CN109574024A - The method for preparing silica nano material using natural 1-dimention nano clay mineral - Google Patents
The method for preparing silica nano material using natural 1-dimention nano clay mineral Download PDFInfo
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- CN109574024A CN109574024A CN201910033272.4A CN201910033272A CN109574024A CN 109574024 A CN109574024 A CN 109574024A CN 201910033272 A CN201910033272 A CN 201910033272A CN 109574024 A CN109574024 A CN 109574024A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/182—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by reduction of a siliceous material, e.g. with a carbonaceous reducing agent and subsequent oxidation of the silicon monoxide formed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of method for preparing silica nano material using natural 1-dimention nano clay mineral, be by natural 1-dimention nano clay mineral powder and reducing agent after evenly mixing, in 300 ~ 600 DEG C of 1 ~ 2h of thermal activation；Thermal activation clay mineral is distributed in acid solution by solid-liquid mass ratio 1:5 ~ 1:10, sour corrosion handles 2 ~ 7.5h at a temperature of 40 ~ 75 DEG C, and obtained product, which passes through, to be separated by solid-liquid separation, is dry, crushing, and sieving obtains silica nano material.Fe (III) in octahedral layer in natural 1-dimention nano clay mineral is changed into Fe (II) by reduction process by the present invention, sour corrosion processing is carried out with lower acid concentration, natural 1-dimention nano clay mineral is changed into one-dimensional silica nano material, and the length of one-dimensional silica nano material is not reduced, product draw ratio is high, stability is good, epigranular, can be used for engineering plastics, rubber, catalysis, etc. multiple fields.
Description
Technical field
Natural 1-dimention nano clay mineral is utilized to prepare silicon dioxide nano rod, nanofiber and receive the present invention relates to a kind of
The method of mitron belongs to nonmetallic ore deep processing and technical field of nanometer material preparation.
Background technique
1-dimention nano earth silicon material is excellent because having high surface, low-expansion coefficient and good electrical insulating property etc.
Characteristic, high molecular material is toughened and reinforced, photovoltaic solar cells, catalyst carrier and the neck such as electrode of lithium cell and diaphragm material
Irreplaceable important function is played in domain.The method of preparation nanometer silicon dioxide material is mainly template at present, is utilized
The guiding role of template forms presoma, then removes template and 1-dimention nano earth silicon material can be obtained.However, template legal system
Standby 1-dimention nano silica is usually required using template or template removal agent, and preparation process is more complicated, and working condition is severe
It carves, high production cost, but also environmental pollution can be caused.Therefore, developing low-cost, efficient 1-dimention nano silica material
The preparation of material is of great significance.
The natural clay minerals such as attapulgite, sepiolite and galapectite have monodimension nano stick, nanofiber and nanotube
Shape crystal morphology, structural framework are mainly made of oxygen-octahedron and aluminium (or magnesium, iron) oxygen octahedra.Tetrahedral layer and octahedron
Layer is keyed by Si-O-M, forms the different clay mineral of crystal morphology.In acid condition, the oxidation in crystal structure
Silicon skeleton is relatively stable, but the metal ion in octahedral layer can be dissolved out by acid, to obtain and the initial pattern of clay mineral
Identical earth silicon material provides new approaches to prepare one-dimensional earth silicon material.At present to attapulgite, sepiolite and
The research that the clay minerals such as galapectite carry out sour processing is more, but be concentrated mainly on remove carbonate impurities, activating surface group,
In terms of dredging duct and improving whiteness, and utilize the research and application of natural one-dimensional clay mineral preparation nanometer silicon dioxide material
Concern is few.
CN1506305A discloses a kind of method with attapulgite clay production nano bar-shape active silica, with height
In concentration sulfuric acid solution (25 ~ 50%) removal attapulgite after metal ion, silica product has been obtained.But bumps used
Stick stone clay is without purification processes, other than containing attapulgite, also contains other mineral constituents, therefore in obtained product not
It can avoid silica and impure mineral containing non-Rod-like shape.CN101434393A, which is disclosed, a kind of uses attapulgite clay
The method for preparing nano-scale amorphous silica, although having obtained purity 90% or more, silica of the partial size in 80 ~ 200nm
Particle, but due to containing other mineral in raw material, so obtaining the SiO of product2Content is not achieved 99%, nor can confirm
Obtained product is nano bar-shape silica.CN104528743A discloses a kind of high specific surface area and mesoporous one-dimensional silica
The preparation method of nanofiber is that the sepiolite powder of acidification is distributed in the aqueous solution containing surfactant, is adjusted
PH to 8 ~ 13 stirs 2 ~ 8h under the conditions of 60 ~ 80 DEG C, then in 100 ~ 200 DEG C of 24 ~ 96h of hydro-thermal reaction, then is fired and handles
To mesoporous silicon dioxide nano fiber.However, the reaction process is complicated, need through peracid treatment --- surface-active is added
Multiple steps are calcined in agent --- hydro-thermal reaction --- again can just obtain product；It can be caused using surfactant during the preparation process
Environmental pollution；The hydro-thermal reaction higher cost of high temperature and pressure, it is difficult to realize prepare with scale.CN102275938A discloses one kind
In the method that galapectite prepares Silica Nanotube as raw material, first to galapectite raw ore carry out centrifugation purification prepare it is high-purity
Then high-purity halloysite is added in sulfuric acid solution by galapectite, handled at 80 ~ 100 DEG C, obtain silica nanometer
Pipe.But sulfuric acid concentration used in the technique is higher (mass fraction is 20.73% ~ 60.45%), according to provided galapectite and sulphur
The ratio (1:20-1:60) of acid solution, can be calculated, and the minimum mass that 1 g galapectite of every processing needs to consume sulfuric acid is
4.146g~12.438g.In addition, it can be seen that, obtained nanotube is shorter, and tubulose is unobvious from electron microscope, and part is managed
Shape is destructurized to form particle.CN105905908B discloses a kind of method for preparing nano-silicon based on galapectite raw material,
By pickling by length be 0.02 ~ 30 μm, outer diameter be 20 ~ 200 nm, internal diameter be 10 ~ 100 nm galapectite be changed into nanometer
Silica, then by nano silica, alkali metal chloride and/or alkaline earth metal chloride, magnesium powder under an argon atmosphere with 1
The heating rate of ~ 20 DEG C/min is warming up to 600 ~ 1000 DEG C, is further dissolved in diluted acid, and filtering is dissolved in hydrofluoric acid and reacting, obtains
To silicon nanoparticle.It after pickling galapectite, is only capable of obtaining silica, cannot get nanotube-shaped silica, so in magnesium
What is obtained after thermal reduction is only silicon nano.In addition, to also use hydrofluoric acid etc. during the reaction toxic by the preparation process
Chemical reagent.
As seen from the above analysis, although being mentioned with a variety of different methods processing attapulgite, sepiolite or galapectite
High SiO2Content has had a correlative study, but these techniques or needs high temperature and pressure or need higher acid concentration, and
And silicon dioxide nano rod identical with attapulgite, sepiolite or galapectite initial length, nanofiber cannot be obtained or received
Mitron.
Summary of the invention
Silica nano material is prepared using natural 1-dimention nano clay mineral the object of the present invention is to provide a kind of
Method.
The method that the present invention prepares silica nano material is by natural 1-dimention nano clay mineral powder and reducing agent
After evenly mixing, in 300 ~ 600 DEG C of 1 ~ 2h of thermal activation；Thermal activation clay mineral is distributed in acid solution by solid-liquid mass ratio,
Sour corrosion handles 2 ~ 7.5h at a temperature of 40 ~ 75 DEG C, and obtained product, which passes through, to be separated by solid-liquid separation, is dry, crushing, and sieving obtains two
Aoxidize silicon nano material.
The natural 1-dimention nano clay mineral powder is natural nano rodlike attapulgite of the purity not less than 95%, receives
Rice fibrous sepiolite or nanotube-shaped galapectite.
The reducing agent is vitamin C, amion acetic acid, ammonium citrate, sodium citrate, hydroxylamine hydrochloride, sodium tartrate, oxalic acid
At least one of potassium, potassium citrate, ammonium oxalate, potassium tartrate；The additional amount of reducing agent is natural 1-dimention nano clay mineral
The 1 ~ 5% of quality.
The acid solution is the mixture by inorganic acid and organic acid.Wherein inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid
One of；Organic acid is acetic acid, in formic acid, oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid, malic acid, acrylic acid, citric acid
It is a kind of；And the molar ratio of organic acid and inorganic acid is 1:4 ~ 1:1, the molar concentration of mixed acid is 0.5 ~ 2 mol/L.
Fig. 1,3,5 are respectively attapulgite, sepiolite, galapectite and prepare silica nano material using it as raw material
TEM figure.It can be seen from TEM figure after process of the present invention, attapulgite, sepiolite and galapectite are distinguished
It is changed into corresponding one-dimensional silicon dioxide nano rod, nanofiber and nanotube, and length variation before and after the processing is little.
Fig. 2,4,6 are respectively attapulgite, sepiolite, galapectite and prepare silica nano material using it as raw material
XRD diagram.By XRD analysis it is found that after process of the present invention, the feature of attapulgite, sepiolite and galapectite is spread out
Peak disappearance is penetrated, and is changed into pure silica crystal phase, illustrates that silica purity generated is very high.Through x-ray fluorescence light
Spectrometer measures, SiO in obtained silicon dioxide nano rod, nanofiber and nanotube product2Content is all larger than 99%.
In conclusion the present invention passes through reduction process for Fe in the octahedral layer in natural 1-dimention nano clay mineral powder
(III) it is changed into Fe (II), is conducive to the dissolution of ion；Sour corrosion processing is carried out with lower acid concentration in atmospheric conditions, it will
Natural 1-dimention nano clay mineral is changed into one-dimensional silicon dioxide nano rod, nanofiber or nanotube, obtained one-dimensional dioxy
SiClx nano material is identical as attapulgite, sepiolite or galapectite initial length, and product draw ratio is high, and stability is good, granularity
Uniformly, engineering plastics, rubber, catalysis, adsorbing separation, energy battery, functional coating, pigment, biomedical material be can be widely used for
The many aspects such as material and tissue engineering material.Moreover, preparation process of the present invention is simple, production cost is low, and sour dosage is few, Er Qieshui
It can recycle, environmental pollution is small.
Detailed description of the invention
Fig. 1 is the TEM figure that attapulgite and technique of the present invention prepare silicon dioxide nano rod.
Fig. 2 is the XRD diagram that attapulgite and technique of the present invention prepare silicon dioxide nano rod.
Fig. 3 is that sepiolite and technique of the present invention prepare silica nano fibrous TEM figure.
Fig. 4 is that sepiolite and technique of the present invention prepare silica nano fibrous XRD diagram.
Fig. 5 is the TEM figure that galapectite and technique of the present invention prepare Silica Nanotube.
Fig. 6 is the XRD diagram that galapectite and technique of the present invention prepare Silica Nanotube.
Specific embodiment
It is described further below by the method that specific embodiment prepares silica nano material to the present invention.
Embodiment 1
It is respectively that 10 kg purity are abundant with 0.5 kg ammonium citrate respectively for 95% attapulgite, sepiolite or galapectite powder
It mixes, is subsequently placed in Muffle furnace, is heat-treated 2h at 300 DEG C, obtain the attapulgite, sepiolite or galapectite of thermal activation；
4.9 kg phosphoric acid and 9.6 kg citric acids are dissolved into 50 L water, mixed acid solution is obtained；Then respectively by the bumps of activation
Stick stone, sepiolite or galapectite mineral are distributed in mixed acid solution under mechanical agitation, react 2h at 75 DEG C；So
Product is centrifuged afterwards, dry, crushing and sieving processing respectively obtain silicon dioxide nano rod, nanofiber and receive
Mitron.It is measured through x-ray fluorescence spectrometry instrument, SiO in obtained silicon dioxide nano rod, nanofiber and nanotube product2Contain
Amount is respectively 99.31%, 99.02% and 99.24%.
Embodiment 2
It is respectively that 10 kg purity are abundant with 0.1 kg vitamin C respectively for 95% attapulgite, sepiolite or galapectite powder
It mixes, is subsequently placed in Muffle furnace, is heat-treated 1h at 300 DEG C, obtain the attapulgite, sepiolite or galapectite of thermal activation；
7.88 kg concentrated hydrochloric acids (mass fraction 37%) and 2.69 kg malic acid are dissolved into 100 L water, mixed acid solution is obtained；So
The attapulgite of activation, sepiolite or galapectite mineral are distributed in mixed acid solution, under mechanical agitation 75 afterwards
7.5h is reacted at DEG C, then product is centrifuged, and dry, crushing and sieving processing respectively obtain silica nanometer
Stick, nanofiber and nanotube.It is measured through x-ray fluorescence spectrometry instrument, obtained silicon dioxide nano rod, nanofiber, nanometer
SiO in pipe product2Content is respectively 99.06%, 99.27% and 99.36%.
Embodiment 3
It is respectively that 10 kg purity are abundant with 0.2 kg hydroxylamine hydrochloride respectively for 95% attapulgite, sepiolite or galapectite powder
It mixes, is subsequently placed in Muffle furnace, 1.5 h are heat-treated at 400 DEG C, obtain the attapulgite, sepiolite or angstrom Lip river of thermal activation
Stone；By the 1.25 kg concentrated sulfuric acids (mass fraction 98%) and 1.14 kg dissolving oxalic acids into 50 L water, mixed acid solution is obtained；So
The attapulgite of activation, sepiolite or galapectite mineral are distributed in mixed acid solution, under mechanical agitation 60 afterwards
React 5h at DEG C, then product be centrifuged, it is dry, crush and sieving processing, respectively obtain silicon dioxide nano rod,
Nanofiber and nanotube product.It measures, obtained silicon dioxide nano rod, nanofiber and receives through x-ray fluorescence spectrometry instrument
SiO in nanotube product2Content is respectively 99.25%, 99.01% and 99.14%.
Embodiment 4
It is respectively that 10 kg purity are abundant with 0.4 kg potassium tartrate respectively for 95% attapulgite, sepiolite or galapectite powder
It mixes, is subsequently placed in Muffle furnace, 2 h are heat-treated at 600 DEG C, obtain the attapulgite, sepiolite or galapectite of thermal activation；
By 6.85 kg concentrated nitric acids (mass fraction 69%) and 1.5 kg acetic acids into 50 L water, mixed acid solution is obtained；Then will
Attapulgite, sepiolite or the galapectite mineral of activation are distributed in mixed acid solution, at 75 DEG C under mechanical agitation
4h is reacted, then product is centrifuged, dry, crushing and sieving processing respectively obtain silicon dioxide nano rod, nanometer
Fiber and nanotube product.It is measured through x-ray fluorescence spectrometry instrument, obtained silicon dioxide nano rod, nanofiber and nanotube
SiO in product2Content is respectively 99.32%, 99.09% and 99.11%.
Embodiment 5
Attapulgite, sepiolite or galapectite powder that 10 kg purity are 95% are sufficiently mixed with 0.5 kg ammonium oxalate respectively respectively
It is even, it is subsequently placed in Muffle furnace, 1 h is heat-treated at 500 DEG C, obtain the attapulgite, sepiolite or galapectite of thermal activation；It will
The 5 kg concentrated sulfuric acids (mass fraction 98%) and 1.8 kg acrylic acid are dissolved into 50 L water, obtain mixed acid solution；It then will activation
Attapulgite, sepiolite or galapectite mineral under mechanical agitation, be distributed in mixed acid solution, reacted at 60 DEG C
Then 7.5h product is centrifuged, dry, crushing and sieving processing respectively obtain silicon dioxide nano rod, Nanowire
Peacekeeping nanotube product.It is measured through x-ray fluorescence spectrometry instrument, obtained silicon dioxide nano rod, nanofiber, nanotube produces
In product, SiO2Content is respectively 99.04%, 99.37% and 99.03%.
Claims (8)
1. the method for preparing silica nano material using natural 1-dimention nano clay mineral is by natural 1-dimention nano clay
Mineral powder and reducing agent after evenly mixing, in 300 ~ 600 DEG C of 1 ~ 2h of thermal activation；Thermal activation clay mineral is pressed into solid-liquid mass ratio
1:5 ~ 1:10 is distributed in acid solution, and sour corrosion handles 2 ~ 7.5h at a temperature of 40 ~ 75 DEG C, and obtained product is by solid-liquid point
From, it is dry, crush, sieving obtains silica nano material.
2. the method for preparing silica nano material using natural 1-dimention nano clay mineral as described in claim 1, special
Sign is: the natural 1-dimention nano clay mineral powder is natural nano rodlike attapulgite of the purity not less than 95%, nanometer
Fibrous sepiolite or nanotube-shaped galapectite.
3. the method for preparing silica nano material using natural 1-dimention nano clay mineral as described in claim 1, special
Sign is: the reducing agent is vitamin C, amion acetic acid, ammonium citrate, sodium citrate, hydroxylamine hydrochloride, sodium tartrate, oxalic acid
At least one of potassium, potassium citrate, ammonium oxalate, potassium tartrate.
4. the method for preparing silica nano material using natural 1-dimention nano clay mineral as claimed in claim 3, special
Sign is: the additional amount of reducing agent is the 1 ~ 5% of natural 1-dimention nano clay mineral quality.
5. the method for preparing silica nano material using natural 1-dimention nano clay mineral as described in claim 1, special
Sign is: the acid solution is the mixture by inorganic acid and organic acid.
6. the method for preparing silica nano material using natural 1-dimention nano clay mineral as claimed in claim 5, special
Sign is: the inorganic acid is one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
7. the method for preparing silica nano material using natural 1-dimention nano clay mineral as claimed in claim 5, special
Sign is: the organic acid is acetic acid, in formic acid, oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid, malic acid, acrylic acid, citric acid
One kind.
8. the method for preparing silica nano material using natural 1-dimention nano clay mineral as claimed in claim 5, special
Sign is: the molar ratio of the organic acid and inorganic acid is 1:4 ~ 1:1, and the molar concentration of mixed acid is 0.5 ~ 2 mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436471A (en) * | 2019-09-06 | 2019-11-12 | 中国科学院兰州化学物理研究所 | The method for preparing the mixed dimension nano silicon material of white using red attapulgite stone clay |
| CN113381120A (en) * | 2021-06-11 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
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| CN1657409A (en) * | 2005-02-21 | 2005-08-24 | 浙江大学 | Method for preparing high-purity ultrnfine silicone powder and aluminium sulphate using kadin as raw material |
| CN101434393A (en) * | 2007-11-16 | 2009-05-20 | 辽宁科技大学 | Method for preparing nano-scale amorphous silica from attapulgite clay |
| CN102275938A (en) * | 2011-07-21 | 2011-12-14 | 中国地质大学（武汉） | Method for preparing silicon dioxide nanotubes from halloysite used as raw material |
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| CN1657409A (en) * | 2005-02-21 | 2005-08-24 | 浙江大学 | Method for preparing high-purity ultrnfine silicone powder and aluminium sulphate using kadin as raw material |
| CN101434393A (en) * | 2007-11-16 | 2009-05-20 | 辽宁科技大学 | Method for preparing nano-scale amorphous silica from attapulgite clay |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436471A (en) * | 2019-09-06 | 2019-11-12 | 中国科学院兰州化学物理研究所 | The method for preparing the mixed dimension nano silicon material of white using red attapulgite stone clay |
| CN110436471B (en) * | 2019-09-06 | 2022-10-28 | 中国科学院兰州化学物理研究所 | Method for preparing white dimension-mixed nano silicon material by using red attapulgite clay |
| CN113381120A (en) * | 2021-06-11 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
| CN113381120B (en) * | 2021-06-11 | 2022-07-12 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
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