CN1132694C - Nanotitanium dioxide column supported bentonite and its preparation method - Google Patents
Nanotitanium dioxide column supported bentonite and its preparation method Download PDFInfo
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- CN1132694C CN1132694C CN 01125659 CN01125659A CN1132694C CN 1132694 C CN1132694 C CN 1132694C CN 01125659 CN01125659 CN 01125659 CN 01125659 A CN01125659 A CN 01125659A CN 1132694 C CN1132694 C CN 1132694C
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Abstract
The present invention relates to nanometer TiO2 column-supported bentonite and a preparation method thereof. Nanometer TiO2 column-supported bentonite is a novel substance in which a TiO2 column-supported substance whose grain size is smaller than 1 nm is inserted into an interlayer channel of betonite. The preparation method comprises the following steps: taking anhydrous alcohol, butyl titanate and nitric acid whose concentration is 1M in a molar ratio of (5-18): 1:1.6; adding the butyl titanate into the anhydrous alcohol, and stirring the mixture to obtain a light-yield solution (A); dripping (A) into the nitric acid, and stirring the mixture to obtain a transparent solution; regulating the solution by using strong alkali to make a pH value reach 1 to 2.5; simultaneously and fully stirring the mixture to obtain a transparent solution (B); taking bentonite whose dose is 5 to 15 times of that of the mole number of the butyl titanate; moistening the bentonite by using water; adding the bentonite into the solution (B); stirring the mixture for more than 1 hour; carrying out solid-liquid separation and water washing until the pH value of supernatant fluid is from 6 to 7; carrying out baking and grinding at a temperature lower than 80 DEG C; finally calcining the mixture for 2 to 5 hours at a temperature of 400 to 700 DEGC, and grinding the mixture into powder after cooling. The nanometer TiO2 column-supported bentonite is a photocatalyst used for catalyzing and degrading organic pollutants with high efficiency.
Description
Technical field
The present invention relates to a kind of Nanotitanium dioxide column supported bentonite and preparation method thereof.It is a kind of can efficient degradation the photochemical catalyst of organic pollution, be mainly used in environmental improvement, as the water purified treatment of industrial wastewater, sanitary sewage etc.
Background technology
In the environmental improvement process, meet the organic pollution that some are difficult to degrade through regular meeting, it directly has influence on the effect of environmental improvement, even governance process can't be carried out.In recent years, advanced oxidation processes, particularly photocatalytic-oxidation metallization processes have caused people's common concern in the unique advantage aspect the processing persistent organic pollutants.The research of high efficiency photocatalyst is to study one of focus both at home and abroad always, discover, the photocatalytic activity of semiconductor light-catalyst increases along with reducing of grain diameter, especially when the particle diameter of semiconductor grain during less than 10nm, quantum size effect is obvious, the separative efficiency of photic electronics and photo-induced hole improves, and the generation probability of oxide of high activity species-hydroxyl increases, thereby improves reaction rate greatly.The scientific research personnel takes a hint from this theory, and is key subjects with the semiconductor grain of developing this quantum size, to solve the difficult problem that persistent organic pollutants are administered in the current environmental improvement.
The scientific research personnel is when solving an above-mentioned difficult problem, consider another problem again, the particle diameter of semiconductor grain that is quantum size is too little, so be difficult to from suspended state, it be separated, so that after use, it can't be reclaimed, thereby cause waste, the cost of environment protection treating is improved greatly, and be difficult to be promoted application.Therefore need obtain a kind of effect that can play the efficient catalytic degradable organic pollutant, can after catalytic reaction, be separated the photochemical catalyst that reclaims quickly and easily again.
Lamellar compound or lamellar clay, because the layer post and the microcellular structure of their uniquenesses, cause people's attention at catalytic field, people imagination designs the viewpoint of catalyst, regulation and control catalytic performance from molecule and atomic level, embeds semiconductive particles at the lamellar clay interlayer and may demonstrate very high photocatalysis performance.
Summary of the invention
The objective of the invention is to fill up above-mentioned blank of the prior art, a kind of Nanotitanium dioxide column supported bentonite and preparation method thereof is provided.This material has the effect of energy efficient catalytic degradable organic pollutant, is easy to separate characteristics such as recovery again; Simultaneously, its preparation method has simple possible again, materials are convenient and lower-price characteristic.
The structure of Nanotitanium dioxide column supported bentonite of the present invention, be a kind of be that titanium dioxide below the 1nm is pillared thing with the particle diameter, be embedded in the novel substance of passage between bentonite bed with this pillared thing.
Nanotitanium dioxide column supported bentonite of the present invention is a kind of photochemical catalyst that is used for catalyze and degrade organic pollutants.
The preparation method of Nanotitanium dioxide column supported bentonite of the present invention is as follows:
1) getting absolute ethyl alcohol, butyl titanate, concentration is that the nitric acid of 1M (being 1mol/l) (is HNO
3), their mol ratio is (5-18): 1: 1.6, stand-by;
2) earlier above-mentioned off-the-shelf butyl titanate is added in the absolute ethyl alcohol, makes it to form flaxen solution (A) through fully stirring; Then this solution (A) is added drop-wise in the above-mentioned nitric acid, generates transparent solution through vigorous stirring; After this be not higher than the pH value that the highly basic (as NaOH, potassium hydroxide etc.) of 1M (that is 1mol/l) removes to regulate this solution with concentration again, make the pH value reach 1-2.5, fully stir simultaneously, until generating clear solution (B), stand-by;
3) take bentonite, its amount for (5-15) of butyl titanate molal quantity doubly, and its measurement unit is with g (i.e. gram) expression, and after using water with the same quality of bentonite fully to soak into, it is added in the above-mentioned clear solution (B), and is not less than 1 hour abundant stirring; Again it being carried out Separation of Solid and Liquid, washing, is 6-7 until the pH of its supernatant value; Again this mixture is dried not being higher than under 80 ℃ the temperature then, row is fully fine ground again after the oven dry; After this again 400-700 ℃ temperature lower calcination 2-5 hour; At last, treat to be crushed into powder again after its cooling, be Nanotitanium dioxide column supported bentonite of the present invention, and be placed on the dark place and preserve and to get final product.
The advantage of Nanotitanium dioxide column supported bentonite of the present invention is: 1) it is a kind ofly to have inlayed the nano-scale photocatalyst that particle diameter is about semiconductive particles below the 1nm at bentonitic interlayer, it has higher catalytic degradation organic compound activity, particularly quantum size effect is obvious, photic electronics raises with the probability that separates in hole, the hydroxyl generating rate improves, thereby has improved photocatalytic degradation speed; 2) Nanotitanium dioxide column supported bentonite of the present invention has the general general character of loaded catalyst, promptly is easy to it is separated recovery from suspended state; 3) according to the heterogeneous reaction theory, response matrix concentration is high more, and reaction rate is fast more; Bentonite itself has absorption property preferably, can create a high local concentrations " subenvironment " around catalyst, thereby further improve the degradation rate of organic pollution.
In sum, Nanotitanium dioxide column supported bentonite of the present invention is the photochemical catalyst of the high-speed and high-efficiency degradation of organic substances thirsted for of a kind of efforts at environmental protection person of the world today, and it also has characteristics such as easy recovery.
Nanotitanium dioxide column supported bentonite preparation method's of the present invention advantage is:
1) its materials kind is few, simple to operate, and control is convenient, and device therefor is simple, versatility is good;
2) its materials amount is in the majority with bentonite, this soil is to be the clay of laminar silicate mineral of main component with the montmorillonite, and it is comparatively extensive to distribute at occurring in nature, draws materials easily, cheap, therefore make the manufacturing cost of Nanotitanium dioxide column supported bentonite of the present invention lower.
Description of drawings
Fig. 1 is the TiO after purification bentonite, the 50 ℃ of processing
2/ bentonite sample, and the TiO after 500 ℃ of heat treatment
2The XRD figure spectrum (angle of diffraction 3-70 °) of/bentonite sample.
The specific embodiment
Embodiment 1. Nanotitanium dioxide column supported bentonites of the present invention, be a kind of be that titanium dioxide below the 1nm is received and is pillared thing with the particle diameter, be embedded in the novel substance of passage between bentonite bed with this pillared thing.Because the limitation of experiment test technology, and because of the interlayer structure of Nanotitanium dioxide column supported bentonite of the present invention too little, so fail to represent, but its titanium dioxide granule particle size can be done following reckoning by Fig. 1 and in conjunction with relevant theory with the Electronic Speculum picture.
Fig. 1 is that the XRD of three kinds of samples composes entirely, wherein curve I be that the bentonitic XRD of expression composes entirely, curve II be expression with calcining heat be that the XRD of the titanium dioxide pillared bentonite sample of 50 ℃ of processing composes entirely, curve III represents with calcining heat to be that the XRD of 500 ℃ of processing samples of the present invention compose entirely.D (001) is the ultimate range corresponding to gap between bentonite bed, and angle of diffraction 2 θs corresponding with d (001) are respectively: pure bentonite is that 5.88 °, calcining heat are that 50 ℃ sample is that 5.60 °, calcining heat are that sample of the present invention after 500 ℃ of processing is 9.06 °.Its corresponding spacing is respectively 1.502nm and 1.577nm, 0.982nm.From then on as can be seen, in the sample after 50 ℃ of processing, bentonitic 001 diffraction maximum moves to low-angle (5.60 °), and ion-exchange has taken place this hydrated cation that shows cation and butyl titanate hydrolysis generation between bentonite bed, and hydrated cation enters interlayer; Because the particle diameter of hydrated cation is obviously greater than the Na between former bentonite bed
+With Ca
2+Deng inorganic cation, thereby bentonite is strutted stratification, the interlayer channel height is obviously increased; And after 500 ℃ of processing, represent the diffraction maximum of product layer spacing size to move to high angle (9.06 °), also we can say, hydrated cation is in air after 500 ℃ of calcination processing, originally served as the compound this moment of the decomposition fully of pillar at interlayer, serving as the pillar that supports laminate for it should be the TiO that interlayer forms after oxidation Decomposition
2Particle.In addition, because its interlamellar spacing d (001) only is 0.982nm, therefore, the TiO of interlayer
2The free height of pillar is below 1nm, so the present invention is with the TiO below the particle diameter 1nm
2The formed Nanotitanium dioxide column supported bentonite of the pillared layered bentonite of particle.
The preparation method of present embodiment Nanotitanium dioxide column supported bentonite is as follows:
1) getting fully absolute ethyl alcohol, butyl titanate, concentration is that the nitric acid of 1M (being 1mol/l) (is HNO
3), their mol ratio is 5.5: 1: 1.6; Stand-by;
2) earlier above-mentioned stand-by butyl titanate is added in the absolute ethyl alcohol, makes it to form flaxen solution (A) through fully stirring; Then this solution (A) is added drop-wise in the above-mentioned nitric acid, generates transparent solution through vigorous stirring; At this moment be not higher than the pH value that highly basic-NaOH of 1M (that is 1mol/l) removes to regulate this solution with concentration again, make this pH value reach 1.5, fully stir simultaneously, until generating clear solution (B), stand-by;
3) take bentonite, its amount is 10 times of butyl titanate molal quantity, and its measurement unit is with g (i.e. gram) expression, and after using water with the same quality of bentonite fully to soak into, it is added in the above-mentioned clear solution (B), and is not less than 1 hour abundant stirring; Again it being carried out Separation of Solid and Liquid, washing, is 6 until the pH of its supernatant value; Again this mixture is dried not being higher than under 80 ℃ the temperature then, row is fully fine ground again after the oven dry; After this again 510 ℃ temperature lower calcination 3.8 hours; At last, treat to be crushed into powder again after its cooling, be of the present invention, and be placed on the dark place and preserve and to get final product with Nanotitanium dioxide column supported bentonite.
Different is that it is tested with the example (I, II, III, IV, V, VI, VII, VIII, IX, X) of joining of one group of ten different molal quantity for embodiment 2. and embodiment 1, and prepared Nanotitanium dioxide column supported bentonite of the present invention is identical.The molal quantity such as the following table one of this each material of group:
Table one
| The material name | Molal quantity | |||||||||
| I | II | III | IV | V | VI | VII | VIII | IX | X | |
| Absolute ethyl alcohol | 5 | 6 | 8 | 10 | 12 | 14 | 15 | 16 | 17 | 18 |
| Butyl titanate | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Nitric acid (1M) | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
Different is for embodiment 3. and embodiment 1; Adopt its corresponding calcination time of different calcining heats of one group of seven example (I, II, III, IV, V, VI, VII) among its preparation method, the result who makes is basic identical.This is organized its corresponding calcination time of each routine calcining heat and is listed in the table below two:
Table two
| Example | I | II | III | IV | V | VI | VII |
| Calcining heat (℃) | 400 | 450 | 500 | 550 | 600 | 650 | 700 |
| Calcination time (hour) | 5.0 | 4.5 | 4.0 | 3.5 | 2.5 | 2.2 | 2.0 |
Different is the batching (as shown in Table 1) that it had both adopted one group of ten different molal quantity among the embodiment 2 for embodiment 4. and embodiment 1, adopted its corresponding calcination time of different calcining heats (as shown in Table 2) among the embodiment 3 again, the result of its preparation is also basic identical.
Claims (3)
1, a kind of Nanotitanium dioxide column supported bentonite is characterized in that: be a kind of be that titanium dioxide below the 1nm is pillared thing with the particle diameter, be embedded in the material of passage between bentonite bed with this pillared thing.
2, the preparation method as Nanotitanium dioxide column supported bentonite as described in claims 1 is:
1) getting absolute ethyl alcohol, butyl titanate, concentration is the nitric acid of 1M, and their mol ratio is (5-18): 1: 1.6, stand-by;
2) earlier the above-mentioned butyl titanate that is equipped with of getting is added in the absolute ethyl alcohol, makes it to form flaxen solution (A) through fully stirring; Then this solution (A) is added drop-wise in the above-mentioned nitric acid, generates transparent solution through vigorous stirring; At this moment be not higher than the pH value that the highly basic of 1M removes to regulate this solution with concentration again, make this pH value reach 1-2.5, fully stir simultaneously, until generating clear solution (B), stand-by;
3) take bentonite, its amount for (5-15) of butyl titanate molal quantity doubly, and its measurement unit represents with g, and after using water with the same quality of bentonite fully to soak into, it is added in the above-mentioned clear solution (B), and is not less than 1 hour abundant stirring; Again it being carried out Separation of Solid and Liquid, washing, is 6-7 until the pH of its supernatant value; Again this mixture is dried not being higher than under 80 ℃ the temperature then, row is fully fine ground again after the oven dry; After this again 400-700 ℃ temperature lower calcination 2-5 hour; At last, treat to be crushed into powder again after its cooling, be Nanotitanium dioxide column supported bentonite of the present invention, and be placed on the dark place and preserve and to get final product.
3, as the purposes of Nanotitanium dioxide column supported bentonite as described in claims 1, it is that a kind of catalytic degradation that is used for pollutes organic photochemical catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01125659 CN1132694C (en) | 2001-08-27 | 2001-08-27 | Nanotitanium dioxide column supported bentonite and its preparation method |
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| CN 01125659 CN1132694C (en) | 2001-08-27 | 2001-08-27 | Nanotitanium dioxide column supported bentonite and its preparation method |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386144C (en) * | 2005-03-12 | 2008-05-07 | 山西大学 | Process for preparing nano titanium dioxide bentonite composite material |
| CN100444960C (en) * | 2005-07-08 | 2008-12-24 | 中国科学院广州地球化学研究所 | Organic decoration nano-titanium column clay, and its prepn. method |
| CN100413805C (en) * | 2006-06-27 | 2008-08-27 | 上海电力学院 | Method for preparing nano MgO-TiO2-Al2O3/mesoporous montmorillonite composites |
| CN101104525B (en) * | 2007-08-06 | 2010-05-26 | 浙江大学 | Method for preparing anatase type bentonite-base porous titanium dioxide nano material |
| CN102113519B (en) * | 2009-12-31 | 2013-07-17 | 西南科技大学 | Method for preparing and using pillaring layer bearing/doped semiconductor type multifunctional composite material |
| CN102614859A (en) * | 2012-02-23 | 2012-08-01 | 常州水木环保科技有限公司 | Synthesis method of load type carbon modified titanium dioxide photocatalyst |
| CN104448952B (en) * | 2014-11-17 | 2016-07-27 | 哈密市神土新材料科技有限公司 | The preparation method with the bentonite inorganic gel of photocatalysis performance |
| CN105778878B (en) * | 2016-04-22 | 2018-10-02 | 东北大学 | A kind of degradable polypropylene amide oil displacement agent and preparation method thereof |
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