CN102320749B - Black microlite containing coal gangue and preparation method thereof - Google Patents
Black microlite containing coal gangue and preparation method thereof Download PDFInfo
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- CN102320749B CN102320749B CN 201110250391 CN201110250391A CN102320749B CN 102320749 B CN102320749 B CN 102320749B CN 201110250391 CN201110250391 CN 201110250391 CN 201110250391 A CN201110250391 A CN 201110250391A CN 102320749 B CN102320749 B CN 102320749B
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Abstract
The invention relates to black microlite containing coal gangue and a preparation method thereof, wherein the black microlite comprises the following glass batches in parts by weight: 30-40 parts of coal gangue, 32-37 parts of quartz sand, 3.2-4.0 parts of calcined soda, 13-16 parts of calcium carbonate, 3.2-4.0 parts of zinc oxide, 4.2-5.0 parts of barium carbonate, 0-0.5 part of borax, 3.4-5.8 parts of ferric oxide, 0-0.1 part of sodium nitrate and 0-0.2 part of manganese dioxide. Because a black-microlite product has the excellent physicochemical characteristics of high strength, abrasion resistance, corrosion resistance, weather resistance, no water absorption, convenience in cleaning and maintenance, no radioactive harm and the like and the excellent appearance characteristics of uniform tone, soft, glittering and translucent luster, compact and flawless surface and the like, the black microlite as a new product with novel assortments and a high added value can be widely applied to the decoration projects of various buildings, such as inner and outer walls, floors, porch pillars, tabletops and the like.
Description
Technical field
The present invention relates to a kind of black microlite and preparation method thereof.
Background technology
Microlite is to use new and high technology to form through high temperature sintering under the condition of high temperature.The existing special microlitic structure of microlite has again special glass matrix structure, and quality is fine and smooth, and the plate face is sparkling and crystal-clear beautiful, can be used for any places that need stone material construction, decoration such as interior wall face, ground, cylinder, table top and furniture decoration of buildings.
Producing the employed raw material of microlite at present all is industrial purifying worker raw material basically except quartz sand.The shortcoming of this frit is that cost is high, and the glass melting temperature is high, and fuel consumption is large, and glass metal is serious to the erosion of kiln refractory materials.Industrial chemicals in the glass batch is more, has also increased the weight of the corrosive effect of glass metal to the melting furnaces refractory materials.
Coal gangue is the solid waste that forms in a kind of coal mining, and spontaneous combustion occurs for its land occupation, polluted water and atmospheric environment, even might cause and fire the disastrous accident that causes the threat to life property safety.Coal gangue is used in the glass batch can all replaces the conventional raw materials for production such as aluminum oxide, Partial Replacement quartz sand, soda ash, calcium carbonate, ferric oxide.But because the coal gangue place of production is different, the chemical component fluctuation of various places coal gangue is very large.As adopt coal gangue as the main component of glass batch, and also need the chemical component difference for coal gangue and black glass admixtion, add other raw materials and carry out proportioning.As not considering the chemical component difference of different places of production coal gangue, select the coal gangue of any composition as glass batch, then can't finish the preparation of microlite.
At present the assortment market requirement of black microlite is prosperous, and economy return is high, but microlite painted is the difficult problem in the microlite preparation always.Because the black colorant kind of using in the existing glass batch is single, proportioning science not, makes the black microlite product color of preparing dark and gloomy, dirty, has greatly affected promoting the use of of black microlite product.In addition, the tinting material that uses in the glass batch of black microlite in the market is expensive, and the inventive method adopts common tinting material, and is cheap, so that this glass batch raw materials cost reduces greatly.
Summary of the invention
The invention provides a kind of black microlite that contains coal gangue and preparation method thereof, solve the technical problem that existing black microlite glass batch is expensive, color and luster is not good, and glass melting temperature drift when solving existing black microlite and preparing, equipment is corroded serious technical problem.
The technical solution adopted for the present invention to solve the technical problems is:
This black microlite that contains coal gangue, its glass batch is as follows by weight ratio:
30～40 parts of coal gangues, 32～37 parts of quartz sands, 3.2～4.0 parts of soda ash, 13～16 parts in calcium carbonate, 3.2～4.0 parts in zinc oxide, 4.2～5.0 parts of barium carbonates, 0～0.5 part of borax, 3.4～5.8 parts of ferric oxide, 0～0.1 part of SODIUMNITRATE, 0～0.2 part of Manganse Dioxide;
The chemical composition of described coal gangue forms: SiO
255.60%, Al
2O
319.61%, CaO 1.21%, and MgO 1.19%, K
2O+Na
2O 3.16%, Fe
2O
34.52%, TiO
20.98%, SO
30.12%, P
2O
50.15%, surplus is impurity;
Described ferric oxide, SODIUMNITRATE and Manganse Dioxide are the black colorant composition of black microlite.
The chemical composition of its glass batch forms: SiO2 53～66%; Al
2O
35.8～7.8%; CaO 13～22%; MgO 0～8%; Na
2O+K
2O 3～6%; Fe
2O
31～8%; B
2O
30～3%; ZnO 2～6%; BaO 4～8%.
Its glass batch best proportioning by weight is as follows:
40 parts of coal gangues, 32 parts of quartz sands, 13 parts in calcium carbonate, 3.5 parts of soda ash, 3.2 parts in zinc oxide, 4.3 parts of barium carbonates, 0.5 part of borax, 0.1 part of ferric oxide 3.4, SODIUMNITRATE.
Described quartz sand is that vein quartz, quartzite or silica are through Mechanical Crushing, ball mill grinding, the dry mash of the 80 order grades that are filtered into.
This described preparation method who contains the black microlite of coal gangue, preparation process is as follows:
Step 1, coal gangue carried out Mechanical Crushing, ball mill grinding after, be filtered into dry mash;
Step 2 is in proportion with each glass batch weighing, mixing;
Step 3 became glass metal with above-mentioned glass batch in 2 hours in 1450～1500 ℃ of lower fusings of temperature;
Step 4, fusing make after finishing glass metal flow directly into that the shrend cooling becomes the glass particle material in the water;
Step 5 is tiled in the glass particle material and carries out crystallization in the fireproof die, and crystallization temperature is 1040～1060 ℃;
Step 6 is with the black microlite sheet material grinding and cutting that obtains.
The fineness of dry mash is 60 order grades in the described step 1.
The used equipment of glass batch fusing is cell furnace, pot furnace or cabinet-type electric furnace in the described step 3.
The viscosity of glass metal is 10～12Pa.s in the described step 4.
The used equipment of glass particle material crystallization is shuttle kiln or cabinet-type electric furnace in the described step 5.
The heat-up rate of glass particle material crystallization is 5 ℃/min in the described step 5, the nucleation temperature point is 650 ℃, and nucleation time is 0.5～1.2 hour, and the top temperature point of crystallization is 1060 ℃, crystallization pressure is 23 Pa, and the crystallization firing period of black microlite sheet material is 25～34 hours.
Beneficial effect of the present invention is as follows:
1, the present invention's sintering process technique of sampling, the chemical composition combination range proportioning that proposes black microlite is: SiO2 53～66%; Al
2O
35.8～7.8%; CaO 13～22%; MgO 0～8%; Na
2O+K
2O 3～6%; Fe
2O
31～8%; B
2O
30～3%; ZnO 2～6%; BaO 4～8%; And with this design considerations as coal gangue introducing amount.
Table black microlite material chemical component combination range table
| Sequence number | The oxide compound title | Combination range |
| 01 | SiO 2 | 53~66% |
| 02 | Al 2O 3 | 5.8~7.8% |
| 03 | CaO | 13~22% |
| 04 | MgO | 0~8% |
| 05 | K 2O+Na 2O | 3~6% |
| 06 | Fe 2O 3 | 1~8% |
| 07 | B 2O 3 | 0~3% |
| 08 | ZnO | 2~6% |
| 09 | BaO | 4~8% |
2, the reason of introducing 30～40 parts of coal gangues in glass batch is: because the chemical composition Al of coal gangue
2O
3Content is 19.61%, and at the black microlite of sampling sintering process technique preparation its frit component design chemical composition is made up desired Al
2O
3The oxide compound compositing range must be controlled between 5.8～7.8 so that coal gangue mixes 30～40 weight part, just can replace its chemical composition combination Al fully
2O
3Oxide compound scope control usage quantity, namely can realize all having replaced aluminum oxide fully.The umber amount that coal gangue can also partly replace other traditional raw materials all according to this reason for calculating according to designing.
3, the black colorant material combination composition in the black microlite production formula of the present invention is ferric oxide, SODIUMNITRATE and Manganse Dioxide.This colorant combination reaches the effect of regulating the black shade of color of product, make product present pure, the naturally soft black of color and luster, solved the not good technical barrier of existing black microlite color and luster, can also make conventional black tinting material raw materials cost reduce by 20 ~ 30% simultaneously.
4, the invention provides a kind of new assortment product of black microlite that contains coal gangue, filled up China in the past coal gangue can't prepare the technological gap of black these assortment of color microlite and the blank of coal gangue production high added value type material product, be a novelty, the hatching property new and high technology in China Technology of Comprehensive Utilization of Coal Gangue field.
5, take full advantage of resource, turn waste into wealth.Coal gangue is fully utilized as a kind of composite minerals raw material, can be beneficial to mine entironment and recover and protection.
6, the cost that saves material.Coal gangue is used in the glass batch can all replaces the conventional raw materials for production such as aluminum oxide, Partial Replacement quartz sand, soda ash, calcium carbonate, ferric oxide, can reduce the glass batch cost more than 28%.
7, behind the introducing coal gangue, need not add albite, the present invention has reduced the consumption of the industrial chemicals such as soda ash, calcium carbonate, ferric oxide again, and soda ash wherein, ferric oxide raw material have stronger erosion action to the used refractory materials of melting furnaces equipment.Therefore, under the constant condition of glass composition and temperature of fusion, can alleviate glass metal to the corrosive effect of melting furnaces refractory materials.
8, with behind the process of Si Al Fe part industrial chemicals, some has become compound in these infusibility components of silicon-dioxide, aluminum oxide and ferric oxide.The glass melting temperature that makes cell furnace is reduced to 1500 ℃ from 1550 ℃, has reduced the part producing energy consumption.
9, soda ash can provide sodium oxide in glass.Its Main Function is the viscosity that reduces glass metal, and the fusing of glass can be carried out smoothly, but consumption crosses at most and can make deformation of products, and the present invention has further reduced the content of soda ash, and the suitable introducing amount that proposes soda ash is 3.2～4.0%.
10, barium carbonate can reduce the viscosity of glass metal, is conducive to the fusing of glass, and the disadvantageous effect of glass properties being come little, suitable consumption compared with sodium oxide is 4.2～5.0%.
Below be the present invention with all with the contrast of the common microlite characteristic of industrial raw material production:
The common microlite of material black microlite of the present invention
Mechanical property: bending strength (Mpa) 48 40 ~ 50
Ultimate compression strength (Mpa) 348.6 341.3
Resistance to impact shock (Pa) 2,507 2452
Young's modulus (* 104MPa) 5
Mohs' hardness 66
Vickers' hardness (100g) 600
Proportion 2.62 2.60 ~ 2.65
Chemical property acid resistance (1%H
2SO
4) 0.03 0.08
Alkali resistance (1%NaOH) 0.06 0.05
Sea water resistance (mg/cm2) 0.08
Water-intake rate (%) 00
Frost resistance (%) 0.028
The thermal characteristic coefficient of expansion (10-7/30 ℃-380 ℃) 62
Thermal conductivity (w/m.k) 1.6
Specific heat (Cal/q ° of .C) 0.19
Optical characteristics whiteness (L degree) 89
Diffuse reflectance (%) 80
The present invention has not only surpassed the common microlite of the industrial raw material production of whole usefulness at aspect of performance, can also reduce the raw materials for production cost, reduces temperature of fusion and the production energy consumption of glass, and coal gangue is turned waste into wealth, and has reduced environmental pollution.This black microlite product since have intensity high, resistance to wear, corrosion-resistant, weather resistance, do not absorb water, the good physicochemical properties such as cleaning convenience, "dead" harm, and soft sparkling and crystal-clear, the excellent appearance characteristics such as surface compact is had no time of uniform hue, gloss, make it as a kind of high added value product innovation of novel assortment, can be widely used in the fitting-out work of all kinds of buildingss such as interior exterior wall, ground, corridor post, table top.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is preparation method's schema of the present invention.
Embodiment
Embodiment one, this black microlite that contains coal gangue, and its glass batch is as follows by weight ratio:
40 parts of coal gangues, 32 parts of quartz sands, 13 parts in calcium carbonate, 4 parts of soda ash, 3.2 parts in zinc oxide, 4.3 parts of barium carbonates, 3.4 parts of ferric oxide, 0.1 part of SODIUMNITRATE.
This preparation method who contains the black microlite of coal gangue, coal gangue carried out Mechanical Crushing, ball mill grinding after, be filtered into the dry mash of 60 order grades; In proportion with each glass batch weighing, mixing; Above-mentioned glass batch is placed in the mullite crucible, is that fusing became glass metal in 2 hours in 1480 ℃ the cabinet-type electric furnace in temperature, and after fusing is finished glass metal being poured into water the shrend cooling becomes the glass particle material; 500 gram glass pellets are tiled in the mould that the fire-resistant lath that is of a size of 80 * 80 millimeters is combined into, carry out crystallization in cabinet-type electric furnace, crystallization temperature is 1040 ℃; The black microlite sheet material grinding and cutting that obtains is obtained 80 * 80 * 20 millimeters black microlite.
Embodiment two: this black microlite that contains coal gangue, and its glass batch is as follows by weight ratio:
35 parts of coal gangues, 35 parts of quartz sands, 13 parts in calcium carbonate, 3.4 parts of soda ash, 4 parts in zinc oxide, 5 parts of barium carbonates, 4.5 parts of ferric oxide, 0.1 part of SODIUMNITRATE.
This preparation method who contains the black microlite of coal gangue, coal gangue carried out Mechanical Crushing, ball mill grinding after, be filtered into the dry mash of 60 order grades; In proportion with each glass batch weighing, mixing; It is that fusing became glass metal in 2 hours in 1490 ℃ the cell furnace that above-mentioned glass batch is placed on temperature, and after fusing is finished glass metal being poured into water the shrend cooling becomes the glass particle material; 116 kilograms of glass particle material are tiled in the fireproof die that is of a size of 1.20 * 1.80 meters, carry out crystallization in the shuttle kiln take liquefied petroleum gas as fuel, crystallization temperature is 1060 ℃; The black microlite sheet material grinding and cutting that obtains is obtained 1200 * 1800 * 18 millimeters black microlite.
Embodiment three: this black microlite that contains coal gangue, and its glass batch is as follows by weight ratio:
30 parts of coal gangues, 37 parts of quartz sands, 16 parts in calcium carbonate, 3.2 parts of soda ash, 3.5 parts in zinc oxide, 4.2 parts of barium carbonates, 5.8 parts of ferric oxide, 0.2 part of Manganse Dioxide, 0.1 part of SODIUMNITRATE.
This preparation method who contains the black microlite of coal gangue, coal gangue carried out Mechanical Crushing, ball mill grinding after, be filtered into the dry mash of 60 order grades; In proportion with each glass batch weighing, mixing; It is that fusing became glass metal in 2 hours in 1490 ℃ the cell furnace that above-mentioned glass batch is placed on temperature, and after fusing is finished glass metal being poured into water the shrend cooling becomes the glass particle material; 116 kilograms of glass particle material are tiled in the fireproof die that is of a size of 1.20 * 1.80 meters, carry out crystallization in the shuttle kiln take liquefied petroleum gas as fuel, crystallization temperature is 1060 ℃; The black microlite sheet material grinding and cutting that obtains is obtained 1200 * 1800 * 18 millimeters black microlite.
Embodiment four, this black microlite that contains coal gangue, and its glass batch is as follows by weight ratio:
38 parts of coal gangues, 36 parts of quartz sands, 3.6 parts of soda ash, 15 parts in calcium carbonate, 3.4 parts in zinc oxide, 4.7 parts of barium carbonates, 0.4 part of borax, 4.0 parts of ferric oxide, 0.1 part of SODIUMNITRATE, 0.1 part of Manganse Dioxide.
The preparation method of this black microlite that contains coal gangue is above-mentioned identical with embodiment one.
In above-described embodiment one to four, the chemical composition of described coal gangue composition is by weight percentage: SiO
255.60%, Al
2O
319.61%, CaO 1.21%, and MgO 1.19%, K
2O+Na
2O 3.16%, Fe
2O
34.52%, TiO
20.98%, SO
30.12%, P
2O
50.15%, surplus is impurity.
Claims (9)
1. black microlite that contains coal gangue, it is characterized in that: its glass batch is as follows by weight ratio:
30～40 parts of coal gangues, 32～37 parts of quartz sands, 3.2～4.0 parts of soda ash, 13～16 parts in calcium carbonate, 3.2～4.0 parts in zinc oxide, 4.2～5.0 parts of barium carbonates, 0～0.5 part of borax, 3.4～5.8 parts of ferric oxide, 0～0.1 part of SODIUMNITRATE, 0～0.2 part of Manganse Dioxide;
The chemical composition of described coal gangue forms: SiO
255.60%, Al
2O
319.61%, CaO 1.21%, and MgO 1.19%, K
2O+Na
2O 3.16%, Fe
2O
34.52%, TiO
20.98%, SO
30.12%, P
2O
50.15%, surplus is impurity;
Described ferric oxide, SODIUMNITRATE and Manganse Dioxide are the black colorant composition of black microlite;
The described black microlite that contains coal gangue is to be prepared from by following steps:
Step 1, coal gangue carried out Mechanical Crushing, ball mill grinding after, be filtered into dry mash;
Step 2 is in proportion with each glass batch weighing, mixing;
Step 3 became glass metal with above-mentioned glass batch in 2 hours in 1450～1500 ℃ of lower fusings of temperature;
Step 4, fusing make after finishing glass metal flow directly into that the shrend cooling becomes the glass particle material in the water;
Step 5 is tiled in the glass particle material and carries out crystallization in the fireproof die, and crystallization temperature is 1040～1060 ℃;
Step 6 is with the black microlite sheet material grinding and cutting that obtains.
2. the black microlite that contains coal gangue according to claim 1 is characterized in that: the chemical composition of its glass batch forms and is by weight percentage: SiO
253～66%; Al
2O
35.8～7.8%; CaO 13～22%; MgO 0～8%; Na
2O+K
2O 3～6%; Fe
2O
31～8%; B
2O
30～3%; ZnO 2～6%; BaO 4～8%.
3. the black microlite that contains coal gangue according to claim 1, it is characterized in that: its glass batch best proportioning by weight is as follows:
40 parts of coal gangues, 32 parts of quartz sands, 13 parts in calcium carbonate, 3.5 parts of soda ash, 3.2 parts in zinc oxide, 4.3 parts of barium carbonates, 0.5 part of borax, 0.1 part of ferric oxide 3.4, SODIUMNITRATE.
4. the black microlite that contains coal gangue according to claim 1 is characterized in that: described quartz sand is that vein quartz, quartzite or silica are through Mechanical Crushing, ball mill grinding, the dry mash of the 80 order grades that are filtered into.
5. the described preparation method who contains the black microlite of coal gangue according to claim 1, it is characterized in that: the fineness of dry mash is 60 order grades in the described step 1.
6. the described preparation method who contains the black microlite of coal gangue according to claim 1, it is characterized in that: the used equipment of glass batch fusing is cell furnace, pot furnace or cabinet-type electric furnace in the described step 3.
7. the described preparation method who contains the black microlite of coal gangue according to claim 1, it is characterized in that: the viscosity of glass metal is 10～12Pa.s in the described step 4.
8. the described preparation method who contains the black microlite of coal gangue according to claim 1, it is characterized in that: the used equipment of glass particle material crystallization is shuttle kiln or cabinet-type electric furnace in the described step 5.
9. the described preparation method who contains the black microlite of coal gangue according to claim 1, it is characterized in that: the heat-up rate of glass particle material crystallization is 5 ℃/min in the described step 5, the nucleation temperature point is 650 ℃, nucleation time is 0.5～1.2 hour, the top temperature point of crystallization is 1060 ℃, crystallization pressure is 23 Pa, and the crystallization firing period of black microlite sheet material is 25～34 hours.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
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| CN102320749B true CN102320749B (en) | 2013-04-10 |
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| CN106587614A (en) * | 2016-12-15 | 2017-04-26 | 贺云峰 | Glass and preparation method thereof |
| CN106927672A (en) * | 2017-03-17 | 2017-07-07 | 泰山玻璃纤维有限公司 | A kind of black fiberglass and preparation method thereof |
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| CN1216737C (en) * | 2003-04-07 | 2005-08-31 | 陈家仪 | Microcrystalline glass ceramic composite plates and manufacture thereof |
| CN101767933B (en) * | 2009-12-30 | 2012-05-30 | 陕西乾盛环保建材工程有限公司 | Method utilizing coal gangue to manufacture microcrystalline glass plate material |
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