CN106824120B - Recyclable carbon fiber adsorbent and preparation and application thereof - Google Patents
Recyclable carbon fiber adsorbent and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a recyclable carbon fiber adsorbent, and preparation and application thereof, and particularly discloses carbon fiber adsorbents, wherein the carbon fiber adsorbents comprise modified carbon fibers, and the modified carbon fibers comprise a carbon fiber substrate, a modified polymer film layer combined on the surface of the carbon fiber substrate and microspherical modified particles combined on the surface of the modified polymer film layer.
Description
Technical Field
The invention relates to the field of materials, in particular to recyclable carbon fiber adsorbents and preparation and application thereof.
Background
Lead, chromium and other heavy metal elements flood in rocks, soil, river water, seawater and atmosphere in the crust of the earth, and are kinds of strong pollutants, and when entering a water body in the process of ecological cycle, the heavy metal elements pose serious threats to human health.
At present, although reports show that activated carbon can be used as an adsorbent to pretreat water, the activated carbon can only remove solid impurity particles, oil stains and the like in the water; in addition, the active carbon has the problems of poor recycling performance and secondary pollution to water bodies along with the prolonging of the service time in the use process.
Therefore, there is an urgent need in the art to develop novel heavy metal ion adsorbents which have excellent adsorption performance, can be recycled, and do not cause secondary pollution to water.
Disclosure of Invention
The invention aims to provide novel heavy metal ion adsorbents which have excellent adsorption performance, can be recycled and do not cause secondary pollution to water.
In of the present invention, carbon fiber adsorbents are provided, which include modified carbon fibers including a carbon fiber matrix, a modified polymer film layer bonded to a surface of the carbon fiber matrix, and micro-spherical modified particles bonded to a surface of the modified polymer film layer.
In another preferred embodiment , the carbon fiber adsorbent is in the form of fibers.
In another preferred embodiment of , the modified polymer film layer has a thickness of 0.05-0.4 μm, and/or
The microspherical modified particles are coated on the surface of the modified polymer film layer, and the coating rate is 10-95%.
In another preferred embodiment , the modified polymer film layer has a thickness of 0.05-0.3 μm, preferably 0.1-0.2 μm.
In another preferred embodiment of , the coating rate is 20-85%, preferably 30-70%, more preferably 40-50%.
In another preferred embodiment, the carbon fiber matrix has a diameter of 3-10 μm, preferably 5-8 μm.
In another preferred embodiment, a (small amount of) microporous structure is present in the modified polymer film layer.
In another preferred embodiment of , the diameter D of the modified microspherical particles is 0.3-1.5 μm.
In another preferred embodiment of , the diameter D of the modified microspherical particles is 0.3-0.8. mu.m, preferably 0.4-0.6. mu.m.
In another preferred embodiment , the microspherical modified particles are uniformly distributed on the surface of the modified polymer film layer.
In another preferred embodiment of , the modified polymer film layer and the microspherical modified particles have substantially the same composition and are both copolymers of th modifier and a second modifier.
In another preferred embodiment of , the modifier is hexachlorocyclotriphosphazene, and/or
The second modifier is 4, 4' -dihydroxydiphenyl sulfone.
In another preferred embodiment , the adsorption capacity of the carbon fiber adsorbent to lead (II) is greater than or equal to 65mg/g, preferably 70 mg/g.
In another preferred embodiment , the carbon fiber adsorbent has an adsorption capacity of greater than or equal to 110mg/g, preferably 118mg/g, for chromium (VI).
In another preferred embodiment , the carbon fiber adsorbent has a lead (II) removal rate of 85% or more, preferably 88% or more.
In another preferred embodiment , the carbon fiber adsorbent has a chromium (VI) removal rate of 88% or more, preferably 91% or more.
In a second aspect of the present invention, there is provided methods for preparing the carbon fiber adsorbent of the aspect of the present invention, comprising the steps of:
1) providing a carbon fiber material, th modified solution and a second modifier, wherein,
the th modification solution comprises th modifier and th solvent;
2) adding the carbon fiber material into the th modified solution under the stirring condition, heating the obtained mixture, and reacting to obtain a mixture containing the carbon fiber material modified by th modifying agent;
3) adding the second modifier into the reaction mixture obtained in the step 2) under the stirring condition, and reacting to obtain the th modifier and the copolymer modified carbon fiber adsorbent of the second modifier.
In another preferred embodiment, the th solvent is anhydrous acetonitrile.
In another preferred embodiment, the th modifier and the second modifier are as described in the th aspect of the invention.
In another preferred embodiment, the modified solution further comprises a reaction promoter, such as triethylamine.
In another preferred embodiment , step 1) is preceded by the step of activating the carbon fiber material.
In another preferred embodiment , in step 2), the mass ratio of the th modifier to the carbon fiber material is 0.5 to 15, preferably 0.8 to 12, and more preferably 1 to 10.
In another preferred embodiment of , the heating temperature for the heating in step 2) is 30-70 deg.C, preferably 35-60 deg.C, more preferably 38-45 deg.C.
In another preferred embodiment, the reaction time at said heating temperature in step 2) is 0.1-5 hours, preferably 0.3-3 hours.
In another preferred embodiment of , step 3) is performed under an inert gas atmosphere.
In another preferred embodiment, the inert gas is nitrogen.
In another preferred embodiment, in step 3), the mass ratio of the second modifier to the carbon fiber material is 1-15, preferably 2-13, and more preferably 3-10.
In another preferred embodiment of , the reaction temperature for the reaction described in step 3) is from 30 to 70 deg.C, preferably from 35 to 60 deg.C, more preferably from 38 to 45 deg.C.
In another preferred embodiment, the reaction of step 3) is carried out at constant temperature.
In another preferred embodiment of , the reaction time at the reaction temperature in 3) is 2 to 10 hours, preferably 3 to 8 hours.
In another preferred embodiment , the method further comprises the following steps after the step 3):
4) removing unreacted monomers and/or byproducts in the previous step;
5) optionally washing the product obtained in the previous step;
6) optionally drying the product obtained in the previous step.
In another preferred embodiment of , the removal is performed by extraction with an extractant such as solvent.
In another preferred embodiment of , the drying treatment temperature is 40-80 deg.C and the drying treatment time is 5-24 hr.
In a third aspect of the invention, water purification methods are provided, wherein the carbon fiber adsorbent of the aspect of the invention is used for adsorption treatment of water.
In a fourth aspect of the invention, articles comprising or consisting of the carbon fiber adsorbent of aspect of the invention are provided.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) can be combined with one another to form new or preferred embodiments.
Drawings
Fig. 1 and 2 show SEM results of carbon fiber adsorbent 1 obtained in example 1.
Fig. 3 shows the results of XPS full spectrum analysis of the carbon fiber adsorbent 1.
Detailed Description
The inventor of the invention has long and intensive research, and has unexpectedly prepared novel adsorbents with excellent comprehensive properties by adopting a specific preparation process, in particular, the inventor firstly adopts a corrosion-resistant and oxidation-resistant carbon fiber material as an adsorption material matrix, and prepares heavy metal ion adsorbents with excellent adsorption properties, recycling performance and no secondary pollution to water bodies by combining two times of surface modification and a specific preparation process.
Carbon fiber adsorbent
The invention provides carbon fiber adsorbents, which comprise modified carbon fibers, wherein the modified carbon fibers comprise a carbon fiber matrix, a modified polymer film layer bonded to the surface of the carbon fiber matrix and microspherical modified particles bonded to the surface of the modified polymer film layer.
In another preferred embodiment , the carbon fiber adsorbent is in the form of fibers.
In another preferred embodiment of , the modified polymer film layer has a thickness of 0.05-0.4 μm, and/or
The microspherical modified particles are coated on the surface of the modified polymer film layer, and the coating rate is 10-95%.
In another preferred embodiment , the modified polymer film layer has a thickness of 0.05-0.3 μm, preferably 0.1-0.2 μm.
In another preferred embodiment of , the coating rate is 20-85%, preferably 30-70%, more preferably 40-50%.
In another preferred embodiment, the carbon fiber matrix has a diameter of 3-10 μm, preferably 5-8 μm.
In another preferred embodiment, a (small amount of) microporous structure is present in the modified polymer film layer.
In another preferred embodiment of , the diameter D of the modified microspherical particles is 0.3-1.5 μm.
In another preferred embodiment of , the diameter D of the modified microspherical particles is 0.3-0.8. mu.m, preferably 0.4-0.6. mu.m.
In another preferred embodiment , the microspherical modified particles are uniformly distributed on the surface of the modified polymer film layer.
In another preferred embodiment of , the modified polymer film layer and the microspherical modified particles have substantially the same composition and are both copolymers of th modifier and a second modifier.
In another preferred embodiment of , the modifier is hexachlorocyclotriphosphazene, and/or
The second modifier is 4, 4' -dihydroxydiphenyl sulfone.
In another preferred embodiment , the adsorption capacity of the carbon fiber adsorbent to lead (II) is greater than or equal to 65mg/g, preferably 70 mg/g.
In another preferred embodiment , the carbon fiber adsorbent has an adsorption capacity of greater than or equal to 110mg/g, preferably 118mg/g, for chromium (VI).
In another preferred embodiment , the carbon fiber adsorbent has a lead (II) removal rate of 85% or more, preferably 88% or more.
In another preferred embodiment , the carbon fiber adsorbent has a chromium (VI) removal rate of 88% or more, preferably 91% or more.
The adsorption is a process of enriching components in liquid or gas on the surface of an adsorbent by utilizing the selective adsorption capacity of the adsorbent, and the adsorption mainly comprises two adsorption modes, namely physical adsorption and chemical adsorption, wherein the physical adsorption acting force is intermolecular attraction, namely Van der Waals force, and is not selective and does not need high activation energy, an adsorption layer can be a single layer or a multilayer, the adsorption and desorption speeds are usually high, and the physical adsorption quantity is reduced along with the rise of temperature.
The modified polymer film layer and the modified particles exist on the surface of the carbon fiber adsorbent, and the modified polymer film layer and the modified particles have synergistic effect, so that the surface energy of the adsorbent can be remarkably improved, and the physical adsorption efficiency of the adsorbent is improved; and the adsorbent can also perform chemical reaction with heavy metal ions in the water body, so that the adsorbent also has chemical adsorption capacity.
Therefore, the invention provides novel adsorbents which combine physical adsorption capacity and chemical adsorption capacity, the adsorbents still have excellent adsorption capacity after being desorbed and simply treated for reuse, and can be recycled for multiple times (the cycle number is more than or equal to 10, the adsorption retention rate is more than or equal to 60% during 10 cycles, and the performance is very stable).
Preparation method
The invention also provides a preparation method of carbon fiber adsorbents, which comprises the following steps:
1) providing a carbon fiber material, th modified solution and a second modifier, wherein,
the th modification solution comprises th modifier and th solvent;
2) adding the carbon fiber material into the th modified solution under the stirring condition, heating the obtained mixture, and reacting to obtain a mixture containing the carbon fiber material modified by th modifying agent;
3) adding the second modifier into the reaction mixture obtained in the step 2) under the stirring condition, and reacting to obtain the th modifier and the copolymer modified carbon fiber adsorbent of the second modifier.
In another preferred embodiment, the th solvent is anhydrous acetonitrile.
In another preferred embodiment, the th modifier and the second modifier are as described in the th aspect of the invention.
In another preferred embodiment, the modified solution further comprises a reaction promoter, such as triethylamine.
In another preferred embodiment , step 1) is preceded by the step of activating the carbon fiber material.
In another preferred embodiment , in step 2), the mass ratio of the th modifier to the carbon fiber material is 0.5 to 15, preferably 0.8 to 12, and more preferably 1 to 10.
In another preferred embodiment of , the heating temperature for the heating in step 2) is 30-70 deg.C, preferably 35-60 deg.C, more preferably 38-45 deg.C.
In another preferred embodiment, the reaction time at said heating temperature in step 2) is 0.1-5 hours, preferably 0.3-3 hours.
In another preferred embodiment of , step 3) is performed under an inert gas atmosphere.
In another preferred embodiment, the inert gas is nitrogen.
In another preferred embodiment, in step 3), the mass ratio of the second modifier to the carbon fiber material is 1-15, preferably 2-13, and more preferably 3-10.
In another preferred embodiment of , the reaction temperature for the reaction described in step 3) is from 30 to 70 deg.C, preferably from 35 to 60 deg.C, more preferably from 38 to 45 deg.C.
In another preferred embodiment, the reaction of step 3) is carried out at constant temperature.
In another preferred embodiment of , the reaction time at the reaction temperature in 3) is 2 to 10 hours, preferably 3 to 8 hours.
In another preferred embodiment , the method further comprises the following steps after the step 3):
4) removing unreacted monomers and/or byproducts in the previous step;
5) optionally washing the product obtained in the previous step;
6) optionally drying the product obtained in the previous step.
In another preferred embodiment of , the removal is performed by extraction with an extractant such as solvent.
In another preferred embodiment of , the drying treatment temperature is 40-80 deg.C and the drying treatment time is 5-24 hr.
Applications of
The invention also provides water purification methods, which are used for carrying out adsorption treatment on water bodies by using the carbon fiber adsorbent.
The invention also provides products, which contain or consist of the carbon fiber adsorbent.
Compared with the prior art, the invention has the following main advantages:
(1) novel heavy metal ion adsorbents are provided, and the adsorbents have the characteristics of corrosion resistance, oxidation resistance, excellent adsorption performance and the like;
(2) the adsorbent has good physical and chemical stability and excellent mechanical strength, and the desorption treatment is simple, so the adsorbent can be recycled for multiple times;
(3) the adsorbent is convenient and easy to operate in the using process, and does not need to use auxiliary materials, so that secondary pollution to a water body is avoided;
(4) the adsorbent has low requirements on a water body to be treated, and can be suitable for a wider acid-base range;
(5) the adsorbent is easy to separate and recover after use, and has the characteristic of environmental protection;
(6) the preparation method of the adsorbent is simple, the process is easy to control, the energy consumption is low, no pollution is caused, and the industrial production is easy to realize;
(7) the adsorbent matrix is a carbon fiber fabric and has a filtering and purifying function on water.
The invention is further illustrated at in connection with specific examples, it being understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1 carbon fiber adsorbent 1
(1) Carbon fiber activation treatment: soaking 2g of Polyacrylonitrile (PAN) carbon fiber into 400mL of concentrated hydrochloric acid solution, stirring and reacting at a constant temperature of 90 ℃ for 2h, cooling to room temperature, washing to neutrality by using deionized water, and drying at a vacuum temperature of 80 ℃ to obtain activated Carbon Fiber (CFO)1 with the diameter of about 6.75 microns;
(2) organic carbon fiber treatment: in a round-bottomed flask, 0.3g of hexachlorocyclotriphosphazene was added, respectively
(HCCP), 30mL of anhydrous acetonitrile and 0.2g of activated carbon fiber 1, dripping 3mL of triethylamine, heating to 40 ℃ under the condition of stirring, and reacting for 1h at constant temperature of 40 ℃ to obtain HCCP grafted organic carbon fiber (HCCP-CFO) 2;
(3) preparation of poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent: in N2Under protection, adding 0.65g of 4, 4' -dihydroxy diphenyl sulfone (BPS) into the product obtained in the round bottom flask in the step (2), stirring and reacting at the constant temperature of 40 ℃ for 4-6 h, cooling, putting the product into a Soxhlet extractor for extraction, extracting for 8-12 h by using anhydrous acetonitrile as an extracting agent, removing unreacted monomers and byproducts adhered to the surface of the fiber, washing the product with deionized water and a small amount of ethanol, and putting the product into a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 12h to obtain 0.28g of fibrous poly-sulfone (BPS)(cyclotriphosphazene-co-4, 4' -dihydroxydiphenylsulfone) microsphere modified carbon fiber adsorbent 1.
Results
Fig. 1 and 2 show SEM results of carbon fiber adsorbent 1 obtained in example 1.
As can be seen from fig. 1, the surface of the carbon fiber is coated with polymer layers with a thickness of about 0.1 μm, and a considerable amount of polymeric microspheres are fixed on the surface of the polymer layers, and the coating rate of the polymeric layers is about 30%.
From the step in FIG. 2, it can be seen that the polymer film layer is not dense, and micropores are observed, which have small and uniform pore size, simple structure, high adsorption speed and easy desorption.
Fig. 3 shows the results of XPS full spectrum analysis of the carbon fiber adsorbent 1.
As can be seen from fig. 3, after modification, the elemental composition on the surface of the carbon fiber is significantly changed, more active groups are introduced to the surface of the carbon fiber, and mainly include oxygen-containing groups such as carboxyl, carbonyl, hydroxyl, and the like, and functional groups such as sulfur-containing groups, nitrogen elements, and the like, which can effectively improve the surface chemical activity of the obtained carbon fiber adsorbent, so that the obtained carbon fiber adsorbent has unique surface chemical properties, and the chemical adsorption capacity of the carbon fiber adsorbent is enhanced.
Example 2 carbon fiber adsorbent 2
(1) Carbon fiber activation treatment: soaking 2g of Polyacrylonitrile (PAN) carbon fiber into 500mL of concentrated hydrochloric acid solution, stirring and reacting at constant temperature of 100 ℃ for 2h, cooling to room temperature, washing to neutrality by using deionized water, and drying at vacuum of 80 ℃ to obtain activated Carbon Fiber (CFO) 2;
(2) organic carbon fiber treatment: respectively adding 1g of Hexachlorocyclotriphosphazene (HCCP), 40mL of anhydrous acetonitrile and 0.2g of activated carbon fiber 2 into a round-bottom flask, dripping 5mL of triethylamine, heating to 40 ℃ under the stirring condition, keeping the temperature at 40 ℃ and reacting for 1h to prepare HCCP grafted organic carbon fiber (HCCP-CFO) 2;
(3) poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbentPreparation of the additive: in N2Under the protection condition, 1.6g of 4,4 '-dihydroxy diphenyl sulfone (BPS) is added into the round bottom flask in the step (2), the mixture is stirred and reacted for 4-6 h at the constant temperature of 40 ℃, the mixture is cooled and then placed into a Soxhlet extractor for extraction, anhydrous acetonitrile is used as an extracting agent for extraction for 8-12 h, unreacted monomers and byproducts adhered to the surface of the fiber are removed, the mixture is washed by deionized water and a small amount of ethanol, and then the mixture is placed into a vacuum drying oven at 60 ℃ for vacuum drying for 12h, so that the poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 2 is obtained.
The SEM results and XPS results of the carbon fiber adsorbent 2 obtained in example 2 were substantially the same as those of example 1.
Example 3 carbon fiber adsorbent 3
(1) Carbon fiber activation treatment: soaking 2g of Polyacrylonitrile (PAN) carbon fiber into 200mL of concentrated hydrochloric acid solution, stirring and reacting at constant temperature of 100 ℃ for 2h, cooling to room temperature, washing with deionized water to be neutral, and drying at vacuum of 80 ℃ to obtain activated carbon fiber 3;
(2) organic carbon fiber treatment: respectively adding 1.5g of Hexachlorocyclotriphosphazene (HCCP), 50mL of anhydrous acetonitrile and 0.2g of activated carbon fiber 3 into a round-bottom flask, dripping 8mL of triethylamine, heating to 40 ℃ under the condition of stirring, keeping the temperature at 40 ℃ and reacting for 1h to prepare HCCP grafted organic carbon fiber (HCCP-CFO) 3;
(3) preparation of poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent: in N2Under the protection condition, 1.8g of 4,4 '-dihydroxy diphenyl sulfone (BPS) is added into the round bottom flask in the step (2), the mixture is stirred and reacted for 4-6 h at the constant temperature of 40 ℃, the mixture is cooled and then placed into a Soxhlet extractor for extraction, anhydrous acetonitrile is used as an extracting agent for extraction for 8-12 h, unreacted monomers and byproducts adhered to the surface of the fiber are removed, the mixture is washed by deionized water and a small amount of ethanol, and then the mixture is placed into a vacuum drying oven at 60 ℃ for vacuum drying for 12h, so that the poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 3 is obtained.
The SEM results and XPS results of the carbon fiber adsorbent 3 obtained in example 3 were substantially the same as those of example 1.
Example 4 adsorption Performance testing
Pb2+Is suckedAttached with
Weighing 0.20g of poly (cyclotriphosphazene-co-4, 4 ' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 2 obtained in example 2, placing the poly (cyclotriphosphazene-co-4, 4 ' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 2 into a 250mL conical flask, adding 100mL of lead (II) standard solution with the concentration of 500mg/L, adjusting the pH value of the system to be within the range of 1.0-10.0 by using dilute acid or alkali respectively, oscillating and adsorbing for 40-60min on a shaking bed at room temperature, taking supernatant, measuring the concentration of lead (II) by using an electrochemical method, and calculating the adsorption capacity of the poly (cyclotriphosphazene-co-4, 4 ' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 2 on lead (II) according to the concentration difference of lead (II) in water.
The result shows that the adsorption capacity of the adsorbent 2 on the lead (II) is the largest and stable within the pH value range of 7.5-10.0, the lead is basically adsorbed in a saturated manner by oscillating adsorption for 60min at room temperature, and the adsorption capacity of the lead (II) can reach 72 mg/g.
Cr6+Adsorption of (2)
Weighing 0.30g of poly (cyclotriphosphazene-co-4, 4 '-dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 1 obtained in example 1, placing the mixture in a 250mL conical flask, adding 100mL of a chromium (VI) standard solution with the concentration of 600mg/L, respectively adjusting the pH value of the system to be within the range of 1.0-10.0 by using dilute acid or alkali, shaking and adsorbing the mixture on a shaking bed at room temperature for 40-60min, taking a supernatant, measuring the concentration of chromium (VI) by using a spectrophotometry method, and calculating the adsorption capacity of the poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 1 on chromium (VI) according to the concentration difference of chromium (VI) in water before and after adsorption.
The result shows that the adsorption capacity of the adsorbent 1 to chromium (VI) is the largest and stable within the pH value of 5.0-7.0, the chromium (VI) is adsorbed by shaking for 70min at room temperature, the adsorption of the chromium (VI) is basically saturated, and the adsorption capacity of the chromium (VI) can reach 126 mg/g.
Example 5 removal Performance test
Pb2+Removal of
Weighing 1.0g of poly (cyclotriphosphazene-co-4, 4 '-dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 3 obtained in example 3, placing the mixture in a 250mL conical flask, adding 100mL of lead (II) standard solution with the concentration of 200mg/L, adjusting the pH value of the system to be within the range of 5.5-8.0 by using dilute acid or alkali, oscillating and adsorbing for 60 inches on a shaking table at room temperature, taking supernatant, measuring the concentration of lead (II) by using an electrochemical method, and calculating the removal rate of the poly (cyclotriphosphazene-co-4, 4' -dihydroxy diphenyl sulfone) microsphere modified carbon fiber adsorbent 3 to lead according to the concentration difference of lead in water before and after adsorption.
The results show that the removal rate of lead (II) in water by the adsorbent 3 is 90%.
Cr6+Removal of
Weighing 1.0g of the poly (cyclotriphosphazene-co-4, 4 ' -dihydroxydiphenylsulfone) microsphere modified carbon fiber adsorbent 3 obtained in example 3, placing the poly (cyclotriphosphazene-co-4, 4 ' -dihydroxydiphenylsulfone) microsphere modified carbon fiber adsorbent 3 in a 250mL conical flask, adding 100mL of a chromium (VI) standard solution with the concentration of 200mg/L, adjusting the pH value of a system to be within the range of 5.0-7.0 by using dilute acid or alkali, shaking and adsorbing for 70min on a shaking bed at room temperature, taking a supernatant, measuring the concentration of the chromium (VI) by using a spectrophotometry method, and calculating the removal rate of the poly (cyclotriphosphazene-co-4, 4 ' -dihydroxydiphenylsulfone) microsphere modified carbon fiber adsorbent 3 on the chromium (VI) according to the concentration difference of the chromium (VI) in water before.
The results showed that the removal rate of chromium (vi) by the adsorbent 3 in water was 92.5%.
Example 6 Desorption followed by adsorption test
Desorbing, also called desorbing, after the poly-microsphere modified carbon fiber adsorbent adsorbs heavy metal ions, soaking the carbon fiber adsorbent into a dilute hydrochloric acid solution, and stirring at the constant temperature of 80 ℃ for 1-3 hours to perform desorption and activation treatment on the adsorbent. And carrying out secondary modification in the step 2) and the step 3) to obtain the carbon fiber adsorbent 4.
In the same manner as in example 4, when lead and chromium were adsorbed by using the adsorbent 4 after the desorption treatment, it was found that: the adsorption capacity of the carbon fiber adsorbent 4 to lead (II) can reach 70mg/g, the adsorption capacity of chromium (VI) can reach 118mg/g, and the adsorption performance of the carbon fiber adsorbent 2 before desorption is equivalent to that of the carbon fiber adsorbent 1.
Example 7 post-detachment removal test
In the same manner as in example 5, the desorption-treated adsorbent 4 obtained in example 6 was used to perform a lead and chromium removal test, and it was found that: the removal rate of the adsorbent 4 to lead (II) in water is 88 percent, and the removal rate to chromium (VI) in water is 91 percent, which is equivalent to the adsorbent 3.
Further, it will be appreciated that various changes or modifications may be made by those skilled in the art after reading the above teachings of the present invention, and such equivalents are within the scope of the invention as defined by the appended claims.
Claims (11)
- The carbon fiber adsorbent is characterized by comprising modified carbon fibers, wherein the modified carbon fibers comprise a carbon fiber matrix, a modified polymer film layer bound on the surface of the carbon fiber matrix and microspherical modified particles bound on the surface of the modified polymer film layer;the carbon fiber adsorbent is prepared by the following method, and the method comprises the following steps:1) providing a carbon fiber material, th modified solution and a second modifier, wherein,the th modification solution comprises th modifier and th solvent;2) adding the carbon fiber material into the th modified solution under the stirring condition, heating the obtained mixture, and reacting to obtain a mixture containing the carbon fiber material modified by th modifying agent;3) adding the second modifier into the reaction mixture obtained in the step 2) under the stirring condition, and reacting to obtain -th modifier-second modifier copolymer modified carbon fiber adsorbent;the th modifier is hexachlorocyclotriphosphazene;the second modifier is 4, 4' -dihydroxydiphenyl sulfone;and 3) carrying out the step under the protection of nitrogen.
- 2. The carbon fiber adsorbent of claim 1 wherein said modified polymer film layer has a thickness of 0.05-0.4 μm; and/orThe microspherical modified particles are coated on the surface of the modified polymer film layer, and the coating rate is 10-95%.
- 3. The carbon fiber adsorbent of claim 1, wherein the particle size D of the microspheroidal modified particle is in the range of 0.3 to 1.5 μm.
- 4. The carbon fiber adsorbent of claim 1, wherein the particle size D of the microspheroidal modified particle is in the range of 0.3 to 0.8 μm.
- 5. The carbon fiber adsorbent of claim 1, wherein the particle size D of the microspheroidal modified particle is in the range of 0.4 to 0.6 μm.
- 6. The carbon fiber adsorbent of claim 1, wherein the microspheroidal modifying particles are uniformly distributed on the surface of the modified polymer membrane layer.
- 7, A method for preparing the carbon fiber adsorbent of claim 1, comprising the steps of:1) providing a carbon fiber material, th modified solution and a second modifier, wherein,the th modification solution comprises th modifier and th solvent;2) adding the carbon fiber material into the th modified solution under the stirring condition, heating the obtained mixture, and reacting to obtain a mixture containing the carbon fiber material modified by th modifying agent;3) adding the second modifier into the reaction mixture obtained in the step 2) under the stirring condition, and reacting to obtain -th modifier-second modifier copolymer modified carbon fiber adsorbent;the th modifier is hexachlorocyclotriphosphazene, andthe second modifier is 4, 4' -dihydroxydiphenyl sulfone;and 3) carrying out the step under the protection of nitrogen.
- 8. The method of claim 7, further comprising, prior to step 1), the steps of: and activating and treating the carbon fiber material.
- 9. The carbon fiber adsorbent of claim 1 or the method of claim 7, further comprising or more features selected from the group consisting of:the th solvent is anhydrous acetonitrile;the th modified solution also comprises a reaction promoter triethylamine;in the step 2), the mass ratio of the th modifier to the carbon fiber material is 0.5-15;the heating temperature of the step 2) is 30-70 ℃;the reaction time at the heating temperature in the step 2) is 0.1 to 5 hours;in the step 3), the mass ratio of the second modifier to the carbon fiber material is 1-15;the reaction temperature of the reaction in the step 3) is 30-70 ℃; andthe reaction time at the reaction temperature in the step 3) is 2 to 10 hours.
- 10, A method for purifying water, characterized in that the carbon fiber adsorbent of claim 1 is used for adsorption treatment of water.
- An article of manufacture of , wherein the article contains or consists of the carbon fiber adsorbent of claim 1.
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