CN104785793B - The preparation method of cellulose modifying modified Nano iron particle - Google Patents
The preparation method of cellulose modifying modified Nano iron particle Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 454
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 215
- 239000002245 particle Substances 0.000 title claims abstract description 215
- 229920002678 cellulose Polymers 0.000 title claims abstract description 46
- 239000001913 cellulose Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002270 dispersing agent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 161
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 114
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 92
- 238000003756 stirring Methods 0.000 claims description 68
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 56
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 56
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 52
- 238000000967 suction filtration Methods 0.000 claims description 28
- 239000012065 filter cake Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229940084936 gonak Drugs 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 9
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- -1 hydroxypropyl Chemical group 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 42
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 42
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 42
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 42
- 235000010980 cellulose Nutrition 0.000 description 36
- 239000002351 wastewater Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 17
- 239000003344 environmental pollutant Substances 0.000 description 13
- 239000000356 contaminant Substances 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 11
- 229910001431 copper ion Inorganic materials 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 9
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 9
- 229960000282 metronidazole Drugs 0.000 description 9
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229960002415 trichloroethylene Drugs 0.000 description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229950011260 betanaphthol Drugs 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 150000004786 2-naphthols Chemical class 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Abstract
The invention discloses a kind of method of cellulose surface modification nano iron particles, the present invention with two kinds it is environmentally friendly be dispersant without nontoxic cellulose, surface modified, obtained cellulose dispersant modified Nano iron particle is carried out to particle in the preparation process of nano iron particles.Process of the present invention is simple and easy to operate, low cost, nano iron particles good dispersion, can reduce reunion of the particle in water, improves removal efficiency of the particle to organic pollution, dyestuff, agricultural chemicals, nitrate and heavy metal.
Description
Technical field
The invention belongs to water-treatment technology field, it is related to a kind of preparation side of the modified nano iron particles of cellulose modifying
The degraded of antibiotic and gone in method, and the particle removal, the decolouring of waste water from dyestuff, the waste water of organic pollution that are applied in water
Heavy metal in water removal.
Background technology
China's quantity of wastewater effluent is huge, and according to the difference of production method, average production 1t products need to discharge 40~300m3's
Waste water.According to incompletely statistics, China's only dyeing waste water discharge capacity is about daily 3 × 106~4 × 106m3, textile industry and printing and dyeing
A large amount of waste water from dyestuff that industry is produced every year, due to its high chroma and potential toxicity.Conventional waste water treatment frequently with side
Method has：Physisorphtion (such as charcoal absorption), membrane separation process, photocatalysis, ozone oxidation, Coagulation Method and biological oxidation process etc..
For containing various Recalcitrant chemicals in waste water, and with carcinogenicity and teratogenesis, it is difficult at conventional waste water processing method
Reason.The research team of the professor Zhang Weixian leader of Lehigh universities of the U.S. in 1997 is successfully synthesized with liquid phase chemical reduction technology and receives
Rice Zero-valent IronAnd be used for after underground water in-situ immobilization first, nano zero valence iron
Technology starts to be subject to the extensive concern of domestic and international researcher.Nano zero valence iron specific grain surface product is big, reactivity is strong, can
By the multiple pollutant in the effective degradation water of reduction.Nano iron particles can also be in subsurface flow with form of suspension
Transmission, nano iron particles can be applied to original position and the showering of underground water and soil pollution.But nano zero valence iron is reduced
Activity is very strong, unstable chemcial property, is easily oxidized.Because the polarity of itself causes nano zero-valence iron particle easily to cause group
Poly-, so as to lose the reactivity point position of a large amount of nano zero-valence iron particles, the serious agglomeration of particle causes that it is effective with pollutant
Contact area reduces, degradation efficiency declines.And reunion greatly reduces Nanoscale Iron mobility in environment water and soil, right
The repair of environmental pollution is unfavorable.Therefore, should effectively carry out and nano zero valence iron is modified, so as to suppress nano particle group
Gather, improve particle transfer ability in the liquid phase, improve Nanoscale Iron degradation capability to environmental pollutants.
Existing method of modifying includes that load is fixed and disperses.Load is fixed as nano iron particles being carried on solid carrier
（Such as resin, pvdf membrane, bentonite, clinoptilolite, activated carbon and multi-walled carbon nano-tubes）, the method can improve the ratio of particle
Surface area, suppresses the generation reunited.And disperse modified refers to wrap up polyelectrolytes or table on nano iron particles surface
Face activating agent, such as shitosan, CMC, can reach the purpose of increase granule stability and dispersiveness, and strengthen nano zero valence iron
Mobility of the particle in water body or soil.
The technology of the present invention provides a kind of process is simple, and economical and efficient is simultaneously easy to the dispersant of engineering practice popularization and application and is modified
The preparation method of nano iron particles.Cellulose of the present invention is cheap as one kind, and green environment friendly carbohydrate derives
Thing, surface modified, synthesis is directly carried out by electrostatic repulsion and space steric effect to the nano zero valence iron in aqueous medium
Go out cellulose modification nano iron particles, modified nanoparticle agglomerates degree is obviously reduced, specific surface area increase, in water
The clearance of pollutant is significantly improved, and operation is simple and is easily achieved large-scale promotion application for method of modifying.
The content of the invention
Present invention aim at a kind of preparation method of cellulose modifying modified Nano iron particle is provided, with hydroxypropyl methyl
Cellulose or hydroxyethyl cellulose as dispersant, particle carried out in nano iron particles preparation process it is surface modified,
So as to reduce its reunion in an aqueous medium, increase its decentralization, cellulose modifying modified Nano iron particle is obtained.
The inventive method is completed by following specific steps：
（1）It is 0.5~1.5 by dispersant hydroxyethyl cellulose solution or Gonak and concentration
Mol/L containing Fe2+Or Fe3+Solution is mixed and stirred for that mixed liquor is uniformly obtained, wherein dispersant solution with contain Fe2+Or Fe3+Solution
Volume ratio be 1:33~1:330；
（2）By containing Fe2+Or Fe3+Solution is 1 with the volume ratio of reducing agent:1~1:2 ratio is dense to being instilled in mixed liquor
A kind of solution spent in reducing agent potassium borohydride, sodium borohydride, the Tea Polyphenols for 0.7~5.0 mol/L, stirs, extremely in drop
Continue to stir 5~40min after solution completion of dropping, will react the filtering of complete solution, filter cake deionized water rinsing 1~5 time
After be filtered dry, obtain fully dispersed nano zero-valence iron particle；
（3）After the nano iron particles acetone that will obtain rinses 1~5 time with absolute ethyl alcohol mixed liquor, through suction filtration after it is true
Sky is dried, and dry particulate abrasive is sealed up for safekeeping, that is, obtain cellulose modified nano zero-valence iron particle, all operation steps of the present invention
Suddenly without nitrogen or inert gas shielding.
Dispersant hydroxyethyl cellulose solution of the present invention or Gonak are 1~15g/L of concentration
The aqueous solution.
Acetone of the present invention is 1 with the volume ratio of absolute ethyl alcohol with acetone in absolute ethyl alcohol mixed liquor:2~1:9.
The Fe2+Or Fe3+Solution prepares the molysite of nano zero-valence iron particle for conventional soluble.
The technology of the present invention solves nano iron particles and reunites that serious, degradation treatment effect is undesirable and its is directly used in environment
The problem of oxidizable inactivation during recovery project application, improves degraded clearance of the nano iron particles to various environmental contaminants.
Above-mentioned cellulose modifying modified Nano iron particle material not only has degradation to Heavy Metals in Waters and nitrate, while also
There is decolorization to dyestuffs such as orange beta-naphthols in waste water, to the degradation efficiency of the pollutants such as agricultural chemicals, halogenated organic matters with do not repair
Decorations modified particles are compared and are significantly improved, therefore the cellulose modifying modified Nano iron particle material is at the deep purifying of waste water
The field engineering reparation aspect of reason and polluted water body has real value.
Compared with prior art, the advantage of the method for the invention is：
（1）The present invention carries out nano iron particles and is modified using dispersant hydroxypropyl methyl cellulose and hydroxyethyl cellulose,
Its technical process is simple, and feasibility is high；Products obtained therefrom has good dispersiveness and granulation uniformity, be conducive to adapted soil,
The showering in situ of surface water and underground water, it is easy to accomplish engineering application, with wide implementation prospect；
（2）Dispersant hydroxypropyl methyl cellulose of the present invention and hydroxyethyl cellulose solution are polysaccharide derivative
Thing, with good environment friendly；
（3）The dispersant that the present invention is utilized is hydroxypropyl methyl cellulose and hydroxyethyl cellulose（Chemical structural formula is shown in Table
1）, dispersant there is great amount of hydroxy group and Long carbon chain can form network structure disperse nano iron particles, and the effect of its steric hindrance is big,
And analyzed from Fig. 1 infrared spectrums, hydroxypropyl methyl cellulose and hydroxyethyl cellulose modification nano iron particles
Appearance-CH in infrared spectrum2With-OH characteristic peaks, the technical method provided using the present invention, hydroxypropyl methyl cellulose are illustrated
Or hydroxyethyl cellulose has successfully realized the modification to Nanoscale Iron as dispersant.By the X-ray diffraction to particle
（XRD）The analysis of collection of illustrative plates understands that the crystalline structure of modified particles is α-Fe, and particle is purer, and the impurity of iron oxide does not occur；
By transmission electron microscope（TEM）And specific surface area（BET）Phenetic analysis understand, the particle of modified particles evenly, dispersion, and have
There is bigger specific surface area.
（4）The present invention does not need nitrogen or inert gas shielding during preparing cellulose modifying modified Nano iron particle,
Cost of manufacture is saved.
Table 1：Hydroxyethyl cellulose and hydroxypropyl methyl cellulose chemical structural formula
The present invention is modified nano iron particles using dispersant, not only overcomes the easy group of unmodified nano iron particles
It is poly- and oxidizable, the dispersiveness of nano iron particles is also improved, also effectively increase its degradation efficiency to water pollutant.
Brief description of the drawings
Fig. 1 is cellulose modifying modified Nano iron particle infrared spectrum prepared by the present invention；
Fig. 2 is that cellulose modifying modified Nano iron particle prepared by the present invention is spread out with the X-ray of unmodified nano iron particles
Penetrate（XRD）Comparison schematic diagram；Wherein（a）It is unmodified nano iron particles；（b）It is the nanometer of hydroxyethyl cellulose disperse modified
Iron particle；（c）It is the nano iron particles of hydroxypropyl methyl cellulose disperse modified；
Fig. 3 is the transmission scan of the cellulose modifying modified Nano iron particle with unmodified nano iron particles of present invention preparation
Electronic Speculum（TEM）Comparison schematic diagram；Wherein（a）It is unmodified nano iron particles；（b）It is receiving for hydroxyethyl cellulose disperse modified
Rice iron particle；（c）It is the nano iron particles of hydroxypropyl methyl cellulose disperse modified；
Fig. 4 is different celluloses addition concentration on fiber element modification nano zero valence iron degradation water prepared by the present invention
The effect diagram of middle orange beta-naphthol；
Fig. 5 is cellulose disperse modified nano iron particles and first in unmodified nano iron particles degradation water prepared by the present invention
The effect diagram of nitre azoles；
Fig. 6 is that cellulose disperse modified nano iron particles prepared by the present invention remove copper in water removal with unmodified nano iron particles
The effect diagram of ion.
Specific embodiment
The present invention is described in further detail below by drawings and Examples, but the scope of the present invention is not limited to
Shown content.
Embodiment 1：The preparation and crystal structure analysis of nano zero valence iron
（1）The preparation of unmodified nano zero valence iron
The solution of potassium borohydride of the mol/L of 100ml 5.0 is instilled into the FeSO that 100ml concentration is 0.9 mol/L4In solution,
Stir in drop, to solution completion of dropping after continue to stir 15min, complete solution will be reacted and filtered, the filter cake for obtaining spends
Ionized water is filtered dry after rinsing 3 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol
Volume ratio 1:5）After the nano iron particles that obtain of flushing 3 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping,
Obtain unmodified nano zero valence iron.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
By the FeSO that the hydroxyethyl cellulose solution of concentration 10g/L and 100mL concentration are 0.9 mol/L4Solution mixes simultaneously
Stir, wherein dispersant solution and FeSO4The volume ratio of solution is 1:200；To instillation 100mL 5.0 in mixed liquor
The solution of potassium borohydride of mol/L, stir in drop, to solution completion of dropping after continue to stir 15min, will the complete solution of reaction
It is filtered dry after filtering, filter cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；The Nanoscale Iron that will be obtained
Particle acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:5）Rinse 3 times after, through suction filtration after be vacuum dried,
Dry particulate abrasive is sealed up for safekeeping, that is, obtains hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
By the FeSO that the Gonak of 10g/L and 100ml concentration are 0.9 mol/L4Solution mixes simultaneously
Stir, dispersant solution and FeSO4The volume ratio of solution is 1:200；To instillation 100ml 5.0 mol/L in mixed liquor
Solution of potassium borohydride, stir in drop, to solution completion of dropping after continue to stir 15min, the filtering of complete solution will be reacted, filter
It is filtered dry after cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles that will be obtained use third
Ketone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:5）Rinse 3 times after, through suction filtration after be vacuum dried, will be dry
Particulate abrasive is sealed up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）The unmodified crystal structure analysis with modified Nano nano zero valence iron
To analyze the crystal structure of nano particle, to unmodified particle, hydroxyethyl cellulose modified particle and hydroxypropyl first
The cellulose modified particle of base has carried out XRD detections.From three kinds of particle XRD diffraction patterns（Fig. 2）In it can be seen that Fe0Characteristic peak
(angle of diffraction is respectively 44.67 °, 65.02 ° and 82.33 °), illustrates that three kinds of particle Main Ingredients and Appearances are α-Fe0.But unmodified zero
Valency iron particle is at 35.68 °（Fig. 2 (a)）There is an obvious iron oxidation peak at place, may be Fe2O3Or Fe3O4, and cellulose modifying is modified
Nano iron particles non-oxidation phenomenon occurs (Fig. 2 (b) and Fig. 2 (c)), it can be seen that hydroxyethyl cellulose and hydroxypropyl methyl fiber
Element is favorably improved the antioxygenic property of Zero-valent Iron.
Embodiment 2：Nano zero valence iron is analyzed with the degree of aggregation of cellulose modifying modified Nano iron particle
（1）The preparation of unmodified nano zero-valence iron particle
It is the FeSO of 1.5mol/L that the solution of potassium borohydride of the mol/L of 100ml 3.0 is instilled into 100ml concentration4In solution,
Stir in drop, to solution completion of dropping after continue to stir 40min, complete solution will be reacted and filtered, the filter cake for obtaining spends
Ionized water is filtered dry after rinsing 5 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume
Than 1:9）After the nano iron particles that obtain of flushing 2 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain
Unmodified nano zero valence iron.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
It is the FeSO of 1.5mol/L by the hydroxyethyl cellulose solution of 15g/L and 100ml concentration4Solution is mixed and stirred for
It is even, wherein dispersant and FeSO4The volume ratio of solution is 1:300；To the hydroboration that the mol/L of 150ml 3.0 are instilled in mixed liquor
Potassium solution, stir in drop, to solution completion of dropping after continue to stir 40min, complete solution will be reacted and filtered, filter cake spends
Ionized water is filtered dry after rinsing 5 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone and nothing that will be obtained
Water-ethanol mixed liquor（Acetone and ethanol volume ratio 1:9）Rinse 2 times after, through suction filtration after be vacuum dried, dry particle is ground
Mill is sealed up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
It is the FeSO of 1.5mol/L by the Gonak of 10g/L and 100ml concentration4Solution mixes and stirs
Mix uniform, dispersant and FeSO4The volume ratio of solution is 1:300；To the hydroboration that the mol/L of 150ml 3.0 are instilled in mixed liquor
Potassium solution, stir in drop, to solution completion of dropping after continue to stir 40min, complete solution will be reacted and filtered, filter cake spends
Ionized water is filtered dry after rinsing 5 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone and nothing that will be obtained
Water-ethanol mixed liquor（Acetone and ethanol volume ratio 1:9）Rinse 2 times after, through suction filtration after be vacuum dried, dry particle is ground
Mill is sealed up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）The tem study of cellulose modifying modified Nano iron particle
To analyze the reunion degree of zero-valent iron particle, we use transmission electron microscope（TEM）To unmodified particle, hydroxyl second
The cellulose modified particle of base and hydroxypropyl methyl cellulose modified particles are detected.From the TEM phenograms of three（Fig. 3）In
Can be seen that, all of sample has obvious chain structure.It is observed that the chain structure of non-modified zero-valent iron particle
More reunite（Fig. 3 (a)）.And by contrast, it is hydroxyethyl cellulose modified（Fig. 3 (b)）It is modified with hydroxypropyl methyl cellulose（Fig. 3
(c)）Zero-valent iron particle is but very uniform and dispersion.This characterization result illustrates dispersant hydroxyethyl cellulose and hydroxypropyl methyl
Cellulose acts on the particle size uniformity and dispersive property that can help to zero-valent iron particle by electrostatic interaction and steric hindrance.
Embodiment 3：The specific surface area of cellulose modifying modified Nano iron particle（BET）Analysis
（1）The preparation of unmodified nano zero-valence iron particle
The solution of potassium borohydride of the mol/L of 100ml 1.0 is instilled into the FeSO that 100ml concentration is 0.5 mol/L4In solution,
Stir in drop, to solution completion of dropping after continue to stir 5min, complete solution will be reacted and filtered, the filter cake for obtaining spend from
Sub- water is filtered dry after rinsing 3 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio
1:5）After the nano iron particles that obtain of flushing 3 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain not
Modified nano zero valence iron.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
By the FeSO that the hydroxyethyl cellulose solution of 1g/L and 100mL concentration are 0.5 mol/L4Solution is mixed and stirred for
It is even, wherein dispersant solution and FeSO4The volume ratio of solution is 1:40；To the boron that the mol/L of 200ml 1.0 are instilled in mixed liquor
Hydrogenation potassium solution, stir in drop, to solution completion of dropping after continue to stir 5min, complete solution will be reacted and filtered, filter cake
With being filtered dry after deionized water rinsing 1 time, fully dispersed nano zero-valence iron particle is obtained；The nano iron particles acetone that will be obtained
With absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:2）Rinse 2 times after, through suction filtration after be vacuum dried, by drying
Particulate abrasive seal up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
By the FeSO that the Gonak of 1g/L and 100mL concentration are 0.5 mol/L4Solution mixes and stirs
Mix uniform, dispersant solution and FeSO4The volume ratio of solution is 1:40；To the boron that the mol/L of 200ml 1.0 are instilled in mixed liquor
Hydrogenation potassium solution, stir in drop, to solution completion of dropping after continue to stir 5min, complete solution will be reacted and filtered, filter cake
With being filtered dry after deionized water rinsing 1 time, fully dispersed nano zero-valence iron particle is obtained；The nano iron particles acetone that will be obtained
With absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:2）Rinse 2 times after, through suction filtration after be vacuum dried, by dry
Grain grinding is sealed up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）The unmodified specific surface area analysis with modified Nano zero-valent iron particle
It is further comparative particle's performance, specific area measuring has been carried out to modified and unmodified zero-valent iron particle.Not
The BET test results of modified particles, hydroxyethyl cellulose modified particle and hydroxypropyl methyl cellulose modified particles are respectively
33.7m2/ g, 37.5m2/ g and 38.2m2/g.This result can be explained, and is dispersed through agent hydroxyethyl cellulose and hydroxypropyl methyl is fine
Being modified for dimension element, reduces zero-valent iron particle diameter, and particle is become more dispersed and uniform, so as to increase specific surface area.
Bigger specific surface area contributes to contact of the zero-valent iron particle with pollutant, and improves its degradation rate and efficiency.
Embodiment 4：The selection of dispersant proportioning and the synthesis of modified Nano Zero-valent Iron
（1）The preparation of hydroxyethyl cellulose modified nano zero valence iron
By the FeSO that the hydroxyethyl cellulose solution of 0-15g/L and 100ml concentration are 0.9 mol/L4Solution mixes and stirs
Mix uniform, wherein dispersant and FeSO4The volume ratio of solution is 1:200；To the boron that the mol/L of 100ml 5.0 are instilled in mixed liquor
Hydrogenation potassium solution, stir in drop, to solution completion of dropping after continue to stir 15min, complete solution will be reacted and filtered, filter cake
With being filtered dry after deionized water rinsing 3 times, fully dispersed nano zero-valence iron particle is obtained；The nano iron particles acetone that will be obtained
With absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:5）Rinse 3 times after, through suction filtration after be vacuum dried, by dry
Grain grinding is sealed up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（2）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
By the FeSO that the Gonak of 0-15g/L and 100ml concentration are 0.9 mol/L4Solution mixes
And stir, dispersant and FeSO4The volume ratio of solution is 1:200；To the boron that the mol/L of 100ml 5.0 are instilled in mixed liquor
Hydrogenation potassium solution, stir in drop, to solution completion of dropping after continue to stir 15min, complete solution will be reacted and filtered, filter cake
With being filtered dry after deionized water rinsing 3 times, fully dispersed nano zero-valence iron particle is obtained；The nano iron particles acetone that will be obtained
With absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:5）Rinse 3 times after, through suction filtration after be vacuum dried, by dry
Grain grinding is sealed up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（3）Influence of the different cellulose additions to modified Nano Zero-valent Iron degradation of contaminant efficiency
Cellulose modified nano zero-valence iron particle is added in the waste water water sample containing target contaminant, in normal temperature and pressure
Lower reaction 1h, the dosage of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron is 0.3g/L, and the initial concentration of pollutant is
100mg/L, the initial pH of reaction is 7, after reaction terminates, determines the concentration of dyestuff, calculates clearance, is tested with orange beta-naphthol as mesh
Mark pollutant；
Result is as shown in figure 4, when addition concentration is 0g/L, 2.5g/L, 5g/L, 7.5g/L, 10g/L, 12.5g/L, 15g/L
When, hydroxyethyl cellulose is respectively 72.944% to the clearance of orange beta-naphthol, 72.637%, 71.23%, 74.251%, 82.51%,
62.516% and 52.133%, hydroxypropyl methyl cellulose is then respectively 72.944% to the clearance of orange beta-naphthol, 78.25%,
75.21%th, 74.742%, 87.96%, 80.589 and 79.653%.Both optimal addition concentration can be contrasted and be dividing for 10g/L
The powder aqueous solution, with FeSO4The volume ratio of solution is 1:200.
Embodiment 5：The preparation of cellulose modified nano zero valence iron and the removal to metronidazole in water
（1）The preparation and the removal to metronidazole in water of unmodified nano zero-valence iron particle
The sodium borohydride solution of the mol/L of 100ml 5.0 is instilled into the FeCl that 100ml concentration is 1.2 mol/L3In solution,
Stir in drop, to solution completion of dropping after continue to stir 20min, complete solution will be reacted and filtered, the filter cake for obtaining spends
Ionized water is filtered dry after rinsing 3 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume
Than 1:4）After the nano iron particles that obtain of flushing 2 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain
Unmodified nano zero valence iron.
Unmodified nano zero-valence iron particle is added in the waste water water sample containing target contaminant, in anti-under normal temperature and pressure
2h is answered, the dosage of unmodified nano zero valence iron is 2.5 g/L, and the initial concentration of pollutant is 100mg/L, the initial pH of reaction
It is 5, after reaction terminates, determines the concentration of metronidazole, calculates clearance.
（2）The preparation and the removal to metronidazole in water of hydroxyethyl cellulose modified nano zero-valence iron particle
By the FeCl that the hydroxyethyl cellulose solution of 10g/L and 100mL concentration are 1.2 mol/L3Solution is mixed and stirred for
Uniformly, wherein dispersant hydroxyethyl cellulose element and FeCl3The volume ratio of solution is 1:330；Instilled in mixed liquor
The sodium borohydride solution of 100mL5.0 mol/L, while drop while stir, to solution completion of dropping after continue stirring 20min, will react
It is filtered dry after complete solution filtering, filter cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；Will
The nano iron particles acetone for arriving and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:4）After rinsing 2 times, through suction filtration
Later it is vacuum dried, dry particulate abrasive is sealed up for safekeeping, that is, obtains hydroxyethyl cellulose modified nano zero-valence iron particle.
Hydroxyethyl cellulose modified nano zero-valence iron particle is added in the waste water water sample containing target contaminant, Yu Chang
2h is reacted under normal temperature and pressure, the dosage of hydroxyethyl cellulose modified nano zero valence iron is 2.5g/L, and the initial concentration of pollutant is
100mg/L, the initial pH of reaction is 5, after reaction terminates, determines the concentration of metronidazole, calculates clearance.
（3）The preparation and the removal to metronidazole in water of hydroxypropyl methyl cellulose modified Nano zero-valent iron particle
By the FeCl that the Gonak of 10g/L and 100ml concentration are 1.2 mol/L3Solution mixes simultaneously
Stir, wherein dispersant hydroxypropyl methyl cellulose and FeCl3The volume ratio of solution is 1:330；Instilled in mixed liquor
The sodium borohydride solution of the mol/L of 100ml 5.0, while drop while stir, to solution completion of dropping after continue stirring 20min, will react
It is filtered dry after complete solution filtering, filter cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；Will
The nano iron particles acetone for arriving and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:4）After rinsing 2 times, through suction filtration
Later it is vacuum dried, dry particulate abrasive is sealed up for safekeeping, that is, obtains the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose；
The nano zero-valence iron particle that hydroxypropyl methyl cellulose is modified is added in the waste water water sample containing target contaminant,
In reacting 2h under normal temperature and pressure, the dosage of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron is 2.5g/L, pollutant just
Beginning concentration is 100mg/L, and the initial pH of reaction is 5, after reaction terminates, determines the concentration of metronidazole, calculates clearance；
By comparing, hydroxyethyl cellulose modified nano zero-valence iron particle is to the clearance of metronidazole than unmodified
Nano zero-valence iron particle improve 25.1%.Removal of the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose to metronidazole
Rate improves 28.9% than unmodified nano zero-valence iron particle（See Fig. 5）.
Embodiment 6：Cellulose modified nano zero valence iron and the removal to heavy metal copper ion in water
（1）The preparation and the removal to heavy metal in water of unmodified nano zero-valence iron particle
The sodium borohydride solution of the mol/L of 100mL 5.0 is instilled into the FeSO that 100mL concentration is 1 mol/L4In solution, side
The stirring of drop side, to solution completion of dropping after continue to stir 15min, will react the filtering of complete solution, the filter cake for obtaining spend from
Sub- water is filtered dry after rinsing 2 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio
1:7）After the nano iron particles that obtain of flushing 1 time, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain not
Modified nano zero valence iron.
Unmodified nano zero-valence iron particle is added in the waste water water sample containing target contaminant copper ion respectively, Yu Chang
30min is reacted under normal temperature and pressure, the dosage of unmodified nano zero valence iron is 4g/L, and pollutant copper ion initial concentration is 50mg/
L, it is 7 to react initial pH, after reaction terminates, determines content of beary metal, calculates clearance.
（2）The preparation and the removal to heavy metal copper ion in water of hydroxyethyl cellulose modified nano zero-valence iron particle
By the FeSO that the hydroxyethyl cellulose solution of 10g/L and 100ml concentration are 1 mol/L4Solution is mixed and stirred for
It is even, wherein dispersant hydroxyethyl cellulose element and FeSO4The volume ratio of solution is 1:100；To instilling 100ml in mixed liquor
The sodium borohydride solution of 5.0 mol/L, while drop while stir, to solution completion of dropping after continue stir 15min, will reaction completely
Solution is filtered, and is filtered dry after filter cake deionized water rinsing 2 times, obtains fully dispersed nano zero-valence iron particle；By receiving for obtaining
Rice iron particle acetone and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:7）After rinsing 1 time, through suction filtration after it is true
Sky is dried, and dry particulate abrasive is sealed up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
Hydroxyethyl cellulose modified nano zero-valence iron particle is added in the waste water water sample containing target contaminant, Yu Chang
30min is reacted under normal temperature and pressure, the dosage of modified Nano Zero-valent Iron is 4g/L, and pollutant copper ion initial concentration is 50mg/L,
It is 7 to react initial pH, after reaction terminates, determines heavy metal copper ion concentration, calculates clearance.
（3）The preparation and the removal to heavy metal copper ion in water of hydroxypropyl methyl cellulose modified Nano zero-valent iron particle
By the FeSO that the Gonak of 10g/L and 100ml concentration are 1 mol/L4Solution mixes and stirs
Mix uniform, wherein dispersant hydroxypropyl methyl cellulose and FeSO4The volume ratio of solution is 1:100；Instilled in mixed liquor
The sodium borohydride solution of the mol/L of 100ml 5.0, while drop while stir, to solution completion of dropping after continue stirring 15min, will react
It is filtered dry after complete solution filtering, filter cake deionized water rinsing 2 times, obtains fully dispersed nano zero-valence iron particle；Will
The nano iron particles acetone for arriving and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:7）After rinsing 1 time, through suction filtration
Later it is vacuum dried, dry particulate abrasive is sealed up for safekeeping, that is, obtains the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
The nano zero-valence iron particle that hydroxypropyl methyl cellulose is modified is added to the waste water containing target contaminant copper ion
In water sample, in 30min is reacted under normal temperature and pressure, the dosage of modified Nano Zero-valent Iron is 4g/L, and copper ion initial concentration is
50mg/L, it is 7 to react initial pH, after reaction terminates, determines heavy metal copper ion concentration, calculates clearance.
By comparing, hydroxypropyl methyl cellulose is modified and hydroxyethyl cellulose modified nano zero-valence iron particle pair
The clearance of copper ion has been respectively increased 15.62% and 13.92% than unmodified nano zero-valence iron particle（See Fig. 6）.
Embodiment 7：The removal of the preparation method and trichloro ethylene of this cellulose modifying modified Nano iron particle
（1）The preparation of unmodified nano zero valence iron
The Tea Polyphenols solution of the mol/L of 100ml 5.0 is instilled into the FeSO that 100ml concentration is 0.9 mol/L4In solution, side
The stirring of drop side, to solution completion of dropping after continue to stir 15min, will react the filtering of complete solution, the filter cake for obtaining spend from
Sub- water is filtered dry after rinsing 3 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol body
Product compares 1:3）After the nano iron particles that obtain of flushing 3 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain
To unmodified nano zero valence iron.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
By the FeSO that the hydroxyethyl cellulose solution of concentration 10g/L and 100mL concentration are 0.9 mol/L4Solution mixes simultaneously
Stir, wherein dispersant solution and FeSO4The volume ratio of solution is 1:200；To instillation 100mL 5.0 in mixed liquor
The Tea Polyphenols solution of mol/L, stir in drop, to solution completion of dropping after continue to stir 15min, will the complete solution mistake of reaction
It is filtered dry after filter, filter cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；The Nanoscale Iron that will be obtained
Grain acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:3）Rinse 3 times after, through suction filtration after be vacuum dried, will
Dry particulate abrasive is sealed up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
By the FeSO that the Gonak of 10g/L and 100ml concentration are 0.9 mol/L4Solution mixes simultaneously
Stir, dispersant solution and FeSO4The volume ratio of solution is 1:200；To instillation 100ml 5.0 mol/L in mixed liquor
Tea Polyphenols Solutions Solution, stir in drop, to solution completion of dropping after continue to stir 15min, complete solution will be reacted and filtered,
It is filtered dry after filter cake deionized water rinsing 3 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles that will be obtained are used
Acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:3）Rinse 3 times after, through suction filtration after be vacuum dried, by drying
Particulate abrasive seal up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）Removal of this cellulose modifying modified Nano iron particle to trichloro ethylene in water
Cellulose modifying modified Nano iron particle and unmodified Nanoscale Iron are added to containing the chloroethene of target contaminant three respectively
In the waste water water sample of alkene, in 30min is reacted under normal temperature and pressure, the dosage of nano zero valence iron is 10g/L, and trichloro ethylene is initially dense
It is 50mg/L to spend, and it is 7 to react initial pH, after reaction terminates, determines trichloro ethylene content, calculates clearance.Result shows, hydroxyl second
The cellulose modified nano zero-valence iron particle of base is improved to the clearance of trichloro ethylene than unmodified nano zero-valence iron particle
17.9%.The modified nano zero-valence iron particle of hydroxypropyl methyl cellulose is to the clearance of trichloro ethylene than unmodified nanometer zero
Valency iron particle improves 26.3%.
Embodiment 8：The preparation method of this cellulose modifying modified Nano iron particle and the removal to nitrate
（1）The preparation of unmodified nano zero-valence iron particle
It is the FeSO of 1.5mol/L that the Tea Polyphenols solution of the mol/L of 100ml 3.0 is instilled into 100ml concentration4In solution, side
The stirring of drop side, to solution completion of dropping after continue to stir 40min, will react the filtering of complete solution, the filter cake for obtaining spend from
Sub- water is filtered dry after rinsing 5 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio
1:9）After the nano iron particles that obtain of flushing 2 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, obtain not
Modified nano zero valence iron.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
It is the FeSO of 1.5mol/L by the hydroxyethyl cellulose solution of 15g/L and 100ml concentration4Solution is mixed and stirred for
It is even, wherein dispersant and FeSO4The volume ratio of solution is 1:300；To the Tea Polyphenols that the mol/L of 150ml 3.0 are instilled in mixed liquor
Solution, stir in drop, to solution completion of dropping after continue to stir 40min, complete solution will be reacted and filtered, filter cake spend from
Sub- water is filtered dry after rinsing 5 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone that will be obtained with it is anhydrous
Alcohol mixeding liquid（Acetone and ethanol volume ratio 1:9）Rinse 2 times after, through suction filtration after be vacuum dried, by dry particulate abrasive
Seal up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
It is the FeSO of 1.5mol/L by the Gonak of 10g/L and 100ml concentration4Solution mixes and stirs
Mix uniform, dispersant and FeSO4The volume ratio of solution is 1:300；To the Tea Polyphenols that the mol/L of 150ml 3.0 are instilled in mixed liquor
Solution, stir in drop, to solution completion of dropping after continue to stir 40min, complete solution will be reacted and filtered, filter cake spend from
Sub- water is filtered dry after rinsing 5 times, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone that will be obtained with it is anhydrous
Alcohol mixeding liquid（Acetone and ethanol volume ratio 1:9）Rinse 2 times after, through suction filtration after be vacuum dried, by dry particulate abrasive
Seal up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）This cellulose modifying modified Nano iron particle and the removal to nitrate in water
Cellulose modifying modified Nano iron particle and unmodified Nanoscale Iron are added to sodium nitrate containing target contaminant respectively
Waste water water sample in, in 30min is reacted under normal temperature and pressure, the dosage of nano zero valence iron is 7.5 g/L, sodium nitrate initial concentration
It is 80mg/L, it is 4 to react initial pH, after reaction terminates, determines nitric acid sodium content, calculates clearance.Result shows that ethoxy is fine
The modified nano zero-valence iron particle of dimension element improves 17.5% to the clearance of sodium nitrate than unmodified nano zero-valence iron particle.Hydroxyl
The modified nano zero-valence iron particle of propyl methocel is carried to the clearance of sodium nitrate than unmodified nano zero-valence iron particle
It is high by 23.8%.
Embodiment 9：The preparation method of this cellulose modifying modified Nano iron particle and the removal to agricultural chemicals
（1）The preparation of unmodified nano zero-valence iron particle
The Tea Polyphenols solution of the mol/L of 100ml 1.0 is instilled into the FeSO that 100ml concentration is 0.5 mol/L4In solution, side
The stirring of drop side, to solution completion of dropping after continue to stir 5min, the filtering of complete solution, the filter cake deionization for obtaining will be reacted
Water is filtered dry after rinsing 3 times, obtains nano zero-valence iron particle；With acetone and absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:
5）After the nano iron particles that obtain of flushing 3 times, through suction filtration after be vacuum dried, dry particulate abrasive is sealed up for safekeeping, do not changed
The nano zero valence iron of property.
（2）The preparation of hydroxyethyl cellulose modified nano zero valence iron
By the FeSO that the hydroxyethyl cellulose solution of 1g/L and 100mL concentration are 0.5 mol/L4Solution is mixed and stirred for
It is even, wherein dispersant solution and FeSO4The volume ratio of solution is 1:40；To the tea that the mol/L of 200ml 1.0 are instilled in mixed liquor
Many phenol solutions, stirs in drop, to solution completion of dropping after continue to stir 5min, the filtering of complete solution, filter cake use will be reacted
It is filtered dry after deionized water rinsing 1 time, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone that to obtain with
Absolute ethyl alcohol mixed liquor（Acetone and absolute ethyl alcohol volume ratio 1:2）Rinse 2 times after, through suction filtration after be vacuum dried, will be dry
Particulate abrasive is sealed up for safekeeping, that is, obtain hydroxyethyl cellulose modified nano zero-valence iron particle.
（3）The preparation of hydroxypropyl methyl cellulose modified Nano Zero-valent Iron
By the FeSO that the Gonak of 1g/L and 100mL concentration are 0.5 mol/L4Solution mixes and stirs
Mix uniform, dispersant solution and FeSO4The volume ratio of solution is 1:40；To the tea that the mol/L of 200ml 1.0 are instilled in mixed liquor
Many phenol solutions, stirs in drop, to solution completion of dropping after continue to stir 5min, the filtering of complete solution, filter cake use will be reacted
It is filtered dry after deionized water rinsing 1 time, obtains fully dispersed nano zero-valence iron particle；The nano iron particles acetone that to obtain with
Absolute ethyl alcohol mixed liquor（Acetone and ethanol volume ratio 1:2）Rinse 2 times after, through suction filtration after be vacuum dried, by dry particle
Grinding is sealed up for safekeeping, that is, obtain the modified nano zero-valence iron particle of hydroxypropyl methyl cellulose.
（4）This cellulose modifying modified Nano iron particle and the removal to atrazine
Cellulose modifying modified Nano iron particle and unmodified Nanoscale Iron are added to atrazine containing target contaminant respectively
Waste water water sample in, in 90min is reacted under normal temperature and pressure, the dosage of nano zero valence iron is 12.5g/L, atrazine initial concentration
It is 20mg/L, it is 2 to react initial pH, after reaction terminates, atrazine content is determined with high performance liquid chromatograph, calculates clearance.
Result shows, hydroxyethyl cellulose modified nano zero-valence iron particle is to the clearance of atrazine than unmodified nano zero valence iron
Particle improves 20.5%.The modified nano zero-valence iron particle of hydroxypropyl methyl cellulose is to the clearance of atrazine than unmodified
Nano zero-valence iron particle improves 22.1%.
Claims (3)
1. a kind of preparation method of cellulose modifying modified Nano iron particle, it is characterised in that：With hydroxyethyl cellulose or hydroxypropyl
Ylmethyl cellulose as dispersant, particle carried out in nano iron particles preparation process it is surface modified, so as to reduce
Its reunion in an aqueous medium, increases its decentralization, and cellulose modifying modified Nano iron particle is obtained；
The above method is specifically carried out as follows：
（1）It is 0.5~1.5 mol/L by dispersant hydroxyethyl cellulose solution or Gonak and concentration
Containing Fe2+Or Fe3+Solution is mixed and stirred for that mixed liquor is uniformly obtained, wherein dispersant solution with contain Fe2+Or Fe3+The volume of solution
Than being 1:33~1:330；
（2）By containing Fe2+Or Fe3+Solution is 1 with the volume ratio of reducing agent:1~1:2 ratio in mixed liquor instill concentration be
A kind of solution in reducing agent potassium borohydride, sodium borohydride, the Tea Polyphenols of 0.7~5.0 mol/L, stirs, to solution in drop
Continue to stir 5~40min after completion of dropping, will react the filtering of complete solution, filter cake after deionized water rinsing 1~5 time with filtering
It is dry, obtain fully dispersed nano zero-valence iron particle；
（3）After the nano iron particles acetone that will obtain rinses 1~5 time with absolute ethyl alcohol mixed liquor, through suction filtration after vacuum do
It is dry, dry particulate abrasive is sealed up for safekeeping, that is, obtain cellulose modified nano zero-valence iron particle.
2. the preparation method of cellulose modifying modified Nano iron particle according to claim 1, it is characterised in that：Dispersant
Hydroxyethyl cellulose solution or Gonak are the aqueous solution of 1~15g/L of concentration.
3. the preparation method of cellulose modifying modified Nano iron particle according to claim 2, it is characterised in that：Acetone with
Acetone and the volume ratio of absolute ethyl alcohol are 1 in absolute ethyl alcohol mixed liquor:2~1:9.
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| CN106077624B (en) * | 2016-07-26 | 2019-01-04 | 昆明理工大学 | A kind of micelle modified modified Nano nulvalent iron particle and its preparation method and application |
| CN107570213A (en) * | 2017-10-12 | 2018-01-12 | 湖北工业大学 | A kind of preparation method of ferroso-ferric oxide paper substrate heterogeneous catalysis material |
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| CN110538331B (en) * | 2019-10-15 | 2021-10-15 | 南京晓庄学院 | Method for preparing magnetic nano-particles with improved dispersibility and particle uniformity |
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| CN113058614A (en) * | 2021-03-31 | 2021-07-02 | 沈阳航空航天大学 | Regeneration method of deactivated flue gas denitration catalyst template |
| CN113477937B (en) * | 2021-07-05 | 2023-04-07 | 扬州工业职业技术学院 | Method for green synthesis of composite nano iron particles and application thereof |
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