CN113996271A - Bimetal modified carbon nanotube adsorbent and preparation method and application thereof - Google Patents
Bimetal modified carbon nanotube adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bimetal modified carbon nanotube adsorbent and a preparation method and application thereof, wherein the bimetal modified carbon nanotube adsorbent comprises the following components: a basic structure, which is a carbon nanotube; functional groups with adsorption capacity are bonded on the carbon nano tubes; the functional material is loaded on the surface of the carbon nano tube, and the effective component loaded on the functional material on the surface of the carbon nano tube comprises Mg (OH)2、Al(OH)3、Fe(OH)3One or more of them. By adopting the technical scheme of the invention, the bimetallic modified carbon nanotube adsorbent has large adsorption capacity, good mechanical strength, good dynamic performance, regeneration performance and selectivity, and can be widely appliedHigh selectivity removal of heavy metal ions in polluted water.
Description
Technical Field
The invention relates to the technical field of nano adsorbents, in particular to a bimetal modified carbon nanotube adsorbent, a preparation method of the bimetal modified carbon nanotube adsorbent and application of the bimetal modified carbon nanotube adsorbent.
Background
With the rise of the tanning industry and the textile industry, a large amount of toxic heavy metals are introduced into underground water and surface water environment as pollutants coexisting with synthetic dyes, and further harm is caused to marine environment. In the related art, conventional physical and chemical treatment methods such as ion exchange, chemical precipitation and electrochemical treatment are generally used to treat chromium-contaminated water. However, these processes typically involve single and multiple complex stages, are inefficient in treating high-concentration metal wastewater, and are costly for large-scale applications. Therefore, there is a great need to develop sustainable, cost-effective heavy metal removal treatment technologies.
The properties of carbon nanotubes have led to their widespread use in the field of adsorption. Compared with activated carbon, the carbon nano tube has larger specific surface area, provides a large number of physically adsorbed active sites, has more special atomic size than the activated carbon, and has the adsorption active sites capable of performing adsorption reaction with almost any molecules. Some studies have been conducted at home and abroad on the preparation and adsorption properties of carbon nanotubes, for example, patent 201910880829.8 (a magnetic nitrogen-doped carbon nanotube water treatment adsorbent and a preparation method thereof) discloses a preparation method of an adsorbent using carbon nanotubes as a matrix, and the adsorption selectivity of the synthesized carbon nanotube adsorbent for chlorinated organic compounds in water to chlorinated organic compounds in trace water in an aqueous solution is greatly improved.
However, the adsorption capacity of carbon nanotubes to heavy metals is not ideal, and the production conditions are also severe. Meanwhile, because the carbon nano tube generally exists in the form of extremely fine particles (the diameter is about 2-20nm, the length-diameter ratio can reach more than 100), the carbon nano tube is very difficult to recycle and is difficult to directly realize industrial adsorption application. The conventional carbon nanotube adsorbent has poor selectivity to heavy metals, when other common ions such as Na in water body+、K+、Ca2+、Cu2+When the concentration is higher, the adsorption selectivity of the heavy metal ion is poorer, and the application cost is higher.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, the invention aims to provide a bimetal modified carbon nanotube adsorbent, a preparation method of the bimetal modified carbon nanotube adsorbent and application of the bimetal modified carbon nanotube adsorbent.
In order to achieve the above object, a first aspect of the present invention provides a bimetallic-modified carbon nanotube adsorbent, including: a basic structure, which is a carbon nanotube; functional groups with adsorption capacity are bonded on the carbon nano tubes; the functional material is loaded on the surface of the carbon nano tube, and the effective component loaded on the functional material on the surface of the carbon nano tube comprises Mg (OH)2、Al(OH)3、Fe(OH)3One or more of them.
In the above technical solution, preferably, the functional group bonded to the surface of the carbon nanotube includes one or more of an amino group, a hydroxyl group, and a carboxylic acid group.
In any of the above technical solutions, preferably, the particle size of the bimetallic modified carbon nanotube adsorbent is 0.5mm-1.5mm, and the content of amino group, hydroxyl group and carboxyl group is 0.05 mmol/g-0.9 mmol/g respectively.
In any of the above embodiments, preferably, Mg (OH)2And Al (OH)3The mass sum of the adsorbent accounts for 2 to 15 percent of the total mass of the adsorbent; or Al (OH)2And Fe (OH)3The mass sum of the adsorbent accounts for 2 to 15 percent of the total mass of the adsorbent; or Mg (OH)2And Fe (OH)3The mass sum of (a) is 2-15% of the total mass of the adsorbent.
The technical scheme of the second aspect of the invention also provides a preparation method of the bimetal modified carbon nanotube adsorbent, which comprises the following steps:
respectively dissolving aluminum chloride hexahydrate and magnesium chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the concentration of the magnesium chloride are 0.2-2.0 mol/L, mixing an aluminum chloride solution and a magnesium chloride solution according to a certain proportion to prepare a solution A, wherein the volume ratio of the aluminum chloride solution to the magnesium chloride solution is 1:1-6: 1; or respectively dissolving aluminum chloride hexahydrate and ferric chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the concentration of the magnesium chloride are 0.2-2.0 mol/L, mixing an aluminum chloride solution and a ferric chloride solution according to a certain proportion to prepare a solution A, wherein the volume ratio of the aluminum chloride solution to the ferric chloride solution is 1:1-6: 1; or respectively dissolving magnesium chloride and ferric chloride in deionized water, wherein the concentration of the magnesium chloride and the ferric chloride is 0.2-2.0 mol/L, and mixing the magnesium chloride solution and the ferric chloride solution in a certain ratio to prepare a solution A, wherein the volume ratio of the magnesium chloride solution to the ferric chloride solution is 1:1-6: 1;
mixing NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration of (A) is 0.05 mol/L to 0.6 mol/L, NaOH solution and Na are added2CO3Mixing the solution according to a certain proportion to obtain solution B, NaOH solution and Na2CO3The volume ratio of the solution is 1:1-6: 1;
weighing carbon nanotubes, dissolving the carbon nanotubes in deionized water, adding 1g-12.5g of carbon nanotubes into each 100mL of deionized water, placing the mixture in a water bath, stirring, wherein the temperature of the water bath is not lower than 40 ℃, simultaneously adding the solution A and the solution B into a mixed system according to a certain proportion, and adjusting the pH value of the mixed system to 7-12;
placing the mixed system in a water bath for ultrasonic treatment for 30min, wherein the water bath temperature during ultrasonic treatment is not lower than 40 ℃, and then aging in the water bath for 8-15 h, wherein the water bath temperature during aging is not lower than 50 ℃;
separating the carbon nano tube from the mixed system, adding deionized water, stirring and cleaning, repeating the cleaning for 3-5 times, wherein the cleaning time is not less than 2h each time, and drying after the cleaning;
and calcining the dried carbon nano tube at the temperature of not less than 380 ℃ for 4 hours to obtain the bimetal modified carbon nano tube adsorbent.
Preferably, the solution A is formed by mixing an aluminum chloride solution and a magnesium chloride solution according to a volume ratio of 2: 1; solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 4: 1; the water bath temperature of the carbon nano tube is 45 ℃ when the carbon nano tube is stirred in the water bath; and mixing the solution A and the solution B according to the ratio of 3:1, adding the mixture into a mixed system, and adjusting the pH of the mixed system to 9 +/-0.1; the water bath temperature of the mixed system during ultrasonic treatment in the water bath is 45 ℃, the water bath temperature of the mixed system during aging in the water bath is 50 ℃, and the aging time is 8 hours; the calcination temperature for calcining the dried carbon nano tube is 380 ℃.
Preferably, the solution A is formed by mixing an aluminum chloride solution and an iron chloride solution according to a volume ratio of 2.5: 1; solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 4: 1; the water bath temperature of the carbon nano tube is 60 ℃ when the carbon nano tube is stirred in the water bath; adding the solution A and the solution B into a mixed system according to the volume ratio of 1.5:1, and adjusting the pH of the mixed system to 9 +/-0.1; the temperature of the water bath of the mixed system during ultrasonic treatment in the water bath is 60 ℃, the temperature of the water bath of the mixed system during aging in the water bath is 50 ℃, and the aging time is 8 hours; the calcination temperature for calcining the dried carbon nano tube is 480 ℃.
Preferably, the solution A is formed by mixing a magnesium chloride solution and an iron chloride solution according to a volume ratio of 4: 1; solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 2: 1; the water bath temperature of the carbon nano tube is 55 ℃ when the carbon nano tube is stirred in the water bath; adding the solution A and the solution B into a mixed system according to the volume ratio of 1:1, and adjusting the pH of the mixed system to 9 +/-0.1; the temperature of the water bath of the mixed system during ultrasonic treatment in the water bath is 50 ℃, the temperature of the water bath of the mixed system during aging in the water bath is 60 ℃, and the aging time is 8 hours; the calcination temperature for calcining the dried carbon nano tube is 450 ℃.
Preferably, the carbon nanotubes to be weighed include one or more of CNTs300, YZ-CN10, YZ-CN30 and YZ-CN 60.
The technical scheme of the third aspect of the invention also provides an application of the bimetal modified carbon nano tube adsorbent, and the bimetal modified carbon nano tube adsorbent is used for adsorbing and removing heavy metals in wastewater.
The bimetal modified carbon nanotube adsorbent, the preparation method and the application thereof provided by the invention have the following beneficial technical effects:
(1) the invention provides a bimetalModified carbon nanotube adsorbent Mg (OH)2、Al(OH)3、Fe(OH)3Any two of the functional groups are loaded on the surface of the carbon nano tube, the surface-bonded functional groups comprise two or three of hydroxyl and carboxylic acid groups, the metal oxyhydroxide has strong stability and still has excellent adsorption performance when various ions coexist, and the adsorbent can be widely applied to the high-selectivity removal of heavy metal ions in the polluted water body.
(2) The bimetallic modified carbon nanotube adsorbent provided by the invention has the advantages of large adsorption capacity, good mechanical strength, and excellent dynamic performance and selectivity.
(3) The invention provides a bimetal modified carbon nano tube adsorbent containing Mg (OH)2And Al (OH)3The content is as follows: about 100mg/g to 450mg/g carbon nanotubes, Mg (OH)2、Al(OH)3、Fe(OH)3The existence of any two of them greatly reduces the coexistence ions such as Na in water+，K+，Cl-，NO3 -The interference on the adsorption of heavy metal ions such as chromium and the like greatly improves the selectivity and the adsorption efficiency of the heavy metal ions, and meanwhile, the adsorption capacity is improved by 90 to 200 percent.
(4) The preparation method of the bimetal modified carbon nano tube adsorbent provided by the invention is simple and has strong reliability.
(5) The bimetallic modified carbon nanotube adsorbent provided by the invention has a stable structure and strong cyclic adsorption capacity, and the adsorption effect can still reach more than 90% of that before adsorption after 5-7 times of adsorption and desorption cycles.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
All figures and reference numerals in the figures referred to in the patent application are described as follows:
fig. 1 is a diagram of a nitrogen adsorption-desorption isotherm of the aluminum magnesium bimetal modified carbon nanotube adsorbent in example 1 of the present invention.
Detailed Description
The invention discloses a bimetal modified carbon nanotube adsorbent and a preparation method and application thereof, and a person skilled in the art can use the contents for reference and appropriately improve process parameters to realize the bimetal modified carbon nanotube adsorbent. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
A preparation method of a bimetal modified carbon nanotube adsorbent comprises the following steps:
respectively dissolving aluminum chloride hexahydrate and magnesium chloride in deionized water, wherein the concentrations of the aluminum chloride hexahydrate and the magnesium chloride are 2mol/L, mixing the aluminum chloride hexahydrate and the magnesium chloride solution according to a certain proportion to prepare a solution A, the mixing proportion is 2:1, and adding NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration is 4mol/L, NaOH and Na are added2CO3The solution B is prepared by mixing the solution according to a certain ratio to prepare a solution B, the mixing ratio is 4:1, 2g of carbon nano tube is weighed and dissolved in 80mL of deionized water, the solution is stirred in a water bath at 45 ℃, meanwhile, A, B solution is added into the system according to the volume ratio of 3:1, the pH value of the system is adjusted to 9 +/-0.1, ultrasound is carried out in the water bath at 45 ℃ for 30min, then the aging is carried out in the water bath at 50 ℃ for 8h, the carbon nano tube is separated, deionized water is added, stirring and cleaning are carried out for 2h, the operation is repeated for 5 times, drying is carried out, and the dried carbon nano tube is calcined at 380 ℃ for 4h, thus obtaining the aluminum-magnesium bimetal modified carbon nano tube adsorbent.
As can be seen from FIG. 1, it was found that the pressure at the relative pressure (C) was measured by the nitrogen adsorption-desorption techniquePAnd in the range of/Po) = 0.7-1.0, a hysteresis loop appears on an isothermal line, which indicates that the adsorbent has a mesoporous channel structure.
Evaluation conditions were as follows: weighing 20mL of 1mmoL/L hexavalent chromium ion solution, adjusting the pH value to be =6, adding 10mg of adsorbent, mixing, oscillating and adsorbing at 20 ℃ and 110rpm for 3h, and performing centrifugal separation to obtain a water sample with chromium ions removed.
The results show that: after the treatment of the aluminum-magnesium bimetal modified carbon nano tube adsorbent, the removal rate of chromium ions can reach 99.1%.
The regeneration conditions of the adsorbent are as follows: after the aluminum-magnesium bimetal modified carbon nano tube is subjected to adsorption separation, the adsorbent is washed by deionized water for 1 time, then the adsorbent is placed into 10 mL of sodium carbonate solution with the concentration of 0.1 mol/L, stirred for 60min, washed by the deionized water for 2 times after centrifugal separation, and then dried for 24h at the temperature of 100 ℃.
The results show that: the aluminum-magnesium bimetal modified carbon nanotube still has very good adsorption and separation performances after being recycled for 4 times. The test results are as follows: the adsorbent is used for the 1 st time, the chromium ion removal rate can reach 98.9%, the adsorbent is used repeatedly for the 2 nd time, the chromium ion removal rate can reach 98.1%, the adsorbent is recycled for the 3 rd time, the chromium ion removal rate is 96.9%, the adsorbent is recycled for the 3 rd time, the chromium ion removal rate is 95.5%, the catalyst is recycled for the 4 th time, the chromium ion removal rate is 93.8%, the adsorbent is recycled for the 5 th time, the chromium ion removal rate is 92.4%, the adsorbent is recycled for the 6 th time, and the chromium ion removal rate is 91.3%.
Example 2
A preparation method of a bimetal modified carbon nanotube adsorbent comprises the following steps:
respectively dissolving aluminum chloride hexahydrate and ferric chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the ferric chloride solution is 1mol/L, mixing the aluminum chloride hexahydrate and the ferric chloride solution according to the volume ratio of 2.5:1 to prepare a solution A, and mixing NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration is 4mol/L, NaOH and Na are added2CO3Mixing the solutions at a certain ratio to obtain solution B, weighing 2g of carbon nanotube, dissolving in 80mL of deionized water at a mixing ratio of 4:1, stirring in 60 deg.C water bath, adding A, B solution into the system at a volume ratio of 1.5:1, adjusting pH to 9 + -0.1, performing ultrasonic treatment in 60 deg.C water bath for 30min, aging in 50 deg.C water bath for 8h, and separating out carbon nanotubeAnd adding deionized water into the rice tube, stirring and cleaning for 2h, repeating for 5 times, drying, and calcining the dried carbon nano tube for 4h at 480 ℃ to obtain the aluminum-iron bimetal modified carbon nano tube adsorbent.
Evaluation conditions were as follows: weighing 20mL of 1mmoL/L hexavalent chromium ion solution, adjusting the pH value to be =6, adding 10mg of adsorbent, mixing, oscillating and adsorbing at 20 ℃ and 110rpm for 3h, and performing centrifugal separation to obtain a water sample with chromium ions removed.
The results show that: after the treatment of the aluminum-iron bimetal modified carbon nano tube adsorbent, the removal rate of chromium ions can reach 97.6%.
Example 3
A preparation method of a bimetal modified carbon nanotube adsorbent comprises the following steps:
respectively dissolving magnesium chloride and ferric chloride in deionized water, wherein the concentration of the magnesium chloride solution and the ferric chloride solution is 1mol/L, mixing the magnesium chloride solution and the ferric chloride solution according to the volume ratio of 4:1 to prepare a solution A, and adding NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration is 4mol/L, NaOH and Na are added2CO3The solution is mixed according to a certain proportion to prepare a solution B, the mixing proportion is 2:1, 2g of carbon nano tube is weighed and dissolved in 80mL of deionized water, the solution is stirred in a water bath at 55 ℃, meanwhile, A, B solution is added into the system according to the volume ratio of 1:1, the pH value of the system is adjusted to be 9 +/-0.1, ultrasound is carried out in the water bath at 50 ℃ for 30min, then the system is aged in the water bath at 60 ℃ for 8h, the carbon nano tube is separated out, deionized water is added, stirring and cleaning are carried out for 2h, the operation is repeated for 5 times, drying is carried out, and the dried carbon nano tube is calcined at 450 ℃ for 4h, so that the magnesium-iron bimetal modified carbon nano tube adsorbent is obtained.
Evaluation conditions were as follows: weighing 20mL of 1mmoL/L hexavalent chromium ion solution, adjusting the pH value to be =6, adding 10mg of adsorbent, mixing, oscillating and adsorbing at 20 ℃ and 110rpm for 3h, and performing centrifugal separation to obtain a water sample with chromium ions removed.
The results show that: after the treatment of the magnesium-iron bimetal modified carbon nano tube adsorbent, the removal rate of chromium ions can reach 94%.
Comparative example 1
Chlorine hexahydrateDissolving aluminum oxide in deionized water to obtain solution A with the concentration of 4mol/L, and adding NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration is 4mol/L, NaOH and Na are added2CO3The solution is mixed according to a certain proportion to prepare a solution B, the mixing proportion is 4:1, 2g of carbon nano tube is weighed and dissolved in 80mL of deionized water, the solution is stirred in a water bath at 45 ℃, meanwhile, A, B solution is added into the system according to the volume ratio of 3:1, the pH value of the system is adjusted to be 9 +/-0.1, ultrasound is carried out in the water bath at 45 ℃ for 30min, then the aging is carried out in the water bath at 50 ℃ for 8h, the carbon nano tube is separated, deionized water is added, stirring and cleaning are carried out for 2h, the operation is repeated for 5 times, drying is carried out, and the dried carbon nano tube is calcined for 4h at 380 ℃, so that the aluminum single metal modified carbon nano tube adsorbent is obtained.
Evaluation conditions were as follows: weighing 20mL of 1mmoL/L hexavalent chromium ion solution, adjusting the pH value to be =6, adding 10mg of adsorbent, mixing, oscillating and adsorbing at 20 ℃ and 110rpm for 3h, and performing centrifugal separation to obtain a water sample with chromium ions removed.
The results show that: after the treatment of the aluminum single-metal modified carbon nano tube adsorbent of the comparative example, the removal rate of chromium ions is 38.2 percent.
Comparative example 2
Respectively dissolving aluminum chloride hexahydrate and ferric chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the ferric chloride solution is 1mol/L, mixing the aluminum chloride hexahydrate and the ferric chloride solution according to the volume ratio of 2.5:1 to prepare a solution A, and mixing NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration is 4mol/L, NaOH and Na are added2CO3The solution B is prepared by mixing the solution according to a certain ratio to prepare a solution B, the mixing ratio is 4:1, 2g of carbon nano tube is weighed and dissolved in 80mL of deionized water, the solution is stirred in a water bath at 60 ℃, meanwhile, A, B solution is added into the system according to the volume ratio of 1.5:1, the pH value of the system is adjusted to be 9 +/-0.1, ultrasound is carried out in the water bath at 60 ℃ for 30min, then the aging is carried out in the water bath at 50 ℃ for 8h, the carbon nano tube is separated, deionized water is added, stirring and cleaning are carried out for 2h, the operation is repeated for 5 times, drying is carried out, and the dried carbon nano tube is calcined for 4h at 480 ℃, so that the aluminum-iron bimetal modified carbon nano tube adsorbent is obtained.
Coexisting ion competitive adsorption conditions: weighing 100mL of 1mmoL/L hexavalent chromium ion solution, adding a proper amount of salt solid ferric chloride and sodium sulfate of coexisting ions (the concentration of the coexisting ions is 1 mmoL/L), adjusting the pH to be =6, taking 20mL of the solution, mixing the solution with 10mg of adsorbent, oscillating and adsorbing the mixture at 20 ℃ and 110rpm for 3 hours, and performing centrifugal separation to obtain a water sample with chromium ions removed.
The results show that: the comparative example is Fe-Al-Fe bimetal modified carbon nanotube3+，Cl-， SO4 2-The catalyst still has very good adsorption separation performance in a coexisting environment and shows excellent selectivity. The test results are as follows: in Cl-When the ion concentration is 1mmol/L, the removal rate of the adsorbent to chromium ions can reach 98.3 percent; in SO4 2-When the ion concentration is 1mmol/L, the removal rate of the adsorbent to chromium ions can reach 96.5 percent; in Fe3+When the ion concentration is 1mmol/L, the removal rate of the chromium ions by the adsorbent can reach 97.9 percent.
Claims (10)
1. A bimetallic-modified carbon nanotube adsorbent, comprising:
a basic structure, which is a carbon nanotube; functional groups with adsorption capacity are bonded on the carbon nano tubes; the functional material is loaded on the surface of the carbon nano tube, and the effective component loaded on the functional material on the surface of the carbon nano tube comprises Mg (OH)2、Al(OH)3、Fe(OH)3One or more of them.
2. The bi-metal modified carbon nanotube adsorbent of claim 1,
the functional group bonded on the surface of the carbon nano tube comprises one or more of amino, hydroxyl and carboxylic acid groups.
3. The bi-metal modified carbon nanotube adsorbent of claim 2,
the particle size of the bimetallic modified carbon nano tube adsorbent is 0.5mm-1.5mm, and the content of amino, hydroxyl and carboxylic acid group is 0.05 mmol/g-0.9 mmol/g respectively.
4. The bi-metal modified carbon nanotube adsorbent of any one of claims 1 to 3,
Mg(OH)2and Al (OH)3The mass sum of the adsorbent accounts for 2 to 15 percent of the total mass of the adsorbent; or Al (OH)2And Fe (OH)3The mass sum of the adsorbent accounts for 2 to 15 percent of the total mass of the adsorbent; or Mg (OH)2And Fe (OH)3The mass sum of (a) is 2-15% of the total mass of the adsorbent.
5. A preparation method of a bimetal modified carbon nanotube adsorbent is characterized by comprising the following steps:
respectively dissolving aluminum chloride hexahydrate and magnesium chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the concentration of the magnesium chloride are 0.2-2.0 mol/L, mixing an aluminum chloride solution and a magnesium chloride solution according to a certain proportion to prepare a solution A, wherein the volume ratio of the aluminum chloride solution to the magnesium chloride solution is 1:1-6: 1; or respectively dissolving aluminum chloride hexahydrate and ferric chloride in deionized water, wherein the concentration of the aluminum chloride hexahydrate and the concentration of the magnesium chloride are 0.2-2.0 mol/L, mixing an aluminum chloride solution and a ferric chloride solution according to a certain proportion to prepare a solution A, wherein the volume ratio of the aluminum chloride solution to the ferric chloride solution is 1:1-6: 1; or respectively dissolving magnesium chloride and ferric chloride in deionized water, wherein the concentration of the magnesium chloride and the ferric chloride is 0.2-2.0 mol/L, and mixing the magnesium chloride solution and the ferric chloride solution in a certain ratio to prepare a solution A, wherein the volume ratio of the magnesium chloride solution to the ferric chloride solution is 1:1-6: 1;
mixing NaOH and Na2CO3Dissolving in deionized water, wherein NaOH and Na2CO3The concentration of (A) is 0.05 mol/L to 0.6 mol/L, NaOH solution and Na are added2CO3Mixing the solution according to a certain proportion to obtain solution B, NaOH solution and Na2CO3The volume ratio of the solution is 1:1-6: 1;
weighing carbon nanotubes, dissolving the carbon nanotubes in deionized water, dissolving 1g-12.5g of carbon nanotubes in each 100mL of deionized water, placing the mixture in a water bath, stirring, wherein the temperature of the water bath is not lower than 40 ℃, simultaneously adding the solution A and the solution B into a mixed system according to a certain proportion, and adjusting the pH value of the mixed system to 7-12;
placing the mixed system in a water bath for ultrasonic treatment for 30min, wherein the water bath temperature during ultrasonic treatment is not lower than 40 ℃, and then aging in the water bath for 8-15 h, wherein the water bath temperature during aging is not lower than 50 ℃;
separating the carbon nano tube from the mixed system, adding deionized water, stirring and cleaning, repeating the cleaning for 3-5 times, wherein the cleaning time is not less than 2h each time, and drying after the cleaning;
and calcining the dried carbon nano tube at the temperature of not less than 380 ℃ for 4 hours to obtain the bimetal modified carbon nano tube adsorbent.
6. The method of claim 5,
the solution A is formed by mixing an aluminum chloride solution and a magnesium chloride solution according to the volume ratio of 2: 1;
solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 4: 1;
the water bath temperature of the carbon nano tube is 45 ℃ when the carbon nano tube is stirred in the water bath;
adding the solution A and the solution B into a mixed system according to the volume ratio of 3:1, and adjusting the pH of the mixed system to 9 +/-0.1;
the water bath temperature of the mixed system during ultrasonic treatment in the water bath is 45 ℃, the water bath temperature of the mixed system during aging in the water bath is 50 ℃, and the aging time is 8 hours;
the calcination temperature for calcining the dried carbon nano tube is 380 ℃.
7. The method of claim 5,
the solution A is formed by mixing an aluminum chloride solution and an iron chloride solution according to the volume ratio of 2.5: 1;
solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 4: 1;
the water bath temperature of the carbon nano tube is 60 ℃ when the carbon nano tube is stirred in the water bath;
adding the solution A and the solution B into a mixed system according to the volume ratio of 1.5:1, and adjusting the pH of the mixed system to 9 +/-0.1;
the temperature of the water bath of the mixed system during ultrasonic treatment in the water bath is 60 ℃, the temperature of the water bath of the mixed system during aging in the water bath is 50 ℃, and the aging time is 8 hours;
the calcination temperature for calcining the dried carbon nano tube is 480 ℃.
8. The method of claim 5,
the solution A is formed by mixing a magnesium chloride solution and an iron chloride solution according to the volume ratio of 4: 1;
solution B is prepared from NaOH solution and Na2CO3The solution is mixed according to the volume ratio of 2: 1;
the water bath temperature of the carbon nano tube is 55 ℃ when the carbon nano tube is stirred in the water bath;
adding the solution A and the solution B into a mixed system according to the volume ratio of 1:1, and adjusting the pH of the mixed system to 9 +/-0.1;
the temperature of the water bath of the mixed system during ultrasonic treatment in the water bath is 50 ℃, the temperature of the water bath of the mixed system during aging in the water bath is 60 ℃, and the aging time is 8 hours;
the calcination temperature for calcining the dried carbon nano tube is 450 ℃.
9. The method for preparing the bimetal modified carbon nanotube adsorbent according to any one of claims 5 to 8,
the selected carbon nano tube is weighed and comprises one or more of CNTs300, YZ-CN10, YZ-CN30 and YZ-CN 60.
10. The application of the bimetal modified carbon nanotube adsorbent is characterized in that the bimetal modified carbon nanotube adsorbent is used for adsorbing and removing heavy metals in wastewater.
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| WO2015122856A1 (en) * | 2014-02-13 | 2015-08-20 | Ústav Polymérov Sav | A process for preparation of composite sorbent for removal contaminants from water |
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| CN102432085A (en) * | 2011-12-20 | 2012-05-02 | 华北电力大学（保定） | Method for removing mercury ions in water and regeneration method of adsorbent used in same |
| WO2015122856A1 (en) * | 2014-02-13 | 2015-08-20 | Ústav Polymérov Sav | A process for preparation of composite sorbent for removal contaminants from water |
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