CA2120573C - Method of producing glass materials from ash-slag waste - Google Patents
Method of producing glass materials from ash-slag waste Download PDFInfo
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- CA2120573C CA2120573C CA002120573A CA2120573A CA2120573C CA 2120573 C CA2120573 C CA 2120573C CA 002120573 A CA002120573 A CA 002120573A CA 2120573 A CA2120573 A CA 2120573A CA 2120573 C CA2120573 C CA 2120573C
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Abstract
A method of obtaining glass materials from ash-slag waste wherein the waste is heated to a melting point temperature and melted in a reducing medium. The obtained melt is cooled by a thermal shock to form a foamed glass material. Prior to heating the charge, the carbon content therein is brought to 3.0 - 8.0 wt %, and the foamed glass material is foamed under a flow of a gaseous medium resulting from decomposition of carbides formed in the melt as a result of carbon content adjustment. Carbon addition also reduces iron oxide present in the waste, this reduction facilitating iron separation from the foamed material.
Description
212fl~3 METHOD OF PRODLTC:ING GLASS MATERIALS FROM ASH-SLAG WASTE
Field of the invention The present invention relates to construction ma-tarials, and, particularly, to a method of producing glass materials from ash-slag v~aste which can also find wide application in the chemical industry, in radio electronics and other branches of industry.
Background of the Invention ~;.nown in the art is a method of producing glass ma-terials consisting in. that a charge including tae following i agred ie at s (wt o) ; , 47.6 Si02, 29. 6 A120~, '15.8 Fe203, 4.2 CaO, 0.6 f~:g0, 1.7 g20, 0.5 Na20 is heated to a melting point temperature and melted in a graphite crucible, where-upon the melt obtained is slowly cooled (F.J. I?eguire, S.H. Risbud. Journal of materials science, v.19, N 6 (1934) 1'760-17b6 'rCrystallisation and properties of .glasses prepared from Illinois coal fly ash.").
The kno~ya method gives a non-transparent material with a large content of iron (15 rvt ) which substantially reduces the field of its application, and particularly, makes it applicable only in the construction industry and quite~inappli-cabla in optical devices. .
Known in the art is a ~thod of preparation of glass materials from ash-slag waste consisting in that a charge of the folloc~iag composition (wt %) CaO total 5.0-x'1.0 Ca0 unbound 4.0-13.0 s i02 13 . 0-'75 . o A 1203 5 .0-26 . 0 c arb o a 1 .0-2. 0 Fe203 . 1-2~ ' r~gp~ 2 . 0-6 . 0 Na20 0.'t-1.0 ~
g20 0 .2-1, 0 So3 0. ~-0.6 Ti02 0.2 ~,124.5~3 is heated to the melting point in a reducing medium, whereupon the obtained melt is cooled by a thermal shock till a glass material is formed (Preprint of the Institute of Physics of Siberian Division of the Academy of Sciences oz the US~~R, 1d 74, ~~9'1 ~.rasnoyarsk, Pavlov V.F
et al. ''A technique of Processing, eshes,coals F~AT~s'K") In practice, i.t is passiole t~o obtain glass materials from all known ash--slag vaaste mat~:rti~als featuring comparatively low r,onduci~:vity whereby they are widely applicable as heat--insults ring ma tarials. ~owevar., this :~:etbod fails to attain complete purification of the ash-slag ~~raste being processed from impurities of transition me talc, which to a great extant reduces the range of application of the glass materials since they cats not be utilized in the syanufGcture of optically transparent alts ss ~ ma teria 1s.
Disclosure of the Invention It is an object of the present invention to provide a method of producing glass materials from ash-slag waste, 20 which vrill considerably improve the quality of the glass materials obtained due to complete purification of the charge from admixtures . of transition metals and binding of free calcium oxide.
25 The object of the invention is attained by providing a method of producing glass materials from ash-slag waste having the following composition, (wt o):
Ca0 total 5.0-41.0 .
Ca0 uab o and 4.0--.'13 . 0 30 Si02 X3.0-?5.0 A1203 5.0-26.0 carbon 1.0-2.0 Fe203 1.0-24.0 2.0-6.0, 35 Na20 0.'I-'1.0 g20 0 . 2-'1. 0 i 'S03 0.1-0.6 Ti02 0 . 2 The ash-slag waste is heated to a melting point temperature and melted in a reducing medium, whereupon the melt obtained is cooled by a thermal shock, i.e. immersion in a cooling bath, preferably water, until a glass material is formed.
According to the invention, prior to heating the charge, the carbon content therein is brought to 3.0 - 8.0 wt ~, and the structure formation of the glass material is carried out in a controlled flow of a gaseous medium.
In cases where it is required to obtain a glass material with a maximum porosity adapted for use as a heat insulating material, the gaseous medium is in fact gases resulting from decomposition of carbides in water.
If it is necessary to obtain a glass material of a spherical shape which finds wide application in diverse branches of industry, for instance from chemical industry (as filters) to aircraft industry (as a light heat-insulating material), the gas medium should additionally contain inert gas fed thereto.
It is possible that the gaseous medium is essentially a mixture of the additionally fed inert gas and the gases resulting from decomposition of carbides in water.
This will enable one to obtain glass materials from ash-slag waste with maximum porosity and low content of aluminum oxides and calcium oxides.
For the manufacture of lime bricks, wall facing tiles used in the construction industry, advantageously,.the obtained glass material is additionally disintegrated and press-moulded with subsequent roasting.
The obtained material may be additionally heated to form a melt and then slowly cooled.
This helps on to obtain glass ceramic wear-resistant materials.
To produce optical materials with a wide transmassivity and a high transparency in the visible and infrared spectra of electromagnetic waves, the material obtained should be additionally heated to form a melt and then cooled with subsequent roasting.
Preferred Embodiments of the Invention The proposed method of producing glass materials from ash-slag waste consists in that the charge of the following composition (wt %):
Ca0 total 5.0-41.0 Ca0 unbound 4.0-13.0 Si02 13.0-75.0 A1z03 5. 0-26 . 0 Carbon 1.0-2.0 Fe203 1. 0 - 24 . 0 Mg0 2.0-6.0 NazO 0 .1-1. 0 K20 0.2-1.0 S03 0.1-0.6 Ti02 0 . 2 is heated to a melting point temperature and melted in a reducing medium, whereupon the obtained melt is cooled by a thermal shock with simultaneous structural formation of the glass material in a controlled gaseous medium flow.
In ash-slag waste formed as a result of burning coals of various deposits, the carbon content generally does not exceed 5 wt % which is not sufficient for carrying out the process, complete recovery of iron oxides and formation of carbides.
Therefore, for carrying out the process of direct recovery of iron oxides, prior to heating of the charge, the carbon content is brought to 3.0-8.0 wt %. This quantity range of the carbon is dependent upon the percentage content of iron oxides in the initial ash-slag waste material.
-s-To prepare a glass material with a reguisite structure, used in the process are gases resulting from decomposition of carbides, inert gases or a mixture of both.
Given oelov~ are specific examples of carrying out the method of producing glass materials from ash-slag Vl2Ste.
Exempla '1 500 g of ash-slag waste formed by burning coals of ~0 the following compasi Lion (cat ;:,;j;
Ca0 total 20.0 Ca0 unb o and 4 .0 ,.
Si02 4~.4?
A1203 x;.43 carbon r a 2 03 0 .,p rfig0 0,3~
Na20 ~ . 0.3'1 ' 0.36 20 So3 0.~3 Ti02 0.2 is melted in a graphite crucible at a temperature of from X350 to '1450°C foil tvro hours and a half. Prior to heating, the carbon content in the charge is brought 25 to 3.0 wt ~. The produced melt with total iron content of 0.'f5 wt ;o is cooled under the conditions of thermal shock by pouring into water. °
This causes instantaneous foaming of the glass material. The obtained porous material is disintegrated 30 to attain a required fineness and ca lcined,to strengthen the pores by heating to 850° C, and the n cooled. The obtaived glass material has a bulk density of ~i50 kg/m3:
Example 2 500 g of ash :Formed by burning coals of a composi-35 Lion similar to that of Example '~- is melted in a graphite a -G-crucible at a temperature of from '1j50 to X450°C for tvro hour. The obtained melt having a total iron content of 0.'I wt ;o is cooled under the condit ions of a thermal shock bar pouring into water. This causes instantaneous foaming of the glass material. The obtained porous glass material is disinterated to attain a requir.ad fineness and roasted by heating ~to a temperature of 850°C to strengthen the pores, a;~hereupoc~ it is cooled. The material thus prepared has a buli~ der_sity of X20 kg/m3.
example 3 500 g of ash formed by burning coals of the composition similar to that of Fxample ~ is melted in a graphite cxzucible at a tamperatu,re of X350-X450°C for four hours.
The obtained melt having a total iron content of O.OS wt o -~5 is cooled under the conditions of a thermal shock b~y pouring into water, whereby instantaneous foaming of the glass material takes place. The foamed glass material thus prepared is disintegrated to attain a requisite fineness and heated to 85o°e to strengthen the pores, whereupon it 20 is cooled. The prepared glass material has a bulk density of 80 kg/m3. ' example 4 500 g of ash ford by burning coals of the following composition (wt ~);
25 Ca0 total 20.5 Ca0 unbound ~~,~
Si02 4~.3 A1203 5.0 carbon 3,0 3o Fe2o3 X2.0 4~5 Na20 'I .2 g20 0.4 so3 0.2 35 Ti02 0.2 _7_ is heated and melted in a graphite crucible at a tempera-tore of '1350-'1450°C for two hours and a half. Prior to heatinb of the charge, the carbon content therein is brought to 3 vJt ~~. The malt thus obtained having a total iron content of 0.'15w=~t ~ is cooled under the conditions of a thermal shock by pouring into water. This causes instantaneous .foaming of the mass. The obtained porous .
glass material is disintegrated to attain a requisite fineness and beat-treated by the method depicted in Example ~. The prepared glass material features a bulk density of X50 kg/ac'.
example 5 500 6 of ash after burning of coals of .the composition indicated in 3xar~pie 4 is melted in a graphite crucible for -~5 three hours. vhe obtained melt vJith a total iron content of 0.'i wt % is cooled under the cg ndit ions of a thermal shock by pouring into water, whereby instantaneous foaming of the mass takes place. the obtained porous ;;lass material is heat-treated by the method of ~cample '1.
20 The prepared glass material features a bulk dec~sity of '100 ko/m3.
Example 6 500 g of ash prepared by burning coals of the composi tion described in Example 4 is melted for four hours. The 25 obtaiaed melt with an iron content of 0.05 wt 7, chromium., 0.02 wt ~ and titanium, 0.~ wt ~, is cooled in a similar way as is h'xamples 4 and 5. The obtained glass material hag a bulk density of 50 kg/m3.
Example 7 500 g of ash after burning of coals with the following composition, wt %:
Ca0 t of al ' 3 .'1 ~a0 unbound none Si02 5a.5 ;, i A1z03 19.2 carbon 5.0 Fea03 2 0 . 0 Mg0 0.6 NazO 0 . 2 Kz0 0 . 9 S03 0.4 Ti02 0 . 2 10is heated and melted.
Prior to heating the charge, the carbon content in the charge is brought to 8 wt %, then the charge is melted in a graphite crucible at a temperature of 1350 to 1450Ctwo for hours and a half. The melt thus produced having a total iron 15content of 0.15 wt % is cooled under the conditions of rmal a the shock by pouring into water.
This causes instantaneous foaming of the mass. The obta ined porous glass material is heat-treated similarly to ExampleThe 2.
glass material produced is characterized by a bulk density150 of 20kg/m3.
Example 8 500 g of ash after burning of coals having the composition listed in Example 7 is melted and heat-treated similarly to Example 2. The prepared glass material has a bulk density of 120 25 kg/m' .
Example 9 500 g of ash after burning of coals of the composition indicated in Example 7 is melted and heat-treated similarly to Example 3. The produced glass material features a bulk density of 30 80 kg/m3.
Example 10 500 g of ash after burning of coals having the following composition (wt %):
Ca0 total 20.0 35 Cao unbound 4.0 __._ SiOz 58 . _ A1z03 9 . 4 I. I
Fe203 1. 0 Mg0 5.3 NaaO 0 . 3 K20 0.4 so3 0 .13 TiOz 0 . 2 wherein the carbon content in the charge is brought to 3 wt %, is heated and melted in a graphite crucible at a temperature of 1350 to 1450°C for an hour and a half. The obtained melt with a total iron content amounting to 0.15 wt % is cooled under the conditions of a thermal shock by pouring into water, whereby instantaneous foaming of the glass material is caused. The obtained porous glass material is disintegrated to attain a requisite fineness and roasted to a temperature of 850°C, and subsequently cooled. The prepared glass material has a bulk density of 150 kg/m3.
Example 11 500 g of ash after burning of coals of the composition specified in Example l0 is melted in a graphite crucible at a temperature of 1340-1450°C for two hours. The melt obtained with a total iron content of 0.1 wt % is cooled under the conditions of a thermal shock by pouring into water, whereby instantaneous foaming of the material is caused. The obtained porous glass material is processed similarly to Example 10. The prepared glass material is characterized by a bulk density of 120 kg/m3.
Example 12 500 g of ash having the composition of Example 10 is melted in a graphite crucible at a temperature of 1350-1450°C for two hours and a half: The melt thus prepared with a total iron content of 0.05 wt % is cooled under the conditions of a thermal shock by pouring into water. This causes instantaneous foaming of the glass material.
-1~-The obtained glass material is processed as in Example 10.
The density of the glass material is 80 kg/m'.
Example 13 500 g of ash after burning of coals having the composition specified in Example 1 is melted and heat-treated in a way similar to that of Example 1. The obtained glass material is dispersed to a fineness of. from 0 to 80 Vim, then cubes of 100x100x10omm size and bars of 40x40x160mm size are press moulded from the powder.
The moulded articles are dried and roasted at a temperature of 950°C for 50 min. with subsequent cooling in the furnace. The produced samples have the following characteristics:
ultimate compression strength, Mpa 39.3 ultimate bending strength, Mpa 7.7 Example 14 500 g of ash after burning of coals of the composition indicated in Example 1 is melted and heat-treated as in Example 2.
The obtained glass material is dispersed to a fineness of from 0 to 80~,m, then cubes of 100x100x100mm size and bars of 40x40x160mm size are press-moulded from the powder. The moulded articles are dried and then roasted at a temperature of 950°C for 30 min.
with subsequent cooling in the furnace. The obtained samples have the following characteristics:
ultimate compression strength, Mpa 40.0 ultimate bending strength, Mpa 8.0 Example 15 500 g of ash after burning of coals of the composition indicated in Example 1 is melted and heat treated similarly to Example 3. The obtained glass material is dispersed to a fineness of foam from 0 to 80 hem, then moulded and heat treated as in Example 10. The obtained samples feature the following characteristics:
z ultimata compression strength, Iv~?a 4j.2 ultimate bending strength, IWa 8.1 ~sxample 16 500 g of ash after burning of coals having the composition specified in :~~sample 4 is melted and heat-trea ted in a z:ay s i~ilar t o tha t of Exa mple ~i, ~h a articles are moulded and roasted as in Exarsple 13. The obtained samples have th~ .following characteristics:
ultimata compression strength, r~Fa 39.0 ult imate bending strength, Lea 7.5 r~:campla 17 500 g of ash after burning of coals having a composition. similar to that of ixa~uple 4 is melted and heat-treated as in yxample 2. Then the material is dispersed, moulded and heat-treated in the same manner as in example 13. The obtained samples have the follov~ing characteristics:
ultimate compression strength, NiPa 43.0 ultimate bending strength, ~Pa 8:3 ~x a iap l a 18 500 g of ash formed after burning of~ coals having the composition indicated in nxaraple 4 i:s melted, heat-treated, moulded and roasted in a similar vJay as in Examples 3 and 13. The obtained samples have the folloyring characteristics:
ultimate compression strength ~a 44.2 ultimate bending strength, lL~a 8.5 Example 19 500 g of ash foru~d after burning of coals having th8 C.Dmp091.tiDn Indicated in ~txample 7 is melted, heat-treated and roasted . similarly .to. Examples 1 and 13. The obtaina.d ~samplas have the following characteristics:
ultimate compression strength, MPa '19,1 ultimata bending strength, MPa 2.6 .~
-~2-Example 20 500 g of ash after burning of coals of the composition specified in Example 7 is melted, heat-treated, moulded and roasted similarly to Examples 2 and 13. The obtained samples have the following characteristics:
ultimate compression strength, u'1'a 1'x~5 ultimate bendir~ strength, . lrPa ~ 2.7 ~'x amo 1 a 21 50~J g of ash formed after burning, of coals havit~;
the composition specified in example 7 is melted, heat treated,moulded and roasted in a may similar to that' o f Fxamp 1e s 3 arid 13 .
'lhe obtained samples have the following proper ties:
ultimate compression strength, ~?IIPa 20.0 ultimate bending strength I:~a 2.6 ~ampla 22 5~J0 g -of ash after burc:ing of. coals having a composition similar to that of Example ? is melted, heat-treated and moulded as in ~xamola 3 and 13, while roasting is carried out at a temperature of 1050°C,for thirty minutes with subsequent cooling in the furnace. The obtained samples have the following characteristics:
ultimate compression strength, I~Pa 60.0 ultimate bending strength, 1'r~a Example 23 500 g of ash formed after burning of coals of the composition of Example 1 is melted in a graphite crucible at a temperature of from 1350 to '1450°C for two hours and a half. The obtained melt havit~. a total iron content of 0.'15 wt j is poured into graphite moulds preheated' to 550°C, then the temperature is raised to 800 - 850°C, and the melt stands at this temperature for an hour and a half with subsequent cooling in the electric furnace to room temperature. The prepared glass ceramic materials have the follov~ing characteristics:
,,,,.
light transmission factor, % 30.0 thermal conductivity, w/m~K 0.8 linear expansion coefficient °C'1 6 x 10'6 ultimate bending strength, Mpa 75.0 Example 24 500 g of ash after burning of coals having the composition specified in Example 1 is melted as in Example 2. The obtained melt is poured into the mould and heat-treated in the way similar to that of Example 23. The prepared glass ceramic materials have the following properties:
light transmission factor, % 40.0 thermal conductivity, W/ m~K 0.8 linear expansion coefficient, °C'1 5 x 10'6 ultimate bending strength, Mpa 75.0 Example 25 500 g of ash obtained after burning of coals having the composition indicated in Example 1 is melted in the way similar to that of Example 3, moulded and roasted as in Example 23. The produced glass ceramic materials have the following characteristics:
Light transmission factor, % 50.0 thermal conductivity, W/m~K 0.7 linear expansion coefficient, °C'1 5 x 10'6 ultimate bending strength, Mpa 80.0 Example 26 500 g of ash obtained after burning of coals of the composition specified in Example 4 is processed as disclosed in Example 23. The glass ceramic materials produced have the following properties:
light transmission factor, % 30.0 thermal conductivity, W/m~K 0.8 linear expansion coefficient, °C'1 6 x 10'6 ultimate bending strength, Mpa 75.0 Example 27 500 g of ash after burning of coals having the composition specified in Example 4 is processed as in Example 24. The obtained glass ceramic materials have the following characteristics:
light transmission factor, ~ 40.0 thermal conductivity, W/m~K 0.75 linear expansion coefficient, °C-1 5.5 x 10-6 ultimate bending strength, Mpa 75.0 Example 28 500 g of ash obtained after burning of coals with the composition of Example 4 is processed in the way similar to Example 25. The obtained glass ceramic materials have the following properties:
light transmission factor, ~ 50.0 thermal conductivity, w/m~K 0.7 linear expansion coefficient, °C-1 5 x 10-6 ultimate bending strength, Mpa 80.0 Example 29 500 g of ash obtained by burning of coals having the composition indicated in Example 7 is heat-treated in a way similar to that of Example 23. The produced glass ceramic materials feature the following characteristics:
light transmission factor, ~ 30.0 thermal conductivity, w/m~K 0.8 linear expansion coefficient, °C-1 5 x 10-6 ultimate bending strength, Mpa 90.0 Example 30 500 g of ash after burning of coals of the composition indicated in Example 7 is heat-treated as in Example 24. The obtained glass ceramic materials have the following characteristics:
light transmission factor, % 40.0 thermal conductivity w/m~K . 0.75 linear expansion coefficient, °C'' 5 x 10'6 Example 31 500 g of ash obtained after burning of coals having the composition indicated in Example 7 is heat-treated in the way similar to that of Example 25. The glass ceramic materials produced have the following characteristics:
light transmission factor, % 50.0 thermal conductivity, w/m~K ~ 0.7 linear expansion coefficient, °C~l 5 x 10-6 ultimate bending strength, Mpa 100 Example 32 500 g of the porous glass material obtained in Example 1 is placed into an ~jundun~*crucible and melted at a temperature of from 1450 - 1500°C far 2 hours, poured into graphite moulds which have been preheated to 550°C, heated to 850°C, whereupon the melt stands at this temperature for two hours with subsequent cooling in the furnace to a room temperature.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples is equal to 75%.
Example 33 500 g of the porous glass.material obtained in Example 2 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the obtained samples is 85%.
Example 34 500 g of the porous glass material obtained in Example 3 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced amounts to 95%.
r * Trademark for a line of products made from fused alumina.
' -16-Example 35 500 g of the porous glass material obtained in Example 4 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced is 70%.
Example 36 500 g of porous glass material prepared in Example 5 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves is 80%.
Example 37 500 g of porous glass material obtained in Example 6 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced amounts to 90%.
Example 38 500 g of porous glass material obtained in Example 7 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the sample produced is 70%.
Example 39 500 g of porous material obtained in Example 8 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the glass seramic material obtained is 80%.
Example 40 500 g of porous material obtained in Example 9 is melted and heat-treated similarly to the process of Example 29. The transmissivity in the visible and infrared spectra of electromagnetic waves of the glass ceramic materials produced amounts to 95%.
Example 41 500 g of ash after burning of coals having the composition specified in Example 4 is melted as in Example 4.
i . . -1~7_ The obtained melt is cooled under the conditions of a thermal shock by pouring it onto an ascending flow of inert gas (C02).
This results in that the obtained glass material acquires a hollow spherical shape with the density of its granules amounting to 1000 kg/m3.
Example 42 500 g of ash formed after burning of coals having the composition indicated in Example 4 is melted as described above.
The obtained melt cooled under the condition s of a thermal shock by pouring into water, accompanied by blowing in of inert gas (COZ), whereby more than 50% of the glass material has a hollow spherical shape of various diameters with a granules density of 500 kg/m3.
Example 43 500 g of ash after burning of coals having the composition specified in Example 4 is melted as in Example 4. The obtained melt is cooled under the conditions of a thermal shock by pouring the melt into water through the foamed material.
Consequently, less than 50% of the total mass of the glass material produced has a hollow spherical shape of different diameters with the density of the granules ranging from 100 to 300 kg/m3 .
Industrial Applicability The present invention can be most effectively used for the production of construction materials of diverse purposes (bricks, heat- and sound-insulating materials, facing and ceramic materials) filtering materials, and chemically stable materials.
Moreover, the proposed method helps one to obtain glass materials featuring a high light transmission factor which can be utilized in magneto-optics (magneto-optical memory disks, liquid crystal light modulators), as well as in astronomical optics.
Field of the invention The present invention relates to construction ma-tarials, and, particularly, to a method of producing glass materials from ash-slag v~aste which can also find wide application in the chemical industry, in radio electronics and other branches of industry.
Background of the Invention ~;.nown in the art is a method of producing glass ma-terials consisting in. that a charge including tae following i agred ie at s (wt o) ; , 47.6 Si02, 29. 6 A120~, '15.8 Fe203, 4.2 CaO, 0.6 f~:g0, 1.7 g20, 0.5 Na20 is heated to a melting point temperature and melted in a graphite crucible, where-upon the melt obtained is slowly cooled (F.J. I?eguire, S.H. Risbud. Journal of materials science, v.19, N 6 (1934) 1'760-17b6 'rCrystallisation and properties of .glasses prepared from Illinois coal fly ash.").
The kno~ya method gives a non-transparent material with a large content of iron (15 rvt ) which substantially reduces the field of its application, and particularly, makes it applicable only in the construction industry and quite~inappli-cabla in optical devices. .
Known in the art is a ~thod of preparation of glass materials from ash-slag waste consisting in that a charge of the folloc~iag composition (wt %) CaO total 5.0-x'1.0 Ca0 unbound 4.0-13.0 s i02 13 . 0-'75 . o A 1203 5 .0-26 . 0 c arb o a 1 .0-2. 0 Fe203 . 1-2~ ' r~gp~ 2 . 0-6 . 0 Na20 0.'t-1.0 ~
g20 0 .2-1, 0 So3 0. ~-0.6 Ti02 0.2 ~,124.5~3 is heated to the melting point in a reducing medium, whereupon the obtained melt is cooled by a thermal shock till a glass material is formed (Preprint of the Institute of Physics of Siberian Division of the Academy of Sciences oz the US~~R, 1d 74, ~~9'1 ~.rasnoyarsk, Pavlov V.F
et al. ''A technique of Processing, eshes,coals F~AT~s'K") In practice, i.t is passiole t~o obtain glass materials from all known ash--slag vaaste mat~:rti~als featuring comparatively low r,onduci~:vity whereby they are widely applicable as heat--insults ring ma tarials. ~owevar., this :~:etbod fails to attain complete purification of the ash-slag ~~raste being processed from impurities of transition me talc, which to a great extant reduces the range of application of the glass materials since they cats not be utilized in the syanufGcture of optically transparent alts ss ~ ma teria 1s.
Disclosure of the Invention It is an object of the present invention to provide a method of producing glass materials from ash-slag waste, 20 which vrill considerably improve the quality of the glass materials obtained due to complete purification of the charge from admixtures . of transition metals and binding of free calcium oxide.
25 The object of the invention is attained by providing a method of producing glass materials from ash-slag waste having the following composition, (wt o):
Ca0 total 5.0-41.0 .
Ca0 uab o and 4.0--.'13 . 0 30 Si02 X3.0-?5.0 A1203 5.0-26.0 carbon 1.0-2.0 Fe203 1.0-24.0 2.0-6.0, 35 Na20 0.'I-'1.0 g20 0 . 2-'1. 0 i 'S03 0.1-0.6 Ti02 0 . 2 The ash-slag waste is heated to a melting point temperature and melted in a reducing medium, whereupon the melt obtained is cooled by a thermal shock, i.e. immersion in a cooling bath, preferably water, until a glass material is formed.
According to the invention, prior to heating the charge, the carbon content therein is brought to 3.0 - 8.0 wt ~, and the structure formation of the glass material is carried out in a controlled flow of a gaseous medium.
In cases where it is required to obtain a glass material with a maximum porosity adapted for use as a heat insulating material, the gaseous medium is in fact gases resulting from decomposition of carbides in water.
If it is necessary to obtain a glass material of a spherical shape which finds wide application in diverse branches of industry, for instance from chemical industry (as filters) to aircraft industry (as a light heat-insulating material), the gas medium should additionally contain inert gas fed thereto.
It is possible that the gaseous medium is essentially a mixture of the additionally fed inert gas and the gases resulting from decomposition of carbides in water.
This will enable one to obtain glass materials from ash-slag waste with maximum porosity and low content of aluminum oxides and calcium oxides.
For the manufacture of lime bricks, wall facing tiles used in the construction industry, advantageously,.the obtained glass material is additionally disintegrated and press-moulded with subsequent roasting.
The obtained material may be additionally heated to form a melt and then slowly cooled.
This helps on to obtain glass ceramic wear-resistant materials.
To produce optical materials with a wide transmassivity and a high transparency in the visible and infrared spectra of electromagnetic waves, the material obtained should be additionally heated to form a melt and then cooled with subsequent roasting.
Preferred Embodiments of the Invention The proposed method of producing glass materials from ash-slag waste consists in that the charge of the following composition (wt %):
Ca0 total 5.0-41.0 Ca0 unbound 4.0-13.0 Si02 13.0-75.0 A1z03 5. 0-26 . 0 Carbon 1.0-2.0 Fe203 1. 0 - 24 . 0 Mg0 2.0-6.0 NazO 0 .1-1. 0 K20 0.2-1.0 S03 0.1-0.6 Ti02 0 . 2 is heated to a melting point temperature and melted in a reducing medium, whereupon the obtained melt is cooled by a thermal shock with simultaneous structural formation of the glass material in a controlled gaseous medium flow.
In ash-slag waste formed as a result of burning coals of various deposits, the carbon content generally does not exceed 5 wt % which is not sufficient for carrying out the process, complete recovery of iron oxides and formation of carbides.
Therefore, for carrying out the process of direct recovery of iron oxides, prior to heating of the charge, the carbon content is brought to 3.0-8.0 wt %. This quantity range of the carbon is dependent upon the percentage content of iron oxides in the initial ash-slag waste material.
-s-To prepare a glass material with a reguisite structure, used in the process are gases resulting from decomposition of carbides, inert gases or a mixture of both.
Given oelov~ are specific examples of carrying out the method of producing glass materials from ash-slag Vl2Ste.
Exempla '1 500 g of ash-slag waste formed by burning coals of ~0 the following compasi Lion (cat ;:,;j;
Ca0 total 20.0 Ca0 unb o and 4 .0 ,.
Si02 4~.4?
A1203 x;.43 carbon r a 2 03 0 .,p rfig0 0,3~
Na20 ~ . 0.3'1 ' 0.36 20 So3 0.~3 Ti02 0.2 is melted in a graphite crucible at a temperature of from X350 to '1450°C foil tvro hours and a half. Prior to heating, the carbon content in the charge is brought 25 to 3.0 wt ~. The produced melt with total iron content of 0.'f5 wt ;o is cooled under the conditions of thermal shock by pouring into water. °
This causes instantaneous foaming of the glass material. The obtained porous material is disintegrated 30 to attain a required fineness and ca lcined,to strengthen the pores by heating to 850° C, and the n cooled. The obtaived glass material has a bulk density of ~i50 kg/m3:
Example 2 500 g of ash :Formed by burning coals of a composi-35 Lion similar to that of Example '~- is melted in a graphite a -G-crucible at a temperature of from '1j50 to X450°C for tvro hour. The obtained melt having a total iron content of 0.'I wt ;o is cooled under the condit ions of a thermal shock bar pouring into water. This causes instantaneous foaming of the glass material. The obtained porous glass material is disinterated to attain a requir.ad fineness and roasted by heating ~to a temperature of 850°C to strengthen the pores, a;~hereupoc~ it is cooled. The material thus prepared has a buli~ der_sity of X20 kg/m3.
example 3 500 g of ash formed by burning coals of the composition similar to that of Fxample ~ is melted in a graphite cxzucible at a tamperatu,re of X350-X450°C for four hours.
The obtained melt having a total iron content of O.OS wt o -~5 is cooled under the conditions of a thermal shock b~y pouring into water, whereby instantaneous foaming of the glass material takes place. The foamed glass material thus prepared is disintegrated to attain a requisite fineness and heated to 85o°e to strengthen the pores, whereupon it 20 is cooled. The prepared glass material has a bulk density of 80 kg/m3. ' example 4 500 g of ash ford by burning coals of the following composition (wt ~);
25 Ca0 total 20.5 Ca0 unbound ~~,~
Si02 4~.3 A1203 5.0 carbon 3,0 3o Fe2o3 X2.0 4~5 Na20 'I .2 g20 0.4 so3 0.2 35 Ti02 0.2 _7_ is heated and melted in a graphite crucible at a tempera-tore of '1350-'1450°C for two hours and a half. Prior to heatinb of the charge, the carbon content therein is brought to 3 vJt ~~. The malt thus obtained having a total iron content of 0.'15w=~t ~ is cooled under the conditions of a thermal shock by pouring into water. This causes instantaneous .foaming of the mass. The obtained porous .
glass material is disintegrated to attain a requisite fineness and beat-treated by the method depicted in Example ~. The prepared glass material features a bulk density of X50 kg/ac'.
example 5 500 6 of ash after burning of coals of .the composition indicated in 3xar~pie 4 is melted in a graphite crucible for -~5 three hours. vhe obtained melt vJith a total iron content of 0.'i wt % is cooled under the cg ndit ions of a thermal shock by pouring into water, whereby instantaneous foaming of the mass takes place. the obtained porous ;;lass material is heat-treated by the method of ~cample '1.
20 The prepared glass material features a bulk dec~sity of '100 ko/m3.
Example 6 500 g of ash prepared by burning coals of the composi tion described in Example 4 is melted for four hours. The 25 obtaiaed melt with an iron content of 0.05 wt 7, chromium., 0.02 wt ~ and titanium, 0.~ wt ~, is cooled in a similar way as is h'xamples 4 and 5. The obtained glass material hag a bulk density of 50 kg/m3.
Example 7 500 g of ash after burning of coals with the following composition, wt %:
Ca0 t of al ' 3 .'1 ~a0 unbound none Si02 5a.5 ;, i A1z03 19.2 carbon 5.0 Fea03 2 0 . 0 Mg0 0.6 NazO 0 . 2 Kz0 0 . 9 S03 0.4 Ti02 0 . 2 10is heated and melted.
Prior to heating the charge, the carbon content in the charge is brought to 8 wt %, then the charge is melted in a graphite crucible at a temperature of 1350 to 1450Ctwo for hours and a half. The melt thus produced having a total iron 15content of 0.15 wt % is cooled under the conditions of rmal a the shock by pouring into water.
This causes instantaneous foaming of the mass. The obta ined porous glass material is heat-treated similarly to ExampleThe 2.
glass material produced is characterized by a bulk density150 of 20kg/m3.
Example 8 500 g of ash after burning of coals having the composition listed in Example 7 is melted and heat-treated similarly to Example 2. The prepared glass material has a bulk density of 120 25 kg/m' .
Example 9 500 g of ash after burning of coals of the composition indicated in Example 7 is melted and heat-treated similarly to Example 3. The produced glass material features a bulk density of 30 80 kg/m3.
Example 10 500 g of ash after burning of coals having the following composition (wt %):
Ca0 total 20.0 35 Cao unbound 4.0 __._ SiOz 58 . _ A1z03 9 . 4 I. I
Fe203 1. 0 Mg0 5.3 NaaO 0 . 3 K20 0.4 so3 0 .13 TiOz 0 . 2 wherein the carbon content in the charge is brought to 3 wt %, is heated and melted in a graphite crucible at a temperature of 1350 to 1450°C for an hour and a half. The obtained melt with a total iron content amounting to 0.15 wt % is cooled under the conditions of a thermal shock by pouring into water, whereby instantaneous foaming of the glass material is caused. The obtained porous glass material is disintegrated to attain a requisite fineness and roasted to a temperature of 850°C, and subsequently cooled. The prepared glass material has a bulk density of 150 kg/m3.
Example 11 500 g of ash after burning of coals of the composition specified in Example l0 is melted in a graphite crucible at a temperature of 1340-1450°C for two hours. The melt obtained with a total iron content of 0.1 wt % is cooled under the conditions of a thermal shock by pouring into water, whereby instantaneous foaming of the material is caused. The obtained porous glass material is processed similarly to Example 10. The prepared glass material is characterized by a bulk density of 120 kg/m3.
Example 12 500 g of ash having the composition of Example 10 is melted in a graphite crucible at a temperature of 1350-1450°C for two hours and a half: The melt thus prepared with a total iron content of 0.05 wt % is cooled under the conditions of a thermal shock by pouring into water. This causes instantaneous foaming of the glass material.
-1~-The obtained glass material is processed as in Example 10.
The density of the glass material is 80 kg/m'.
Example 13 500 g of ash after burning of coals having the composition specified in Example 1 is melted and heat-treated in a way similar to that of Example 1. The obtained glass material is dispersed to a fineness of. from 0 to 80 Vim, then cubes of 100x100x10omm size and bars of 40x40x160mm size are press moulded from the powder.
The moulded articles are dried and roasted at a temperature of 950°C for 50 min. with subsequent cooling in the furnace. The produced samples have the following characteristics:
ultimate compression strength, Mpa 39.3 ultimate bending strength, Mpa 7.7 Example 14 500 g of ash after burning of coals of the composition indicated in Example 1 is melted and heat-treated as in Example 2.
The obtained glass material is dispersed to a fineness of from 0 to 80~,m, then cubes of 100x100x100mm size and bars of 40x40x160mm size are press-moulded from the powder. The moulded articles are dried and then roasted at a temperature of 950°C for 30 min.
with subsequent cooling in the furnace. The obtained samples have the following characteristics:
ultimate compression strength, Mpa 40.0 ultimate bending strength, Mpa 8.0 Example 15 500 g of ash after burning of coals of the composition indicated in Example 1 is melted and heat treated similarly to Example 3. The obtained glass material is dispersed to a fineness of foam from 0 to 80 hem, then moulded and heat treated as in Example 10. The obtained samples feature the following characteristics:
z ultimata compression strength, Iv~?a 4j.2 ultimate bending strength, IWa 8.1 ~sxample 16 500 g of ash after burning of coals having the composition specified in :~~sample 4 is melted and heat-trea ted in a z:ay s i~ilar t o tha t of Exa mple ~i, ~h a articles are moulded and roasted as in Exarsple 13. The obtained samples have th~ .following characteristics:
ultimata compression strength, r~Fa 39.0 ult imate bending strength, Lea 7.5 r~:campla 17 500 g of ash after burning of coals having a composition. similar to that of ixa~uple 4 is melted and heat-treated as in yxample 2. Then the material is dispersed, moulded and heat-treated in the same manner as in example 13. The obtained samples have the follov~ing characteristics:
ultimate compression strength, NiPa 43.0 ultimate bending strength, ~Pa 8:3 ~x a iap l a 18 500 g of ash formed after burning of~ coals having the composition indicated in nxaraple 4 i:s melted, heat-treated, moulded and roasted in a similar vJay as in Examples 3 and 13. The obtained samples have the folloyring characteristics:
ultimate compression strength ~a 44.2 ultimate bending strength, lL~a 8.5 Example 19 500 g of ash foru~d after burning of coals having th8 C.Dmp091.tiDn Indicated in ~txample 7 is melted, heat-treated and roasted . similarly .to. Examples 1 and 13. The obtaina.d ~samplas have the following characteristics:
ultimate compression strength, MPa '19,1 ultimata bending strength, MPa 2.6 .~
-~2-Example 20 500 g of ash after burning of coals of the composition specified in Example 7 is melted, heat-treated, moulded and roasted similarly to Examples 2 and 13. The obtained samples have the following characteristics:
ultimate compression strength, u'1'a 1'x~5 ultimate bendir~ strength, . lrPa ~ 2.7 ~'x amo 1 a 21 50~J g of ash formed after burning, of coals havit~;
the composition specified in example 7 is melted, heat treated,moulded and roasted in a may similar to that' o f Fxamp 1e s 3 arid 13 .
'lhe obtained samples have the following proper ties:
ultimate compression strength, ~?IIPa 20.0 ultimate bending strength I:~a 2.6 ~ampla 22 5~J0 g -of ash after burc:ing of. coals having a composition similar to that of Example ? is melted, heat-treated and moulded as in ~xamola 3 and 13, while roasting is carried out at a temperature of 1050°C,for thirty minutes with subsequent cooling in the furnace. The obtained samples have the following characteristics:
ultimate compression strength, I~Pa 60.0 ultimate bending strength, 1'r~a Example 23 500 g of ash formed after burning of coals of the composition of Example 1 is melted in a graphite crucible at a temperature of from 1350 to '1450°C for two hours and a half. The obtained melt havit~. a total iron content of 0.'15 wt j is poured into graphite moulds preheated' to 550°C, then the temperature is raised to 800 - 850°C, and the melt stands at this temperature for an hour and a half with subsequent cooling in the electric furnace to room temperature. The prepared glass ceramic materials have the follov~ing characteristics:
,,,,.
light transmission factor, % 30.0 thermal conductivity, w/m~K 0.8 linear expansion coefficient °C'1 6 x 10'6 ultimate bending strength, Mpa 75.0 Example 24 500 g of ash after burning of coals having the composition specified in Example 1 is melted as in Example 2. The obtained melt is poured into the mould and heat-treated in the way similar to that of Example 23. The prepared glass ceramic materials have the following properties:
light transmission factor, % 40.0 thermal conductivity, W/ m~K 0.8 linear expansion coefficient, °C'1 5 x 10'6 ultimate bending strength, Mpa 75.0 Example 25 500 g of ash obtained after burning of coals having the composition indicated in Example 1 is melted in the way similar to that of Example 3, moulded and roasted as in Example 23. The produced glass ceramic materials have the following characteristics:
Light transmission factor, % 50.0 thermal conductivity, W/m~K 0.7 linear expansion coefficient, °C'1 5 x 10'6 ultimate bending strength, Mpa 80.0 Example 26 500 g of ash obtained after burning of coals of the composition specified in Example 4 is processed as disclosed in Example 23. The glass ceramic materials produced have the following properties:
light transmission factor, % 30.0 thermal conductivity, W/m~K 0.8 linear expansion coefficient, °C'1 6 x 10'6 ultimate bending strength, Mpa 75.0 Example 27 500 g of ash after burning of coals having the composition specified in Example 4 is processed as in Example 24. The obtained glass ceramic materials have the following characteristics:
light transmission factor, ~ 40.0 thermal conductivity, W/m~K 0.75 linear expansion coefficient, °C-1 5.5 x 10-6 ultimate bending strength, Mpa 75.0 Example 28 500 g of ash obtained after burning of coals with the composition of Example 4 is processed in the way similar to Example 25. The obtained glass ceramic materials have the following properties:
light transmission factor, ~ 50.0 thermal conductivity, w/m~K 0.7 linear expansion coefficient, °C-1 5 x 10-6 ultimate bending strength, Mpa 80.0 Example 29 500 g of ash obtained by burning of coals having the composition indicated in Example 7 is heat-treated in a way similar to that of Example 23. The produced glass ceramic materials feature the following characteristics:
light transmission factor, ~ 30.0 thermal conductivity, w/m~K 0.8 linear expansion coefficient, °C-1 5 x 10-6 ultimate bending strength, Mpa 90.0 Example 30 500 g of ash after burning of coals of the composition indicated in Example 7 is heat-treated as in Example 24. The obtained glass ceramic materials have the following characteristics:
light transmission factor, % 40.0 thermal conductivity w/m~K . 0.75 linear expansion coefficient, °C'' 5 x 10'6 Example 31 500 g of ash obtained after burning of coals having the composition indicated in Example 7 is heat-treated in the way similar to that of Example 25. The glass ceramic materials produced have the following characteristics:
light transmission factor, % 50.0 thermal conductivity, w/m~K ~ 0.7 linear expansion coefficient, °C~l 5 x 10-6 ultimate bending strength, Mpa 100 Example 32 500 g of the porous glass material obtained in Example 1 is placed into an ~jundun~*crucible and melted at a temperature of from 1450 - 1500°C far 2 hours, poured into graphite moulds which have been preheated to 550°C, heated to 850°C, whereupon the melt stands at this temperature for two hours with subsequent cooling in the furnace to a room temperature.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples is equal to 75%.
Example 33 500 g of the porous glass.material obtained in Example 2 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the obtained samples is 85%.
Example 34 500 g of the porous glass material obtained in Example 3 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced amounts to 95%.
r * Trademark for a line of products made from fused alumina.
' -16-Example 35 500 g of the porous glass material obtained in Example 4 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced is 70%.
Example 36 500 g of porous glass material prepared in Example 5 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves is 80%.
Example 37 500 g of porous glass material obtained in Example 6 is melted and heat-treated similarly to the process of Example 32.
The transmissivity in the visible and infrared spectra of electromagnetic waves of the samples produced amounts to 90%.
Example 38 500 g of porous glass material obtained in Example 7 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the sample produced is 70%.
Example 39 500 g of porous material obtained in Example 8 is melted and heat-treated as in Example 32. The transmissivity in the visible and infrared spectra of electromagnetic waves of the glass seramic material obtained is 80%.
Example 40 500 g of porous material obtained in Example 9 is melted and heat-treated similarly to the process of Example 29. The transmissivity in the visible and infrared spectra of electromagnetic waves of the glass ceramic materials produced amounts to 95%.
Example 41 500 g of ash after burning of coals having the composition specified in Example 4 is melted as in Example 4.
i . . -1~7_ The obtained melt is cooled under the conditions of a thermal shock by pouring it onto an ascending flow of inert gas (C02).
This results in that the obtained glass material acquires a hollow spherical shape with the density of its granules amounting to 1000 kg/m3.
Example 42 500 g of ash formed after burning of coals having the composition indicated in Example 4 is melted as described above.
The obtained melt cooled under the condition s of a thermal shock by pouring into water, accompanied by blowing in of inert gas (COZ), whereby more than 50% of the glass material has a hollow spherical shape of various diameters with a granules density of 500 kg/m3.
Example 43 500 g of ash after burning of coals having the composition specified in Example 4 is melted as in Example 4. The obtained melt is cooled under the conditions of a thermal shock by pouring the melt into water through the foamed material.
Consequently, less than 50% of the total mass of the glass material produced has a hollow spherical shape of different diameters with the density of the granules ranging from 100 to 300 kg/m3 .
Industrial Applicability The present invention can be most effectively used for the production of construction materials of diverse purposes (bricks, heat- and sound-insulating materials, facing and ceramic materials) filtering materials, and chemically stable materials.
Moreover, the proposed method helps one to obtain glass materials featuring a high light transmission factor which can be utilized in magneto-optics (magneto-optical memory disks, liquid crystal light modulators), as well as in astronomical optics.
Claims (24)
1. A method of producing foamed glass materials from ash-slag waste derived from burning coals comprising the steps of:
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge; and c) forming said foamed glass material by pouring said melted charge into a water bath;
wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3, content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass materials.
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge; and c) forming said foamed glass material by pouring said melted charge into a water bath;
wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3, content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass materials.
2. A method according to claim 1, wherein said step of adding carbon to the charge effects adjustment of the carbon content of the charge to 3.0 to 8.0 wt % carbon.
3. A method according to claim 1, wherein said melt is contacted with an inert gas.
4. A method according to claim 3, comprising blowing the inert gas into the water bath.
2 ~~
2 ~~
5. The method of claim 3 wherein the inert gas is injected into said melt during the pouring of said melt into said water bath.
6. The method of claim 1 further comprising the steps of disintegrating said foamed glass material, heating said disintegrated glass material in air to increase its strength and cooling said heated glass material to increase the bulk density of said glass material.
7. The method of claim 1 further comprising the steps of disintegrating said foamed glass material, press molding said disintegrated glass material to a predetermined shape, heating said press molded glass material in air to increase its strength and cooling said heated glass material to form a molded article.
8. The method of claim 1 further comprising the step of melting said foamed glass materials, heating said melted glass material and cooling said heated material to form an optical material.
9. The method of claim 1 wherein the charge of the providing step has the following composition:
CaO total 5.0-41.0 CaO unbound 4.0-13.0 SiO2 13.0-75.0 A1 2O3 5.0-26.0 carbon 1.0-2.0 Fe2O3 1.0-24.0 MgO 2.0-6.0 Na2O 0.1-1.0 K2O 0.2-1.0 SO3 0.1-0.6 TiO2 0.2 ;
the carbon content of the charge after addition of said carbon thereto ranging between 3.0 and 8.0 wt %.
CaO total 5.0-41.0 CaO unbound 4.0-13.0 SiO2 13.0-75.0 A1 2O3 5.0-26.0 carbon 1.0-2.0 Fe2O3 1.0-24.0 MgO 2.0-6.0 Na2O 0.1-1.0 K2O 0.2-1.0 SO3 0.1-0.6 TiO2 0.2 ;
the carbon content of the charge after addition of said carbon thereto ranging between 3.0 and 8.0 wt %.
10. A foamed glass material comprising a plurality of porous enclosed structures of ash slag waste with an iron content of less than 0.150 by weight, made by the process steps of:
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge; and c) forming said plurality of porous enclosed structures by pouring said melted charge into a water bath;
d) wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3, content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the porous enclosed structures.
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge; and c) forming said plurality of porous enclosed structures by pouring said melted charge into a water bath;
d) wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3, content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the porous enclosed structures.
11. A spherical foamed glass material comprising a plurality of generally spherically shaped porous enclosed structures of ash slag waste with an iron content less than 0.15% by weight, the generally spherically shaped porous enclosed structures made by the process steps of:
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0~
;
b) heating and melting the charge; and c) forming said plurality of generally spherically shaped porous enclosed structures by pouring said melted charge into a water bath;
d) wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the porous enclosed structures comprising blowing inert gas into the water bath and wherein the gaseous medium is a mixture of the inert gas blown into said water bath and the gaseous medium generated from the carbides.
a) providing a charge of the ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0~
;
b) heating and melting the charge; and c) forming said plurality of generally spherically shaped porous enclosed structures by pouring said melted charge into a water bath;
d) wherein, prior to said heating and melting of the charge, carbon is added to the charge of ash-slag waste in order to reduce the Fe2O3 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the porous enclosed structures comprising blowing inert gas into the water bath and wherein the gaseous medium is a mixture of the inert gas blown into said water bath and the gaseous medium generated from the carbides.
12. A glass ceramic optical material comprising an ash-slag waste having an iron content less than 0.15 % by weight and having a light transmissivity factor ranging between 70 and 95% for visible and infrared spectra of electromagnetic waves, the glass ceramic material made by the process steps of:
a) providing a charge of ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge;
c) forming a foamed glass material by pouring said melted charge into a water bath, wherein, prior to said heating and melting of the charge, carbon is added to the ash-slag waste in order to reduce the Fe203 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass materials;
d) melting said foamed glass materials; and e) heating said melted glass material and cooling said heated material to form said glass ceramic optical material.
a) providing a charge of ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 - 13.0 Fe2O3 1.0 - 24.0 b) heating and melting the charge;
c) forming a foamed glass material by pouring said melted charge into a water bath, wherein, prior to said heating and melting of the charge, carbon is added to the ash-slag waste in order to reduce the Fe203 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass materials;
d) melting said foamed glass materials; and e) heating said melted glass material and cooling said heated material to form said glass ceramic optical material.
13. A molded article of an ash slag waste having an iron content less than 0.15% by weight and a compression strength of at least 30 MPa, the molded article made by the process steps of:
a) providing a charge of an ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 -~13.0 Fe2O3 1.0 -~24.0 ;
b) heating and melting the charge;
c) forming a foamed glass material by pouring said melted charge into a water bath, wherein, prior to said heating and melting of the charge, carbon is added to the ash-slag waste in order to reduce the Fe2O3 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass material;
d) reducing said foamed glass material in size;
e) press molding said reduced foamed glass material to a shape;
f) heating said press molded glass material in atmosphere to increase its strength; and g) cooling said heated glass material to form the molded article.
a) providing a charge of an ash-slag waste including calcium oxide and iron oxide in the following amounts of wt %:
CaO total 5.0 - 41.0 CaO unbound 4.0 -~13.0 Fe2O3 1.0 -~24.0 ;
b) heating and melting the charge;
c) forming a foamed glass material by pouring said melted charge into a water bath, wherein, prior to said heating and melting of the charge, carbon is added to the ash-slag waste in order to reduce the Fe2O3 content of the charge to less than 1% by weight and to form carbides in said melt whereby a gaseous medium is generated from the carbides to foam said melt to produce the foamed glass material;
d) reducing said foamed glass material in size;
e) press molding said reduced foamed glass material to a shape;
f) heating said press molded glass material in atmosphere to increase its strength; and g) cooling said heated glass material to form the molded article.
14. A foamed glass material of claim 10 having a thermal conductivity ranging between 0.04 and 0.09 watts/micron °
C.
C.
15. The foamed glass material of claim 10 having a porosity ranging between 10 to 80%.
16. The foamed glass material of claim 10 having a thermal conductivity of 0.04 to 0.08 watts/micron ° C.
17. The foamed glass material of claim 10 having a density ranging between 50 and 300 kg/m3.
18. The foamed glass material of claim 17 having a thermal conductivity of 0.04 to 0.08 watts/micron ° C.
19. The spherical foamed glass material of claim 13 having a bulk density ranging between 100 and 1000 kg/m3.
20. The molded article of claim 13 having a thermal conductivity ranging between 0.025 and 0.65 watts/micron ° C.
21. The molded article of claim 13 having a density ranging between 250 and 350 kg/m3.
22. The molded article of claim 13 having a water adsorption within. one hour of 5 to 7% of the weight of the molded article.
23. The molded article of claim 20 having a density ranging between 250 and 350 kg/m3.
24. The molded article of claim 23, having a water adsorption within one hour of 5 to 7% of the weight of the molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002120573A CA2120573C (en) | 1994-04-05 | 1994-04-05 | Method of producing glass materials from ash-slag waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002120573A CA2120573C (en) | 1994-04-05 | 1994-04-05 | Method of producing glass materials from ash-slag waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2120573A1 CA2120573A1 (en) | 1995-10-06 |
| CA2120573C true CA2120573C (en) | 2003-07-01 |
Family
ID=4153308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002120573A Expired - Fee Related CA2120573C (en) | 1994-04-05 | 1994-04-05 | Method of producing glass materials from ash-slag waste |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2120573C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2470879C1 (en) * | 2011-05-03 | 2012-12-27 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Foamed glass based on thermal power plant slag |
-
1994
- 1994-04-05 CA CA002120573A patent/CA2120573C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2120573A1 (en) | 1995-10-06 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |