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CN-121991680-A - Modified fly ash ceramsite propping agent and preparation method, combined propping agent and preparation method and application

CN121991680ACN 121991680 ACN121991680 ACN 121991680ACN-121991680-A

Abstract

The invention discloses a modified fly ash ceramsite propping agent, a preparation method, a combined propping agent, a preparation method and an application, and relates to the technical field of shale oil gas fracturing. The environment-friendly propping agent solves the problems of high production cost and high application cost of the fracturing propping agent taking aluminum-containing minerals as main raw materials, and gives consideration to the recycling of resources and the harmless treatment of industrial waste in the whole industrial chain of petrochemical industry, and applies the industrial waste downstream of the oil refining industry to the upstream petroleum fracturing propping agent.

Inventors

  • Su Fangru

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油工程技术研究院有限公司

Dates

Publication Date
20260508
Application Date
20241101

Claims (12)

  1. 1. The modified fly ash ceramsite propping agent is characterized by comprising the following components in a mixed granulating way: Fly ash, bauxite, barite powder, recycled molecular sieve, recycled mesoporous material, optionally local relief powder and optionally bentonite; based on 100 weight percent of the total weight of the fly ash, bauxite, barite powder, recycled molecular sieve, recycled mesoporous material, optional local relief powder and optional bentonite: 45-80wt% of fly ash; 10-55wt% of bauxite; 1-10wt% of barite powder; recovering 5-12wt% of molecular sieve; 3-15wt% of a recycled mesoporous material; 0-10wt% of calcite powder; 0-10wt% of bentonite.
  2. 2. The modified fly ash ceramsite proppant of claim 1, wherein: based on 100 weight percent of the total weight of the fly ash, bauxite, barite powder, recycled molecular sieve, recycled mesoporous material, optional local relief powder and optional bentonite: 55-75wt% of fly ash; 25-35wt% of bauxite; 5-10wt% of barite powder; recovering 5-10wt% of molecular sieve; recovering 2.5-10wt% of mesoporous materials; 5-10wt% of calcite powder; 5-10wt% of bentonite.
  3. 3. The modified fly ash ceramsite proppant of claim 1 or 2, wherein: The modified fly ash ceramsite propping agent is 40-70 meshes, and/or has a bulk density of 1.4-1.7 g/cm 3 , and/or has a apparent density of 2.3-2.9 g/cm 3 .
  4. 4. The modified fly ash ceramsite proppant of claim 1 or 2, wherein: the particle size of the fly ash, bauxite, barite powder, recycled molecular sieve, recycled mesoporous material, calcite powder and bentonite is less than 35 microns, preferably less than 25 microns.
  5. 5. The modified fly ash ceramsite proppant of claim 1 or 2, wherein: the fly ash is II-grade concrete fly ash, and/or, The bauxite has a content of 60% -70% of aluminum oxide and/or, The bentonite is at least one of sodium bentonite, calcium bentonite and organic bentonite.
  6. 6. A method of preparing the modified fly ash ceramsite proppant of any one of claims 1-5, comprising: Mixing activated fly ash, premixed calcined bauxite and barite powder, a mixed solution of recycled molecular sieve and recycled mesoporous material after ultrasonic treatment, optionally decomposed powder and bentonite, granulating to obtain a blank ball, sealing and firing the blank ball, and cooling to obtain the modified fly ash ceramsite proppant.
  7. 7. The method according to claim 6, wherein: The activation treatment comprises the steps of carrying out an activation reaction on the fly ash and an alkaline solution, washing and filtering to obtain activated fly ash, wherein the weight ratio of the fly ash to solute in the alkaline solution is (3-10): 1, preferably (4-8): 1, and/or the alkaline solution is sodium hydroxide solution, and/or the reaction temperature of the activation reaction is 80-90 ℃, and/or the reaction time is 1-3 hours, preferably 1.5-2.5 hours, and/or, The calcination temperature of the pre-mixed calcination is 600-800 ℃, and/or the calcination time is 1-3 hours, preferably 1.5-2.5 hours, and/or, The total concentration of the recovered molecular sieve and the recovered mesoporous material in the mixed solution of the recovered molecular sieve and the recovered mesoporous material is 10-15wt%, and/or the solvent of the mixed solution of the recovered molecular sieve and the recovered mesoporous material is ethanol, and/or the ultrasonic treatment frequency is 20 kHz-50 MHz, preferably 20 kHz-40 kHz, and/or the time is 20-40 minutes, preferably 25-30 minutes, and/or, The granulation is a spray drying process, preferably with a feed concentration of 10-60%, and/or a feed flow rate of 5-40mL/min, and/or an inlet temperature of 150-300 ℃, and/or an outlet temperature of 80-120 ℃, and/or a spray pressure of 1-10MPa, and/or an atomizing gas flow rate of 0.2-0.5m 3 /min, and/or a drying tower gas flow rate of 0.5-1.5m/s, and/or a drying tower relative humidity of 20-40%, and/or, The blank ball is 10-100 mesh, preferably 30-70 mesh, and/or, The sealing firing is performed by heating to 650-670 ℃ at a heating rate of 4-6 ℃ per minute, heating to 1000-2000 ℃ at a heating rate of 15-20 ℃ per minute, firing for more than 1 hour, preferably 1-3 hours, and/or, The cooling rate is 12-17 ℃ per minute, and/or the cooling atmosphere is nitrogen and/or inert gas, preferably nitrogen and/or argon, and/or the cooling gas flow rate is 10-50L/min, and/or the cooling pressure is 0.9-1atm.
  8. 8. The method of claim 6, further comprising surface modifying the modified fly ash ceramsite proppant, preferably, The surface modification treatment comprises the step of carrying out coupling reaction on the modified fly ash ceramsite proppants and a silane coupling agent solution, and more preferably, The concentration of the modified fly ash ceramsite propping agent in the silane coupling agent solution is 0.5-3wt%, more preferably 1-2wt%, and/or, The concentration of the silane coupling agent solution is 1 to 5vol%, more preferably 2 to 3vol%, and/or, The silane coupling agent is 3-aminopropyl triethoxy silane and/or octyl triethoxy silane, and/or, The solvent of the silane coupling agent solution is ethanol, and/or, The reaction temperature of the coupling reaction is 20 to 80 ℃, more preferably 50 to 70 ℃, and/or the reaction time is 30 to 120min, more preferably 45 to 60min.
  9. 9. A composite proppant characterized in that the composite proppant comprises the modified fly ash ceramsite proppant of any one of claims 1-5 or the modified fly ash ceramsite proppant prepared by the method of any one of claims 6-8, a mixed proppant; the mixed propping agent is at least one of recycled molecular sieve, recycled mesoporous material, quartz sand and ceramic sand.
  10. 10. The combination proppant of claim 9, wherein: the weight ratio of the modified fly ash ceramsite propping agent to the mixed propping agent is (4-6): 1, preferably (4-5): 1, and/or, The particle size of the mixed proppants is 50-210 mu m.
  11. 11. A method of preparing a combination proppant as set forth in claim 9 or 10, characterized in that the method comprises: The components are mixed to prepare the combined propping agent.
  12. 12. Use of a combination proppant as set forth in claim 9 or 10 or a combination proppant made by the method of claim 11 as a shale oil and gas fracturing proppant.

Description

Modified fly ash ceramsite propping agent and preparation method, combined propping agent and preparation method and application Technical Field The invention relates to the technical field of shale oil gas fracturing, in particular to a modified fly ash ceramsite propping agent and a preparation method thereof, a combined propping agent and a preparation method and application thereof. Background Currently, quartz sand and ceramsite are the main technical materials for fracturing propping agents for horizontal wells. The traditional quartz sand and ceramsite have wide sources and lower relative density, but the single well fracturing cost is too high due to the large consumption, and the traditional quartz sand and ceramsite are limited in the application of shale oil gas multi-section horizontal wells and deep ultra-deep horizontal wells. The coated propping agent has improved sphericity, reduces the apparent density and the volume density of the propping agent, increases the anti-crushing capability, and can also reduce the dosage of the fracturing fluid, but because the unit price is too high, the coated propping agent is used for controlling the cost, and often cannot be used in a large amount in fracturing construction. Fly ash is fine ash collected from flue gas after coal combustion, and fly ash is main solid waste discharged from coal-fired power plants. The main oxide composition of the fly ash of the thermal power plant in China is SiO 2、Al2O3、FeO、Fe2O3、CaO、TiO2 and the like. Along with the development of the power industry, the emission of the fly ash of the coal-fired power plant is increased year by year, and the fly ash becomes one of industrial waste residues with larger current discharge capacity in China. A large amount of fly ash can generate dust and pollute the atmosphere without being treated, but the fly ash can be recycled, such as being used as an admixture of concrete, an admixture of fracturing propping agent and the like. The molecular sieve is a kind of artificially synthesized hydrated aluminosilicate with molecular screening function, also called zeolite, its chemical general formula is (M '2M)O·Al2O3·xSiO2·yH2 O, M' and M are monovalent and divalent cations, such as K +、Na+ and Ca 2+、Ba2+, etc. its structure has many holes with uniform pore size and ordered arrangement, the molecular sieves with different pore sizes can separate the molecules with different sizes and shapes, and its adsorption capacity is strong, selectivity is strong, strength is good, high-temp. resistance. Mesoporous materials refer to a class of porous materials with pore diameters between 2 and 50 nm. The mesoporous material has the characteristics of extremely high specific surface area, regular and ordered pore canal structure, narrow pore diameter distribution, continuous and adjustable pore diameter size and the like, so that the mesoporous material plays a role in adsorption and separation of macromolecules which are difficult to complete by a plurality of microporous zeolite molecular sieves, in particular catalytic reactions. Moreover, the ordered pore canal of the material can be used as a micro-reactor, and becomes a main and guest material after being assembled with a uniform and stable guest material with nano scale, and the main and guest effect between the main and the guest and the small size effect, quantum size effect and the like possibly possessed by the guest material can make the ordered pore canal of the material hopefully widely applied to the fields of electrode materials, photoelectric devices, microelectronic technology, chemical sensors, nonlinear optical materials and the like. Therefore, the mesoporous material has wide application in the fields of biology, photoelectricity, petrochemical industry and the like. At present, along with the demand of petroleum refining and productivity removal of large petrochemical enterprises, a large amount of mesoporous materials for catalysis are eliminated and recovered. In recent years, proppant replacement materials using ceramsite and propping agents as base materials and industrial waste materials as supplementary materials are rapidly developed. The industrial waste materials have the characteristics of high strength, good roundness and sphericity, regular and ordered pore structure, proper granularity, stable chemical property, low cost, green and harmless property and the like, and greatly meet the application specification and requirement of the fracturing propping agent. Chinese patent CN103805160a relates to a method for preparing a high-doped fly ash ceramsite proppant. The method mainly overcomes the defects in the prior art, the mixing amount of the fly ash can reach 30% -75%, and specifically comprises the following steps of 1) mixing 20% -65% of bauxite, 30% -75% of fly ash, 0% -5% of calcite powder, 0% -10% of talcum powder, 1% -5% of titanium dioxide, 0% -20% of soft refractory clay and 1% -5% of barite powder uniformly to