CN103723739B - 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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- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 64
- 239000011032 tourmaline Substances 0.000 title claims abstract description 64
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- 238000005516 engineering process Methods 0.000 claims description 4
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- 229910052708 sodium Chemical group 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
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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 prepare the preparation method of industrial feather weight nano-tourmaline powder.The present invention mainly uses 10L autoclave, utilizes commercially available tourmaline powder, alkali and water-alcohol solution for main raw material, and obtained feather weight particle size range is the tourmalinite nano-powder of 50 ~ 70nm.The present invention is mainly to obtain grain diameter uniform feather weight tourmalinite nano-powder by simple technique, makes it be applied to the industrial circles such as health care, building materials, household electrical appliances and water treatment widely.
Background technology
Tourmalinite is the ring silicate mineral of a kind of boracic, 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.Electrostatic field phenomenon is there is around Japanese scholars Kubo1989 Late Cambrian tourmaline particles, after this, scholars can supply a large amount of research work of the characteristic spread developed to the electrical effect, self power generation polarity, infrared radiation property, Negative ion disengagement etc. of tourmalinite micro mist, relates 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 very large by the impact of its chemical composition, 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 (natural black tourmalinite infrared signature is studied. Tongji University's journal, 2002,30 (2): 183 ~ 187) think that the crystalline structure speciality of tourmalinite and pyroelectric effect thereof are that it produces the major cause of stronger ir radiation.Dong Ying (tourmalinite infrared signature and Zeta potential are studied. The Chinese Geology Univ. (Beijing) master thesis .2005.05) and 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 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 DEG C, infrared emittance reaches maximum value.
The present 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 the reduction of the reduction of population in unit volume and the raising of thermal radiation transmission depth and specific refraction and absorptive index, tourmaline particle super-refinement is reached nano level, the tourmaline particle of high infrared radiance can be obtained.
Patent CN1265887C (2006) describes a kind of preparation method of tourmalinite micro mist, relate to the superfine comminution technique of powder, can obtain the tourmaline powder of particle diameter 15 ~ 60nm, but it needs the technological processs such as comminution by gas stream, wet ball grinding, spraying dry, powder reuniting.Its obtained tourmaline powder particle diameter tourmaline powder particle diameter made with the present invention is close, but its technical process is comparatively complicated, higher and need high-temperature calcination to processing conditions requirement, 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 μm.CN1473759A(2004), the median size of the tourmalinite that the preparation method of superfine white tourmaline powder produces is 0.5 μm, does not specifically provide clear and definite d50, d90, d97 equigranular size and distribution situation, is difficult to meet technique needs.
The patent CN102491354A of this seminar describes a kind of preparation method of nano-scale tourmaline powder, join in the mixing solutions of water alcohol by commercial grade micron-size tourmaline body, acid and tensio-active agent, obtaining particle size range through hydro-thermal reaction is 50 ~ 70nm tourmaline powder.This patent is the preparation of this seminar use in early stage 100mL autoclave band polytetrafluoroethylliner liner, due to for kettle less, need not stir and the equipment such as manometer, institute thinks tetrafluoroethylene all standing, substantially etching problem is there is not in acid solution to kettle itself, but this invents the powder amount obtained and is only 5g less, is difficult to meet industrialization needs.And along with the reduction of powder granularity, agglomeration is serious, needs to add a large amount of tensio-active agents, the only nano-tourmaline powder of obtained about 5g, just need the tensio-active agents such as the cetyl trimethylammonium bromide of the left and right adding 10g, cost is relatively high.When this seminar carries out industrialization amplification test, when preparing nano-powder with the scale of feather weight, adopt the 10L autoclave with equipment such as stirring and manometers.But still use acid as in the process of additive at old terms, find due to impossible complete coated tetrafluoroethylene in link position such as autoclave kettle, kettle cover and manometers, produce in the process of tourmalinite nano-powder, the volatilization of acid solution can produce strong corrosive nature to the kettle of reactor, kettle cover and manometer etc., 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 being widely used in synthesis, 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 preparing nano particle or single crystal powder.Domestic and international research shows, relative to solid phase method, uses liquid phase method and vapor phase process to be a kind of methods better preparing the ultrafine powder of good dispersity.In solid system, the skewness of solid particle size, structure and microtexture can not ensure in claimed range.And liquid phase method and vapor phase process can adjust ultra-fine particle sizes to nano level, and process is easy to control.Hydrothermal method can think the synthesis system of liquid phase method and vapor phase process.Hydrothermal method prepares ultrafine powder, better crystallinity degree, shape, size and distributed components, and crystalline form is controlled, and consume energy little, cost is low, is a kind of most suitable method 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 for the demand of current industrial application to ultra-fine tourmaline powder, feather weight is provided to prepare nano-tourmaline raw powder's production technology, the method uses 10L reactor, prepares tourmalinite nano-powder by the method for hydrothermal method simulating nature circle Hydrothermal Deposits.Tourmaline mineral is 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 produces corrosive nature between tourmaline intermediate layer, make tourmaline particle along impurity interlayer faults, thus particle diameter is reduced.Adding stirring in the present invention makes Granularity of Tourmaline be evenly distributed, and the alkali added in water-heat process and alcoholic solution generate alkoxide does not have volatility substantially, avoids 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, thus prepares particle diameter at nano level superfine powder, and significantly can reduce production cost.
Technical scheme of the present invention is:
A kind of feather weight prepares nano-tourmaline raw powder's production technology, comprises the following steps:
(1) prepare burden: 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; Carry out hydro-thermal reaction after being sealed by autoclave kettle cover, hydrothermal temperature is 100 ~ 200 DEG C, and the time is 20 ~ 50h, and stirring velocity is 20 ~ 60r/min;
(2) wash: reacted tourmalinite slurries are filtered and obtains tourmalinite pressed powder, be placed in container heating in water bath to 30 ~ 40 DEG C and stir 0.5 ~ 3h, carry out suction filtration to gained slurries, filter cake uses dehydrated alcohol and deionized water wash, until pH equals 7;
(3) dry: complete for washing suction filtration gained filter cake to be placed in 80 ~ 100 DEG C 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 focuses on chemically and crystallography is started with, liquid phase method and the synergistic hydrothermal method of vapor phase process is adopted by chemical action, tourmalinite self to be ruptured completely along its defect and cleavage surface, reduce its granularity, thus the tourmalinite nano-powder of feather weight can be obtained, 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, adding stirring in the present invention makes Granularity of Tourmaline be evenly distributed, tensimeter monitoring reacting kettle inner pressure situation, the alkali added in water-heat process and alcoholic solution generate alkoxide does not have volatility substantially, avoids 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, thus prepares particle diameter at nano level superfine powder, and significantly can reduce production cost.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 illustrates:
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 automatic control reactor company limited of Weihai in Shandong province, and model is WHFG-10L.Major ingredient material contact material 316L stainless steel, band polytetrafluoroethylliner liner in still, a set of coated tetrafluoroethylene of stir shaft, stirring rake, temp-measuring protective tube wrapped in teflon.
Embodiment 1:
(1) in the polytetrafluoroethylliner liner of autoclave, 1 kilogram of tourmaline powder (2.74 μm) is added successively, 3L deionized water, 3L dehydrated alcohol, sodium hydroxide 250g;
(2), after being sealed by the kettle cover of autoclave, arranging hydrothermal temperature is 180 DEG C, and stirring velocity is 30r/min, and the hydro-thermal time is 48h;
(3) filtration of completely reacted tourmalinite slurries is obtained tourmaline powder, and the beaker water-bath to 30 DEG C being placed in 5L heated and stirs 0.5h, carries out suction filtration to gained slurries, using dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete for washing suction filtration gained filter cake is placed in 80 DEG C 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, 1.5 kilograms of tourmaline powders (2.74 μm) are added successively, 3L deionized water, 3L dehydrated alcohol, potassium hydroxide 500g;
(2), after being sealed by the kettle cover of autoclave, arranging hydrothermal temperature is 180 DEG C, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) completely reacted tourmalinite slurries are filtered obtain tourmaline powder, and be placed in the beaker heating in water bath to 30 DEG C of 5L and stir 1h, suction filtration is carried out to gained slurries, uses dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete for washing suction filtration gained filter cake is placed in 80 DEG C 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, 2 kilograms of tourmaline powders (2.74 μm) are added successively, 3L deionized water, 3L ethylene glycol, sodium ethylate 500g;
(2), after being sealed by the kettle cover of autoclave, arranging hydrothermal temperature is 200 DEG C, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) filtration of completely reacted tourmalinite slurries is obtained tourmaline powder, and be placed in the beaker heating in water bath 40 DEG C of 5L and stir 1.5h, suction filtration is carried out to gained slurries, use dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete for washing suction filtration gained filter cake is placed in 80 DEG C 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, 2.5 kilograms of tourmaline powders (2.74 μm) are added successively, 4L deionized water, 4L ethylene glycol, potassium ethylate 500g;
(2), after being sealed by the kettle cover of autoclave, arranging hydrothermal temperature is 200 DEG C, and stirring velocity is 50r/min, and the hydro-thermal time is 48h;
(3) filtration of completely reacted tourmalinite slurries is obtained tourmaline powder, and be placed in the beaker heating in water bath 40 DEG C of 5L and stir 2h, suction filtration is carried out to gained slurries, use dehydrated alcohol and deionized water wash, until pH equals 7;
(4) complete for washing suction filtration gained filter cake is placed in 80 DEG C of oven dry in baking oven, finally obtains the tourmaline powder that median size is 58nm.
Fig. 1 is that the made product of example 1 ~ example 4 of the present invention and tourmalinite material powder test the XRD spectra of gained through x-ray powder diffraction instrument (German Bruker company D8Focus).As seen from Figure 1, the thing phase absorption peak of the sample obtained by example 1 ~ example 4 of the present invention matches with the thing phase absorption peak of tourmalinite material powder, therefore can find out that the thing of the product tourmalinite after process of the present invention does 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 tested gained TEM through transmission electron microscope (NEC company JEM-2100 type) and schemed.Doing obtained tourmaline powder by the visible example 1 ~ example 4 of the present invention of Fig. 2 ~ Fig. 5 is spherical particle, and grain diameter is even.Obtain the median size (see table 1) of tourmaline powder according to Scherrer formula and TEM image results simultaneously.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 calculated, need be converted into radian (rad); θ is diffraction angle; λ is X-ray wavelength, is 0.154956.Found out by table 1, the product cut size that the present invention obtains, 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 use laser particle analyzer to characterize the granularity of product.
The particle diameter of the crystal grain of the product that table 1 example of the present invention 1 ~ example 4 is made
| 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, feather weight scale can prepare nano-tourmaline powder, by tourmaline powder super-refinement to 50 ~ 70nm, greatly reduce the granularity of tourmaline powder, have processing requirement simple, low to requirement for environmental conditions, equipment anticorrosion requires low, simple to operate, without the need to adding tensio-active agent, cost is low, and the cycle is short, can be widely used in the advantages such as industrialization scale operation.
Claims (1)
1. feather weight prepares a nano-tourmaline raw powder's production technology, it is characterized by and comprises the following steps:
(1) prepare burden: 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; Carry out hydro-thermal reaction after being sealed by autoclave kettle cover, hydrothermal temperature is 100 ~ 200 DEG C, and the time is 20 ~ 50h, and stirring velocity is 20 ~ 60r/min;
(2) wash: reacted tourmalinite slurries are filtered and obtains tourmalinite pressed powder, be placed in container heating in water bath to 30 ~ 40 DEG C and stir 0.5 ~ 3h, carry out suction filtration to gained slurries, filter cake uses dehydrated alcohol and deionized water wash, until pH equals 7;
(3) dry: complete for washing suction filtration gained filter cake to be placed in 80 ~ 100 DEG C of oven dry in baking oven, finally to obtain nano-scale tourmaline powder;
Described alkali is 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DD135185A1 (en) * | 1977-11-09 | 1979-04-18 | Sonja Koppe | METHOD FOR OBTAINING BORONIC COMPOUNDS FROM BOROUNCIOUS OROCHES |
| JP4035314B2 (en) * | 2001-12-05 | 2008-01-23 | 株式会社日立製作所 | Tourmaline synthesis equipment |
| CN101654254A (en) * | 2009-09-16 | 2010-02-24 | 山东大学 | Synthesis method of tourmaline |
| 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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DD135185A1 (en) * | 1977-11-09 | 1979-04-18 | Sonja Koppe | METHOD FOR OBTAINING BORONIC COMPOUNDS FROM BOROUNCIOUS OROCHES |
| JP4035314B2 (en) * | 2001-12-05 | 2008-01-23 | 株式会社日立製作所 | Tourmaline synthesis equipment |
| CN101654254A (en) * | 2009-09-16 | 2010-02-24 | 山东大学 | Synthesis method of tourmaline |
| 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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