CN103708598B - One is utilized method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment - Google Patents
One is utilized method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment Download PDFInfo
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Abstract
The invention discloses one and utilize method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, comprise liquid storage tank, peristaltic pump, water distribution dividing plate, reaction-filling post, heat-insulation system, sample tap, whole reaction unit is anaerobic environment, to the composite solution that passes into the second alcohol and water of PCB77 in the packed column of Ni-Fe duplex metal nano granule and quartz sand mixture is housed, catalytic hydrogenation at Ni-Fe duplex metal nano granule issues rawore, and the degradation rate of PCB77 can reach more than 90%. The hydraulic detention time of the composite solution of the second alcohol and water of technical solution of the present invention control PCB77 in reactor and reaction total time, have very high degradation rate for persistent pollutant PCB in water environment, and processing cost is lower, do not cause secondary pollution.
Description
Technical field
The invention belongs to the recovery technique field of water environment pollution, more particularly, relate to polychlorinated biphenyl in water environmentThe harmless treatment of material, is specially one and utilizes the side of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environmentMethod and device.
Background technology
Polychlorinated biphenyls (PolychlorinatedBiphenyls is called for short PCBs) is that in environment, a kind of typical persistence is organicPollutant. Because it has higher chemical inertness, heat endurance, anti-flammability, thermal conductivity and insulating properties, once extensively shouldFor fields such as power industry, Plastics Processing Industry, chemical industry and printings. According to the World Health Organization's statistics,Since eighties of last century starts to produce the twenties, to the end of the eighties, the whole world has produced approximately 2 × 10 altogether7T Industrial PC Bs,Wherein approximately 31% be discharged in environment. Because PCBs has biological accumulation and " three cause " effect, can be at global modelEnclose interior long-distance migration, and in its migration, conversion process, can be bioaccumulation amplification, its concentration level may be carriedEven hundreds of times of high decades of times, produce threat greatly to ecological environment and health. United Nations Environment Programme is by itClassify one of preferential 12 kinds of persistence toxic organic pollutants controlling in the whole world as, and most industry country is in 20 generationRecord after the seventies, stopped producing Polychlorinated biphenyls, but due to its stable in properties, be difficult for degrading in environment, many chlorineBiphenyl also will continue a very long time to the pollution of environment.
In view of the generality that PCBs exists in water body, Chinese scholars has been carried out for the degraded of PCBs in recent ten yearsA series of research, research shows, the committed step of PCBs degraded is dechlorination reaction, the method for employing mainly contain hydrogenization method,Chlorinolysis method, reversion method and metal deoxidization etc. Wherein, utilizing metal deoxidization to process Polychlorinated biphenyls is to live most at presentThe investigative technique jumping, has very large potential, is even considered to have most abroad one of method of application prospect.Zero-valent metal is owing to having very strong reproducibility, and cheap and easy to get, therefore can be used as reducing agent, makes Polychlorinated biphenyls slough chlorineAtom, thereby the toxicity of reduction Polychlorinated biphenyls. Conventional zero-valent metal has iron, aluminium, magnesium, zinc and tin etc., numerous zeroIn valency metal, utilize the reduction of Zero-valent Iron and compound thereof to remove the most study of halogenated organic and Polychlorinated biphenyls, and iron forEnvironment is safe from harm, so become more conventional Polychlorinated biphenyls catalysis dechlorination method.
Metal deoxidization has good application prospect aspect Polychlorinated biphenyls in removal water environment. Grittini studies and shows,Under normal temperature and pressure conditions, Zero-valent Iron is generally difficult to react with Polychlorinated biphenyls, if but use Pd/Fe combination just canMake the dechlorination of Polychlorinated biphenyls fast restore. Wherein Pd has played the effect of catalysis dechlorination. Expensive due to Pd, canConsider to replace Pd as catalyst with Ni, also can reach higher Degradation Level. Ni/Fe duplex metal nano granule costLow, preparation technology is simple and easy to control, and reaction condition gentleness is removed Polychlorinated biphenyls speed high, and the reaction time also contracts than feShort much, therefore Ni/Fe duplex metal nano granule has larger application prospect in the time processing in water environment PCBs. ForIncrease the application of polluter in Ni/Fe duplex metal nano granule degradation water environment, designed a kind of packed column and can followLoop reactor, is fixed on Ni/Fe duplex metal nano granule in the middle of filler, has avoided duplex metal nano granule to be entrained inIn water body, cause secondary pollution, this device has larger application prospect.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, for the water body that contains Polychlorinated biphenyls, provide a kind of and utilizeThe method of Ni-Fe duplex metal nano granule degradation of polychlorinated biphenyl, after the immobilization of Ni/Fe duplex metal nano granule, carriesFor a kind of device that more has using value.
Technical purpose of the present invention is achieved by following technical proposals:
One is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, comprises liquid storage tank, wrigglesMoving pump, the first water distribution dividing plate, the second water distribution dividing plate, reaction-filling post, heat-insulation unit, outflow tube, return duct and reactionDevice, wherein:
Described liquid storage tank is connected with peristaltic pump pipeline, and described peristaltic pump is connected with the bottom pipeline of reactor;
Reaction-filling post is set in described reactor, and arrange at the lower surface place of described reaction-filling post the first water distribution everyPlate, arranges the second water distribution dividing plate in the upper end surface of described reaction-filling post;
In the outer setting heat-insulation unit of described reactor, it utilizes temperature sensor and heat hot galvanic couple to being provided with reactionThe reactor of packed column heats and temperature control, so that the temperature kept stable of reaction-filling post;
The top of described reactor is connected with return duct with outflow tube respectively by pipeline, and the top of described reactor is passed through backStream pipe is connected with liquid storage tank.
In above-mentioned reaction unit, in the vertical direction of reactor, bottom-up the first sample tap, second that sets gradually is gotSample mouth and the 3rd sample tap, below, the second sample tap that described the first sample tap is arranged on the first water distribution dividing plate are arranged on insteadAnswer centre and the 3rd sample tap of packed column to be arranged on the top of the second water distribution dividing plate, to the water of the reactor of flowing through is carried outSampling detects.
In above-mentioned reaction unit, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume, adopts Ni-Fe twoMetal nanoparticle and quartz sand mix and form, the mixing of wherein said Ni-Fe duplex metal nano granule and quartz sandVolume ratio is 1:(8-12), preferably adopt mechanical agitation mode to mix; Described quartz sand is 60-80 orders, instituteThe particle of stating Ni-Fe duplex metal nano granule is 40-70nm, and specific area is 25-35m2/ g, according to following stepBe prepared:
Step 1, is dissolved in the PVP of 5 mass parts in deionized water, obtains mass body volume concentrations and be 10% PVP solution;
Step 2, takes NiCl2·6H2O is dissolved in deionized water, obtains NiCl2Solution;
Step 3, gets the NiCl that PVP solution that step 1 obtains and step 2 obtain2Solution, then add deionized water and secondAlcohol, obtains mixed solution, and passes into deoxygenation after inert gas, and PVP solution, step 2 that wherein step 1 obtains obtainNiCl2The volume ratio of solution, deionized water and ethanol is (7-8): 1:(20-22): 20, preferably 7.5:1:21.5:20, described inert gas is selected nitrogen, argon gas or helium, and the deoxygenation time is 20-30min;
Step 4, takes FeSO4·7H2O adds in the mixed solution that step 3 obtains, and fully dissolves, and is chosen in rotating speedBe to mix 15-20min under the mechanical agitation condition of 1500-2000r/min, make FeSO4·7H2O powder fully dissolves;
Step 5 drips NaBH in the solution obtaining in step 44Solution completes dropping in 15-20min, dripsAdd after end under the mechanical agitation condition that is 1500-2000r/min at rotating speed and stir 20-30min, described NaBH4SolutionBe the NaBH of 0.12-0.13g4Powder is dissolved in percentage by volume 40% ethanol water of 10ml, after stirringArrive;
Step 6, after stirring finishes, after collecting by magnetic method, washing is dried, and can obtain Ni-Fe duplex metal nano granule;
Wherein Fe2+And BH4 —Molar ratio 1:2, for reduction reaction is fully carried out, preferably excessive NaBH4MoltenLiquid; The consumption of described nickel is 2%-5% of ferrous iron (being ferro element) quality; In technique scheme, a step realizesFollowing whole course of reaction:
Fe2++6H2O+2BH4 -→Fe↓+2Be(OH)3+7H2↑
Ni2++6H2O+2BH4 -→Ni↓+2Be(OH)3+7H2↑
In this course, because the addition of elemental nickel is less and system is carried out fully under churned mechanically condition continuingMix and reaction, after drop reaction finishes, can form the composite nanometer particle of nickel and iron. Metal Ni plays catalystAct on, can accelerate the dechlorination efficiency of Zero-valent Iron, conventionally select Ni/Fe duplex metal nano granule degraded cheap and easy to get manyChlordiphenyl. The liquid phase reduction of selecting has simple to operate, and process controllability is strong, and cost is the advantage such as lower also, conventionally choosingPrepare Ni/Fe duplex metal nano granule with sodium borohydride liquid phase reduction, but the nano particle of preparing easily reunites,Affect degradation efficiency, so add stabilizing agent PVP(K30 in liquid phase preparation process), PVP(K30) can preventThe reunion of nano particle, also can not exert an influence to the degradation process of bimetallic system.
In above-mentioned reaction unit, described reaction unit is airtight on the whole, in order to avoid oxygen enters in reaction unit, rightNi-Fe duplex metal nano granule causes oxidation, causes reaction rate greatly to reduce.
In above-mentioned reaction unit, described outflow tube is connected by triple valve with return duct.
In above-mentioned reaction unit, on described the first water distribution dividing plate and the second water distribution dividing plate, be uniformly distributed water distributing pore, described water distributionThe aperture in hole is 0.01mm-0.3mm; For preventing the seepage of quartz sand and Ni-Fe duplex metal nano granule, describedIn the one side contacting with reaction-filling post of one water distribution dividing plate and the second water distribution dividing plate, gauze is set; Described the first water distribution dividing plateBe lucite with the material of the second water distribution dividing plate, thickness is 3-5mm.
Utilize the method for Polychlorinated biphenyls in above-mentioned reaction unit degradation water environment, carry out according to following step:
Step 1, is placed in liquid storage tank by the solution that contains Polychlorinated biphenyls, and opens peristaltic pump;
Step 2, described in contain Polychlorinated biphenyls solution entered by reactor bottom, after water-distributing device water distribution uniformity, logicalCross reaction-filling post;
Step 3, the state of adjustment triple valve, so that the solution that contains Polychlorinated biphenyls is back in liquid storage tank via return duct;
Step 4, repeats above-mentioned steps so that the solution that contains Polychlorinated biphenyls circulates in reactor, and divides by sample tapAnalyse the removal effect of Polychlorinated biphenyls;
Step 5, in the time that the removal effect of Polychlorinated biphenyls reaches preset requirement, adjusts the state of triple valve, so that solution is by going out streamPipe flows out.
In such scheme, by regulating the Flow-rate adjustment solution of the peristaltic pump hydraulic detention time in reaction-filling post, everyThe hydraulic detention time of individual circulation is 60min-90min, and the total hrt of whole reaction is 48-72h.
In such scheme, to move under constant temperature by the whole reaction of heat-insulation unit control, temperature is 30-40 DEG C.
In such scheme, described in contain Polychlorinated biphenyls solution in, the concentration of Polychlorinated biphenyls is 3mg/L-5mg/L.
In such scheme, in described reaction unit, comprise that reactor, liquid storage tank, reaction-filling post and pipeline thereof are all pre-First use inert gas (as nitrogen, helium, argon gas) to carry out deoxygenation.
The present invention utilizes Ni/Fe duplex metal nano granule, the pollution by polychlorinated biphenyles thing in efficient degradation water environment, and employing is filled outFill post loop reactor, flow process is simple, and controllability is strong, and cost is also lower. The one that the present invention proposes is utilized Ni/FeIn duplex metal nano granule degradation water environment, the method for Polychlorinated biphenyls, is fixed on quartz sand by Ni/Fe duplex metal nano granuleIn filler, when Polychlorinated biphenyls ethanol-aqueous solution passes through filler continuously, bimetallic carries out dechlorination to Polychlorinated biphenyls.
Brief description of the drawings
Fig. 1 is the structural representation that one of the present invention is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environmentFigure, wherein 1 is liquid storage tank, and 2 is peristaltic pump, and 3-1 is the first water distribution dividing plate, and 3-2 is the second water distribution dividing plate, 4 areReaction-filling post, 5 is heat-insulation unit (system), and 6 is outflow tube, and 7 is return duct, and 8 is triple valve, 9-1 isOne sample tap, 9-2 is the second sample tap, and 9-3 is the 3rd sample tap, and 10 is reactor.
Fig. 2 is the structural representation of the water distribution dividing plate that uses in the present invention, and 11 is water distributing pore.
Fig. 3 is the SEM photo of Ni-Fe duplex metal nano granule of using in the present invention.
Fig. 4 is the design sketch while utilizing device of the present invention to degrade PCB77 ethanol-aqueous solution.
Detailed description of the invention
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
As shown in accompanying drawing 1-2, utilize the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, bagDraw together liquid storage tank, peristaltic pump, the first water distribution dividing plate, the second water distribution dividing plate, reaction-filling post, heat-insulation unit, outflow tube,Return duct and reactor, wherein:
Described liquid storage tank is connected with peristaltic pump pipeline, and described peristaltic pump is connected with the bottom pipeline of reactor;
Reaction-filling post is set in described reactor, and arrange at the lower surface place of described reaction-filling post the first water distribution everyPlate, arranges the second water distribution dividing plate in the upper end surface of described reaction-filling post;
In the outer setting heat-insulation unit of described reactor, it utilizes temperature sensor and heat hot galvanic couple to being provided with reactionThe reactor of packed column heats and temperature control, so that the temperature kept stable of reaction-filling post;
The top of described reactor is connected with return duct with outflow tube respectively by pipeline, and the top of described reactor is passed through backStream pipe is connected with liquid storage tank.
In above-mentioned reaction unit, in the vertical direction of reactor, bottom-up the first sample tap, second that sets gradually is gotSample mouth and the 3rd sample tap, below, the second sample tap that described the first sample tap is arranged on the first water distribution dividing plate are arranged on insteadAnswer centre and the 3rd sample tap of packed column to be arranged on the top of the second water distribution dividing plate, to the water of the reactor of flowing through is carried outSampling detects.
In above-mentioned reaction unit, described reaction unit is airtight on the whole, in order to avoid oxygen enters in reaction unit, rightNi-Fe duplex metal nano granule causes oxidation, causes reaction rate greatly to reduce. Described outflow tube and return duct are by threewayValve connects. On described the first water distribution dividing plate and the second water distribution dividing plate, be uniformly distributed water distributing pore, the aperture of described water distributing poreFor 0.1mm-0.3mm; For preventing the seepage of quartz sand and Ni-Fe duplex metal nano granule, at described the first water distribution dividing plateWith in the one side contacting with reaction-filling post of the second water distribution dividing plate, gauze is set; Described the first water distribution dividing plate and the second water distributionThe material of dividing plate is lucite, and thickness is 3-5mm.
In above-mentioned reaction unit, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume, adopts the two gold of Ni-FeMetal nano-particle and quartz sand mix and form, the mixture of wherein said Ni-Fe duplex metal nano granule and quartz sandLong-pending than being 1:(8-12), preferably adopt mechanical agitation mode to mix; Described quartz sand is 60-80 orders, described inThe particle of Ni-Fe duplex metal nano granule is 40-70nm, and specific area is 25-35m2/ g(is as shown in Figure 3),Be prepared according to following step:
(1) by 5gPVP(K30) be dissolved in deionized water, fully mix by magnetic agitation, be settled to 50ml, obtainMass body volume concentrations is 10% PVP solution.
(2) take the NiCl of metered amount2·6H2O powder, is dissolved in deionized water, obtains its standard liquid.
NiCl2·6H2The quality of O powder determines by Ni/Fe, and the use amount of nickel is weight of iron 2-5%, its metered amount phaseWhen dissolve NiCl in every milliliter of standard liquid2·6H2The quality of O powder is in 0.00168-0.0042 scope.NiCl2·6H2O and FeSO4·7H2The relation of O is as following table:
(3) get as described in (1) 7.5mlPVP solution, add 1ml(2) NiCl2Standard liquid, deionized water 21.5ml,Ethanol 20ml, proceeds in there-necked flask after mixing, letting nitrogen in and deoxidizing 20-30min. Overall solution volume is 50ml.
(4) take 0.417gFeSO4·7H2O powder adds in above-mentioned solution, the machinery that is 1500-2000r/min at rotating speedUnder stirring condition, mix 15-20min, make FeSO4·7H2O powder fully dissolves, now FeSO4·7H2O moleConcentration is 0.03mol/L.
(5) slowly in there-necked flask, drip NaBH4Solution, according to n (Fe2+) and n (BH4 —) ratio 1:2, NaBH4For0.003mol, considers a small amount of Ni of reduction2+Needs and operating process loss, carry out configuration NaBH for ensureing to react completely4When solution, claim slightly excessive NaBH4Powder, the NaBH of weighing 0.12-0.13g4It is molten that powder is dissolved in 40% ethanol of 10mlIn liquid, after stirring, obtain NaBH4Solution completes dropping in 15-20min, after dropping finishes, at rotating speed isUnder the mechanical agitation condition of 1500-2000r/min, stir 20-30min.
(6) after stirring finishes, collect by magnetic method, the Ni-Fe nano particle obtaining washs 3-4 times with deoxidation distilled water,Absolute ethanol washing 1-2 times, can the auxiliary washing of ultrasonic dispersion to remove residual ion and organic matter in solution. WashingAfter end, collect by magnetic method, the Ni/Fe duplex metal nano granule obtaining, through vacuum drying, weighs, and is about a 0.1g left sideRight.
Obtain the concentration of the PCB77 of each sample point by GC-ECD Instrument measuring, the concentration of 0h is designated as initial concentrationC0, the concentration recording is afterwards designated as measurement concentration C, and degradation rate calculates by following formula, as shown in Figure 4.
The solution that contains Polychlorinated biphenyls is the ethanol-aqueous solution of Polychlorinated biphenyls, selects PCB77 as target stainsThing is implemented, the reaction-filling post that Ni/Fe duplex metal nano granule prepared by use said method and quartz sand mix.
Embodiment 1
The small aperture of water distribution dividing plate is 0.01mm, and in reaction-filling post, the floor height of quartz sand accounts for 3/5 of whole cylinder. ?Before liquid storage tank adds PCB77 ethanol-aqueous solution, whole device in advance logical nitrogen makes it in anaerobic environment, whole reactionIn process, reaction unit keeps the constant temperature of 30 DEG C by heat-insulation system. Reaction-filling post is put into quartz sand and Ni/Fe in advanceThe homogeneous mixture of duplex metal nano granule, mixed proportion is 1:9. In liquid storage tank, adding concentration is the PCB77 of 5mg/LEthanol-aqueous solution, this solution also carried out letting nitrogen in and deoxidizing in advance. Open peristaltic pump, make the stop of solution in filled columnTime is 60min, changes in the 3rd sample tap sampling and measuring PCB77 solution concentration, and in 48h, solution is filled out by reactionWhen stock column, outflow tube is all in closure state, and solution is back to liquid storage tank by return duct. In the time that the reaction time is 48h,Closed return duct, starts outflow tube, and reaction finishes. In course of reaction, observe PCB77 solution in the 3rd sample tap positionChange in concentration, finally recording degradation efficiency is 88%.
Embodiment 2
The small aperture of water distribution dividing plate is 0.1mm, and in reaction-filling post, the floor height of quartz sand accounts for 3/5 of whole cylinder. In storageBefore liquid pool adds PCB77 ethanol-aqueous solution, whole device in advance logical nitrogen makes it in anaerobic environment, whole reactionIn journey, reaction unit keeps the constant temperature of 40 DEG C by heat-insulation system. Quartz sand put in advance by reaction-filling post and Ni/Fe is twoThe homogeneous mixture of metal nanoparticle, mixed proportion is 1:12. In liquid storage tank, adding concentration is the PCB77 of 5mg/LEthanol-aqueous solution, this solution also carried out letting nitrogen in and deoxidizing in advance. Open peristaltic pump, make the stop of solution in filled columnTime is 90min, changes in the 3rd sample tap sampling and measuring PCB77 solution concentration, and in 60h, solution is filled out by reactionWhen stock column, outflow tube is all in closure state, and solution is back to liquid storage tank by return duct. In the time that the reaction time is 60h,Closed return duct, starts outflow tube, and reaction finishes. In course of reaction, observe PCB77 solution in the 3rd sample tap positionChange in concentration. Finally recording degradation efficiency is 93%.
Embodiment 3
The small aperture of water distribution dividing plate is 0.3mm, and in reaction-filling post, the floor height of quartz sand accounts for 2/3 of whole cylinder. In storageBefore liquid pool adds PCB77 ethanol-aqueous solution, whole device in advance logical nitrogen makes it in anaerobic environment, whole reactionIn journey, reaction unit keeps the constant temperature of 35 DEG C by heat-insulation system. Quartz sand put in advance by reaction-filling post and Ni/Fe is twoThe homogeneous mixture of metal nanoparticle, mixed proportion is 1:8. In liquid storage tank, adding concentration is the PCB77 of 5mg/LEthanol-aqueous solution, this solution also carried out letting nitrogen in and deoxidizing in advance. Open peristaltic pump, make the stop of solution in filled columnTime is 80min, changes in the 3rd sample tap sampling and measuring PCB77 solution concentration, and in 72h, solution is filled out by reactionWhen stock column, outflow tube is all in closure state, and solution is back to liquid storage tank by return duct. In the time that the reaction time is 72h,Closed return duct, starts outflow tube, and reaction finishes. In course of reaction, observe PCB77 solution in the 3rd sample tap positionChange in concentration. Finally recording degradation efficiency is 97.4%.
Above the present invention is done to exemplary description, should be noted that in the situation that not departing from core of the present invention,The replacement that is equal to that any simple distortion, amendment or other those skilled in the art can not spend creative work all fallsEnter protection scope of the present invention.
Claims (5)
1. a device that utilizes Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, is characterized in that, comprises liquid storage tank, peristaltic pump, the first water distribution dividing plate, the second water distribution dividing plate, reaction-filling post, heat-insulation unit, outflow tube, return duct and reactor, wherein:
Described liquid storage tank is connected with peristaltic pump pipeline, and described peristaltic pump is connected with the bottom pipeline of reactor;
Reaction-filling post is set in described reactor, and at the lower surface place of described reaction-filling post, the first water distribution dividing plate is set, the second water distribution dividing plate is set in the upper end surface of described reaction-filling post;
In the outer setting heat-insulation unit of described reactor, it utilizes temperature sensor and heat hot galvanic couple to heat and temperature control being provided with the reactor of reaction-filling post, so that the temperature of reaction-filling post keeps stable;
The top of described reactor is connected with return duct with outflow tube respectively by pipeline, and the top of described reactor is connected with liquid storage tank by return duct, and described outflow tube is connected by triple valve with return duct;
Bottom-up the first sample tap, the second sample tap and the 3rd sample tap of setting gradually in the vertical direction of reactor, described the first sample tap is arranged on the below of the first water distribution dividing plate, centre and the 3rd sample tap that the second sample tap is arranged on reaction-filling post is arranged on the top of the second water distribution dividing plate, to the water of the reactor of flowing through is sampled to detection;
Described reaction-filling post adopts Ni-Fe duplex metal nano granule and quartz sand to mix and forms, and the mixed volume of wherein said Ni-Fe duplex metal nano granule and quartz sand is than being 1:(8-12); Described quartz sand is 60-80 orders, and the particle of described Ni-Fe duplex metal nano granule is 40-70nm, and specific area is 25-35m2/ g, is prepared according to following step:
Step 1, is dissolved in 5gPVP (K30) in deionized water, fully mixes by magnetic agitation, is settled to 50ml, obtains mass body volume concentrations and be 10% PVP solution;
Step 2, takes NiCl2·6H2O is dissolved in deionized water, obtains NiCl2Solution;
Step 3, gets the NiCl that PVP solution that step 1 obtains and step 2 obtain2Solution, then add deionized water and ethanol, obtain mixed solution, and pass into inert gas deoxygenation, the PVP solution that wherein step 1 obtains, the NiCl that step 2 obtains2The volume ratio of solution, deionized water and ethanol is (7-8): 1:(20-22): 20, described inert gas is selected nitrogen, argon gas or helium, and the deoxygenation time is 20-30min;
Step 4, takes FeSO4·7H2O adds in the mixed solution that step 3 obtains, and fully dissolves, and is chosen in rotating speed and is under the mechanical agitation condition of 1500-2000r/min to mix 15-20min, makes FeSO4·7H2O powder fully dissolves;
Step 5 drips NaBH in the solution obtaining in step 44Solution completes dropping in 15-20min, drips after finishing under the mechanical agitation condition that is 1500-2000r/min at rotating speed and stirs 20-30min, described NaBH4Solution is the NaBH of 0.12-0.13g4Powder is dissolved in percentage by volume 40% ethanol water of 10mL, after stirring, obtains;
Step 6, after stirring finishes, after collecting by magnetic method, washing is dried, and can obtain Ni-Fe duplex metal nano granule;
Wherein Fe2+And BH4 -Molar ratio 1:2; The consumption of nickel is 2%-5% of ferrous iron quality.
2. one according to claim 1 is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, it is characterized in that, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume.
3. one according to claim 1 is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, it is characterized in that, on described the first water distribution dividing plate and the second water distribution dividing plate, be uniformly distributed water distributing pore, the aperture of described water distributing pore is 0.01mm-0.3mm, the material of described the first water distribution dividing plate and the second water distribution dividing plate is lucite, and thickness is 3-5mm.
4. one according to claim 3 is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, it is characterized in that, for preventing the seepage of quartz sand and Ni-Fe duplex metal nano granule, in the one side contacting with reaction-filling post of described the first water distribution dividing plate and the second water distribution dividing plate, gauze is set.
5. one according to claim 1 is utilized the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment, it is characterized in that, described device is airtight on the whole, in order to avoid oxygen enters in reaction unit, Ni-Fe duplex metal nano granule is caused to oxidation, cause reaction rate greatly to reduce.
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| CN105195758B (en) * | 2015-08-27 | 2017-11-21 | 太原理工大学 | A kind of Preparation method and use of nano zero-valence iron-copper bi-metal particle |
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| CN103708598A (en) | 2014-04-09 |
| CN104817156B (en) | 2017-07-21 |
| CN104817156A (en) | 2015-08-05 |
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