CN106829933A - A kind of method for going to remove water reclaimed water dirt and heavy metal ion - Google Patents
A kind of method for going to remove water reclaimed water dirt and heavy metal ion Download PDFInfo
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- CN106829933A CN106829933A CN201710163288.8A CN201710163288A CN106829933A CN 106829933 A CN106829933 A CN 106829933A CN 201710163288 A CN201710163288 A CN 201710163288A CN 106829933 A CN106829933 A CN 106829933A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
A kind of method for going to remove water reclaimed water dirt and heavy metal ion, it is related to water technology, CNT ultrasonic disperse in absolute ethyl alcohol, will then mix with the absolute ethyl alcohol dispersion liquid of graphene oxide after purification, then graphene oxide/carbon nano tube compound material will be obtained through ultrasound, suction filtration, vacuum drying.The composite belongs to nano material, and with good characteristic, and surface has the various active group such as hydroxyl, carboxyl, by the suction-operated of surface group and heavy metal ions in sewage, is capable of achieving the removal of pollutant.Cooperative effect can be formed with composite in the presence of externally-applied magnetic field, reach the purpose of scale removal.The method do not have secondary pollution, with functions such as absorption, technological process is simple, and dependable performance can be used for the fields such as environmental protection, targeted drug preparation, pollutant monitoring.Technological process of the invention is succinct, and material is prepared simply, with low cost, be can be mass.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to go to remove water the technology of reclaimed water dirt and heavy metal ion.
Background technology
Two kinds of new carbons of CNT and Graphene are respectively at 1991 and 2004 by Japanese Electronic Speculum scholar
Two scientist Andre Geim, Konstantin the Novoselov discovery of Iijima S and Univ Manchester UK, this
Two kinds of new carbons have lot of advantages, such as excellent electric conductivity, specific surface area are big, space structure is unique, mass density is light,
Act on stronger etc. between contaminant molecule, at home and abroad each field has started research boom.But both new carbons
Also have disadvantages that, for example easily reuniting each other, wind, folding, surface can be high, in all kinds of solvents more indissoluble etc., this limit
Its application in many fields is made.By both after certain method is prepared into composite, can solve to a certain extent
Certainly two kinds of respective shortcomings of carbon material.Such as be prepared into specific surface area increase after composite, reunite, wrapping phenomena is significantly reduced.
Also tool plays a very important role in water process in another magnetic field.For example under externally-applied magnetic field, the microorganism in water can be played and gone out
It is living to act on, do not produce any murder by poisoning to water.Additionally, there may be small investment, using convenient, the low advantage of operating cost.Based on above-mentioned
Consider, graphene oxide and CNT are prepared into composite by the present invention first, then in the presence of externally-applied magnetic field, will
The composite carries out adsorption experiment in putting into recirculated water.So as to prove that externally-applied magnetic field is deposited with composite in adsorption process
There is synergy.
Patent [TW201323538A] discloses a kind of charcoal base coating material, its surface be coated with one layer containing mercapto,
The functional group of epoxy radicals and carboxyl, this kind of material can be used for the coating of radiating plate surface.Patent [CN104399431A] is public
The magnetic carbon-nano tube composite material and preparation method of a kind of amino and mercapto modification are opened, this kind of method has prepared dispersion
Property preferable CNT, introduce functional group efficiency is higher, functionalization degree is higher etc., can be used for heavy metal ions in sewage with
The absorption of organic matter.Document [Wu Lirui, a blue heart, in winged etc., aminated carbon nano tube/graphene aerogel PARA FORMALDEHYDE PRILLS(91,95) suction
Attached research [J] China Environmental Sciences 2015,35 (11):3251-3256.] report with amido modified CNT/
Graphene composite material and for indoor pollutant formaldehyde absorption study, also achieve good result.
Research report at present to magnetic field and adsorbent synergy is also little.That is reported at present prepares graphene/carbon
The method of nanotube there are CNT order between graphene layer and arrange not high, Graphene and CNT reunion sternly
The shortcomings of weight.Another composite material surface functional group is less so that Graphene/carbon nanotube composite material adsorption capacity is weak.
The content of the invention
It is an object of the invention to provide a kind of method gone and remove water reclaimed water dirt and heavy metal ion.
The present invention is a kind of method gone and remove water reclaimed water dirt and heavy metal ion, and its step is：
（1）Original carbon nanotubes are distributed in mixing acid solution, are reacted 1~3 hour at 60~80 DEG C, subsequent filtration washing,
80~120 DEG C of 8 ~ 12h of drying, obtain product as purifying carbon nano-tube；
（2）Native graphite is added in the concentrated sulfuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Sodium nitrate and potassium permanganate are added, temperature is maintained at 0 ~ 10 DEG C, continue to stir 2.5 ~ 4 hours；
（3）Mixture is put into 25 ~ 35 DEG C of thermostat water bath, deionized water is slowly added to, mixture is then put into 90 ~
Mechanical agitation 20 ~ 40 minutes in 100 DEG C of water-bath, add deionized water to be diluted to 600-1000ml, stir 5-15 minutes, plus
Enter the hydrogen peroxide of mass fraction 30%, by product with the centrifugation of 8000-10000r/min, by the solid matter after centrifugation point
Sonic oscillation 30 ~ 60 minutes in ethanol solution are dispersed in, are vacuum dried 12 ~ 24 hours, obtain product as graphite oxide
Alkene；
（4）The graphene oxide and purifying carbon nano-tube of quality such as weigh, each ultrasound 2 hours, then by purifying carbon nano-tube
In dropwise entering graphene oxide, continue ultrasound 30 ~ 60 minutes, obtained after being vacuum dried 8 ~ 12 hours after suction filtration graphene oxide/
Carbon nano tube compound material；
（5）Deionized water is added in circulation, heavy metal ion and calcium ion is added, by graphene oxide/CNT
Composite is added in circulation, adjusts temperature and water speed；
（6）Magnetic field intensity is adjusted using controlling magnetic field equipment, circulation is opened and is circulated；
（7）The concentration of 10ml water sample detections heavy metal ion and calcium ion was taken every 2 hours, until stopping after water process 12 hours
Detection.
Usefulness of the present invention is：The present invention has fine adsorption capacity to heavy metal ions in sewage, organic pollution,
Mainly the physicochemical properties of graphene oxide, carbon nanotube are combined, are a kind of good function nano particle
Carrier.Heavy metal pollution and the harm of incrustation scale in water removal can simultaneously be gone.Preparation method process is simple, easy to operate and condition temperature
With preparing product adsorption capacity has greatly excellent biocompatibility.Have in fields such as biological medicine, environmental protection potential
Application value.
Brief description of the drawings
Fig. 1 is that the high-resolution transmitted electron of graphene oxide/carbon nano tube compound material in the specific embodiment of the invention 1 shows
Micro mirror (TEM), Fig. 2 is the Fourier-infrared light of graphene oxide/carbon nano tube compound material in the specific embodiment of the invention 1
Spectrogram, during Fig. 3 magnetic fields-composite collective effect during 4 magnetic fields of calcium ion concentration variation diagram-composite collective effect lead from
Sub- change in concentration.
Specific embodiment
The present invention is a kind of method gone and remove water reclaimed water dirt and heavy metal ion, and its step is：
（1）Original carbon nanotubes are distributed in mixing acid solution, are reacted 1~3 hour at 60~80 DEG C, subsequent filtration washing,
80~120 DEG C of 8 ~ 12h of drying, obtain product as purifying carbon nano-tube；
（2）Native graphite is added in the concentrated sulfuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Sodium nitrate and potassium permanganate are added, temperature is maintained at 0 ~ 10 DEG C, continue to stir 2.5 ~ 4 hours；
（3）Mixture is put into 25 ~ 35 DEG C of thermostat water bath, deionized water is slowly added to, mixture is then put into 90 ~
Mechanical agitation 20 ~ 40 minutes in 100 DEG C of water-bath, add deionized water to be diluted to 600-1000ml, stir 5-15 minutes, plus
Enter the hydrogen peroxide of mass fraction 30%, by product with the centrifugation of 8000-10000r/min, by the solid matter after centrifugation point
Sonic oscillation 30 ~ 60 minutes in ethanol solution are dispersed in, are vacuum dried 12 ~ 24 hours, obtain product as graphite oxide
Alkene；
（4）The graphene oxide and purifying carbon nano-tube of quality such as weigh, each ultrasound 2 hours, then by purifying carbon nano-tube
In dropwise entering graphene oxide, continue ultrasound 30 ~ 60 minutes, obtained after being vacuum dried 8 ~ 12 hours after suction filtration graphene oxide/
Carbon nano tube compound material；
（5）Deionized water is added in circulation, heavy metal ion and calcium ion is added, by graphene oxide/CNT
Composite is added in circulation, adjusts temperature and water speed；
（6）Magnetic field intensity is adjusted using controlling magnetic field equipment, circulation is opened and is circulated；
（7）The concentration of 10ml water sample detections heavy metal ion and calcium ion was taken every 2 hours, until stopping after water process 12 hours
Detection.
Above-described CNT is many walls or SWCN.
The above mixed acid solution is that the concentrated sulfuric acid and concentrated nitric acid are constituted, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
The mass ratio of above-described native graphite and the concentrated sulfuric acid is 50:1~80:1.
The mass ratio of above-described sodium nitrate and native graphite is 1:2~2:1.
The mass ratio of above-described potassium permanganate and native graphite is 3:1~6:1.
The volume ratio of above-described hydrogen peroxide and the concentrated sulfuric acid is 1:2~1:4.
Above-described heavy metal ion and calcium ion initial concentration ratio are 1:1.
Above-described magnetic field intensity is 0.2 ~ 0.54T, 10 ~ 30 DEG C of temperature, 0.17 ~ 0.54m/s of water speed.
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.In addition, it is to be understood that after the reading present invention tells about content, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1：
The pretreatment of step 1 CNT：
By the original multi-walled carbon nano-tubes of 1g（It is prepared by chemical vapour deposition technique）It is distributed to the 30ml concentrated sulfuric acids and 10ml concentrated nitric acid groups
Into mixed acid solution in, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours.
The preparation of step 2 graphene oxide：
The natural crystalline flake graphites of 2g are taken with electronic balance, the concentrated sulfuric acid for measuring 46ml with graduated cylinder is poured into the three-necked bottle of 1000ml,
It is cooled between 0 ~ 5 DEG C, load weighted 2g graphite is added in the 46ml concentrated sulfuric acids, it is straight to be cooled to 0 ~ 5 DEG C of stirring using ice bath
It is completely dissolved to graphite, adds 1g sodium nitrate and 6g potassium permanganate to be stirred vigorously simultaneously with certain speed, makes the temperature of mixture
Degree is maintained at less than 10 DEG C to be continued to stir 2.5 hours；Remove ice-water bath to be put into 35 DEG C of thermostat water bath, be slowly added to 92ml
Warm deionized water is stirred 30 minutes；Three-necked bottle is put into stirring reaction 24 minutes in 90 DEG C of thermostat water bath, warm is added
Deionized water be diluted to 280ml, stirring adds 20ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）5 points of insulation
Clock, product is poured into centrifuge tube and is washed with the centrifugation of 8000r/min, is detected with barium chloride until without sulfuric acid in supernatant
Radical ion is present；Solid matter after centrifugation is put into ultrasound in ethanol solution to be vacuum dried 24 hours after 30 minutes.
The preparation of step 3 Graphene/carbon nanotube composite material：
0.1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml alcohol, respectively
Ultrasound 2 hours；During carbon pipe dropwise is instilled into graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter suction filtration, vacuum drying is ground after 8 hours and obtains graphene oxide/carbon nano tube compound material.Such as Fig. 1 and Tu
Shown in 2, between CNT is interspersed in graphene layer or graphenic surface is attached to, and there is thin film on surface.
To 10L deionized waters are added in circulation, regulation magnetic field intensity is 0.54T, 30 DEG C of temperature, water speed 0.17m/
s。
21.9g calcium chloride hexahydrates are measured, 33.1g plumbi nitras is added in circulation, weighs 0.5g graphene oxides/carbon
Nanometer tube composite materials are added in circulation.
10ml water samples were taken every 2 hours, heavy metal ion, calcium ion concentration in water are surveyed with Atomic Absorption Spectrometer.Such as Fig. 3
It is shown, compared to being not added with magnetic field（0T）, calcium ion concentration content increases in water, shows that the purpose of scale removal is played in magnetic field.Such as Fig. 4
Shown, plumbum ion concentration content is gradually reduced in water, shows that magnetic field-composite plays the purpose of heavy-metal ion removal.
Embodiment 2：
The pretreatment of step 1 CNT：
By the original multi-walled carbon nano-tubes of 2g（It is prepared by chemical vapour deposition technique）It is distributed to the 60ml concentrated sulfuric acids and 20ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours.
The preparation of step 2 graphene oxide：
The natural crystalline flake graphites of 4g are taken with electronic balance, the concentrated sulfuric acid for measuring 92ml with graduated cylinder is poured into the three-necked bottle of 1000ml,
It is cooled between 0 ~ 5 DEG C, load weighted 4g native graphites is added in the 92ml concentrated sulfuric acids, being cooled to 0 ~ 5 DEG C using ice bath stirs
Mix up to graphite is completely dissolved, add 2g sodium nitrate and 12g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature be maintained at less than 10 DEG C continue stir 2.5 hours；Remove ice-water bath to be put into 35 DEG C of thermostat water bath, be slowly added to
92ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into stirring reaction 24 minutes in 90 DEG C of thermostat water bath, is added
The deionized water of warm is diluted to 280ml, and stirring adds 20ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation
5 minutes, product is poured into centrifuge tube and is washed with the centrifugation of 8000r/min, detected up to nothing in supernatant with barium chloride
Sulfate ion is present；Vacuum drying 24 is small after solid matter after centrifugation is put into ethanol solution into ultrasound 30 minutes
When.
The preparation of step 3 Graphene/carbon nanotube composite material：
0.2g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml alcohol, respectively
Ultrasound 2 hours；During carbon pipe dropwise is instilled into graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter suction filtration, vacuum drying is ground after 8 hours and obtains graphene oxide/carbon nano tube compound material.As shown in Figure 1, Figure 2
Shown, between CNT is interspersed in graphene layer or being attached to graphenic surface, and there is thin film on surface.
To 10L deionized waters are added in circulation, regulation magnetic field intensity is 0.54T, 20 DEG C of temperature, water speed 0.17m/
s。
21.9g calcium chloride hexahydrates are measured, 16.1g zinc sulfate is added in circulation, weighs 0.5g graphene oxides/carbon
Nanometer tube composite materials are added in circulation.
10ml water samples were taken every 2 hours, heavy metal ion, calcium ion concentration in water are surveyed with Atomic Absorption Spectrometer.
Embodiment 3：
The pretreatment of step 1 CNT：
By the original multi-walled carbon nano-tubes of 0.5g（It is prepared by chemical vapour deposition technique）It is distributed to the 15ml concentrated sulfuric acids and 5ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours.
The preparation of step 2 graphene oxide：
The natural crystalline flake graphites of 2g are taken with electronic balance, the concentrated sulfuric acid for measuring 46ml with graduated cylinder is poured into the three-necked bottle of 1000ml,
It is cooled between 0 ~ 5 DEG C, load weighted 2g native graphites is added in the 92ml concentrated sulfuric acids, being cooled to 0 ~ 5 DEG C using ice bath stirs
Mix up to graphite is completely dissolved, add 2g sodium nitrate and 12g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature be maintained at less than 10 DEG C continue stir 2.5 hours；Remove ice-water bath to be put into 35 DEG C of thermostat water bath, be slowly added to
92ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into stirring reaction 24 minutes in 90 DEG C of thermostat water bath, is added
The deionized water of warm is diluted to 280ml, and stirring adds 10ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation
5 minutes, product is poured into centrifuge tube and is washed with the centrifugation of 8000r/min, detected up to nothing in supernatant with barium chloride
Sulfate ion is present；Vacuum drying 24 is small after solid matter after centrifugation is put into ethanol solution into ultrasound 30 minutes
When.
The preparation of step 3 Graphene/carbon nanotube composite material：
0.1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml alcohol, respectively
Ultrasound 2 hours；During carbon pipe dropwise is instilled into graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter suction filtration, vacuum drying is ground after 8 hours and obtains graphene oxide/carbon nano tube compound material.
To 10L deionized waters are added in circulation, regulation magnetic field intensity is 0.54T, 10 DEG C of temperature, water speed 0.17m/
s。
Measure 21.9g calcium chloride hexahydrates, 33.1g plumbi nitras, in adding circulation, weigh 0.5g graphene oxides/
Carbon nano tube compound material is added in circulation.
10ml water samples were taken every 2 hours, heavy metal ion, calcium ion concentration in water are surveyed with Atomic Absorption Spectrometer.
Embodiment 4：
The pretreatment of step 1 CNT：
By the original multi-walled carbon nano-tubes of 0.5g（It is prepared by chemical vapour deposition technique）It is distributed to the 15ml concentrated sulfuric acids and 5ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours.
The preparation of step 2 graphene oxide：
The natural crystalline flake graphites of 2g are taken with electronic balance, the concentrated sulfuric acid for measuring 46ml with graduated cylinder is poured into the three-necked bottle of 1000ml,
It is cooled between 0 ~ 5 DEG C, load weighted 2g native graphites is added in the 92ml concentrated sulfuric acids, being cooled to 0 ~ 5 DEG C using ice bath stirs
Mix up to graphite is completely dissolved, add 2g sodium nitrate and 12g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature be maintained at less than 10 DEG C continue stir 2.5 hours；Remove ice-water bath to be put into 35 DEG C of thermostat water bath, be slowly added to
92ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into stirring reaction 24 minutes in 90 DEG C of thermostat water bath, is added
The deionized water of warm is diluted to 280ml, and stirring adds 10ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation
5 minutes, product is poured into centrifuge tube and is washed with the centrifugation of 8000r/min, detected up to nothing in supernatant with barium chloride
Sulfate ion is present；Vacuum drying 24 is small after solid matter after centrifugation is put into ethanol solution into ultrasound 30 minutes
When.
The preparation of step 3 Graphene/carbon nanotube composite material：
0.1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml alcohol, respectively
Ultrasound 2 hours；During carbon pipe dropwise is instilled into graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter suction filtration, vacuum drying is ground after 8 hours and obtains graphene oxide/carbon nano tube compound material.
To 10L deionized waters are added in circulation, regulation magnetic field intensity is 0.2T, 20 DEG C of temperature, water speed 0.23m/
s。
Measure 21.9g calcium chloride hexahydrates, 33.1g plumbi nitras, in adding circulation, weigh 0.5g graphene oxides/
Carbon nano tube compound material is added in circulation.
10ml water samples were taken every 2 hours, heavy metal ion, calcium ion concentration in water are surveyed with Atomic Absorption Spectrometer.
Embodiment 5：
The pretreatment of step 1 CNT：
By the original multi-walled carbon nano-tubes of 0.5g（It is prepared by chemical vapour deposition technique）It is distributed to the 15ml concentrated sulfuric acids and 5ml concentrated nitric acids
In mixed acid solution, stirring reaction 3 hours at 60 DEG C are washed to neutrality with distillation, standby after 80 DEG C of vacuum drying 12 hours.
The preparation of step 2 graphene oxide：
The natural crystalline flake graphites of 2g are taken with electronic balance, the concentrated sulfuric acid for measuring 46ml with graduated cylinder is poured into the three-necked bottle of 1000ml,
It is cooled between 0 ~ 5 DEG C, load weighted 2g native graphites is added in the 92ml concentrated sulfuric acids, being cooled to 0 ~ 5 DEG C using ice bath stirs
Mix up to graphite is completely dissolved, add 2g sodium nitrate and 12g potassium permanganate to be stirred vigorously simultaneously with certain speed, make mixture
Temperature be maintained at less than 10 DEG C continue stir 2.5 hours；Remove ice-water bath to be put into 35 DEG C of thermostat water bath, be slowly added to
92ml warm deionized waters are stirred 30 minutes；Three-necked bottle is put into stirring reaction 24 minutes in 90 DEG C of thermostat water bath, is added
The deionized water of warm is diluted to 280ml, and stirring adds 10ml, 30% hydrogen peroxide after 5 minutes（Color is changed into golden yellow）Insulation
5 minutes, product is poured into centrifuge tube and is washed with the centrifugation of 8000r/min, detected up to nothing in supernatant with barium chloride
Sulfate ion is present；Vacuum drying 24 is small after solid matter after centrifugation is put into ethanol solution into ultrasound 30 minutes
When.
The preparation of step 3 Graphene/carbon nanotube composite material：
0.1g graphene oxides are taken respectively and purifying carbon nano-tube is added separately in the three-necked bottle equipped with 100ml alcohol, respectively
Ultrasound 2 hours；During carbon pipe dropwise is instilled into graphene oxide under ultrasonication, completion of dropping continues ultrasound 30 minutes；With
0.45 micron membrane filter suction filtration, vacuum drying is ground after 8 hours and obtains graphene oxide/carbon nano tube compound material.
To 10L deionized waters are added in circulation, regulation magnetic field intensity is 0.2T, 30 DEG C of temperature, water speed 0.54m/
s。
Measure 2.19g calcium chloride hexahydrates, 3.31g plumbi nitras, in adding circulation, weigh 0.05g graphene oxides/
Carbon nano tube compound material is added in circulation.
10ml water samples were taken every 2 hours, heavy metal ion, calcium ion concentration in water are surveyed with Atomic Absorption Spectrometer.
Claims (9)
1. a kind of method for going to remove water reclaimed water dirt and heavy metal ion, it is characterised in that its step is：
（1）Original carbon nanotubes are distributed in mixing acid solution, are reacted 1~3 hour at 60~80 DEG C, subsequent filtration washing,
80~120 DEG C of 8 ~ 12h of drying, obtain product as purifying carbon nano-tube；
（2）Native graphite is added in the concentrated sulfuric acid of mass fraction 98%, mechanical agitation is dissolved completely up to graphite, then
Sodium nitrate and potassium permanganate are added, temperature is maintained at 0 ~ 10 DEG C, continue to stir 2.5 ~ 4 hours；
（3）Mixture is put into 25 ~ 35 DEG C of thermostat water bath, deionized water is slowly added to, mixture is then put into 90 ~
Mechanical agitation 20 ~ 40 minutes in 100 DEG C of water-bath, add deionized water to be diluted to 600-1000ml, stir 5-15 minutes, plus
Enter the hydrogen peroxide of mass fraction 30%, by product with the centrifugation of 8000-10000r/min, by the solid matter after centrifugation point
Sonic oscillation 30 ~ 60 minutes in ethanol solution are dispersed in, are vacuum dried 12 ~ 24 hours, obtain product as graphite oxide
Alkene；
（4）The graphene oxide and purifying carbon nano-tube of quality such as weigh, each ultrasound 2 hours, then by purifying carbon nano-tube
In dropwise entering graphene oxide, continue ultrasound 30 ~ 60 minutes, obtained after being vacuum dried 8 ~ 12 hours after suction filtration graphene oxide/
Carbon nano tube compound material；
（5）Deionized water is added in circulation, heavy metal ion and calcium ion is added, by graphene oxide/CNT
Composite is added in circulation, adjusts temperature and water speed；
（6）Magnetic field intensity is adjusted using controlling magnetic field equipment, circulation is opened and is circulated；
（7）The concentration of 10ml water sample detections heavy metal ion and calcium ion was taken every 2 hours, until stopping after water process 12 hours
Detection.
It is 2. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：The carbon nanometer
Manage is many walls or SWCN.
It is 3. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：The nitration mixture is molten
Liquid is that the concentrated sulfuric acid and concentrated nitric acid are constituted, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
It is 4. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Native graphite and
The mass ratio of the concentrated sulfuric acid is 50:1~80:1.
It is 5. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Sodium nitrate and day
The mass ratio of right graphite is 1:2~2:1.
It is 6. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Potassium permanganate and
The mass ratio of native graphite is 3:1~6:1.
It is 7. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Hydrogen peroxide and dense
The volume ratio of sulfuric acid is 1:2~1:4.
It is 8. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Heavy metal ion
It is 1 with calcium ion initial concentration ratio:1.
It is 9. according to claim 1 to go to remove water dirty and heavy metal ion the method for reclaimed water, it is characterised in that：Magnetic field intensity is
0.2 ~ 0.54T, 10 ~ 30 DEG C of temperature, 0.17 ~ 0.54m/s of water speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710163288.8A CN106829933B (en) | 2017-03-19 | 2017-03-19 | A method of going scale and heavy metal ion in water removal |
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|---|---|---|---|
| CN201710163288.8A CN106829933B (en) | 2017-03-19 | 2017-03-19 | A method of going scale and heavy metal ion in water removal |
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Cited By (8)
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| CN108083377A (en) * | 2017-12-25 | 2018-05-29 | 中国科学院合肥物质科学研究院 | A kind of method for reducing heavy metal arsenic toxicity |
| CN109928521A (en) * | 2019-04-24 | 2019-06-25 | 成都纳海川环境工程有限公司 | Inorganic microparticle scale dispersing agent and preparation method thereof |
| CN110771688A (en) * | 2019-11-06 | 2020-02-11 | 江阴国能绿地新能源科技有限公司 | Heating system for making bean products |
| CN112944666A (en) * | 2021-02-18 | 2021-06-11 | 内蒙古尚上商务咨询有限责任公司 | Water tank for life |
| CN113277591A (en) * | 2021-06-08 | 2021-08-20 | 哈尔滨工程大学 | Method for removing heavy metal ions in water by using magadiite/graphene oxide nanosheet compound |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
| CN115582094A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN115626633A (en) * | 2022-10-13 | 2023-01-20 | 佛山科学技术学院 | Purification method of single-walled carbon nanotube |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108083377A (en) * | 2017-12-25 | 2018-05-29 | 中国科学院合肥物质科学研究院 | A kind of method for reducing heavy metal arsenic toxicity |
| CN109928521A (en) * | 2019-04-24 | 2019-06-25 | 成都纳海川环境工程有限公司 | Inorganic microparticle scale dispersing agent and preparation method thereof |
| CN110771688A (en) * | 2019-11-06 | 2020-02-11 | 江阴国能绿地新能源科技有限公司 | Heating system for making bean products |
| CN112944666A (en) * | 2021-02-18 | 2021-06-11 | 内蒙古尚上商务咨询有限责任公司 | Water tank for life |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
| CN113277591A (en) * | 2021-06-08 | 2021-08-20 | 哈尔滨工程大学 | Method for removing heavy metal ions in water by using magadiite/graphene oxide nanosheet compound |
| CN113277591B (en) * | 2021-06-08 | 2022-06-17 | 哈尔滨工程大学 | Preparation method of two-dimensional magadiite/graphene oxide nanosheet composite |
| CN115582094A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN115582094B (en) * | 2021-07-05 | 2024-04-19 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN115626633A (en) * | 2022-10-13 | 2023-01-20 | 佛山科学技术学院 | Purification method of single-walled carbon nanotube |
| CN115626633B (en) * | 2022-10-13 | 2024-02-02 | 佛山科学技术学院 | Purification method of single-walled carbon nanotube |
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