CN101428221A - Process for producing nano-Ni/Fe bimetallic material - Google Patents
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Abstract
The invention provides a method for preparing nano-sized Ni/Fe duplex metal, which comprises the following steps: firstly, preparation of iron nanoparticles: adding an ethanol aqueous solution of water-soluble Fe salts in a container, adding an aqueous solution of NaBH4 into the container under stirring in the presence of nitrogen gas to obtain black iron nanoparticles, and washing with diluted HCl and deoxygenated and deionized water for 3 to 5 times in the presence of nitrogen gas; then, soaking the iron nanoparticles in an ethanol aqueous solution of water-soluble Ni salts, and washing the resulting particles with anhydrous alcohol for 3 to 5 times; and finally, filtering and oven-drying to obtain the final product of nano-sized Ni/Fe duplex metal.
Description
Technical field
The present invention relates to be used for the dechlorination preparation methods of degrading halogenated hydrocarbons in water, be specifically related to a kind of preparation method of nanometer Ni/Fe bimetallic material.
Background technology
The research starting that " Zero-valent Iron technology " is applied to water treatment very early, but owing to there are following two key factors, serious restriction this The Application of Technology:
1, very long hydraulic detention time of this Technology Need generally needs 10～18 hours;
2, reactivity is low during zero-valent iron particle degradating chloro hydrocarbon, DCM (carrene) can not be degraded effectively, and have the chloro degree is lower, toxicity is stronger intermediate product to form and accumulation (Gillham R W, et al.Ground Water.1994,32:958-967).
Nano particle is because of having the extremely people's concern of high specific area, multistage specific surface and high surface energy.The combination of nano material and reduction dechlorination technology is greatly improved reaction rate.Simultaneously theoretical calculating show, when particle grain size less than 1 μ m, in porous media, gravity is very little to the motion and the deposition affects of colloidal solid, Brownian movement (warm-up movement) play a leading role (Yao K M, et al., Environ.Sci.Technol.1971,5 (1): 1105-1112).In the aqueous solution, as long as mild agitation, nano particle just can keep suspended state.Therefore, need not set up the reaction grid, nano-metal particle can be injected directly into (the Lien H L of processing on the spot that contaminated soil, sedimentary deposit and water-bearing layer are used for chlorohydrocarbon, et al., Colloid Surface A:Physiochem.Eng.Aspects.2001,191:97-106), also useful nanometer iron is removed heavy metal (Ponder S M, et al.Environ.Sci.Technol.2000 34:2564-2569) transforms (as NO with nitrogen
3 -) (Choe S, et al., Chemosphere.2000, report 41:1307-1311), in addition, nano particle also can be attached on the solid support, be used for open-air polluted-water and Industrial Wastewater Treatment as active carbon, zeolite and diatomite, compare as extraction-processing, aeration or reaction grid with traditional treatment technology, it provides a cheap relatively selection scheme (Lien H L, et al.Journal of Environmental Engineering.1999,1042-1047).
Wang (Wang C B, et al.Environ.Sci.Technol.1997,31 (7): 2154-2156) reported that (2～5g/100mL) can make TCE (trichloro-ethylene) and PCBs (Polychlorinated biphenyls) also dechlorination fully fast, the reaction rate constant (K after standardization to a spot of nanometer Pd/Fe metallic particles
SA) bigger 10～100 times than Zero-valent Iron.(Lien H L.Nanoscale bimetallic particles for dehalogenation ofhalogenated aliphatic compounds.Lien Hsing-Lung ' s Thesis (Ph.D)-Lehigh University.2000) such as the Lien of Lehigh university (comprises chloromethane with bimetallic nano Pd/Fe to 20 kinds of halogenated aliphatic hydrocarbons, chloro ethene, chloric ethane and haloform) when carrying out the dehalogenation test, find that nanometer Pd/Fe is not except having the dechlorination effect carrene and dichloroethanes, to other effectively dechlorination of compound, and the dechlorination product is nontoxic hydro carbons such as methane, ethane or ethene.
Zhou Hongyi of Zhejiang University (2003) and Xu Xinhua (2004) with nanometer palladium/iron as reaction material, by changing pollutant initial concentration, reaction material dosage and palladium rate factor, judge its influence, simultaneously dechlorination mechanism is inquired into the degraded of a-chlorophenol.
Above-mentioned studies show that, plate on the surface of a kind of reducing agent (as Fe, Zn) skim rise catalytic action metal (as Pt, Pd), improve dechlorination rate simultaneously just can effectively reduce activation energy, what is more important can reduce the amount of chloro accessory substance.For the bimetallic system, palladium/iron is the fastest to the dechlorination rate of chlorohydrocarbon; Simultaneously, can produce still less centre or end product.But palladium is a noble metal, and the engineering application cost is higher.Therefore need to seek cheap catalyst and replace precious metal palladium, for the technology of Zero-valent Iron is provided by the better development prospect that provides.
Summary of the invention
For solving the aforementioned problems in the prior, the invention provides the bimetallic preparation method of a kind of nanometer Ni/Fe.With the Pd/Fe bimetallic of the synthetic alternative costliness of cheap Ni/Fe bimetallic of this method dechlorination material as degrading halogenated hydrocarbons in water.
This method may further comprise the steps:
A. water-soluble Fe salt is dissolved in that to make concentration in the aqueous solution that contains 0～60% volume ethanol be 0.5mol/L～saturated Fe salt-ethanol-water solution;
B. nitrogen environment stirs the isopyknic NaBH that adds 0.5～3 times of described Fe salinity down
4The aqueous solution obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.2～1.0mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 0～60% volume ethanol aqueous solution soaking 0.5～30 minute of the water-soluble Ni salt of 0.1mmol/L～1mol/L with concentration, promptly make nanometer Ni/Fe bimetallic;
E. with nanometer Ni/Fe bimetallic absolute ethanol washing 3～5 times that make;
F. filter, dry.
In another embodiment of the present invention, this method may further comprise the steps:
A. water-soluble Fe salt is dissolved in and makes the solution that concentration is 0.8～1.2mol/L in the aqueous solution that contains 30～50% volume ethanol;
B. nitrogen environment stirs the isopyknic NaBH that adds 1.2～2 times of described Fe salinity down
4The aqueous solution obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.2～1.0mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 30～50% volume ethanol-aqueous solution soaking 5～20 minutes of the water-soluble Ni salt of 0.001～0.2mol/L with concentration, promptly make nanometer Ni/Fe bimetal granule;
E. with nanometer Ni/Fe bimetal granule absolute ethanol washing 3～5 times that make;
F. filter, dry.
In another embodiment of the present invention, this method may further comprise the steps:
A. water-soluble Fe salt is dissolved in and makes the solution that concentration is 1mol/L in the aqueous solution that contains 30% volume ethanol;
B. nitrogen environment stirs the isopyknic NaBH that adds 1.6 times of described Fe salinity down
4The aqueous solution obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.5mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 30% volume ethanol-aqueous solution soaking 10～20 minutes of the water-soluble Ni salt of 0.002mol/L with concentration, promptly make nanometer Ni/Fe bimetal granule;
E. with nanometer Ni/Fe bimetallic absolute ethanol washing 3～5 times that make;
F. filter, dry.
The bimetallic preparation method of aforesaid nanometer Ni/Fe, wherein, the temperature of described baking step can be 40～120 ℃.
The bimetallic preparation method of aforesaid nanometer Ni/Fe, wherein, described water-soluble Fe salt can be selected from iron chloride or ferric sulfate.
The bimetallic preparation method of aforesaid nanometer Ni/Fe, wherein, described water-soluble Ni salt can be selected from nickel chloride or nickelous sulfate.
Beneficial effect of the present invention is: method of the present invention can prepare the nanometer Ni/Fe bimetallic material that Ni content is 0～38% (mass percent), particularly the nanometer Ni/Fe bimetallic material of 2～8% (mass percents) has good dechlorination reaction performance, and its average diameter of particles is at 20～60nm.This material is except that the dechlorination reaction performance that possesses nanometer Fe, and it is fast also to have dechlorination speed, these poisonous middle chloro-product accumulations of no TCE, DCE and VC (vinyl chloride), and the advantage of preserving easily, and cheap.This preparation methods is economic, practical, efficient.
Description of drawings
Figure 1 shows that with H-8100 type transmission electron microscope, the transmission electron microscope spectrogram (TEM) of the nanometer Fe that the observed Fe salting liquid that does not contain ethanol makes when amplifying 80,000 times.
Figure 2 shows that with H-8100 type transmission electron microscope, the transmission electron microscope spectrogram (TEM) of the nanometer Fe that the observed Fe salting liquid that contains 30% volume ethanol makes when amplifying 80,000 times.
Figure 3 shows that with H-8100 type transmission electron microscope, the transmission electron microscope spectrogram (TEM) of the nanometer Fe that the observed Fe salting liquid that contains 50% volume ethanol makes when amplifying 80,000 times.
Figure 4 shows that the ESEM spectrogram (SEM) of the synthesis of nano Fe that obtains when using ESEM (S-4300F type, Japan) to amplify 30,000 times.
Figure 5 shows that obtain when amplifying 30,000 times with ESEM (S-4300F type, Japan) with the bimetallic ESEM spectrogram of synthesis of nano Ni/Fe (2%) (SEM).
C/C when Figure 6 shows that nanometer Ni/Fe degraded PCE
0'～t and ln (C/C
0)～t change curve.
Figure 7 shows that nanometer Ni/Fe degraded PCE and product and time curve.
Figure 8 shows that nanometer Ni/Fe degraded CT product M/M
0～t variation relation curve.
CT and product quality thereof compare variation relation curve in time when Figure 9 shows that nanometer Fe degraded CT.
The specific embodiment
The bimetallic preparation method of nanometer Ni/Fe of the present invention may further comprise the steps: at first prepare nano iron particles, in the ethanol water adding container with water-soluble Fe salt, nitrogen environment adds NaBH under stirring in container
4The aqueous solution obtains black nano iron particle, and nitrogen environment successively respectively washs nano iron particles 3～5 times with rare HCl and deoxidation deionized water down; Then, the ethanol water with water-soluble Ni salt soaks above-mentioned nano iron particles, absolute ethanol washing 3～5 times of the particle of acquisition; Filter, dry and make nanometer Ni/Fe bimetallic material.
Said method is in preparation nanometer iron and nanometer Ni/Fe step, used solvent is the aqueous solution of 0～60% volume ethanol in solubility Fe salt or the Ni salting liquid, the prepared nanoparticle size difference of the ethanolic solution of different volumes percentage is illustrated in figure 1 as the transmission electron microscope spectrogram of the nanometer Fe that the Fe salting liquid that do not add ethanol makes; Figure 2 shows that the transmission electron microscope spectrogram of the nanometer Fe that the Fe salting liquid that contains 30% volume ethanol in the solvent makes; Figure 3 shows that the transmission electron microscope spectrogram that contains the nanometer Fe that 50% volume ethanol Fe salting liquid makes in the solvent.As seen, it is bigger than the nano iron particles size that adding ethanol makes not add ethanol, and cluster is more serious; Compare with 50% ethanol and add 30% ethanol, not evident difference.Therefore in the synthesis of nano particle process, when preparation Fe or Ni solution, preferably in water, add v/v=30～50% ethanol; Consider the problem of cost, more preferably add v/v=30% ethanol.
The nanometer Ni/Fe bimetallic material that the bimetallic preparation method of aforesaid nanometer Ni/Fe can prepare nanometer Ni/Fe bimetallic material, particularly 2～8% weight that Ni content is 0～38% weight has good dechlorination reaction performance.The soak time of Ni content and nano iron particles in its product, the initial concentration of Ni salt is directly proportional.
The preparation of embodiment 1 nanometer Fe
With 1.0mol/L FeCl
36H
2O ethanol-water solution (containing the v/v=30% absolute ethyl alcohol) places closed system, inflates 2h with high pure nitrogen, and purpose is to remove dissolved oxygen in the solution.At 22 ℃ ± 1 ℃, under the magnetic stirrer condition, with 1.6mol/L NaBH
4The aqueous solution slowly joins equal-volume 1.0mol/L FeCl
36H
2In the O solution, treat all NaBH
4After solution has added, continue reaction 5min again, just can make nano iron particles.Fe
3+Be reduced and generate precipitation, reaction equation is:
4Fe
3++3BH
4-+9H
2O→4Fe
0↓+3H
2BO
3 -+12H
++6H
2↑ (1)
With the nanometer Fe for preparing successively respectively with 0.5mol/L HCl and the washing of deoxidation deionized water 3～5 times, above all operations all in nitrogen stream, carry out.
The microscopic appearance of synthetic material:
(1) Figure 2 shows that with H-8100 type transmission electron microscope, the transmission electron microscope spectrogram (TEM) of observed synthesis of nano Fe when amplifying 80,000 times.
(2) Figure 4 shows that the ESEM spectrogram (SEM) of the synthesis of nano Fe that obtains when amplifying 30,000 times with ESEM (S-4300F type, Japan).
By SEM as can be known: the average diameter scope of synthesis of nano Fe is 20～60nm (this analysis result is provided by chemistry institute of Chinese Academy of Sciences Electron Microscopy Room).
Take by weighing the nanometer Fe of 0.4g embodiment 1 preparation, use 30mL281mg/L NiCl
2Ethanol-water solution (containing the v/v=30% absolute ethyl alcohol) soaks 10min, because Ni
2+Be reduced and be deposited on the surface of iron, so just can plate skim Ni on the Fe surface.Reaction equation:
Ni
2++Fe→Ni↓+Fe
2+ (2)
The solid precipitation that generates is used absolute ethanol washing 3～5 times again, is that Bush's funnel of 0.2 μ m filter membrane filters again through built-in aperture, at last black particle is transferred in the reaction bulb in 100 ℃ of baking 4h, obtains nanometer Ni/Fe bimetallic material.Use aas determination, Ni content is 2.05%.
The bimetallic specific area of nanometer Ni/Fe that adopts nitrogen adsorption method (Autosorb-1 type specific surface and lacunarity analysis instrument, the U.S.) to measure acquisition is: 52.61 (m
2/ g).(specific area measuring is measured by The Chinese Geology Univ. (Beijing) Experiment of Analytical Chemistry chamber).
The microscopic appearance of synthetic material:
Figure 5 shows that obtain when amplifying 30,000 times with ESEM (S-4300F type, Japan) with the bimetallic ESEM spectrogram of synthesis of nano Ni/Fe (2%) (SEM).
By SEM as can be known: the average diameter scope of synthesis of nano Ni/Fe (w/w=2%) bimetal granule is 20～60nm (this analysis result is provided by chemistry institute of Chinese Academy of Sciences Electron Microscopy Room).
Embodiment 3 Ni content are the preparation of 5% nanometer Ni/Fe bimetallic material
Take by weighing the nanometer Fe of 0.4g embodiment 1 preparation, use 50mL983mg/L NiCl
2Ethanol-water solution (containing the v/v=30% absolute ethyl alcohol) soaks 6min, because Ni
2+Be reduced and be deposited on the surface of iron, so just can plate skim Ni on the Fe surface.The solid precipitation that generates is used absolute ethanol washing 3～5 times again, is that Bush's funnel of 0.2 μ m filter membrane filters again through built-in aperture, at last black particle is transferred in the reaction bulb in 100 ℃ of baking 4h, obtains nanometer Ni/Fe bimetallic material.Use aas determination, Ni content is 4.96%.
Except that soak time was 12min, other operation was identical with embodiment 3, obtains nanometer Ni/Fe bimetallic material.Use aas determination, Ni content is 8.02%.
The preservation experiment of embodiment 5 nanometer Ni/Fe and nanometer Fe:
The nanometer Ni/Fe of embodiment 2～4 preparations and the nanometer Fe of embodiment 1 preparation are placed a couple of days naturally, the result shows, the nanometer Fe of not plating Ni can be observed its surface in very short time obviously oxidized, fresh synthetic nanometer Fe is a black, in several hrs, will become light brown, become rufous within a couple of days, its surface is oxidized to iron oxide.If the nanometer Fe reaction bottle cap that oven dry is housed is opened rapidly, just can observe, the nanometer Fe of black immediately fire burns, and emit a large amount of heats.Its surface still is a black after some days and the nanometer Ni/Fe particle of oven dry is placed.When air enters into when nanometer Ni/Fe reaction bulb is housed, do not observe obvious color yet and change, illustrate that nanometer Ni/Fe is more stable in air.
(1) clearance of nanometer Ni/Fe bimetallic degraded PCE
The nanometer Ni/Fe bimetallic of embodiment 2 preparation is carried out the experimental study on degradation of PCE, and the bimetallic quality of nanometer Ni/Fe of participating in reaction is 0.39g, the PCE initial concentration C of degraded simulation
0' be 18.08mg/L, C/C when result such as table 1 and shown in Figure 6, Fig. 6 are degraded PCE for nanometer Ni/Fe
0'～t and ln (C/C
0)～t change curve.Control wherein that PCE concentration all is relative concentration in liquid and the reactant liquor, promptly the ratio of test concentrations and initial concentration is designated as C respectively
0/ C
0' and C/C
0', and ln (C/C in the reactant liquor
0) be expression reaction solution concentration and the logarithm value of controlling sample concentration ratio.The corresponding control sample PCE concentration excursion in entire reaction course of this batch experiment is 94%～102%, can ignore because of the error that causes in volatilization or the operating process in the illustrative experiment process, therefore, PCE concentration descends owing to existing nanometer Ni/Fe bimetallic to cause in reaction system in nanometer Ni/Fe bimetallic～PCE reaction system.
Table 1 nanometer Ni/Fe bimetallic degraded PCE (Ni/Fe=2%, 0.39g, C
0'=18.08mg/L)
Nanometer Ni/Fe bimetallic has tangible dechlorination effect to PCE as can be seen from Table 1: reaction is carried out 2.5h, test concentrations and initial concentration ratio C/C in the PCE reaction bulb
0' be 0.395, promptly clearance is 60.5%; 9.5h the time, nanometer Ni/Fe is 99.6% to the PCE clearance, shows that PCE is degraded substantially fully.
(2) the dechlorination product of nanometer Ni/Fe bimetallic degraded PCE
Table 2 and Fig. 7 are the dechlorination result of nanometer Ni/Fe bimetallic simulation PCE solution, and each constituent mass is used respectively and controlled total carbon molar fraction (M/M in the sample
0) expression.
Table 2 nanometer Ni/Fe degraded PCE and product result thereof
By table 2 and Fig. 7 as can be known, along with PCE concentration constantly reduces, C
2H
6Concentration immediately and increase sharply, its change in concentration is little behind 4.0h, accounts for 103% of initial PCE total carbon, is main catabolite.In the whole process of experiment, detect a spot of C is arranged
2H
4Produce, reach maximum when 1h, account for total carbon 6.3%, and its concentration increases afterwards earlier and reduce, behind the 4.0h, concentration is lower than detection limit; And C
2H
2Concentration be lower than the method detection limit always.Therefore, can think and in the process of PCE dechlorination, not have TCE, DCE and these poisonous middle chloro-products generations of VC that end product is an ethane.
Embodiment 7 nanometer Ni/Fe bimetallics degraded CT
Get the nanometer Ni/Fe bimetallic of 0.39g embodiment 2 preparations, adding the 50mL initial concentration is in the simulation reaction liquid of 26.28mg/LCT, oscillation rate 170 times/minute.Experimental result such as table 3 and shown in Figure 8, when 0.5h was carried out in reaction, nanometer Ni/Fe reached 90% to the CT clearance, produce the TCM (25%) of maximum simultaneously, but when 4h, TCM was degraded fully again.In degradation process, detected 15%DCM and along with the reaction time increase to change little.
Product situation when table 3 nanometer Ni/Fe degrades to CT
Comparative example 1 nanometer Fe degraded CT
Get the nanometer Fe of 0.38g embodiment 1 preparation, adding the 50mL initial concentration is in the simulation reaction liquid of 26.28mg/L CT, oscillation rate 170 times/minute.Experimental result such as table 4 and shown in Figure 9, when reaction 1h, nanometer Fe is 89% to the CT clearance, and produced simultaneously TCM accounts for total carbon 59%, and then along with reaction is proceeded, TCM reduces again gradually, and when 8h, TCM reduces to 33%.Along with the reaction time increases, DCM slowly increases.Along with the reaction time increases, CH
4Amount increases gradually, as reaction 6h, 19% CH is arranged
4Produce, remain unchanged substantially then.
Product situation when table 4 nanometer Fe is degraded to CT
The experimental result of comparing embodiment 7 and comparative example 1 as can be known, the speed of the nanometer Ni/Fe bimetallic of the inventive method preparation degraded CT is fast than nanometer Fe, and produces harmful intermediate product TCM still less.
Claims (6)
1. the bimetallic preparation method of nanometer Ni/Fe is characterized in that, may further comprise the steps:
A. water-soluble Fe salt is dissolved in that to make concentration in the aqueous solution that contains 0～60% volume ethanol be 0.5mol/L～saturated Fe salt-ethanol-water solution;
B. nitrogen environment stirs the isopyknic NaBH4 aqueous solution that adds 0.5～3 times of described Fe salinity down, obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.2～1.0mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 0～60% volume ethanol aqueous solution soaking 0.5～30 minute of the water-soluble Ni salt of 0.1mmol/L～1mol/L with concentration, promptly make nanometer Ni/Fe bimetallic;
E. with nanometer Ni/Fe bimetallic absolute ethanol washing 3～5 times that make;
F. filter, dry.
2. the bimetallic preparation method of nanometer Ni/Fe according to claim 1 is characterized in that, may further comprise the steps:
A. water-soluble Fe salt is dissolved in and makes the solution that concentration is 0.8～1.2mol/L in the aqueous solution that contains 30～50% volume ethanol;
B. nitrogen environment stirs the isopyknic NaBH that adds 1.2～2 times of described Fe salinity down
4The aqueous solution obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.2～1.0mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 30～50% volume ethanol-aqueous solution soaking 5～20 minutes of the water-soluble Ni salt of 0.001～0.2mol/L with concentration, promptly make nanometer Ni/Fe bimetal granule;
E. with nanometer Ni/Fe bimetal granule absolute ethanol washing 3～5 times that make;
F. filter, dry.
3. the bimetallic preparation method of nanometer Ni/Fe according to claim 2 is characterized in that, may further comprise the steps:
A. water-soluble Fe salt is dissolved in and makes the solution that concentration is 1mol/L in the aqueous solution that contains 30% volume ethanol;
B. nitrogen environment stirs the isopyknic NaBH that adds 1.6 times of described Fe salinity down
4The aqueous solution obtains black nano iron particle;
C. nitrogen environment successively respectively washs nano iron particles 3～5 times with 0.5mol/L HCl and deoxidation deionized water down;
D. be the above-mentioned nano iron particles of 30% volume ethanol-aqueous solution soaking 5～20 minutes of the water-soluble Ni salt of 0.002mol/L with concentration, promptly make nanometer Ni/Fe bimetal granule;
E. with nanometer Ni/Fe bimetallic absolute ethanol washing 3～5 times that make;
F. filter, dry.
4. according to the bimetallic preparation method of each described nanometer Ni/Fe in the claim 1～3, it is characterized in that the temperature of described baking step is 40～120 ℃.
5. according to the bimetallic preparation method of each described nanometer Ni/Fe in the claim 1～3, it is characterized in that described water-soluble Fe salt is selected from iron chloride or ferric sulfate.
6. according to the bimetallic preparation method of each described nanometer Ni/Fe in the claim 1～3, it is characterized in that described water-soluble Ni salt is selected from nickel chloride or nickelous sulfate.
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