CN1317041C - Ultra-fine highly effective anion powder material and its preparation method - Google Patents
Ultra-fine highly effective anion powder material and its preparation method Download PDFInfo
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Abstract
The present invention relates to superfine high-efficiency negative ion powder material and a preparation method thereof. The powder material comprises 60% to 95% of natural negative ion releasing material, 2% to 30% of excitation material and 3% to 25% of energy transmission material by weight. The powder material is obtained by preparing the natural negative ion releasing material, the excitation material and the energy transmission material in the processing mode of combining dry grinding superfine pulverization processing and wet grinding superfine pulverization processing. The negative ion releasing capability of the powder material of the present invention is increased by more than 20 times as compared with that of natural tourmaline and by more than 3 times as compared with the theoretical negative ion releasing capability of the material used by the present invention, and simultaneously, the granularity of the powder of the present invention reaches a nanometer-submicron scale. The powder material also has the function of high far-infrared radiation and has the advantages of safety and no poison.
Description
Technical field
The present invention relates to ultra-fine efficient anion powder material and preparation method thereof.Particularly relate to a kind of natural anion releasable material, excitation material and energy delivery material of utilizing, the anion powder material that obtains by the superfine communication technique mixed processing.
Background technology
At present, about the production of anion releasable material, main what adopt is to excite the piezoelectricity of anion material and electricity from polarity by calcination processing, increases the anion release rate, and the granularity of its anion powder is D
50〉=5 microns.Another kind method is by adding a large amount of rare-earth compounds or the rare earth complex salt excites tourmaline, but its radioactivity exceeds standard, and line outside line emissivity simultaneously far away is low.There is following defective in prior art: 1. powder body anion release rate is low; 2. production process energy consumption height is wasted resource; 3. a powder granule degree is big, and the scope of application is narrow; 4. pollute easily when producing, be unfavorable for environment; 5. powder body far infrared emissivity is low.
Summary of the invention
At the defective of prior art, the object of the invention is to provide a kind of ultra-fine efficient anion powder material.
Another object of the present invention provides the ultra-fine efficient anion powder preparation methods of a kind of the present invention.
Material of the present invention is piezoelectricity and pyroelectricity, the activation technique of excitation material and the catalyst effect of energy delivery material that has fully utilized natural anion releasable material, and the anion release rate of material, infrared radiation rate are increased, and safer.Described ultra-fine efficient anion powder material, natural by weight percentage anion releasable material content is 60%～95%, and excitation material content is 2%～30%, and the energy delivery material content is 3%～25%.Natural anion releasable material wherein is one or more in crude tourmaline ore deposit, opal matrix, serpentine ore, the volcanic rock ore deposit; Excitation material wherein is one or more in Rare Earth Mine, rare earth oxide, rare-earth element salt, the rare earth element monomer; Energy delivery material wherein is one or more in titanium dioxide, zinc oxide and the zirconium oxide.
Natural anion releasable material is introduced
1. crude tourmaline ore deposit
Tourmaline (Tourmaline) ore deposit is a kind of silicic acid rock mineral, and its technology name is called " tourmaline ".Tourmaline is the natural minerals of multielement, and its chemical constituent is silicate, boron, magnesium, aluminum, and its chemical formula is: (Na, Ca) R
3B
3Al
6Si
6(O, OH, F)
31And contain the element to the human body beneficial such as trace chromium, manganese, titanium, caesium.R represents metal cation in the formula, when R is Mg
2+, Fe
2+Or (Li
++ Al
3+) time, constitute dravite, schorl and three end member's mineral species of elbaite respectively.The tourmaline crystal is nearly leg-of-mutton column, two ends crystal form difference, and cylinder tool longitudinal grin often is column, needle-like, radial and block aggregation.Tourmaline has piezoelectricity and pyroelectricity, produces electric self poling performance, polarization energy come from the outside energy and variations in temperature, and the pyroelectric coefficient of tourmaline is 10
-7～4 * 10
-6Ccm
-2K
-1, and tourmaline powder can produce anion under passive condition, and hazardous organic molecules such as catalytic decomposition formaldehyde promote the sedimentation of float in the air, thereby purify air; The far infrared radiation rate of tourmaline can reach 0.85.
2. natural serpentine ore
Serpentine is a kind of layer silicate mineral, and it is low temperature metasomasis or middle low area metamorphism in the ultrabasic rock warp, and olivine and pyroxene generation serpentinization effect in the rock are formed.Serpentine is a kind of high magnesium mineral, and its chemical formula is: Mg6[Si4O10] (OH) 8, wherein contain MgO 43.6%, SiO243.3%, H2O 13.1%, sneaks into compositions such as a little amount of FeO, Fe2O3, NiO sometimes.Be serpentine antigorite, chrysotile, lizardite etc. as the main mineral composition of general name of serpentine family mineral in the mineralogy, next has magnetic iron ore, ilmenite, chromite, shepardite, magnesium ferrum carbonate.
3. native protein stone ore
Opal chemistry composition SiO2nH2O, generally more than 90%, water content is indefinite for SiO2 content, is generally 4-9%, reaches as high as 20%, and major impurity is Al2O3, Fe2O3, CaO, MgO in addition.Fe in redness or the brown opal
2O
3Content is very high.The X-ray diffraction proves that opal is micro-boundary, a kind of Asia crystalline aggregate of cristobalite crystallite, and contains big water gaging, cryptocrystalline bulk or stalactitic aggregation.Colourless or impurely be various tones.Hardness 5.5-6.5, proportion 1.99-2.25 can reduce to 1.8 in siliceous sinter and other porous plastids.Refractive index 1.435-1.455, easily dehydration chaps white.Multiple colors such as that opaline outward appearance is is white, grey, light orchid, exquisite quality, homogeneous grain diameter, the water absorption rate height, adsorptivity is strong, and specific surface area is big, the porosity height, bulk density is little, and hardness is low, and property is crisp.Opal can form from the siliceous solution of hot spring, shallow one-tenth hydrothermal solution or surface water, normal and low quartz association, and the opal colloid is aging to gradually become calcedony or crystal quartz.
4. natural volcanic rock ore deposit
Volcanic rock is that magma solidifies the back generation after the volcano eruption, and its complex chemical composition mainly comprises: SiO
2, AI
2O
3, Fe
2O
3, CaO, MgO etc., outward appearance is multiple colors such as ash, white, Huang more, quality complexity, granularity be heterogeneity extremely, and hole is arranged more, hardness 1.3-4.7 differs.Its main component is diatomaceous volcanic rock ore deposit, and other pegmatite ore deposit of association has certain piezoelectricity and pyroelectricity.
Choosing of excitation material
Rare Earth Mine in the excitation material, rare earth oxide, rare-earth element salt, rare earth element monomer, it all contains rare earth elements such as La, Ce, Nd, Re.Since rare earth element outermost layer be two 6s electronics, trilaminar 4f electronics from 0 to 14, especially preceding several element 4f electronic shell filling electron numbers that atomic number is little are few, these electronic structure characteristics determined rare earth elements are easy to generate electron transfer, pass through the element charge transfer and emitted energy in normal condition.
Because Rare Earth Mine rare-earth compound content 〉=15% contains other materials, so its radioactivity satisfies security requirement well below rare-earth compound, rare-earth element salt, rare earth element monomer.So the present invention selects the excitation material of Rare Earth Mine as the anion powder material for use.
Choosing of energy delivery material
The energy delivery material adopts catalysis material, and catalysis material when reaching nanoscale, has great photocatalyst effect owing to have unstability and self photolytic activity.Select the big catalysis material of photolytic activity for use, then it being carried out micronizing with natural anion releasable material and excitation material handles, purpose is to increase its photolytic activity and photocatalyst effect, absorb the excitation energy of luminous energy and excitation material, the self poling energy of anion releasable material simultaneously, carry out the regulating action of surface field intensity.Foregoing catalysis material has titanium dioxide, zinc oxide, zirconium oxide etc., wherein effective catalysis material is an anatase titanium dioxide, there is the crystal formation unstability in it, can absorbing light medium ultraviolet light, absorb other energy simultaneously, and launch the various energy of its absorption with the photocatalyst effect to the external world.
Described ultra-fine efficient anion powder material can prepare by the following method: natural anion releasable material and Rare Earth Mine direct mechanical are pulverized; Natural anion releasable material, Rare Earth Mine and energy delivery material after pulverizing are directly joined in the ball mill, ground 4～6 hours, cross 325 mesh sieves; Previous step gained composite and water are made into slurry, and add 0.5%～5% dispersant, in rotary mill, ground 6～12 hours with the corundum ball; Serosity after grinding is squeezed in the roating sphere grinding machine again, ground matter and be changed to the zirconium ball, rotate and ground 12～56 hours; 110 ℃～200 ℃ dryings, slough slurry moisture; Powder body material dispersion grinding in the air-flow grinding machine of oven dry, powder body material granularity D
50≤ 0.5 micron.Wherein said dispersant is chelating type lactic acid titanium salt or single alkoxy type titanate esters.
For the present invention, the pulverization process technology chooses the comparison key.Pulverize by mechanical lapping, change the chemism of anion powder material, make natural anion releasable material be excited material and energy delivery material parcel simultaneously.By ball mill is the corase grind grinding of medium with water, can make powder granule more tiny, and parcel is more closely with even.And the dispersant that adds is by the parcel at powder body material surface, block the direct contact on its innovation surface, thereby the electric polarity captivation of the powder body material that discharges anion is reduced, reduce the reunion of subparticle, when grinding, play lubrication simultaneously, make to pulverize to be more prone to.By the pulverization process of airflow milling, be that the powder body material that discharges anion is further disperseed and grinds, deduct the letter sorting bulky grain operation in the former superfine grinding simultaneously.Pulverization process technology of the present invention is that machinery is pulverized earlier, wet grinding again, and last dry grinding can make the ultra micro anion powder material granule that processes even, observes regular shape slyness, no corner angle lunge under scanning electron microscope.Powder granule size inequality, out-of-shape and the serious problem of reunion that former micronizing is handled have been solved.
The mechanism of action of the present invention: it is compound to utilize natural anion releasable material, excitation material and energy delivery material directly to carry out machinery, utilize the rare-earth compound activation energy of excitation material to transmit material, produce the photocatalyst effect, hydrone around decomposing, simultaneously energy is delivered to again on the natural anion releasable material, excites the piezoelectricity and the pyroelectricity of natural anion releasable material self, produce the bio electricity flow field, hydrone around decomposing makes hydration hydroxyl ion H
3O
2 -Increase, improve the releasability of anion.Remaining electric energy is transferred to excitation material and energy delivery material again, the photocatalyst effect of excitation rare-earth element activity and energy delivery material simultaneously.These three kinds of materials all have the emission and the transmission of self-energy, form the circulation of an energy delivery, combined effect and decompose hydrone around it, the release anion.
Ultra-fine anion powder material provided by the present invention can be widely used in fields such as pottery, coating, plastics and fiber.The present invention has the following advantages: 1, the anion release rate improves greatly, can reach 2000/s.cm
32, produce to one method pulverization process technology, reduced energy consumption, reduced dust pollution; 3, the powder body material of Sheng Chaning reaches nano-micron, has improved anion release rate and far-infrared radiation, has increased the scope of application of powder body material; 4, overcome the agglomeration traits of superfine powdery material; 5, the ultra-fine anion powder material particle size of Sheng Chaning is even, and grain shape is oval and circular, smooth surface, no corner angle lunge; 6, the far-infrared radiation rate of powder body material reaches 0.91.
The specific embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.In following examples, the content of each raw material components is weight percentage.
Embodiment 1
Take by weighing column iron tourmaline ore deposit 80%, rare earth ore concentrate 10% and anatase titanium dioxide 10%, with the crude tourmaline ore deposit, the preliminary mechanical activation comminution of Rare Earth Mine, with the crude tourmaline ore deposit, Rare Earth Mine and anatase titanium dioxide are by 4～6 hours ground and mixed of ball mill, and mistake 325 mesh sieves, with powder body after sieving and corundum ball, water is made into 1: 1: 4 serosity, and add 0.5%～5% chelating type lactic acid titanium salt or single alkoxy type titanate esters, ground 6～12 hours in rotary mill, serosity after grinding is squeezed in the roating sphere grinding machine, grind matter and be changed to the zirconium ball, rotate and ground 12～56 hours, 110 ℃～200 ℃ dryings, slough slurry moisture, the powder body of oven dry disperses in the air-flow grinding machine, pulverize, grind final size D
50≤ 0.5 micron.
The powder body material performance indications that test obtains: 1. anion burst size.Method of testing: the powder body material 500 that makes is restrained in the valve bag that is placed on 500 milliliters, keep flat desktop, evenly spread out, use Japanese ECO-HOLISTIC, the ION TESTER anion detector that ING. company produces directly detects the anion burst size.2. far infrared radiation.With the IRE-2 of Shanghai Institute of Technical Physics infrared radiometer, probe temperature is 50 ℃, and survey is 5-14 μ m with wave band.3. particle size distribution detects. and used instrument is the desk-top laser particle size analyzer of the Winner2000 of Jinan micro-nano Instr Ltd..In table 1, listed measurement result.
Embodiment 2
Repeat the method for embodiment 1 by following constituent content: column iron tourmaline ore deposit 75%, rare earth ore concentrate 15%, anatase titanium dioxide 10%.
Embodiment 3
Repeat the method for embodiment 1 by following constituent content: column iron tourmaline ore deposit 95%, rare earth ore concentrate 2%, anatase titanium dioxide 3%.
Embodiment 4
Repeat the method for embodiment 1 by following constituent content: column iron tourmaline ore deposit 90%, rare earth ore concentrate 10%.
Embodiment 5
Repeat the method for embodiment 1 by following constituent content: column iron tourmaline ore deposit 90%, anatase titanium dioxide 10%.
Table 1
| Measurement result | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Anion burst size (unit: individual/s.cm 3) | Theoretical value | 412 | 537 | 112 | 297 | 70 |
| Measured value | 1677 | 2049 | 245 | 698 | 135 | |
| The far infrared radiation rate | 0.90 | 0.91 | 0.86 | 0.87 | 0.85 | |
| Particle size distribution detects (D 50) | ≤ 0.47 | ≤ 0.46 | ≤ 0.47 | ≤ 0.45 | ≤ 0.46 | |
| Annotate: crude tourmaline raw ore anion burst size is 75; Crude tourmaline raw ore far infrared radiation is 0.82. | ||||||
By example one, two, three, four, five as can be seen, only under the common effect that cooperates of natural anion releasable material, excitation material Rare Earth Mine and energy delivery material light catalysis material three, just can reach best anion and discharge and higher far infrared radiation rate.The combination pulverizing preparation technology that wets that does simultaneously of the present invention can reach nanometer-submicron level.
Claims (3)
1, a kind of ultra-fine efficient anion powder material, it is characterized in that, by the energy delivery material of the natural anion releasable material of percentage by weight 60%～95%, 2%～30% excitation material and 3%～25% by do, the wet grinding grinding mode forms, wherein, natural anion releasable material is one or more in opal matrix, serpentine ore, the volcanic rock ore deposit, excitation material is one or more in Rare Earth Mine, rare earth oxide, the rare earth element monomer, and the energy delivery material is one or more in zinc oxide and the zirconium oxide.
2, the method for the ultra-fine according to claim 1 efficient anion powder material of a kind of preparation is characterized in that, may further comprise the steps:
(1) natural anion releasable material and Rare Earth Mine direct mechanical are pulverized;
(2) natural anion releasable material, Rare Earth Mine and the energy delivery material after will pulverizing directly joins in the ball mill, grinds 4～6 hours, crosses 325 orders and with top sieve;
(3) be made into slurry with step (2) gained composite and water, and add 0.5%～5% dispersant, in rotary mill, ground 6～12 hours with the corundum ball;
(4) serosity after will grinding is squeezed in the roating sphere grinding machine again, grinds matter and is changed to the zirconium ball, rotates and grinds 12～56 hours;
(5) 110 ℃～200 ℃ dryings, slough slurry moisture;
(6) Hong Gan powder body dispersion grinding in the air-flow grinding machine makes powder body material granularity D
50≤ 0.5 micron.
3, according to shining the described method of claim 2, it is characterized in that: the dispersant in the step (3) is chelating type lactic acid titanium salt or single alkoxy type titanate esters.
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