CN110252246A - A kind of coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material and its preparation method and application - Google Patents
A kind of coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the preparation methods that a kind of coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material, first, potassium salt is configured to uniform solution, wrap up and be filled in coal fly ash hollow micro bead surface and hollow interior, flyash is removed after carbonization treatment, leave the hollow structure of flyash, then the multi-stage porous carbon material that micropore prepares high-specific surface area is generated in conjunction with high-temperature alkali activation method, the present invention is hard template using solid industrial waste coal ash cenosphere (FACs), it is applied to the processing of fluoroquinolone antibiotics sewage using cheap biological material potassium salt as multi-stage porous carbon material prepared by carbon source, show good effect.
Description
Technical field
The present invention relates to technical field of environment function material preparation, more particularly to a kind of coal fly ash hollow micro bead
For template potassium salt Quito hole carbon adsorbing material and its preparation method and application.
Background technique
Third generation fluoroquinolone antibiotics (such as Ciprofloxacin, Enrofloxacin etc.) belong to artificial synthesized novel kill
Bacterium property antibacterials have the characteristics that antibacterial activity is strong, has a broad antifungal spectrum, bioavailability are high, can decompose each tissue, quilt rapidly
Be widely used in human medical, poultry, in domestic animal and aquaculture disease treatment and prevention.The abuse of drug, violated use
Lead to a large amount of antibiotic residue being discharged into water body and soil by human and animal, nowadays, including China
Many countries, fluoroquinolone antibiotics are continually detected in the water outlet of sewage treatment plant, surface water and groundwater
Come.The residual enrichment of fluoroquinolone antibiotics in the environment has resulted in potential threat to human health.Therefore, one kind is established
The effective method of fast, economical has important research significance to remove fluoroquinolone antibiotics in environment.
Multi-stage porous carbon material refers to while having macropore, mesoporous and three kinds of aperture structures of micropore sorbent material, has
The advantages that high specific surface area, excellent chemistry and thermal stability, stable physicochemical property and be widely used in water environment
The removal of middle organic pollutant, but the porous carbon materials of prior art preparation are only single to have superhigh specific surface area or single
Have multi-stage artery structure, significantly limit the large-scale production of porous carbon materials.
Coal fly ash hollow micro bead (FACs) is a kind of one of maximum solid industrial waste of thermal power plant discharge amount, is
A kind of nonmetallic hollow micron grade particles, main component be composite inorganic oxide (such as: SiO2, Al2O3Deng), density is
2-216t/m3, bulk density 550-658kg/m3, thermal stability with higher.Since flyash is coal dust in suspension combustion
Under the conditions of be cooled into after heating surface absorbs heat, therefore under the action of surface tension, flyash surface porosity is porous, have
Unique hollow structure, good mechanical performance, the high specific surface area of coal fly ash hollow micro bead, excellent chemistry and thermostabilization
Property, it is ideal one-dimensional patterned substrate material, has broad application prospects, but there are no to flyash sky in the prior art
The effective use of heart microballon.
Therefore, how a kind of fly ash hollow that can be made full use of to resource and adsorption effect is good is provided
Microballon is the problem of template potassium salt Quito hole carbon adsorbing material is those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention is hard template using solid industrial waste coal ash cenosphere (FACs), with price
Cheap biological material potassium salt is that carbon source is prepared for potassium salt base multi-stage porous carbon material.Firstly, potassium salt is matched
Uniform solution is made, wraps up and is filled in coal fly ash hollow micro bead surface and hollow interior, remove flyash after carbonization treatment,
The hollow structure of flyash is left, then generates the multi-stage porous carbon that micropore prepares high-specific surface area in conjunction with high-temperature alkali activation method
Material, the multi-stage porous carbon material prepared are applied to the processing of fluoroquinolone antibiotics sewage, show good effect.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of coal fly ash hollow micro bead is the preparation method of template potassium salt Quito hole carbon adsorbing material, including following step
It is rapid:
(1) pretreatment of coal fly ash hollow micro bead
It is added in acid solution after flyash is ground, suction filtration, washing are into after reacting a period of time in a heated condition
Property, drying, obtain pretreated coal fly ash hollow micro bead；Wherein acid solution is selected from nitric acid, hydrochloric acid, dilution heat of sulfuric acid, preferably
Nitric acid solution；
(2) coal fly ash hollow micro bead/potassium salt based composites preparation
Pretreated coal fly ash hollow micro bead is mixed with potassium acetate solution, strong stirring makes it be uniformly dispersed, will
High speed centrifugation after the mixed liquor arrived stands a period of time under condition of negative pressure, drying to constant weight, obtains coal fly ash hollow micro bead/second
Acid potassium salt based composites；
(3) coal fly ash hollow micro bead is the preparation of the template carbon material of template
Coal fly ash hollow micro bead/potassium salt based composites are placed in tube furnace, under nitrogen protection pyrocarbon
It is cooled to room temperature after changing 2h-4h；Then cooling carbonized product is impregnated with potassium hydroxide solution, it will using potassium hydroxide solution
Effective component alumino-silicate dissolves out in flyash, removes flyash template, filters, washing to neutral, drying to constant weight, obtain with
Coal fly ash hollow micro bead is the template carbon material of template；
(4) coal fly ash hollow micro bead is the preparation of template potassium salt base porous carbon materials
Template carbon material and solid potassium hydroxide mixed grinding that coal fly ash hollow micro bead is template are uniformly placed in pipe
It in formula furnace, under nitrogen protection after high-temperature activation 2h-4h, is cooled to room temperature, washs, drying is obtained with coal fly ash hollow micro bead
For the potassium salt base porous carbon materials of template.
Step (4) of the invention generates a large amount of micropores by potassium hydroxide chemical activation method, is interconnected to be made
Multi-stage porous carbon material not only has relatively high specific surface area, and has good chemical stability and thermal stability, due to
The presence of hierarchical porous structure, macropore can form buffering reservoir to be reduced to interior surface diffusion length, and micropore abundant provides
Bigger specific surface area and smaller transport resistance, greatly improves adsorption capacity.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, the ratio of flyash and acid solution is 3-5g:10mL in step (1), and wherein the concentration of acid solution is 2-4mol/L.
The beneficial effect of above-mentioned technical proposal is: the setting of aforementioned proportion and solution concentration can make porous carbon adsorbing material
Reach optimal activation effect.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, 200 meshes are crossed after flyash grinding in step (1).
The beneficial effect of above-mentioned technical proposal is: crossing 200 meshes after flyash grinding, can greatly improve fly ash hollow
The specific surface area of microballon, and then can also be improved the specific surface that coal fly ash hollow micro bead is template potassium salt base porous carbon materials
Product, the absorption property of reinforcing material.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, heating condition described in step (1) reacts 4h-6h in the environment of being 60-80 DEG C.
The beneficial effect of above-mentioned technical proposal is: being dried in above-mentioned temperature and time, it is ensured that material is dry
To constant weight.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, the mass ratio of coal fly ash hollow micro bead and potassium acetate solution is 1:3-5 in step (2), wherein the quality of potassium acetate solution point
Number is 30-40%.
The beneficial effect of above-mentioned technical proposal is: ensure that prepared multilevel hole material has micropore abundant and larger
Specific surface area.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, negative pressure pressure described in step (2) is -0.2- (- 0.4) MPa, time of repose 3h-5h.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, ultracentrifugal revolving speed described in step (2) is 2000r/min-4000r/min, centrifugation time 2h-3h.
The beneficial effect of above-mentioned technical proposal is: after mixture is stood under condition of negative pressure, high speed centrifugation is to reach
To closelypacked effect.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, drying temperature described in step (2)-step (4) is 60-70 DEG C.
The beneficial effect of above-mentioned technical proposal is: it dries at the temperature disclosed above, can not only guarantee that material is dried to constant weight, but also
The chemical property of material is not changed.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, the condition of high temperature cabonization described in step (3) is to be warming up to 500 DEG C -700 DEG C with the rate of 5-7 DEG C/min.
The beneficial effect of above-mentioned technical proposal is: by the control to temperature in carbonisation, realizing to char-forming material hole
The control of type structure, synthesize have high-specific surface area and pore volume activated carbon, and make it have good chemical stability and
Thermal stability.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, the mass fraction of potassium hydroxide solution is 20-30% in step (3).
The beneficial effect of above-mentioned technical proposal is: this concentration can guarantee chemical activation effect, a large amount of micropores be generated, to make
The multi-stage porous carbon material that must be interconnected, greatly improves adsorption capacity.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, coal fly ash hollow micro bead is the template carbon material of template in step (4) and the mass ratio of solid potassium hydroxide is 1:3-4.
The beneficial effect of above-mentioned technical proposal is: important drilling, hole are played the role of in activation of potassium hydroxide agent in activation
Structure is enriched as activator incorporation increases in a certain range, by a series of hole carbon materials for comparing different condition preparations
Material, above-mentioned technological parameter are optimal parameter.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, the condition of high-temperature activation described in step (4) is to be warming up to 600 DEG C -800 DEG C with the rate of 5-8 DEG C/min.
The beneficial effect of above-mentioned technical proposal is: important drilling, hole are played the role of in activation of potassium hydroxide agent in activation
Structure is enriched as activator incorporation increases in a certain range；And activation temperature be also regulate and control one of pore structure it is important
Parameter, activation generates a large amount of micropores based on deep activation in certain temperature range, and is more than that certain temperature range is then main
It is width activation, partial pore is converted into mesoporous, macroporous structure.By comparing a series of hole carbon material of different condition preparations,
Above-mentioned technological parameter is optimal parameter.
In order to guarantee the speed and effect of activation, a large amount of micropores are produced by KOH chemical activation method, to be made mutual
The multi-stage porous carbon material of connection, due to the presence of hierarchical porous structure, macropore can form buffering reservoir to be reduced to interior surface
Diffusion length, micropore abundant and it is mesoporous bigger specific surface area and smaller transport resistance can be provided, lead to adsorption energy
Power is excellent, is successfully realized the efficient quick adsorption to fluoroquinolone antibiotics in water environment.
Preferably, in the preparation method that above-mentioned coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
In, washing described in step (4) with the hydrochloric acid of 2-4mol/L to wash away impurity, then with volume ratio be 3-4:1 deionized water and
The mixed solution of ethyl alcohol is cleaned repeatedly to neutrality.
The beneficial effect of above-mentioned technical proposal is: certain density hydrochloric acid is added for removing the carbon generated in reaction process
The impurity such as sour potassium；It is cleaned repeatedly with the mixing that volume ratio is 3-4:1 deionized water and ethyl alcohol is molten, it is therefore an objective to wash away impurity and be washed till
It is neutral.
It is template potassium salt the present invention also provides a kind of coal fly ash hollow micro bead being prepared according to the above method
Quito hole carbon adsorbing material；
And it is a kind of according to the above-mentioned coal fly ash hollow micro bead being prepared be template potassium salt Quito hole carbon adsorption material
Expect the application of the fluoroquinolone antibiotics in removal water environment.
It can be seen via above technical scheme that compared with prior art, the present invention makes full use of resource, with cheap
Biological material potassium salt is carbon source, with solid industrial waste coal ash cenosphere (FACs) for hard template, in conjunction with height
Warm alkali activation method prepares the multi-stage porous carbon material of high-specific surface area, and for removing fluoroquinolone antibiotics in water environment,
A kind of economic, efficient new method is provided for the preparation of multilevel hole material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is that template carbon material and coal fly ash hollow micro bead of the present invention are template potassium salt base porous carbon materials
SEM figure；
Fig. 2 attached drawing is that coal fly ash hollow micro bead and coal fly ash hollow micro bead of the invention are template potassium salt base porous carbon
The infrared spectrogram of material；
Fig. 3 attached drawing is that pH of the present invention is that template potassium salt base porous carbon materials absorption cyclopropyl is husky to coal fly ash hollow micro bead
The influence of star and Enrofloxacin；
Fig. 4 attached drawing be coal fly ash hollow micro bead of the present invention be template potassium salt base porous carbon materials absorption Ciprofloxacin and
The isollaothermic chart of Enrofloxacin；
Fig. 5 attached drawing be coal fly ash hollow micro bead of the present invention be template potassium salt base porous carbon materials absorption Ciprofloxacin and
The dynamics figure of Enrofloxacin.
Specific embodiment
Below in conjunction with the attached drawing of the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
It is template potassium salt Quito hole carbon adsorbing material the embodiment of the invention discloses a kind of coal fly ash hollow micro bead
Preparation method, the specific steps are as follows:
(1) pretreatment of coal fly ash hollow micro bead
Table mountain Yaomeng power plant flyash is derived from by crossing 200 meshes after ball mill grinding, and it is molten to be added to 2-4mol/L acid
In liquid, the ratio of flyash and acid solution is 3-5g:10mL, and heating reaction 4-6h, filters under the conditions of 60-80 DEG C, a large amount of to distill
Water is rinsed to neutrality, and drying can obtain pretreated coal fly ash hollow micro bead.
(2) coal fly ash hollow micro bead/potassium salt based composites preparation
It is 1:3-5 according to the mass ratio of coal fly ash hollow micro bead and potassium acetate solution, by pretreated fly ash hollow
Microballon is mixed with the potassium acetate solution that mass fraction is 30-40%, and strong stirring makes it be uniformly dispersed, and obtained mixed liquor is existed
Condition of negative pressure stands 3h-5h under the conditions of being -0.2- (- 0.4) Mpa；Then with 2000-4000r/min high speed centrifugation 2h-3h, so
Drying to constant weight under the conditions of 60-70 DEG C afterwards, obtains coal fly ash hollow micro bead/potassium salt based composites.
(3) coal fly ash hollow micro bead is the preparation of the template carbon material of template
Coal fly ash hollow micro bead/potassium salt based composites are placed in tube furnace, under nitrogen protection, with 5-7
DEG C/500-700 DEG C of min heating rate heating, carbonization time 2h-4h is then cooled to room temperature.Then by above-mentioned carbonized product
It is impregnated with the potassium hydroxide solution that mass fraction is 20-30% and removes flyash template, then filtered, a large amount of deionized water washings
To neutrality, drying to constant weight in 60-70 DEG C of baking oven, obtains the template carbon material using coal fly ash hollow micro bead as template.
(4) coal fly ash hollow micro bead is the preparation of template potassium salt base porous carbon materials
Above-mentioned template carbon material and solid potassium hydroxide are mixed according to the ratio of mass ratio 1:3-4, after grinding uniformly, put
It is placed in tube furnace under nitrogen protection, is heated up 600 DEG C -800 DEG C with 5 DEG C -8 DEG C/min heating rate, activate 2h-4h, then
It is cooled to room temperature.Impurity then is washed away with the hydrochloric acid of 2-4mol/L, is then 3:1 deionized water and ethyl alcohol with a large amount of volume ratio
Mixed solution cleaned repeatedly to neutrality, drying to constant weight under the conditions of 60-70 DEG C of temperature, obtain be with coal fly ash hollow micro bead
The potassium salt base porous carbon materials of template.
It is the potassium salt base porous carbon that the coal fly ash hollow micro bead that the present invention is prepared is template referring to attached drawing 1-2
The detection that material carries out is as follows:
From Fig. 1 (a, b) it can be seen that sphere shape is presented in carbonized product, shows that fly ash micro-sphere is completely removed, leave ball
The pattern of shape, surface are relatively smooth；From Fig. 1 (c, d) it can be found that after activation of potassium hydroxide is handled, multi-stage porous carbon is still
Preferable pattern is so kept, big change does not occur for shape, however its surface becomes more coarse, after showing activation of potassium hydroxide
Generate a large amount of micropore.
Fig. 2 (a) (b) is respectively coal fly ash hollow micro bead and coal fly ash hollow micro bead is template potassium salt base porous carbon
The infrared spectrogram of material, corresponding infrared signature peak can be used to verify the presence of some functional groups.Know from Fig. 2 (a),
3428cm-1And 1630cm-1The absorption peak at place is the stretching vibration of coal fly ash hollow micro bead inner surface hydroxyl and internal layer water deformation vibration
Characteristic peak, 1028cm-1And 735cm-1The absorption peak at place is that the stretching vibration of coal fly ash hollow micro bead Si-O-Si and Si-O are inhaled
Receive peak；It is found that 1700cm from Fig. 2 (b)-1The stretching vibration peak of the corresponding C=O for carboxy CO OH, shows biomass carbon
In the presence of；1025cm-1The absorption peak at place is the stretching vibration peak of C=O in carbon skeleton；900cm-1-650cm-1The absorption peak in region is
Carbon structure skeleton China and foreign countries' plain bending vibration peak.
It is template potassium acetate alkali to the coal fly ash hollow micro bead that the present invention is prepared below with reference to specific implementation example
Application of the porous carbon adsorbing material in sewage treatment is described further:
Static state is utilized to the absorption property evaluation that coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material
Adsorption test is completed.
It takes 25ml Ciprofloxacin and 25ml Enrofloxacin solution to be added in centrifuge tube respectively first, then adds thereto respectively
Entering 10mg coal fly ash hollow micro bead is template potassium salt base porous carbon materials, is stood in room-temperature water bath, investigates solution respectively
The influence of pH, different initial concentrations and time of contact to Ciprofloxacin and Enrofloxacin adsorption capacity.After absorption reaches saturation,
Supernatant liquor is collected by filtration respectively with 0.45um miillpore filter, is measured respectively with ultraviolet-visible photometer unadsorbed in solution
Ciprofloxacin and Enrofloxacin molecular concentration (take Ciprofloxacin and Enrofloxacin supernatant in absorbing wavelength 276nm respectively and
Absorbance is measured at 271nm).Calculate to obtain adsorption capacity (q)
Q=[(C0-Ce)V]/W
C0(μm ol/L) and CeIt is dense when (μm ol/L) is respectively the initial concentration and balance of Ciprofloxacin and Enrofloxacin
Degree, V (mL) and W (mg) are respectively the dosage of liquor capacity and adsorbent.
Test example 1: adjusting pH value of solution with 1.0moL/LHCl and 1.0moL/LNaOH is 2.0-11.0, investigates pH value to suction
The influence of attached process.Ciprofloxacin that 25ml initial concentration is 150 μm of ol/L and Enrofloxacin solution is taken to be added to centrifugation respectively
Guan Zhong, being separately added into 10mg coal fly ash hollow micro bead is template potassium salt base porous carbon materials, is respectively placed in test solution
After standing 120min in room temperature water bath, supernatant liquor is collected, unadsorbed Ciprofloxacin and Enrofloxacin molecular concentration are used
Ultraviolet-uisible spectrophotometer measurement, calculates adsorption capacity.
From figure 3, it can be seen that coal fly ash hollow micro bead is template potassium salt base porous carbon materials when pH value is 6.0
Maximum is reached to the adsorption capacity of Ciprofloxacin and Enrofloxacin, respectively reaches 44.00umol/g and 40.55umol/g.With ring
For third husky star, the surface charge and molecular conformation of this experimental phenomena and adsorbent material and Ciprofloxacin under condition of different pH are close
Cut phase is closed.Contain-COOH and-NH in Ciprofloxacin molecule3(pKaValue is respectively 8.76 and 6.18), as pH > 8.76, cyclopropyl
- the COOH of Sha Xing (CIP) is in conjunction with OH and mainly with CIP-Form exists, as pH < 6.18 ,-the NH of Ciprofloxacin (CIP)3
With H in solution+In conjunction with and in CIPH2 +Form, as 5 < pH < pKa (6.18), porous carbon materials surface is conducive to negative electrical charge
Ciprofloxacin is adsorbed, adsorption capacity is higher, as pH < 5.0, excessive H+Competitive Adsorption point is understood with Ciprofloxacin, so that more
Hole carbon material reduces the adsorption capacity of Ciprofloxacin, therefore optimal pH is 6.0.
Test example 2: taking 25ml initial concentration respectively is respectively 10,20,30,50,60,80,100,150,200 μm of ol/L
Ciprofloxacin and Enrofloxacin solution are added in centrifuge tube, and being separately added into 10mg coal fly ash hollow micro bead is template potassium salt
Test solution is placed in room temperature water bath stands 2h respectively, collects supernatant liquor, unadsorbed cyclopropyl by base porous carbon materials
Sha Xing and Enrofloxacin molecular concentration are measured with ultraviolet-uisible spectrophotometer, calculate adsorption capacity, show to inhale shown in Fig. 4
Attached capacity increases with the raising of concentration, and maximum equilibrium adsorption capacities reach 51.95umol/g and 41.80umol/g.
Test example 3: take respectively Ciprofloxacin that 25ml initial concentration is 150 μm of ol/L and Enrofloxacin solution be added to from
In heart pipe, addition 10mg coal fly ash hollow micro bead is template potassium salt base porous carbon materials, and test solution is placed in room respectively
After standing 2,5,10,30,45,60,90,120 and 150min respectively in warm water bath, supernatant liquor, unadsorbed ring are collected
Third husky star and Enrofloxacin molecular concentration are measured with ultraviolet-uisible spectrophotometer, calculate adsorption capacity, as can be known from Fig. 5,
Originally with the increase of adsorption time, adsorption capacity increases sharply, and absorption reaches balance after 30min, in entire adsorption time,
Potassium salt base porous carbon materials show good absorption property to Ciprofloxacin and Enrofloxacin, and time of contact is in 120min
When, porous carbon materials respectively reach 48.80umol/g and 39.40umol/g to Ciprofloxacin and Enrofloxacin adsorption capacity.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. the preparation method that a kind of coal fly ash hollow micro bead is template potassium salt Quito hole carbon adsorbing material, which is characterized in that
The following steps are included:
(1) pretreatment of coal fly ash hollow micro bead
It is added in acid solution after flyash is ground up, sieved, is filtered after reacting 4-6h under 60-80 DEG C of heating condition, washed
To neutrality, drying obtains pretreated coal fly ash hollow micro bead；
(2) coal fly ash hollow micro bead/potassium salt based composites preparation
Pretreated coal fly ash hollow micro bead is mixed with potassium acetate solution, strong stirring makes it be uniformly dispersed, by what is obtained
High speed centrifugation after mixed liquor stands a period of time under condition of negative pressure, drying to constant weight under the conditions of 60-70 DEG C, obtains flyash sky
Heart microballon/potassium salt based composites；
(3) coal fly ash hollow micro bead is the preparation of the template carbon material of template
Coal fly ash hollow micro bead/potassium salt based composites are placed in tube furnace, under nitrogen protection after high temperature cabonization
It is cooled to room temperature；Then cooling carbonized product is impregnated with the potassium hydroxide solution that mass fraction is 20-30% and removes fine coal
Grey template filters, washing to neutrality, and drying to constant weight under the conditions of 60-70 DEG C, obtains the mould using coal fly ash hollow micro bead as template
Plate carbon material；
(4) coal fly ash hollow micro bead is the preparation of template potassium salt base porous carbon materials
Template carbon material and solid potassium hydroxide mixed grinding that coal fly ash hollow micro bead is template are uniformly placed in tube furnace
In, it is cooled to room temperature, washs after high-temperature activation under nitrogen protection, dry, obtain micro- with fly ash hollow under the conditions of 60-70 DEG C
Pearl is the potassium salt base porous carbon materials of template.
2. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that the ratio of flyash and acid solution is 3-5g:10mL in step (1), and wherein the concentration of acid solution is 2-
4mol/L。
3. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that the mass ratio of coal fly ash hollow micro bead and potassium acetate solution is 1:3-5 in step (2), and wherein potassium acetate is molten
The mass fraction of liquid is 30-40%.
4. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that negative pressure pressure described in step (2) is -0.2- (- 0.4) MPa, time of repose 3-5h.
5. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that high temperature cabonization described in step (3) is that 500-700 DEG C is warming up to the rate of 5-7 DEG C/min, and be carbonized 2h-
4h。
6. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that coal fly ash hollow micro bead is the template carbon material of template and the mass ratio of solid potassium hydroxide in step (4)
For 1:3-4.
7. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that high-temperature activation described in step (4) is that 600 DEG C -800 DEG C are warming up to the rate of 5 DEG C -8 DEG C/min, is lived
Change 2h-4h.
8. the preparation side that coal fly ash hollow micro bead according to claim 1 is template potassium salt Quito hole carbon adsorbing material
Method, which is characterized in that washing described in step (4) is then that 3:1 is gone with volume ratio to wash away impurity with the hydrochloric acid of 2-4mol/L
The mixed solution of ionized water and ethyl alcohol is cleaned repeatedly to neutrality.
9. the coal fly ash hollow micro bead that any one of -8 the methods are prepared a kind of according to claim 1 is template potassium salt
Quito hole carbon adsorbing material.
10. the coal fly ash hollow micro bead that any one of -8 the methods are prepared a kind of according to claim 1 is template potassium acetate
The application of the porous carbon adsorbing material of alkali fluoroquinolone antibiotics in removal water environment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114014553A (en) * | 2021-12-13 | 2022-02-08 | 中南大学 | Method for improving hollow balling rate of coal slime floating beads |
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