CA2743283A1 - Glass composition and process of proppants manufacture based thereon - Google Patents
Glass composition and process of proppants manufacture based thereon Download PDFInfo
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- CA2743283A1 CA2743283A1 CA 2743283 CA2743283A CA2743283A1 CA 2743283 A1 CA2743283 A1 CA 2743283A1 CA 2743283 CA2743283 CA 2743283 CA 2743283 A CA2743283 A CA 2743283A CA 2743283 A1 CA2743283 A1 CA 2743283A1
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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
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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
- 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
- C03C10/0036—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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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
- 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
- C03C10/16—Halogen containing crystalline phase
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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
- C03C12/00—Powdered glass; Bead compositions
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
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- Glass Compositions (AREA)
Abstract
A glass composition for producing proppants comprising by weight percent, oxides of (a) from 45 to 52% SiO 2, (b) from 28 to 34% MgO, (c) from 7 to 10%
Al2O3, (d) from 1.6 to 4.5% FeO, (e)from 5 to 8% CaO, (f)from 0.3 to 0.6%
Na2O, (g) from 0.3 to 1,5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 3.2% F, and (h) from 0.1 to 3.6% MnO. A
method for making glass proppants comprising heating a glass composition comprising the foregoing ratio of oxides.
Al2O3, (d) from 1.6 to 4.5% FeO, (e)from 5 to 8% CaO, (f)from 0.3 to 0.6%
Na2O, (g) from 0.3 to 1,5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 3.2% F, and (h) from 0.1 to 3.6% MnO. A
method for making glass proppants comprising heating a glass composition comprising the foregoing ratio of oxides.
Description
TITLE OF THE INVENTION
GLASS COMPOSITION AND PROCESS OF PROPPANTS MANUFACTURE
BASED THEREON
FIELD OF THE INVENTION
The present invention refers to propping agents for gas and oil wells and, more particularly, to the glass composition and to the manufacture process of glass spheres used as such propping agents.
BACKGROUND OF THE INVENTION
Glasseeramics are known, having the composition containing SiO2 - 67,1 weight %; A1203- 12,5%; MgO- 5,6; Li20- 9,9; K20- 3,3; F- 2,7; B203 -1,0.(see French Patent No. 1159785, 1958).
Also known is the glass for glassceramics containing: SiO2 25-60; B203-3-15;, MgO -4-25; A1203-5-25; F- 4-20,R20, where there is used at least one oxide of the group K20-2-15; Na20-2-1 5; Li20-2-7; Rb20-2-20; Cs2 0-2-20 as R20 (see Russian Patent No. SU-631065, 09.08.1971).
The known glass compositions for glassceramics cannot be used in the manufacture of proppants because their main task is to improve dielectric properties and mechanical workability. According to the international ISO
13053 standard, the main characteristics of proppants are crush resistance, sphericity and roundness substantially determining the conductivity of proppants layers in a well. Proppants of natural gravel quartz sand prevail for economic considerations. However, the sphericity and the roundness of gravel sand generally do not exceed the value 0,7 as per ISO 13053, and its usage is limited to shallow wells because of low crush resistance. To improve its conductivity the natural sand may be covered by a film of phenol and formaldehyde, which considerably increases its'cost but insignificantly increases its conductivity.
Also known are proppants corresponding to glass spheres that have high sphericity and roundness, smooth surface but low crush resistance (see US
Patent No. 3,497,008). In addition, glass proppants have low resistance to mud acid (mixture of hydrochloric and hydrofluoric acids) thereby making unpractical their use in wells subject to acid treatment.
Proppants of silica--alumina and silica-magnesia raw materials manufactured in accordance with ceramic processing have been widely used over the last years. Ceramic proppants have satisfactory acid-resistance and high mechanical strength, which allow their use in deep wells during hydraulic fracturing (pressure at 1000 atm). At the same time, ceramic proppants, because of the singularity of their manufacturing process, have sphericity and roundness not exceeding 0,9 and there are always irregularities on their surface thereby making oil laminar flow difficult. Ceramic proppants have microscopic open pores that decrease their strength underwater in wells (temperature up to 130 C).
Another deficiency of ceramic proppants is the presence of pores in their structure (15-25% of proppant volume). Fine pores appear as a result of vacuum capture during ceramics sintering and large pores arise during granules layer rolling-on of powder masses. The presence of structural defects results in a partial failure of the granules during hydraulic fracturing. All of the above mentioned defects of ceramic granules account for poor conductivity of ceramic proppants layer injected in a well.
To remedy these shortcomings of silica-alumina proppants, US Patent Publication No. 2007/0062699A1 suggests producing silica-alumina proppants by the method of melt blowing during electrosmelting.
GLASS COMPOSITION AND PROCESS OF PROPPANTS MANUFACTURE
BASED THEREON
FIELD OF THE INVENTION
The present invention refers to propping agents for gas and oil wells and, more particularly, to the glass composition and to the manufacture process of glass spheres used as such propping agents.
BACKGROUND OF THE INVENTION
Glasseeramics are known, having the composition containing SiO2 - 67,1 weight %; A1203- 12,5%; MgO- 5,6; Li20- 9,9; K20- 3,3; F- 2,7; B203 -1,0.(see French Patent No. 1159785, 1958).
Also known is the glass for glassceramics containing: SiO2 25-60; B203-3-15;, MgO -4-25; A1203-5-25; F- 4-20,R20, where there is used at least one oxide of the group K20-2-15; Na20-2-1 5; Li20-2-7; Rb20-2-20; Cs2 0-2-20 as R20 (see Russian Patent No. SU-631065, 09.08.1971).
The known glass compositions for glassceramics cannot be used in the manufacture of proppants because their main task is to improve dielectric properties and mechanical workability. According to the international ISO
13053 standard, the main characteristics of proppants are crush resistance, sphericity and roundness substantially determining the conductivity of proppants layers in a well. Proppants of natural gravel quartz sand prevail for economic considerations. However, the sphericity and the roundness of gravel sand generally do not exceed the value 0,7 as per ISO 13053, and its usage is limited to shallow wells because of low crush resistance. To improve its conductivity the natural sand may be covered by a film of phenol and formaldehyde, which considerably increases its'cost but insignificantly increases its conductivity.
Also known are proppants corresponding to glass spheres that have high sphericity and roundness, smooth surface but low crush resistance (see US
Patent No. 3,497,008). In addition, glass proppants have low resistance to mud acid (mixture of hydrochloric and hydrofluoric acids) thereby making unpractical their use in wells subject to acid treatment.
Proppants of silica--alumina and silica-magnesia raw materials manufactured in accordance with ceramic processing have been widely used over the last years. Ceramic proppants have satisfactory acid-resistance and high mechanical strength, which allow their use in deep wells during hydraulic fracturing (pressure at 1000 atm). At the same time, ceramic proppants, because of the singularity of their manufacturing process, have sphericity and roundness not exceeding 0,9 and there are always irregularities on their surface thereby making oil laminar flow difficult. Ceramic proppants have microscopic open pores that decrease their strength underwater in wells (temperature up to 130 C).
Another deficiency of ceramic proppants is the presence of pores in their structure (15-25% of proppant volume). Fine pores appear as a result of vacuum capture during ceramics sintering and large pores arise during granules layer rolling-on of powder masses. The presence of structural defects results in a partial failure of the granules during hydraulic fracturing. All of the above mentioned defects of ceramic granules account for poor conductivity of ceramic proppants layer injected in a well.
To remedy these shortcomings of silica-alumina proppants, US Patent Publication No. 2007/0062699A1 suggests producing silica-alumina proppants by the method of melt blowing during electrosmelting.
Proppants manufactured by this method have smooth surfaces, high sphericity and roundness (more than 0,97). High strength and permeability are also declared in this Patent Publication, but data given in the description indicate that the characteristics of such proppants cede to those of ceramic proppants.
Comparative data regarding properties of known silica-alumina proppants (fraction 20/40) are presented in the Table 1:
Table 1 Cop osition and information source Ceramics Electrosmelting Characteristics Glass silica-alumina metrics US Patents CarboLightx sphere No. 3497008,5 Patents US Patent No. 3976138 No. 4427068, Publication No.
No.4068718 2007/0062699A1 Conductivity Darcy, at 5000 250 410 230 250 Psi w 350 atm Conductivity md.f at 5000 Psi 5200 7450 4000 350 atrn Sphericity and 0,97/0,97 0,9/0,9 0,95/0,95 roundness Apparently, poor conductivity of electrosmelted spheres having low strength results from defects generated by molten drops quenching. According to US Patent Publication No. 2007/0062699A1, the transition of silica-alumina materials from liquid state to solid state occurs at the same temperature as crack formation results in the sphere's body during quenching because crystal oxide materials are incapable of plastic deformation.
Another process of proppants manufacture is the proppants production of glass spheres (see Russian Federation Patent No. 2336293, 24.09.2007), including oxide melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling.
Proppants produced by this manufacturing process have in whole high operational properties for wells after hydraulic fracturing.
Amongst disadvantages of common glass ceramic proppants are their insufficient strength and poor permeability at high pressures during hydraulic fracturing in deep wells. This is due to the fact that the above-mentioned Russian Federation Patent has only addressed the issue of proppants production method, whereas the question of glass ceramic specific composition has not been examined.
SUMMARY OF THE INVENTION
Therefore, in accordance with the present invention, there is provided a glass composition of proppants including Si02, MgO, A1203, Na2O, K20, F, and further containing FeO, CaO, P205, C5r203, TiO2, MnO, with the following rate of mixture, mass%:
SiOz - 45 - 52 MgO-28-34 FeO -1,6 - 4,5 CaO-5-8 Na2O - 0,3 - 0,6 K20 - 0,3 -1,5 P205 - 0,1-0,3 Cr203 -0,1-0.8 Ti02 - 0,3 - 0,7 F- 1,0 - 3,2 MnO -0,1-3,6 The above process is characterized in that general number of oxides FeO +
Na2O + K20 + Cr203 + Ti02 + MnO is in the range of 2,6-11,4 mass %.
Also in accordance with the present invention, there is provided a glass proppant manufacturing method including oxides melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling; characterized in that glass fusion and its dispersion are made at the temperature range of 1600-1700 C, and crystallization burning at the temperature range of 1100-1270 C.
The above manufacturing method is also characterized in that the oxides melt production and melt jet dispersion are effected in EAF (electric arc furnace).
The above manufacturing method is further characterized in that the melt jet diameter for dispersion is chosen in the range of 5-30 mm.
The above manufacturing method is further characterized in that the rotary speed of water-cooled wheel is chosen in the range of 1200 - 1800 rpm.
DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE
INVENTION
The glass composition properties of the proppants of the present invention as well as the present operating practices result in an increase in the glass ceramic proppants strength and durable conductivity at high pressure during hydraulic fracturing process in deep wells.
The above mentioned result is obtained by the fact that to the common glass composition including Si02, MgO, A1203, Na20, KKO, F, there further contains FeO, CaO, P205, Cr2O3, TiO2, MnO, along the following ratios of components, mass %:
Si02 - 45 - 52 MgO-28-34 FeO -1,6 - 4,5 CaO-5-8 Na20 - 0,3 - 0,6 K20 - 0,3 -1,5 P205 - 0,1-0,3 Cr203- 0,1-0,8 TiO2- 0,3 - 0,7 F- 1,0 - 3,2 MnO -0,1-3,6 In the above, the general number of oxides FeO + Na20 + K20 + Cr203 +
TiO2 + MnO is in the range of 2,6-11,4 mass %.
The present glass proppant manufacturing method includes oxides melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling; glass fusion and its dispersion are made at the temperature range of 1600-1700 C, and crystallization burning at the temperature range of 1100-1270 C.
Oxides melt production and melt jet dispersion are achieved in an electrical are furnace, with the melt jet diameter for dispersion being chosen in the range of 5-30 mm and with the rotation rate of the water-cooled wheel being in the range of 1200 -1800 revolutions per minute.
The present glass composition does not correspond to glass ceramics of pyroxenic and cordierite composition.
According to X-ray phase analysis, the main crystal phase is klinoenstatite or its solid solution with malacolite. The second phase of glass ceramics is glass (up to 30% by volume) with a high content of A1203. The third phase is oxide (3-5% by volume) - MgO, FeO, Cr203, TiO2, MnO compounds.
The proposed composition allows to effect glass melting and homogenization at a temperature less than 1700 C in a short period of time.
The melt has low viscosity and high surface stress that allows melt jet dispersion and glass balls production at a temperature of more than 1300 C
virtually without fiber formation, but at lower dispersion temperatures the fiber glass portion sharply increases. The advantage of this composition is the possibility to use such inexpensive raw materials as serpentinite, quartz and arkose sand, dolomite, magnesite, clay, shale, apatite, fluorite and other rocks, the combination of which gives the present glass composition.
A preferred process of glass melt production according to the present invention has the melting being carried out in an electric arc furnace under charge bank at a temperature of 1600 - 1700 C, which allows to avoid essential losses of such elements as F, P2O5 Na20, K20.
The melt jet dispersion step can be efficiently effected on a rotary wheel with cross shoulders. Other dispersion methods (air or vapor blowing, supersonic stream of hot gas) result in jet partial bending toward blowing as well as the formation of fiber, cotton and droplets with tails. Additionally, these methods are extremely power-consuming.
Recommended dispersion modes on the wheel:
- melt jet diameter of not more than 30 mm;
- wheel rotary speed of 1200-2800 rpm; and - melt jet temperature of 1600-1700 'C.
If the melt jet diameter is less than 10 mm intense cooling of the exterior part of the jet and non-spherical glass and fiber parts formation occur. If the diameter is more than 30 mm the jet is deformed in a tangential direction and the catching of the glass balls in the collection chamber is made difficult. The optimal jet diameter is 15-20 mm. When the glass melt volume is large it is necessary to split the jet into a few jets each having a diameter of not more than 30 mm. Wheel rotary speed and the number of cross shoulders are determined by specific proppants fractional composition: maximum values for 40/70, minimum values for 20/40.
The melt jet temperature delivered on the wheel determines the quality of the finished products: the hotter the melt, the larger it is, i.e. melt delivery to the dispersion wheel should be done through a heat-insulated spout having low heat capacity and high resistance to melt, for instance through tubes of carbon and oxide with outside heat insulation of mullite fiber. The diameter and width of the wheel are not a matter of principle and are rather determined by the cooling system - overheating of wheel results in its deformation and short life.
Unlike proppants manufactured by common methods (for example, see aforementioned Russian Federation Patent No. 2336293), crystallization burning of the proposed glass composition should be done: first, at a higher temperature of 1100-1200 'C, second optimal temperature of coarse balls crystallization should be higher than the temperature of fine ones. Apparently, this is due to the fact that glass ceramics crystallization starts from the surface. Cocrystallization of several fractions is possible but in this case proppants burned at optimum temperature will have inferior properties. In this respect, an additional operation, such as fractional sieving, is recommended before crystallization burning. In connection with some quantity of fiber and cotton presence in the glass spheres (up to 10%) sizing on vibrosieves is not always efficient because of sieve blocking. Air classification is more valid. Prior to burning it is also recommended to remove non-spheric particles by the instrumentality of a vibrodynamic classifier or a spiral separator. Siftings and non-spherical particles are returned for melting.
Example.
Initial charges were made-up of Bajenovsky and Anatolievsky serpentinite formation (Ural), asbestos tailing from Thetford Mines (Canada), Pyshminsky quartz-feldspar sand (Ural), chamotte from Troitsko-Baynovsky and Nizhny-Uvelsky deposits (Ural), shale (Quebec, Canada), apatite concentrate (Karelia), fluorite concentrate (Mongolia, Mexico), dolomite (Bilimbay) and magnesite (Satka).
Charges melting were made at the temperature 1600 C and 1700 C in a three-phase EAF under initial charge bank. Furnace lining is made of chromomagnesite bricks and periclase ramming mass. Glass melt discharge was made through heat-insulated chute of corundum and graphite to insulated crucible of corundum and graphite with two (2) openings of 17 mm diameter, through which melt was delivered to a water-cooled wheel having a 700 mm diameter with shoulders. After cooling in settling chamber, sieving at air classifier and spiral separator, three (3) main fractions of glass balls 40/70, 30/50 and 20/40 were produced. Yield was 40-75% of initial working mass. Chemical composition of produced glass balls is presented in the Table 2. Compositions with high contents of silicon and aluminum oxides (total of Si02 + A1203 ?
62%) produced a large amount of fibers interrupting spheric granules separation at all examined melting practices, even with large quantities of additives being used to reduce viscosity, and consequently were judged unpromising.
Chemical analysis were carried out with an X-ray fluorescent energy-dispersing spectrometer Quant x. It should be noted that the compositions in Table 2 are brought to 100% as per 12 components, though in some cases the device registered insignificant quantities of sulfur, nickel, cobalt and zirconium.
Fluorine test was carried out in analytic laboratories of Uralmechanobr Institute (Yekaterinbourg), Polevsky cryolite factory and in Quebec's laboratory (Canada).
Table 2 Chemical composition of glass balls Charge Oxides content, mass %
# SiO2 MgO A1203 FeO CaO Na2O 120 P205 Cr203 Ti02 F MnO
1 50,3 27,4 6,3 5,4 4,5 1,7 2,0 0,8 0,5 0,3 0,7 0,1 2 43,6 24,3 9,2 4,8 8,9 0,5 1,1 0,2 0,2 0,4 3,0 3,8 3 41,5 35,1 6,9 6,2 5,1 0,8 1,7 0,4 1,0 0,8 0,4 0,1 4 56,2 20,8 12,6 1,4 3,1 2,4 1,6 0,4 0,2 1,3 0,0 0,0 47,1 30,8 8,1 2,8 6,7 0,4 0,9 0,2 0,4 L 0,5 1,8 0,3 6 52,2 27,8 10,1 2,1 5,2 0,3 0,2 0,0 0,2 0,4 4,3 0,2 7 45,3 29,4 8,1 4,3 7,9 0,6 0,3 0,1 0,6 0,5 2,7 0,2 8 45,9 28,0 9,8 4,3 7,0 0,6 0,5 0,2 0,8 0,7 1,9 0,3 9 45,2 33,8 7,2 4,5 5,0 0,3 0,2 0,0 0,2 0,6 2,8 0,2 45,4 28,1 7,1 2,2 7,2 0,5 1,5 0,1 0,7 0,4 3,2 3,6 11 48,2 29,4 8,0 2,9 5,3 0,4 1,2 0,3 0,4 0,5 2,2 1,2 12 51,4 28,5 10,0 1,7 5,1 0,9 0,3 0,0 0,2 0,6 1,0 0,3 The produced glass spheres were burned at the temperature range of 900-1200 C. Proppants strength resistance in accordance with ISO 13053 is indicated in Table 3.
Table 3 Proppants strength resistance of examined compositions Charge Broken granules percentage at different pressures, %
number Fraction 20/40 Fraction 30/50 Fraction 40/70 as per 7500 10000 12500 15000 7500 10000 12500 15000 7500 10000 12500 15000 Table 2 Psi psi Psi Psi Psi Psi Psi Psi Psi Psi Psi Psi 1 7,4 12,9 18,8 23,7 1,9 2,7 6,5 13,8 0,4 1,6 5,4 13,2 2 10,3 13,4 19,7 26,9 2,1 3,8 9,0 16,5 0,5 2,0 4,3 11,4 3 11,8 20,1 27,5 33,1 4,0 10,2 15,6 21,8 0,9 2,8 8,6 10,0 4 6,9 14,4 17,9 24,8 2,0 3,2 7,5 13,6 0,6 2,4 4,1 8,8 8,1 15,0 20,7 25,5 2,2 3,0 8,4 14,9 0,7 2,9 6,6 10,4 6 9,6 17,3 24,9 30,8 2,7 5,3 16,1 19,7 0,8 3,0 7,0 9,2 7 3,2 5,7 9,0 13,6 1,0 1,9 6,5 10,9 0,3 1,0 2,8 6,1 8 3,0 4,9 8,4 12,9 0,8 2,1 6,0 9,6 0,3 0,8 2,4 5,1 9 2,1 3,1 5,9 10,7 0,4 1,8 5,0 8,3 0,2 0,7 2,7 3,4 1,9 2,4 5,0 9,3 0,5 1,9 4,8 7,0 0,2 0,6 2,5 3,8 11 1,3 1,7 6,4 10,9 0,5 0,9 3,0 4,8 0,2 0,9 2,2 4,0 12 1,6 1,9 5,3 8,1 0,6 2,0 4,3 6,2 0,3 0,9 3,1 5,2 Data analysis of Tables 2 and 3 allows to split conditionally the examined compositions into two (2) groups: stronger (7-12) and less strong (1-6).
Proppants manufactured with glass compositions 7 to 12 are limited by the following ratio of components:
Si02 -45-52mass %
MgO-28-34mass%
A1203 - 7 -- 10 mass %
it FeO-1,6-4,2mass%
Ca0-5-8mass%
Na2,,O - 0,3 - 0,6 mass %
K20 - 0,3 - 1,5 mass %
P205- 0,1- 0,3 mass %
Cr203 - 0,1-- 0,8 mass TiO2 - 0,3 - 0,7 mass %
F- 1,0 - 372 mass 11/o MnO -0,1-3,6mass%
The major specially introduced charge elements are SiO2, MgO, A1203, CaO, P205 and F. Other components are always associated additives of used material and furnace lining; their quantity however is also very important for the proppants manufacturing process (FeO, P205, Cr203 and Ti02 are glass crystallization initiators; and K20, Na2O, FeO, MnO reduce viscosity and increase melt superficial tension). The total quantity of FeO, Na2O, K20, Cr203, 'Y i02 and MnO should be in the range of 2,6 -11,4 mass %.
Some of the examined proppants were sent to FracTech and Stim-Lab laboratories for long-terra conductivity determination. The results are presented in Table 4.
Table 4 Proppants long-term conductivity in accordance with ISO 13203-2/APJRP
Charge N as per Table 2, Conductivity, and-ft, at pressure, Psi Proppant fraction 2000 4000 6000 8000 10000 12000 1, fraction 20/40 7478 6000 2988 1101 388 -11, fraction 20/40 7560 6295 4436 2673 1338 627 2, fraction 30/50 2863 1496 1186 448 - -3, fraction 30/50 2693 1303 1009 459 - -6, fraction 30/50 3267 1960 1453 725 70,3 -7, fraction 30/50 2699 2413 1984 1374 777 506 10, fraction 30/50 3259 2833 2324 1689 967 513 12, fraction 30/50 2908 2570 2209 1573 964 -4, fraction 40/70 1693 1303 1009 459 - -8, fraction 40/70 1554 1351 1171 888 619 -9, fraction 30/50 3259 2833 2324 1689 967 513 Thus, glass ceramic proppants of offered compositions have high long-term conductivity.
Comparative data regarding properties of known silica-alumina proppants (fraction 20/40) are presented in the Table 1:
Table 1 Cop osition and information source Ceramics Electrosmelting Characteristics Glass silica-alumina metrics US Patents CarboLightx sphere No. 3497008,5 Patents US Patent No. 3976138 No. 4427068, Publication No.
No.4068718 2007/0062699A1 Conductivity Darcy, at 5000 250 410 230 250 Psi w 350 atm Conductivity md.f at 5000 Psi 5200 7450 4000 350 atrn Sphericity and 0,97/0,97 0,9/0,9 0,95/0,95 roundness Apparently, poor conductivity of electrosmelted spheres having low strength results from defects generated by molten drops quenching. According to US Patent Publication No. 2007/0062699A1, the transition of silica-alumina materials from liquid state to solid state occurs at the same temperature as crack formation results in the sphere's body during quenching because crystal oxide materials are incapable of plastic deformation.
Another process of proppants manufacture is the proppants production of glass spheres (see Russian Federation Patent No. 2336293, 24.09.2007), including oxide melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling.
Proppants produced by this manufacturing process have in whole high operational properties for wells after hydraulic fracturing.
Amongst disadvantages of common glass ceramic proppants are their insufficient strength and poor permeability at high pressures during hydraulic fracturing in deep wells. This is due to the fact that the above-mentioned Russian Federation Patent has only addressed the issue of proppants production method, whereas the question of glass ceramic specific composition has not been examined.
SUMMARY OF THE INVENTION
Therefore, in accordance with the present invention, there is provided a glass composition of proppants including Si02, MgO, A1203, Na2O, K20, F, and further containing FeO, CaO, P205, C5r203, TiO2, MnO, with the following rate of mixture, mass%:
SiOz - 45 - 52 MgO-28-34 FeO -1,6 - 4,5 CaO-5-8 Na2O - 0,3 - 0,6 K20 - 0,3 -1,5 P205 - 0,1-0,3 Cr203 -0,1-0.8 Ti02 - 0,3 - 0,7 F- 1,0 - 3,2 MnO -0,1-3,6 The above process is characterized in that general number of oxides FeO +
Na2O + K20 + Cr203 + Ti02 + MnO is in the range of 2,6-11,4 mass %.
Also in accordance with the present invention, there is provided a glass proppant manufacturing method including oxides melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling; characterized in that glass fusion and its dispersion are made at the temperature range of 1600-1700 C, and crystallization burning at the temperature range of 1100-1270 C.
The above manufacturing method is also characterized in that the oxides melt production and melt jet dispersion are effected in EAF (electric arc furnace).
The above manufacturing method is further characterized in that the melt jet diameter for dispersion is chosen in the range of 5-30 mm.
The above manufacturing method is further characterized in that the rotary speed of water-cooled wheel is chosen in the range of 1200 - 1800 rpm.
DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE
INVENTION
The glass composition properties of the proppants of the present invention as well as the present operating practices result in an increase in the glass ceramic proppants strength and durable conductivity at high pressure during hydraulic fracturing process in deep wells.
The above mentioned result is obtained by the fact that to the common glass composition including Si02, MgO, A1203, Na20, KKO, F, there further contains FeO, CaO, P205, Cr2O3, TiO2, MnO, along the following ratios of components, mass %:
Si02 - 45 - 52 MgO-28-34 FeO -1,6 - 4,5 CaO-5-8 Na20 - 0,3 - 0,6 K20 - 0,3 -1,5 P205 - 0,1-0,3 Cr203- 0,1-0,8 TiO2- 0,3 - 0,7 F- 1,0 - 3,2 MnO -0,1-3,6 In the above, the general number of oxides FeO + Na20 + K20 + Cr203 +
TiO2 + MnO is in the range of 2,6-11,4 mass %.
The present glass proppant manufacturing method includes oxides melt production, melt jet dispersion by water-cooled wheel to form glass spheres, their crystallization burning and cooling; glass fusion and its dispersion are made at the temperature range of 1600-1700 C, and crystallization burning at the temperature range of 1100-1270 C.
Oxides melt production and melt jet dispersion are achieved in an electrical are furnace, with the melt jet diameter for dispersion being chosen in the range of 5-30 mm and with the rotation rate of the water-cooled wheel being in the range of 1200 -1800 revolutions per minute.
The present glass composition does not correspond to glass ceramics of pyroxenic and cordierite composition.
According to X-ray phase analysis, the main crystal phase is klinoenstatite or its solid solution with malacolite. The second phase of glass ceramics is glass (up to 30% by volume) with a high content of A1203. The third phase is oxide (3-5% by volume) - MgO, FeO, Cr203, TiO2, MnO compounds.
The proposed composition allows to effect glass melting and homogenization at a temperature less than 1700 C in a short period of time.
The melt has low viscosity and high surface stress that allows melt jet dispersion and glass balls production at a temperature of more than 1300 C
virtually without fiber formation, but at lower dispersion temperatures the fiber glass portion sharply increases. The advantage of this composition is the possibility to use such inexpensive raw materials as serpentinite, quartz and arkose sand, dolomite, magnesite, clay, shale, apatite, fluorite and other rocks, the combination of which gives the present glass composition.
A preferred process of glass melt production according to the present invention has the melting being carried out in an electric arc furnace under charge bank at a temperature of 1600 - 1700 C, which allows to avoid essential losses of such elements as F, P2O5 Na20, K20.
The melt jet dispersion step can be efficiently effected on a rotary wheel with cross shoulders. Other dispersion methods (air or vapor blowing, supersonic stream of hot gas) result in jet partial bending toward blowing as well as the formation of fiber, cotton and droplets with tails. Additionally, these methods are extremely power-consuming.
Recommended dispersion modes on the wheel:
- melt jet diameter of not more than 30 mm;
- wheel rotary speed of 1200-2800 rpm; and - melt jet temperature of 1600-1700 'C.
If the melt jet diameter is less than 10 mm intense cooling of the exterior part of the jet and non-spherical glass and fiber parts formation occur. If the diameter is more than 30 mm the jet is deformed in a tangential direction and the catching of the glass balls in the collection chamber is made difficult. The optimal jet diameter is 15-20 mm. When the glass melt volume is large it is necessary to split the jet into a few jets each having a diameter of not more than 30 mm. Wheel rotary speed and the number of cross shoulders are determined by specific proppants fractional composition: maximum values for 40/70, minimum values for 20/40.
The melt jet temperature delivered on the wheel determines the quality of the finished products: the hotter the melt, the larger it is, i.e. melt delivery to the dispersion wheel should be done through a heat-insulated spout having low heat capacity and high resistance to melt, for instance through tubes of carbon and oxide with outside heat insulation of mullite fiber. The diameter and width of the wheel are not a matter of principle and are rather determined by the cooling system - overheating of wheel results in its deformation and short life.
Unlike proppants manufactured by common methods (for example, see aforementioned Russian Federation Patent No. 2336293), crystallization burning of the proposed glass composition should be done: first, at a higher temperature of 1100-1200 'C, second optimal temperature of coarse balls crystallization should be higher than the temperature of fine ones. Apparently, this is due to the fact that glass ceramics crystallization starts from the surface. Cocrystallization of several fractions is possible but in this case proppants burned at optimum temperature will have inferior properties. In this respect, an additional operation, such as fractional sieving, is recommended before crystallization burning. In connection with some quantity of fiber and cotton presence in the glass spheres (up to 10%) sizing on vibrosieves is not always efficient because of sieve blocking. Air classification is more valid. Prior to burning it is also recommended to remove non-spheric particles by the instrumentality of a vibrodynamic classifier or a spiral separator. Siftings and non-spherical particles are returned for melting.
Example.
Initial charges were made-up of Bajenovsky and Anatolievsky serpentinite formation (Ural), asbestos tailing from Thetford Mines (Canada), Pyshminsky quartz-feldspar sand (Ural), chamotte from Troitsko-Baynovsky and Nizhny-Uvelsky deposits (Ural), shale (Quebec, Canada), apatite concentrate (Karelia), fluorite concentrate (Mongolia, Mexico), dolomite (Bilimbay) and magnesite (Satka).
Charges melting were made at the temperature 1600 C and 1700 C in a three-phase EAF under initial charge bank. Furnace lining is made of chromomagnesite bricks and periclase ramming mass. Glass melt discharge was made through heat-insulated chute of corundum and graphite to insulated crucible of corundum and graphite with two (2) openings of 17 mm diameter, through which melt was delivered to a water-cooled wheel having a 700 mm diameter with shoulders. After cooling in settling chamber, sieving at air classifier and spiral separator, three (3) main fractions of glass balls 40/70, 30/50 and 20/40 were produced. Yield was 40-75% of initial working mass. Chemical composition of produced glass balls is presented in the Table 2. Compositions with high contents of silicon and aluminum oxides (total of Si02 + A1203 ?
62%) produced a large amount of fibers interrupting spheric granules separation at all examined melting practices, even with large quantities of additives being used to reduce viscosity, and consequently were judged unpromising.
Chemical analysis were carried out with an X-ray fluorescent energy-dispersing spectrometer Quant x. It should be noted that the compositions in Table 2 are brought to 100% as per 12 components, though in some cases the device registered insignificant quantities of sulfur, nickel, cobalt and zirconium.
Fluorine test was carried out in analytic laboratories of Uralmechanobr Institute (Yekaterinbourg), Polevsky cryolite factory and in Quebec's laboratory (Canada).
Table 2 Chemical composition of glass balls Charge Oxides content, mass %
# SiO2 MgO A1203 FeO CaO Na2O 120 P205 Cr203 Ti02 F MnO
1 50,3 27,4 6,3 5,4 4,5 1,7 2,0 0,8 0,5 0,3 0,7 0,1 2 43,6 24,3 9,2 4,8 8,9 0,5 1,1 0,2 0,2 0,4 3,0 3,8 3 41,5 35,1 6,9 6,2 5,1 0,8 1,7 0,4 1,0 0,8 0,4 0,1 4 56,2 20,8 12,6 1,4 3,1 2,4 1,6 0,4 0,2 1,3 0,0 0,0 47,1 30,8 8,1 2,8 6,7 0,4 0,9 0,2 0,4 L 0,5 1,8 0,3 6 52,2 27,8 10,1 2,1 5,2 0,3 0,2 0,0 0,2 0,4 4,3 0,2 7 45,3 29,4 8,1 4,3 7,9 0,6 0,3 0,1 0,6 0,5 2,7 0,2 8 45,9 28,0 9,8 4,3 7,0 0,6 0,5 0,2 0,8 0,7 1,9 0,3 9 45,2 33,8 7,2 4,5 5,0 0,3 0,2 0,0 0,2 0,6 2,8 0,2 45,4 28,1 7,1 2,2 7,2 0,5 1,5 0,1 0,7 0,4 3,2 3,6 11 48,2 29,4 8,0 2,9 5,3 0,4 1,2 0,3 0,4 0,5 2,2 1,2 12 51,4 28,5 10,0 1,7 5,1 0,9 0,3 0,0 0,2 0,6 1,0 0,3 The produced glass spheres were burned at the temperature range of 900-1200 C. Proppants strength resistance in accordance with ISO 13053 is indicated in Table 3.
Table 3 Proppants strength resistance of examined compositions Charge Broken granules percentage at different pressures, %
number Fraction 20/40 Fraction 30/50 Fraction 40/70 as per 7500 10000 12500 15000 7500 10000 12500 15000 7500 10000 12500 15000 Table 2 Psi psi Psi Psi Psi Psi Psi Psi Psi Psi Psi Psi 1 7,4 12,9 18,8 23,7 1,9 2,7 6,5 13,8 0,4 1,6 5,4 13,2 2 10,3 13,4 19,7 26,9 2,1 3,8 9,0 16,5 0,5 2,0 4,3 11,4 3 11,8 20,1 27,5 33,1 4,0 10,2 15,6 21,8 0,9 2,8 8,6 10,0 4 6,9 14,4 17,9 24,8 2,0 3,2 7,5 13,6 0,6 2,4 4,1 8,8 8,1 15,0 20,7 25,5 2,2 3,0 8,4 14,9 0,7 2,9 6,6 10,4 6 9,6 17,3 24,9 30,8 2,7 5,3 16,1 19,7 0,8 3,0 7,0 9,2 7 3,2 5,7 9,0 13,6 1,0 1,9 6,5 10,9 0,3 1,0 2,8 6,1 8 3,0 4,9 8,4 12,9 0,8 2,1 6,0 9,6 0,3 0,8 2,4 5,1 9 2,1 3,1 5,9 10,7 0,4 1,8 5,0 8,3 0,2 0,7 2,7 3,4 1,9 2,4 5,0 9,3 0,5 1,9 4,8 7,0 0,2 0,6 2,5 3,8 11 1,3 1,7 6,4 10,9 0,5 0,9 3,0 4,8 0,2 0,9 2,2 4,0 12 1,6 1,9 5,3 8,1 0,6 2,0 4,3 6,2 0,3 0,9 3,1 5,2 Data analysis of Tables 2 and 3 allows to split conditionally the examined compositions into two (2) groups: stronger (7-12) and less strong (1-6).
Proppants manufactured with glass compositions 7 to 12 are limited by the following ratio of components:
Si02 -45-52mass %
MgO-28-34mass%
A1203 - 7 -- 10 mass %
it FeO-1,6-4,2mass%
Ca0-5-8mass%
Na2,,O - 0,3 - 0,6 mass %
K20 - 0,3 - 1,5 mass %
P205- 0,1- 0,3 mass %
Cr203 - 0,1-- 0,8 mass TiO2 - 0,3 - 0,7 mass %
F- 1,0 - 372 mass 11/o MnO -0,1-3,6mass%
The major specially introduced charge elements are SiO2, MgO, A1203, CaO, P205 and F. Other components are always associated additives of used material and furnace lining; their quantity however is also very important for the proppants manufacturing process (FeO, P205, Cr203 and Ti02 are glass crystallization initiators; and K20, Na2O, FeO, MnO reduce viscosity and increase melt superficial tension). The total quantity of FeO, Na2O, K20, Cr203, 'Y i02 and MnO should be in the range of 2,6 -11,4 mass %.
Some of the examined proppants were sent to FracTech and Stim-Lab laboratories for long-terra conductivity determination. The results are presented in Table 4.
Table 4 Proppants long-term conductivity in accordance with ISO 13203-2/APJRP
Charge N as per Table 2, Conductivity, and-ft, at pressure, Psi Proppant fraction 2000 4000 6000 8000 10000 12000 1, fraction 20/40 7478 6000 2988 1101 388 -11, fraction 20/40 7560 6295 4436 2673 1338 627 2, fraction 30/50 2863 1496 1186 448 - -3, fraction 30/50 2693 1303 1009 459 - -6, fraction 30/50 3267 1960 1453 725 70,3 -7, fraction 30/50 2699 2413 1984 1374 777 506 10, fraction 30/50 3259 2833 2324 1689 967 513 12, fraction 30/50 2908 2570 2209 1573 964 -4, fraction 40/70 1693 1303 1009 459 - -8, fraction 40/70 1554 1351 1171 888 619 -9, fraction 30/50 3259 2833 2324 1689 967 513 Thus, glass ceramic proppants of offered compositions have high long-term conductivity.
Claims (7)
1. A glass composition for producing proppants comprising by weight percent, oxides of:
(a) from 45 to 52% SiO2, (b) from 28 to 34% MgO, (c) from 7 to 10% Al2O3, (d) from 1.6 to 4.5% FeO, (e) from 5 to 8% CaO, (f) from 0,3 to 0.6% Na 2O, (g) from 0.3 to 1.5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 32% F, and (h) from 0.1 to 3.6% MnO.
(a) from 45 to 52% SiO2, (b) from 28 to 34% MgO, (c) from 7 to 10% Al2O3, (d) from 1.6 to 4.5% FeO, (e) from 5 to 8% CaO, (f) from 0,3 to 0.6% Na 2O, (g) from 0.3 to 1.5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 32% F, and (h) from 0.1 to 3.6% MnO.
2. A method for making glass proppants, the method comprising:
(i) heating a glass composition comprising by weight percent, oxides of:
(a) from 45 to 52% SiO2, (b) from 28 to 34% MgO, (c) from 7 to 10% Al2O3, (d) from 1.6 to 4.5% FeO, (e) from 5 to 8% CaO, (f) from 0.3 to 0.6% Na 2O, (g) from 0.3 to 1.5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 3.2% F, and (h) from 0.1 to 3.6% MnO, to produce a melt jet;
(ii) dispersing the melt jet to produce glass spheres;
(iii)crystallization burning of the glass spheres; and (iv)cooling the glass spheres.
(i) heating a glass composition comprising by weight percent, oxides of:
(a) from 45 to 52% SiO2, (b) from 28 to 34% MgO, (c) from 7 to 10% Al2O3, (d) from 1.6 to 4.5% FeO, (e) from 5 to 8% CaO, (f) from 0.3 to 0.6% Na 2O, (g) from 0.3 to 1.5% K2O, (h) from 0.1 to 0.3% P2O5, (i) from 0.1 to 0.8% Cr2O3, (j) from 0.3 to 0.7% TiO2, (k) from 1.0 to 3.2% F, and (h) from 0.1 to 3.6% MnO, to produce a melt jet;
(ii) dispersing the melt jet to produce glass spheres;
(iii)crystallization burning of the glass spheres; and (iv)cooling the glass spheres.
3. The method of claim 2, wherein the heating step (i) is performed at temperatures ranging from 1600-1700°C.
4. The method of claim 2, wherein the crystallization burning is performed at temperatures ranging from 1100-1270°C.
5. The method of claim 2, wherein the melt jet has a diameter ranging from 5-30 mm.
6. The method of claim 2, wherein step (ii) is performed using a water-cooled wheel.
7. The method of claim 6, wherein the rotary speed of the water-cooled wheel ranges from 1200-1800 rpm.
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| CA2707877A CA2707877A1 (en) | 2010-06-15 | 2010-06-15 | Glass composition and process of proppants manufacture based thereon |
| CA 2743283 CA2743283A1 (en) | 2010-06-15 | 2011-06-15 | Glass composition and process of proppants manufacture based thereon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106892560A (en) * | 2017-03-23 | 2017-06-27 | 合肥协耀玻璃制品有限公司 | A kind of high finished product rate glass and its production technology |
| CN106904832A (en) * | 2017-03-23 | 2017-06-30 | 合肥协耀玻璃制品有限公司 | A kind of high quality glass and its production technology |
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| GB2553757A (en) * | 2016-08-08 | 2018-03-21 | Glass Tech Services Limited | Proppant and method of selecting a proppant |
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- 2010-06-15 CA CA2707877A patent/CA2707877A1/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892560A (en) * | 2017-03-23 | 2017-06-27 | 合肥协耀玻璃制品有限公司 | A kind of high finished product rate glass and its production technology |
| CN106904832A (en) * | 2017-03-23 | 2017-06-30 | 合肥协耀玻璃制品有限公司 | A kind of high quality glass and its production technology |
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