CN104310940B - A kind of olivet rock and swelling product and preparation method thereof - Google Patents
A kind of olivet rock and swelling product and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of olivet rock and swelling product and preparation method thereof, olivet rock, with calcium-base bentonite, alkali metal silicate aqueous solution for raw material, is suitably introduced into miscellaneous function auxiliary agent; Through uniform temperature expanding treatment, obtaining olivet rock swelling product, preparation method is molding ageing mixture method and mechanical shearing method. Olivet rock of the present invention, raw material availability is high, and swelling temperature is low; Swelling product wide variety and physicochemical property are stablized controlled, have good mechanical strength, and fire protecting performance is good; Preparation technology is simple and preparation process does not produce dust pollution substantially, is suitable to industrialized production.
Description
Technical field
The invention belongs to perlite material and preparation field thereof, particularly to a kind of olivet rock and swelling product and preparation method thereof.
Background technology
Behind natural peral series of rocks magma ejection earth's surface, being subject to air cooling effect, magma condenses rapidly, and a large amount of water vapour fail loss from magma, the moisture glassy lava of formation; Because it has Margarita fissured structure, therefore named perlite. Perlite is mainly made up of volcanic glass, and containing crystalline minerals such as quartz, plagioclases, its XRD spectra is as shown in Figure 1.
Natural peral rock belongs to nonmetallic mineral, has pearly luster, is light gray, dark green, HUANGBAI(sic) or brown more; Including perlite, obsidian and pitchstone, three's chemical composition is identical, and main component is SiO2��Al2O3��CaO��R2The chemical combination water of crystallization of O and certain content, but contained humidity ratio is different. Natural peral rock has Margarita fissured structure, and chip edge is transparent or translucent, moisture 2��6wt%, and perlitic general chemistry consists of SiO268.0��74.0wt%, Al2O3About 12.0wt%, Fe2O30.5��3.6wt%, MgO0.3��0.5wt%, CaO0.7��1.0wt%, K2O2.0��3.0wt%, Na2O4.0��5.0wt%, H2O2.0��6.0wt%.
Natural peral rock is pulverized through artificial, screening, classification processing obtains the ore grain of certain particle diameter, under instantaneous high-temperature under the effect of (1050��1350 DEG C), ore in sand form internal crystallization water vapor produces expanded power, making the perlite ore granule moment under molten condition expanded, its expanded performance size is relevant with the chemical composition in Ore and vitreous content. Generally, moisture content is high, and iron content is low, the Ore that nature of glass content is high, and popping fold is big, otherwise then little; Perlitic popping fold is generally 4��25.
Natural peral rock forms the light granular material of porous white, i.e. expanded perlite after high temperature puffing, cooling, safe handling temperature is-200��+850 DEG C, and physical and chemical performance is stable, and space is trickle, refractoriness is high, and sound absorption sound insulation value is good, and (weight water absorption rate is generally about 200% for water absorption and moisture pick-up properties ideal, mention that volume water absorption rate is generally about 30%), good frost resistance, comprcssive strength is superior, has good electrical insulating property, lonizing radiation can be absorbed, and nonpoisonous and tasteless.Based on above feature, expanded perlite tool has been widely used.
Application in building industry field:
(1) materials for wall: the cement perlite concrete panel manufactured for raw material with expanded perlite, than lightweight concrete slab cheap 17%, than common brick cheap 40%, has good soundproof effect;
(2) roofing: insulation, water resistance is good and low cost; Its ratio adopts loose slag to do roofing cheap 31% of heat-insulation layer, ratio mineral wool felt heat insulation house surface cheap 39.4%, ratio mud coal plate heat insulation house surface cheap 48.7%, than foam concrete thermal insulation layer roofing cheap 52.8%;
(3) coating material: expanded perlite coating material has excellent insulation, heat insulation, sound-absorbing, a performance such as fire-resistant, and also have on constructing use immediately, hardening is fast, low cost and other advantages;
(4) packing material: in frame light plate building, fills expanded perlite, can reach good insulation, heat insulation effect.
Application in filtration art:
(1) filter aid: expanded perlite is nontoxic, without the inanimate matter that can dissolve in a liquid or organic matter, the fragrance of liquid and the absorbability of pigment composition is low, and also the rate of filtration is fast, thus be a kind of good filter aid;
(2) produce special filter paper: with kieselguhr and perlite filter powder in addition cellulose serosity through ion modifying agent forge with vacuum adhesion, dry make filter paper, it is simply that one of them method. This method is especially suitable for the liquid in filtering food processing industry and in pharmaceutical industries.
Application at agricultural horticultural field:
Expanded perlite can transform adjustment soil compaction, it is prevented that crops lodge, and controls fertilizer efficiency and fertilizer degree; Also can as the diluent of insecticide or herbicide, the carrier etc. of soilless culture.
Although natural peral rock is with a wide range of applications in multiple fields, but still there are the following problems:
(1) natural peral rock is as a kind of natural silicate mineral, its nature of glass content and every physicochemical property are completely by the geological conditions in mineral formation area and the decision of geological transformation process, the natural peral rock grade difference that different mining areas produce is big, most natural peral rocks are by the impact of local environment, devitrification is serious, popping fold is low, it is impossible to reach perlitic production requirement;
(2) swelling temperature of natural peral rock is high, and energy consumption is big, and production cost is higher. Due to the perlite mineral constituent of various places, nature of glass content, mineralization difference, its swelling temperature is different. In theory, its swelling temperature is 850��1350 DEG C; It practice, except the perlite that Greece and Philippine are found that 1000 DEG C of once swelling temperatures, other perlitic swelling temperature all more than 1000 DEG C, the natural artificial perlite that China finds, swelling temperature is generally 1050��1350 DEG C;
(3) natural peral rock is in the course of processing, and the ore in sand form productivity ratio meeting production standard is relatively low. The utilization of natural peral rock is only limitted to the ore in sand form of more than 0.18mm, and all the other fine ores all abandon as mine tailing, owing to natural peral rock adopts the processing mode of Mechanical Crushing, in process of production, has the perlite breeze of 30��40% to produce; The stacking of these breezes does not only take up a large amount of soil, and dust from flying, cause the secondary pollution of environment;
(4) natural peral rock produces a large amount of dust in process of production, shows according to the study, and perlite dust has fibrosis ability for lung, and the health for workman has harm.Natural peral rock ore in sand form in transport, receive external impacts and be susceptible to fragmentation, efflorescence; These breezes after high temperature puffing, weight saving, floating in atmosphere, the short time is difficult to settle, and causes dust pollution;
Goods after natural peral rock is directly expanded are based on light granular material, and form is single; To prepare sheet material etc., it is necessary to introduce organic or inorganic binding agent, not only increase cost, and being limited to kind and the performance of binding agent, the physicochemical property such as the sheet material resistance to water of preparation is unsatisfactory.
Summary of the invention
The technical problem to be solved is to provide a kind of olivet rock and swelling product and preparation method thereof, olivet rock of the present invention, and raw material availability is high, and swelling temperature is low; Swelling product wide variety and physicochemical property are stablized controlled, have good mechanical strength, and fire protecting performance is good; Preparation technology is simple and preparation process does not produce dust pollution substantially, is suitable to industrialized production.
A kind of olivet rock of the present invention, by weight percentage, raw material is calcium-base bentonite 10-75wt%, alkali metal silicate aqueous solution 25-90wt%, function additive 0-5wt%; The chemical constituent of olivet rock includes: SiO260-75wt%, Al2O36-14wt%, CaO1-5wt%, R2O3-25wt%, H2The hydrosilicate non-crystalline solids material of O5-25wt%, wherein R2O is alkali metal oxide.
Described alkali metal silicate aqueous solution (is commonly called as waterglass), and chemical formula is R2O��mSiO2��9H2O, wherein R is alkali metal, wherein 2.5��m��3.3, and m is the molal quantity ratio of silicon dioxide and alkali metal oxide, is called the modulus of waterglass.
Described alkali metal is one or more in Li, Na, K.
Described alkali metal oxide R2O is Li2O, Na2O, K2One or more in O.
Described alkali metal oxide Na2O/K2The ratio of O is 0.5-5.0.
Described function additive is for expanding layer agent, alkali activator, puffing adjuvant, one or more in polymer modifiers.
Described expansion layer agent is glycerol; Alkali activator is one or more in sodium hydroxide, Lithium hydrate, potassium hydroxide, puffing adjuvant is one or more in boric acid, magnesium carbonate, zinc carbonate, and polymer modifiers is one or more in styrene-acrylate emulsion, styrene-acrylic emulsion, styrene-butadiene emulsion, acrylate and vinyl acetate emulsion, vac-veova emulsion.
A kind of olivet rock swelling product of the present invention, by olivet rock through 400��1000 DEG C of expanding treatments, obtains olivet rock swelling product.
Described olivet rock swelling product is light porous gap material, comprises the various ways such as particulate material, bulk, sheet material.
The preparation method of a kind of olivet rock of the present invention, according to realizing the difference of Montmorillonite Crystal aSi��H film principle in calcium-base bentonite, preparation technology comprises two kinds.
A kind of preparation method of the olivet rock of the present invention, including:
Molding ageing mixture method: raw material is blended, obtains plastic, is then shaped technique, obtains moulding material; Then moulding material is carried out ageing mixture process, the Montmorillonite Crystal in bentonite because being subject to alkali corrosion function, silicon-oxy tetrahedron structural break and be converted into amorphous state, dried control moisture content, to obtain final product;
Or mechanical shearing method: raw material is mixed, obtain the slurry having viscosity, slurry is carried out high speed machine shear treatment, aquashear, clash into, under the effect of tearing etc., the Montmorillonite Crystal layer structure in bentonite is peeling-off, break and be converted into amorphous state, obtains highly viscous slurry, do not need ageing mixture, being made directly moulding process molding, dried controls moisture content, to obtain final product.
Described ageing mixture treatment temperature is for being not less than 20 DEG C, and the time is 7-90 days.
In described high speed machine shear treatment, shear rate is not less than 15000s-1, rotor speed is generally not less than 1000r/min.
Described moulding process is: the common prillings such as same mist projection granulating, granulating powders or extruder grain, and by injection molding, the demoulding, obtains the mould-forming process (moulding material) of different size, shaped solids; Dry be: baking temperature 70-300 DEG C, drying time 4-72h.
After described dried, the moisture content of olivet rock is 5��25%.
In a kind of olivet rock of the present invention and swelling product thereof, miscellaneous function auxiliary agent, by its effect difference, can be divided into expansion layer agent, alkali activator, puffing adjuvant, polymer modifiers, be specifically described as follows:
1. expand layer agent:
Main component montmorillonite in calcium-base bentonite, there is layered crystal structure, interlayer easily adsorbs polar molecule, after absorption, Montmorillonite Crystal interlamellar spacing increases, by introducing the expansion layer agent not making waterglass precipitate, hardening, such as glycerol, montmorillonite interlayer distance can be made to increase, release effect is sheared for the alkali diffusion in ageing mixture process and high speed machine and is respectively provided with good facilitation.
2. alkali activator:
The introducing of alkali ROH, wherein R is alkali metal or their mixture such as Li, Na, K, not only scalable R2The content of O, and can pass through to provide OH-, strengthen the alkali corrosion function in ageing mixture process, promote the carrying out of ageing mixture reaction.
3. puffing adjuvant:
Difference according to puffing adjuvant action principle, can be divided into two categories below:
1. the inorganic salt that heat is decomposed, such as zinc carbonate, magnesium carbonate etc. Its heat decomposes the gas produced, and for the extra power of artificial perlitic expanded offer, can be favorably improved the popping fold of olivet rock;
2. the inorganic salt of low melting point, such as boric acid etc. Utilizing the characteristic of its watery fusion, improve the surface viscosity in the puffing process of olivet rock, the blowing power such as encapsulation is more thorough, aqueous vapor are not easily overflowed, and contribute to regulating, reducing the unit weight of olivet rock swelling product;
4. polymer modifiers:
The polymer modifiers selected in the present invention, is have with waterglass identical electrically not cause the emulsion polymerization of sodium silicate gel, such as styrene-acrylic emulsion, styrene-butadiene emulsion, acrylate and vinyl acetate emulsion, vac-veova emulsion etc. High polymer is for the chemical stability of olivet rock swelling product, resistance to water and mechanical property are all significantly improved and promote, and, in olivet rock puffing process, high polymer decomposed, it is also possible to provide extra power for artificial pearl stone puffing process.
Above-mentioned miscellaneous function auxiliary agent, has for the preparation process of olivet rock and the physicochemical property of swelling product thereof and regulates the effect optimized, and can choose whether the kind introducing and introducing as required.
A kind of olivet rock of the present invention and swelling product and preparation technology thereof, innovative point is in that:
The aSi��H film of mineral crystal is realized by the corrosion function of alkali or high speed machine shear action, and then the amorphization of the melted and instantaneous cooling process of replacement natural peral rock forming process Minerals, prepare a kind of moisture silicate non-crystalline solids material; The light material of the various ways such as swelling product is not limited to granular materials, can directly prepare sheet material, bulk.
The preparation technology of olivet rock of the present invention, realizes the difference of Montmorillonite Crystal aSi��H film principle in bentonite according to it, and preparation technology comprises molding ageing mixture method and mechanical shearing method two kinds, and both preparation technologies are specifically described as follows:
1. molding ageing mixture method:
Technological principle: Montmorillonite Crystal is under the corrosion function of alkali, and silicon-oxy tetrahedron attachment structure ruptures and is converted into amorphous state, obtains the hydrosilicate non-crystalline solids material of longrange disorder, and its XRD spectra is as shown in Figure 2.Molding ageing mixture method specifically includes molding, ageing mixture, dry three steps:
(1) molding:
Form by the primary chemical of described olivet rock, by blended for raw material and obtain plastic, again through granulating and forming technique or mould-forming process, the plastic of blended for raw material gained is prepared into the solid material of particulate material or required form.
(2) ageing mixture:
Ageing mixture is the core procedure of molding ageing mixture method, and it can be divided into again alkali to spread, decrystallized two stages:
1) alkali diffusion phase:
Ion diffusion is there is between montmorillonite and liquid phase alkali in calcium-base bentonite; Liquid phase alkali, is also called effective alkali, is the alkali existed in the form of an ion in pore water solution. OH in liquid phase alkali-Being diffused in montmorillonite layered crystal, contact with the activated silica in montmorillonite, activated aluminum, the cation in montmorillonite lamella is diffused in liquid-phase substrate, and this stage will not cause Montmorillonite Crystal structural damage.
2) the decrystallized stage:
Due to the corrosion function of liquid phase the alkali, [SiO in montmorillonite4]4-Tetrahedron attachment structure ruptures, Al3+It is gradually transitions 4 coordinations by 6 coordinations, forms [AlO4]5-, mineral dissolve gradually, the Al of dissolving3+��Si4+Ion and R+Ionic reaction generates hydrated product [Mx(AlO2)y(SiO2)z��nROH��mH2O], it has three-dimensional, amorphous structure, wherein, R+Entering structure and participate in charge balance, its course of reaction is as shown in Figure 3.
(3) dry:
By the material of ageing mixture gained, controlling its moisture content according to different needs, at the temperature of 90��300 DEG C, dry 12��72h, obtains the olivet rock that moisture content is 5��25%.
2. mechanical shearing method:
Technological principle: the montmorillonite in calcium-base bentonite is the silicate crystal mineral of layer structure, is linked by molecular force between crystal layer, and structure comparison is loose, and Montmorillonite Crystal structure is as shown in Figure 4. Fluid power shearing, clash into, tear etc. under mechanism, Montmorillonite Crystal layer structure is peeling-off, lattice breaks and is converted into amorphous state, obtains moisture silicate non-crystalline solids material. Mechanical shearing method specifically includes preparation slurry, high speed shear, sizing material forming and dry three steps.
(1) preparation slurry:
Form by the primary chemical of described olivet rock, raw material is blended, obtain the slurry with certain viscosity.
(2) high speed shear:
High speed shear is the core procedure of mechanical shearing method, is injected in machinery shear by the slurry prepared, carries out high speed shear process, and mechanical shearing stripping off device is as shown in Figure 5. The powerful kinetic energy that high tangential velocity produced by rotor high speed rotating and high frequency machinery effect belt come, make slurry (0.2��0.4mm) high-speed motion in the narrow gap of stator and rotor, form turbulent flow, it is poor that slurry inside and outside stator produces huge radial velocity, speed difference creates huge aquashear and shock tears effect, and in mechanical shearing stripping off device running, the mobility status of slurry is as shown in Figure 6. Under this violent mechanical external force effect, the crystal structure of montmorillonite destroys, and in disordered state, forms highly viscous slurry, and Montmorillonite Crystal structure amorphization is as shown in Figure 7.
Montmorillonite Crystal completes decrystallized under high speed machine shear action, and reaction, in XRD spectra, shows as montmorillonite diffraction and substantially disappears, and the diffraction maximum of material is disperse peak type. The XRD spectra of olivet rock prepared by mechanical shearing method and calcium-base bentonite contrasts as shown in Figure 8.
(3) sizing material forming and dry:
Highly viscous slurry after high speed shear process, it is not necessary to ageing mixture processes, and prepares required particulate material or block materials either directly through granulating and forming technique or mould-forming process;Then at the temperature of 90��300 DEG C, dry 12��72h controls its moisture content, can obtain the olivet rock that moisture content is 5��25%.
By both the above preparation technology, all can prepare olivet rock, and the olivet rock grade prepared is basically identical. The photo comparison of olivet rock and natural peral rock is as shown in Figure 9. Olivet rock, under swelling temperature, surface softens, internal moisture rapid vaporization, under the sealing process of softening shell, boil-off gas can not be overflowed, forming the granule of internal cellular shape structure, sheet material or block materials, the outward appearance of the expanded front and back of olivet rock particulate material contrasts as shown in Figure 10. The XRD spectra of olivet rock and natural peral rock swelling product and outward appearance contrast as shown in Figure 11,12.
The crucial governing factor of two kinds of olivet rock preparation technologies of the present invention is as follows:
(1) ageing mixture condition and the time: in molding ageing mixture method, the temperature of ageing mixture is generally not less than 20 DEG C; According to the chemical composition that olivet rock is different, the ageing mixture time be 7��90d not etc.
Mechanical shearing speed: in mechanical shearing method, the experiment proved that, to obtain good decrystallized effect, shear rate is generally not less than 15000s-1, in this kind of situation, the rotating speed of device rotor is generally not less than 1000r/min; Material XRD spectra under different shear rate effect contrasts as shown in figure 13.
The present invention is relative to existing report: the method that bentonite carries out mechanical shearing process has been reported, but it is based on the patent of the method, the method of report in publication number CN1660713A, CN101503197A, first it is modified natural montmorillonite processing, again modified alta-mud is carried out mechanical shearing process, purpose is refinement bentonite clay particle, prepares nano-bentonite or aqueous nano bentonite that particle diameter is 1��100nm. And heretofore described mechanical shearing method and molding ageing mixture method, it is realize the decrystallized two kinds of preparation technologies of Montmorillonite Crystal in calcium-base bentonite, shear produced aquashear by high speed machine, clash into, the corrosion function of the effect of tearing or effective alkali, make that Montmorillonite Crystal structure is peeling-off, break and be converted into amorphous state, and then obtain amorphous solid material.
The method introducing aluminum-containing mineral in alkali metal silicate aqueous solution has been reported, but it is based on the patent of the method, the method of report in publication number CN102795780A, CN102795781A, CN102807326A, the introducing of aluminum-containing mineral is as the Nucleating Agent in sodium borated silicate glass or Network former, purpose is to improve the chemical stability of foam glass, and the crystal structure of itself is not damaged. And the present invention is to develop calcium-base bentonite new application for starting point, sheared by high speed machine or the crystal structure of montmorillonite in alkali erosion damage calcium-base bentonite, realize its aSi��H film, thus preparing the hydrosilicate non-crystalline solids material that aluminum content is higher, this material have with natural peral petrofacies like macroscopic features and expanded performance, and swelling temperature is lower, entirely different with the invention thinking of above-mentioned report and invention goods.
Beneficial effect
(1) olivet rock is as a kind of artificial hydrosilicate non-crystalline solids material, and without geographical restrictions, and expanded performance all can reach production requirement to grade, and physicochemical property can realize manual control according to regulation and control chemical composition;
(2) swelling temperature of olivet rock is all below 1000 DEG C, minimum only need 400 DEG C, swelling temperature compared to 1050��1350 DEG C of natural peral rock, olivet rock swelling temperature substantially reduces, moreover, the physicochemical property such as the popping fold of olivet rock swelling product, unit weight, chemical stability can manual control;
(3) olivet rock raw material availability is high; Owing to adopting wet chemical method to prepare, can directly prepare required form material by granulating and forming technique or mould-forming process, the not only size of material, pattern is uniform, and raw material availability can, close to 100%, be accomplished without waste substantially;
(4) olivet rock preparation process does not produce dust pollution substantially; No matter molding ageing mixture method or mechanical shearing method, in operation, is all not related to broken processing, and olivet rock receives not broken, efflorescence after external impacts, no matter prepares or transportation, does not substantially produce dust pollution;
(5) olivet rock swelling product wide variety, swelling product includes the multiple light materials such as particulate material, bulk, sheet material, swelling product satisfactory mechanical property, and chemical stability is high, and various shapes can meet different needs;
(6) olivet rock of the present invention, raw material availability is high, and swelling temperature is low; Swelling product wide variety and physicochemical property are stablized controlled, have good mechanical strength, and fire protecting performance is good; Preparation technology is simple and preparation process does not produce dust pollution substantially, is suitable to industrialized production.
Figure of description
The XRD spectra of Fig. 1 natural peral rock and ore;
Olivet rock XRD spectra prepared by Fig. 2 molding ageing mixture method;
The amorphous hydrated product formation stages chemical reaction process of Fig. 3;
Fig. 4 Montmorillonite Crystal structural representation;
Fig. 5 mechanical shearing stripping off device schematic diagram (1: rotating speed controllable engine; 2: rotate axle; 3: work head; 4: rotor; 5: stator);
Pulp flow situation schematic diagram in Fig. 6 mechanical shearing stripping off device running;
Fig. 7 high speed machine shear stage montmorillonite layered crystal structure amorphization schematic diagram;
Olivet rock prepared by Fig. 8 mechanical shearing method contrasts spectrogram (1: calcium-base bentonite with calcium-base bentonite XRD; 2: olivet rock);
Photo comparison (a: olivet rock of Fig. 9 olivet rock and natural peral rock; B: natural peral rock);
Photo comparison (a: unpuffed olivet rock of the expanded front and back of Figure 10 olivet rock; B: the olivet rock after expanded);
Figure 11 olivet rock swelling product contrasts spectrogram (1: artificial expanded perlite with natural peral rock swelling product XRD; 2: natural expanded perlite);
The outward appearance of Figure 12 olivet rock swelling granular and natural expanded perlite contrasts (a: District, Xinyang Area, Henan Province produces No. 70 expanded perlites; B: No. 100 expanded perlites are produced in Shenyang, Liaoning; C: artificial expanded perlite);
The XRD spectra (1: shear rate is 15000s of material under Figure 13 different shear rate-1; 2: shear rate is 1500s-1);
Before and after Figure 14 molding ageing mixture method ageing mixture, material XRD contrasts spectrogram (1: before ageing mixture; 2: after ageing mixture).
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
In the present embodiment, calcium-base bentonite used, chemical composition and content are such as shown in table 1-1; Sodium silicate used, modulus m=2.8, solid content are 37%, and its parameters is such as shown in table 1-2.Experiment material selected in experiment, is qualified technical grade raw material, does not all carry out any optimization processed before the experiments were performed.
The chemical composition of table 1-1 calcium-base bentonite and content
| Chemical composition | SiO2 | Al2O3 | Fe2O3 | FeO | TiO | CaO | MgO | MnO | K2O | Na2O | P2O5 |
| Content (wt%) | 65.04 | 16.08 | 1.12 | 0.20 | 0.27 | 5.01 | 2.13 | 0.29 | 1.00 | 0.22 | 0.05 |
The parameter of table 1-2 sodium silicate
With natural peral petrofacies ratio, in the chemical composition of calcium-base bentonite, Al2O3Higher (the Al in natural peral rock of content2O3Content is 9��12%), Na2O content is relatively low, all the other chemical compositions and content broadly similar. Consider swelling temperature and the Al of natural peral rock2O3Content become positive correlation, with Al2O3Content is major variable, by regulating different proportioning raw materials, it is achieved Al2O3The excursion of content is 4��14wt%; By Al2O3Content from high to low, called after formula 1-1��1-11 successively. Through Theoretical Calculation, the proportioning raw materials of olivet rock is such as shown in table 1-3:
Table 1-3 olivet rock proportioning raw materials
According to of the present invention, the preparation technology of olivet rock includes molding ageing mixture method and mechanical shearing method two kinds. In the present embodiment, adopt above two preparation technology, prepare the olivet rock of formula 1-1��1-11 respectively.
It is the plant equipment high speed shear effect for Montmorillonite Crystal that mechanical shearing method realizes the decrystallized central principle of montmorillonite, and under different shear rate, the XRD spectra of the olivet rock of preparation is shown by Figure 13.
It is that in ageing mixture process, effective alkali is for the corrosion function of Montmorillonite Crystal that molding ageing mixture method realizes the decrystallized central principle of montmorillonite, and material XRD spectra before and after ageing mixture processes is as shown in figure 14. It is shown that after ageing mixture processes, the montmorillonite in bentonite disappears mutually substantially.
Test result indicate that, no matter be which formula in 1-1��1-11, the olivet rock physicochemical property prepared by mechanical shearing method or molding ageing mixture method is basically identical. By the said ratio olivet rock that molding ageing mixture method or mechanical shearing method are prepared, its primary chemical consists of SiO260��75wt%, Al2O36��14wt%, CaO1��5wt%, R2O3��25wt%, H2O5��25wt%; The comparison of the Main physical character of olivet rock and natural peral rock is such as shown in table 1-4:
The comparison of table 1-4 olivet rock and natural peral rock Main physical performance
The artificial perlitic moisture content of gained is measured by following manner:
1. utilize material in the middle of a certain amount of solid-state of projection electronic weighing, be designated as M1;
2. expect weighing in the middle of complete solid-state as, in ceramic crucible with cover, weighing overall weight, be designated as M2;
3. crucible is placed in muffle furnace, is heated to 1000 DEG C, be incubated 2h;
4. weigh the crucible after being cooled to room temperature, be designated as M3, so, in the middle of solid-state, the computing formula of the moisture content W of material is:
According to different needs, by controlling baking temperature and drying time in drying process, the moisture content of olivet rock can be regulated artificially. By the comparison of olivet rock Yu natural peral rock, olivet rock is close with the Main physical performance of natural peral rock, and possesses preparation process substantially without dust, the advantage that the natural peral rocks such as raw material availability is high do not possess; Moreover, compared to the limitation that natural peral rock grade is determined by geological conditions completely, the chemical composition of olivet rock and physical and chemical performance all can realize artificial adjustment, without geographical restrictions.
Embodiment 2
The widely used reason of natural peral rock is in that it is met high temperature and can be puffed to the internal light material in honeycomb texture, but the swelling temperature of natural peral rock is higher, is 1050��1350 DEG C;And popping fold depends primarily on the grade in natural peral rock ore deposit. Olivet rock not only has the expanded feature the same with natural peral rock, and swelling temperature is low, and preparation process does not need Mechanical Crushing, does not substantially produce dust pollution, and swelling product chemical stability is outstanding. In the present embodiment, test artificial perlitic popping fold in the following manner:
1. take appropriate sample to be tested with 10ml graduated cylinder, be about 1ml, be denoted as V1(vibrating compacting as far as possible, until volume no longer changes);
2. sample is poured into rapidly in the porcelain evaporating dishes of calcination (action wants fast, and sample scatters) as far as possible, closes upper furnace door timing, and observed by fire door observation port, no longer expanded until sample or till the hiss that sends when no longer having expanded;
3. rapidly porcelain evaporating dishes is taken out, measure the volume of puff after cooling again with 10ml graduated cylinder, be denoted as V2(when not destroying granule, vibratory compaction as far as possible), the computing formula of olivet rock popping fold K is:
Every a three parts of K of sample are worth error��0.5 times that is parallel to each other, and take arithmetic mean of instantaneous value; As overproof, roasting three parts again.
Weight-loss ratio is the outstanding feature of expanded perlite chemical stability, and in the present embodiment, the weight-loss ratio method of testing of olivet rock swelling product is as follows:
1. take appropriate olivet rock swelling product and be placed in stone roller body, mill 40 times;
2. weigh the fine powder pulverized and be about 3g (be accurate to arithmetic point after 4), pour in beaker filled with hot water, it is ensured that there is no particle;
3. beaker is placed on 2h on the heater of 100 DEG C, then filters (filter paper is weighed in advance), be placed in together with filter paper in the baking oven of 100 DEG C and be dried to constant weight. The expression formula of weight-loss ratio is as follows:
In formula: w is the weight-loss ratio of material, represents with percent; G0For the original weight of material, unit is kilogram (kg); G is the quality after 2h hot water boils, and unit is kilogram (kg).
Proportioning raw materials mode according to embodiment 1, adopt the olivet rock needed for molding ageing mixture method or mechanical shearing method preparation, by the chemical stability of the expanded performance of the olivet rock of said method test formulations 1-1��1-11 and swelling product, the expanded performance of olivet rock and the weight-loss ratio test result of swelling product such as shown in table 2-1:
Table 2-1 olivet rock expanded performance and swelling product weight-loss ratio test result
Embodiment 3
In the present embodiment, the modulus of water glass impact for olivet rock of the present invention and the properties of swelling product thereof will be probed into. Selecting the sodium silicate that two kinds of moduluses of 1#, 2# are different, the parameter of waterglass is such as shown in table 3-1:
3-1 tests two kinds of waterglass parameters used
Respectively with above two waterglass for raw material, it is defined as 1# with the olivet rock that 1# waterglass is raw material, is defined as 2# with the olivet rock that 2# waterglass is raw material, according to Al2O3Content is by 14%��4%, and the formula defining 1# and 2# olivet rock respectively is 3-1��3-11 and 3-12��3-22, adopts molding ageing mixture method or mechanical shearing method to prepare the olivet rock of above-mentioned formula. Test result indicate that, adopt olivet rock outward appearance prepared by two kinds of different modulus waterglass basically identical, 1# hardness is slightly below 2#, and two kinds of the performance test results making perlitic expanded performance and swelling product are such as shown in table 3-2,3-3:
Table 3-21# olivet rock expanded performance and swelling product the performance test results
Table 3-32# olivet rock expanded performance and swelling product the performance test results
Test result indicate that, compared to soluble glass of high modulus, olivet rock swelling temperature prepared by low modulus water glass is low, and popping fold is high, and the unit weight of swelling product is low, and chemical stability is slightly poor.
Embodiment 4
In reporting about the research of natural peral rock and expanded perlite, the popping fold of natural peral rock and Na2O/K2The ratio of O is relevant. For this, in the present embodiment, by introduce KP1 regulate Na in olivet rock2O/K2The ratio of O, probes into Na2O/K2The ratio of O is for the impact of olivet rock and swelling product thereof; The parameter of KP1 used is such as shown in table 4-1.
Table 4-1 experiment KP1 parameter used
Set Na in olivet rock respectively2O/K2The ratio of O is 0.5,1.0,1.5,2,2.5,3,3.5,4,4.5,5.0, tests in embodiment 1 based on the formula of 1-1��1-11, R in ensureing every kind of formula2When O content is constant, by regulating the consumption of sodium silicate and KP1 so that Na in each formula2O/K2The ratio of O reaches setting value. Concrete formula and experimental result are as follows.
Table 4-2Na2O/K2O ratio is the proportioning raw materials of 0.5
Test result indicate that, Na2O/K2When O ratio is 0.5, the impact for olivet rock expanded performance is inconspicuous, and concrete outcome is such as shown in table 4-3.
Table 4-3Na2O/K2O ratio is 0.5 impact on popping fold
-Biao 4-4Na2O/K2O ratio is the proportioning raw materials of 1.0
Test result indicate that, Na2O/K2When O ratio is 1.0, the expanded performance for olivet rock has certain optimization function, and concrete outcome is such as shown in table 4-5.
Table 4-5Na2O/K2O ratio is 1.0 impacts on popping fold
Table 4-6Na2O/K2O ratio is the proportioning raw materials of 1.5
Experimental result is such as shown in table 4-7.
Table 4-7Na2O/K2O ratio is 1.5 impacts on popping fold
Table 4-8Na2O/K2O ratio is the proportioning raw materials of 2.0
Experimental result is such as shown in table 4-9.
Table 4-9Na2O/K2O ratio is 2.0 impacts on popping fold
Table 4-10Na2O/K2O ratio is the proportioning raw materials of 2.5
Experimental result is such as shown in table 4-11.
Table 4-11Na2O/K2O ratio is 2.5 impacts on popping fold
Table 4-12Na2O/K2O ratio is the proportioning raw materials of 3.0
Experimental result is such as shown in table 4-13.
Table 4-13Na2O/K2O ratio is 3.0 impacts on popping fold
Table 4-14Na2O/K2O ratio is the proportioning raw materials of 3.5
Test result indicate that, Na2O/K2When O ratio is 3.5, the impact for olivet rock expansion ratio is inconspicuous, and concrete outcome is such as shown in table 4-15.
Table 4-15Na2O/K2O ratio is 3.5 impacts on popping fold
Table 4-16Na2O/K2O ratio is the proportioning raw materials of 4.0
Experimental result is such as shown in table 4-17.
Table 4-17Na2O/K2O ratio is 4.0 impacts on popping fold
Table 4-18Na2O/K2O ratio is the proportioning raw materials of 4.5
Experimental result is such as shown in table 4-19.
Table 4-19Na2O/K2O ratio is 4.5 impacts on popping fold
Table 4-20Na2O/K2O ratio is the proportioning raw materials of 5.0
Experimental result is such as shown in table 4-21.
Table 4-21Na2O/K2O ratio is 5.0 impacts on popping fold
Test result indicate that, regulate Na by introducing KP12O/K2The ratio of O, different Na2O/K2Olivet rock difference in appearance under O ratio is little, but different Na2O/K2The ratio of O has certain impact for the expanded performance of olivet rock, sums up as shown in table 4-22:
Table 4-22Na2O/K2The O ratio impact on olivet rock expanded performance
Embodiment 5
Olivet rock of the present invention and swelling product thereof, according to different needs, can be suitably introduced into miscellaneous function auxiliary agent, as expanded a layer agent, alkali activator, puffing adjuvant, one or more in polymer modifiers, can play promotion preparation process, optimize the effect of swelling product physicochemical property. In the present embodiment, the various miscellaneous function auxiliary agents of introducing are as shown in Table 5-1:
The miscellaneous function auxiliary agent introduced in table this example of 5-1
Based on formula 1-1��1-11 in embodiment 1, add above-mentioned miscellaneous function auxiliary agent respectively, add the glycerol experimental formula as expansion layer agent such as shown in table 5-2.
Table 5-2 introduces glycerol experiment proportioning
After introducing glycerol, beneficial effect is produced for the ageing mixture process in olivet rock preparation process, shown in its result such as table 5-3��5-6:
Table 5-3 glycerol introduction volume is the 0.5wt% impact for ageing mixture process
Table 5-4 glycerol introduction volume is the 1.0wt% impact for ageing mixture process
Table 5-5 glycerol introduction volume is the 1.5wt% impact for ageing mixture process
Table 5-6 glycerol introduction volume is the 2.0wt% impact for ageing mixture process
Time, it is shown that being introduced in of glycerol has promoted ageing mixture process to a certain extent, shortens the ageing mixture time. The present embodiment introduces the experimental formula of sodium hydroxide as illustrated in tables 5-7.
Table 5-7 introduces sodium hydroxide experiment proportioning
Introducing sodium hydroxide as alkali activator, have for ageing mixture process and have facilitation, experimental result is such as shown in table 5-8��5��12.
Table 5-8 sodium hydroxide introduction volume is the 1.0wt% impact for ageing mixture process
Table 5-9 sodium hydroxide introduction volume is the 2.0wt% impact for ageing mixture process
Table 5-10 sodium hydroxide introduction volume is the 3.0wt% impact for ageing mixture process
Table 5-11 sodium hydroxide introduction volume is the 4.0wt% impact for ageing mixture process
Table 5-12 sodium hydroxide introduction volume is the 5.0wt% impact for ageing mixture process
Test result indicate that, the introducing of sodium hydroxide has good facilitation for ageing mixture process. Owing to the two all has good facilitation for ageing mixture, therefore, in an experiment, selecting both common additions, experimental formula is such as shown in table 5-13.
Table 5-13 glycerol mixes addition proportioning raw materials with sodium hydroxide
Test result indicate that, glycerol mixes addition and becomes apparent from than the impact being introduced separately into glycerol or sodium hydroxide for ageing mixture process with sodium hydroxide, and specific experiment data are such as shown in table 5-14.
Table 5-14 glycerol mixes addition experimental data with sodium hydroxide
In the present embodiment, as the introduction volume of boric acid of puffing adjuvant such as shown in table 5-15.
The introduction volume of table 5-15 boric acid
The fusing point of boric acid is low, can improve the low temperature viscosity in pearl stone puffing process, can improve the popping fold of olivet rock swelling product to a certain extent, and its experimental result is such as shown in table 5-16,5-17.
Table 5-16 boric acid introduction volume is the 0.5wt% impact for popping fold
Table 5-17 boric acid introduction volume is the 1.0wt% impact for popping fold
In the present embodiment, the magnesium carbonate heat introduced as puffing adjuvant is decomposed, and can provide extra power for puffing process, and what this experiment was selected is basic magnesium carbonate, and experiment proportioning is such as shown in table 5-18.
Table 5-18 introduces basic magnesium carbonate experiment proportioning
Shown in experimental result such as table 5-19��5-21.
Table 5-19 basic magnesium carbonate introduction volume is the 1.0wt% impact for popping fold
Table 5-20 basic magnesium carbonate introduction volume is the 2.0wt% impact for popping fold
Table 5-21 basic magnesium carbonate introduction volume is the 3.0wt% impact for popping fold
Owing to olivet rock puffing process is all played facilitation by both the above miscellaneous function auxiliary agent, in an experiment, being simultaneously introduced two kinds of puffing adjuvants, formula is such as shown in table 5-22.
Table 5-22 boric acid mixes addition proportioning raw materials with magnesium carbonate
Test result indicate that, the mixing of two kinds of puffing adjuvants adds, and the impact for the expanded performance of olivet rock swelling product is better than being introduced separately into puffing adjuvant, and its concrete outcome is such as shown in table 5-23.
Table 5-23 boric acid mixes addition experimental result with magnesium carbonate
The introducing of polymer, mechanical property and resistance to water for olivet rock swelling product have optimization function, and the polymer introduced in the present embodiment is styrene-acrylate emulsion, its proportioning such as table 5-24
Table 5-24 introduces styrene-acrylate emulsion experiment proportioning
Test result indicate that, along with the introducing of polymer, mechanical property and the chemical stability of olivet rock swelling product all have a degree of lifting, shown in concrete outcome such as table 5-25��5-27.
Table 5-25 introduces the experimental result of 1.0wt% styrene-acrylate emulsion
Table 5-26 introduces the experimental result of 3.0wt% styrene-acrylate emulsion
Table 5-27 introduces the experimental result of 5.0wt% styrene-acrylate emulsion
In the present embodiment, with the olivet rock being not introduced into any miscellaneous function auxiliary agent and swelling product thereof for contrast object, test result indicate that, introduce preparation process and the swelling product physicochemical property thereof for olivet rock of miscellaneous function auxiliary agent all create certain beneficial effect, and the beneficial effect of its generation is totally concluded as described in table 5-28:
The impact on olivet rock and swelling product thereof of the table 5-28 miscellaneous function auxiliary agent
Embodiment 6
In the swelling product of natural peral rock, expanded perlite sheet material is subject to increasing favor, but, owing to board making process needing introduce binding agent, can not only adding cost, and be subject to the restriction of binding agent kind and performance, the sheet material chemical stability of preparation is poor, unit weight is high, fails the feature having given play to perlite light weight, chemical stability is good.
Olivet rock of the present invention, swelling product is not limited solely to particle product, and can directly be puffed to sheet material or block materials, one-shot forming, does not need to introduce any binding agent. Olivet rock expanded preparation of plates method is various,
One of which is specifically addressed by the present embodiment, to reach effect is described.
It is used for preparing the olivet rock of expanded sheet material, in its chemical composition, Al2O3Content be generally 4��7wt%, specific embodiment is as follows:
1. the raw material configured is obtained highly viscous slurry by mechanical shearing method;
2. highly viscous slurry is poured in the mould of required size, is dried to regulation moisture content at a certain temperature;
3. it is put into after form removal in high temperature furnace, carries out expanding treatment by the temperature schedule of regulation, after cooling, obtain the expanded sheet material of olivet rock.
In the process of expanding treatment, according to specific needs, may select in resistant to elevated temperatures closed mould expanded, or select in the expanding apparatus of large volume, expanded go out large volume bulk, then cut into sheet material or the bulk of required size as required. By the expanded sheet material of olivet rock prepared by the present invention, mechanical property is good, and heat conductivity is little, and abscess pore size is consistent and is evenly distributed, will according to Al2O3The difference of content, by Al2O3The making sheet formula that content is 4��7wt% is defined as formula A��D, carries out correlated performance test according to the expanded sheet material of olivet rock that formula A��D obtains, its result as shown in Table 6-1:
The expanded plate property test result of table 6-1 olivet rock
The expanded sheet material of olivet rock of the present invention, good mechanical performance, abscess pore size uniformity, preparation process is simple, workable, is suitable to industrialized production.
Claims (10)
1. an olivet rock, it is characterised in that: by weight percentage, raw material is calcium-base bentonite 10-75wt%, alkali metal silicate aqueous solution 25-90wt%, function additive 0-5wt%; The chemical constituent of olivet rock includes: SiO260-75wt%, Al2O36-14wt%, CaO1-5wt%, R2O3-25wt%, H2The hydrosilicate non-crystalline solids material of O5-25wt%, wherein R2O is alkali metal oxide.
2. a kind of olivet rock according to claim 1, it is characterised in that: described alkali metal silicate aqueous solution, chemical formula is R2O��mSiO2��9H2O, wherein R is alkali metal, wherein 2.5��m��3.3.
3. a kind of olivet rock according to claim 2, it is characterised in that: described alkali metal is one or more in Li, Na, K.
4. a kind of olivet rock according to claim 1, it is characterised in that: described function additive is for expanding layer agent, alkali activator, puffing adjuvant, one or more in polymer modifiers.
5. a kind of olivet rock according to claim 4, it is characterised in that: described expansion layer agent is glycerol; Alkali activator is one or more in sodium hydroxide, Lithium hydrate, potassium hydroxide, puffing adjuvant is one or more in boric acid, magnesium carbonate, zinc carbonate, and polymer modifiers is one or more in styrene-acrylate emulsion, styrene-acrylic emulsion, styrene-butadiene emulsion, acrylate and vinyl acetate emulsion, vac-veova emulsion.
6. an olivet rock swelling product, it is characterised in that: by the olivet rock described in claim 1 through 400��1000 DEG C of expanding treatments, obtain olivet rock swelling product.
7. a preparation method for olivet rock as claimed in claim 1, including:
Raw material is blended, then it is shaped technique, obtains moulding material; Then moulding material is carried out ageing mixture process, dried, to obtain final product; Wherein ageing mixture treatment temperature is not less than 20 DEG C;
Or raw material is mixed, obtain slurry, slurry is carried out high speed machine shear treatment, be then shaped technological forming, dried, to obtain final product; Wherein in high speed machine shear treatment, shear rate is not less than 15000s-1, rotor speed is not less than 1000r/min.
8. the preparation method of a kind of olivet rock according to claim 7, it is characterised in that: the described ageing mixture process time is 7-90 days.
9. the preparation method of a kind of olivet rock according to claim 7, it is characterised in that: described baking temperature 70-300 DEG C, drying time 4-72h.
10. the preparation method of a kind of olivet rock according to claim 7, it is characterised in that: after described dried, the moisture content of olivet rock is 5��25%.
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| CN103626476A (en) * | 2013-12-03 | 2014-03-12 | 信阳方浩实业有限公司 | Method for producing light-weight heat-insulating decorative ceramic plate by using solid waste in production and processing course of expanded pearlite |
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| CN103626476A (en) * | 2013-12-03 | 2014-03-12 | 信阳方浩实业有限公司 | Method for producing light-weight heat-insulating decorative ceramic plate by using solid waste in production and processing course of expanded pearlite |
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