CN103071449B - Preparation method and application of amino-functionalized mesoporous alumina-based bifunctional adsorbent - Google Patents
Preparation method and application of amino-functionalized mesoporous alumina-based bifunctional adsorbent Download PDFInfo
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Abstract
The invention relates to a preparation method of amino-functionalized mesoporous alumina-based bifunctional adsorbent, and the application of the bifunctional adsorbent. The method comprises the steps of: adding concentrated nitric acid or concentrated hydrochloric acid into the ethanol solution of a Pluronic triblock copolymer P123 or F127 at the room temperature, evenly stirring and adding aluminium isopropoxide into the mixed solution; carrying out constant temperature evaporation on the solution formed by stirring to obtain mesoporous alumina-P123/F127 composite raw powder; adding the raw powder into the ethanol solution of tetraethylenepentamine, polyethyleneimine or triethanolamine; and sequentially carrying out mixing impregnation, centrifugal separation, ethanol washing and drying at the room temperature to obtain the adsorbent. The preparation method has the advantages of simple technology, template agent removal, amino-functionalization one-step completion and the like; and the amino-functionalized mesoporous alumina-based bifunctional adsorbent has good adsorptive property for Cr (VI) and CO2, especially has the removal rate of more than 90% for the Cr (VI) within 1min, and has the removal rate of 100% for the Cr (VI) solution with the concentration of less than 50mg/ L.
Description
Technical field
The technical field that the present invention relates to the preparation of support type alumina composite material and application is exactly a kind of for hypertoxic pollutant Cr (VI) and main greenhouse gas CO
2the preparation method and application of the difunctional compound adsorbent of amino functional meso-porous alumina base of absorption.
Background technology
Heavy metal chromium pollutes and is mainly derived from the industrial wastewaters such as mining, chemical industry, plating, leather and percolate etc.The valence state that chromium exists in water environment is mainly Cr (III) and Cr (VI), and wherein Cr (VI) is generally with Cr
2o
4 2-, Cr
2o
7 2-and CrO
4 2-three kinds of anionic forms exist, and are subject to the impact of the conditions such as organic matter in water, redox materials, temperature and hardness.The toxicity of DIFFERENT Cr compound is different, and maximum with the toxicity of Cr (VI), its toxicity is 100 times of Cr (III) toxicity, and is easily absorbed by the body and at body body accumulation.Chromium to the harm main manifestations of human body is: (1) has and stimulates and irritated effect skin; (2) can cause the respiratory system damage such as nasal septum perforate membrane, sphagitis and pneumonia; (3) can cause harmful effect to stomach and liver; (4) Long Term Contact can cause lung cancer.In addition, ocean aquatile has stronger accumulation ability to chromium, can make fish poisoning when chromium concn is 5mg/L, and concentration can make fish kills while reaching 20mg/L; In soil, excessive chromium can suppress the growth of the crops such as corn, paddy rice, cotton and radish, makes its underproduction in various degree, and can reduce the quantity of germination percentage and the root of crops.Serious harm in view of Cr (VI) pollutes, just seems very necessary to its improvement.
Separated with liquid-liquid extraction, ion-exchange, counter-infiltration, chemical precipitation and film etc. at interior method of wastewater treatment, compare, the advantages such as easy, easy operation that absorption method has, selective height and highly versatile, especially its effective effluent containing heavy metal ions of purifying low-concentration.CN101890338A discloses a kind of nanometer SiO
2the preparation method of sorbing material and purposes.First prepare nanometer SiO
2, and by its pretreatment 4h at 110 ℃; By pretreated nanometer SiO
2be dissolved in toluene, ultrasonic degas, adds after the functionalized reagents such as aminopropyl triethoxysilane, again ultrasonic degas.At N
2under protective condition, at 75 ~ 80 ℃, more than stirring reaction 7h, add afterwards ClOC-C
6h
4cH
2p(C
6h
5)
3br, 1,2-dichloroethanes and anhydrous pyridine make functionalized nano SiO more than 80 ℃ of reaction 6h
2sorbing material, and use it for Environmental Trace Cr
2o
7 2-separation/enrichment.But the poisonous critical defects of organic solvent such as the method exists, and operation is more, complex process, condition harshness and toluene.
In recent years, the climate warming that " greenhouse effects " cause has become a global environmental problem, and the CO that the combustion of fossil fuel such as coal produce
2it is the main cause that causes global warming.CO
2catch and store one of effective means being regarded as reduction of greenhouse gas discharge, at present CO
2the separation method of catching mainly contain solvent absorption, membrane separation process and porosu solid absorption method etc.Solvent absorption can be realized CO well
2separation, but energy consumption is large, expense is high, serious to equipment corrosion.Membrane material in membrane separation process is mainly high molecular polymer, and this type of material not only regenerability is poor, and under high temperature, is easy to decompose, and has limited its application.Porosu solid absorption method is easier to realize adsorption-desorption cyclic process, the solid absorbent adopting comprises carbon (base) material, zeolite, metal organic frame compound, metal oxide and hydrotalcite-based compound etc., by load organic amine, it is carried out to modification, improving its surface alkalinty bit quantity and base strength is to improve its CO
2the effective ways of adsorption capacity.
CN102284273A discloses a kind of compound mesoporous silica/organic matter CO
2the preparation method and application of adsorbent, first the method prepares mesopore molecular sieve MCF and SBA-15, then adopts infusion process at organically-modified materials such as mesoporous material area load polymine, TEPA and polyethylene glycol, to improve adsorbent to CO
2adsorptive selectivity and the stability of adsorption desorption repeatedly.But first the method needs to prepare mesopore molecular sieve carrier, then prepares product by dipping process, and technique is more complicated, and the process of roasting removed template method also can lot of energy and destroy the pore structure of predecessor.
To sum up, easy, the mild condition of exploitation preparation method, to hypertoxic pollutant Cr (VI) and greenhouse gases CO
2the low-cost dual-function adsorbent all with excellent absorption property has important scientific meaning and good application prospect.
Summary of the invention
Technical problem to be solved by this invention is: provide that a kind of preparation method is easy, mild condition and do not need to remove by roasting the preparation and application of the difunctional adsorbent of amino functional meso-porous alumina base of removing masterplate agent, prepared product is to hypertoxic pollutant Cr (VI) and greenhouse gases CO in water body
2all there is good absorption property.
The present invention solves its technical problem and adopts following technical scheme:
First, 0.01-3g Pluronic triblock copolymer is at room temperature fully stirred to be dissolved in 1-20ml ethanol.Subsequently, in above-mentioned solution, add the red fuming nitric acid (RFNA) of 0.1-1.5ml, 65wt% or the concentrated hydrochloric acid of 37wt%, under room temperature, be uniformly mixed.Then, in above-mentioned mixed solution, add 0.4-3.06g aluminium isopropoxide, at room temperature fully stir and form clear solution.Above-mentioned clear solution is put into baking oven, and evaporation at constant temperature obtains meso-porous alumina-P123 or the former powder of F127 composite after a period of time.By stirring and dissolving under a certain amount of organic amine room temperature in ethanol, getting the above-mentioned former powder of 0.2-3g joins in the ethanolic solution of this organic amine, under room temperature, fully stir after dipping, through centrifugation, ethanol washing, except masterplate agent and dry, make amino functional meso-porous alumina adsorbing material.
Described Pluronic triblock copolymer is P123(EO
20pO
70eO
20), F127(EO
106pO
70eO
106) or their mixture.
Described organic amine is the mixture of any one or they in TEPA, polymine and triethanolamine, and quality is 2 ~ 10g.
Described organic amine solvent is ethanol, and volume is 20 ~ 100ml.
The baking temperature of described amino functional meso-porous alumina base impregnation product is that 80 ~ 100 ℃, drying time are 6 ~ 12h.
The difunctional adsorbent of described amino functional meso-porous alumina base is used for to hypertoxic pollutant Cr (VI) and main greenhouse gas CO
2absorption.
When the described difunctional adsorbent of amino functional meso-porous alumina base is applied to the absorption of hypertoxic pollutant Cr (VI), its concentration is that the pH of 10 ~ 200mg/l, solution is 2 ~ 6.
The fundamental reaction principle of foundation of the present invention is: on the one hand, the amino of introducing in functionalization process is the positively charged NH of protonated formation in acidic aqueous solution
3 +, then mainly by the Cr of electrostatic interaction adsorption band negative electrical charge
2o
7 2-; On the other hand, amino by with CO
2form the compounds such as carbaminate, realize CO
2absorption fix.At meso-porous alumina-P123 or the former powder preparatory phase of F127 composite, by the structure-directing effect of Pluronic triblock copolymer, form meso-hole structure; In amino functional process, having of Pluronic triblock copolymer is beneficial to the dispersion of organic amine on carrier, thereby effectively promotes prepared amino functional product to Cr (VI) and CO
2absorption.
The present invention compares with the technology of preparing of existing porosu solid adsorbent, has following major advantage:
1) technique is simple, and a step that has realized template removal and amino functional completes;
2) mild condition, avoids adopting harsh reaction condition, has especially saved the process that Pluronic triblock copolymer is removed in roasting, has significantly reduced energy consumption;
3) the functional mesoporous alumina matrix composite of prepared amino functional is to main greenhouse gas CO
2all there is good absorption property with the hypertoxic pollutant Cr (VI) in water body, there is difunctional characterization of adsorption.
4) prepared amino functional meso-porous alumina based composites is exceedingly fast to the rate of adsorption of Cr (VI), and adsorbance is very large.
Accompanying drawing explanation
Fig. 1 is that the prepared amino functional meso-porous alumina adsorbing material of embodiment 1 ~ 6 is at room temperature to CO
2adsorption isotherm.
Fig. 2 is that the prepared meso-porous alumina-P123 of embodiment 1 ~ 6 or the former powder of F127 composite are at room temperature to CO
2adsorption isotherm.
Fig. 3 is the at room temperature curve of adsorption kinetics to Cr (VI) of the prepared amino functional meso-porous alumina adsorbing material of embodiment 1 and the former powder of meso-porous alumina;
Fig. 4 is the at room temperature adsorption isotherm to Cr (VI) of the prepared amino functional meso-porous alumina adsorbing material of embodiment 1 and the former powder of meso-porous alumina.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, and these embodiment are only the descriptions to better embodiment of the present invention, but are not limited to described content below.
embodiment 1:
First by 3g P123 at room temperature fully stirring and dissolving in 20ml ethanol.Then, add the red fuming nitric acid (RFNA) of 1.5ml, 65wt%, under room temperature, be uniformly mixed.Then, add 3.06g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain the former powder of meso-porous alumina-P123.Further at room temperature by 3g TEPA stirring and dissolving in 20ml ethanol, form the ethanolic solution of TEPA, and add the former powder of 3g meso-porous alumina-P123, at room temperature fully stir after dipping 24h, dry 12h at the washing of centrifugation, ethanol and 80 ℃, makes amino functional meso-porous alumina based composites successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.70mmol/g(Fig. 1), and under same test condition the former powder of meso-porous alumina-P123 to CO
2adsorbance be only 0.07mmol/g(Fig. 2).
Further with potassium bichromate, prepare Cr (VI) solution of 100mL, 50mg/L, and with hydrochloric acid solution, its pH is adjusted to 2.0, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records Cr in filtrate (VI) is 3.1mg/L, and adsorption rate is 94.1%, adsorbance is 23.5mg/g.
embodiment 2:
First by 1g F127 at room temperature fully stirring and dissolving in 20ml ethanol.Then, add the concentrated hydrochloric acid of 1.5ml, 37wt%, under room temperature, be uniformly mixed.Then, add 2.04g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain the former powder of meso-porous alumina-F127.Further at room temperature by 4g triethanolamine stirring and dissolving in 100ml ethanol, form the ethanolic solution of triethanolamine, and add the former powder of 2g meso-porous alumina-F127, at room temperature fully stir after dipping 12h, dry 6h at the washing of centrifugation, ethanol and 100 ℃, makes amino functional meso-porous alumina adsorbing material successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.54mmol/g(Fig. 1), and under same test condition the former powder of meso-porous alumina-F127 to CO
2adsorbance be only 0.06mmol/g(Fig. 2).
Further with potassium bichromate, prepare the potassium bichromate solution of the Cr (VI) of 100mL, 200mg/L, and with hydrochloric acid solution, its pH is adjusted to 3.0, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records Cr in filtrate (VI) is 105.4mg/L, and adsorption rate is 47.3%, adsorbance is 47.3mg/g.
embodiment 3:
First by the mixture of 0.4g P123 and 0.4g F127 at room temperature fully stirring and dissolving in 10ml ethanol.Then, add the concentrated hydrochloric acid of 0.9ml, 37wt%, under room temperature, be uniformly mixed.Then, add 1g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain meso-porous alumina-P123 and the former powder of F127.Further at room temperature by 5g polymine stirring and dissolving in 50ml ethanol, form the ethanolic solution of polymine, and add 1.1g meso-porous alumina-P123 and the former powder of F127, at room temperature fully stir after dipping 6h, dry 12h at the washing of centrifugation, ethanol and 60 ℃, makes amino functional meso-porous alumina adsorbing material successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.51mmol/g(Fig. 1), and under same test condition meso-porous alumina-P123 and the former powder of F127 to CO
2adsorbance be only 0.09mmol/g(Fig. 2).
Further with potassium bichromate, prepare the potassium bichromate solution of the Cr (VI) of 100mL, 10mg/L, and with hydrochloric acid solution, its pH is adjusted to 6.0, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records Cr in filtrate (VI) is 0mg/L, and adsorption rate is 100%, adsorbance is 5.0mg/g.
embodiment 4:
First by 1g F127 at room temperature fully stirring and dissolving in 20ml ethanol.Then, add the red fuming nitric acid (RFNA) of 1.5ml, 65wt%, under room temperature, be uniformly mixed.Then, add 2.04g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain the former powder of meso-porous alumina-F127.Further at room temperature by 2g polymine and 2g triethanolamine stirring and dissolving in 50ml ethanol, form the ethanolic solution of polymine and triethanolamine, and add the former powder of 2g meso-porous alumina-F127, at room temperature fully stir after dipping 12h, through centrifugation, ethanol washing and 100 ℃ of dry 12h, make amino functional meso-porous alumina adsorbing material successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.21mmol/g(Fig. 1), and under same test condition the former powder of meso-porous alumina to CO
2adsorbance be only 0.09mmol/g(Fig. 2).
Prepare 100 mL, containing the potassium bichromate solution of 100 mg/L Cr (VI), the pH of solution is adjusted to 2.0 with hydrochloric acid solution, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records chromium in filtrate is 25.4 mg/L, and adsorption rate is that 74.6 %, adsorbance are 37.3 mg/g.
embodiment 5:
First by 0.01g P123 in the abundant stirring and dissolving of lower room temperature in 1ml ethanol.Then, add the red fuming nitric acid (RFNA) of 0.1ml, 65wt%, under room temperature, be uniformly mixed.Then, add 0.4g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain the former powder of meso-porous alumina-P123.Further at room temperature by 2g TEPA stirring and dissolving in 50ml ethanol, form the ethanolic solution of TEPA, and add the former powder of 0.2g meso-porous alumina-P123, at room temperature fully stir after dipping 24h, through centrifugation, ethanol washing and 80 ℃ of dry 12h, make amino functional meso-porous alumina adsorbing material successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.57mmol/g(Fig. 1), and under same test condition the former powder of meso-porous alumina-P123 to CO
2adsorbance be only 0.08mmol/g(Fig. 2).
The potassium bichromate solution of preparation 100mL, 20mg/L Cr (VI), the pH of solution is adjusted to 2.0 with hydrochloric acid solution, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records chromium in filtrate is 0mg/L, and adsorption rate is 100%, adsorbance is 10.0mg/g.
embodiment 6:
First by 1g F127 at room temperature fully stirring and dissolving in 20ml ethanol.Then, add the concentrated hydrochloric acid of 1.0ml, 37wt%, under room temperature, be uniformly mixed.Then, add 2.04g aluminium isopropoxide, under stirring at room, fully dissolve to obtain clear solution.Above-mentioned clear solution is put into 60 ℃ of baking ovens, after evaporation at constant temperature 48h, obtain the former powder of meso-porous alumina-F127.Further at room temperature by 2g TEPA stirring and dissolving in 80ml ethanol, form the ethanolic solution of TEPA, and add the former powder of 2g meso-porous alumina-F127, at room temperature fully stir after dipping 12h, through centrifugation, ethanol washing and 80 ℃ of dry 12h, make amino functional meso-porous alumina adsorbing material successively.Prepared amino functional meso-porous alumina based composites is at room temperature to CO
2adsorbance be 0.48mmol/g(Fig. 1), and under same test condition the former powder of meso-porous alumina to CO
2adsorbance be only 0.06mmol/g(Fig. 2).
The potassium bichromate solution of preparation 100mL, 40mg/L Cr (VI), the pH of solution is adjusted to 2.0 with hydrochloric acid solution, under stirring, moderate strength adds the above-mentioned adsorbent of 0.2g subsequently, certain hour reaches after adsorption equilibrium, the residual concentration that records chromium in filtrate is 0.16mg/L, and adsorption rate is 99.6%, adsorbance is 19.9mg/g.
embodiment 7:
In order to investigate amino functional impact on Cr (VI) rate of adsorption on meso-porous alumina adsorbing material, done again that " embodiment 1
"cr (VI) curve of adsorption kinetics of prepared amino functional sample and the former powder of meso-porous alumina-P123, the preparation process of sample is as described in " embodiment 1 ".The adsorption kinetic data process is as follows:
The potassium bichromate solution of preparation 100mL, 50 mg/L Cr (VI), the pH of solution is adjusted to 2.0 with hydrochloric acid solution, under moderate strength stirs, add the above-mentioned amino functional sample of 0.2g subsequently, respectively 1,5,20,30,60 and sample during 90min and measure filtrate in the concentration (Fig. 3) of Cr (VI).
Adsorbent changes the former powder of meso-porous alumina-P123 into, repeats above-mentioned experimentation, the results are shown in Figure 3.
Fig. 3 demonstration, after amino functional, the adsorption rate of meso-porous alumina adsorbing material obviously improves, and the time that reaches adsorption equilibrium significantly shortens, and the 90min before functionalization is sharply reduced to the 30min functionalization.Especially after amino functional, meso-porous alumina adsorbing material can reach the more than 90% of its balance clearance to the clearance of Cr (VI) in 1min, has the adsorption dynamics adsorption kinetics being exceedingly fast.
embodiment 8:
In order to investigate the impact of amino functional on meso-porous alumina sill absorption Cr (VI) performance, also done that " embodiment 1
"cr (VI) adsorption isotherm of prepared amino functional sample and the former powder of meso-porous alumina-P123, the preparation process of sample is as described in " embodiment 1 ".Adsorption isotherm experimentation is as follows:
Preparation 100mL, respectively containing 10,20,50,100,150 and each two parts of the potassium bichromate solutions of 200mg/L, the pH of solution is adjusted to 2.0 with hydrochloric acid solution, the parallel above-mentioned amino functional sample of 0.2g and the former powder of meso-porous alumina-P123 of adding respectively under moderate strength stirs subsequently, after 2h, reach adsorption equilibrium, sample and measure the concentration (Fig. 4) of Cr in filtrate (VI).
Fig. 4 shows, after amino functional, the adsorbance of meso-porous alumina adsorbing material obviously improves, and the 23.5mmol/g of saturated extent of adsorption former powder of meso-porous alumina-P123 before functionalization is significantly increased to the 59.9mmol/g of sample functionalization.Especially the clearance that amino functional sample is less than 50mg/L solution to Cr (VI) concentration can reach 100%.
CO under room temperature in above-described embodiment 1 ~ 6
2the TriStar II of new generation 3020 type adsorption analysis instrument that the mensuration of adsorbance adopts U.S. Merck & Co., Inc to produce, Cr under room temperature (VI) concentration adopts diphenyl carbazide spectrophotometry to measure, and the ultraviolet-uisible spectrophotometer adopting is Japanese Shimadzu UVmini-1240 type.
It is important to emphasize, above-described embodiment be only used to clearly to illustrate the present invention does for example, and the not restriction completely to embodiment.Those of ordinary skill in the field can also make other multi-form change on the basis of the above description; here cannot also without the embodiment to all, provide embodiment, but the apparent change of being amplified out is thus still in protection scope of the present invention.
Claims (7)
1. the preparation method of the difunctional adsorbent of amino functional meso-porous alumina base, it is characterized in that comprising the following steps: at room temperature fully stir, 0.01-3g Pluronic triblock copolymer is dissolved in 1-20ml ethanol, and described Pluronic triblock copolymer is P123 or F127; In this solution, add the red fuming nitric acid (RFNA) of 0.1-1.5ml, 65wt% or the concentrated hydrochloric acid of 37wt%, under room temperature, fully stir, obtain mixed solution; Then, in described mixed solution, add 0.4-3.06g aluminium isopropoxide, at room temperature fully stir and form clear solution; Described clear solution is put into baking oven evaporation at constant temperature, obtain meso-porous alumina-P123 or the former powder of F127 composite; Get the above-mentioned former powder of 0.2-3g and join in the ethanolic solution of organic amine, under room temperature, fully stir dipping, through centrifugation, ethanol washing, except masterplate agent and dry, make the difunctional adsorbent of amino functional meso-porous alumina base.
2. the preparation method of the difunctional adsorbent of amino functional meso-porous alumina base according to claim 1, it is characterized in that described organic amine is the mixture of any one or they in TEPA, polymine and triethanolamine, quality is 2 ~ 10g.
3. the preparation method of the difunctional adsorbent of amino functional meso-porous alumina base according to claim 1, the volume that it is characterized in that described ethanol is 20 ~ 100ml.
4. the preparation method of the difunctional adsorbent of amino functional meso-porous alumina base according to claim 1, is characterized in that the mixing time of the described described former powder of organic amine ethanolic solution dipping is 6 ~ 24h.
5. the preparation method of the difunctional adsorbent of amino functional meso-porous alumina base according to claim 1, the baking temperature that it is characterized in that described amino functional meso-porous alumina base impregnation product is that 80 ~ 100 ℃, drying time are 6 ~ 12h.
6. the application of the adsorbent that in claim 1 to 5 prepared by the preparation method of the difunctional adsorbent of arbitrary described amino functional meso-porous alumina base, is characterized in that prepared amino functional meso-porous alumina base adsorbent is for adsorbing hypertoxic pollutant Cr (VI) and greenhouse gases CO
2.
7. the application of the difunctional adsorbent of amino functional meso-porous alumina base according to claim 6, it is characterized in that prepared amino functional meso-porous alumina base adsorbent when adsorbing hypertoxic pollutant Cr (VI), its concentration is 10 ~ 200mg/l, and the pH of solution is 2 ~ 6.
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| CN103406092B (en) * | 2013-08-28 | 2015-12-09 | 武汉理工大学 | The mesoporous γ of a kind of functional amido-Al 2o 3the preparation method of adsorbent |
| CN103521187B (en) * | 2013-10-25 | 2015-12-02 | 武汉理工大学 | Under normal temperature, organic amine modifies meso-porous alumina CO 2the preparation method of adsorbent |
| CN105344336A (en) * | 2015-12-08 | 2016-02-24 | 无锡拓能自动化科技有限公司 | Preparation method of sulfur dioxide adsorbent |
| CN106512949A (en) * | 2016-10-25 | 2017-03-22 | 武汉理工大学 | Preparation method of high-selectivity amino-functionalized mesoporous gamma-aluminum oxide-based composite adsorbent |
| CN107081132B (en) * | 2017-05-19 | 2020-06-19 | 武汉理工大学 | Preparation method of amino functionalized gamma-aluminum oxide film |
| CN108163995A (en) * | 2017-12-25 | 2018-06-15 | 江苏世邦生物工程科技有限公司 | Composite biological agent for city river sewage disposal and its preparation method and application |
| CN109216548A (en) * | 2018-10-22 | 2019-01-15 | 东莞理工学院 | A kind of perovskite solar battery scrapes coating preparation method |
| CN113769703A (en) * | 2021-08-20 | 2021-12-10 | 绍兴蓝竹新材料科技有限公司 | Preparation method of amino functionalized ordered mesoporous silica adsorbent |
| CN115779849B (en) * | 2022-11-21 | 2024-03-22 | 南京工业大学 | Mesoporous alumina adsorbent and preparation method and application thereof |
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| CN102698704A (en) * | 2012-05-22 | 2012-10-03 | 武汉理工大学 | Preparation method of mesoporous alumina composite adsorbent functionalized by alkali metal |
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