CN102731105B - Method for preparing composite fracturing propping agent by using gold tailings and alumina fibers - Google Patents
Method for preparing composite fracturing propping agent by using gold tailings and alumina fibers Download PDFInfo
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- CN102731105B CN102731105B CN201210201332.7A CN201210201332A CN102731105B CN 102731105 B CN102731105 B CN 102731105B CN 201210201332 A CN201210201332 A CN 201210201332A CN 102731105 B CN102731105 B CN 102731105B
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Abstract
The invention relates to a method for preparing a composite fracturing propping agent by using gold tailings and alumina fibers. According to the method, gold tailings, alumina powder and polycrystal alumina fire-resistant short-cut fibers are mixed and added to a gum aqueous solution to sequentially carry out uniform mixing, wet grinding and pelletizing; the resulting particles are placed in an alumina crucible, and the crucible is placed in a silicon carbon rod resistance furnace, and is heated to the temperature of 1230 DEG C from the room temperature at a temperature increasing speed of 5-10 DEG C per minute; a thermal insulation treatment is performed for 0.5-1 hour; a heating treatment is performed to the temperature of 1350-1400 DEG C at a temperature increasing speed of 5-7 DEG C per minute; a thermal insulation treatment is performed for 2-3 hours; the resulting material is naturally cooled along with the furnace, removed, and is screened with a sieve with a mesh of 20-40 to obtain the composite fracturing propping agent. According to the present invention, the idea of the composite material is integrated in the non-dense ceramic propping agent, a high temperature reaction self-generation manner is combined to provide the fibers (crystal whisker) required by enhancing and toughening, and the high-strength, high-toughness, low density and low breakage rate composite fracturing propping agent are prepared with the method of the present invention.
Description
Technical field
The present invention relates to a kind of method of utilizing waste material to prepare ceramic composite, particularly a kind of method of utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents.
Background technology
Fracturing propping agents are not long as emerging industry ， China development time, and its product structure and kind are still far from perfect, and the process scale of industry and level are all in the developmental stage at initial stage.Most of oil gas field belongs to middle deep, requires fracturing propping agents to have high strength, low percentage of damage, to bear the various corrosion in the huge pressure in rock stratum and ground environment.In the world adopt alundum goods as in, deep-seated oil gas field fracturing propping agents, although this goods on physicochemical property, can meet the demands, raw material sources difficulty, complete processing is complicated, and energy consumption is large, cost is high, and its application is restricted.The closed fracturing material of nonpetroleum deep-well forming with ceramic sintering method sintering, be in natural siliceous sand, coated composite particles, glass sphere, Metal Ball etc., the substitute of low strength propping agent, there is high, the low density feature of intensity, thereby become one of study hotspot of petrochemical complex material.Current, the subject matter that fracturing propping agents haydite faces is how under hot conditions, by controlling chemical composition and microstructure, to improve its comprehensive mechanical property, effectively reduces the fragility of material, to improve the practical application effect of this material.
Existing propping agent haydite preparation method has meltblown method, Coated with Organic Matter solidification method, sintering process etc.
Tang Minhui etc. [development of Support Grains for Oil Well [J]. HarBin Building University's journal, 1995,28 (4): 73-76] take basalt is the furnace charge of main raw material preparation, through fusing, special one-tenth pearl and thermal treatment process, has been developed into pyroxene type microcrystal silicon hydrochlorate pearl body.Patent disclose " a kind of Selid propping agent and manufacture method thereof " (Zhousheng is military, application number: 89102544.8), be main raw material with bauxitic clay, through the balling-up of electric arc furnace meltblown, have ultimate compression strength high, percentage of damage is low, density moderate with the feature such as cost is low.Although the propping agent application to some extent in practice that meltblown legal system is standby,, by the method, prepare ceramsite propping agent and have the defects such as energy consumption is high, balling-up is wayward, proppant strength is low, be seldom used at present.
Coated with Organic Matter solidification method is to using organic binder bond as solidifying agent, take artificial or natural powder as raw material, and adhesive solidification is unburned to be formed, although intensity is low, density is little, has certain feature.Sun Hu, Wang Yi sends out preparation method and the preparation technology > > of patent (application number 200710188410) < < low-density propping agent, Zhou Fujian patent (application number 201010278084) < < fiber composite sand control material and preparation method thereof > >, utilize respectively vegetable fibre or organic fibrous material as raw material, organicly solidify non-sintered moulding or mix the effect of playing sand prevention Oil Guide in fracturing liquid.This series products is not proppant in high intensity truly.
In addition have investigator to prepare fracturing propping agents with FMS-△ G type, FMS-(R) type resin coating method, its product increases subtracting aspect crisp, but obviously aspect intensity, has defect.
Sintering process is to adopt ceramic raw material and traditional ceramic process to prepare the technology of fine and close ceramsite propping agent.The existing many documents of development and the patent report of with raw mineral materialss such as bauxitic clays, preparing oil fracturing ceramsite propping agent.Gao Haili etc. [development of high-strength petroleum fracturing propping agent [J]. pottery, 2006, (10): 43-46] to take the local two beach bauxitic clays of Flos Bombacis Malabarici, bauxitic clay raw material and high-titanium blast furnace slag be main raw material, is developed into high-strength petroleum fracturing propping agent.The patent such as Zhao Shiao, Wu Bailin (application number 201010143771.8), < < preparation method > > without silicon or low-silicon acidproof ceramic fracturing propping agent; The preparation method > > of the patents such as Tian little Rang (application number 200710168057) < < acid-resistant pressing crack supporting agent; R. patent (application number 200580030660.3) the < < sintered spherical pellets > > philosophy such as Di Enkeer, M. Ai Mengzi adopts sintering process, take bauxitic clay or aluminum oxide as major ingredient, add feldspar, titanium oxide or contain barium carbonate or bar fusing assistant, prepare high-strength low close propping agent, improved intensity and the acid fastness of material.Sintering process is still to prepare at present the main stream approach of propping agent.
With sintering process, prepare propping agent, the major ingredient adopting is bauxitic clay, and this resource to high-quality is a waste greatly, therefore, with solid waste vast scale substitution of Al alumina cheaply, preparation pressure break ceramsite propping agent is the inexorable trend of home and abroad technical progress and development.This has been reported on the one hand: mono-kind of Li Qing dimension patent (application number 201010552791.0) < < utilizes petroleum propping agent prepared by oil shale waste and preparation method thereof > > to substitute part bauxitic clay with oil shale waste and prepares the propping agent that meets GB.Yin Guoxun etc. [utilize the industrial solid wastes such as red mud to prepare haydite [J]. Institutes Of Technology Of He'nan's journal (natural science edition), 2008,27 (4): 491-496].Tian little Rang patent (application number 200710137758.X) " utilizes red mud to prepare the method for acid-resistant pressing crack supporting agent ".Open and pass magnesium patent (application number 02134274.1) " ceramic slag haydite and preparation method thereof ".Zhai Guanjie etc. [trial-production of high blending flyash sintering ceramsite [J]. flyash .2008, (1): 42-43] manufactured experimently high blending flyash sintering ceramsite.Zhang Yujun patent (application number 200910015979.9) " a kind of high-strength compress supporting agent for coarse oil and preparation method thereof ", utilizes petroleum fracturing propping agent prepared by the ceramic rod waste material of high alumina content to have high-strength, acidproof feature.
The quality of propping agent haydite performance, depends on the internal microstructure of product, to the existing understanding fully of this investigator, and has carried out some useful explorations.Lee accounts for firm patent (application number CN201010136972.5) < < low-density ceramic proppant and preparation method thereof > >, change molding mode, utilize the ingenious mode of multilayer cladding, the synthetic propping agent with the nodular enhancement type of inner core and shell, product performance have been improved, but molding mode is too complicated, handling not strong, the prospect that has affected suitability for industrialized production and applied.
At present, the low crisp corrosion-resistant main research tendency of propping agent haydite that becomes of low-density high-strength, for realizing this goal, in propping agent formula, introduce different high temperature fusing assistants and optimized the mode of haydite moulding, improved to a certain extent the mechanical property of propping agent, improve acid resistance and the salt tolerance of material, however, still can not fundamentally solve the shortcoming of ceramsite propping agent mechanical property poor (fragility is larger).
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and means, a kind of method of utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents is provided.By preparation method of the present invention, can prepare the compound fracturing propping agents of high-strength and high ductility, low density and LB rate, make this product can be applied in, in profound pressure break environment, realize the object of frscturing.
For achieving the above object, the technical solution used in the present invention is:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, then cross respectively 120 mesh sieves;
2) gold ore tailing after sieving 40%～55% by mass percentage, 30%～45% aluminum oxide powder and 10%～15% the fire-resistant chopped strand of polycrystal alumina join in ball mill after mixing, to adding mass concentration in ball mill, be that 10% the gummy aqueous solution mixes wet-milling and forms mixing mud again, mud is crossed 300 mesh sieves;
3) will sieve after mud adopt press spray granulator granulation, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 5 ℃/min～10 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 5 ℃/min～7 ℃/min is warming up to 1350 ℃～1400 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Described step 1) dry grinding is to utilize alumina balls masonry for grinding medium, and the mass ratio of controlling abrading-ball and raw material is (2～3): 1, and difference ball milling 0.5h～2h.
Described step 2) wet-milling is to utilize alumina balls masonry for grinding medium, and the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is (2～3): 1: (0.3～0.4), grind 0.5h～3h.
Described step 3) granulation: sponging granulator inlet temperature is 300 ℃～500 ℃, hot-blast furnace temperature is 600 ℃～800 ℃, and temperature of outgoing air is 80 ℃～95 ℃, and mud pressure is 1.2MPa～1.5MPa.
Described aluminum oxide powder is industrial Alpha-alumina (lapis amiridis), its corundum content > 98%, and powder grain is through < 10 μ m.
The fusing point of the described fire-resistant chopped strand of polycrystal alumina is greater than 2050 ℃.
Synthesized of the present invention be the composite proppant haydite of tool grain refining and dispersion, it is comprised of matrix phase and wild phase two portions, matrix phase is mainly by quartzy, lime feldspar and a small amount of glassy phase, pore phase composite; Wild phase is that the corundum of grain refining is, the sapphire whisker of introducing and generated in-situ not Lay mineral wool phase.The moiety of material than (% by weight) is: wild phase 5-15%, matrix phase 85-95%.
The present invention introduces high temperature oxidation resisting aluminum fiber, the theory of matrix material is integrated among the ceramsite propping agent of non-densification, by the mode of external introducing and pyroreaction self-generating, provide enhancing toughness reinforcing necessary fiber, by in fiber reinforcement and two kinds of means of particle enhancing, at least one prepares the compound propping agent haydite of high-strength and high ductility, low density and LB rate, make this product can be applied in, in profound pressure break environment, realize the final purpose of frscturing.
Embodiment
Embodiment 1:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 2: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 40% by mass percentage, 45% aluminum oxide powder and 15% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 2: 1: 0.3, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 500 ℃, hot-blast furnace temperature is 800 ℃, temperature of outgoing air is 95 ℃, mud pressure is 1.2MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 5 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 5 ℃/min is warming up to 1350 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Embodiment 2:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 2.5: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 55% by mass percentage, 30% aluminum oxide powder and 15% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 2.5: 1: 0.35, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 300 ℃, hot-blast furnace temperature is 600 ℃, temperature of outgoing air is 80 ℃, mud pressure is 1.4MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 8 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 6 ℃/min is warming up to 1380 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Embodiment 3:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 3: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 50% by mass percentage, 40% aluminum oxide powder and 10% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 3: 1: 0.38, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 400 ℃, hot-blast furnace temperature is 700 ℃, temperature of outgoing air is 88 ℃, mud pressure is 1.3MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 6 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 7 ℃/min is warming up to 1360 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Embodiment 4:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 2.3: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 45% by mass percentage, 43% aluminum oxide powder and 12% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 2.3: 1: 0.33, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 350 ℃, hot-blast furnace temperature is 650 ℃, temperature of outgoing air is 84 ℃, mud pressure is 1.5MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 7 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 5 ℃/min is warming up to 1390 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Embodiment 5:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 2.8: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 52% by mass percentage, 35% aluminum oxide powder and 13% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 2.8: 1: 0.4, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 450 ℃, hot-blast furnace temperature is 750 ℃, temperature of outgoing air is 92 ℃, mud pressure is 1.2MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 10 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 5 ℃/min is warming up to 1370 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
Embodiment 6:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is 3: 1, and then ball milling 0.5h～2h crosses respectively 120 mesh sieves respectively;
2) gold ore tailing after sieving 50% by mass percentage, 36% aluminum oxide powder and 14% the fire-resistant chopped strand of polycrystal alumina are put into ball mill, adding mass concentration is that 10% the gummy aqueous solution mixes and utilizes alumina balls masonry for grinding medium again, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is 3: 1: 0.4, grind 0.5h～3h and form mixing mud, mud is crossed 300 mesh sieves;
Wherein, aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m; The fire-resistant chopped strand of polycrystal alumina, its fusing point is greater than 2050 ℃, and the thermostability that tool is high can be applied in more than 1400 ℃ environment.Maximum operation (service) temperature is 1600 ℃, and life-time service temperature can reach 1500 ℃;
3) will sieve after mud adopt press spray granulator granulation, sponging granulator inlet temperature is 380 ℃, hot-blast furnace temperature is 680 ℃, temperature of outgoing air is 90 ℃, mud pressure is 1.5MPa, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 9 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 7 ℃/min is warming up to 1400 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
The present invention utilizes trade waste-gold ore tailing for major ingredient, thinking with " adjusting chemical composition+optimization microstructure ", by technological operation simple and easy to control, provide a kind of when introducing and utilizing reaction in－situ self-generating and there is fibrous crystals, make the fine particle of fiber and generation between disperse matrix phase, further optimize the concrete grammar that forms fibrous/granular composite ceramic material, " dual disperse " technology is combined with Ceramic Composite technology, both developed discarded slag, improve again the chemical constitution of propping agent, optimize the microstructure of haydite, overcome the fragility of stupalith, be expected to further improve the over-all properties of propping agent ceramsite material.
Take gold ore tailing as major ingredient, in the time of by introducing high temperature oxidation resisting aluminum fiber, utilize pyroreaction, the fibrous 3Al of original position self-forming
2o
32SiO
2the matrix material of granular dispersion consolidatedization of crystal in Lay stone crystal and porcelain body not, not only have cheap for manufacturing cost, and fibrous not Lay stone have larger specific surface area and surface can with granular corundum, cristobalite, lime feldspar ceramic matrix relies on strong crystal boundary power to combine, fibrous crystals is distributed in corundum on the one hand, cristobalite, between lime feldspar particle, form fiber/particle disperse structure, on the other hand, synthetic corundum crystal tool " grain refining " structure, even dispersion is at cristobalite, around the crystal such as lime feldspar, form the stack of particle/particle secondary disperse." dual disperse " causes the formation of fiber/granular compound disperse structure, effectively improved the microstructure of porcelain body, played conclusive effect, thereby the over-all properties of this material is greatly improved to improving intensity and the toughness of porcelain body.
In ceramsite propping agent formula, introduce and can at high temperature fully react the chemical composition that forms fibrous crystals, using it as necessary initial feed, through pyroreaction, make fibrous crystals and new formation between granular crystal, synthesized " dual disperse " microstructural matrix material.Due to each different forming under uniform temp, environment and condition mutually, cause fiber reinforcement phase and Particle Phase and pore to there is good stress consistency and wettability between mutually, effectively improve and optimized the microstructure of haydite, the comprehensive mechanical property of this material is significantly improved.
The present invention prepares petroleum fracturing propping agent with gold ore tailing as major ingredient.Tailings is the inevitable waste residue producing during gold is produced, and has a large capacity and a wide range, and does not obtain at present good development and utilization.According to the geologic feature of domestic gold output, goldmine tailing essential mineral be take quartzy (30%～60%), pyrite (5%～20%), plagioclase (10%～30%), potassium felspar sand (15%～30%), sericite (5%～15%) as main, and chemical constitution is generally with SiO
2(40%～60%), Al
2o
3(15%～25%), Fe
2o
3(2%～10%), TiO
2(0～2%), K
2o(3%～8%), Na
2o(2%～5%) etc. oxide compound forms and exists, and profile is that fine-grained powder powder is semi-solid, and discharge is piled up loose, and tailings granularity is between 70 order～160 orders (0.22mm～0.097mm).Gold ore tailing both provided pyroreaction necessary component, had played again the effect of high temperature composite fluxing agent.Tailings embodies on composition: the feature of high silicon, low aluminium, high ferro, potassium, sodium, and in the feature that shows low melting point in nature, efficiently fluxes.The main source of mullite fiber is the SiO in waste residue under high temperature
2with the Al in aluminum oxide powder
2o
3reaction forms mullite cylinder or fiber, and fiber phase/Particle Phase/pore has formed the microstructure of disperse state mutually.Non-α-Al
2o
3be transformed into the particulate corundum of wild phase, corundum wild phase is also thin crystalline substance-disperse state and is distributed in lime feldspar, cristobalite around, has formed the microstructure of dual disperse.The generation of corundum and mullite has been played conclusive effect to proppant strength.In tailings, be flux component K on the other hand
2o, Na
2o, CaO, MgO, Fe
2o
3, TiO
2deng, can effectively reduce the low eutectic point of compound, propping agent sintering temperature is reduced, and a small amount of glassy phase forming with other component interactions, be filled in because of pyroreaction and emit in gas or the formed pore of crystalline form conversion volumetric expansion, to improving the intensity of propping agent, played effectively supplementary.
The present invention utilizes gold ore tailing, aluminum oxide powder, chopped sapphire whisker through sintering process, simultaneously synthetic at matrix phase and wild phase by pyroreaction, and make matrix phase " grain refining ", " dispersion ", wild phase and matrix phase again " disperse ", composite proppant haydite has been prepared in dual disperse.Because this material combines the advantage of grain refining stupalith and filamentary material, and make pore wherein also be disperse state to be mutually uniformly distributed, intensity and the toughness of haydite have been guaranteed on the one hand, effectively reduce on the other hand the density of material, make the comprehensive mechanical property of this material obtain further raising.In addition, on raw material, introduce in a large number rejects cheaply, reduced firing temperature, in burning till fast, realized grain refining and dispersion, reduced production cost simultaneously.The present invention does not change existing technique, do not increase any equipment, the technical indicator of its product and use properties meet oil and gas industry standard SY/T5108-2006 < < fracturing propping agents performance index and evaluation test method > > completely.
The present invention prepares compound petroleum fracturing propping agent with sapphire whisker and gold ore tailing as major ingredient, not only can bring into play waste residue fine size, high silicon, low aluminium, iron, titanium, potassium, sodium component content is large, fusing point is low, the high temperature significant advantage of effect of fluxing, can also pass through process regulation pyroreaction, make the granular crystal (lime feldspar of existing high-intensity disperse state in petroleum fracturing propping agent, cristobalite, corundum), have again and strengthen toughness reinforcing fibrous crystals (aluminum oxide, Mo Laishi), the two presents disperse-thin brilliant orderly fiber/particle microtexture, thereby effectively improve intensity and the acid fastness of propping agent, reduce its percentage of damage.Form the proppant material of excellent performance.
Effect of the present invention is embodied in:
(1) main raw material of the present invention is the trade waste of inevitable discharge in ore dressing process, prepares fracturing propping agents not only contribute to save natural resource with gold ore tailing, reduces production costs, and is conducive to environment protection.
(2) tailings raw material is mainly micron-size spherical particles, compares with natural mineral, and raw material is without using high-power crusher in crushing, and between each component, batch mixing is even, has effectively reduced a large amount of energy consumptions that raw material ball milling produces.
(3) mineralogical chemistry of gold ore tailing form and character show there is high silicon, low aluminium, iron, titanium foreign matter content is large, the fusing point low and high temperature effect outstanding feature of fluxing, both provided necessary SiO in pyroreaction
2, Al
2o
3deng component, supplied with again antiflux component K
2o, Na
2o, Fe
2o
3, TiO
2, CaO, MgO etc., reduce production cost.
(4) take the theory of matrix material is guidance, introduce sapphire whisker, make the corundum crystal of existing high-intensity disperse in petroleum fracturing propping agent-thin crystalline state form the disperse structure of particle/particle, there is again the fiber/particle disperse structure that strengthens toughness reinforcing fibrous dispersion, dual disperse has effectively improved the microstructure of porcelain body, the intensity and the acid-resistant corrosion that improve propping agent, reduce its percentage of damage.
(5) the fracturing propping agents intensity of preparing can reach 95MPa～135MPa, has that intensity is high, a light weight, the good characteristic such as high temperature resistant, corrosion-resistant, in can be used as, the fracturing propping agents of deep-seated oil gas field.Table 1 is for introducing fiber and take gold ore tailing as major ingredient is in the performance index of 1400 ℃ of prepared fracturing propping agents haydite samples.
The performance of 1400 ℃ of prepared fracturing propping agents haydite samples of table 1
Claims (6)
1. utilize gold ore tailing and sapphire whisker to prepare a method for compound fracturing propping agents, it is characterized in that:
1) gold ore tailing and aluminum oxide powder are put into respectively to ball mill for dry grinding, then cross respectively 120 mesh sieves;
2) gold ore tailing after sieving 40%～55% by mass percentage, 30%～45% aluminum oxide powder and 10%～15% the fire-resistant chopped strand of polycrystal alumina join in ball mill after mixing, to adding mass concentration in ball mill, be that 10% the gummy aqueous solution mixes wet-milling and forms mixing mud again, mud is crossed 300 mesh sieves;
3) will sieve after mud adopt press spray granulator granulation, the spheroidal particle that granulation forms is crossed 18 orders and 30 mesh sieves, and the screenings particle between two sieves is collected and waited to burn;
4) particle to be burnt is put into alumina crucible, and be placed in globars resistance furnace, rate of heating with 5 ℃/min～10 ℃/min is warming up to 1230 ℃ from room temperature, insulation 0.5h～1h, rate of heating with 5 ℃/min～7 ℃/min is warming up to 1350 ℃～1400 ℃, and insulation 2h～3h, with taking out after stove naturally cooling, cross 20 order～40 mesh sieves, obtain composite fracturing propping agent.
2. the method for utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents according to claim 1, it is characterized in that: described step 1) dry grinding is to utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball and raw material is (2～3): 1, and difference ball milling 0.5h～2h.
3. the method for utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents according to claim 1, it is characterized in that: described step 2) wet-milling is to utilize alumina balls masonry for grinding medium, the mass ratio of controlling abrading-ball, compound and the gummy aqueous solution is (2～3): l: (0.3～0.4), grind 0.5h～3h.
4. the method for utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents according to claim 1; it is characterized in that: described step 3) granulation: sponging granulator inlet temperature is 300 ℃～500 ℃; hot-blast furnace temperature is 600 ℃～800 ℃; temperature of outgoing air is 80 ℃～95 ℃, and mud pressure is 1.2MPa～1.5MPa.
5. the method for utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents according to claim 1, it is characterized in that: described aluminum oxide powder is industrial Alpha-alumina, its corundum content > 98%, diameter of particle < 10 μ m.
6. the method for utilizing gold ore tailing and sapphire whisker to prepare compound fracturing propping agents according to claim 1, is characterized in that: the fusing point of the described fire-resistant chopped strand of polycrystal alumina is greater than 2050 ℃.
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| CN1274376A (en) * | 1998-07-22 | 2000-11-22 | 博登化学公司 | Composite proppant, composite filtration media and methods for making and using same |
| CN101585698A (en) * | 2009-07-03 | 2009-11-25 | 陕西科技大学 | Method for preparing porcelain granules by using fly ash |
| CN102352241A (en) * | 2011-09-02 | 2012-02-15 | 濮阳市强胜石油支撑剂有限公司 | High-strength ceramic proppant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1274376A (en) * | 1998-07-22 | 2000-11-22 | 博登化学公司 | Composite proppant, composite filtration media and methods for making and using same |
| CN101585698A (en) * | 2009-07-03 | 2009-11-25 | 陕西科技大学 | Method for preparing porcelain granules by using fly ash |
| CN102352241A (en) * | 2011-09-02 | 2012-02-15 | 濮阳市强胜石油支撑剂有限公司 | High-strength ceramic proppant and preparation method thereof |
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