CN103708598A - Method and device for degrading polychlorinated biphenyl (PCB) in water environment by using Ni-Fe bimetal nanoparticles - Google Patents
Method and device for degrading polychlorinated biphenyl (PCB) in water environment by using Ni-Fe bimetal nanoparticles Download PDFInfo
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Abstract
The invention discloses a method and device for degrading polychlorinated biphenyl (PCB) in a water environment by using Ni-Fe bimetal nanoparticles. The device comprises a liquid storage tank, a peristaltic pump, a water distribution clapboard, a reaction packing column, a heat insulation system and a sampling port. The whole reaction device is in an anaerobic environment. An ethanol and water compound solution of PCB77 is introduced into the packing column filled with a mixture of the Ni-Fe bimetal nanoparticles and quartz sand, mineralization is generated under the catalytic hydrogenation effect of the Ni-Fe bimetal nanoparticles, and the PCB77 degradation rate can reach more than 90 percent. Due to the adoption of the technical scheme, the hydraulic retention time and the total reaction time of the ethanol and water compound solution of PCB77 in a reactor can be controlled; a high degradation rate of persistent pollutant, namely PCB in the water environment is achieved; in addition, the treatment cost is relatively low and no secondary pollution is caused.
Description
Technical field
The invention belongs to the recovery technique field of water environment pollution, more particularly, relate to the harmless treatment of polychlorinated biphenyl material in water surrounding, be specially method and the device of polychlorobiphenyl in a kind of Ni of utilization-Fe duplex metal nano granule degradation water environment.
Background technology
Polychlorobiphenyl (PolychlorinatedBiphenyls is called for short PCBs) is a kind of typical persistence organic pollutant in environment.Because it has higher unreactiveness, thermostability, flame retardant resistance, thermal conductivity and insulativity, be once widely used in the fields such as power industry, Plastics Processing Industry, chemical industry and printing.According to the World Health Organization (WHO) statistics, since eighties of last century starts production the twenties, to the end of the eighties, the whole world has produced approximately 2 * 10 altogether
7t Industrial PC Bs, wherein approximately 31% is discharged in environment.Because PCBs has biological accumulation and " three cause " effect, long-distance migration in the world, and in its migration, conversion process, can be bioaccumulation amplification, its concentration level may improve even hundreds of times of decades of times, and ecotope and HUMAN HEALTH are produced to threat greatly.United Nations Environment Programme (UNEP) is classified as one of preferential 12 kinds of persistence toxic organic pollutants controlling in the whole world, and most industry country is after 20 century 70s, stopped producing polychlorobiphenyl, but due to its stable in properties, be difficult for degrading in environment, polychlorobiphenyl also will continue a very long time to the pollution of environment.
The ubiquity existing in water body in view of PCBs, Chinese scholars has been carried out a series of research for the degraded of PCBs in recent ten years, research shows, the committed step of PCBs degraded is dechlorination reaction, and the method for employing mainly contains hydride process, chlorinolysis method, reversion method and metal deoxidization etc.Wherein, utilizing metal deoxidization to process polychlorobiphenyl is a current most active investigative technique, 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 reductibility, and cheap and easy to get, therefore can be used as reductive agent, makes polychlorobiphenyl slough chlorine atom, thereby reduces the toxicity of polychlorobiphenyl.Conventional zero-valent metal has iron, aluminium, magnesium, zinc and tin etc., in numerous zero-valent metals, utilize Zero-valent Iron and compound reduction thereof to remove the most study of organic halide and polychlorobiphenyl, and iron is safe from harm for environment, so become more conventional polychlorobiphenyl catalysis dechlorination method.
Metal deoxidization has good application prospect aspect polychlorobiphenyl in removing water surrounding.Grittini research shows, under normal temperature and pressure conditions, Zero-valent Iron is generally difficult to react with polychlorobiphenyl, if but use Pd/Fe combination just can make the dechlorination of polychlorobiphenyl fast restore.Wherein Pd has played the effect of catalysis dechlorination.Expensive due to Pd, can consider to replace Pd as catalyzer with Ni, also can reach higher Degradation Level.Ni/Fe duplex metal nano granule cost is lower, preparation technology is simple and easy to control, and reaction conditions is gentle, removes polychlorobiphenyl speed high, reaction times has also shortened much than fe, so Ni/Fe duplex metal nano granule has larger application prospect during PCBs in processing water surrounding.In order to increase the applicability of pollution substance in Ni/Fe duplex metal nano granule degradation water environment, designed a kind of packed column circulation type reactor, Ni/Fe duplex metal nano granule is fixed in the middle of filler, avoided duplex metal nano granule to be entrained in 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 polychlorobiphenyl, the method of a kind of Ni of utilization-Fe duplex metal nano granule degradation of polychlorinated biphenyl is provided, after the immobilization of Ni/Fe duplex metal nano granule, provides a kind of device that more has using value.
Technical purpose of the present invention is achieved by following technical proposals:
A device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment, comprises liquid storage tank, peristaltic pump, and the first water distribution dividing plate, the second water distribution dividing plate, reaction-filling post, heat-insulation unit, outflow tube, return line 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 place, lower surface 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 kept stable of reaction-filling post;
The top of described reactor is connected with return line with outflow tube respectively by pipeline, and the top of described reactor is connected with liquid storage tank by return line.
In above-mentioned reaction unit, bottom-up the first thief hole, the second thief hole and the 3rd thief hole of setting gradually in the vertical direction of reactor, described the first thief hole is arranged on the below of the first water distribution dividing plate, centre and the 3rd thief hole that the second thief hole 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.
In above-mentioned reaction unit, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume, adopting Ni-Fe duplex metal nano granule and quartz sand to mix forms, the mixed volume of wherein said Ni-Fe duplex metal nano granule and quartz sand is than being 1:(8-12), preferably adopt mechanical stirring mode to mix; Described quartz sand is 60-80 orders, and the particle of described Ni-Fe duplex metal nano granule is 40-70nm, and specific surface area is 25-35m
2/ g, is prepared according to following step:
Step 2, takes NiCl
26H
2o is dissolved in deionized water, obtains NiCl
2solution;
Step 3, gets the NiCl that PVP solution that step 1 obtains and step 2 obtain
2solution, then add deionized water and ethanol, obtains mixing solutions, and passes into deoxygenation after rare gas element, the PVP solution that wherein step 1 obtains, the NiCl that step 2 obtains
2the volume ratio of solution, deionized water and ethanol is (7-8): 1:(20-22): 20, and preferred 7.5:1:21.5:20, described rare gas element is selected nitrogen, argon gas or helium, and the deoxygenation time is 20-30min;
Step 4, takes FeSO
47H
2o adds in the mixing solutions that step 3 obtains, and fully dissolves, and is chosen in rotating speed and is under the mechanical stirring condition of 1500-2000r/min to mix 15-20min, makes FeSO
47H
2o powder fully dissolves;
Step 5 drips NaBH in the solution obtaining in step 4
4solution completes dropping in 15-20min, drips after finishing under the mechanical stirring condition that is 1500-2000r/min at rotating speed and stirs 20-30min, described NaBH
4solution is the NaBH of 0.12-0.13g
4powder is dissolved in percent by volume 40% aqueous ethanolic solution of 10ml, after stirring, obtains;
Fe wherein
2+and BH
4 -molar ratio 1:2, for reduction reaction is fully carried out, preferred excessive NaBH
4solution; The consumption of described nickel is 2%-5% of ferrous iron (being ferro element) quality; In technique scheme, a step is achieved as follows whole reaction process:
Fe
2++6H
2O+2BH
4 -→Fe↓+2Be(OH)
3+7H
2↑
Ni
2++6H
2O+2BH
4 -→Ni↓+2Be(OH)
3+7H
2↑
In this course, because the addition of elemental nickel is less and system is fully mixed and reacts under churned mechanically condition continuing, after drop reaction finishes, can form the composite nanometer particle of nickel and iron.Metal Ni plays catalyzer, can accelerate the dechlorination efficiency of Zero-valent Iron, conventionally selects Ni/Fe duplex metal nano granule degradation of polychlorinated biphenyl cheap and easy to get.The liquid phase reduction of selecting has simple to operate, process controllability is strong, cost is the advantage such as lower also, conventionally select sodium borohydride liquid phase reduction to prepare Ni/Fe duplex metal nano granule, but the nano particle of preparing is easily reunited, and affects degradation efficiency, so add stablizer PVP(K30 in liquid phase preparation process), PVP(K30) can prevent the reunion of nanoparticle, also can not exert an influence to the degradation process of bimetal system.
In above-mentioned reaction unit, described reaction unit is airtight on the whole, in order to avoid oxygen enters in reaction unit, Ni-Fe duplex metal nano granule is caused to oxidation, causes speed of reaction greatly to reduce.
In above-mentioned reaction unit, described outflow tube is connected by T-valve with return line.
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, the aperture of described water distributing pore is 0.01mm-0.3mm; 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; The material of described the first water distribution dividing plate and the second water distribution dividing plate is synthetic glass, and thickness is 3-5mm.
Utilize the method for polychlorobiphenyl in above-mentioned reaction unit degradation water environment, according to following step, carry out:
Step 2, described in contain polychlorobiphenyl solution by reactor bottom, entered, after water-distributing device water distribution uniformity, by reaction-filling post;
Step 3, the state of adjustment T-valve, so that the solution that contains polychlorobiphenyl is back in liquid storage tank via return line;
Step 4, repeats above-mentioned steps so that the solution that contains polychlorobiphenyl circulates in reactor, and by thief hole, analyzes the removal effect of polychlorobiphenyl;
Step 5, when the removal effect of polychlorobiphenyl reaches preset requirement, adjusts the state of T-valve, so that solution is flowed out by outflow tube.
In such scheme, the hydraulic detention time of the Flow-rate adjustment solution by regulating peristaltic pump in reaction-filling post, the hydraulic detention time of each circulation is 60min-90min, the total hrt of whole reaction is 48-72h.
In such scheme, by heat-insulation unit, to control whole reaction and move under constant temperature, temperature is 30-40 ℃.
In such scheme, described in contain polychlorobiphenyl solution in, the concentration of polychlorobiphenyl 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 used rare gas element (as nitrogen, helium, argon gas) to carry out deoxygenation in advance.
The present invention utilizes Ni/Fe duplex metal nano granule, and the pollution by polychlorinated biphenyles thing in efficient degradation water surrounding adopts packed column loop reactor, and flow process is simple, and controllability is strong, and cost is also lower.A kind of method of utilizing polychlorobiphenyl in Ni/Fe duplex metal nano granule degradation water environment that the present invention proposes, Ni/Fe duplex metal nano granule is fixed in quartz sand filler, when polychlorobiphenyl ethanol-aqueous solution passes through filler continuously, bimetal carries out dechlorination to polychlorobiphenyl.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of polychlorobiphenyl in the present invention a kind of Ni of utilization-Fe duplex metal nano granule degradation water environment, and wherein 1 is liquid storage tank, and 2 is peristaltic pump, 3-1 is the first water distribution dividing plate, and 3-2 is the second water distribution dividing plate, and 4 is reaction-filling post, 5 is heat-insulation unit (system), 6 is outflow tube, and 7 is return line, and 8 is T-valve, 9-1 is the first thief hole, 9-2 is the second thief hole, and 9-3 is the 3rd thief hole, 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.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.
As shown in accompanying drawing 1-2, utilize the device of polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment, comprise 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 line 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 place, lower surface 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 kept stable of reaction-filling post;
The top of described reactor is connected with return line with outflow tube respectively by pipeline, and the top of described reactor is connected with liquid storage tank by return line.
In above-mentioned reaction unit, bottom-up the first thief hole, the second thief hole and the 3rd thief hole of setting gradually in the vertical direction of reactor, described the first thief hole is arranged on the below of the first water distribution dividing plate, centre and the 3rd thief hole that the second thief hole 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.
In above-mentioned reaction unit, described reaction unit is airtight on the whole, in order to avoid oxygen enters in reaction unit, Ni-Fe duplex metal nano granule is caused to oxidation, causes speed of reaction greatly to reduce.Described outflow tube is connected by T-valve with return line.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 0.1mm-0.3mm; 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; The material of described the first water distribution dividing plate and the second water distribution dividing plate is synthetic glass, and thickness is 3-5mm.
In above-mentioned reaction unit, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume, adopting Ni-Fe duplex metal nano granule and quartz sand to mix forms, the mixed volume of wherein said Ni-Fe duplex metal nano granule and quartz sand is than being 1:(8-12), preferably adopt mechanical stirring mode to mix; Described quartz sand is 60-80 orders, and the particle of described Ni-Fe duplex metal nano granule is 40-70nm, and specific surface area is 25-35m
2/ g(is as shown in Figure 3), according to following step, be prepared:
(1) by 5gPVP(K30) be dissolved in deionized water, by magnetic agitation, fully mix, be settled to 50ml, obtain mass body volume concentrations and be 10% PVP solution.
(2) take the NiCl of metered amount
26H
2o powder, is dissolved in deionized water, obtains its standardized solution.
NiCl
26H
2the quality of O powder determines by Ni/Fe, and the usage quantity of nickel is weight of iron 2-5%, and its metered amount is equivalent to dissolve NiCl in every milliliter of standardized solution
26H
2the quality of O powder is in 0.00168-0.0042 scope.NiCl
26H
2o and FeSO
47H
2the relation of O is as following table:
(3) get as described in (1) 7.5mlPVP solution, add 1ml(2) NiCl
2standardized solution, 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 0.417gFeSO
47H
2o powder adds in above-mentioned solution, under the mechanical stirring condition that is 1500-2000r/min, mixes 15-20min at rotating speed, makes FeSO
47H
2o powder fully dissolves, now FeSO
47H
2the volumetric molar concentration of O is 0.03mol/L.
(5) slowly in there-necked flask, drip NaBH
4solution, according to n (Fe
2+) and n (BH
4 -) ratio 1:2, NaBH
4for 0.003mol, consider a small amount of Ni of reduction
2+needs and operating process loss, for guaranteeing to react completely, carry out configuration NaBH
4during solution, claim slightly excessive NaBH
4powder, the NaBH of weighing 0.12-0.13g
4powder is dissolved in 40% ethanolic soln of 10ml, after stirring, obtains NaBH
4solution completes dropping in 15-20min, drips after finishing under the mechanical stirring condition that is 1500-2000r/min at rotating speed and stirs 20-30min.
(6) after stirring and finishing, by magnetic method, collect, deoxidation distilled water wash 3-4 times for the Ni-Fe nano particle obtaining, absolute ethanol washing 1-2 times, can the auxiliary washing of ultrasonic dispersion to remove residual ion and organism in solution.After washing finishes, by magnetic method, collect, the Ni/Fe duplex metal nano granule obtaining, through vacuum-drying, weighs, and is about 0.1g left and right.
By GC-ECD Instrument measuring, obtain the concentration of the PCB77 of each sampling spot, the concentration of 0h is designated as initial concentration C
0, 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 polychlorobiphenyl is the ethanol-aqueous solution of polychlorobiphenyl, selects PCB77 to implement as target contaminant, the reaction-filling post that Ni/Fe duplex metal nano granule prepared by use aforesaid method and quartz sand mix.
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, and in whole reaction process, reaction unit keeps the constant temperature of 30 ℃ by heat-insulation system.Reaction-filling post is put into the uniform mixture of quartz sand and Ni/Fe duplex metal nano granule in advance, and blending ratio is 1:9.In liquid storage tank, adding concentration is PCB77 ethanol-aqueous solution of 5mg/L, and this solution also carried out letting nitrogen in and deoxidizing in advance.Open peristaltic pump, making the residence time of solution in filled column is 60min, changes, when in 48h, solution is by reaction filled column in the 3rd thief hole sampling and measuring PCB77 strength of solution, outflow tube is all in closure state, and solution is back to liquid storage tank by return line.When the reaction times is 48h, closed return line, starts outflow tube, and reaction finishes.In reaction process, observe the change in concentration of PCB77 solution in the 3rd thief hole position, 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.Before liquid storage tank adds PCB77 ethanol-aqueous solution, whole device in advance logical nitrogen makes it in anaerobic environment, and in whole reaction process, reaction unit keeps the constant temperature of 40 ℃ by heat-insulation system.Reaction-filling post is put into the uniform mixture of quartz sand and Ni/Fe duplex metal nano granule in advance, and blending ratio is 1:12.In liquid storage tank, adding concentration is PCB77 ethanol-aqueous solution of 5mg/L, and this solution also carried out letting nitrogen in and deoxidizing in advance.Open peristaltic pump, making the residence time of solution in filled column is 90min, changes, when in 60h, solution is by reaction filled column in the 3rd thief hole sampling and measuring PCB77 strength of solution, outflow tube is all in closure state, and solution is back to liquid storage tank by return line.When the reaction times is 60h, closed return line, starts outflow tube, and reaction finishes.In reaction process, in the 3rd thief hole position, observe the change in concentration of PCB77 solution.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.Before liquid storage tank adds PCB77 ethanol-aqueous solution, whole device in advance logical nitrogen makes it in anaerobic environment, and in whole reaction process, reaction unit keeps the constant temperature of 35 ℃ by heat-insulation system.Reaction-filling post is put into the uniform mixture of quartz sand and Ni/Fe duplex metal nano granule in advance, and blending ratio is 1:8.In liquid storage tank, adding concentration is PCB77 ethanol-aqueous solution of 5mg/L, and this solution also carried out letting nitrogen in and deoxidizing in advance.Open peristaltic pump, making the residence time of solution in filled column is 80min, changes, when in 72h, solution is by reaction filled column in the 3rd thief hole sampling and measuring PCB77 strength of solution, outflow tube is all in closure state, and solution is back to liquid storage tank by return line.When the reaction times is 72h, closed return line, starts outflow tube, and reaction finishes.In reaction process, in the 3rd thief hole position, observe the change in concentration of PCB77 solution.Finally recording degradation efficiency is 97.4%.
Above the present invention has been 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, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. a device that utilizes polychlorobiphenyl 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 line 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 place, lower surface 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 kept stable of reaction-filling post;
The top of described reactor is connected with return line with outflow tube respectively by pipeline, and the top of described reactor is connected with liquid storage tank by return line;
Bottom-up the first thief hole, the second thief hole and the 3rd thief hole of setting gradually in the vertical direction of reactor, described the first thief hole is arranged on the below of the first water distribution dividing plate, centre and the 3rd thief hole that the second thief hole 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 surface area is 25-35m
2/ g, is prepared according to following step:
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 NiCl
26H
2o is dissolved in deionized water, obtains NiCl
2solution;
Step 3, gets the NiCl that PVP solution that step 1 obtains and step 2 obtain
2solution, then add deionized water and ethanol, obtains mixing solutions, and passes into deoxygenation after rare gas element, the PVP solution that wherein step 1 obtains, the NiCl that step 2 obtains
2the volume ratio of solution, deionized water and ethanol is (7-8): 1:(20-22): 20, and described rare gas element is selected nitrogen, argon gas or helium, and the deoxygenation time is 20-30min;
Step 4, takes FeSO
47H
2o adds in the mixing solutions that step 3 obtains, and fully dissolves, and is chosen in rotating speed and is under the mechanical stirring condition of 1500-2000r/min to mix 15-20min, makes FeSO
47H
2o powder fully dissolves;
Step 5 drips NaBH in the solution obtaining in step 4
4solution completes dropping in 15-20min, drips after finishing under the mechanical stirring condition that is 1500-2000r/min at rotating speed and stirs 20-30min, described NaBH
4solution is the NaBH of 0.12-0.13g
4powder is dissolved in percent by volume 40% aqueous ethanolic solution 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;
Fe wherein
2+and BH
4 -molar ratio 1:2; The consumption of described nickel is 2%-5% of ferrous iron quality.
2. a kind of device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment according to claim 1, is characterized in that, described reaction-filling post accounts for 3/5-2/3 of whole reactor volume.
3. a kind of device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment according to claim 1, is characterized in that, described outflow tube is connected by T-valve with return line.
4. a kind of device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment according to claim 1, 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 synthetic glass, and thickness is 3-5mm.
5. a kind of device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment according to claim 4, 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.
6. a kind of device that utilizes polychlorobiphenyl in Ni-Fe duplex metal nano granule degradation water environment according to claim 1, it is characterized in that, described reaction unit 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 speed of reaction greatly to reduce.
7. utilize the method for polychlorobiphenyl in the device degradation water environment as described in one of claim 1-6, it is characterized in that, according to following step, carry out:
Step 1, is placed in liquid storage tank by the solution that contains polychlorobiphenyl, and opens peristaltic pump;
Step 2, described in contain polychlorobiphenyl solution by reactor bottom, entered, after water-distributing device water distribution uniformity, by reaction-filling post;
Step 3, the state of adjustment T-valve, so that the solution that contains polychlorobiphenyl is back in liquid storage tank via return line;
Step 4, repeats above-mentioned steps so that the solution that contains polychlorobiphenyl circulates in reactor, and by thief hole, analyzes the removal effect of polychlorobiphenyl;
Step 5, when the removal effect of polychlorobiphenyl reaches preset requirement, adjusts the state of T-valve, so that solution is flowed out by outflow tube.
8. the method for polychlorobiphenyl in degradation water environment according to claim 7, it is characterized in that, the hydraulic detention time of Flow-rate adjustment solution by regulating peristaltic pump in reaction-filling post, the hydraulic detention time of each circulation is 60min-90min, and the total hrt of whole reaction is 48-72h.
9. the method for polychlorobiphenyl in degradation water environment according to claim 7, is characterized in that, by heat-insulation unit, control whole reaction and move under constant temperature, temperature is 30-40 ℃.
10. the method for polychlorobiphenyl in degradation water environment according to claim 7, it is characterized in that, in described reaction unit, comprise that reactor, liquid storage tank, reaction-filling post and pipeline thereof are all used rare gas element (as nitrogen, helium, argon gas) to carry out deoxygenation in advance.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410008446.9A CN103708598B (en) | 2014-01-02 | 2014-01-02 | One is utilized method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment |
| CN201510178927.9A CN104817156B (en) | 2014-01-02 | 2014-01-02 | Utilize the method for Polychlorinated biphenyls in Ni-Fe duplex metal nano granules degraded water environment |
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| CN201410008446.9A CN103708598B (en) | 2014-01-02 | 2014-01-02 | One is utilized method and the device of Polychlorinated biphenyls in Ni-Fe duplex metal nano granule degradation water environment |
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| CN104817156B (en) | 2017-07-21 |
| CN103708598B (en) | 2016-05-11 |
| CN104817156A (en) | 2015-08-05 |
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