CN102343261A - Carbon nanotube-bamboo charcoal composite material and preparation method and application thereof - Google Patents
Carbon nanotube-bamboo charcoal composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon nanotube-bamboo charcoal composite material and a preparation method and application thereof, which relate to a composite material of a carbon nanotube and bamboo charcoal and a preparation method and application thereof and are used for solving the problems of small capability of removing ammonia nitrogen from polluted water and unremarkable effect of removing micro-pollution existing in the conventional water treating process. The carbon nanotube-bamboo charcoal composite material is obtained by calcining a mixture prepared by mixing a carboxylated carbon nanotube with bamboo charcoal in the mass ratio 1:(1-10) for 4-6 hours. The composition material is applied to a method for removing ammonia nitrogen from water of a low-temperature water source. The carboxylated carbon nanotube with capability of optically catalyzing and oxidizing ammonia nitrogen is loaded with modified bamboo charcoal, so that removing efficiency of ammonia nitrogen in a polluted water body at low temperature by using the carbon nanotube-bamboo charcoal composite material is up to 60-80 percent, and a part of heavy metals and durable organic pollutants can be removed. The preparation method is simple.
Description
Technical field
The present invention relates to composite, its preparation method and the application of a kind of CNT and bamboo charcoal.
Background technology
In recent years, along with rapid development of economy, most of surface water of China and underground water have received pollution in various degree, and ammonia nitrogen is one of major pollution thing.Handle or deal with improperly if contaminated source water does not add, cause the ammonia-nitrogen content in the water outlet of waterworks higher, can cause in the pipe network breeding of nitrococcus and nitrifier to grow, thereby make the content overproof of nitrate and nitrite in the pipe network.The excessive meeting of nitrate makes the baby suffer from methemoglobinemia, nitrate nitrogen (NO in drinking water
3--will make red blood cell can not be with oxygen and cause baby's death by suffocation when N) content is higher than 10mg/L; In addition, nitrate and nitrite be converted into can produce " cancer, mutagenesis, teratogenesis " behind the nitrosamine three cause material.
The method that ammonia nitrogen in the drinking water is handled mainly contains: Activated Zeolite Adsorption, electric absorption method, aeration ammonia elimination process, break point chlorination ammonia elimination process, biological treatment and membrane filter method etc.Yet, at northern area because the water temperature in winter is very low, more than traditional method and be not suitable for removing the ammonia nitrogen in the water at low temperature.
CNT has another name called Baji-tube; It is a kind of One-dimensional Quantum material with special construction; Reel " microtubule " of seamless, the hollow that forms every layer of face of cylinder of forming through the hexagon that is constituted behind sp2 hydridization and 3 the complete bondings of carbon atom on every side by a carbon atom by certain helical angle around central shaft by the single or multiple lift graphite flake.According to the difference of formation condition, CNT exists multi-walled carbon nano-tubes (MWNTS) and two kinds of forms of SWCN (SWNT).Which floor MWNTS generally be made up of to the coaxial coiling of tens layers graphite flake, and the interlayer spacing is about 0.34nm, and its typical diameter and length are respectively 2-30nm and 0.1-50um.It mainly is made up of several layers to tens of layers coaxial pipe layer and the layer the carbon atom that is hexagonal array and keeps fixing distance.CNT is always not straight, but concave and convex phenomenon appears in regional area, and this is owing in hexagon braiding process, pentagon and heptagon have occurred.Because electronic structure and physicochemical characteristics that it is unique, its application in every field has caused various countries scientist's common concern.(1) key of high-strength carbon fiber material decision enhanced fiber intensity is length and diameter ratio.The length diameter ratio that present material engineering Shi Xiwang obtains is 20: 1 at least.Yet in the getable even now length of calculating with nanometer, the length of nanotube also is several thousand times of diameter, thereby is known as " super fiber ".Their strength ratio steel is high 100 times, but weight has only the sixth of steel.(2) matrix usable resins, charcoal, metal and the inorganic material etc. of composite carbon nano tube compound material.With the plastics that carbon nano-tube material strengthens, not only good mechanical performance, and antifatigue, creep resistant, scantling are stablized; Because it is coefficient of friction is little,, good again with compared with metal vibration attenuation property so sliding capability is good; (3) nano electron device since the CNT wall energy by some chemical reaction institute " dissolving ", so they can be used as easy-to-handle mould.(4) industry of catalysis fibre and film side beam and seminar thereof pour into the important catalyst vanadium oxide of using in sulfuric acid industry and the petrochemical industry into or are coated on the CNT, and vanadium oxide can arrive in the gap of graphite linings of nanotube tube wall sometimes.The discovery of this solid carbon of CNT, and the potential superiority that itself had have determined that it still is that material supply section educational circles all will have great development prospect at physics, chemistry.Particularly be with a wide range of applications in the material for water treatment.
Summary of the invention
The objective of the invention is to the invention provides a kind of CNT-bamboo charcoal composite in order to solve in the existing water treatment technology to the unconspicuous problem of the relatively poor and little pollution removal effect of the removal ability of ammonia nitrogen in the polluted water.
CNT of the present invention-bamboo charcoal composite is to be that the mixture of 1: 1～10 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
The preparation method of CNT of the present invention-bamboo charcoal composite realizes through following steps: one, CNT is carried out carboxylated and handle, obtain carboxylic carbon nano-tube; Two, the carboxylic carbon nano-tube and the bamboo charcoal that step 1 are obtained are the even mixtures that get of 1: 1～10 mixed by mass ratio; Then mixture is calcined 4～6h at 400～600 ℃; The washing of cooling back is drying to obtain CNT-bamboo charcoal composite to the water white transparency of filtrating, accomplish the preparation of CNT-bamboo charcoal composite.
Adopting existing open method that CNT is carried out the carboxylated processing in the step 1 of the present invention gets final product.
Application in the method for CNT of the present invention-bamboo charcoal composite ammonia nitrogen in removing low-temperature water source water.
The present invention adds CNT-bamboo charcoal composite to polluted water; Stirring reaction 10～30min gets final product; Wherein the temperature of polluted water is 2 ℃～5 ℃, and the concentration that control adds the CNT-bamboo charcoal composite to the micro-polluted source water is 5～15mg/L.
In the application in the method for CNT of the present invention-bamboo charcoal composite ammonia nitrogen in removing low-temperature water source water, stir speed (S.S.) is 100～200 rev/mins (rpm).
CNT of the present invention-bamboo charcoal composite is loaded to carboxylic carbon nano-tube on the bamboo charcoal, and bamboo charcoal is carried out modification.Bamboo wood is as a kind of porous media material; The bamboo charcoal that forms after the destructive distillation pyrolysis has greater porosity; Its hole comprises macrovoid, mesopore, micropore. bamboo charcoal has abundant porosity distribution and high-specific surface area, the surface functional group of other elements such as oxygen-containing functional group such as the carboxyl that there is carboxyl in its surface, exist with the lactone form, phenolic hydroxyl group and a small amount of sulfur-bearing, hydrogen, chlorine.Composite back carboxylic carbon nano-tube gets in the hole of bamboo charcoal; Make bamboo charcoal not only bring into play the physics usefulness of absorption ammonia nitrogen; The ability that has had the photochemical catalytic oxidation ammonia nitrogen of carboxylic carbon nano-tube Large ratio surface simultaneously; Improved the removal efficient of CNT-bamboo charcoal composite, simultaneously persistence organic pollutant in the polluted water body has been had certain suction-operated, obtained effect preferably ammonia nitrogen in the polluted water body under the low temperature.
The preparation method of CNT of the present invention-bamboo charcoal composite is simple, but suitability for industrialized production.
CNT of the present invention-bamboo charcoal composite is good to the removal effect of the ammonia nitrogen pollutant in the source water under the low temperature; Simultaneously persistence organic pollutant in the drinking water had certain suction-operated; The efficient of removing ammonia nitrogen reaches 60～80%, and heavy metal and persistence organic pollutant can access part and remove.
Step 1 adopts following steps that CNT is carried out the carboxylated processing among the preparation method of CNT of the present invention-bamboo charcoal composite: one, multi-walled carbon nano-tubes is placed round-bottomed flask; In round-bottomed flask, add mass fraction again and be 20%～40% glacial acetic acid; Reflux condensation mode, collection and agitating device have been refilled; Constant temperature backflow 0.8～1.5h after being heated to 60～80 ℃; Be cooled to room temperature again and get mixed liquor, wherein, the ratio of control multi-walled carbon nano-tubes quality and glacial acetic acid volume is 1g: 60～100mL; Two, the mixed liquor that step 1 is obtained filters, and washs the black powder on the filter paper then, to filtrate water white transparency and pH value for neutral, the black powder vacuum drying after will washing then must carboxylic carbon nano-tube.
Description of drawings
Fig. 1 is the scanning electron micrograph of the multi-walled carbon nano-tubes of the specific embodiment eight; Fig. 2 is that the x ray photoelectron diffraction of the carboxylic carbon nano-tube for preparing of the specific embodiment can spectrogram; Fig. 3 remains the ammonia nitrogen concentration curve map in the water outlet after CNT-bamboo charcoal composite of different carboxylic carbon nano-tubes and bamboo charcoal mass ratio is handled in the specific embodiment 20; Fig. 4 is the residue ammonia nitrogen concentration curve map in the polluted water water outlet after treatment of different temperatures; Wherein " ■-" is that carboxylic carbon nano-tube and bamboo charcoal mass ratio are CNT-bamboo charcoal composite of 1: 4; "-●-" be contrast experiment 1, " ▲-" be contrast experiment 2; Fig. 5 is to the residue ammonia nitrogen concentration curve map in the water outlet of polluted water after CNT-bamboo charcoal composite is handled of the initial ammonia nitrogen concentration of difference in the specific embodiment 23.
The specific embodiment
Technical scheme of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any between each specific embodiment.
The specific embodiment one: this embodiment is CNT-bamboo charcoal composite, and it is to be that the mixture of 1: 1～10 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
CNT of the present invention-bamboo charcoal composite is loaded to carboxylic carbon nano-tube on the bamboo charcoal, and bamboo charcoal is carried out modification.Bamboo wood is as a kind of porous media material; The bamboo charcoal that forms after the destructive distillation pyrolysis has greater porosity; Its hole comprises macrovoid, mesopore, micropore. bamboo charcoal has abundant porosity distribution and high-specific surface area, the surface functional group of other elements such as oxygen-containing functional group such as the carboxyl that there is carboxyl in its surface, exist with the lactone form, phenolic hydroxyl group and a small amount of sulfur-bearing, hydrogen, chlorine.Composite back Au-TiO
2Nanometer powder gets in the hole of bamboo charcoal; Make bamboo charcoal not only bring into play the physics usefulness of absorption ammonia nitrogen; The ability that has had the photochemical catalytic oxidation ammonia nitrogen of CNT Large ratio surface simultaneously; Improved under CNT-bamboo charcoal composite low temperature the removal efficient of ammonia nitrogen in the polluted water body, simultaneously persistence organic pollutant in the polluted water body has been had certain suction-operated, obtained effect preferably.
The specific embodiment two: this embodiment and the specific embodiment one are different is that CNT-bamboo charcoal composite is to be that the mixture of 1: 2～6 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
The specific embodiment three: this embodiment and the specific embodiment one are different is that CNT-bamboo charcoal composite is to be that the mixture of 1: 3～5 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
The specific embodiment four: this embodiment and the specific embodiment one are different is that CNT-bamboo charcoal composite is to be that the mixture of 1: 4 mixed obtains at 450 ℃ 400～600 ℃ calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
The specific embodiment five: what this embodiment was different with one of specific embodiment one to four obtains at 420～500 ℃ of calcining 4.5～5.5h.Other parameter is identical with one of specific embodiment one to four.
The specific embodiment six: what this embodiment was different with one of specific embodiment one to four obtains at 450 ℃ of calcining 5h.Other parameter is identical with one of specific embodiment one to four.
The specific embodiment seven: the preparation method like the specific embodiment one described CNT-bamboo charcoal composite realizes through following steps: one, CNT is carried out carboxylated and handle, obtain carboxylic carbon nano-tube; Two, the carboxylic carbon nano-tube and the bamboo charcoal that step 1 are obtained are the even mixtures that get of 1: 1～10 mixed by mass ratio; Then mixture is calcined 4～6h at 400～600 ℃; The washing of cooling back is drying to obtain CNT-bamboo charcoal composite to the water white transparency of filtrating, accomplish the preparation of CNT-bamboo charcoal composite.
The preparation method of the CNT of this embodiment-bamboo charcoal composite is simple, but suitability for industrialized production.
The specific embodiment eight: this embodiment and the specific embodiment seven are different is that step 1 adopts following steps that CNT is carried out carboxylated to handle: a, multi-walled carbon nano-tubes is placed round-bottomed flask; In round-bottomed flask, add mass fraction again and be 20%～40% glacial acetic acid; Reflux condensation mode, collection and agitating device have been refilled; Constant temperature backflow 0.8～1.5h after being heated to 60～80 ℃; Be cooled to room temperature again and get mixed liquor, wherein, the ratio of control multi-walled carbon nano-tubes quality and glacial acetic acid volume is 1g: 60～100mL; B, the mixed liquor that step 1 is obtained filter, and wash the black powder on the filter paper then, to filtrate water white transparency and pH value for neutral, the black powder vacuum drying after will washing then must carboxylic carbon nano-tube.
The multi-walled carbon nano-tubes that adopts among the step a of this embodiment is the commercially available prod, and its scanning electron micrograph is as shown in Figure 1.
The x ray photoelectron diffraction ability spectrogram of the carboxylic carbon nano-tube that this embodiment prepares, as shown in Figure 2.Can know by Fig. 2, this embodiment handled back multi-wall carbon nano-tube tube-surface realized carboxylated.
The specific embodiment nine: that this embodiment and the specific embodiment eight are different is constant temperature backflow 1h after being heated to 70 ℃ among the step a.Other step and parameter are identical with the specific embodiment eight.
The specific embodiment ten: this embodiment is different with the specific embodiment eight or nine is that the ratio of control multi-walled carbon nano-tubes quality and glacial acetic acid volume is 1g: 80mL among the step a.Other step and parameter are identical with the specific embodiment eight or nine.
The specific embodiment 11: what this embodiment was different with one of specific embodiment seven to ten is that carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 is obtained is the even mixtures that get of 1: 2～6 mixed by mass ratio.Other step and parameter are identical with one of specific embodiment eight to ten.
The specific embodiment 12: what this embodiment was different with one of specific embodiment seven to ten is that carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 is obtained is the even mixtures that get of 1: 3～5 mixed by mass ratio.Other step and parameter are identical with one of specific embodiment eight to ten.
The specific embodiment 13: what this embodiment was different with one of specific embodiment seven to ten is that carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 is obtained is 1: 4 even mixture that gets of mixed by mass ratio.Other step and parameter are identical with one of specific embodiment eight to ten.
The specific embodiment 14: this embodiment is like the application in the method for the specific embodiment one described CNT-bamboo charcoal composite ammonia nitrogen in removing low-temperature water source water.
CNT of the present invention-bamboo charcoal composite is good to the removal effect of the ammonia nitrogen pollutant in the source water under the low temperature; Simultaneously persistence organic pollutant in the drinking water had certain suction-operated; The efficient of removing ammonia nitrogen reaches 60～80%, and heavy metal and persistence organic pollutant can access part and remove.
The specific embodiment 15: the application in the method for this embodiment ammonia nitrogen that is CNT-bamboo charcoal composite in removing low-temperature water source water; Specific as follows: that CNT-bamboo charcoal composite is added to polluted water; Stirring reaction 10～30min gets final product; Wherein the temperature of polluted water is 2 ℃～5 ℃, and the concentration that control adds the CNT-bamboo charcoal composite to the micro-polluted source water is 5～15mg/L.
After stirring reaction finishes in this embodiment CNT-bamboo charcoal composite being filtered reuse gets final product.
The specific embodiment 16: this embodiment and the specific embodiment 15 are different is that the concentration that control adds the CNT-bamboo charcoal composite to the micro-polluted source water is 8～12mg/L.Other step and parameter are identical with the specific embodiment 15.
The specific embodiment 17: this embodiment and the specific embodiment 15 are different is that the concentration that control adds the CNT-bamboo charcoal composite to the micro-polluted source water is 10mg/L.Other step and parameter are identical with the specific embodiment 15.
The specific embodiment 18: what this embodiment and the specific embodiment 15,16 or 17 were different is that stir speed (S.S.) is 100～200 rev/mins (rpm) in the stirring reaction process.Other step and parameter are identical with the specific embodiment 15,16 or 17.
The specific embodiment 19: what this embodiment and the specific embodiment 15,16 or 17 were different is that stir speed (S.S.) is 160 rev/mins (rpm) in the stirring reaction process.Other step and parameter are identical with the specific embodiment 15,16 or 17.
The specific embodiment 20: this embodiment is eight kinds of CNTs-bamboo charcoal composite, and it is to be that the mixture of 1: 3,1: 4,1: 5,1: 6,1: 7,1: 8,1: 9 and 1: 10 mixed obtains at 450 ℃ of calcining 5h by mass ratio respectively with carboxylic carbon nano-tube and bamboo charcoal.
This embodiment is that the CNT-bamboo charcoal composite that obtained in 1: 3,1: 4,1: 5,1: 6,1: 7,1: 8,1: 9 and 1: 10 is defined as first to eight kind of CNT-bamboo charcoal composite successively with the mass ratio of carboxylic carbon nano-tube and bamboo charcoal.
This embodiment is applied to remove eight kinds of CNTs-bamboo charcoal composite in the method for ammonia nitrogen in the low-temperature water source water respectively; Specific as follows: that eight kinds of CNTs-bamboo charcoal composite is added respectively to polluted water; In stir speed (S.S.) is under the 160rpm condition, and stirring reaction 30min must be through the water outlet after the CNT-bamboo charcoal composite of different carboxylic carbon nano-tubes and bamboo charcoal mass ratio is handled; Wherein the ammonia nitrogen initial concentration in the polluted water is 5mg/L; PH is 6.5～7, and the temperature of polluted water is 5 ℃, and the concentration that control adds the CNT-bamboo charcoal composite to the polluted water is 10mg/L.Polluted water is the water distribution of simulation ammonia nitrogen.
Residue ammonia nitrogen concentration in the water outlet is measured; Residue ammonia nitrogen concentration curve map is as shown in Figure 3 in the water outlet after obtaining CNT-bamboo charcoal composite through different CNTs and bamboo charcoal mass ratio and handling; As shown in Figure 3, when the mass ratio of carboxylic carbon nano-tube and bamboo charcoal is 1: 4-1: during 3 left and right sides, CNT-bamboo charcoal composite is most effective to the removal of ammonia nitrogen; When 5 ℃ of low temperature, be about about 80%, heavy metal and persistence organic pollutant can access part and remove.And when the mass ratio of carboxylic carbon nano-tube and bamboo charcoal during greater than 1: 3, CNT-bamboo charcoal composite does not change to the removal effect of ammonia nitrogen basically, and visible carboxylic acid multi-walled carbon nano-tubes has reached absorption on the bamboo charcoal surface saturated.
The specific embodiment 21: this embodiment is the preparation method of the specific embodiment 20 described eight kinds of CNTs-bamboo charcoal composites: one, CNT is carried out carboxylated processing: a, multi-walled carbon nano-tubes is placed round-bottomed flask; In round-bottomed flask, add mass fraction again and be 20%～40% glacial acetic acid; Reflux condensation mode, collection and agitating device have been refilled; Constant temperature backflow 0.8h after being heated to 80 ℃; Be cooled to room temperature again and get mixed liquor, wherein, the ratio of control multi-walled carbon nano-tubes quality and glacial acetic acid volume is 1g: 80mL; B, the mixed liquor that step 1 is obtained filter, and wash the black powder on the filter paper then, to filtrate water white transparency and pH value for neutral, the black powder vacuum drying after will washing then must carboxylic carbon nano-tube; Two, carboxylic carbon nano-tube that respectively step 1 is obtained and bamboo charcoal by mass ratio be 1: 3,1: 4,1: 5,1: 6,1: 7,1: 8,1: 9 and 1: 10 mixed even eight mixtures; Then eight mixtures are calcined 5h at 450 ℃ respectively; The washing of cooling back is drying to obtain CNT-bamboo charcoal composite to the water white transparency of filtrating, accomplish the preparation of CNT-bamboo charcoal composite.
The specific embodiment 22: this embodiment is that the specific embodiment 20 described second kind of CNT-bamboo charcoal composites are applied to remove in the method for ammonia nitrogen in the low-temperature water source water; Specific as follows: as second kind of CNT of 1g-bamboo charcoal composite added to the temperature of 100mL to be respectively in the polluted water of 1 ℃, 2 ℃, 3 ℃, 4 ℃ and 5 ℃; In stir speed (S.S.) is under the 160rpm condition; Stirring reaction 30min; Get the water outlet of polluted water after CNT-bamboo charcoal composite is handled of different temperatures, wherein the ammonia nitrogen initial concentration in the polluted water is 5mg/L, and pH is 6.5～7.Polluted water is the water distribution of simulation ammonia nitrogen.
In this embodiment in second kind of CNT-bamboo charcoal composite the mass ratio of carboxylic carbon nano-tube and bamboo charcoal be 1: 4.
Residue ammonia nitrogen concentration in the water outlet after CNT-bamboo charcoal composite is handled of the polluted water of different temperatures is tested, curve map that must be shown in " ■-" among Fig. 4.Visible by Fig. 4, the residue ammonia nitrogen concentration is 1.0mg/L in the water outlet of 5 ℃ polluted water after CNT-bamboo charcoal composite is handled, and ammonia nitrogen removal efficient reaches about 80%; The residue ammonia nitrogen concentration is 2.0mg/L in the water outlet of 1 ℃ polluted water after CNT-bamboo charcoal composite is handled, and ammonia nitrogen removal efficient reaches about 60%.
As a comparison, carry out following contrast test 1 and contrast test 2:
Contrast test 1: 1g bamboo charcoal powder added to the temperature of 100mL be respectively in the polluted water of 1 ℃, 2 ℃, 3 ℃, 4 ℃ and 5 ℃; In stir speed (S.S.) is under the 160rpm condition; Stirring reaction 30min; Get the water outlet of polluted water after 1g bamboo charcoal powder-processed of different temperatures, wherein the ammonia nitrogen initial concentration in the polluted water is 5mg/L, and pH is 6.5～7.Polluted water is the water distribution of simulation ammonia nitrogen.The concentration that adds of bamboo charcoal is 10mg/L.
Residue ammonia nitrogen concentration in the water outlet of polluted water after the bamboo charcoal powder-processed of different temperatures is tested, curve map that must be shown in " ●-" among Fig. 4.It is thus clear that the residue ammonia nitrogen concentration is 3.2mg/L in the water outlet of 5 ℃ polluted water after the bamboo charcoal powder-processed, ammonia nitrogen removal efficient reaches about 36%; Ammonia nitrogen concentration is 4.8mg/L in the water outlet of 1 ℃ polluted water after the bamboo charcoal powder-processed, and ammonia nitrogen removal efficient reaches about 4%.
Contrast test 2: 2g bamboo charcoal powder added to the temperature of 100mL be respectively in the polluted water of 1 ℃, 2 ℃, 3 ℃, 4 ℃ and 5 ℃; In stir speed (S.S.) is under the 160rpm condition; Stirring reaction 30min; Get the water outlet of polluted water after 2g bamboo charcoal powder-processed of different temperatures, wherein the ammonia nitrogen initial concentration in the polluted water is 5mg/L, and pH is 6.5～7.Polluted water is the water distribution of simulation ammonia nitrogen.The concentration that adds of bamboo charcoal is 20mg/L.
Residue ammonia nitrogen concentration in the water outlet of polluted water after the bamboo charcoal powder-processed of different temperatures is tested, curve map that must be shown in " ▲-" among Fig. 4.It is thus clear that the residue ammonia nitrogen concentration is 2.5mg/L in the water outlet of 5 ℃ polluted water after the bamboo charcoal powder-processed, ammonia nitrogen removal efficient reaches about 50%; Ammonia nitrogen concentration is 4.75mg/L in the water outlet of 1 ℃ polluted water after the bamboo charcoal powder-processed, and ammonia nitrogen removal efficient reaches about 5%.
Can know that by Fig. 4 CNT-bamboo charcoal composite is superior to unmodified bamboo charcoal powder to the removal effect of ammonia nitrogen.
The specific embodiment 23: this embodiment is that the specific embodiment 20 described second kind of CNT-bamboo charcoal composites are applied to remove in the method for ammonia nitrogen in the low-temperature water source water; Specific as follows: it is that 5 ℃ initial ammonia nitrogen concentration is respectively in 1mg/L, 2mg/L, 3mg/L, 4mg/L and the 5mg/L polluted water that second kind of CNT of 1g-bamboo charcoal composite is added to the temperature of 100mL; In stir speed (S.S.) is under the 160rpm condition; Stirring reaction 30min; Get the water outlet of polluted water after CNT-bamboo charcoal composite is handled of different initial ammonia nitrogen concentrations, wherein the pH of polluted water is 6.5～7.Polluted water is the water distribution of simulation ammonia nitrogen.
Residue ammonia nitrogen concentration in the water outlet of polluted water after CNT-bamboo charcoal composite is handled of different ammonia nitrogen concentrations is tested, and gets as shown in Figure 5.It is thus clear that 5 ℃ initial ammonia nitrogen concentration is that the residue ammonia nitrogen concentration is 0.4mg/L in the water outlet of polluted water after CNT-bamboo charcoal composite is handled of 1mg/L, ammonia nitrogen removal efficient reaches about 60%; 5 ℃ initial ammonia nitrogen concentration is that ammonia nitrogen concentration is 1mg/L in the water outlet of polluted water after CNT-bamboo charcoal composite is handled of 5mg/L, and ammonia nitrogen removal efficient reaches about 80%.Visible by Fig. 5, when CNT-bamboo charcoal composite is 1mg/L at the initial concentration of ammonia nitrogen, under 5 ℃ of low temperature, ammonia nitrogen is still had the removal effect about 60%.
Claims (10)
1. CNT-bamboo charcoal composite is characterized in that CNT-bamboo charcoal composite is is that the mixture of 1: 1～10 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
2. CNT according to claim 1-bamboo charcoal composite is characterized in that CNT-bamboo charcoal composite is is that the mixture of 1: 2～6 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
3. CNT according to claim 1-bamboo charcoal composite is characterized in that CNT-bamboo charcoal composite is is that the mixture of 1: 3～5 mixed obtains at 400～600 ℃ of calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
4. CNT according to claim 1-bamboo charcoal composite is characterized in that CNT-bamboo charcoal composite is is that the mixture of 1: 4 mixed obtains at 450 ℃ 400～600 ℃ calcining 4～6h by mass ratio with carboxylic carbon nano-tube and bamboo charcoal.
5. the preparation method of CNT as claimed in claim 1-bamboo charcoal composite; The preparation method who it is characterized in that CNT-bamboo charcoal composite realizes through following steps: one, CNT is carried out carboxylated and handle, obtain carboxylic carbon nano-tube; Two, the carboxylic carbon nano-tube and the bamboo charcoal that step 1 are obtained are the even mixtures that get of 1: 1～10 mixed by mass ratio; Then mixture is calcined 4～6h at 400～600 ℃; The washing of cooling back is drying to obtain CNT-bamboo charcoal composite to the water white transparency of filtrating, accomplish the preparation of CNT-bamboo charcoal composite.
6. the preparation method of CNT according to claim 5-bamboo charcoal composite; It is characterized in that step 1 adopts following steps that CNT is carried out carboxylated processing: a, multi-walled carbon nano-tubes is placed round-bottomed flask; In round-bottomed flask, add mass fraction again and be 20%～40% glacial acetic acid; Refilled reflux condensation mode, collection and agitating device, be heated to 60～80 ℃ after the constant temperature 0.8～1.5h that refluxes, be cooled to room temperature again and get mixed liquor; Wherein, the ratio of control multi-walled carbon nano-tubes quality and glacial acetic acid volume is 1g: 60～100mL; B, the mixed liquor that step 1 is obtained filter, and wash the black powder on the filter paper then, to filtrate water white transparency and pH value for neutral, the black powder vacuum drying after will washing then must carboxylic carbon nano-tube.
7. according to the preparation method of claim 5 or 6 described CNT-bamboo charcoal composites, it is characterized in that the carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 are obtained are the even mixtures that get of 1: 2～6 mixed by mass ratio.
8. according to the preparation method of claim 5 or 6 described CNT-bamboo charcoal composites, it is characterized in that the carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 are obtained are the even mixtures that get of 1: 3～5 mixed by mass ratio.
9. according to the preparation method of claim 5 or 6 described CNT-bamboo charcoal composites, it is characterized in that the carboxylic carbon nano-tube and the bamboo charcoal that in the step 2 step 1 are obtained are 1: 4 even mixture that gets of mixed by mass ratio.
10. the application in the method for CNT as claimed in claim 1-bamboo charcoal composite ammonia nitrogen in removing low-temperature water source water.
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| CN106082934A (en) * | 2016-06-12 | 2016-11-09 | 安徽广燕新材料科技有限责任公司 | A kind of preparation method of the artificial stone with anion function |
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| CN1605816A (en) * | 2003-10-10 | 2005-04-13 | 欧阳永定 | Improved solid absorbent bed |
| CN101555045A (en) * | 2009-04-30 | 2009-10-14 | 华中科技大学 | Method for adsorbing, recycling and disposing wastewater |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605816A (en) * | 2003-10-10 | 2005-04-13 | 欧阳永定 | Improved solid absorbent bed |
| CN101555045A (en) * | 2009-04-30 | 2009-10-14 | 华中科技大学 | Method for adsorbing, recycling and disposing wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 周珊 等: "改性竹炭对氨氮的吸附性能研究", 《浙江大学学报(农业与生命科学版)》, vol. 33, no. 5, 31 December 2007 (2007-12-31), pages 584 - 590 * |
| 王祝来,等: "竹炭对水溶液中氨氮的吸附特性研究", 《工业用水与废水》, vol. 40, no. 4, 31 August 2009 (2009-08-31), pages 70 - 72 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082934A (en) * | 2016-06-12 | 2016-11-09 | 安徽广燕新材料科技有限责任公司 | A kind of preparation method of the artificial stone with anion function |
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