CN102688746B - Granular adsorbing material as well as preparation method and application thereof - Google Patents
Granular adsorbing material as well as preparation method and application thereof Download PDFInfo
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- CN102688746B CN102688746B CN201210173099.6A CN201210173099A CN102688746B CN 102688746 B CN102688746 B CN 102688746B CN 201210173099 A CN201210173099 A CN 201210173099A CN 102688746 B CN102688746 B CN 102688746B
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Abstract
The invention provides a granular adsorbing material as well as a preparation method and an application thereof. The granular adsorbing material comprises a porous basal body and carbon nano tubes, wherein the porous basal body is made of porous alumina, and the carbon nano tubes are distributed in the porous basal body. The reusable granular carbon nano tube adsorbing material used for purifying fluids has the characteristics of high mechanical strength, good stability, strong adsorbability, and low energy consumption for regeneration.
Description
Technical field
The present invention relates to water-treatment technology field.Concrete, the present invention relates to granular adsorption material and its preparation method and application.
Background technology
Conventional adsorbent-the active carbon of extensive use at present after saturated by organic pollution, need to be heated to more than 900 ℃, and pass into steam or CO in nitrogen atmosphere
2make it reactivate to regenerate, and in regenerative process, tend to produce certain mass loss.Yet, as the CNT of powder body material, because self nano level size makes its use and inconvenience very of the Separation of Solid and Liquid after absorption in engineering, greatly hindered it and as organic pollution, controlled application prospect of material.
Therefore, the current sorbing material for bodies for purifying fluids still haves much room for improvement.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
In a first aspect of the present invention, the present invention proposes a kind of granular adsorption material.According to embodiments of the invention, granular adsorption material, comprising: porous matrix, and described porous matrix is made by Woelm Alumina; And CNT, described CNT is distributed in described porous matrix.
Compare with active carbon, CNT has excellent thermal stability, makes it under the condition of 400 ℃ of aerobics, complete regeneration, has reduced regeneration energy consumption.And in the process of aerobic thermal regeneration, the oxidized degraded of organic pollution meeting of adsorbing, has solved the just problem of pollutant phase transfer of absorption.CNT is a kind of nanotube-shaped material " being rolled into " by graphite linings, according to the difference of the graphite number of plies, can be divided into SWCN and multi-walled carbon nano-tubes.Due to its high-graphitized architectural feature, CNT has shown outstanding electricity, calorifics and mechanical performance, according to embodiments of the invention, due to the theoretical specific area of its superpower hydrophobicity and superelevation, (the theoretical specific area of SWCN can reach 3000m to CNT
2thereby can be used as a kind of sorbing material that organic pollution is good of removing/g).In addition, according to embodiments of the invention, CNT is distributed in described porous matrix, thereby can form the particle that granularity is larger, and for example, according to embodiments of the invention, the granularity of granular adsorption material can be 1 ~ 5mm, preferably 3mm.Thus, the use in engineering and some the inconvenient difficult problems very of the Separation of Solid and Liquid after absorption that the nano level size of CNT self causes have been overcome.Therefore, the granular adsorption material of the embodiment of the present invention is controlled material as organic pollution, has excellent application prospect.
In a second aspect of the present invention, the invention allows for a kind of method of preparing granular adsorption material noted earlier.According to embodiments of the invention, the method comprises the following steps: aluminium oxide, nitric acid, surfactant to mix, to form colloidal sol; In described colloidal sol, add CNT, to obtain the mixture that contains aluminium oxide and CNT; In the described mixture that contains aluminium oxide and CNT, add ammoniacal liquor, to form gel; And described gel is carried out to grainy treatment, and carry out successively aging, the second dry and calcination processing, to obtain described granular adsorption material.Utilize the method, can effectively prepare foregoing granular adsorption material.The applicable equally the method for the feature and advantage of granular adsorption material, repeats no more.
In a third aspect of the present invention, the present invention proposes a kind of method of bodies for purifying fluids.According to embodiments of the invention, the method comprises described fluid to be clean is contacted with foregoing granular adsorption material.Thus, suction-operated that can be by granular adsorption material effectively convection cell purifies.
In a fourth aspect of the present invention, the present invention proposes a kind of method that granular adsorption material noted earlier is regenerated.According to embodiments of the invention, the method comprises: granular adsorption material to be regenerated, under aerobic conditions, is heated at the temperature of 400 ~ 450 degrees Celsius.Thus, can be effectively to the processing of regenerating of used granular adsorption material, thereby improve service efficiency, reduced commercial Application cost.
Thus, according to embodiments of the invention, according to the technical scheme of the embodiment of the present invention, at least there is one of following advantages:
1, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare with powder nanometer tube material and use simply, be easy to Separation of Solid and Liquid.
2, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare with powder nanometer tube material reclaim simple, good at water stability, do not have the phenomenon of stripping or loss.
3, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare dispersed raising with powder nanometer tube material, will be higher than carbon powder nano-tube material to the adsorbance of carbamazepine, part has solved CNT the problem of reuniting has occurred in water.
4, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare Heat stability is good with conventional active carbon adsorption material, realize holomorphosis under can be under aerobic conditions and lower temperature, and in regenerative process almost without mass loss, can Reusability.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 has shown according to the schematic flow sheet of the method for the granular adsorption material for the preparation of bodies for purifying fluids of the embodiment of the present invention;
Fig. 2 has shown according to the stereoscan photograph of the granulated carbon nanotube macro morphology of the embodiment of the present invention;
Fig. 3 has shown according to different proportion CNT in the granulated carbon nanotube of the embodiment of the present invention and porous matrix adsorption effect figure;
Fig. 4 has shown granulated carbon nanotube (1:1), CNT, gama-alumina Adsorption Diclofenac, the carbamazepine comparison diagram according to the embodiment of the present invention; And
Fig. 5 has shown according to adsorbing the effect schematic diagram of Diclofenac (a) and carbamazepine (b) in 10 regeneration of granulated carbon nanotube of the embodiment of the present invention.
The specific embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In addition, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".In description of the invention, the implication of " a plurality of " is two or more, unless otherwise expressly limited specifically.In this article, unless separately had clearly, describe, " room temperature " refers to 20 ~ 35 degrees Celsius.
Granular adsorption material
In a first aspect of the present invention, the present invention proposes a kind of granular adsorption material.According to embodiments of the invention, granular adsorption material, comprises porous matrix and CNT.According to embodiments of the invention, porous matrix can be made by Woelm Alumina.According to embodiments of the invention, CNT is distributed in described porous matrix.
Compare with active carbon, CNT has excellent thermal stability, makes it under the aerobic conditions of 400 ℃, complete regeneration, has reduced regeneration energy consumption.And in the process of aerobic thermal regeneration, the oxidized degraded of organic pollution meeting of adsorbing, has solved the just problem of pollutant phase transfer of absorption.CNT is a kind of nanotube-shaped material " being rolled into " by graphite linings, according to the difference of the graphite number of plies, can be divided into SWCN and multi-walled carbon nano-tubes.Due to its high-graphitized architectural feature, CNT has shown the features such as outstanding electricity, calorifics and mechanical performance, according to embodiments of the invention, due to the theoretical specific area of its superpower hydrophobicity and superelevation, (the theoretical specific area of SWCN can reach 3000m to CNT
2thereby can be used as a kind of sorbing material that organic pollution is good of removing/g).In addition, according to embodiments of the invention, CNT is distributed in described porous matrix, thereby can form the particle that granularity is larger, and for example, according to embodiments of the invention, the granularity of granular adsorption material can be 1 ~ 5mm, preferably 3mm.Thus, the use in engineering and the inconvenient problem very of the Separation of Solid and Liquid after absorption that the nano level size of CNT self causes have been overcome.Therefore, the granular adsorption material of the embodiment of the present invention is controlled material as organic pollution, has broad application prospects.
According to embodiments of the invention, CNT is distributed in the distribution mode of porous matrix and is not particularly limited, and embodiment according to the present invention can be distributed in the surface of porous matrix or embed in the hole of porous matrix.Thus, can realize better adsorption effect.
According to example of the present invention, at least a portion of CNT embeds in the hole of porous matrix, and in addition according to embodiments of the invention, the specific area of the granulated carbon nano-tube material of the described porous matrix of porous matrix is 273m
2/ g, average pore size is 2.8nm.Thus, can realize higher carbon nanotube loaded amount, and then realize better adsorption effect.
According to embodiments of the invention, the kind of Woelm Alumina is also not particularly limited, and can be at least one of Alpha-alumina, beta-alumina, gama-alumina and θ-aluminium oxide, and preferably Woelm Alumina is gama-alumina.Thus, can realize higher carbon nanotube loaded amount, and then realize better adsorption effect.
According to embodiments of the invention, the kind of CNT is also not particularly limited, and can be at least one of multi-walled carbon nano-tubes and SWCN.Thus, can realize better adsorption effect.According to embodiments of the invention, the structure type of multi-walled carbon nano-tubes is also not particularly limited.
According to embodiments of the invention, the weight ratio of CNT and porous matrix can be 2:1 ~ 1:11, wherein preferred 2:1 ~ 1:9, more preferably 1:1.Thus, in granular adsorption material, porous matrix quality is minimum and mechanical strength can reach application requirements, and the stability in water is better.According to embodiments of the invention, the CNT in granular adsorption material can be distributed in porous matrix equably.About CNT (CNT) and the ratio of alumina weight ratio and the relation of adsorption capacity (Diclofenac clearance), visible Fig. 3.
The granularity of this granular adsorption material is 1 ~ 5mm, preferably 3mm.Thus, CNT is scattered in activated aluminum matrix equably as the active ingredient of absorption, porous matrix plays the effect of skeleton, has also played the effect of dispersing Nano carbon tubes, the excellent absorption property while making CNT still retain as nano-powder material after moulding.
According to the granular adsorption material of the embodiment of the present invention, there is following advantages one of at least:
1, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare with powder nanometer tube material and use simply, be easy to Separation of Solid and Liquid.
2, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare with powder nanometer tube material reclaim simple, good at water stability, do not have the phenomenon of stripping or loss.
3, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare dispersed raising with powder nanometer tube material, will be higher than carbon powder nano-tube material to the adsorbance of carbamazepine, part has solved CNT the problem of reuniting has occurred in water.
4, according to the granulated carbon nano-tube material of the embodiment of the present invention, compare Heat stability is good with conventional active carbon adsorption material, realize holomorphosis under can be under aerobic conditions and lower temperature, and in regenerative process almost without mass loss, can Reusability.
The method of preparing granular adsorption material
In a second aspect of the present invention, the present invention proposes a kind of method of preparing granular adsorption material.With reference to figure 1, according to embodiments of the invention, the method for preparing granular adsorption material comprises the following steps:
S100: aluminium oxide, nitric acid, surfactant are mixed to get to colloidal sol.
According to embodiments of the invention, for making aluminium oxide, the nitric acid of colloidal sol, the content of surfactant being not particularly limited.According to examples more of the present invention, for making the aluminium oxide of colloidal sol and the w/v of nitric acid for (0.24 ~ 2.12g): (5 ~ 15mL), the concentration of nitric acid is 1.3 % by weight, and the weight ratio of aluminium oxide and surfactant is (0.24 ~ 2.12g): (0.04 ~ 0.2g).Wherein aluminium oxide used and surfactant are also not particularly limited, according to embodiments of the invention, aluminium oxide is that the form with boehmite provides, surfactant is to be selected from least one of alkyl polyglycol ether and dodecyl sodium sulfate, preferred alkyl polyglycol ether, plays the effect that disperses boehmite and CNT.Thus, can more effectively prepare the granular adsorption material according to the embodiment of the present invention.
S200: obtain the mixture that contains aluminium oxide and CNT to adding CNT in colloidal sol.
According to embodiments of the invention, the weight ratio of aluminium oxide and CNT can be 2:1 ~ 1:10,2:1 ~ 1:9, and wherein 1:1 is best, because the minimum while mechanical strength of its contained porous matrix quality has reached application requirements, and the stability in water is better.Inventor is surprised to find, and the absorption property of the granular adsorption material that employing aforementioned proportion finally obtains is excellent, and mechanical strength is high.
S300: add ammoniacal liquor to form gel in the mixture that contains aluminium oxide and CNT.
According to embodiments of the invention, can be to the ammoniacal liquor that drips 0.15 ~ 0.25mL in the mixture that contains aluminium oxide and CNT, thereby limit drips ammoniacal liquor limit, rock this mixture and form gel, wherein the concentration of ammoniacal liquor is 14 % by weight.Thus, can further improve the efficiency of preparation granular adsorption material.
S400: gel is carried out, after the first dry processing, dried gel being carried out to grainy treatment.
According to embodiments of the invention, can under 80 degrees Celsius, dry this gel and within 15 minutes, carry out the first dry processing after the residual ammoniacal liquor of removal, this dry rear gel is carried out to grainy treatment.This gel is carried out the method for grainy treatment and is not particularly limited, according to examples more of the present invention, gained desiccant gel is pinched into coccoid with hand.
S500: this granulating gel is carried out to aging, the second dry and calcination processing and obtain granular adsorption material.
According to embodiments of the invention, can carry out aging, the second dry and calcination processing to coccoid gel, thereby obtain granular adsorption material.According to some embodiments of the present invention, agingly by room temperature being kept, coccoid gel carries out at least 8 hours; Then under 50 degrees Celsius, keep within least 10 hours, carrying out second and be dried, 12 hours the bests; Finally under 450 degrees Celsius, keep calcining at least 2 hours, 4 hours the bests, and naturally cool to room temperature.
According to embodiments of the invention, after obtaining granular adsorption material, can further include it is carried out to clean step, for example can use high purity water to carry out at least one times it, for example 3 above cleaning, dry for example oven dry obtains final granular adsorption material.
Thus, utilize preparation method according to an embodiment of the invention, can make a kind of high strength, granulating and can utilize simple thermal treatment is reproducible carbon nanotube adsorption material.
The method of bodies for purifying fluids
As previously mentioned, granular adsorption material has excellent adsorption effect according to an embodiment of the invention.Thereby, granular adsorption material according to an embodiment of the invention can be applied to bodies for purifying fluids.For this reason, the invention allows for a kind of method of bodies for purifying fluids.According to embodiments of the invention, the method comprises described fluid to be clean is contacted with foregoing granular adsorption material.Thus, can pass through the suction-operated of granular adsorption material, convection cell purifies effectively.
Inventor is surprised to find, according to an embodiment of the invention granular adsorption material adsorb organic compound effectively.In addition, the term that used in this article " fluid " comprises gas and liquid.The implication of the term that used in this article " contact " is not particularly limited, as long as can realize the adsorption function of sorbing material, for example, granular adsorption material can be joined to fluid for example in liquid solution.
According to embodiments of the invention, type of fluid to be clean is also not particularly limited, according to instantiation of the present invention, fluid to be clean is for containing organic solution, and organic matter is to be selected from the Diclofenac that contains 15.5 μ mol/L or at least one of carbamazepine.The use amount of sorbing material is also not particularly limited, and according to embodiments of the invention, the weight of sorbing material can be (5 ~ 50mg): 100mL with the ratio of the volume that contains organic solution.Inventor finds, utilizes this ratio, granulated carbon nanotube can effectively be removed in water two kinds of Common drugs-Diclofenacs and carbamazepine, and Separation of Solid and Liquid is very simple, has solved a difficult problem for the little molecule organic micro-pollutants that conventional water treatment process cannot remove.Diclofenac and carbamazepine, as two kinds of common medicines, due to its a large amount of production and use, are detected in natural environment water body and effluent of municipal sewage plant, and the mankind and ecological environment are caused to potential threat.Conventional water treatment process cannot effectively be removed this micromolecular organic micro-pollutants, therefore, uses granulated carbon nanotube to carry out Adsorption to it, and is regenerated and made its oxidative degradation have good application prospect by heat.
Renovation process
In a fourth aspect of the present invention, the present invention proposes a kind of method that made granular adsorption material is regenerated.According to embodiments of the invention, the method comprises: granular adsorption material to be regenerated, under aerobic conditions, is heated at the temperature of 400 ~ 450 degrees Celsius.According to embodiments of the invention, can be by granular adsorption material to be regenerated under aerobic conditions, according to the programming rate of 10 degrees celsius/minute, be warming up to 450 degrees Celsius and carry out heat treated, and keep 2 hours under 450 degrees Celsius, thereby reach the object that granular adsorption material is regenerated.The kind of granular adsorption material to be regenerated is also not particularly limited, and according to example of the present invention, granular adsorption material to be regenerated is by the saturated granular adsorption material of organic matter.The organic matter of this saturated granular adsorption material is also not particularly limited, and according to instantiation of the present invention, organic matter is to be selected from least one of Diclofenac and carbamazepine.Thus, granular adsorption material can obtain reactivating regeneration under the condition of low power consuming, and in the process of aerobic thermal regeneration, the oxidized degraded of organic pollution meeting of adsorbing, has solved the just problem of pollutant phase transfer of absorption.
Below by specific embodiment, present invention is described, it should be noted that, these embodiment only for the purpose of illustration, and the scope not limiting the present invention in any way.
In following examples 1-5, CNT used is multi-walled carbon nano-tubes, external diameter is 50 ~ 80nm, in embodiment 6-7, CNT used is multi-walled carbon nano-tubes, and external diameter is 10 ~ 20nm, and the method for the invention is all applicable to the multi-walled carbon nano-tubes of other external diameter and SWCN.
Embodiment 1:
The preparation process of adsorbent is: it is in 13% dilute nitric acid solution that 0.24g boehmite is joined to 5mL concentration, then adds 0.04g Brij-35, and edged hand rolling in limit disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.15mL 12%, limit edged forms gel with hand rolling.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, and keeps 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 50mg granulated carbon nanotube (1:1), 25mg CNT and 25mg activated aluminum are added in the Diclofenac solution and carbamazepine solution that initial concentration is 15.5 μ mmol/L respectively.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac and carbamazepine in solution after spectrophotometer analysis absorption.Result is as shown in Figure 4: granulated carbon nanotube has with powder carbon nanotube two kinds of clearances that pollutant is suitable, to the clearance of Diclofenac, is wherein 63%, to the clearance of carbamazepine, is 72%.In general, dusty material is in forming process, binding agent (herein for aluminium oxide) is certain to the part surface of coated carbon nanotube (CNT), so that granulated carbon nanotube can keep is suitable with powder carbon nanotube adsorption effect, its moulding is described after dispersiveness improved.It is comparatively obvious that this embodies on the adsorption effect of carbamazepine, and the adsorption capacity of granulated carbon nanotube is greater than the adsorption capacity of powder carbon nanotube, and aluminium oxide to it without absorption.
Regeneration effect experimental procedure is: 50mg granulated carbon nanotube (1:1) is put in the Diclofenac and carbamazepine solution that initial concentration is 15.5 μ mmol/L respectively, in shaking table, under 150rpm, shake 72h, by the concentration of Diclofenac and carbamazepine after spectrophotometer analysis absorption.After the saturated granulated carbon nanotube of absorption is dried, be placed in Muffle furnace and regenerate by following heating schedule: 10 ℃/min rises to 400 ℃, keep 2h.Adsorbent after regeneration is put in the Diclofenac and carbamazepine solution of 15.5 μ mmol/L again, carries out second and takes turns absorption.So repeatedly carry out the experiment of 10 absorption regenerations, as shown in Figure 5, the granulated carbon nanotube after 10 times of regenerating still has good clearance to Diclofenac and carbamazepine to result.
Embodiment 2:
The preparation process of adsorbent is: 0.71g boehmite is joined in 7.5mL 13% dilute nitric acid solution, then add 0.04g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.15mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 100mg granulated carbon nanotube (1:3) is added in the Diclofenac solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac in solution after spectrophotometer analysis absorption.It is 66% to the clearance of Diclofenac.
Present embodiment regeneration effect experimental procedure is: 100mg granulated carbon nanotube (1:3) is put in the Diclofenac solution that initial concentration is 15.5 μ mmol/L respectively, in shaking table, under 150rpm, shake 72h, by the concentration of Diclofenac and carbamazepine after spectrophotometer analysis absorption.After the saturated granulated carbon nanotube of absorption is dried, be placed in Muffle furnace and regenerate by following heating schedule: 10 ℃/min rises to 450 ℃, keep 2h.Adsorbent after regeneration is put in the Diclofenac and carbamazepine solution of 15.5 μ mmol/L again, carries out second and takes turns absorption.So repeatedly carry out the experiment of 5 absorption regenerations, result still has good clearance to Diclofenac for granulated carbon nanotube after regeneration 5 times.
Embodiment 3:
The preparation process of adsorbent is: 1.18g boehmite is joined in 10mL 13% dilute nitric acid solution, then add 0.04g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.2mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 150mg granulated carbon nanotube (1:5) is added in the Diclofenac solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac in solution after spectrophotometer analysis absorption.It is 77% to the clearance of Diclofenac.
Present embodiment regeneration effect experimental procedure is: 150mg granulated carbon nanotube (1:5) is put in the Diclofenac solution that initial concentration is 15.5 μ mmol/L respectively, in shaking table, under 150rpm, shake 72h, by the concentration of Diclofenac and carbamazepine after spectrophotometer analysis absorption.After the saturated granulated carbon nanotube of absorption is dried, be placed in Muffle furnace and regenerate by following heating schedule: 10 ℃/min rises to 450 ℃, keep 2h.Adsorbent after regeneration is put in the Diclofenac and carbamazepine solution of 15.5 μ mmol/L again, carries out second and takes turns absorption.So repeatedly carry out the experiment of 5 absorption regenerations, result still has good clearance to Diclofenac for granulated carbon nanotube after regeneration 5 times.
Embodiment 4:
The preparation process of adsorbent is: 1.65g boehmite is joined in 12.5mL 13% dilute nitric acid solution, then add 0.04g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.25mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 200mg granulated carbon nanotube (1:7) is added in the Diclofenac solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac in solution after spectrophotometer analysis absorption.It is 80% to the clearance of Diclofenac.
Regeneration effect experimental procedure is: 200mg granulated carbon nanotube (1:7) is put in the Diclofenac solution that initial concentration is 15.5 μ mmol/L respectively, in shaking table, under 150rpm, shake 72h, by the concentration of Diclofenac and carbamazepine after spectrophotometer analysis absorption.After the saturated granulated carbon nanotube of absorption is dried, be placed in Muffle furnace and regenerate by following heating schedule: 10 ℃/min rises to 450 ℃, keep 2h.Adsorbent after regeneration is put in the Diclofenac and carbamazepine solution of 15.5 μ mmol/L again, carries out second and takes turns absorption.So repeatedly carry out the experiment of 5 absorption regenerations, result still has good clearance to Diclofenac for granulated carbon nanotube after regeneration 5 times.
Embodiment 5:
The preparation process of adsorbent is: 2.12g boehmite is joined in 15mL 13% dilute nitric acid solution, then add 0.04g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.25mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 200mg granulated carbon nanotube (1:7) is added in the Diclofenac solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac in solution after spectrophotometer analysis absorption.It is 82% to the clearance of Diclofenac.
Regeneration effect experimental procedure is: 250mg granulated carbon nanotube (1:9) is put in the Diclofenac solution that initial concentration is 15.5 μ mmol/L respectively, in shaking table, under 150rpm, shake 72h, by the concentration of Diclofenac and carbamazepine after spectrophotometer analysis absorption.After the saturated granulated carbon nanotube of absorption is dried, be placed in Muffle furnace and regenerate by following heating schedule: 10 ℃/min rises to 450 ℃, keep 2h.Adsorbent after regeneration is put in the Diclofenac and carbamazepine solution of 15.5 μ mmol/L again, carries out second and takes turns absorption.So repeatedly carry out the experiment of 5 absorption regenerations, result still has good clearance to Diclofenac for granulated carbon nanotube after regeneration 5 times.
Embodiment 6:
The preparation process of adsorbent is: 0.24g boehmite is joined in 5mL 13% dilute nitric acid solution, then add 0.2g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.15mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 50mg granulated carbon nanotube (1:1) is added in the Diclofenac and carbamazepine solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac and carbamazepine in solution after spectrophotometer analysis absorption.It is 63% to the clearance of Diclofenac, to the clearance of carbamazepine, is 57%.
Embodiment 7:
The preparation process of adsorbent is: 0.24g boehmite is joined in 5mL 13% dilute nitric acid solution, then add 0.12g Brij-35, the hand rolling of limit edged, disperses to form colloidal sol completely to it.Slowly add wherein 0.2g CNT, limit edged stirs again, and to it, forms the mixture of homogeneous.Drip wherein at once the ammoniacal liquor of 0.15mL 12%, the hand rolling of limit edged, to mixture formation gel.This gel is positioned in baking oven, dries 10min at 80 ℃ to remove the unnecessary ammoniacal liquor in surface.The gel having dried is pinched into coccoid with hand, be then placed on aging 8h under room temperature.Aging good bead is put into baking oven, dry 12h at 50 ℃.Dried bead is placed in to Muffle furnace, by following heating schedule, calcines: 2 ℃/min rises to 450 ℃, keep 4h.Bead after calcining obtains granulated carbon nanotube finished product after high purity water repeatedly cleans, dries.
Adsorption effect experimental procedure is: 50mg granulated carbon nanotube (1:1) is added in the Diclofenac and carbamazepine solution that initial concentration is 15.5 μ mmol/L.In shaking table, under 150rpm, shake 72h.Concentration with Diclofenac and carbamazepine in solution after spectrophotometer analysis absorption.It is 52% to the clearance of Diclofenac, to the clearance of carbamazepine, is 55%.
In the description of this description, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, modification, replacement and modification.
Claims (14)
1. a method of preparing granular adsorption material, is characterized in that, comprises the following steps:
Aluminium oxide is scattered in nitric acid, and adds surfactant in resulting dispersion liquid, stir, to form colloidal sol;
In described colloidal sol, add CNT, to obtain the mixture that contains aluminium oxide and CNT;
In the described mixture that contains aluminium oxide and CNT, drip the ammoniacal liquor of 0.15～0.25mL, to form gel;
Described gel is carried out to the first dry processing, to remove residual ammoniacal liquor; And
To carry out grainy treatment through the described first dry gel of processing, and carry out successively aging, the second dry and calcination processing, to obtain described granular adsorption material,
Wherein,
Described aluminium oxide, nitric acid and proportion of surfactant are (0.24～2.12g): (5～15mL): (0.04～0.2g), described surfactant is to be selected from least one of alkyl polyglycol ether and dodecyl sodium sulfate, the concentration of described nitric acid is 1.3 % by weight, the weight ratio of described aluminium oxide and CNT is 1:1, the concentration of described ammoniacal liquor is 14 % by weight, described calcining is to keep at least 2 hours under 450 degrees Celsius
Described granular adsorption material comprises:
Porous matrix, described porous matrix is made by Woelm Alumina; And
CNT, described CNT is distributed in described porous matrix,
The weight ratio of described CNT and porous matrix is 1:1,
The specific area of described granular adsorption material is 273m
2/ g, average pore size is 2.8nm,
The granularity of described granular adsorption material is 3mm,
Described aluminium oxide is gama-alumina, and described CNT is to be selected from least one of multi-walled carbon nano-tubes and SWCN,
Described matrix is spherical.
2. method according to claim 1, is characterized in that, described aluminium oxide is that the form with boehmite provides.
3. method according to claim 1, is characterized in that, the described first dry processing by described gel is dried and carried out for 15 minutes under 80 degrees Celsius.
4. method according to claim 1, is characterized in that, described aging by described gel is at room temperature kept carrying out at least 8 hours.
5. method according to claim 1, is characterized in that, the described second dry maintenance under 50 degrees Celsius 12 hours and carrying out.
6. method according to claim 1, is characterized in that, described calcining keeps 4 hours and carries out under 450 degrees Celsius.
7. a method for bodies for purifying fluids, is characterized in that, comprising:
The granular adsorption material that described fluid to be clean is prepared with the method described in any one in claim 1-6 contacts.
8. method according to claim 7, is characterized in that, described fluid is for containing organic solution, and the ratio of the weight of described sorbing material and the volume of described solution is (5～50mg): 100mL.
9. method according to claim 8, is characterized in that, described organic matter is to be selected from least one of Diclofenac and carbamazepine.
10. method according to claim 8, is characterized in that, the Diclofenac that described solution contains 15.5 μ mol/L or carbamazepine.
11. 1 kinds of methods that granular adsorption material prepared by the method described in any one in claim 1-6 is regenerated, is characterized in that, comprising:
Granular adsorption material to be regenerated, under aerobic conditions, is heated at the temperature of 400～450 degrees Celsius.
12. methods according to claim 11, is characterized in that, described in granular adsorption material to be regenerated be by the saturated granular adsorption material of organic matter.
13. methods according to claim 11, is characterized in that, granular adsorption material to be regenerated, under aerobic conditions, is warming up to 450 degrees Celsius according to the programming rate of 10 degrees celsius/minute, and under 450 degrees Celsius, keeps 2 hours.
14. methods according to claim 12, is characterized in that, described organic matter is to be selected from least one of Diclofenac and carbamazepine.
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