CN103785855B - The preparation method of the bentonite embedding year nano zero valence iron that a kind of multicomponent is organically-modified - Google Patents
The preparation method of the bentonite embedding year nano zero valence iron that a kind of multicomponent is organically-modified Download PDFInfo
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Abstract
The invention discloses the preparation method of the organically-modified bentonite of a kind of multicomponent embedding year nano zero valence iron.The method is as follows: 1) bentonite pretreatment; 2) by 20-50g/L, bentonite clay particle is added 0.1MFeCl
3in solution, the fully centrifugal abandoning supernatant of mixing, repeats said process and obtains Fe 2 times
3+saturated bentonite clay particle; 3) by Fe
3+saturated bentonite clay particle drops into deionized water and regulates pH to 2-3.5, under inert gas shielding, press NaBH
4with Fe
3+mol ratio 25-35:1 adds NaBH
4, react 1-3min under room temperature, high speed centrifugation obtains the embedding Zero-valent iron-carrying of bentonite; 4) in the deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add three kinds of organic cation modifier HDTMA, TPMA and TMA, displacement reaction 15-30min in oxygen-free environment, high speed centrifugation obtains product.The present invention can improve the agglomeration of Nanoscale Iron in complicated heavy nonaqueous phase environment, promote hydrophobic properties of the surface, by three kinds of components, organically-modified and bentonite adsorption and Fe3+ reduction effect, make its environmental behaviour and form improve, and finally improve its degradation efficiency.
Description
Technical field
The invention belongs to groundwater environment pollution remediation technology field, be specifically related to the preparation method of the organically-modified bentonite of a kind of multicomponent embedding year nano zero valence iron.
Background technology
Along with the fast development of economy, China's groundwater environment pollution situation is more and more serious, wherein Organic Contamination of Groundwater is a kind of common and pollutant of difficult degradation, and how can remove the organic pollution in underground water cost-effectively, be the target that groundwater environment pollution amelioration circle is pursued always.
Since late 1980s has people to report, Zero-valent Iron can [R.W.Gillham since chlorinatedorganic in in-situ remediation of underground water, A.F.O'Hannesin.Ehanced degradation ofhalogenated aliphatics byzero-valent iron.Ground Water, 1994,32:958-967.], utilize Zero-valent Iron process organic pollutants in water body to be very popular research field always.In recent years, Zero-valent Iron has been widely used for the organic pollution materials degrading and remove in environment and inorganic pollution material.Zero-valent Iron chemical property is active, and abundance is cheap, and has certain specific area, and electronegativity is very large, electrode potential E
0(Fe
2+/ Fe)=-0.44V, there is reducing power, can will arrange in metal replacement thereafter out and be deposited on the surface of iron in metal activity series table, also can by ion stronger for oxidisability or compound and the reduction of some organic matter.Fe
2+there is reproducibility, E
0(Fe
3+/ Fe
2+)=0.771V, thus when there being oxidant to exist in water, Fe
2+fe can be oxidized to further
3+, and under certain pH condition, the hydroxide of iron can be formed, it has the effect of Adsorption and flocculation to the pollutant in solution.
Nano material refers in space three-dimensional the material having at least one dimension to be in nanoscale scope or to be formed using it as elementary cell.See region because the transition between its Commen powder between macroscopic view and elementide of microcosmic is situated between, therefore present the character of some uniquenesses, one of them important characteristic is skin effect.Skin effect refers to that the ratio of nanoparticle surface atom and total atom number diminishes with particle diameter and sharply increases rear caused qualitative change.Research shows, reduce with particle diameter, the percentage that surface atom accounts for total atom sharply increases; Meanwhile, the surface area of nano particle and surface energy also increase rapidly.Extraction and nanometer iron metal specific area is than conventional Zero-valent Iron generally large more than tens times [C.B.Wang, W.X.Zhang.Synthesizing nanoscale ironparticles for rapid and complete dechorination of TCE and PCBs.EnvironmentalScience and Technology, 1997,31 (7): 2154-2156.].This makes nano material have excellent adsorption and chemical reactivity.Just because of nano material has some new features that traditional material does not possess, become the forward position hot fields of current research.
But, the subject matter that Nanoscale Iron exists in process pollutant process is: colloidal nature and its intrinsic ferromagnetism of nano iron particles make easily to reunite when it and pollutant reaction, oxidizable, poor stability, thus have impact on its reducing power, service life and the transfer ability [T.Phenrat in porous media, T.C.Long, G.V.Lowry, B.Veronsi.Partial oxidation (aging) and surface modification decreasethe toxicity of nanosized zerovalent iron.Environmental Science and Technology, 2009, 43:195-200.].Therefore, adopt suitable carrier material and carrying method, processability is stablized, loaded with nano-iron that reactivity is high is one of Nanoscale Iron problem that must solve in actual waste water process.
Natural clay is cheap and easy to get, and specific area is large, has certain adsorption capacity to inorganic, organic pollution.Recently, some scholars, with the carrier of natural clay as Nanoscale Iron, obtain desirable result.Bentonite is a class aboundresources, cheap stratiform natural minerals clay, and its main component is montmorillonite.Bentonite basic structure is that two-layer Si-O tetrahedron therebetween one deck Al-O is octahedra, wherein Si
4+, Al
3+can by Mg
2+, Fe
2+, Li
+, Ni
2+deng ion replacement at a low price, thus cause bentonite structure cell electricity price unsaturated, make between bentonite bed, to be with permanent negative electrical charge.The hydrated cation that this negative electrical charge has exchangeability by interlayer usually balances.Therefore, natural montmorillonite have good ion exchangeable [Ren Jianmin, Fu is all over red, and Wu Siwei .CTMA intercalation modifying bentonite is to the characterization of adsorption of methyl orange. University Of Chongqing journal .2010,33:120-125.].
In view of the distinctive physicochemical property of bentonite, researcher introduces the preparation process of nano zero valence iron used as carrier, nano iron particles decentralization after load and stability are improved, and effectively decrease the agglomeration of Nanoscale Iron, and removal efficiency to environmental pollutants gets a promotion.In order to acquired can better bentonite carrier, researcher starts to utilize its ion-exchange performance to carry out suitable organic or inorganic modified to bentonite according to different environment objects, then nano zero valence iron to be carried on modified bentonite and to be applied to deoxidization, degradation aqueous phase pollutant, [Hu Liujiang, Li Yimin. organobentonite loaded with nano-iron removes Nitrobenzene in Wastewater. ACTA Scientiae Circumstantiae, 2008,28 (6): 1107-1112.].
The alta-mud loaded nano iron of modification promotes the removal efficiency of pollutant and is mainly derived from the following aspects: (1) surface area increases, this mainly for be inorganic modified method, because the layer structure that bentonite particle diameter is less, and most of exposed surface area and cation exchange site mainly concentrate on its interlayer environment [Zhu L Z, Tian S L, Zhu J X, et al.Silylated pillared clay (SPILC): A novel bentonite-basedinorgano-organo composite sorbent synthesized by integration of pillaring andsilylation [J] .Journal ofColloid and Interface Science, 2007, 315:191-199.], bentonitic interlamellar spacing can be made after inorganic modified to strengthen further, thus improve the transport efficiency of pollutant, the more Nanoscale Iron of effective exposure.(2) organic adsorption effect, this mainly for be organically-modified method, bentonite surface after organically-modified defines certain hydrophobic environment, more " tend to " dissolve in hydrophobic environment [Wu X Q according to the organic pollution in " similar compatibility " principle aqueous solution, Yang Q, Xu D C, et al.Simultaneousadsorption/reduction of bromate by nanoscale zerovalent iron supported on modifiedactivated carbon [J] .Environmental Science and Technology, 2013, 52 (35): 12571-12581.], thus improve the contact probability of pollutant and Nanoscale Iron, ultimately improve degradation reaction effect.
But, the part persistent organic pollutants paid close attention in the reparation of underground water Zero-valent Iron are mainly free in heavy nonaqueous phase, this phase water content is mainly organic phase less, the enhancement effect that modified Nano zero-valent iron particle has in aqueous phase modification might not be suitable in nonaqueous phase, particularly consider complexity and the diversity of nonaqueous phase environment, the pollutant of current existing method of modifying in process nonaqueous phase has certain limitation.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provides a kind of preparation method of the bentonite embedding year nano zero valence iron organically-modified for the treatment of the multicomponent of organic pollution in the complicated nonaqueous phase of underground water.
The method adopts embedding year Nanoscale Iron of environmentally friendly carrier material bentonite synthesis high reaction activity, and (this Zero-valent Iron is owing to synthesizing between bentonite bed, particle diameter is controlled in 1 ran, different from the alta-mud loaded nano iron of routine, the synthesis particle diameter of Nanoscale Iron is less, activity is higher, so be called bentonite embedding year Nanoscale Iron), and the typical organic cation activating agent applying three kinds of differing chemical properties carries out organically-modified to the embedding bentonite surface being loaded with nano zero valence iron, can improve the environmental behaviour of Zero-valent Iron in complex environment medium simultaneously.
Technical scheme of the present invention is as follows:
The preparation method of the bentonite embedding year nano zero valence iron that a kind of multicomponent is organically-modified is as follows:
1) bentonitic pretreatment: before composite preparation, bentonite is purified, bentonite clay particle is added in deionized water, stir after 6-10 hour, 600 ~ 650rpm low-speed centrifugal ~ 10min, bentonite clay particle particle diameter being greater than 2 microns is removed;
2) bentonitic iron ion is saturated: bentonite clay particle is added the FeCl of 0.1M by the amount adding 20 ~ 50g by often liter of solution
3in solution (bentonite concentration is 20 ~ 50g/L), under the effect of magnetic agitation, mix about 24 hours, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 20 ~ 50g by often liter of solution is again added the FeCl of 0.1M
3be uniformly mixed about 24 hours in solution and centrifugal, then repeat this process once, obtain Fe
3+saturated bentonite clay particle, then add washed with de-ionized water;
3) preparation of the embedding Zero-valent iron-carrying of bentonite: after saturated for iron ion bentonite clay particle is dropped into deoxidation deionized water, with the hydrochloric acid conditioning solution pH of 1M to 2 ~ 3.5, under inert gas shielding, by NaBH
4(sodium borohydride) adds (NaBH in particulate slurry fast
4be 25 ~ 35:1 with the mol ratio of Fe), cover tightly bottle cap rapidly, at room temperature react 1 ~ 3 minute, high speed centrifugation, obtain the embedding Zero-valent iron-carrying of bentonite;
4) the embedding Zero-valent iron-carrying of bentonite is organically-modified: in the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add three kinds of organic cation modifier HDTMA (softex kw), TPMA (trimethylphenyl tribromide ammonium) and TMA (4 bromide), wherein the exchange total amount of 3 kinds of modifier is the cation exchange capacity (CEC) of bentonite 100%; Agitating solution in oxygen-free environment, displacement reaction is about 15-30 minute, high speed centrifugation, obtains the embedding Zero-valent iron-carrying of bentonite that multicomponent is organically-modified.
In said method, the exchange capacity of HDTMA, TPMA and TMA tri-kinds of modifier can be the same, is respectively the cation exchange capacity (CEC) of bentonite 1/3.Further, different according to the characteristic of liquid phase reactor environment (the complicated nonaqueous phase namely residing for Organic Chemicals In Groundwater and liquid phase background solution), the displacement ratio of three kinds of organic cation modifier can be regulated.In above-mentioned three kinds of modifier, the polarity of TMA is comparatively large, is arrange for the liquid phase background solution that polarity is larger; The polarity of HDTMA is less, is to arrange for the liquid phase background solution that polarity is less; TPMA polarity is moderate, but has benzene ring structure, is to arrange for the liquid phase background solution containing phenyl.So, if liquid phase background solution polarity is large, then relatively suitably heighten the ratio of TMA; Otherwise, if liquid phase background solution polarity is little, then relatively suitably heighten the ratio of HDTMA; If liquid phase background solution containing benzene ring structure, then relatively suitably heightens the ratio of TPMA.
Beneficial effect of the present invention:
The present invention take natural montmorillonite as the efficient nano iron that the method for carrier liquid-phase reduction prepares embedding year type between argillic horizon, and select three kinds of figuratrix activating agents HDTMA, TPMA and TMA, by simple cation exchange reaction to the embedding bentonite modifying surface being loaded with nano zero valence iron, make the embedding bentonite surface being loaded with Nanoscale Iron have three species specificity hydrophobic groupings, improve Nanoscale Iron in complex environment to the reduction removal effect of pollutant and recycle efficiency.
The bentonite embedding year nano zero valence iron that the multicomponent that the present invention synthesizes is organically-modified, the organobentonite having a good adsorption properties to organic pollution is adopted to make the carrier of Nanoscale Iron, not only can make pollutant easily by the surface of adsorption and enrichment at loaded with nano-iron, promote the synergy of three kinds of organic modified bentonite absorption and Nanoscale Iron reduction, more owing to adding while the organically-modified group of difference, the hydrophobic performance on bentonite clay particle surface is made to have certain universality, the environmental behaviour of bentonite-zero-valent iron particle in complicated nonaqueous phase environment and form are improved, and final its degradation efficiency of raising.
Compared with the prior art, beneficial effect of the present invention is also embodied in:
(1) the inventive method operation is relatively simple, with low cost;
(2) selected in the present invention support materials bentonite is a kind of common surrounding medium, does not need Prof. Du Yucang; Three kinds of organic cations belong to environment-friendly modified material, less to environmental hazard risk;
(3) the organically-modified molecule proposing first simultaneously to use three kinds of typical cases to have different chemical property carries out modification to the embedding Zero-valent iron-carrying of clay, and the ability making Zero-valent Iron tackle complicated nonaqueous phase environment significantly promotes.
Detailed description of the invention
Below by way of specific embodiment, the invention will be further described.
Embodiment 1:
Purify to bentonite before composite preparation, added by bentonite clay particle in deionized water, stir after 6 hours, 600rpm low-speed centrifugal 10min, bentonite clay particle particle diameter being greater than 2 microns is removed; Bentonite clay particle is added the FeCl of 0.1M by the amount adding 20g by often liter of solution
3in solution, under the effect of magnetic agitation, mix about 24 hours, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 20g by often liter of solution is again added the FeCl of 0.1M
3be uniformly mixed about 24 hours in solution and centrifugal, then repeat this process once, obtain Fe
3+saturated particle, then add washed with de-ionized water; After saturated for iron ion bentonite is dropped into deoxidation deionized water, with the hydrochloride adjusted solution pH of 1M to about 2, under nitrogen protection, relative for molal quantity Fe is measured the NaBH of 25 times
4add fast in particulate slurry, cover tightly bottle cap rapidly, at room temperature react 1 minute, high speed centrifugation obtains the embedding Zero-valent iron-carrying of bentonite; In the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add 3 kinds of organic cation modifier (HDTMA, TPMA and TMA), wherein the exchange capacity of 3 kinds of modifier is respectively the cation exchange capacity (CEC) of bentonite 1/3 (namely 33.3%).Agitating solution in oxygen-free environment, reacts 15 minutes, and high speed centrifugation obtains the organically-modified embedding Zero-valent iron-carrying of bentonite of multicomponent.
The particle diameter of this Zero-valent Iron in 70% methanol aqueous solution is less than unmodified Zero-valent Iron by 35%, sinking speed slow 58%.
Embodiment 2:
Purify to bentonite before composite preparation, added by bentonite clay particle in deionized water, stir after 8 hours, 650rpm low-speed centrifugal 10min, bentonite clay particle particle diameter being greater than 2 microns is removed; Bentonite clay particle is added the FeCl of 0.1M by the amount adding 30g by often liter of solution
3in solution, under the effect of magnetic agitation, mix about 24 hours, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 30g by often liter of solution is again added the FeCl of 0.1M
3be uniformly mixed about 24 hours in solution and centrifugal, then repeat this process once, obtain Fe
3+saturated particle, then add washed with de-ionized water; After saturated for iron ion bentonite is dropped into deoxidation deionized water, with the hydrochloride adjusted solution pH of 1M to about 2.5, under nitrogen protection, relative for molal quantity Fe is measured the NaBH of 30 times
4add fast in particulate slurry, cover tightly bottle cap rapidly, at room temperature react 3 minutes, high speed centrifugation obtains the embedding Zero-valent iron-carrying of bentonite; In the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add 3 kinds of organic cation modifier (HDTMA, TPMA and TMA), wherein the exchange capacity of 3 kinds of modifier is respectively the cation exchange capacity (CEC) of bentonite 50%, 25% and 25%.Agitating solution in oxygen-free environment, reacts 25 minutes, and high speed centrifugation obtains the organically-modified embedding Zero-valent iron-carrying of bentonite of multicomponent.
With the decabromodiphenyl oxide in 60% aqueous acetone solution for target contaminant, when identical iron dosage, the Zero-valent Iron of the method synthesis than conventional nano Zero-valent Iron, do not carry out the organically-modified alta-mud loaded nano Zero-valent Iron of organically-modified alta-mud loaded nano Zero-valent Iron, single HDTMA reactivity respectively high by 84%, 37%, 17%.
Embodiment 3:
Purify to bentonite before composite preparation, added by bentonite clay particle in deionized water, stir after 10 hours, 620rpm low-speed centrifugal 10min, bentonite clay particle particle diameter being greater than 2 microns is removed; Bentonite clay particle is added the FeCl of 0.1M by the amount adding 50g by often liter of solution
3in solution, under the effect of magnetic agitation, mix about 24 hours, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 50g by often liter of solution is again added the FeCl of 0.1M
3be uniformly mixed about 24 hours in solution and centrifugal, then repeat this process once, obtain Fe
3+saturated particle, then add washed with de-ionized water; After saturated for iron ion bentonite is dropped into deoxidation deionized water, with hydrochloride adjusted solution pH to about 3, under nitrogen protection, relative for molal quantity Fe is measured the NaBH of 35 times
4add fast in particulate slurry, cover tightly bottle cap rapidly, at room temperature react 2 minutes, high speed centrifugation obtains the embedding Zero-valent iron-carrying of bentonite; In the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add 3 kinds of organic cation modifier (HDTMA, TPMA and TMA), wherein the exchange capacity of 3 kinds of modifier is respectively the cation exchange capacity (CEC) of bentonite 15%, 25% and 60%.Agitating solution in oxygen-free environment, reacts 30 minutes, and high speed centrifugation obtains the organically-modified embedding Zero-valent iron-carrying of bentonite of multicomponent.
The particle diameter of this Zero-valent Iron in 45% acetonitrile solution is less than unmodified Zero-valent Iron by 22%, sinking speed slow 34%.
Embodiment 4:
Purify to bentonite before composite preparation, added by bentonite clay particle in deionized water, stir after 7 hours, 600rpm low-speed centrifugal 10min, bentonite clay particle particle diameter being greater than 2 microns is removed; Bentonite clay particle is added the FeCl of 0.1M by the amount adding 40g by often liter of solution
3in solution, under the effect of magnetic agitation, mix about 24 hours, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 40g by often liter of solution is again added the FeCl of 0.1M
3be uniformly mixed about 24 hours in solution and centrifugal, then repeat this process once, obtain Fe
3+saturated particle, then add washed with de-ionized water; After saturated for iron ion bentonite is dropped into deoxidation deionized water, with the hydrochloride adjusted solution pH of 1M to about 3.5, under nitrogen protection, relative for molal quantity Fe is measured the NaBH of 30 times
4add fast in particulate slurry, cover tightly bottle cap rapidly, at room temperature react 2 minutes, high speed centrifugation obtains the embedding Zero-valent iron-carrying of bentonite; In the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add 3 kinds of organic cation modifier (HDTMA, TPMA and TMA), wherein the exchange capacity of 3 kinds of modifier is respectively the cation exchange capacity (CEC) of bentonite 20%, 65% and 15%.Agitating solution in oxygen-free environment, reacts 20 minutes, and high speed centrifugation obtains the organically-modified embedding Zero-valent iron-carrying of bentonite of multicomponent.
With the hexabromobiphenyl ether in the 50% benzoic acid aqueous solution for target contaminant, when identical iron dosage, the Zero-valent Iron of the method synthesis than conventional nano Zero-valent Iron, do not carry out the organically-modified alta-mud loaded nano Zero-valent Iron of organically-modified alta-mud loaded nano Zero-valent Iron, single TMA reactivity respectively high by 92%, 18%, 14%.
The present invention and existing three kinds of Zero-valent Iron contrast by embodiment, be respectively do not have embedding year of bentonite, have embedding year of bentonite, single organically-modified, activity data is all improved, and illustrates that multicomponent is organically-modified and can produce better effect in different liquid phase environments.Simultaneously, different organically-modified component ratio collocation can be selected for different liquid phase environments, optimize modification result, such as: in embodiment one, liquid phase background solution is 70% methanol aqueous solution, polarity is moderate, the exchange capacity of 3 kinds of modifier is the same, is respectively the cation exchange capacity (CEC) of bentonite 1/3 (namely 33.3%); In embodiment two, liquid phase background solution is 60% aqueous acetone solution, and polarity is on the low side, suitably heightens the reactivity that HDTMA ratio can promote Zero-valent Iron; In embodiment three, liquid phase background solution is 45% acetonitrile solution, and polarity is higher, suitably heightens the reactivity that TMA ratio can promote Zero-valent Iron; In embodiment four, background solution is 50% benzoic acid, containing benzene ring structure, suitably heightens the reactivity that TMPA ratio can promote Zero-valent Iron.
Claims (6)
1. a preparation method for the bentonite embedding year nano zero valence iron that multicomponent is organically-modified, is characterized in that, carry out as follows:
1) bentonitic pretreatment: before composite preparation, bentonite is purified, bentonite clay particle is added in deionized water, stir after 6-10 hour, 600 ~ 650rpm low-speed centrifugal, bentonite clay particle particle diameter being greater than 2 microns is removed;
2) bentonitic iron ion is saturated: bentonite clay particle is added the FeCl of 0.1M by the amount adding 20 ~ 50g by often liter of solution
3in solution, fully mix under the effect of magnetic agitation, centrifugal abandoning supernatant; The amount that the bentonite clay particle of acquisition adds 20 ~ 50g by often liter of solution is again added the FeCl of 0.1M
3abundant mixing in solution is also centrifugal, then repeats this process once, obtains Fe
3+saturated bentonite clay particle, then add washed with de-ionized water;
3) preparation of the embedding Zero-valent iron-carrying of bentonite: after saturated for iron ion bentonite clay particle is dropped into deoxidation deionized water, with hydrochloric acid conditioning solution pH to 2 ~ 3.5, under inert gas shielding, by NaBH
4add fast in particulate slurry, NaBH
4with Fe
3+mol ratio be 25 ~ 35:1, cover tightly bottle cap rapidly, at room temperature react 1 ~ 3 minute, high speed centrifugation, obtain bentonite embedding Zero-valent iron-carrying;
4) the embedding Zero-valent iron-carrying of bentonite is organically-modified: in the deoxidation deionized water being mixed with the embedding Zero-valent iron-carrying of bentonite, add three kinds of organic cation modifier HDTMA, TPMA and TMA, wherein the exchange total amount of 3 kinds of modifier is the cation exchange capacity (CEC) of bentonite 100%; Agitating solution in oxygen-free environment, displacement reaction 15-30 minute, high speed centrifugation, obtains the embedding Zero-valent iron-carrying of bentonite that multicomponent is organically-modified.
2. the preparation method of the bentonite embedding year nano zero valence iron that multicomponent as claimed in claim 1 is organically-modified, is characterized in that: step 1) in, low-speed centrifugal 10min.
3. the preparation method of the bentonite embedding year nano zero valence iron that multicomponent as claimed in claim 1 is organically-modified, is characterized in that, step 2) in, under the effect of magnetic agitation, mix 24 hours.
4. the preparation method of the bentonite embedding year nano zero valence iron that multicomponent as claimed in claim 1 is organically-modified, is characterized in that, step 3) in, with the hydrochloric acid conditioning solution pH of 1M to 2 ~ 3.5.
5. the preparation method of the bentonite embedding year nano zero valence iron that multicomponent as claimed in claim 1 is organically-modified, it is characterized in that, step 4) in, HDTMA, TPMA are the same with the exchange capacity of TMA tri-kinds of modifier, are respectively the cation exchange capacity (CEC) of bentonite 1/3.
6. the preparation method of the bentonite embedding year nano zero valence iron that multicomponent as claimed in claim 5 is organically-modified, is characterized in that, different according to the characteristic of liquid phase reactor environment, regulates the displacement ratio of three kinds of organic cation modifier; If liquid phase background solution polarity is high, then relatively heighten the ratio of TMA, reduce the ratio of HDTMA; If liquid phase background solution polarity is low, then relatively heighten the ratio of HDTMA, reduce the ratio of TMA; If liquid phase background solution containing benzene ring structure, then heightens the ratio of TPMA relatively.
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| CN107032457A (en) * | 2017-04-13 | 2017-08-11 | 齐鲁工业大学 | Application, pulping wastewater treatment method and granule electrode preparation method of the alta-mud loaded nano Zero-valent Iron in three-diemsnional electrode technology |
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