CN103977771A - Preparation method and application of bifunctional functionalized magnetic carbon-based mesoporous silica material - Google Patents
Preparation method and application of bifunctional functionalized magnetic carbon-based mesoporous silica material Download PDFInfo
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- CN103977771A CN103977771A CN201410246540.8A CN201410246540A CN103977771A CN 103977771 A CN103977771 A CN 103977771A CN 201410246540 A CN201410246540 A CN 201410246540A CN 103977771 A CN103977771 A CN 103977771A
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Abstract
The invention relates to a preparation method of a bifunctional functionalized magnetic carbon-based mesoporous silica material and application of the material in treatment of uranium-bearing wastewater. The preparation method specifically comprises the following steps: with beer saccharomycete as a biological macropore template as well as triblock polymer P123 as a mesoporous phase template, preparing mesoporous silica SBA-15 by virtue of a dual-template method; with the mesoporous silica SBA-15 as a template, respectively filling an iron source and a carbon source into hard templates as precursors by virtue of a nano-pouring technique, and carrying out in-situ polymerization reaction so as to prepare and synthesize magnetic carbon-based mesoporous silica with ordered mesoporous structures, wherein the mass ratios of the iron source and the carbon source are different. According to the preparation method, for extending the application range of the magnetic carbon-based mesoporous silica material, organic reagents, namely [3-(trimethoxy silane) propyl] urea (UPTS) and aminopropyl triethoxysilane (APS) are utilized for sequentially modifying and grafting Si-OH on the surface of the material, and then the material has double functions of adsorption and coordination reaction; the bifunctional functionalized magnetic carbon-based mesoporous silica material prepared by utilizing the preparation method has regular and sequential pore passages, is large in specific surface area and has very important practical significances in the treatment of the uranium-bearing wastewater, uranium recovery and the like in uranium mining and metallurgy.
Description
Technical field
The invention belongs to the utilization of resources and field of environment protection, particularly preparation and the application thereof of difunctional functional magnetic charcoal base meso pore silicon oxide material.
Background technology
Compare with traditional poromerics, mesoporous material has that the aperture that allows molecule to enter is large, specific area is high and the feature such as adsorption capacity is large, at catalysis, absorption and separated, new material assembling, the aspect such as biological and medical, have broad application prospects, particularly utilize the adsorption capacity that mesoporous material is stronger, good chemical stability and adsorptive selectivity, can reach the removal of some heavy metal ion and separated object.
In mesoporous family, meso pore silicon oxide material, because synthetic method is simple, specific area is high, has good chemical stability and heat endurance, and acidproof and resistance to irradiation, is more adapted at using in the strong irradiation sour environments such as Uranium uranium-containing waste water.In the last few years, existing many scholars were applied to meso pore silicon oxide material processing and the nuclear environment pollution control of radioactive liquid waste, and had shown good application prospect.
Charcoal and meso pore silicon oxide material all can adsorb the heavy metal ion such as uranyl ion in uranium-containing waste water, but Carbon Materials has micropore, mesoporous and macropore, and pore-size distribution is very wide, poor to the single-minded adsorptivity of certain ion, and its absorption property and regenerability are all lower.Simultaneously, Carbon Materials only has a small amount of mesoporous and large pore material can adsorb preferably uranyl ion, for micropore carbon material, although there is higher specific area, but its duct is irregular, local easily gathering and cause duct to narrow down even stopping up the defect in duct, thus its adsorption effect to uranyl ion affected.And Metaporous silicon dioxide material is owing to itself not having activated centre, cause processing in application at Uranium uranium-containing waste water being subject to very larger restriction, affect the selectivity of its absorption.
Charcoal base meso pore silicon oxide material combines the advantage of traditional active carbon and mesoporous material, compare meso pore silicon oxide material, its surface, duct has the abundant functional group (Ru Han hydrogen-oxygen functional group) as active carbon, and there is good hydrothermally stable performance, be convenient to effective absorption of its object ion in the aqueous solution.Compare active carbon, charcoal base meso pore silicon oxide material has the mesoporous aperture of larger mesoporous pore volume and homogeneous, thereby gives it to the single-minded absorption property of object ion (selective absorption performance) and high-adsorption-capacity.
Existing meso pore silicon oxide material synthetic method is divided into soft template and hard template method, is summed up and mainly contains two large approach, and adopting surfactant is the approach of template and to adopt non-surface-active agent (as starch, carbohydrate etc.) be another new way of template.But, the equal defectiveness of above-mentioned single channel, as adopted cationic surface active agent as template, the mesoporous aperture of the meso pore silicon oxide material of gained is relatively little; Adopt non-ionic surface active agent as template, the meso pore silicon oxide material pore-size distribution of gained is relatively wide, and aperture is relatively large but mesoporous regular order is lower; And while adopting non-surface-active agent to be template, pore passage structure does not have ordering conventionally.Meanwhile, no matter be soft template or hard template, traditional single mode plate preparation method has different shortcomings, as very responsive to solution environmental (ionic strength, pH value and temperature etc.), need to carry out strict control to its synthesis condition.Therefore, further seek template cheapness, reaction temperature and, to operate simple and easy, eco-friendly synthetic route significant.
The present invention adopts two template, take saccharomyces cerevisiae as biological macropore template, take triblock polymer P123 as mesoporous phase template, prepare synthesizing mesoporous monox SBA-15.Magnetic charcoal base meso pore silicon oxide material, also with reference to similar hard template synthetic method, be take mesopore silicon oxide as hard template, inserts respectively the source of iron of different quality ratio and charcoal source as predecessor by nanometer pouring technique in hard template, through home position polymerization reaction, obtains.
In order to expand the range of application of magnetic charcoal base meso pore silicon oxide material, it is effectively applied in the processing of Uranium uranium-containing waste water more, the present invention uses [3-(trimethoxy silane) propyl group] urea (UPTS) and aminopropyl triethoxysilane (APS) organic reagent to carry out rear grafting modification to its surperficial Si-OH, makes it have absorption and complexation reaction dual-use function.
Summary of the invention
The object of this invention is to provide that a kind of template is cheap, reaction temperature and, operate simple and easy, eco-friendly novel preparation method and the application in uranium-containing waste water is processed thereof of preparing difunctional functional magnetic charcoal base meso pore silicon oxide material, specifically take saccharomyces cerevisiae as biological macropore template, take triblock polymer P123 as mesoporous phase template, adopt two template synthesis mesoporous SBA-15s.Take mesoporous SBA-15 as template again, adopt nanometer pouring technique in hard template, to insert respectively the source of iron of different quality ratio and charcoal source as predecessor, through home position polymerization reaction, prepare synthesising mesoporous structurally ordered magnetic charcoal base mesopore silicon oxide.In order to expand the range of application of magnetic charcoal base meso pore silicon oxide material, use [3-(trimethoxy silane) propyl group] urea (UPTS) and aminopropyl triethoxysilane (APS) organic reagent to carry out rear grafting modification to its surperficial Si-OH, make it have absorption and complexation reaction dual-use function.
The present invention is also applied to the synthetic difunctional functional magnetic charcoal base meso pore silicon oxide material of preparation in the adsorption applications of uranium-containing waste water, and by regulating concentration, the pH value of solution and the factors such as input amount of difunctional functional magnetic charcoal base meso pore silicon oxide material of uranium standard liquid, investigate the adsorption effect of magnetic difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium in uranium-containing waste water.
Concrete steps are as follows:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that certain mass gathers, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein the triblock polymer P123 (being Pluronic F-127 ether-poly-propylene oxide ether-Pluronic F-127 ether) of certain mass, 30
oc water bath with thermostatic control lower magnetic force stirs until in the complete dissolving salt acid solution of P123.Subsequently toward wherein adding 6.5 g TEOS(ethyl orthosilicates), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0h in the Muffle furnace of C, removes template and obtains mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
By solubility trivalent iron salt with carbohydrate according to certain mass ratio, put into the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes mesopore silicon oxide template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By the mass concentration of certain mass ratio, be that 20%UPTS solution and mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure the uranium standard liquid of 50 mL variable concentrations, in 150 mL round-bottomed flasks, add subsequently a certain amount of difunctional functional magnetic charcoal base meso pore silicon oxide material, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value, at room temperature magnetic agitation 3.0 h.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant and adopt titanium trichloride reduction/ammonium vanadate oxidimetry to measure the residual concentration of uranium, and calculate the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium according to the concentration of uranium in solution before and after absorption
p(%).
In described step (1), the mass ratio of the discarded mycelium of brewer's yeast and triblock polymer P123 is (16 ~ 20): 1.
In described step (2), the mass ratio of solubility trivalent iron salt and carbohydrate is (0.5 ~ 0.67): 1.
In described step (3), the mass ratio of UPTS solution and APS solution is (2.0-2.5): 1.
Described solubility trivalent iron salt is ferric sulfate, and described carbohydrate is glucose or sucrose.
The adsorption test of described difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium in uranium-containing waste water, the concentration of uranium standard liquid is 0.45 ~ 0.50 mg/L; The quality of difunctional functional magnetic charcoal base meso pore silicon oxide material is 8.0 ~ 12 mg; The pH value of solution is 3.0 ~ 8.0.
The adsorption rate of described difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium in uranium-containing waste water
pall, in 90% left and right, can make uranium in uranium-containing waste water be processed preferably.
Difunctional functional magnetic charcoal base meso pore silicon oxide material preparation method of the present invention and the application in uranium-containing waste water is processed thereof, compared to existing technology, this method have template cheapness, reaction temperature and, operate the multiple advantages such as simple and easy, environmental friendliness.Be embodied in following remarkable advantage:
(1), in mesoporous SBA-15 preparation process, the biological template of use and surfactant templates source is abundant, the particularly discarded mycelial use of brewer's yeast, realized with " giving up ", control useless, thereby avoided the waste of resource.
(2) prepare synthetic mesoporous SBA-15 and build and machine functional modification through magnetic Nano, not only do not change the one dimension hexagonal hole road structure of mesoporous SBA-15, and improved its adsorption effect that uranium-containing waste water is processed, the adsorption rate to uranium
pall more than 90%.
(3) in the preparation process of difunctional functional magnetic charcoal base meso pore silicon oxide material, preparation technology is simple, and reaction condition is gentle, and without any need for chemical industry equipments such as pressurizations, heating condition is also easily realized, and energy consumption is low, and the yield of product is high.
(4) prepare synthetic difunctional functional magnetic charcoal base meso pore silicon oxide material and have that mechanical strength is high, chemical stability is strong, under the stir speed (S.S.) of 10000 r/min, can fully suspend, swelling, indeformable not, and can guarantee and fully contacting containing uranium solution.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the synthetic mesoporous SBA-15 of embodiment 1 preparation,
Fig. 2 is the X-ray diffractogram of the synthetic mesoporous SBA-15 of embodiment 1 preparation,
Fig. 3 is the scanning electron microscope (SEM) photograph of the synthetic difunctional functional magnetic charcoal base meso pore silicon oxide material of embodiment 1 preparation,
Fig. 4 is the X-ray diffractogram of the synthetic difunctional functional magnetic charcoal base meso pore silicon oxide material of embodiment 1 preparation.
The specific embodiment
Below by embodiment is specifically described the present invention; they are just for being further detailed the present invention; can not be interpreted as limiting the scope of the invention; those skilled in the art makes some nonessential improvement or adjustment according to the content of foregoing invention, all belongs to protection domain of the present invention.
Embodiment 1:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 30 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 1.5 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.Meanwhile, use JSM 6360LV type SEM and Rigaku/max-RA type X-ray diffractometer respectively its structure to be characterized, the results are shown in Fig. 1 and 2.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 5.0 g concentration and 10 g glucose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.2 g mass concentrations, be that 20%UPTS solution and 0.6 g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.Meanwhile, use JSM 6360LV type SEM and Rigaku/max-RA type X-ray diffractometer respectively its structure to be characterized, the results are shown in Figure 3 and 4.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for being 0.45 mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 8.0 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 3.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.041 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 90.89%.
Embodiment 2:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 30 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 1.5 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 6.0 g concentration and 10 g glucose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.1g mass concentration, be that 20%UPTS solution and 0.5 g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for for 0.46mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 9.0 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 4.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.038 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 91.74%.
Embodiment 3:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 35 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 2.0 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 6.0 g concentration and 10g glucose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.0 g mass concentrations, be that 20%UPTS solution and 0.4 g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for being 0.47 mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 10 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 5.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.040 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 91.49%.
Embodiment 4:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 35 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 2.0 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 4.0 g concentration and 6.0 g sucrose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.2 g mass concentrations, be that 20%UPTS solution and 0.6 g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for for 0.48mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 11 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 6.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.039 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 91.88%.
Embodiment 5:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 40 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 2.5 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 4.0 g concentration and 6.0 g sucrose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.1 g mass concentrations, be that 20%UPTS solution and 0.5 g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for being 0.49 mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 12 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 7.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.035 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 92.86%.
Embodiment 6:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast that 40 g gather, through 80
oafter C high-temperature sterilization 100 min, use distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed.Then by 10 mL mass concentrations, be that 35% concentrated hydrochloric acid adds in beaker, and add wherein 2.5 g P123,30
oc thermostatted water (ethyl orthosilicate), 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now.Then beaker is put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h.Again suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h.Filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0 h in the Muffle furnace of C, remove template and obtain mesoporous SBA-15.
(2) preparation of magnetic charcoal base mesopore silicon oxide
The ferric nitrate that is 35% by 5.0 g concentration and 10 g glucose are put into respectively the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g mesoporous SBA-15s.Regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6.0 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product.Service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes template, obtains magnetic charcoal base mesopore silicon oxide.
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, are then loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stirs 2.5h.By 1.0 g mass concentrations, be that 20%UPTS solution and 0.4g mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
(4) absorption of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
Measure 50 mL concentration for being 0.50 mg/L uranium standard liquid, in 150 mL round-bottomed flasks, add subsequently 13 g difunctional functional magnetic charcoal base meso pore silicon oxide materials, the HCl that working concentration is 0.1mol/L and NaOH solution regulator solution pH value are 8.0., magnetic agitation 3.0 h at room temperature.After reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant, the residual concentration that adopts titanium trichloride reduction/ammonium vanadate oxidimetry to measure uranium is 0.037 mg/L, the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium
pbe 92.60%.
Claims (8)
1. the preparation of difunctional functional magnetic charcoal base meso pore silicon oxide material, it is characterized in that, first adopt two template, take saccharomyces cerevisiae as biological macropore template, take triblock polymer P123 as mesoporous phase template, prepare synthesizing mesoporous monox SBA-15, take SBA-15 as hard template again, adopt nanometer pouring technique in hard template, to insert respectively source of iron and charcoal source as predecessor, through home position polymerization reaction, and then use hydrofluoric acid to remove template as etching agent, prepare synthesising mesoporous structurally ordered magnetic charcoal base mesopore silicon oxide, re-use 3-trimethoxy silane propyl group urea and aminopropyl triethoxysilane organic reagent, after adopting, grafting is carried out organic functional modification to it, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material,
Concrete steps are as follows:
(1) bimodulus plate is prepared mesoporous SBA-15
Take the discarded mycelium of brewer's yeast of certain mass, through 80
oafter C high-temperature sterilization 100 min, using distilled water and absolute ethyl alcohol to clean 3 times, gained saccharomyces cerevisiae thalline is dispersed in the 250 mL beakers that 100 mL distilled water are housed, is then that 35% concentrated hydrochloric acid adds in beaker by 10 mL mass concentrations, and add wherein triblock polymer P123,30
oc water bath with thermostatic control lower magnetic force stirs until in the complete dissolving salt acid solution of P123, subsequently toward wherein adding 6.5 g ethyl orthosilicates, 45
ounder C water bath with thermostatic control, continue magnetic agitation 1.5 h, there is a large amount of milky white precipitates in beaker now, then beaker put into 30
oin the constant temperature blast drying oven of C, continue reaction 12 h, then suspension is transferred to polytetrafluoroethylene (PTFE) reaction kettle for reaction 2.0 h, subsequently 60
oin the constant temperature blast drying oven of C, continue aging 48 h, filtration under diminished pressure after taking out, is used distilled water and absolute ethyl alcohol that resulting precipitation is respectively washed 3 times, by milky white precipitate 60
oin the constant temperature blast drying oven of C, continue dry 15 h, then the off-white powder obtaining after dry is placed in to 540
oroasting 6.0h in the Muffle furnace of C, removes template and obtains mesoporous SBA-15;
(2) preparation of magnetic charcoal base mesopore silicon oxide
Solubility trivalent iron salt and carbohydrate are put into the 250 mL there-necked flasks that 100 mL distilled water are housed, add subsequently 20 g ethanol solutions to carry out ultrasonic dispersion 2.5 h, and the pH value of the working concentration ammoniacal liquor regulator solution that is 25% is 9.0, in ultrasonic dispersion process, add 1.25 g through the mesoporous SBA-15 of high-temperature calcination, regulating the temperature of mixed solution is 80
oc, controlling the reaction time is 6 h, then reaction mixture is carried out to centrifugation 10 min through the centrifuge of 10000 r/min, uses subsequently distilled water washing 6 times, then the solid-like of gained is placed in to 50
oin C constant temperature blast drying oven, dry, grind and obtain head product, service property (quality) concentration 10% hydrofluoric acid, as etching agent, carries out etching to head product and removes mesopore silicon oxide template, obtains magnetic charcoal base mesopore silicon oxide;
(3) the organic functional modification of magnetic charcoal base mesopore silicon oxide
3.0 g magnetic charcoal base mesopore silicon oxides are suspended in 100 mL toluene solutions, then be loaded in tri-mouthfuls of beakers of 500 mL, adding subsequently 50 mL absolute ethyl alcohols and mass concentration is that 35% concentrated hydrochloric acid carries out ultrasonic dispersion, fully stir 2.5h, by mass concentration, be that 20%UPTS solution and mass concentration are that 50%APS solution slowly adds in there-necked flask again, fully stir 2.0h, heating water bath to 100
oc, makes toluene solution 5.0 h that reflux, and is cooled to room temperature, and filtration under diminished pressure is used distilled water and absolute ethyl alcohol by washing of precipitate each 3 times, 60
oin the constant temperature blast drying oven of C, dry 12h, can obtain difunctional functional magnetic charcoal base meso pore silicon oxide material.
2. the preparation method of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 1, is characterized in that: in described step (1), the mass ratio of the discarded mycelium of brewer's yeast and triblock polymer P123 is (16 ~ 20): 1.
3. the preparation method of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 1, is characterized in that: in described step (2), the mass ratio of trivalent iron salt and carbohydrate is (0.5 ~ 0.67): 1.
4. the preparation method of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 1, is characterized in that: in described step (3), the mass ratio of UPTS solution and APS solution is (2.0-2.5): 1.
5. the preparation method of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 1, is characterized in that: described solubility trivalent iron salt is ferric sulfate, and described carbohydrate is glucose or sucrose.
6. the application of difunctional functional magnetic charcoal base meso pore silicon oxide material in uranium-containing waste water is processed, it is characterized in that: the uranium standard liquid that measures 50 mL variable concentrations, in 150 mL round-bottomed flasks, add subsequently a certain amount of difunctional functional magnetic charcoal base meso pore silicon oxide material, working concentration is HCl and the NaOH solution regulator solution pH value of 0.1mol/L, magnetic agitation 3.0 h at room temperature, after reaction upon adsorption completes, use the centrifuge of 10000 r/min to carry out separated 10 min, get supernatant and adopt titanium trichloride reduction/ammonium vanadate oxidimetry to measure the residual concentration of uranium, and calculate the adsorption rate of difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium according to the concentration of uranium in solution before and after absorption
p.
7. the application of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 6 in uranium-containing waste water is processed, is characterized in that: the concentration of uranium standard liquid is 0.45 ~ 0.50 mg/L; The quality of difunctional functional magnetic charcoal base meso pore silicon oxide material is 8.0 ~ 12 mg; The pH value of solution is 3.0 ~ 8.0.
8. the application of difunctional functional magnetic charcoal base meso pore silicon oxide material according to claim 6 in uranium-containing waste water is processed, is characterized in that: the adsorption rate of described difunctional functional magnetic charcoal base meso pore silicon oxide material to uranium in uranium-containing waste water
p90%.
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| CN109351330A (en) * | 2018-11-09 | 2019-02-19 | 重庆工商大学 | C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent |
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