CN103723739A - Method for preparing nano tourmaline powder on kilogram scale - Google Patents
Method for preparing nano tourmaline powder on kilogram scale Download PDFInfo
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Abstract
The invention discloses a method for preparing nano tourmaline powder on a kilogram scale. The method comprises the following steps: simulating a natural hydatogenesis method through a hydrothermal method by using a 10 L reaction kettle to prepare tourmaline nano-powder; generating high temperature and high pressure through a closed environment of a hydrothermal system; and generating a corrosive effect on a tourmaline interlayer by alkali liquor in a solution so that ourmaline particles break along an impurity interlayer, thus the grain diameter is decreased, the agglomeration of tourmaline powder is effectively reduced, and ultra-fine powder having nano-sized grain diameter is prepared. The method has the advantages of low production cost and short cycle and is capable of performing industrial production on a large scale.
Description
Technical field
The invention belongs to the preparation field of ultra-fine non-metallic mineral powder, particularly the preparation method of the industrial feather weight nano-tourmaline powder of preparation.The present invention uses 10L autoclave, utilizes commercially available tourmaline powder, alkali and water-alcohol solution for main raw material, makes the tourmalinite nano-powder that feather weight grain diameter scope is 50～70nm.The present invention is to obtain the uniform feather weight tourmalinite of grain diameter nano-powder by simple technique, makes it be applied to widely the industrial circles such as health care, building materials, household electrical appliances and water treatment.
Background technology
Tourmalinite is a kind of boracic, the ring silicate mineral of chemical constitution complexity, and its chemical formula is XY
3z
6(BO
3)
3si
6o
18(OH, O, F)
4, wherein X=Na, Ca, (room), Na can part be replaced by K; Y=Fe, Mg, Li, A l, Mn; Z=Al.Japanese scholars Kubo1989 finds that tourmaline particles exists electrostatic field phenomenon around first, after this, the electrical effect of various countries scholar to tourmalinite micro mist, self power generation polarity, infrared radiation property, Negative ion disengagement etc. can be for the characteristic spread developing a large amount of research work, relate to the fields such as water treatment, body-care, electromagnetic shielding.
The people such as Ji Zhijiang (Infrared Emittance Study of iron dravite. functional materials, 2004, year supplementary issue (35): 2579～2582) infrared emittance of iron dravite is studied, result of study shows that the high IR emittance of tourmalinite is subject to the impact of its chemical composition very large, thermal treatment temp can affect the lattice parameter of tourmalinite simultaneously, and then affects the infrared emittance of tourmalinite.The people such as Yang Ruzeng (research of natural black tourmalinite infrared signature. Tongji University's journal, 2002,30 (2): 183～187) think that the crystalline structure speciality of tourmalinite and pyroelectric effect thereof are its major causes that produces stronger ir radiation.Dong Ying (research of tourmalinite infrared signature and Zeta potential. the master thesis .2005.05 of The Chinese Geology Univ. (Beijing)) result of study shows that the essence that tourmalinite has a high IR emittance is that it has multiple infrared active oscillating linkage.The people such as Li Wenwen (research of tourmalinite infrared spectra and infrared signature. colleges and universities' geology journal, 2008,14 (3): 426～432) result of study shows that the essence that tourmalinite has a high IR emittance is the molecular vibration tool infrared active in its crystalline structure, and thermal treatment temp and infrared emittance exist certain corresponding relation, when temperature increases to 800 ℃, infrared emittance reaches maximum value.
The inventor has carried out a large amount of application and fundamental research to the infrared radiation property of tourmalinite.After infrared radiant material super-refinement, the increase of particle average headway can cause reducing and the raising of thermal radiation transmission depth and the reduction of specific refraction and absorptive index of the interior population of unit volume, tourmaline particle super-refinement is reached to nano level, can obtain the tourmaline particle of high infrared radiance.
Patent CN1265887C (2006) has narrated a kind of preparation method of tourmalinite micro mist, related to the ultra micro complete processing of powder, can make the tourmaline powder of particle diameter 15～60nm, but it needs technological processs such as comminution by gas stream, wet ball grinding, spraying are dry, powder reuniting.The made tourmaline powder particle diameter of the tourmaline powder particle diameter that it makes and the present invention is close, but its technical process is comparatively complicated, and processing conditions is had relatively high expectations and needed high-temperature calcination, consumes energy very large.
Patent CN1287888A(2004) preparation method of disclosed tourmaline powder, adopt ultrafine crusher, tourmalinite is processed into the ultrafine powder of granularity 0.1～15 μ m.The median size of the tourmalinite that CN1473759A(2004) preparation method of disclosed superfine white tourmaline powder produces is 0.5 μ m, does not specifically provide clear and definite d50, d90, and d97 equigranular size and distribution situation, be difficult to meet technique needs.
The patent CN102491354A of this seminar has narrated a kind of preparation method of nano-scale tourmaline powder, commercial grade micron-size tourmaline body, acid and tensio-active agent are joined in the mixing solutions of water alcohol, and through hydro-thermal reaction, making grain diameter scope is 50～70nm tourmaline powder.This patent is the preparation of this seminar use in early stage 100mL autoclave band polytetrafluoroethylliner liner, owing to being that kettle is less, need not stir and the equipment such as manometer, institute thinks tetrafluoroethylene all standing, to kettle itself, substantially there is not etching problem in acid solution, but the powder amount that this invention obtains only for 5g, is difficult to meet industrialization needs less.And along with reducing of powder granularity, agglomeration is serious, need to add a large amount of tensio-active agents, only make the nano-tourmaline powder of about 5g, just need to add the tensio-active agent such as cetyl trimethylammonium bromide of the left and right of 10g, cost is relatively high.When this seminar carries out industrialization amplification test, while preparing nano-powder with the scale of feather weight, adopt the 10L autoclave of equipment such as thering is stirring and manometer.But still use in the process of acid as additive at old terms, discovery is because the link positions such as autoclave kettle, kettle cover and manometer can not be coated tetrafluoroethylene completely, produce in the process of tourmalinite nano-powder, kettle, kettle cover and the manometers of the volatilization meeting of acid solution to reactor etc. produce strong corrosive nature, cause the damage of equipment, and need to add a large amount of tensio-active agents, cause the significantly rising of production cost.
Hydrothermal method is a kind of method that is widely used in synthetic, alteration, sedimentary mineral, sandstone and rock at mineralogy and geology, and the steam that High Temperature High Pressure produces and liquid and solid material react.In hydrothermal system, the liquid and gas of High Temperature High Pressure are as the medium of pressure, temperature and mechanical energy.Hydrothermal method is a kind of method of preparing nano particle or single crystal powder.Study and show both at home and abroad, with respect to solid phase method, using liquid phase method and vapor phase process is a kind of method of the ultrafine powder of better preparing good dispersity.In solid system, the skewness of solid particulate size, structure and microtexture can not guarantee in claimed range.And liquid phase method and vapor phase process can be adjusted ultra-fine grain size to nano level, and process is easy to control.Hydrothermal method can be thought the synthesis system of liquid phase method and vapor phase process.Hydrothermal method is prepared ultrafine powder, better crystallinity degree, and shape, size and distributed components, crystalline form is controlled, consumes energy little, and cost is low, is a kind of most suitable method of preparing nanometer powder.Therefore the present invention adopts hydrothermal method to carry out further nano level thinning processing to micron-size tourmaline body.
Summary of the invention
The object of the invention is the demand to ultra-fine tourmaline powder for current industrial application, provide feather weight to prepare the preparation method of nano-tourmaline powder, the method is used 10L reactor, by the method for hydrothermal method simulating nature circle Hydrothermal Deposits, prepares tourmalinite nano-powder.Tourmalinite mineral are in process of growth, with silicate associations such as quartz, tourmaline particle interlayer is mingled with the mineral such as quartz, the closed environment of hydrothermal system produces High Temperature High Pressure, alkali lye in solution is to producing corrosive nature between tourmaline intermediate layer, make tourmaline particle along impurity interlayer faults, thereby particle diameter is reduced.In the present invention, add to stir Granularity of Tourmaline is evenly distributed, the alkali adding in water-heat process and alcoholic solution generate alkoxide does not have volatility substantially, has avoided the corrosion to kettle, kettle cover and tensimeter etc.And the alkoxide that alkali and alcohol generate can substitution list surface-active agent, effectively reduces the reunion of tourmaline powder, thereby prepares particle diameter at nano level superfine powder, and can significantly reduce production costs.
Technical scheme of the present invention is:
Feather weight is prepared a preparation method for nano-tourmaline powder, comprises the following steps:
(1) batching: micron-size tourmaline body, alkali, water-alcohol solution are joined in autoclave, wherein in water-alcohol solution, water alcohol volume ratio is 1: 1, mass ratio is tourmaline powder: water-alcohol solution=1: 3～8, and mass ratio is tourmaline powder: alkali=2～5: 1; To after the sealing of autoclave kettle cover, carry out hydro-thermal reaction, hydrothermal temperature is 100～200 ℃, and the time is 20～50h, and stirring velocity is 20～60r/min;
(2) washing: reacted tourmalinite slurries are filtered and obtain tourmalinite pressed powder, be placed in container heating in water bath to 30～40 ℃ and stir 0.5～3h, gained slurries are carried out to suction filtration, and filter cake is used dehydrated alcohol and deionized water wash, until pH equals 7;
(3) dry: complete washing suction filtration gained filter cake to be placed in to 80～100 ℃ of oven dry in baking oven, finally to obtain nano-scale tourmaline powder.
Described alkali comprises mineral alkali and organic bases.
Described mineral alkali is specially sodium hydroxide or potassium hydroxide.
Described organic bases is specially sodium methylate, sodium ethylate, potassium ethylate, potassium tert.-butoxide, tertiary butyl sodium or sodium isopropylate.
Described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol or glycerol.
Beneficial effect of the present invention is: compared to traditional physical pulverization process, the present invention starts with from chemistry and crystallography emphatically, adopt liquid phase method and the synergistic hydrothermal method of vapor phase process by chemical action, tourmalinite self to be ruptured completely along its defect and cleavage surface, reduce its granularity, thereby can obtain the tourmalinite nano-powder of feather weight, and its even particle size distribution, median size is between 50～70nm.There is processing requirement simple, low to requirement for environmental conditions, operation of equipment is simple, in the present invention, adding to stir is evenly distributed Granularity of Tourmaline, tensimeter monitoring reacting kettle inner pressure situation, the alkali adding in water-heat process and alcoholic solution generate alkoxide does not have volatility substantially, has avoided the corrosion to kettle, kettle cover and tensimeter etc.And the alkoxide that alkali and alcohol generate can substitution list surface-active agent, effectively reduces the reunion of tourmaline powder, thereby prepares particle diameter at nano level superfine powder, and can significantly reduce production costs.It is low that the present invention has production cost, and the cycle is short, can carry out the advantages such as large-scale industrial production.
Accompanying drawing explanation:
Fig. 1 is the XRD figure of tourmalinite material powder and products obtained therefrom in embodiment 1～example 4;
Fig. 2 is the tourmaline powder transmission plot in embodiment 1;
Fig. 3 is the tourmaline powder transmission plot in embodiment 2;
Fig. 4 is the tourmaline powder transmission plot in embodiment 3;
Fig. 5 is the tourmaline powder transmission plot in embodiment 4;
Embodiment
The commercially available micron-size tourmaline body that the tourmaline powder that the present invention uses is produced for Henan Xixia Mine company.
Autoclave used herein is derived from Weihai in Shandong province automatic control reactor company limited, and model is WHFG-10L.Major ingredient material contact material 316L stainless steel, band polytetrafluoroethylliner liner in still, stir shaft, a set of coated tetrafluoroethylene of stirring rake, temp-measuring protective tube wrapped in teflon.
Embodiment 1:
(1) in the polytetrafluoroethylliner liner of autoclave, add successively 1 kilogram of tourmaline powder (2.74 μ m), 3L deionized water, 3L dehydrated alcohol, sodium hydroxide 250g;
(2) by after the kettle cover sealing of autoclave, it is 180 ℃ that hydrothermal temperature is set, and stirring velocity is 30r/min, and the hydro-thermal time is 48h;
(3) completely reacted tourmalinite slurries are filtered and obtain tourmaline powder, and the beaker water-bath to 30 ℃ that is placed in 5L heat and stir 0.5h, gained slurries are carried out to suction filtration, using dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete washing suction filtration gained filter cake is placed in to 80 ℃ of oven dry in baking oven, finally obtains the tourmaline powder that median size is 52nm.
Embodiment 2:
(1) in the polytetrafluoroethylliner liner of autoclave, add successively 1.5 kilograms of tourmaline powders (2.74 μ m), 3L deionized water, 3L dehydrated alcohol, potassium hydroxide 500g;
(2) by after the kettle cover sealing of autoclave, it is 180 ℃ that hydrothermal temperature is set, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) completely reacted tourmalinite slurries are filtered and obtain tourmaline powder, and be placed in the beaker heating in water bath to 30 ℃ of 5L and stir 1h, gained slurries are carried out to suction filtration, use dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete washing suction filtration gained filter cake is placed in to 80 ℃ of oven dry in baking oven, finally obtains the tourmaline powder that median size is 60nm.
Embodiment 3:
(1) in the polytetrafluoroethylliner liner of autoclave, add successively 2 kilograms of tourmaline powders (2.74 μ m), 3L deionized water, 3L ethylene glycol, sodium ethylate 500g;
(2) by after the kettle cover sealing of autoclave, it is 200 ℃ that hydrothermal temperature is set, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) completely reacted tourmalinite slurries are filtered and obtain tourmaline powder, and be placed in 40 ℃ of the beaker heating in water bath of 5L and stir 1.5h, gained slurries are carried out to suction filtration, use dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete washing suction filtration gained filter cake is placed in to 80 ℃ of oven dry in baking oven, finally obtains the tourmaline powder that median size is 61nm.
Embodiment 4:
(1) in the polytetrafluoroethylliner liner of autoclave, add successively 2.5 kilograms of tourmaline powders (2.74 μ m), 4L deionized water, 4L ethylene glycol, potassium ethylate 500g;
(2) by after the kettle cover sealing of autoclave, it is 200 ℃ that hydrothermal temperature is set, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) completely reacted tourmalinite slurries are filtered and obtain tourmaline powder, and be placed in 40 ℃ of the beaker heating in water bath of 5L and stir 2h, gained slurries are carried out to suction filtration, use dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete washing suction filtration gained filter cake is placed in to 80 ℃ of oven dry in baking oven, finally obtains the tourmaline powder that median size is 58nm.
Fig. 1 is the made product of example 1～example 4 of the present invention and tourmalinite material powder are tested gained XRD spectra through x-ray powder diffraction instrument (the German Bruker D8Focus of company).As seen from Figure 1, the thing phase absorption peak of example 1～example 4 prepared samples of the present invention matches with the thing phase absorption peak of tourmalinite material powder, therefore can find out through the thing of the present invention's product tourmalinite after treatment and not change mutually, be still tourmalinite phase, and just particle diameter reduces.Fig. 2～Fig. 5 is that the made product of example 1～example 4 of the present invention is through transmission electron microscope (JEM-2100 of NEC company type) test gained TEM figure.By the visible example 1～example 4 of the present invention of Fig. 2～Fig. 5, do the tourmaline powder making and be spherical particle, grain diameter is even.While obtains the median size (in Table 1) of tourmaline powder according to Scherrer formula and TEM picture result.Scherrer formula is D=K λ/β cos θ, and wherein K is Scherrer constant, and its value is 0.89; D is grain-size (nm); β is the peak width at half height degree of diffraction peak, in the process of calculating, need be converted into radian (rad); θ is diffraction angle; λ is X ray wavelength, is 0.154956.By table 1, found out, the product cut size that the present invention makes, at 50～70nm, belongs to Nano grade.And the accurate sensing range of laser particle analyzer is greater than 100nm, therefore the present invention does not characterize the granularity of product with laser particle analyzer.
The particle diameter of the crystal grain of the made product of table 1 example 1～example 4 of the present invention
| Example | Raw material | Example 1 | Example 2 | Example 3 | Example 4 |
| Median size | 2.7μm | 52nm | 60nm | 61nm | 58nm |
In sum, the present invention adopts hydrothermal method using alkali as additive, can feather weight scale prepare nano-tourmaline powder, by tourmaline powder super-refinement to 50～70nm, greatly reduced the granularity of tourmaline powder, have processing requirement simple, low to requirement for environmental conditions, equipment anticorrosion requires low, simple to operate, without adding tensio-active agent, cost is low, and the cycle is short, can be widely used in the advantages such as large-scale industrialization production.
Claims (4)
1. feather weight is prepared a preparation method for nano-tourmaline powder, it is characterized by and comprises the following steps:
(1) batching: micron-size tourmaline body, alkali, water-alcohol solution are joined in autoclave, wherein in water-alcohol solution, water alcohol volume ratio is 1: 1, mass ratio is tourmaline powder: water-alcohol solution=1: 3～8, and mass ratio is tourmaline powder: alkali=2～5: 1; To after the sealing of autoclave kettle cover, carry out hydro-thermal reaction, hydrothermal temperature is 100～200 ℃, and the time is 20～50h, and stirring velocity is 20～60r/min;
(2) washing: reacted tourmalinite slurries are filtered and obtain tourmalinite pressed powder, be placed in container heating in water bath to 30～40 ℃ and stir 0.5～3h, gained slurries are carried out to suction filtration, and filter cake is used dehydrated alcohol and deionized water wash, until pH equals 7;
(3) dry: complete washing suction filtration gained filter cake to be placed in to 80 ~ 100 ℃ of oven dry in baking oven, finally to obtain nano-scale tourmaline powder;
Described alkali is mineral alkali and organic bases.
2. feather weight as claimed in claim 1 is prepared the preparation method of nano-tourmaline powder, it is characterized by described mineral alkali and is specially sodium hydroxide or potassium hydroxide.
3. feather weight as claimed in claim 1 is prepared the preparation method of nano-tourmaline powder, it is characterized by described organic bases and is specially sodium methylate, sodium ethylate, potassium ethylate, potassium tert.-butoxide, tertiary butyl sodium or sodium isopropylate.
4. feather weight as claimed in claim 1 is prepared the preparation method of nano-tourmaline powder, and it is characterized by described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol or glycerol.
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| CN107720768A (en) * | 2017-04-07 | 2018-02-23 | 中国地质大学（北京） | A kind of method of Solid phase synthesis tourmaline |
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| CN101654254A (en) * | 2009-09-16 | 2010-02-24 | 山东大学 | Synthesis method of tourmaline |
| KR20110044117A (en) * | 2009-10-22 | 2011-04-28 | 백우열 | Functional energy manufacturing method |
| KR20110057050A (en) * | 2009-11-23 | 2011-05-31 | 백우열 | Thermoelectric conversion, functional energy manufacturing |
| CN102491354A (en) * | 2011-12-05 | 2012-06-13 | 河北工业大学 | Preparation method of nano-scale tourmaline powder |
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| DD135185A1 (en) * | 1977-11-09 | 1979-04-18 | Sonja Koppe | METHOD FOR OBTAINING BORONIC COMPOUNDS FROM BOROUNCIOUS OROCHES |
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| KR20110044117A (en) * | 2009-10-22 | 2011-04-28 | 백우열 | Functional energy manufacturing method |
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