side
Formula can be the sewage disposal of fluidized bed type, it is also possible to be infusion formula, or processes tower.That selects the present invention has dirt
The porous magnetic spheroidal material of water and contaminated soil purification function processes raw material, treatment process design spirit as sewage and contaminated soil
Live convenient.
4) matrix resin of the porous magnetic spheroidal material with sewage and contaminated soil purification function of the present invention is cross-linked chitosan
Resin, shitosan is a kind of natural polysaccharide, and after crosslinked process, resistance to biodegradable and natural aging performance is greatly improved, and uses
Life-span is obviously prolonged.The polysaccharide material of this pure natural, in use will not produce secondary pollution, and environmental friendliness feature is bright
Aobvious.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of porous magnetic microballoon prepared by the present invention.
Detailed description of the invention
A kind of porous magnetic spheroidal material, this porous magnetic spheroidal material is the spherical crosslinking shell being coated with nano-composne magnetic particle
Glycan porous material, described nano-composne magnetic particle is nanoscale TiO2Layer is coated with nanometer Fe3O4。
Preferably, the porosity of above-mentioned porous magnetic spheroidal material is 30%～75%.
Preferably, in above-mentioned porous magnetic spheroidal material, the content of nano-composne magnetic particle is mass percent 1%～55%.
Preferably, above-mentioned nanoscale TiO2The thickness of layer is 5～50nm.
Preferably, above-mentioned Fe3O4Size be 50～500nm, saturation magnetization is 55～75emu/g.
Preferably, a diameter of the 0.1～100mm of above-mentioned porous magnetic spheroidal material.
The preparation method of porous magnetic spheroidal material described above, comprises the following steps:
1) preparation of nano-composne magnetic particle: by nanometer Fe3O4Magnetic particle is scattered in the aqueous isopropanol of metatitanic acid four fourth fat,
Nanoscale TiO is obtained through Magneto separate after arrest reaction 2～72h2Layer is coated with nanometer Fe3O4Nano-composne magnetic particle；
2) preparation of porous magnetic spheroidal material: by molten at shitosan acetic acid for the nano-composne magnetic even particulate dispersion of upper step gained
In liquid, ultrasonic disperse, the mixture after dispersion is added dropwise to CuSO4Solution solidifies, crosses leaching filter residue；
After filter residue and drying, in redisperse to glutaraldehyde water solution, process 3～6h in 70～90 DEG C, cross leaching filter residue, by filter residue
In unnecessary copper ion remove, washes clean, be redispersed in water, regulation pH value be neutral, mistake leaching filter residue, after drying
Obtain porous magnetic ball shape material.
Preferably, above-mentioned nanometer Fe3O4The preparation method of magnetic particle is: by trivalent iron salt, divalent iron salt, ammoniacal liquor, poly-second
Alkene alcohol and water mixes, and carries out hydro-thermal reaction 2～15h after fully dissolving under the conditions of 170～190 DEG C, and cooling obtains nanometer through Magneto separate
Fe3O4Magnetic particle.
Preferably, above-mentioned trivalent iron salt, divalent iron salt, ammoniacal liquor, the mass ratio of polyethylene alcohol and water are (0.8～1.2): (1.2～1.6):
(0.25～0.35): (0.05～0.15): (8～12).
Preferably, at least one in ferric nitrate, ferric sulfate, iron chloride, ironic citrate of above-mentioned trivalent iron salt.
Preferably, during above-mentioned divalent iron salt is selected from ferrous nitrate, ferrous sulfate, protochloride, ferrous acetate, ferrous citrate extremely
Few one.
Preferably, the time of above-mentioned ultrasonic disperse is 25～45min.
Preferably, above-mentioned steps 1) described nanometer Fe3O4The mass ratio of magnetic particle and metatitanic acid four fourth fat is (0.15～6): 1.
Preferably, above-mentioned steps 1) described metatitanic acid four fourth fat aqueous isopropanol in the mass concentration of metatitanic acid four fourth fat be
0.1～5%w/w.
Preferably, above-mentioned steps 2) mass concentration of shitosan is 0.5～10.5%w/w in described shitosan acetic acid solution.
Preferably, above-mentioned steps 2) described in the mass ratio of shitosan and nano-composne magnetic particle be (1.2～19): 1.
Preferably, above-mentioned steps 2) described in instill concrete operations be: the metal needle with a diameter of 0.1～100mm is at the uniform velocity
Mixture after dispersion is added dropwise to CuSO4Solution solidifies.
Preferably, above-mentioned steps 2) described CuSO4Solution concentration is 5～35%w/w.
Preferably, above-mentioned steps 2) concentration of described glutaraldehyde water solution is 12～18%w/w.
Preferably, above-mentioned steps 2) described in remove the method for copper ion unnecessary in filter residue for filter residue being immersed in 08～1.2M
Hydrochloric acid solution in remove copper ion.
Preferably, above-mentioned steps 2) described it is dried as vacuum drying, baking temperature is 50～80 DEG C.
The application in sewage and contaminated soil purify of the above-mentioned porous magnetic spheroidal material.
Preferably, sewage described above and contaminated soil purify the removal including organic pollutants and/or heavy metal contaminants.
Below in conjunction with specific embodiment, the present invention is further illustrated, but is not limited thereto.
Embodiment 1
The preparation method of a kind of porous magnetic spheroidal material with sewage purification function, comprises the steps:
1) preparation of magnetic nanoparticle: FeCl2、FeCl3, ammoniacal liquor, polyvinyl alcohol, water press the weight of 1:1.2:0.3:0.1:10
Ratio joins in hydrothermal reaction kettle, after fully dissolving, hydrothermal reaction kettle is sealed locking and puts into stationary water thermal response 5 in 180 DEG C of baking ovens
Hour, take out after cooling and obtain nanometer Fe through Magneto separate washing3O4Magnetic particle；Gained Fe3O4Size be 50～500nm,
Saturation magnetization is 55～75emu/g.
2) prepared by nano-composne magnetic particle: i.e. TiO2Coated magnetic Fe3O4The preparation method of magnetic particle is, is received by 0.3g
Rice Fe3O4Magnetic particle is scattered in the metatitanic acid four fourth fat aqueous isopropanol that mass concentration is 0.1%w/w, arrest reaction 8 hours
Nanoscale TiO is obtained by Magneto separate2Layer is coated with nanometer Fe3O4Composite magnetic particle；Wherein Fe3O4Magnetic particle and titanium
The mass ratio of acid four fourth fat is 3:1.
3) preparation of porous magnetic microballoon: TiO prepared by upper step2Cladding Fe3O4Composite Nano magnetic particle is dispersed in dense
Degree is in 0.5wt% shitosan acetic acid solution, and ultrasonic disperse is after 30 minutes, by the metal needle of a diameter of 5mm with uniformly
Speed is added dropwise to the CuSO that mass concentration is 5%w/w4Solution solidifies, filters, be vacuum dried.Wherein, shitosan is with multiple
The mass ratio closing magnetic nanoparticle is 2:1.
4) product after above-mentioned vacuum drying is further distributed in the glutaraldehyde water solution that mass concentration is 15%w/w,
After 80 DEG C process 5 hours, filter and separate.
5) product after above-mentioned separation is immersed in the hydrochloric acid solution of 1M removal copper ion, washing and filtering, is redispersed in water-soluble
In liquid, adjust pH value to neutrality, washing and filtering, vacuum drying (being dried under the conditions of 50～80 DEG C) by the NaOH solution of 1M
After obtain porous magnetic micro-sphere material.
In porous magnetic spheroidal material prepared by the present embodiment, the content of nano-composne magnetic particle is mass percent 1%～55%；
Wherein nanoscale TiO2The thickness of layer is 5～50nm；The porosity of prepared porous magnetic spheroidal material is 30%～75%, diameter
It is 0.1～100mm.
Embodiment 2
The preparation method of a kind of porous magnetic spheroidal material with sewage purification function, comprises the steps:
1) preparation of magnetic nanoparticle: FeCl2、FeCl3, ammoniacal liquor, polyvinyl alcohol, water press the weight of 1:1.2:0.3:0.1:10
Ratio joins in hydrothermal reaction kettle, after fully dissolving, hydrothermal reaction kettle is sealed locking and puts into stationary water thermal response 5 in 180 DEG C of baking ovens
Hour, take out after cooling and obtain nanometer Fe through Magneto separate washing3O4Magnetic particle；Gained Fe3O4Size be 50～500nm,
Saturation magnetization is 55～75emu/g.
2) prepared by nano-composne magnetic particle: i.e. TiO2Coated magnetic Fe3O4The preparation method of magnetic particle is, by nanometer Fe3O4
Magnetic particle is scattered in the metatitanic acid four fourth fat aqueous isopropanol that mass concentration is 5%w/w, arrest reaction after 8 hours through Magneto separate
Obtain nanoscale TiO2Layer is coated with nanometer Fe3O4Composite magnetic particle；Wherein Fe3O4Magnetic particle and metatitanic acid four fourth fat
Mass ratio is 0.15:1.
3) preparation of porous magnetic microballoon: TiO prepared by upper step2Cladding Fe3O4Composite Nano magnetic particle is dispersed in dense
Degree is in 10.5wt% shitosan acetic acid solution, and ultrasonic disperse is after 25 minutes, by the metal needle of a diameter of 5mm with uniformly
Speed be added dropwise to the CuSO that mass concentration is 35%w/w4Solution solidifies, filters, be vacuum dried.Wherein, shitosan with
The mass ratio of composite Nano magnetic particle is 19:1.
4) product after above-mentioned vacuum drying is further distributed in the glutaraldehyde water solution that mass concentration is 12%w/w,
After 70 DEG C process 6 hours, filter and separate.
5) product after above-mentioned separation is immersed in the hydrochloric acid solution of 1M removal copper ion, washing and filtering, is redispersed in water-soluble
In liquid, adjust pH value to neutrality, washing and filtering, vacuum drying (being dried under the conditions of 50～80 DEG C) by the NaOH solution of 1M
After obtain porous magnetic micro-sphere material.
In porous magnetic spheroidal material prepared by the present embodiment, the content of nano-composne magnetic particle is mass percent 1%～55%；
Wherein nanoscale TiO2The thickness of layer is 5～50nm；The porosity of prepared porous magnetic spheroidal material is 30%～75%, diameter
It is 0.1～100mm.
Embodiment 3
The preparation method of a kind of porous magnetic spheroidal material with sewage purification function, comprises the steps:
1) preparation of magnetic nanoparticle: FeCl2、FeCl3, ammoniacal liquor, polyvinyl alcohol, water press the weight of 1:1.2:0.3:0.1:10
Ratio joins in hydrothermal reaction kettle, after fully dissolving, hydrothermal reaction kettle is sealed locking and puts into stationary water thermal response in 180 DEG C of baking ovens
10 hours, take out after cooling and obtain nanometer Fe through Magneto separate washing3O4Magnetic particle；Gained Fe3O4Size be
50～500nm, saturation magnetization is 55～75emu/g.
2) prepared by nano-composne magnetic particle: i.e. TiO2Coated magnetic Fe3O4The preparation method of magnetic particle is, by nanometer Fe3O4
Magnetic particle is scattered in the metatitanic acid four fourth fat aqueous isopropanol that mass concentration is 2.5%w/w, and arrest reaction divided through magnetic after 8 hours
From obtaining nanoscale TiO2Layer is coated with nanometer Fe3O4Composite magnetic particle；Wherein Fe3O4Magnetic particle and metatitanic acid four fourth fat
Mass ratio be 0.3:1.
3) preparation of porous magnetic microballoon: TiO prepared by upper step2Cladding Fe3O4Composite Nano magnetic particle is dispersed in dense
Degree is in 5wt% shitosan acetic acid solution, and ultrasonic disperse is after 35 minutes, by the metal needle of a diameter of 5mm with uniformly
Speed is added dropwise to the CuSO that mass concentration is 25%w/w4Solution solidifies, filters, be vacuum dried.Wherein, shitosan is with multiple
The mass ratio closing magnetic nanoparticle is 16:1.
4) product after above-mentioned vacuum drying is further distributed in the glutaraldehyde water solution that mass concentration is 18%w/w,
After 90 DEG C process 3 hours, filter and separate.
5) product after above-mentioned separation is immersed in the hydrochloric acid solution of 1M removal copper ion, washing and filtering, is redispersed in water-soluble
In liquid, adjust pH value to neutrality, washing and filtering, vacuum drying (being dried under the conditions of 50～80 DEG C) by the NaOH solution of 1M
After obtain porous magnetic micro-sphere material.
In porous magnetic spheroidal material prepared by the present embodiment, the content of nano-composne magnetic particle is mass percent 1%～55%；
Wherein nanoscale TiO2The thickness of layer is 5～50nm；The porosity of prepared porous magnetic spheroidal material is 30%～75%, diameter
It is 0.1～100mm.
Embodiment 4
The preparation method of a kind of porous magnetic spheroidal material with sewage purification function, comprises the steps:
1) preparation of magnetic nanoparticle: FeCl2、FeCl3, ammoniacal liquor, polyvinyl alcohol, water press the weight of 0.8:1.6:0.35:0.15:8
Amount ratio joins in hydrothermal reaction kettle, and hydrothermal reaction kettle fully seals after dissolving locking, and to put into static hydro-thermal in 190 DEG C of baking ovens anti-
Answer 2 hours, take out after cooling and obtain nanometer Fe through Magneto separate washing3O4Magnetic particle；Gained Fe3O4Size be
50～500nm, saturation magnetization is 55～75emu/g.
2) prepared by nano-composne magnetic particle: i.e. TiO2Coated magnetic Fe3O4The preparation method of magnetic particle is, by nanometer Fe3O4
Magnetic particle is scattered in the metatitanic acid four fourth fat aqueous isopropanol that mass concentration is 0.1%w/w, arrest reaction after 72 hours through magnetic
Isolated nanoscale TiO2Layer is coated with nanometer Fe3O4Composite magnetic particle；Wherein Fe3O4Magnetic particle and metatitanic acid four fourth
The mass ratio of fat is 6:1.
3) preparation of porous magnetic microballoon: TiO prepared by upper step2Cladding Fe3O4Composite Nano magnetic particle is dispersed in dense
Degree is in 0.5wt% shitosan acetic acid solution, and ultrasonic disperse is after 30 minutes, by the metal needle of a diameter of 5mm with uniformly
Speed is added dropwise to the CuSO that mass concentration is 5%w/w4Solution solidifies, filters, be vacuum dried.Wherein, shitosan is with multiple
The mass ratio closing magnetic nanoparticle is 1.2:1.
4) product after above-mentioned vacuum drying is further distributed in the glutaraldehyde water solution that mass concentration is 12%w/w,
After 70 DEG C process 6 hours, filter and separate.
5) product after above-mentioned separation is immersed in the hydrochloric acid solution of 1.2M removal copper ion, washing and filtering, is redispersed in water
In solution, adjust pH value by the NaOH solution of 0.8M and (do under the conditions of 50～80 DEG C to neutrality, washing and filtering, vacuum drying
Dry) after obtain porous magnetic micro-sphere material.
In porous magnetic spheroidal material prepared by the present embodiment, the content of nano-composne magnetic particle is mass percent 1%～55%；
Wherein nanoscale TiO2The thickness of layer is 5～50nm；The porosity of prepared porous magnetic spheroidal material is 30%～75%, diameter
It is 0.1～100mm.
The porous magnetic spheroidal material prepared above-described embodiment below makees the detection of further performance.
One, ESEM detection
The porous magnetic spheroidal material of embodiment 1 preparation is scanned Electronic Speculum detection, and testing result is as it is shown in figure 1, therefrom may be used
To find out that prepared porous magnetic ball has loose open-celled structure, it is possible to process the active table providing abundance abundant for pollutant
Face, and loose open-celled structure can subtract the resistance of mass transfer, improves sewage and contaminated soil purified treatment speed.
Two, porosity detection
Method: fill it up with normal heptane the (W that weighs in specific gravity bottle1), pour out normal heptane, add the preparation of a certain amount of embodiment 1～4 many
Hole magnetic spheroidal material (W), after resin is soaked 2h in normal heptane, fills it up with specific gravity bottle the (W that weighs with normal heptane2), the most dried
The skeleton volume of resin.
(dt be measure at a temperature of the density of normal heptane, ρ=0.683g/cm3), skeletal density
Additionally weigh a certain amount of (G1) water-swellable after porous magnetic ball (as far as possible blotting surface moisture) dry to constant weight in baking oven
(G2), then weight fraction shared by moisture in resin
Porous magnetic ball rate following formula calculates:
(ρH2O=1g/cm3)
The porosity of porous magnetic spheroidal material prepared by the testing result display present invention is 30%～75%.
Three, the detection of heavy metal adsorption effect
Method: the porous magnetic spheroidal material ball accurately weighing 0.1g embodiment 1～3 preparation is placed in 25mL tool plug test tube, adds
Enter 0.1mol/l CuSO4Solution 10mL (or CoSO4、NiSO4), sealing, 30 DEG C of water-bath 100r/min vibration 10h (have proved
Reach saturated), take and after supernatant dilutes in right amount, use determined by ultraviolet spectrophotometry Cu2+Concentration (or Co2+、Ni2+), according to formula:
QCu2+=(C0-C1) V/W calculates its adsorbance (QCu2+, its unit is mmol/g).
In formula: the quality (g) of W porous magnetic ball；V——CuSO4The volume (mL) of solution；C0——CuSO4The concentration of stoste
(mol/L)；C1CuSO after absorption4The concentration of solution, (mol/L).
Table 1 porous magnetic of the present invention spheroidal material heavy metal and the detection of Adsorption of Organic effect
Result: testing result is as shown in table 1, it can be seen that porous magnetic microballoon of the present invention is 0.1mol/L at initial concentration
Time to copper, cobalt, nickel ion saturated extent of adsorption all at more than 2mmol/g, especially to the saturated extent of adsorption of copper ion up to
3.32mmol/g, illustrates that material heavy metal of the present invention has good suction-operated.
Four, the detection of removal organic polluter effect is gone
Method: choose containing 2 respectively, 4-Dichlorophenol or be the waste water of 10mg/L to methylene blue concentration, with the NaOH aqueous solution (or
The HNO3 aqueous solution) regulation waste water pH value be 6～7, the porous magnetic microballoon obtained by embodiment 1,2 and 3 is added respectively
In above-mentioned pending wastewater sample, under the temperature conditions of 28 DEG C, (shaking speed is to be put in oscillating reactions 6h in shaking table
80rpm), with the porous magnetic microsphere adsorbing agent in magnet separating reaction liquid after having reacted, complete in waste water 2,4-dichloro
Phenol or the process to methylene blue.Waste water solution after processing is measured by application UV-Vis spectrum, calculates porous magnetic microballoon
To 2,4-Dichlorophenol and the clearance of methylene blue.
Measurement result is shown in Table 1, there it can be seen that the porous magnetic microballoon of embodiment of the present invention gained is to 2,4-Dichlorophenol,
Two kinds of organic clearances of methylene blue are all more than 97%；And, the porous magnetic microballoon prepared by the technology of the present invention is at weight
After using 10 times again, the clearance to organic matter (methylene blue) is still up to about 90%, illustrates that material of the present invention is to organic matter
Pollutant has good suction-operated, has a good application prospect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention being not restricted to the described embodiments,
The change made under other any Spirit Essence without departing from the present invention and principle, modify, substitute, combine, simplify, all should
For equivalence substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a porous magnetic spheroidal material, it is characterised in that: this porous magnetic spheroidal material is the spherical cross-linked chitosan porous material being coated with nano-composne magnetic particle, and described nano-composne magnetic particle is nanoscale TiO2Layer is coated with nanometer Fe3O4。
A kind of porous magnetic spheroidal material the most according to claim 1, it is characterised in that: the porosity of this porous magnetic spheroidal material is 30% ~ 75%.
A kind of porous magnetic spheroidal material the most according to claim 1, it is characterised in that: in this porous magnetic spheroidal material, the content of nano-composne magnetic particle is mass percent 1% ~ 55%.
A kind of porous magnetic spheroidal material the most according to claim 1, it is characterised in that: described nanoscale TiO2The thickness of layer is 5 ~ 50nm.
5. the preparation method of the arbitrary described porous magnetic spheroidal material of claim 1 ~ 4, it is characterised in that: comprise the following steps:
1) preparation of nano-composne magnetic particle: by nanometer Fe3O4Magnetic particle is scattered in the aqueous isopropanol of metatitanic acid four fourth fat, obtains nanoscale TiO through Magneto separate after arrest reaction 2 ~ 72h2Layer is coated with nanometer Fe3O4Nano-composne magnetic particle；
2) preparation of porous magnetic spheroidal material: by the nano-composne magnetic even particulate dispersion of upper step gained in shitosan acetic acid solution, ultrasonic disperse, the mixture after dispersion is added dropwise to CuSO4Solution solidifies, crosses leaching filter residue；
After filter residue and drying, in redisperse to glutaraldehyde water solution, process 3 ~ 6h in 70 ~ 90 DEG C, cross leaching filter residue, copper ion in filter residue acid solution is removed, washes clean, be redispersed in water, regulation pH value is neutral, crosses leaching filter residue, the most i.e. obtains porous magnetic ball shape material.
Method the most according to claim 5, it is characterised in that: nanometer Fe described in step 1)3O4The mass ratio of magnetic particle and metatitanic acid four fourth fat is (0.15 ~ 6): 1.
Method the most according to claim 5, it is characterised in that: in the aqueous isopropanol of metatitanic acid four fourth fat described in step 1), the mass concentration of metatitanic acid four fourth fat is 0.1 ~ 5%w/w.
Method the most according to claim 5, it is characterised in that: step 2) described in the mass ratio of shitosan and nano-composne magnetic particle be (1.2 ~ 19): 1.
9. claim 1 ~ 4 arbitrary described porous magnetic spheroidal material application in sewage and contaminated soil purify.
Application the most according to claim 9, it is characterised in that described sewage and contaminated soil purify the removal including organic pollutants and/or heavy metal contaminants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610243110.XA CN105854821B (en) | 2016-04-19 | 2016-04-19 | A kind of porous magnetic spheroidal material and preparation method thereof with sewage purification function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610243110.XA CN105854821B (en) | 2016-04-19 | 2016-04-19 | A kind of porous magnetic spheroidal material and preparation method thereof with sewage purification function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105854821A true CN105854821A (en) | 2016-08-17 |
| CN105854821B CN105854821B (en) | 2018-11-09 |
Family
ID=56632551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610243110.XA Expired - Fee Related CN105854821B (en) | 2016-04-19 | 2016-04-19 | A kind of porous magnetic spheroidal material and preparation method thereof with sewage purification function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854821B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236546A (en) * | 2017-06-23 | 2017-10-10 | 河北麦森钛白粉有限公司 | With the preparation method of soil remediation accelerator associated with plant and/or microorganism |
| CN109530418A (en) * | 2018-12-31 | 2019-03-29 | 南京格洛特环境工程股份有限公司 | Heavy-metal contaminated soil restorative procedure |
| CN111170436A (en) * | 2020-01-18 | 2020-05-19 | 运城学院 | Flocculating agent for treating printing and dyeing sewage and sewage treatment method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319590A (en) * | 2011-05-27 | 2012-01-18 | 湖北富邦科技股份有限公司 | Tri-iron tetroxide/shitosan/TiO 2The nano composite photocatalytic preparation methods |
-
2016
- 2016-04-19 CN CN201610243110.XA patent/CN105854821B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319590A (en) * | 2011-05-27 | 2012-01-18 | 湖北富邦科技股份有限公司 | Tri-iron tetroxide/shitosan/TiO 2The nano composite photocatalytic preparation methods |
Non-Patent Citations (2)
| Title |
|---|
| V. J. SAWANT ET AL: ""Functionalization of TiO2 nanoparticles and curcumin loading for enhancement of biological activity"", 《DER PHARMACIA LETTRE》 * |
| 宋海南等: ""Fe3O4/ TiO2磁性催化剂的制备及在污水治理中的应用"", 《分子催化》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236546A (en) * | 2017-06-23 | 2017-10-10 | 河北麦森钛白粉有限公司 | With the preparation method of soil remediation accelerator associated with plant and/or microorganism |
| CN107236546B (en) * | 2017-06-23 | 2019-07-23 | 河北麦森钛白粉有限公司 | With plant and/or microorganism associated with soil remediation promotor preparation method |
| CN109530418A (en) * | 2018-12-31 | 2019-03-29 | 南京格洛特环境工程股份有限公司 | Heavy-metal contaminated soil restorative procedure |
| CN111170436A (en) * | 2020-01-18 | 2020-05-19 | 运城学院 | Flocculating agent for treating printing and dyeing sewage and sewage treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105854821B (en) | 2018-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yi et al. | Key role of FeO in the reduction of Cr (VI) by magnetic biochar synthesised using steel pickling waste liquor and sugarcane bagasse | |
| Peng et al. | Magnetic Fe3O4@ silica–xanthan gum composites for aqueous removal and recovery of Pb2+ | |
| CN102527347B (en) | Magnetic chitosan/cationic surface active agent modified zeolite adsorbent and preparation method and application thereof | |
| CN106076261B (en) | A kind of adsorbent for heavy metal and preparation method and application | |
| Sun et al. | Adsorption of boron by CA@ KH-550@ EPH@ NMDG (CKEN) with biomass carbonaceous aerogels as substrate | |
| Zhang et al. | Removal of Cd (II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems | |
| CN106475066B (en) | Preparation method, product and the application of Magnaglo acticarbon | |
| Xiao et al. | Magnetically recoverable Ni@ carbon nanocomposites: solid-state synthesis and the application as excellent adsorbents for heavy metal ions | |
| CN106637929B (en) | Hydrophobic oleophylic cotton fiber and preparation method and application thereof | |
| Dai et al. | Magnetic mesoporous sodium citrate modified lignin for improved adsorption of calcium ions and methylene blue from aqueous solution | |
| CN108176368A (en) | A kind of charcoal Chitosan Composites and its preparation method and application | |
| CN105668757B (en) | Graphene/sodium alginate bead of nano zero valence iron modification and its preparation method and application | |
| Khoshsang et al. | Rapid removal of lead (II) ions from aqueous solutions by saffron flower waste as a green biosorbent | |
| CN105771895A (en) | Graphene three-dimensional composite material and preparation method and application thereof | |
| CN106745317A (en) | One-step method prepares method and its application of porous ferroferric oxide magnetic Nano microsphere | |
| CN105771936A (en) | Magnetic zirconium/iron composite oxide nanometer material, and preparation method and application thereof | |
| CN105854821B (en) | A kind of porous magnetic spheroidal material and preparation method thereof with sewage purification function | |
| CN106040165B (en) | A kind of magnetic modified zeolite material and the preparation method and application thereof for adsorbing except nickel | |
| Yang et al. | High removal rate and selectivity of Hg (II) ions using the magnetic composite adsorbent based on starch/polyethyleneimine | |
| Lv et al. | Preparation of β-CD and Fe3O4 integrated multifunctional bioadsorbent for highly efficient dye removal from water | |
| He et al. | Enhanced adsorption of fluoride from aqueous solution using an iron‐modified attapulgite adsorbent | |
| CN105921763B (en) | The preparation method of sodium alginate/inorganic mineral combined loading type nano zero valence iron | |
| Teng et al. | Optimization of preparation parameters for environmentally friendly attapulgite functionalized by chitosan and its adsorption properties for Cd 2+ | |
| Peng et al. | A study of adsorption behaviour of Cu (II) on hydroxyapatite-coated-limestone/chitosan composite | |
| CN110280227A (en) | MnO2The preparation and its application of the difunctional composite material of/PEI/TA |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181109 |