CN103950944B - A kind of layer mineral and nano titanium oxide intercalation composite material and preparation method thereof - Google Patents
A kind of layer mineral and nano titanium oxide intercalation composite material and preparation method thereof Download PDFInfo
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- CN103950944B CN103950944B CN201410169590.0A CN201410169590A CN103950944B CN 103950944 B CN103950944 B CN 103950944B CN 201410169590 A CN201410169590 A CN 201410169590A CN 103950944 B CN103950944 B CN 103950944B
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Abstract
The invention discloses a kind of layer mineral and nano titanium oxide intercalation composite material and preparation method thereof.It is a kind of matrix material that the titanium dioxide granule being inserted with nanometer grade between the crystalline texture layer of mineral is formed.Its preparation methods steps is as follows: 1) use mineral acid and reductive agent to activate and removal of impurities layer mineral; 2) dewater after acid activation, dry; 3) layer mineral and TiO 2 precursor co-ground, forms intercalation compound; 4) presoma is titanium hydroxide at inter-layer position in-situ hydrolysis; 5) titanium hydroxide forms nano titanium oxide in interlayer dehydration.Products therefrom is layer mineral and nano titanium oxide intercalation composite material.The present invention is successfully by TiO
2be intercalation in silicate minerals, its interlayer restraint force is utilized effectively to inhibit the reunion of nano particle, the product of preparation has broad prospect of application in photochemical catalysis, functional coating field, and its cost far below nano titanium oxide, and has higher chemically reactive.
Description
Technical field
The present invention relates to a kind of layer mineral and nano titanium oxide intercalation composite material and preparation method thereof.
Background technology
Nano titanium oxide has extensive use in functional paint, photocatalysis field.Prepare nano titanium oxide technical sophistication and cost is higher; In addition, the reuniting effect of nano particle can cause its performance to reduce.The technology of preparing of low cost and anti-agglomeration technology are the effective ways expanding fields of nano material application.Also someone attempts the carrier of natural mineral as nano titanium oxide, but just using the carrier of the surface of natural mineral as nano titanium oxide, uses surface recombination technology.The surface recombination of nano titanium oxide and natural mineral can reduce costs to a certain extent, but can not suppress the reunion between nano particle.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of layer mineral and nano titanium oxide intercalation composite material and preparation method thereof are provided.
Layer mineral and nano titanium oxide intercalation composite material are: a kind of matrix material that the titanium dioxide granule being inserted with nanometer grade between the crystalline texture layer of layer mineral is formed.
Described layer mineral is talcum, serpentine, kaolinite, halloysite, pyrophyllite, mica group, illite, chlorite, vermiculite, montmorillonite, and they are clay, mud stone, shale or massive ore in natural output form.
The step of the preparation method of layer mineral and nano titanium oxide intercalation composite material is as follows:
1) through the layer mineral of separating-purifying, add 5 to 10 times of weight, mass percentage concentration is the hydrochloric acid of 3% to 10%, add the V-Brite B of layer mineral weight 0.5% to 2% again, stir and make suspension ore pulp, react 6 ~ 24 hours at normal temperatures, period constantly stirs;
2) filtration or centrifuge dehydration, clean 2 ~ 4 times, and 60 to 80 ° of C are dried;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 0.8 to 1.5 weight part butyl (tetra) titanate, grinds 1 to 2 hour in high shear grinding machine after stirring;
4) add 3 to 5 times of water to stir, standing and reacting 4 to 10 hours, filter or centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 280 to 300 ° of C, constant temperature 2-4 hour, obtained layer mineral and nano titanium oxide intercalation composite material.
Described high shear grinding machine is ball mill, roller mill, rod mill or ball mill.
The present invention first utilizes the mechanical-chemical power of process of lapping, the precursor butyl (tetra) titanate of titanium dioxide is inserted the crystalline texture layer of layer mineral, by hydrolysis reaction, makes butyl (tetra) titanate be hydrolyzed to titanium hydroxide at interlayer, generates titanium dioxide by after calcined dehydration.Due to the constraint of crystalline texture layer, the titanium dioxide formed is the single-size of particle diameter about 5 nanometer.The layer mineral prepared by the present invention and nano titanium oxide intercalation composite material can replace nano titanium oxide in photochemical catalysis, functional coating field, and its cost far below nano titanium oxide, and has higher chemically reactive.
Embodiment
Layer mineral and nano titanium oxide intercalation composite material are: a kind of matrix material that the titanium dioxide granule being inserted with nanometer grade between the crystalline texture layer of layer mineral is formed.
Described layer mineral is talcum, serpentine, kaolinite, halloysite, pyrophyllite, mica group, illite, chlorite, vermiculite, montmorillonite, and they are clay, mud stone, shale or massive ore in natural output form.
The step of the preparation method of layer mineral and nano titanium oxide intercalation composite material is as follows:
1) through the layer mineral of separating-purifying, add 5 to 10 times of weight, mass percentage concentration is the hydrochloric acid of 3% to 10%, add the V-Brite B of layer mineral weight 0.5% to 2% again, stir and make suspension ore pulp, react 6 ~ 24 hours at normal temperatures, period constantly stirs;
Consider recommendation hydrochloric acid from the combined factors such as cost, effect, also can use other mineral acid.Acid treatment can remove the acid soluble impurities that may exist, on the one hand as carbonate and iron and manganese oxides, sulfide etc.; In addition, acid treatment can make mineral surface be activated, and is conducive to follow-up intercalation and carries out.Add that V-Brite B can make iron, manganese is reduced, increase its clearance.
2) filtration or centrifuge dehydration, clean 2 ~ 4 times, and 60 to 80 ° of C are dried;
Dehydration, oven dry are in order to avoid moisture content and butyl (tetra) titanate generation hydrolysis reaction before next step reaction.
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 0.8 to 1.5 weight part butyl (tetra) titanate, grinds 1 to 2 hour in high shear grinding machine after stirring;
Butyl (tetra) titanate has another name called tetra-n-butyl titanate, is used as the precursor of titanium dioxide here.Butyl (tetra) titanate has hydrophilic, lipophilicity, has very high chemically reactive to water.By means of the mechanize educational level of process of lapping, butyl (tetra) titanate can enter the crystalline texture layer of layer mineral, forms intercalation compound.
4) add 3 to 5 times of water to stir, standing and reacting 4 to 10 hours, filter or centrifuge dehydration;
After adding water, Butyl Phthalate is hydrolyzed rapidly, forms titanium hydroxide.Hydrolytic process is carried out between layer mineral, and the titanium hydroxide of formation is also retained between the crystalline texture layer of mineral.
5) by step 4) material after dehydration is progressively heated to 280 to 300 ° of C, constant temperature 2-4 hour, obtained layer mineral and nano titanium oxide intercalation composite material.
In heat-processed, titanium hydroxide loses crystal water and hydroxide radical, generates titanium dioxide.Due to the effect of contraction of crystallizable mineral structural sheet, effectively inhibit the reunion of titanium dioxide granule, the titanium dioxide that dehydration generates is that the size distribution of granularity between 3 to 6 nanometers is between crystallizable mineral structural sheet.
Described high shear grinding machine is ball mill, roller mill, rod mill or ball mill.
embodiment 1
1) through the talcum of separating-purifying, add 10 times of weight, mass percentage concentration is the hydrochloric acid of 3%, then adds the V-Brite B of talcum weight 0.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 2 times, 60 DEG C of oven dry;
3) after being cooled to normal temperature, the step 2 of each weight part) material after dehydration adds 0.8 part of butyl (tetra) titanate, grinding in ball grinder 1 hour after stirring;
4) add 3 times of water to stir, standing and reacting 4 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 280 DEG C, constant temperature 4 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 2
1) through the sericite of separating-purifying, add 5 times of weight, mass percentage concentration is the hydrochloric acid of 10%, then adds the V-Brite B of sericite weight 2%, stirs and makes suspension ore pulp, and react 24 hours at normal temperatures, period constantly stirs;
2) centrifuge dehydration, cleans 4 times, 80 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.5 parts of butyl (tetra) titanates, grinding in ball grinder 2 hours after stirring;
4) add 5 times of water to stir, standing and reacting 10 hours, centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 300 °, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 3
1) through the serpentine of separating-purifying, add 8 times of weight, mass percentage concentration is the sulfuric acid of 8%, then adds the V-Brite B of serpentine weight 1%, stirs and makes suspension ore pulp, and react 18 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 3 times, 70 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1 part of butyl (tetra) titanate, grinds 1.5 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 8 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 290 DEG C, constant temperature 3 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 4
1) through the kaolinite of separating-purifying, add 10 times of weight, mass percentage concentration is the nitric acid of 10%, then adds the V-Brite B of kaolinite weight 1.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) centrifuge dehydration, cleans 3 times, 60 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.5 parts of butyl (tetra) titanates, grinds 2 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 4 hours, centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 300 DEG C, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 5
1) through the pyrophyllite of separating-purifying, add 10 times of weight, mass percentage concentration is the hydrochloric acid of 10%, then adds the V-Brite B being equivalent to pyrophyllite weight 1.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 3 times, 80 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.2 parts of butyl (tetra) titanates, grinds 2 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 4 hours, centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 300 DEG C, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 6
1) through the halloysite of separating-purifying, add 5 times of weight, mass percentage concentration is the hydrochloric acid of 10%, then adds the V-Brite B of halloysite weight 2%, stirs and makes suspension ore pulp, and react 24 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 4 times, 80 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.5 parts of butyl (tetra) titanates, grinding in ball grinder 2 hours after stirring;
4) add 5 times of water to stir, standing and reacting 10 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 300 °, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 7
1) through the illite of separating-purifying, add 10 times of weight, mass percentage concentration is the hydrochloric acid of 3%, then adds the V-Brite B being equivalent to illite weight 0.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 2 times, 60 DEG C of oven dry;
3) after being cooled to normal temperature, the illite of every a weight adds 0.8 part of butyl (tetra) titanate, grinding in ball grinder 1 hour after stirring;
4) add 3 times of water to stir, standing and reacting 4 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 280 DEG C, constant temperature 4 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 8
1) through the chlorite of separating-purifying, add 8 times of weight, mass percentage concentration is the sulfuric acid of 8%, then adds the V-Brite B being equivalent to chlorite weight 1%, stirs and makes suspension ore pulp, and react 18 hours at normal temperatures, period constantly stirs;
2) centrifuge dehydration, cleans 3 times, 70 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1 part of butyl (tetra) titanate, grinds 1.5 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 8 hours, centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 290 DEG C, constant temperature 3 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 9
1) through the vermiculite of separating-purifying, add 10 times of weight, mass percentage concentration is the nitric acid of 10%, then adds the V-Brite B of vermiculite weight 1.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) filter dehydration, cleans 3 times, 60 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.5 parts of butyl (tetra) titanates, grinds 2 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 4 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 300 DEG C, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
embodiment 10
1) through the montmorillonite of separating-purifying, add 10 times of weight, mass percentage concentration is the hydrochloric acid of 10%, then adds the V-Brite B being equivalent to montmorillonite weight 1.5%, stirs and makes suspension ore pulp, and react 6 hours at normal temperatures, period constantly stirs;
2) centrifuge dehydration, cleans 3 times, 80 DEG C of oven dry;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 1.2 parts of butyl (tetra) titanates, grinds 2 hours in roller mill after stirring;
4) add 5 times of water to stir, standing and reacting 4 hours, filter dehydration;
5) by step 4) material after dehydration is progressively heated to 300 DEG C, constant temperature 2 hours, obtained layer mineral and nano titanium oxide intercalation composite material.
Claims (3)
1. a preparation method for layer mineral and nano titanium oxide intercalation composite material, is characterized in that its step is as follows:
1) through the layer mineral of separating-purifying, add 5 to 10 times of weight, mass percentage concentration is the hydrochloric acid of 3% to 10%, add the V-Brite B of layer mineral weight 0.5% to 2% again, stir and make suspension ore pulp, react 6 ~ 24 hours at normal temperatures, period constantly stirs;
2) filtration or centrifuge dehydration, clean 2 ~ 4 times, and 60 to 80 ° of C are dried;
3) after being cooled to normal temperature, each weight part step 2) material after dehydration adds 0.8 to 1.5 weight part butyl (tetra) titanate, grinds 1 to 2 hour in high shear grinding machine after stirring;
4) add 3 to 5 times of water to stir, standing and reacting 4 to 10 hours, filter or centrifuge dehydration;
5) by step 4) material after dehydration is progressively heated to 280 to 300 ° of C, constant temperature 2-4 hour, obtained layer mineral and nano titanium oxide intercalation composite material;
Layered mineral and nano titanium oxide intercalation composite material, a kind of matrix material that the titanium dioxide granule being inserted with nanometer grade between the crystalline texture layer of layer mineral is formed.
2. the preparation method of a kind of layer mineral according to claim 1 and nano titanium oxide intercalation composite material, it is characterized in that, described layer mineral is talcum, serpentine, kaolinite, halloysite, pyrophyllite, mica group, illite, chlorite, vermiculite, montmorillonite, and they are clay, mud stone, shale or massive ore in natural output form.
3. the preparation method of a kind of layer mineral according to claim 1 and nano titanium oxide intercalation composite material, is characterized in that, described high shear grinding machine is ball mill, roller mill, rod mill or ball mill.
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| CN110467377B (en) * | 2019-09-10 | 2020-11-03 | 福建省鑫坤建设工程有限公司 | Environment-friendly composite mineral insulation board and preparation process thereof |
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