WO2013044861A1 - 一种压裂支撑剂的制备方法、压裂支撑剂及其应用 - Google Patents

一种压裂支撑剂的制备方法、压裂支撑剂及其应用 Download PDF

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Publication number
WO2013044861A1
WO2013044861A1 PCT/CN2012/082381 CN2012082381W WO2013044861A1 WO 2013044861 A1 WO2013044861 A1 WO 2013044861A1 CN 2012082381 W CN2012082381 W CN 2012082381W WO 2013044861 A1 WO2013044861 A1 WO 2013044861A1
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Prior art keywords
resin
aggregate
fracturing proppant
fracturing
kneading
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PCT/CN2012/082381
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English (en)
French (fr)
Inventor
秦申二
胡宝苓
贾屹海
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北京仁创科技集团有限公司
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Publication of WO2013044861A1 publication Critical patent/WO2013044861A1/zh

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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

Definitions

  • the present invention relates to a method for preparing a fracturing proppant, a fracturing proppant prepared by the preparation method, and uses thereof.
  • Fracturing proppant is used in the deep well mining of oil and natural gas and in the ultra-deep well fracturing process.
  • the role of the fracturing proppant is to form a sand-filling crack with high conductivity in the formation, which provides high circulation for oil and gas. Permeable passage. Therefore, fracturing proppants require a certain strength and conductivity to meet the closure stress requirements of different depth formations.
  • the fracturing proppants used in oil fields are mainly ceramsite and quartz sand.
  • the ceramsite and quartz sand have a high breaking rate, and the ceramsite crushed in the reservoir is prone to migration and the conductivity is poor.
  • Resin coated sand proppant has also been widely used in recent years.
  • the proppant can obtain proppants of various properties by adjusting the type of resin. For example, when oil is collected, oil-repellent resin can improve oil recovery. .
  • the existing method for preparing resin coated sand is generally to add an additive to the resin and mix it uniformly by mechanical stirring. However, the amount of the resin is large by the method, and the obtained fracturing proppant has unstable performance and high fracture rate.
  • the object of the present invention is to overcome the defects of large amount of resin when the fracturing proppant is prepared by the prior method, and the obtained product has high crushing rate and poor conductivity, and provides a method for reducing the amount of resin and obtaining a breaking rate.
  • the invention provides a method for preparing a fracturing proppant, comprising: kneading an additive with a molten resin to obtain a resin-containing mixture; cooling the resin-containing mixture, and crushing; heating the aggregate to be higher than a melting point of the resin.
  • the temperature of the resin-containing mixture is uniformly mixed with the heated aggregate and solidified to form a coating on the surface of the aggregate.
  • the resin is contained in an amount of from 1 to 10 parts by weight based on 100% by weight of the total mass of the aggregate; and the weight ratio of the additive to the resin is from 0.01 to 0.4:1.
  • the kneading conditions include a kneading temperature of 100 to 180 ° C, a kneading time after the resin is melted, and the kneading is performed in a kneader, and the kneading machine has a power of 10 to 20 KW. .
  • the uniformly mixing and solidifying the crushed resin-containing mixture with the heated aggregate comprises: adding the crushed resin-containing mixture to the aggregate, and adding a curing agent to stir and solidify.
  • the conditions for the uniform stirring and curing include: a curing temperature of 100-250 V, a stirring and curing time of 2-30 minutes, based on 100 parts by weight of the resin,
  • the curing agent is contained in an amount of 5 to 30 parts by weight.
  • the resin is selected from one or more of a hydrophobic epoxy resin, a hydrophobic phenol resin, a hydrophobic furan resin, a hydrophobic polyurethane, and an unsaturated polyester.
  • the additive is selected from one or more of the group consisting of silica micropowder, carbon black, graphite, and glass microspheres; and the additive has an average particle diameter of 0.1 to 10 ⁇ m.
  • the aggregate is raw sand and/or ceramsite; the aggregate has a roundness of 0.6 and a sphericity of 0.6; and the aggregate has an average particle diameter of 0.1 to 1.2 mm.
  • the curing agent is selected from one or more of urotropine, p-toluenesulfonic acid, ethylenediamine, benzodimethylamine, m-phenylenediamine, phthalic acid amine, and polyamide.
  • the present invention also provides a fracturing proppant prepared by the above method. Moreover, the present invention also provides the use of the above-described fracturing proppant in a deep well fracturing process.
  • the resin layer coated on the surface of the fracturing proppant obtained by the method of the invention can effectively prevent the aggregate debris from escaping, thereby maintaining the ability of the crack to conduct and improving the oil or natural gas recovery.
  • the inventors of the present invention have found that the performance of the resin can be improved by adding an additive because the strength and antistatic ability of the resin are poor.
  • the existing fracturing proppant has an unstable performance and a high breaking rate by using an existing method of adding an additive to a resin and mixing it by mechanical stirring. The reason is presumably because the viscosity of the resin is large, and the additive is not uniformly dispersed in the resin by mechanical agitation, and the uneven composition of the aggregate coating layer causes unevenness of the single particle strength and the thickness of the coating layer.
  • the prior art generally employs an increase in the amount of resin to enhance the performance of the fracturing proppant.
  • the additive is added under kneading, and The additive is uniformly dispersed in the resin, and the obtained fracturing proppant has greater strength, lower breaking rate, and more stable performance, and the amount of the resin can also be reduced.
  • a method for preparing a fracturing proppant according to the present invention comprising: kneading an additive with a molten resin uniformly to obtain a resin-containing mixture; cooling and breaking the resin-containing mixture; heating the aggregate to a temperature higher than a melting point of the resin Temperature; The crushed resin-containing mixture is uniformly mixed with the heated aggregate and solidified to form a coating on the surface of the aggregate.
  • the addition of an additive to the resin enables the performance of the resin to be improved.
  • the addition of a crosslinking agent enables cross-linking between the resins to improve the mechanical properties of the resin; after the addition of the silicon micropowder, the compressive strength of the resin can be increased; after adding black powder or carbon black, The frictional resistance of the resin is lowered and the fluidity thereof is improved.
  • the resin itself has a large viscosity
  • the additive cannot be well dispersed in the resin, and further, the coating may be caused.
  • the composition of the resin coating on the aggregate surface is not uniform and the thickness is not uniform. Therefore, the obtained fracturing proppant has unstable performance, high fracture rate, and poor conductivity.
  • the resin after the resin is heated and melted, it has a small viscosity and a good fluidity; further, the mixture containing the molten resin and the additive is kneaded. Evenly, the kneading can perform both good dispersion and good mixing, and the additive can be better dispersed in the resin to improve the performance of the resin.
  • the conditions of the kneading are not particularly limited in the present invention as long as it can be ensured that the additive is well dispersed in the resin, and the gp, the resin and the additive can be well solidified together.
  • the conditions of the kneading include the temperature of kneading, the time of kneading; further, the kneading is usually carried out in a kneader, and therefore, the kneading conditions may further include the power of the kneader.
  • the kneading temperature may be varied within a wide range as long as the resin can be kept in a molten state, for example, the kneading temperature may be 100-180 ° C, preferably 120-160 ° C;
  • the kneading time after the resin is melted may be varied within a wide range.
  • the kneading time after the resin is melted may be 0.2 to 2 hours, preferably 0.5 to 1 hour.
  • the kneader kneads the additive and the viscous resin uniformly by generating a strong shearing action, and the shear strength thereof can be adjusted by the power of the kneader.
  • the power of the kneader can be adjusted over a wide range, for example, the power of the kneader can be 10-20 KW, preferably 10-15 KW.
  • the content of each component in the mixture can be selected and adjusted over a wide range.
  • the resin may be included in an amount of from 1 to 10 parts by weight, preferably from 2 to 8 parts by weight, based on the total mass of 100 parts by weight of the aggregate.
  • the amount of the additive may be appropriately selected by the amount of the resin.
  • the weight ratio of the additive to the resin may be from 0.01 to 0.4:1, preferably from 0.01 to 0.1:1.
  • the aggregate has a roundness of 0.6 and a sphericity of 0.6.
  • sphericity refers to the extent to which the particles are close to a sphere
  • roundness refers to the measure of the relative sharpness or curvature of the edges of the particles. The measurement methods of "sphericity” and “roundness” are known to those skilled in the art, and for example, can be measured by a plate method.
  • the aggregate may be any of various existing aggregates that can be used to prepare a fracturing proppant, for example, the aggregate may be raw sand and/or ceramsite.
  • the raw sand is usually called quartz sand, and its hardness is about 7, which is brittle and hard.
  • the original sand has good thermal stability, starts to soften when heated to 1500 °C, and has good acid and alkali corrosion resistance.
  • the main chemical component of the raw sand is silica (Si0 2 ), which contains a small amount of alumina (A1 2 0 3 ) and iron oxide (Fe 2 0 3 ).
  • the content of silica in the raw sand is not less than 96% by weight based on the total weight of the raw sand.
  • the ceramsite is light in weight and high in strength, and the fracturing proppant obtained by mixing and curing the resin-containing mixture of the present invention has excellent mechanical properties.
  • the average particle diameter of the aggregate can be varied over a wide range and can be reasonably selected according to actual needs.
  • the aggregate may have a particle diameter of 0.1 to 1.2 mm, preferably 0.2-. 1 mm.
  • the resin may be various resins known in the art, and is not particularly limited.
  • the oil well or gas well contains water.
  • the oil in the oil well or gas well will be produced along with the oil and gas.
  • the formation pressure will be reduced and the mining will be increased.
  • Difficulty oil and gas mining relies mainly on ground lamination Force).
  • the resin is a hydrophobic resin
  • the hydrophobic resin may be selected from a hydrophobic epoxy resin, a hydrophobic phenol resin, a hydrophobic furan resin, and a hydrophobic One or more of a polyurethane and an unsaturated polyester.
  • the resins are all commercially available.
  • the hydrophobic epoxy resin may be selected, for example, from a bisphenol A type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or an aliphatic type.
  • Epoxy resin polysulfide rubber modified epoxy resin, polyamide resin modified epoxy resin, polyvinyl alcohol tert-butyraldehyde modified epoxy resin, nitrile rubber modified epoxy resin, phenolic resin modified epoxy resin , polyester resin modified epoxy resin, urea-formaldehyde nitrileamine resin modified epoxy resin, furfural resin modified epoxy resin, vinyl resin modified epoxy resin, isocyanate modified epoxy resin and silicone modified ring One or more of oxygen resins.
  • the hydrophobic phenol resin may be, for example, one or more selected from the group consisting of a xylene-modified phenol resin, an epoxy resin-modified phenol resin, and a silicone-modified phenol resin.
  • an additive to the resin can correspondingly improve the performance of the fracturing proppant, for example, when the additive is a curing agent, the mechanical properties of the resin can be improved; when the additive is a reinforcing agent The pressure resistance and the friction resistance of the resin can be improved. Therefore, appropriate additives should be selected according to actual needs.
  • the additive of the present invention may be selected from one or more of the group consisting of silica micropowder, carbon black, graphite, and glass microbeads.
  • the particle diameter of the additive may be selected within a wide range, and is not particularly limited.
  • the additive may have an average particle diameter of 0.1 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m.
  • the silicon micropowder is a micropowder processed by a plurality of processes such as crushing, ball milling (or vibration, jet milling), flotation, pickling, and high-purity water treatment of quartz (Si0 2 ).
  • Silicon micropowder is a non-toxic, odorless, non-polluting inorganic non-metallic material with good temperature resistance, acid and alkali corrosion resistance, insulation and stable chemical properties.
  • the silicon micropowder is an active silicon micropowder.
  • the active silicon micropowder is obtained by modifying the surface of the silicon micropowder particles with a material such as silicon germanium, which can enhance the hydrophobic performance of the silicon micropowder and improve its mechanical properties.
  • the carbon black and graphite are mainly composed of carbon and contain a small amount of oxygen, hydrogen and sulfur, etc., and are common reinforcing agents.
  • the curing agent in order to more completely cure the resin on the surface of the fracturing proppant, it is preferred to add a curing agent during the process of uniformly mixing and solidifying the crushed resin-containing mixture with the heated aggregate.
  • the content of the curing agent may vary over a wide range. Generally, the curing agent is contained in an amount of 5 to 30 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the resin.
  • the type of the curing agent of the present invention is not particularly limited, and can be appropriately selected depending on the kind of the resin to be added.
  • the curing agent may be selected from one or more of urotropine, p-toluenesulfonic acid, ethylenediamine, xylylenediamine, m-phenylenediamine, phthalic acid amine, and polyamide.
  • the curing conditions may include a curing temperature and a curing time, and the curing temperature and the curing time may be selected in a wide range as long as the resin layer coated on the surface of the aggregate particles can be completely cured.
  • the curing temperature is from 100 to 250 ° C and the curing time is from 2 to 30 minutes.
  • heating means used in the step is not limited, and heating can be carried out using any heating means (for example, a muffle furnace) which is conventionally used in the prior art.
  • the apparatus for the step of "mixing and solidifying the crushed resin-containing mixture with the heated aggregate” is not limited, and any conventionally used stirring device (for example, mixing) can be used. Sand kettle) Stir.
  • the present invention also provides a fracturing proppant prepared by the above method.
  • the present invention also provides the use of a fracturing proppant prepared by the above method in a deep well fracturing process, the application comprising forming a crack in a bottom layer of a deep well, and filling a fracturing proppant in the crack, wherein
  • the fracturing proppant is a fracturing proppant prepared according to the above method.
  • the method of filling the fracturing proppant in the crack can be carried out by various methods known in the art, and the specific implementation methods and conditions will not be described herein.
  • the kneading machine in the example was purchased from Rugao First Plastic Machinery Technology Development Co., Ltd., model number NH-300, and the power was 11 KW.
  • Raw sand purchased from Yongdeng Blue Sky Quartz Co., Ltd., with roundness and sphericity of 0.7, and particle diameter of 40/20 mesh (0.425-0.85 mm);
  • Ceramsite purchased from Gongyi Shengquan Water Purification Material Factory; roundness is 0.8, sphericity is 0.8; particle diameter is 70/40 mesh (0.212-0.425 mm);
  • Epoxy resin purchased from Taiwan Changchun Group Corporation, grade: BE188;
  • Phenolic resin purchased from Qingdao Bonni Chemical Co., Ltd., grade: 2123;
  • Furan resin purchased from Zibo Yuao Chemical Co., Ltd., grade: 52#;
  • Ethylenediamine purchased from Shanghai Jinmaotai Chemical Co., Ltd.;
  • Urotropine purchased from Shandong Jinan Hongxin Chemical Co., Ltd.;
  • P-toluenesulfonic acid purchased from Shanghai Jinmaotai Chemical Co., Ltd.;
  • Silicon micropowder purchased from Shandong Sanmei Silicon Powder Materials Co., Ltd., with an average particle diameter of 3 microns;
  • Carbon black purchased from Zhengzhou Tairui Carbon Black Chemical Co., Ltd., with an average particle diameter of 5 microns;
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the kneader was heated to 120 ° C, 30 kg of epoxy resin was added, and the kneading procedure was started. After the resin is melted, 600 g of silicon micropowder and 100 g of carbon black are added, and kneading is continued for 1 hour. After that, pour, cool, and crush.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the resin kneader was heated to 160 ° C, and 30 kg of phenol resin was added to open the kneading procedure. After the resin was melted, 600 g of silicon fine powder and 100 g of carbon black were added, kneaded for 0.5 hours, poured, cooled, and crushed for use.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the resin kneader was heated to 140 ° C, and 30 kg of furan resin was added to open the kneading procedure. After the resin was melted, 600 g of silicon fine powder and 100 g of carbon black were added, kneaded for 0.8 hours, and then poured, cooled, and crushed for use.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 1 except that the amount of the silicon fine powder added was 300 g. Get the product Y4.
  • Example 5 The fracturing proppant was prepared in the same manner as in Example 1 except that the amount of the silicon fine powder added was 300 g. Get the product Y4.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 1 except that the amount of the silicon fine powder added was 450 g. Get the product Y5.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 1 except that the amount of the silicon fine powder added was 900 g. Get the product Y6.
  • Example 7
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 1 except that the amount of the silicon fine powder added was 1200 g. Get product Y7.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 2 except that the amount of the silicon fine powder added was 300 g. Get the product Y8.
  • Example 9
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 2 except that the amount of the silicon fine powder added was 450 g. Get the product Y9.
  • Example 10 The fracturing proppant was prepared in the same manner as in Example 2 except that the amount of the silicon fine powder added was 450 g. Get the product Y9.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 2 except that the amount of the silicon fine powder added was 900 g. Get the product Y10.
  • Example 11 The fracturing proppant was prepared in the same manner as in Example 2 except that the amount of the silicon fine powder added was 900 g. Get the product Y10.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • Example 12 This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 3 except that the amount of the silicon fine powder added was 300 g. Get the product Y12.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 3 except that the amount of the silicon fine powder added was 450 g. Get the product Y13.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 3 except that the amount of the silicon fine powder added was 900 g. Get the product Y14.
  • Example 15
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 3 except that the amount of the silicon fine powder added was 1200 g. Get the product Y15.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • a fracturing proppant was prepared according to the method of Example 1, except that the carbon black added was added. Replace with graphite. Get product Y16.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 2 except that the carbon black added was replaced with graphite. Get the product ⁇ 17.
  • This example is intended to illustrate the preparation of a fracturing proppant provided by the present invention.
  • the fracturing proppant was prepared in the same manner as in Example 3 except that the carbon black added was replaced with graphite. Get the product ⁇ 18. Comparative example 1
  • This comparative example is used to illustrate the preparation of a reference fracturing proppant.
  • the raw material for preparing the fracturing proppant is the same as the raw material of Example 1, and includes the following steps:
  • Comparative Example 2 This comparative example is used to illustrate the preparation of a reference fracturing proppant.
  • the raw material for preparing the fracturing proppant is the same as the raw material of Example 1, and includes the following steps:
  • Breaking rate capability ( ⁇ breaking rate capability ( ⁇ number
  • the fracturing proppant provided by the present invention has good fracture resistance and good conductivity, and is suitable for reservoirs under high closing pressure.

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Abstract

本发明公开了一种压裂支撑剂的制备方法、由该制备方法制备得到的压裂支撑剂及其在深井压裂工艺中的应用，该制备方法包括：将添加剂与熔融态树脂捏合均匀，得到含树脂的混合物；将含树脂的混合物冷却，破碎；将骨料加热至高于所述树脂熔点的温度；将破碎后的含树脂的混合物与加热后的骨料混合均匀并固化，使得骨料表面形成包覆层。采用本发明的方法制备得到的压裂支撑剂的破碎率低且导流能力强，适用于高闭合压力下的储层。

Description

一种压裂支撑剂的制备方法、 压裂支撑剂及其应用 本申请要求于 2011 年 9 月 30 日提交中国专利局、 申请号为 201110300003.3、发明名称为"一种压裂支撑剂及其制备方法和一种深 井压裂方法"的中国专利申请的优先权， 其全部内容通过引用结合在 本申请中。 技术领域
本发明涉及一种压裂支撑剂的制备方法、由该制备方法制备得到 的压裂支撑剂及其应用。
背景技术
在石油、天然气深井开采及超深井的压裂工艺中， 都会用到压裂 支撑剂，压裂支撑剂的作用是在地层中形成一条高导流能力的填砂裂 缝， 为油气的流通提供高渗透性的通道。 因此， 压裂支撑剂需要有一 定的强度和导流能力， 以满足不同深度地层的闭合应力要求。
目前， 油田应用较多的压裂支撑剂主要是陶粒和石英砂。但是陶 粒和石英砂的破碎率高， 在储层中压碎的陶粒易发生迁移， 导流能力 差。树脂包覆砂支撑剂近年来也得到了广泛的应用， 该支撑剂可通过 调节树脂的类型而得到各种不同性能的支撑剂，例如，在采集石油时， 采用亲油性树脂可以提高采收率。现有的制备树脂包覆砂的方法通常 是将添加剂加入到树脂中并利用机械搅拌混合均匀， 但是， 采用该方 法树脂的用量大， 且得到的压裂支撑剂的性能不稳定、 破碎率高、 导 发明内容
本发明的目的在于克服采用现有的方法制备压裂支撑剂时， 树脂 用量大， 且得到的产品破碎率高、 导流能力差的缺陷， 提供一种可降 低树脂用量， 且能够得到破碎率低、导流能力强的压裂支撑剂的制备 方法以及通过该方法制备得到的压裂支撑剂和所述压裂支撑剂在深 井压裂工艺中的应用。
本发明提供的一种压裂支撑剂的制备方法， 包括： 将添加剂与熔 融态树脂捏合均匀， 得到含树脂的混合物； 将含树脂的混合物冷却， 破碎； 将骨料加热至高于所述树脂熔点的温度； 将破碎后的含树脂的 混合物与加热后的骨料混合均匀并固化， 使得骨料表面形成包覆层。
优选地， 以 100重量份骨料的总重量为基准， 所述树脂的含量为 1-10重量份； 所述添加剂与所述树脂的重量比为 0.01-0.4: 1。
优选地， 所述捏合的条件包括捏合的温度为 100-180°C， 树脂熔 融后捏合的时间为 0.2-2小时， 所述捏合在捏合机中进行， 所述捏合 机的功率为 10-20KW。
优选地，所述将破碎后的含树脂的混合物与加热后的骨料混合均 匀并固化包括： 将破碎后的含树脂的混合物加入到所述骨料中， 并加 入固化剂搅拌均匀并固化。
优选地， 所述搅拌均匀并固化的条件包括： 固化的温度 100-250 V， 搅拌并固化的时间为 2-30分钟， 以 100重量份树脂为基准， 所 述固化剂的含量为 5-30重量份。
优选地， 所述树脂选自疏水性环氧树脂、 疏水性酚醛树脂、 疏水 性呋喃树脂、 疏水性聚氨酯和不饱和聚酯中的一种或多种。
优选地， 所述添加剂选自硅微粉、碳黑、 石墨和玻璃微珠的一种 或多种； 所述添加剂的平均颗粒直径为 0.1-10微米。
优选地， 所述骨料为原砂和 /或陶粒； 所述骨料的圆度 0.6、 球 度 0.6； 所述骨料的平均颗粒直径为 0.1-1.2毫米。
优选地， 所述固化剂选自乌洛托品、 对甲苯磺酸、 乙二胺、 苯二 甲胺、 间苯二胺、 邻苯二甲酸胺和聚酰胺中的一种或多种。
本发明还提供了一种采用上述的方法制备得到的压裂支撑剂。 并且， 本发明还提供了上述的压裂支撑剂在深井压裂工艺中的 应用。
采用本发明的方法得到的压裂支撑剂表面包覆的树脂层可以有 效地防止骨料碎屑外逸， 从而保持裂缝导流的能力， 提高石油或天然 气的采收率。本发明的发明人发现， 由于树脂的强度和抗静电能力较 差， 加入添加剂后能够改善所述树脂的性能。但是采用现有的将添加 剂加入到树脂中并利用机械搅拌混合均匀的方法，得到的压裂支撑剂 的性能并不稳定、 且破碎率较高。 推测原因， 可能是由于所述树脂的 粘度较大， 通过机械搅拌并不能使添加剂在树脂中均匀分散， 骨料包 覆层的成分不均一会造成单颗粒强度和包覆层厚度的不均一。 目前， 现有技术通常采用增加树脂的用量来提高所述压裂支撑剂的性能。而 本发明是将树脂加热熔融之后， 再将添加剂在捏合作用下加入， 能够 使得所述添加剂均匀地分散在树脂中，得到的压裂支撑剂具有较大的 强度、 较低的破碎率以及更为稳定的性能， 树脂的用量也可以减少。 具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是， 此 处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本 发明。
根据本发明提供的压裂支撑剂的制备方法， 包括： 将添加剂与熔 融态树脂捏合均匀， 得到含树脂的混合物； 将含树脂的混合物冷却， 破碎； 将骨料加热至高于所述树脂熔点的温度； 将破碎后的含树脂的 混合物与加热后的骨料混合均匀并固化， 使得骨料表面形成包覆层。
通常来说， 在所述树脂中加入添加剂， 能够使所述树脂的性能得 以改善。 例如， 加入交联剂， 能够使所述树脂间发生交联， 从而提高 所述树脂的力学性能；加入硅微粉后，能够提高所述树脂的抗压强度; 加入黑粉或炭黑后， 能够降低所述树脂的摩擦阻力、 提高其流动性。
但是， 由于树脂本身具有较大的粘度， 仅通过将所述树脂与添加 剂利用搅拌的方式混合， 并不能将所述添加剂很好地分散在树脂中， 进一歩地， 会导致包覆在所述骨料表面的树脂包覆层的成分不均一、 厚度不均一， 因此， 得到的压裂支撑剂性能不稳定、 破碎率高、 导流 能力差。
然而， 在本发明中， 将树脂加热熔融后， 其具有较小的粘度、 较 好的流动性； 进一歩地， 将含有熔融态的树脂和添加剂的混合物捏合 均匀， 所述捏合既能起到良好的分散作用又能起到很好的混合作用， 则所述添加剂能够更好地分散在所述树脂中，使所述树脂的性能得以 提高。
本发明对所述捏合的条件没有特别地限制，只要能够保证所述添 加剂很好地分散在树脂中， gp， 树脂和添加剂能够很好地固熔在一起 即可。 通常情况下， 所述捏合的条件包括捏合的温度、 捏合的时间； 此外， 所述捏合通常在捏合机中进行， 因此， 所述捏合的条件还可以 包括捏合机的功率。
所述捏合的温度可以在较大范围内变动，只要能够使所述树脂保 持熔融状态即可， 例如， 所述捏合的温度可以为 100-180°C， 优选为 120-160 °C ; 所述树脂熔融后捏合的时间也可以在较大的范围内进行 变动， 例如， 所述树脂熔融后捏合的时间可以为 0.2-2小时， 优选为 0.5-1小时。所述捏合机是通过产生强烈的剪切作用而将所述添加剂 和粘稠状的树脂捏合均匀的， 其剪切强度可以通过所述捏合机的功 率来进行调节。 所述捏合机的功率可以在较宽范围内进行调整， 例 如， 所述捏合机的功率可以为 10-20KW, 优选为 10-15KW。
根据本发明提供的压裂支撑剂的制备方法，所述混合物中各组分 的含量可以在较大范围内进行选择和调整。例如， 以 100重量份骨料 的总重量为基准， 所述树脂的含量可以为 1-10 重量份， 优选为 2-8 重量份。所述添加剂的用量可以通过所述树脂的用量来进行合理地选 择， 通常来说， 所述添加剂和所述树脂的重量比可以为 0.01-0.4: 1， 优选为 0.01-0.1 :1。 根据本发明，尽管所述骨料的圆度和球度对得到的压裂支撑剂的 性能不会造成显著的影响， 但是为了提高所述压裂支撑剂在石油和 / 或天然气开采中的导流能力， 优选情况下， 所述骨料的圆度 0.6、 球度 0.6。 其中， "球度"指颗粒接近球形的程度； "圆度"指颗粒 棱角的相对锐度或曲率的量度。 "球度"和 "圆度" 的测定方法为本 领域技术人员所公知， 例如， 可采用图版法进行测定。
根据本发明，所述骨料可以为现有的各种能够用于制备压裂支撑 剂的骨料， 例如， 所述骨料可以为原砂和 /或陶粒。 所述原砂通常被 称为石英砂， 其硬度为 7左右， 性脆而坚硬。 原砂热稳定性好， 加热 至 1500°C时开始软化， 具有很好的耐酸碱腐蚀性。 原砂的主要化学 成分是氧化硅 （Si02)， 同时含有少量的氧化铝 （A1203 ) 和氧化铁 (Fe203)。 通常情况下， 以所述原砂的总重量为基准， 所述原砂中二 氧化硅的含量不小于 96重量％。 所述陶粒质轻且强度较高， 将其与 本发明的含树脂的混合物混合固化得到的压裂支撑剂的力学性能极 好。
根据本发明， 所述骨料的平均颗粒直径可以在很大范围内改变， 并可以根据实际需要进行合理地选择， 例如， 所述骨料的颗粒直径可 以为 0.1-1.2毫米， 优选为 0.2-1毫米。
根据本发明， 所述树脂可以为本领域公知的各种树脂， 并无特殊 限制。通常情况下， 所述油井或气井中含有水， 在开采石油或天然气 的过程中， 油井或气井中水会随着油气一起采出， 大量的地下水被采 出后会降低地层压力从而增大开采难度（油气的开采主要依靠地层压 力）。 因此， 为了使油井或气井中的压力保持平衡， 优选情况下， 所 述树脂为疏水性树脂， 所述疏水性树脂可以选自疏水性环氧树脂、疏 水性酚醛树脂、疏水性呋喃树脂、疏水性聚氨酯和不饱和聚酯中的一 种或多种。 所述树脂均可以通过商购得到。
根据本发明， 所述疏水性环氧树脂例如可以选自双酚 A型环氧 树脂、 缩水甘油醚类环氧树脂、 缩水甘油酯类环氧树脂、 缩水甘油胺 类环氧树脂、 脂肪族类环氧树脂、 聚硫橡胶改性环氧树脂、 聚酰胺树 脂改性环氧树脂、聚乙烯醇叔丁醛改性环氧树脂、丁腈橡胶改性环氧 树脂、 酚醛树脂改性环氧树脂、 聚酯树脂改性环氧树脂、 脲醛三聚腈 胺树脂改性环氧树脂、糠醛树脂改性环氧树脂、 乙烯树脂改性环氧树 脂、 异氰酸酯改性环氧树脂和硅树脂改性环氧树脂中的一种或多种。
根据本发明，所述疏水性酚醛树脂例如可以选自二甲苯改性酚醛 树脂、 环氧树脂改性酚醛树脂和有机硅改性酚醛树脂中的一种或多 种。
通常情况下，在所述树脂中加入添加剂可以相应地提高压裂支撑 剂的性能， 例如， 当所述添加剂为固化剂时， 可以改善所述树脂的力 学性能； 当所述添加剂为增强剂时， 可以改善所述树脂的抗压性能和 耐摩擦性能。 因此， 应根据实际的需要选择适当的添加剂。
优选情况下， 本发明所述的添加剂可以选自硅微粉、 碳黑、 石墨 和玻璃微珠的一种或多种。且所述添加剂的颗粒直径可以在较宽范围 内进行选择， 并无特殊限制， 例如， 所述添加剂的平均颗粒直径可以 为 0.1-10微米， 优选为 0.1-5微米。 所述硅微粉是由石英 （Si02 )经破碎、 球磨 （或振动、 气流磨）、 浮选、 酸洗、 高纯水处理等多道工序加工而成的微粉。硅微粉是一种 无毒、 无味、 无污染的无机非金属材料， 具有良好的耐温性、 耐酸碱 腐蚀性、 绝缘性和稳定的化学性能。优选情况下， 所述硅微粉为活性 硅微粉。 所述活性硅微粉是采用硅垸等材料对硅微粉颗粒表面进行 改性处理得到的， 可增强硅微粉的憎水性能， 并提高其机械性能。 所述碳黑和石墨的主要成分均为碳元素， 并含有少量氧、 氢和硫等， 是常见的补强剂。
根据本发明， 为了使压裂支撑剂表面的树脂得以更完全地固化， 优选情况下，在将破碎后的含树脂的混合物与加热后的骨料混合均匀 并固化的过程中， 可以添加固化剂。所述固化剂的含量可以在较大范 围内变动， 通常来说， 以 100重量份树脂为基准， 所述固化剂的含量 为 5-30重量份， 优选为 5-15重量份。
本发明对所述固化剂的种类没有特别地限制，可以根据所加入的 树脂的种类进行合理地选择。 例如， 所述固化剂可以选自乌洛托品、 对甲苯磺酸、 乙二胺、 苯二甲胺、 间苯二胺、 邻苯二甲酸胺和聚酰胺 中的一种或多种。
根据本发明， 固化的条件可以包括固化的温度和固化的时间， 固 化的温度和固化的时间的可选择范围较宽，只要能够使骨料颗粒表面 包覆的树脂层完全固化即可。优选情况下，所述固化的温度为 100-250 °C， 固化的时间为 2-30分钟。
另外， 本发明中对"将骨料加热至高于所述树脂熔点的温度"的 歩骤所用的加热装置没有限制，可以使用任何现有技术常用的加热装 置 （例如： 马弗炉） 进行加热。
并且， 本发明中对 "将破碎后的含树脂的混合物与加热后的骨料 混合均匀并固化"的歩骤所用的装置也没有限制， 可以使用任何现有 技术常用的搅拌装置 （例如： 混砂釜） 进行搅拌。
本发明还提供了通过上述方法制备得到的压裂支撑剂。
此外，本发明还提供了通过上述方法制备得到的压裂支撑剂在深 井压裂工艺中的应用， 该应用包括在深井的底层中形成裂缝， 并将压 裂支撑剂填充在裂缝中， 其中， 所述压裂支撑剂为根据上述方法制备 得到的压裂支撑剂。
根据本发明，将所述压裂支撑剂填充在裂缝中的方法可以采用本 领域公知的各种方法进行， 具体实施方法和条件在此不再赘述。
下面将通过具体实施例对本发明进行进一歩的详细描述。
需要说明的是， 在以下的实施例中： 把"将添加剂与熔融态树脂 捏合均匀， 得到含树脂的混合物"， 和 "将含树脂的混合物冷却， 破 碎"的歩骤统称为： "含树脂的混合物的制备"； 把 "将骨料加热至高 于所述树脂熔点的温度"， 和 "将破碎后的含树脂的混合物与加热后 的骨料混合均匀并固化， 使得骨料表面形成包覆层" 的歩骤统称为： "压裂支撑剂的制备"。
实施例中的捏合机购自如皋市第一塑料机械技术开发有限公司， 型号为 NH-300, 功率为 11KW。
本发明下述实施例和对比例中所用的原料如下： 原砂： 购自永登蓝天石英砂有限公司， 圆度和球度均为 0.7， 颗 粒直径为 40/20目 (0.425-0.85毫米）;
陶粒： 购自巩义市圣泉净水材料厂； 圆度为 0.8， 球度为 0.8; 颗 粒直径为 70/40目 (0.212-0.425毫米）;
环氧树脂： 购自台湾长春集团公司， 牌号： BE188;
酚醛树脂： 购自青岛市邦尼化工有限公司， 牌号： 2123 ;
呋喃树脂： 购自淄博沣澳化工有限公司， 牌号： 52#；
乙二胺： 购自上海金贸泰化工有限公司；
乌洛托品： 购自山东济南鸿鑫化工有限公司；
对甲苯磺酸： 购自上海金贸泰化工有限公司；
硅微粉： 购自山东三美硅粉材料有限公司， 平均颗粒直径为 3微 米；
碳黑： 购自郑州市泰瑞炭黑化工有限责任公司， 平均颗粒直径为 5微米；
石墨： 购自青岛华泰润滑密封科技有限责任公司， 平均颗粒直径 为 6微米。 实施例 1
该实施例用于说明本发明提供的压裂支撑剂的制备。
( 1 ) 含树脂的混合物的制备：
将捏合机升温至 120°C， 加入 30kg环氧树脂， 开启捏合程序。 待树脂熔融后， 加入 600g的硅微粉和 100g的碳黑， 继续捏合 1小时 后， 倒出、 冷却、 破碎备用。
(2) 压裂支撑剂的制备：
取 3kg原砂加热至 250°C， 加入 240g歩骤 （1 ) 得到的含树脂的 混合物， 并加入 24g的固化剂乙二胺， 搅拌 5mm后， 得到产品 Yl。 实施例 2
该实施例用于说明本发明提供的压裂支撑剂的制备。
( 1 ) 含树脂的混合物的制备：
将树脂捏合机升温至 160°C， 加入 30kg酚醛树脂， 开启捏合程 序。 待树脂熔融后， 加入 600g的硅微粉和 100g的碳黑， 捏合 0.5小 时后， 倒出、 冷却、 破碎备用。
(2) 压裂支撑剂的制备：
取 3kg原砂加热至 100°C， 加入 120g歩骤 （1 ) 得到含树脂的混 合物， 并加入 6g的固化剂乌洛托品， 搅拌 30mm后， 得到产品 Y2。 实施例 3
该实施例用于说明本发明提供的压裂支撑剂的制备。
( 1 ) 含树脂的混合物的制备：
将树脂捏合机升温至 140°C， 加入 30kg呋喃树脂， 开启捏合程 序。 待树脂熔融后， 加入 600g的硅微粉和 100g的碳黑， 捏合 0.8小 时后， 倒出、 冷却、 破碎备用。
(2) 压裂支撑剂的制备： 取 3kg原砂加热至 150°C， 加入 40g歩骤 （1 ) 得到含树脂的混 合物，并加入 5g的固化剂对甲苯磺酸，搅拌 15mm后，得到产品 Y3。 实施例 4
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 1的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 300g。 得到产品 Y4。 实施例 5
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 1的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 450g。 得到产品 Y5。 实施例 6
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 1的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 900g。 得到产品 Y6。 实施例 7
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 1的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 1200g。 得到产品 Y7。 实施例 8
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 2的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 300g。 得到产品 Y8。 实施例 9
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 2的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 450g。 得到产品 Y9。 实施例 10
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 2的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 900g。 得到产品 Y10。 实施例 11
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 2的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 1200g。 得到产品 Yll。 实施例 12 该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 3的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 300g。 得到产品 Y12。 实施例 13
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 3的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 450g。 得到产品 Y13。 实施例 14
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 3的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 900g。 得到产品 Y14。 实施例 15
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 3的方法制备压裂支撑剂， 不同的是， 所加入的硅微 粉的量为 1200g。 得到产品 Y15。 实施例 16
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 1的方法制备压裂支撑剂， 不同的是， 所加入的碳黑 用石墨代替。 得到产品 Y16。
实施例 17
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 2的方法制备压裂支撑剂， 不同的是， 所加入的碳黑 用石墨代替。 得到产品 Υ17。 实施例 18
该实施例用于说明本发明提供的压裂支撑剂的制备。
按照实施例 3的方法制备压裂支撑剂， 不同的是， 所加入的碳黑 用石墨代替。 得到产品 Υ18。 对比例 1
该对比例用于说明参比压裂支撑剂的制备。
本对比例中， 制备压裂支撑剂的原料与实施例 1的原料相同， 包 括歩骤：
( 1 ) 含树脂的混合物的制备：
将 30kg环氧树脂升温至 120 °C。 待树脂熔融后， 加入 600g的硅 微粉和 100g的碳黑， 进行机械搅拌 1小时后， 倒出、 冷却、 破碎备 用。
(2) 压裂支撑剂的制备：
取 3kg原砂加热至 250°C， 加入 240g歩骤 （1 ) 得到的含树脂的 混合物， 并加入 24g的固化剂乙二胺， 搅拌 5mm后， 得到产品 Dl。 对比例 2 该对比例用于说明参比压裂支撑剂的制备。
本对比例中， 制备压裂支撑剂的原料与实施例 1的原料相同， 包 括歩骤：
( 1 ) 含树脂的混合物的制备：
在 30kg环氧树脂中， 加入 600g的硅微粉和 100g的碳黑进行机 械搅拌 1小时后， 备用。
( 2 ) 压裂支撑剂的制备：
取 3kg原砂加热至 250 °C， 加入 240g歩骤 （1 ) 得到的含树脂的 混合物， 并加入 24g的固化剂乙二胺， 搅拌 5mm后， 得到产品 D2。
按照标准 SY/T5108-2006分别对上述实施例 1-18制备的压裂支 撑剂产品 Y1-Y18 , 以及对比例 1和对比例 2制备的压裂支撑剂产品 D1和 D2进行性能检测， 检测结果如下表 1所示。
表 1
■^n口 52MPa 40MPa导流 ■^n口 52MPa 40MPa导流 广口口 广口口
破碎率 能力 （μ 破碎率 能力 （μ 序号 序号
(%) m2 · cm) (%) m2 · cm)
Y1 0.81 45.15 Y11 9.05 28.45
Y2 2.41 38.02 Y12 4.54 34.56
Y3 3.30 30.11 Y13 5.55 28.99
Y4 1.11 40.12 Y14 7.18 26.65
Y5 3.01 38.15 Y15 9.66 25.43
Y6 4.66 33.11 Y16 0.78 51.69 Y7 5.19 30.00 Y17 2.45 44.15
Y8 3.10 35.25 Y18 3.43 38.11
Υ9 4.55 32.16 D1 12.11 18.84
Y10 6.87 29.98 D2 14.66 15.63
从上述表 1的结果可以看出，本发明提供的压裂支撑剂具有较好 的抗破碎率和较好的导流能力， 适用于高闭合压力下的储层。
以上实施例仅用于说明本发明， 并非用于限定本发明的保护范 围。 凡在本发明的精神和原则之内所作的任何修改、 等同替换、 改进 等， 均包含在本发明的保护范围内。

Claims

权 利 要 求
1、 一种压裂支撑剂的制备方法， 其特征在于， 包括：
将添加剂与熔融态树脂捏合均匀， 得到含树脂的混合物； 将含树脂的混合物冷却， 破碎；
将骨料加热至高于所述树脂熔点的温度；
将破碎后的含树脂的混合物与加热后的骨料混合均匀并固化，使 得骨料表面形成包覆层。
2、 根据权利要求 1所述的方法， 其特征在于， 以 100重量份骨 料的总重量为基准， 所述树脂的含量为 1-10重量份； 所述添加剂与 所述树脂的重量比为 0.01-0.4:1。
3、 根据权利要求 1所述的方法， 其特征在于， 所述捏合的条件 包括捏合的温度为 100-180°C， 树脂熔融后捏合的时间为 0.2-2小时， 所述捏合在捏合机中进行， 所述捏合机的功率为 10-20KW。
4、 根据权利要求 1所述的方法， 其特征在于， 所述将破碎后的 含树脂的混合物与加热后的骨料混合均匀并固化包括：将破碎后的含 树脂的混合物加入到所述骨料中， 并加入固化剂搅拌均匀并固化。
5、 根据权利要求 4所述的方法， 其特征在于， 所述搅拌均匀并 固化的条件包括： 固化温度 100-250°C， 搅拌并固化的时间为 2-30分 钟， 以 100重量份树脂为基准， 所述固化剂的含量为 5-30重量份。
6、 根据权利要求 1-5任意一项所述的方法， 其特征在于， 所述 树脂选自疏水性环氧树脂、 疏水性酚醛树脂、 疏水性呋喃树脂、 疏水 性聚氨酯和不饱和聚酯中的一种或多种。
7、 根据权利要求 1-5任意一项所述的方法， 其特征在于， 所述 添加剂选自硅微粉、 碳黑、 石墨和玻璃微珠的一种或多种； 所述添加 剂的平均颗粒直径为 0.1-10微米。
8、 根据权利要求 1-5任意一项所述的方法， 其特征在于， 所述 骨料为原砂和 /或陶粒； 所述骨料的圆度 0.6、 球度 0.6； 所述骨料 的平均颗粒直径为 0.1-1.2毫米。
9、 根据权利要求 4或 5所述的方法， 其特征在于： 所述固化剂 选自乌洛托品、 对甲苯磺酸、 乙二胺、 苯二甲胺、 间苯二胺、 邻苯二 甲酸胺和聚酰胺中的一种或多种。
10、一种根据权利要求 1-9中任意一项所述的方法制备得到的压 裂支撑剂。
11、 一种权利要求 10所述的压裂支撑剂在深井压裂工艺中的应 用。
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