CN102718521B - Method of using coal gangue to prepare fracturing propping agent - Google Patents
Method of using coal gangue to prepare fracturing propping agent Download PDFInfo
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- CN102718521B CN102718521B CN201210201367.0A CN201210201367A CN102718521B CN 102718521 B CN102718521 B CN 102718521B CN 201210201367 A CN201210201367 A CN 201210201367A CN 102718521 B CN102718521 B CN 102718521B
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Abstract
The invention discloses a method of using coal gangue to prepare fracturing propping agent. The method includes: mixing coal gangue, alumina powder, barium carbonate and alumina chopped fibers, adding the mixture into gum aqueous solution to be subjected to uniform mixing and wet grinding to form mixed slurry, using a pressure atomizing granulator for granulating, putting particles into an alumina crucible which is positioned in a silicon carbide rod resistance furnace, heating from the room temperature to 1230 DEG C at the speed of 5 DE G C/min-10 DE G C/min, preserving heat for 0.5-1h, heating to 1350-1400 DE GC at the speed of 5 DE G C/min-7 DE G C/min, preserving heat for 2-3h, taking out after natural furnace cooling, and screening with a 20mesh-40mesh sieve to obtain the composite fracturing propping agent. The alumina chopped fibers are introduced, the concept of composite materials is integrated into the noncompact ceramsite propping agent, and fibers (whiskers) necessary for strength and toughness improvement are provided by means of self-generation in high-temperature reaction, and the composite fracturing propping agent which is high in strength and toughness and low in density and breakage rate is prepared by means of fiber enhancement and particle enhancement.
Description
Technical field
The present invention relates to a kind of method of utilizing industrial waste to prepare ceramic composite, particularly a kind of method of utilizing coal gangue to prepare 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 ".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.Li Qinghai patent (application number 200910023599.X) " a kind of petroleum fracturing propping agent that adds coal gangue ", utilizes coal gangue, bauxitic clay and other breeze to prepare propping agent haydite.But do not introduce in its preparation process or form fiber (whisker) by pyroreaction, thereby synthetic compound propping agent haydite.
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 coal gangue to prepare fracturing propping agents is provided, the fracturing propping agents of preparing by preparation method of the present invention are compound fracturing propping agents of a kind 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.
For achieving the above object, the technical solution used in the present invention is:
1) coal gangue and aluminum oxide powder are put into respectively to ball mill for dry grinding, then cross respectively 120 mesh sieves;
2) coal gangue after sieving 40%～55% by mass percentage, 35%～45% aluminum oxide powder, 3%～8% barium carbonate and 5%～10% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be that 10% the gummy aqueous solution mixes wet-milling again, form mixing mud, 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): l: (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.
Aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, and powder grain is through < 10 μ m.
The alumina content of described aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m.
The composite proppant haydite of the grain refining of synthesized of the present invention and dispersion, is characterized in that: it is comprised of matrix phase and wild phase two portions, and matrix phase is mainly by quartz, celsian-felspar and a small amount of glassy phase, pore phase composite; Wild phase is corundum fibers, the generated in-situ not Lay mineral wool phase that the corundum of grain refining, outer introducing come.The moiety of material than (% by weight) is: wild phase 5-15%, matrix phase 85-95%.
The present invention introduces aluminum oxide chopped strand, the theory of matrix material is integrated among the ceramsite propping agent of non-densification, and the mode that is aided with pyroreaction self-generating provides and strengthen toughness reinforcing necessary fiber (whisker), by fiber reinforcement and particle, strengthen the compound fracturing propping agents that two kinds of means are prepared high-strength and high ductility, low density and LB rate.
Accompanying drawing explanation
Fig. 1 is for take the cross-section morphology figure of coal gangue as major ingredient in 1400 ℃ of sintered specimens.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) coal gangue 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 ball milling 0.5h～2h, then crosses respectively 120 mesh sieves respectively;
2) coal gangue after sieving 40% by mass percentage, 45% aluminum oxide powder, 5% barium carbonate and 10% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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) coal gangue 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) coal gangue after sieving 55% by mass percentage, 35% aluminum oxide powder, 3% barium carbonate and 7% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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) coal gangue 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 ball milling 0.5h～2h, then crosses respectively 120 mesh sieves respectively;
2) coal gangue after sieving 45% by mass percentage, 40% aluminum oxide powder, 8% barium carbonate and 7% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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) coal gangue 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) coal gangue, 42% aluminum oxide powder, 3% barium carbonate and the 5% aluminum oxide chopped strand after sieving 50% is by mass percentage mixed to get compound and compound put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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) coal gangue 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) coal gangue after sieving 48% by mass percentage, 43% aluminum oxide powder, 4% barium carbonate and 5% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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) coal gangue 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) coal gangue after sieving 52% by mass percentage, 38% aluminum oxide powder, 5% barium carbonate and 5% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be 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: l: 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 alumina content of aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, and its diameter is at 15-20 μ m, and length is at 50-100 μ m;
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-coal gangue for major ingredient, thinking with " adjusting chemical composition+optimization microstructure ", by technological operation simple and easy to control, provide a kind of when utilizing reaction in－situ self-generating to 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 flyash, 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 proppant material.
Take coal gangue as major ingredient, when introducing sapphire whisker, 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, celsian ceramics matrix relies on strong crystal boundary power to combine, fibrous crystals is distributed in corundum on the one hand, cristobalite, between celsian-felspar particle, form fiber/particle disperse structure (disperse), on the other hand, synthetic corundum crystal tool " grain refining " structure, even dispersion cristobalite, around the crystal such as celsian-felspar (secondary disperse), formed the stack of particle/particle secondary disperse." dual disperse " caused 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 coal gangue as major ingredient.The main chemical compositions that coal gangue is is SiO
2, Al
2o
3, Fe
2o
3, CaO and do not fire charcoal, separately contain the compounds such as a small amount of K, P, S, Mg, profile is block.Coal gangue material forms with quartz, feldspar, rhombohedral iron ore, high-alumina clay mineral, organic charcoal etc.Coal gangue embodies on composition: the feature of middle silicon, high alumina, iron, low potassium, sodium, shows high-melting-point, high fire-resistant feature in nature.The main source of mullite fiber is the SiO 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 celsian-felspar, cristobalite around, has formed the microstructure of dual disperse.The generation of corundum and mullite has been played conclusive effect to proppant strength, and barium carbonate has participated in SiO
2, Al
2o
3, BaO building-up reactions form BaAl
2si
2o
8monocline celsian-felspar, had both improved the intensity of haydite and the ability of acid-alkali-corrosive-resisting, had reduced again the withstand voltage percentage of damage of propping agent, meanwhile, to improving the intensity of propping agent, had played useful effect.In flyash, contain on the other hand a certain amount of flux component K
2o, Na
2o, CaO, MgO, Fe
2o
3, TiO
2deng, can effectively reduce the low eutectic point of compound, sintering temperature is reduced, and with the new a small amount of glassy phase forming of other component interactions, be filled in because of pyroreaction and emit in gas or the formed pore of crystalline form conversion volumetric expansion, the raising of proppant strength has been played effectively and supplemented.
The present invention utilizes coal gangue, aluminum oxide powder, composite fortifier 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 increased on the one hand, effectively reduce on the other hand density and the breakage rate of material, make the comprehensive mechanical property of this material obtain further raising.In addition, on raw material, introduce in a large number coal gangue 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 coal gangue as major ingredient, not only can bring into play silicon in coal gangue, high alumina, iron, titanium, advantage that component content is large, can also pass through process regulation pyroreaction, make the granular crystal of existing high-intensity disperse state (celsian-felspar, cristobalite, corundum) in petroleum fracturing propping agent, have again and strengthen toughness reinforcing fibrous crystals (Mo Laishi, corundum), the two presents disperse-thin brilliant orderly microtexture, thus effectively improve propping agent intensity and acid fastness, 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 inevitable trade waste during coal mining is produced, and prepares fracturing propping agents not only contribute to save natural resource with coal gangue, reduces production costs, and also helps environment protection.
(2) performance of the composition of flyash and character has middle silicon, high alumina, iron, feature that titanium foreign matter content is large, has ensured Al in goods
2o
3content, saved other raw material of high alumina.
(3) take the theory of matrix material is guidance, introduce barium carbonate and sapphire whisker composite fortifier simultaneously, make existing high-intensity disperse in petroleum fracturing propping agent-thin crystalline state granular/granular-crystalline structure, there is again the crystalline structure that strengthens toughness reinforcing fiber/granular dispersion, thereby effectively improved the microstructure of porcelain body, the intensity and the acid-resistant corrosion that improve propping agent, reduce its percentage of damage.
(4) the fracturing propping agents intensity of preparing can reach 85MPa～115MPa, 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.
As seen from Figure 1, this material matrix is by celsian-felspar, cristobalite principal crystalline phase and a certain amount of pore phase composite, and wild phase is Al
2o
3phase and Mo Laishi.This material grains is tiny, is disperse-grain refining structure, and pore is grown, not Lay stone and corundum fibers abrim in pore.Table 1 is for take coal gangue 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 coal gangue to prepare a method for fracturing propping agents, it is characterized in that:
1) coal gangue and aluminum oxide powder are put into respectively to ball mill for dry grinding, then cross respectively 120 mesh sieves;
2) coal gangue after sieving 40%～55% by mass percentage, 35%～45% aluminum oxide powder, 3%～8% barium carbonate and 5%～10% aluminum oxide chopped strand are mixed to get compound and compound are put into ball mill that to add mass concentration be that 10% the gummy aqueous solution mixes wet-milling again, form mixing mud, 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 coal gangue to prepare 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 coal gangue to prepare 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 coal gangue to prepare 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 coal gangue to prepare fracturing propping agents according to claim 1, it is characterized in that: aluminum oxide powder is that industrial Alpha-alumina is lapis amiridis, its corundum content > 98%, powder grain is through < 10 μ m.
6. the method for utilizing coal gangue to prepare fracturing propping agents according to claim 1, it is characterized in that: the alumina content of described aluminum oxide chopped strand is more than 95%, by the fiber without the unidirectional extension of slag of the chopped acquisition of macrofiber, its diameter is at 15-20 μ m, and length is at 50-100 μ m.
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| CN103288430B (en) * | 2013-05-16 | 2014-06-04 | 陕西科技大学 | Method for preparing special fracturing propping agent for shale gas by utilizing low-carbon coal gangue |
| CN103288431B (en) * | 2013-05-28 | 2014-07-02 | 陕西科技大学 | Method for preparing special high-strength fracturing propping agent for shale gas |
| CN106967408B (en) * | 2017-03-28 | 2019-11-15 | 太原理工大学 | A kind of ultra-low-density ceramic proppant and preparation method thereof |
| CN109809724A (en) * | 2018-12-04 | 2019-05-28 | 中国地质调查局沈阳地质调查中心 | A kind of bastard coal ground mass haydite and preparation method thereof |
| CN112126423A (en) * | 2020-10-16 | 2020-12-25 | 邵阳合成新型环保建材有限公司 | Petroleum fracturing propping agent added with coal gangue |
| CN115678533A (en) * | 2021-07-22 | 2023-02-03 | 攀枝花秉扬科技股份有限公司 | Low-density high-strength ceramsite proppant using coal gangue as raw material and preparation method thereof |
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| WO2011081545A1 (en) * | 2009-12-30 | 2011-07-07 | Schlumberger Canada Limited | Hydraulic fracturing proppant containing inorganic fibers |
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