CN100413805C - Method for preparing nano MgO-TiO2-Al2O3/mesoporous montmorillonite composites - Google Patents
Method for preparing nano MgO-TiO2-Al2O3/mesoporous montmorillonite composites Download PDFInfo
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- CN100413805C CN100413805C CNB2006100281922A CN200610028192A CN100413805C CN 100413805 C CN100413805 C CN 100413805C CN B2006100281922 A CNB2006100281922 A CN B2006100281922A CN 200610028192 A CN200610028192 A CN 200610028192A CN 100413805 C CN100413805 C CN 100413805C
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Abstract
The present invention discloses a method for preparing nanometer MgO-TiO2-Al2O3/meson-porous smectite composite material, which comprises: firstly, tetrabutyl titanate is added into absolute alcohol to form light yellow solution, the light yellow solution is added into nitric acid to generate transparent solution, and then, NaOH solution is used for regulation to generate new transparent solution for standby application; secondly, purified sodium base smectite is taken and is sufficiently immersed in water, and then, hexadecyl trimethyl ammonium bromide is added into the sodium base smectite; after 12 to 24 hours of reaction, products are mixed with the solution generated in the first step, magnesium nitrate and aluminum nitrate are added, and the molar ratio of magnesium nitrate to aluminum nitrate is 0.5 to 1.5; the NaOH solution is titrated, solid is separated from liquid, and then, water washing is carried out; thirdly, mixture prepared in the second step is dried at 60 to 100 DEG C and then roasted at 400 to 500 DEG C for 2 to 4 hours. The present invention provides composite material with simple preparing step, low cost and favorable heat stability. The material can remove mercury and other heavy metal pollutants and can be widely used in the environment protective industrial fields of waste water treatment and smoke gas purification.
Description
Technical field
The present invention relates to a kind of with multivariant oxide MgO-TiO
2-Al
2O
3Prepare the method for high performance composite with montmorillonite, this material can be widely used in environment-protecting industrial fields such as sewage disposal, gas cleaning.
Background technology
The coal in China consumption is big, and the environmental pollution of Yin Faing is particularly serious thus.Though the heavy metal contaminants content of coal fired power generation discharging is few, and ecotope is had persistent toxic action.In addition, industrial preparation synthetic gas, coal gas of high temperature, various industry burning gas process also all need to solve the problem that removes heavy metal contaminants.Solve such problem at present, use the activated carbon adsorption material usually, yet the activated carbon adsorption material resources is in short supply, the cost height, bad to the selectively removing effect of heavy metal contaminants, it is low to remove precision.Sound solution is not found in the purification of contaminant trace species at present as yet.Both at home and abroad the traces of heavy metals pollutant control is mainly concentrated in the research, development and application of novel material.In recent years, the development trend of nano material is just synthetic from simple material, the exploration at random of performance is to stressing according to the multi-functional aspect of application build and tilting, at in the environmental protection field such as the improvement of heavy metal contaminants, the exploitation nano composite material has been important and urgent task.
Summary of the invention
It is simple that technical problem to be solved by this invention provides a kind of preparation process, the nano-MgO-TiO of with low cost and Heat stability is good
2-Al
2O
3/ mesoporous montmorillonite matrix material, this material can remove heavy metal contaminants such as mercury, is widely used in environment-protecting industrial fields such as sewage disposal, gas cleaning.
The technical solution used in the present invention: a kind of nano-MgO-TiO
2-Al
2O
3The preparation method of/mesoporous montmorillonite matrix material comprises the following steps:
A. be 10～15: 1～5 according to mol ratio: 1.6～20.6 prepare dehydrated alcohol, tetrabutyl titanate and nitric acid, the concentration of nitric acid is 0.5～1mol/L, earlier tetrabutyl titanate is joined in the dehydrated alcohol, fully stir and make it to form yellow solution, then this yellow solution is added drop-wise in the nitric acid, vigorous stirring generates clear solution, after this be not higher than the pH value that the NaOH solution of 1mol/L is regulated this clear solution with concentration, make it to reach 1～3.5, fully stir simultaneously, it is stand-by to generate new clear solution;
B. get the na-montmorillonite of purification, water fully soaks into, then to wherein adding cetyl trimethylammonium bromide, the mole number of wherein said na-montmorillonite is 5～20 times of tetrabutyl titanate mole number, the mole number of cetyl trimethylammonium bromide is 2～5 times of montmorillonite mole number, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding mole number then is 0.2～1.0 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate mole number, the mol ratio of magnesium nitrate and aluminum nitrate is 0.5～1.5, carry out titration by excess NaOH solution, after treating that it fully reacts, with its solid-liquid separation, washing;
C. the mixture of step b preparation is dried under 60～100 ℃ of temperature, 400～500 ℃ of roasting temperatures 2～4 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.
Beneficial effect of the present invention, dislocation-free or low-dislocation-density zone that the present invention utilizes the nano particle small-size effect to be caused make matrix material reach high temperature resistance and high strength, utilize montmorillonite natural nano layer structure to make material reach cheap large-scale industrial and use.The present invention will be through the combination of oxides MgO-TiO that verifies repeatedly
2-Al
2O
3, stage by stage carry out the matrix material that reaction in is made high specific surface area, made full use of MgO-TiO
2-Al
2O
3And the synergy between the montmorillonite makes material surface form the multiple approaching active centre that fully exposes, is easy to, especially with TiO
2Be the active sites at center, extinction and form electron-hole pair, the Hg steam of oxidation zero-valent state is to its absorption, storage; With MgO and Al
2O
3For the active sites at center fully plays the effect of collaborative absorption, reaction, material has been brought into play the synergy at surperficial multicomponent reactive center when having high thermal stability, reached the high-precision purpose that removes the trace amount environment pollutent.The used main raw material of the present invention is cheapness and abundant mineral and compound, and preparation process is simple, controlled, does not relate to complex apparatus and operation, and cost is very low.The present invention carries out compoundization and porous with multivariant oxide and montmorillonite, has not only significantly improved the thermal stability of system, and use temperature reaches 550 ℃, and environmental friendliness.
Embodiment
The present invention is described in further detail a kind of nano-MgO-TiO below by embodiment
2-Al
2O
3The preparation method of/mesoporous montmorillonite matrix material, comprise the following steps: that a. is 10～15: 1～5 according to mol ratio: 1.6～20.6 prepare dehydrated alcohol, tetrabutyl titanate and nitric acid, the concentration of nitric acid is 1mol/L, earlier tetrabutyl titanate is joined in the dehydrated alcohol, fully stir and make it to form yellow solution, then this yellow solution is added drop-wise in the nitric acid, vigorous stirring generates clear solution, after this be not higher than the pH value that the NaOH solution of 0.5～1mol/L is regulated this clear solution with concentration, make it to reach 1～3.5, fully stir simultaneously, it is stand-by to generate new clear solution; B. get the na-montmorillonite of purification, water fully soaks into, then to wherein adding cetyl trimethylammonium bromide, the mole number of wherein said na-montmorillonite is 5～20 times of tetrabutyl titanate mole number, the mole number of cetyl trimethylammonium bromide is 2～5 times of montmorillonite mole number, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding mole number then is 0.2～1.0 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate mole number, the mol ratio of magnesium nitrate and aluminum nitrate is 0.5～1.5, carry out titration by excess NaOH solution, after treating that it fully reacts, with its solid-liquid separation, washing; C. the mixture of step b preparation is dried under 60～100 ℃ of temperature, 400～500 ℃ of roasting temperatures 2～4 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.The present invention provides a kind of ternary oxide combination to carry out the compound method for preparing novel material of nanometer scale in proportion with montmorillonite first, is mainly used in the improvement of environment contaminant trace species, especially has special and wide application in heavy metal fields such as removing mercury.Matrix material is realized environment remediation after having fixed pollutent, and strong to the adsorption of pollutent, even directly abandon, also secondary pollution must not take place.The present invention adopts Japanese D/Max of science one 2500VB2+/PCX x ray diffractometer x to analyze the diffraction peak that occurs in (XRD) research material Small angle zone, to judge or to confirm existing of meso-hole structure that the structural sheet spacing can be asked for by Bragg formula λ=2dsin θ; Adopt JEM one 2000EX type transmission electron microscope that material is carried out particle diameter and morphology analysis thereof; Adopt U.S. ASAP 2405 absorption instrument (BET method) to measure the material specific surface area.
Embodiment one
Measure mol ratio and be 10: 1: 5 dehydrated alcohol, tetrabutyl titanate, concentration is the nitric acid of 1mol/L, earlier tetrabutyl titanate is added in the dehydrated alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this NaOH solution that is not higher than 1mol/L with concentration is again regulated and to be made pH value reach 2, fully stirs simultaneously, and is stand-by until the generation clear solution.Get the na-montmorillonite of purification, its amount is 10 times of the tetrabutyl titanate mole number, and water fully soaks into, adding mole number again is the cetyl trimethylammonium bromide of 4 times of montmorillonites, through abundant stirring reaction after 12 hours, it is mixed with the above-mentioned clear solution that makes, 80 ℃ of vigorous stirring reactions 2 hours, adding mole number then is 0.6 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate, the mol ratio of magnesium nitrate and aluminum nitrate is 0.5, carry out titration by excess NaOH solution, treat that it fully reacts after, with its solid-liquid separation, washing, then this mixture is dried under 80 ℃ temperature, 400 ℃ roasting temperature 2 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.The interlamellar spacing of XRD determining is 3.15nm, and tem analysis oxide particle particle diameter is between 20-30nm, and the specific surface area that BET measures is 235m
2/ g.
Embodiment two
Measure mol ratio and be 15: 5: 1.6 dehydrated alcohol, tetrabutyl titanate, concentration is the nitric acid of 1mol/L, earlier tetrabutyl titanate is added in the dehydrated alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this NaOH solution that is not higher than 1mol/L with concentration is again regulated and to be made pH value reach 3, fully stirs simultaneously, and is stand-by until the generation clear solution.Get the na-montmorillonite of purification, its amount is 20 times of the tetrabutyl titanate mole number, and fully soak into the water of same quality, adding mole number again is the cetyl trimethylammonium bromide of 5 times of montmorillonites, through abundant stirring reaction after 12 hours, it is mixed with the above-mentioned clear solution that makes, 60 ℃ of vigorous stirring reactions 2 hours, adding mole number then is 1.0 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate, the mol ratio of magnesium nitrate and aluminum nitrate is 1.5, carry out titration by excess NaOH solution, treat that it fully reacts after, with its solid-liquid separation, washing, then this mixture is dried under 60 ℃ temperature, 400 ℃ roasting temperature 2 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.The interlamellar spacing of XRD determining is 3.10nm, and tem analysis oxide particle particle diameter is between 20-25nm, and the specific surface area that BET measures is 211m
2/ g.
Embodiment three
Measure mol ratio and be 12: 3: 20.6 dehydrated alcohol, tetrabutyl titanate, concentration is the nitric acid of 1mol/L, earlier tetrabutyl titanate is added in the dehydrated alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this NaOH solution that is not higher than 1mol/L with concentration is again regulated and to be made pH value reach 2, fully stirs simultaneously, and is stand-by until the generation clear solution.Get the na-montmorillonite of purification, its amount is 15 times of the tetrabutyl titanate mole number, and fully soak into the water of same quality, adding mole number again is the cetyl trimethylammonium bromide of 5 times of montmorillonites, through abundant stirring reaction after 24 hours, it is mixed with the above-mentioned clear solution that makes, 80 ℃ of vigorous stirring reactions 6 hours, adding mole number then is 1.0 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate, the mol ratio of magnesium nitrate and aluminum nitrate is 1, carry out titration by excess NaOH solution, treat that it fully reacts after, with its solid-liquid separation, washing, then this mixture is dried under 100 ℃ temperature, 500 ℃ roasting temperature 4 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.The interlamellar spacing of XRD determining is 2.68nm, and tem analysis oxide particle particle diameter is between 15-20nm, and the specific surface area that BET measures is 201m
2/ g.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. nano-MgO-TiO
2-Al
2O
3The preparation method of/mesoporous montmorillonite matrix material comprises the following steps:
A. be 10～15: 1～5 according to mol ratio: 1.6～20.6 prepare dehydrated alcohol, tetrabutyl titanate and nitric acid, the concentration of nitric acid is 0.5～1mol/L, earlier tetrabutyl titanate is joined in the dehydrated alcohol, fully stir and make it to form yellow solution, then this yellow solution is added drop-wise in the nitric acid, vigorous stirring generates clear solution, after this be not higher than the pH value that the NaOH solution of 1mol/L is regulated this clear solution with concentration, make it to reach 1～3.5, fully stir simultaneously, it is stand-by to generate new clear solution;
B. get the na-montmorillonite of purification, water fully soaks into, then to wherein adding cetyl trimethylammonium bromide, the mole number of wherein said na-montmorillonite is 5～20 times of tetrabutyl titanate mole number, the mole number of cetyl trimethylammonium bromide is 2～5 times of montmorillonite mole number, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding mole number then is 0.2～1.0 times magnesium nitrate and aluminum nitrate of tetrabutyl titanate mole number, the mol ratio of magnesium nitrate and aluminum nitrate is 0.5～1.5, carry out titration by excess NaOH solution, after treating that it fully reacts, with its solid-liquid separation, washing;
C. the mixture of step b preparation is dried under 60～100 ℃ of temperature, 400～500 ℃ of roasting temperatures 2～4 hours, promptly make nano-MgO-TiO subsequently
2-Al
2O
3/ mesoporous montmorillonite matrix material.
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|---|---|---|---|
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| CN102527367B (en) * | 2010-12-27 | 2014-11-26 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof |
| CN106943987B (en) * | 2017-04-10 | 2019-11-05 | 上海理工大学 | Mesoporous nano oxygen carrier and preparation method thereof |
| CN108745274B (en) * | 2018-05-29 | 2021-08-03 | 武汉大学 | Rectorite mesoporous material and preparation method and application thereof |
| CN113072094B (en) * | 2021-03-22 | 2022-02-15 | 安徽江淮汽车集团股份有限公司 | Polyolefin VOC (volatile organic compound) improved filler, preparation method thereof and polyolefin composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1341484A (en) * | 2001-08-27 | 2002-03-27 | 陈英旭 | Nanotitanium dioxide column supported bentonite and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341484A (en) * | 2001-08-27 | 2002-03-27 | 陈英旭 | Nanotitanium dioxide column supported bentonite and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 热处理对TiO2/膨润土纳米复合物结构及其光催化活性的影响. 杨晔，孙振世，陈英旭，袁骏.太阳能学报，第25卷第5期. 2004 |
| 热处理对TiO2/膨润土纳米复合物结构及其光催化活性的影响. 杨晔，孙振世，陈英旭，袁骏.太阳能学报，第25卷第5期. 2004 * |
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