CN100582041C - Microcrystalline glass prepared from oil forming shale ash and method thereof - Google Patents

Microcrystalline glass prepared from oil forming shale ash and method thereof Download PDF

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CN100582041C
CN100582041C CN200710011020A CN200710011020A CN100582041C CN 100582041 C CN100582041 C CN 100582041C CN 200710011020 A CN200710011020 A CN 200710011020A CN 200710011020 A CN200710011020 A CN 200710011020A CN 100582041 C CN100582041 C CN 100582041C
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glass
oil shale
devitrified glass
shale ash
ash
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CN101058479A (en
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薛向欣
李勇
冯宗玉
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Glass Compositions (AREA)

Abstract

The invention discloses a making method of micro-crystal glass through bituminous shale, which comprises the following parts: 45-52% SiO2,15-18% Al2O3, 12-15% CaO, 2-5% MgO, 7-9% Fe2O3,4-6% Na2O, 1-1. 5% K2O,1-2% CaF2,1-2%Cr2O3 and trace quantity of residuals, wherein the apparent specific bulk density is 2. 4-2. 6g.cm-3 with HV microscopic hardness at 900-1250, hydroscopicity at 0. 01%, acid-resistance at 92-99%, alkali-resistance at 92-99% and anti-pressure strength at 400-550Mpa. The technique comprises the following steps: adopting kerabitumen ash, calcium lime, magnesium oxide, sodium carbonate, fluorite and chrome trioxide; allocating; fusing under high temperature; quenching; grinding; shaping; crystallizing under high temperature; fitting for building material and decorative material domains.

Description

A kind of devitrified glass and method thereof of utilizing the oil shale ash preparation
Technical field
The invention belongs to building material field, be specifically related to utilize oil shale ash to make the method for building nucleated glass.
Background technology
Devitrified glass has favorable mechanical performance and physicals, and its hardness is Mohs 6～9, and compressive strength is 6.3T/cm 2, folding strength is 487～1380kg/cm 2, shock strength is 2.5～3.8kg/cm 2, glossiness is 70～120 degree, the coefficient of expansion is 61～77.5 (10/ ℃), and water-intake rate＜0.07%, wear-resisting loss is 0.49g/cm 2And has a good acid-fast alkali-proof performance, therefore be widely used in building materials, sheet material, tubing, it also can be used high, refined, peak products such as the no-reinforcing-bar floor that is used for high strength bearing, high pressure vessel, pressure piping, fermentor tank, building, the strong plate of hollow partition, engine cylinder and airspace engine, spaceship shell, rocket spout with other metallic substance.
The crystallized glass article that has only the advanced country of minority industry such as the U.S., Japanese production short run at present, they are formulated with pure chemistry raw material silicon oxide, aluminum oxide, calcium oxide, magnesium oxide etc. or mill tailings, its production method mainly contains two kinds, a kind of is rolling process, with devitrified glass raw material mechanical pressing, carrying out crystallization then earlier; Another kind is a water quenching, earlier the devitrified glass raw material is fused into the glass slag charge, at mechanical pressing, carries out crystallization then.
Devitrified glass be make by the control crystallization of glass the polycrystalline solid, its micritization implication is meant to make by suitable treatment process and introduces the nucleator in the glass and cause crystal growth, forms microcrystal.All be widely used in fields such as mechanical engineering, Aerospace Engineering, nuclear engineering and food, medical treatment and optics.In view of the cost reason, building microcrystalline glass is made with trade waste mostly, yet except the crystallizing glass sheet material of blast-furnace slag and the production of copper mine tailing has been used for the building field, other is as iron tailings, tungsten mine tailing, kaolin mine tailing and flyash etc., be used to produce building microcrystalline glass and also be limited to breadboard research, this mainly is because color single (being black mostly), and there is big aberration when producing in batches again, even small pore, seesaw and burst and other defects, function singleness does not particularly have industrial test simultaneously, therefore applies being restricted.
Summary of the invention
At the low present situation of oil shale ash utilization ratio, the invention provides a kind of oil shale ash that utilizes and be main raw material, the prescription and the technology of preparation devitrified glass are prepared from sintering process.Reach and alleviate environmental pollution, the purpose of raising material added value.Below be the oil shale ash chemical constitution of China main oil shale factory:
Figure C20071001102000031
A kind of devitrified glass that utilizes the oil shale ash preparation of the present invention is characterized in that the preparation raw material of devitrified glass is: oil shale ash, unslaked lime, magnesium oxide, yellow soda ash, fluorite and chromic oxide; The chemical constitution of devitrified glass is by weight percentage:
Figure C20071001102000041
The present invention utilizes oil shale ash to prepare the method for devitrified glass, and its concrete steps are as follows:
1. batching: according to the chemical composition analysis of oil shale ash and to the requirement of product, by weight batching: oil shale ash 75～80%, unslaked lime 9～12%, magnesium oxide 1～3%, yellow soda ash 6～10%, fluorite 2～3%, chromic oxide 1～1.5%;
2. high temperature melting: with various raw materials after accurate weighing in ball mill uniform mixing, join corundum crucible and put in the Si-Mo rod resistance furnace, at 1250～1350 ℃ of following fusion 90～120min;
3. shrend: glass is melted body pour into rapidly in the tap water, shrend becomes the glass particle of 0.074～0.25mm, in drying baker in 100 ℃ of dry 30min;
4. pulverize: exsiccant shrend glass particle is put into ball mill, and ball milling becomes the glass powder of granularity less than 0.074mm;
5. moulding: the glass powder behind the ball milling is packed in the mould, compression moulding, forming pressure is 10～15MPa;
6. high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 4～8 ℃/min is warmed up to 780～850 ℃, constant temperature sintering 60～180min, temperature rise rate with 5～8 ℃/min is warmed up to 920～990 ℃ then, constant temperature crystallization 60～180min, furnace cooling is to room temperature, through polishing, be polished to devitrified glass then;
7. detect: prepared devitrified glass apparent bulk density 2.4～2.6gcm -3, HV microhardness 900～1250, water-absorbent 0.01%, acid resistance 92～99%, alkali resistance 92～99%, ultimate compression strength 400～550MPa.
The devitrified glass that the inventive method is made can be used as material of construction and finishing material, and the employing oil shale ash is a raw material, has rationally utilized resource, and helps administering environment.
Embodiment
Embodiment 1
1. prepare burden: raw material is by weight: oil shale ash 75%, unslaked lime 11%, magnesium oxide 1%, yellow soda ash 10%, fluorite 2%, chromic oxide 1%;
2. high temperature melting: behind the raw material uniform mixing of weighing, join corundum crucible and put in the Si-Mo rod resistance furnace, at 1250 ℃ of following fusion 90min;
3. shrend: glass is melted body shrend in tap water become the glass particle of 0.074～0.25mm, and use the drying baker drying;
4. pulverize: shrend glass particle ball milling is become the glass powder of granularity less than 0.074mm;
5. moulding: glass powder is packed in the mould, is compression moulding under the 15MPa at pressure;
6. high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 4 ℃/min is warmed up to 850 ℃, constant temperature sintering 60min, temperature rise rate with 5 ℃/min is warmed up to 975 ℃ then, constant temperature crystallization 180min, furnace cooling is to arriving room temperature, through polishing, be polished to devitrified glass then;
7. the prepared devitrified glass chemical constitution of above-mentioned technology is by weight percentage: SiO 2: 48.97%, Al 2O 3: 15.68%, CaO:13.65%, MgO:2.11%, Fe 2O 3: 7.88%, Na 2O:6.65%, K 2O:1.11%, CaF 2: 1.57%, Cr 2O 3: 1.15%, TiO 2: 0.91%, MnO:0.14%, all the other are 0.18% years old.This devitrified glass performance perameter is: density 2.45gcm -3, HV microhardness 971, water-absorbent 0.01%, acid resistance 98.5%, alkali resistance 98.2%, ultimate compression strength 463MPa.
Embodiment 2
1. prepare burden: raw material is by weight: oil shale ash 75%, unslaked lime 12%, magnesium oxide 3%, yellow soda ash 6%, fluorite 2.5%, chromic oxide 1.5%;
2. high temperature melting: raw material weighed joins corundum crucible after mixing, in the Si-Mo rod resistance furnace in 1350 ℃ of following fusion 100min;
3. shrend: with tap water glass is melted the glass particle that the body shrend becomes 0.074～0.25mm, and dry with loft drier;
4. pulverize: with exsiccant shrend glass particle, ball milling becomes the glass powder of granularity less than 0.074mm with ball mill;
5. moulding: glass powder is packed in the mould, is compression moulding under the 10MPa at pressure;
6. high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 7 ℃/min is warmed up to 840 ℃, constant temperature sintering 180min, temperature rise rate with 7 ℃/min is warmed up to 950 ℃ then, constant temperature crystallization 60min, furnace cooling is to room temperature, through polishing, be polished to devitrified glass then;
7. the prepared devitrified glass chemical constitution of above-mentioned technology is by weight percentage: SiO 2: 45.94%, Al 2O 3: 15.23%, CaO:14.68%, MgO:4.59%, Fe 2O 3: 8.89%, Na 2O:4.86%, K 2O:1.09%, CaF 2: 1.66%, Cr 2O 3: 1.87%, TiO 2: 0.92%, MnO:0.14%, all the other are 0.13% years old.This devitrified glass performance perameter is: density 2.57gcm -3, HV microhardness 1237, water-absorbent 0.01%, acid resistance 99.3%, alkali resistance 99.4%, ultimate compression strength 536MPa.
Embodiment 3
1. prepare burden: raw material is by weight: oil shale ash 77%, unslaked lime 9%, magnesium oxide 3%, yellow soda ash 7%, fluorite 3%, chromic oxide 1%;
2. high temperature melting: with raw material weigh mix after, join corundum crucible and put in the sial rod resistance furnace, at 1300 ℃ of following fusion 120min;
3. shrend: with tap water glass is melted the glass particle that the body shrend becomes 0.074～0.25mm, and dry with loft drier.
4. pulverize: with exsiccant shrend glass particle, ball milling becomes the glass powder of granularity less than 0.074mm with ball mill;
5. moulding: glass powder is packed in the mould, compression moulding, forming pressure is 12MPa;
6. high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 8 ℃/min is warmed up to 830 ℃, constant temperature sintering 120min, temperature rise rate with 8 ℃/min is warmed up to 990 ℃ then, constant temperature crystallization 120min, furnace cooling is to room temperature, through polishing, be polished to devitrified glass then;
7. the prepared devitrified glass chemical constitution of above-mentioned technology is by weight percentage: SiO 2: 49.83%, Al 2O 3: 15.91%, CaO:12.05%, MgO:3.83%, Fe 2O 3: 7.99%, Na 2O:5.03%, K 2O:1.12%, CaF 2: 1.79%, Cr 2O 3: 1.22%, TiO 2: 0.95%, MnO:0.15%, all the other are 0.13% years old.This devitrified glass performance perameter is: density 2.48gcm -3, HV microhardness 1013, water-absorbent 0.01%, acid resistance 98.3%, alkali resistance 98.7%, ultimate compression strength 498MPa.
Embodiment 4
1. prepare burden: raw material is by weight: oil shale ash 80%, unslaked lime 10%, magnesium oxide 1%, yellow soda ash 6%, fluorite 2%, chromic oxide 1%;
2. high temperature melting: with admixtion, join corundum crucible and put in the Si-Mo rod resistance furnace, at 1350 ℃ of following fusion 110min;
3. shrend: glass is melted body in tap water, and shrend becomes the glass particle of 0.074～0.25mm, and drying is stand-by;
4. pulverize: exsiccant shrend glass particle is put into the ball mill ball milling become the glass powder of granularity less than 0.074mm;
5. moulding: glass powder is packed in the mould, is compression moulding under the 10MPa at pressure;
6. high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 6 ℃/min is warmed up to 780 ℃, constant temperature sintering 120min, temperature rise rate with 6 ℃/min is warmed up to 920 ℃ then, constant temperature crystallization 120min, furnace cooling is to room temperature, through polishing, be polished to devitrified glass then;
7. the prepared devitrified glass chemical constitution of above-mentioned technology is by weight percentage: SiO 2: 51.35%, Al 2O 3: 17.11%, CaO:12.38%, MgO:2.21%, Fe 2O 3: 8.10%, Na 2O:4.05%, K 2O:1.16%, CaF 2: 1.26%, Cr 2O 3: 1.12%, TiO 2: 0.98%, MnO:0.16%, all the other are 0.12% years old.This devitrified glass performance perameter is: density 2.52gcm -3, HV microhardness 1157, water-absorbent 0.01%, acid resistance 99.3%, alkali resistance 99.3%, ultimate compression strength 523MPa.

Claims (3)

1, a kind of devitrified glass that utilizes the oil shale ash preparation, it is characterized in that the preparation raw material of devitrified glass is: oil shale ash, unslaked lime, magnesium oxide, yellow soda ash, fluorite and chromic oxide, the chemical constitution of devitrified glass is by weight percentage: SiO 2: 45～52%, Al 2O 3: 15～18%, CaO:12～15%, MgO:2～5%, Fe 2O 3: 7～9%, Na 2O:4～6%, K 2O:1～1.5%, CaF 2: 1～2%, Cr 2O 3: 1～2%, all the other trace.
2 according to the described devitrified glass that utilizes the oil shale ash preparation of claim 1, it is characterized in that the apparent bulk density 2.4～2.6gcm of the devitrified glass of described preparation -3, HV microhardness 900～1250, water-absorbent 0.01%, acid resistance 92～99%, alkali resistance 92～99%, ultimate compression strength 400～550MPa.
3, the described method of utilizing oil shale ash to prepare devitrified glass of claim 1 is characterized in that concrete steps are as follows:
1) batching: according to the chemical composition analysis of oil shale ash and to the requirement of product, by weight batching: oil shale ash 75～80%, unslaked lime 9～12%, magnesium oxide 1～3%, yellow soda ash 6～10%, fluorite 2～3%, chromic oxide 1～1.5%;
2) high temperature melting: with various raw materials after accurate weighing in ball mill uniform mixing, join corundum crucible and put in the Si-Mo rod resistance furnace, at 1250～1350 ℃ of following fusion 90～120min;
3) shrend: glass is melted body pour into rapidly in the tap water, shrend becomes the glass particle of 0.074～0.25mm, 100 ℃ of dry 30min in drying baker;
4) pulverize: exsiccant shrend glass particle is put into ball mill, and ball milling becomes the glass powder of granularity less than 0.074mm;
5) moulding: the glass powder after will grinding is packed in the mould, compression moulding, and forming pressure is 10～15MPa;
6) high temperature crystallization: with the glass powder of compression moulding, put in the Si-Mo rod resistance furnace, temperature rise rate with 4～8 ℃/min is warmed up to 780～850 ℃, constant temperature sintering 60～180min, temperature rise rate with 5～8 ℃/min is warmed up to 920～990 ℃ then, constant temperature crystallization 60～180min, furnace cooling is to room temperature, through polishing, be polished to devitrified glass then.
CN200710011020A 2007-04-19 2007-04-19 Microcrystalline glass prepared from oil forming shale ash and method thereof Expired - Fee Related CN100582041C (en)

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CN101718137B (en) * 2009-11-19 2011-07-27 荥经县腾达石材开发有限责任公司 Method for producing microcrystal glass decoration plate material with granite waste material
CN103030297B (en) * 2012-12-05 2016-04-06 毛庆云 A kind of devitrified glass containing modification plant ash and preparation method thereof
CN103288351B (en) * 2013-05-22 2015-06-24 陕西科技大学 Diopside phase glass ceramic and preparation method thereof
CN103641313B (en) * 2013-12-06 2015-09-23 辽宁红山玉科技有限公司 A kind of preparation method of bowlder-like devitrified glass
CN105174725A (en) * 2015-08-17 2015-12-23 昆明理工大学 Microcrystalline glass and preparation method thereof
CN105884200B (en) * 2016-04-11 2018-08-21 大连理工大学 A method of manufacturing devitrified glass ceramics composite material using industrial fly ash and vitrifying slag
CN110240412A (en) * 2019-07-10 2019-09-17 贵州省冶金化工研究所 A kind of high-temperature observation window transparent oxygen Fluorosilicate Glass-Ceramics and preparation method thereof
CN111439932B (en) * 2020-04-08 2022-04-29 维达力实业（赤壁）有限公司 Jade-like microcrystalline glass and preparation method thereof
CN115745380A (en) * 2022-10-31 2023-03-07 苏州大学 Light sintered microcrystal plate and sintering process thereof

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