CN101146888B - Soluble deverting agents - Google Patents

Soluble deverting agents Download PDF

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CN101146888B
CN101146888B CN 200680009369 CN200680009369A CN101146888B CN 101146888 B CN101146888 B CN 101146888B CN 200680009369 CN200680009369 CN 200680009369 CN 200680009369 A CN200680009369 A CN 200680009369A CN 101146888 B CN101146888 B CN 101146888B
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steering
fluid
agent
collagen
water
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CN 200680009369
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CN101146888A (en
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A·R·辛克莱尔
P·R·奥克尔
S·阿克巴
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费尔蒙特矿物有限公司
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Priority to US60/646,231 priority
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Priority to PCT/US2006/001916 priority patent/WO2006088603A1/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/80Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • C09K8/805Coated proppants
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/14Obtaining from a multiple-zone well
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25Methods for stimulating production
    • E21B43/26Methods for stimulating production by forming crevices or fractures
    • E21B43/261Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation

Abstract

Methods and compositions for stimulating single and multiple intervals in subterranean wells by diverting well treatment fluids into a particular direction or into multiple intervals using water soluble coated diverting agents are described. The water soluble coating of the diverting material is preferably a collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol polymer or a mixture thereof applied as a coating on any number of proppants. The method allows for the diverting of the flow of fluids in a downhole formation during awell treatment, such as during a fracturing process. Following completion of a treatment such as a hydraulic stimulation, the soluble diverting agent can be dissolved and removed by the water component of the well production.

Description

可溶性转向剂 Soluble diverting agent

[0001] 本申请要求2005年I月21日提交的美国临时申请SN 60/646, 231的优先权,该申请的全部内容通过引用结合到本文中来。 [0001] This application claims the United States in 2005 I filed May 21, the priority provisional application SN 60/646, 231, the entire contents of which are incorporated herein by reference to. 发明领域 Field of the Invention

[0002] 本发明提供了处理地下井的方法和组合物,更具体地讲,提供了使地下井中多个井段增产的方法和组合物。 [0002] The present invention provides methods and compositions for treating a subterranean well, and more particularly, a plurality of subsurface wells interval stimulation methods and compositions. 具体地说,本发明提供了通过引入涂覆有水溶性聚合物(例如胶原蛋白、聚乙酸乙烯酯/聚乙烯醇、聚烷基氧化物、聚(乳酸)、元素周期表第I或II族(碱金属或碱土金属)的硅酸盐聚合物)的支撑材料或其与重新定向来自油管柱的增产流体流动至地层环境的缓慢溶于水的材料的组合,使井处理流体转向到多个井段的方法和组合物。 More specifically, the present invention provides a water-soluble polymer by the introduction of coated (e.g. collagen, polyvinyl acetate / polyvinyl alcohol, polyalkyl oxides, poly (lactic acid), Group I or Group II (alkali metal or alkaline earth metal) silicate polymer) with a support material or redirect the flow of stimulation fluids from a tubing string formation environment to a combination of water-soluble materials slow the well treatment fluid to a plurality of steering the method and compositions of the interval.

技术背景 technical background

[0003] 井处理(例如地层的酸和压裂处理)通常用于提高或增加烃类的采收率。 [0003] a well treatment (such as acids and fracturing of the formation process) is generally used to improve or increase the recovery of hydrocarbons. 在很多情况下,地层可包括两个或多个具有不同渗透性和/或注入能力的井段。 In many cases, the formation may comprise two or more shaft segments having different permeability and / or injectivity. 一些井段由于渗透性相对低、原地应力高和/或地层损害等原因可能具有相对低的注入能力,或接受注入流体的能力。 Some interval since the relatively low permeability, high in-situ stresses cause and / or formation damage and the like may have a relatively low injectivity, or ability to accept injected fluids. 这类井段可通过在下套管井眼中制备来完井和/或可经裸眼完井法来完井。 Such segments may be well completion and / or completion may be prepared by the method of open hole completion through a cased borehole below. 在一些情况下,这类地层井段可存在于井眼的高度倾斜或水平段中,例如侧流裸眼井段中。 Highly inclined or horizontal section, in some cases, the formation of such segments may be present in the well borehole, such as a side flow in the openhole section. 在任何情况下,当处理具有不同注入能力的多个井段时,即是不是全部,也经常是大多数引入的井处理流体将转移到具有最高注入能力的井段中的一个或少数几个中。 In any case, when processing a plurality of injection wells segments have different capabilities, i.e., is not all, most often introduced well treatment fluid will be transferred to a section of the well with the highest injectivity or a few in. 即使在仅有一个待处理的井段的情况下,裂缝也可能向上或向下生长。 Even in the case where only a section of the well to be treated, the cracks may grow upward or downward. 这取决于原地地层应力和地层的渗透性变化。 Depending on changes in permeability of the formation in-situ stress and formation. 人工裂缝以下可能是含水区。 The following may be an aqueous artificial fracture zone. 如果人工裂缝扩展入这个区,则井可能因存在太多的水和因生产井段的石油组分被截断而毁坏。 If artificial fractures extend into this region, the well may be due to the presence of too much water and in oil production well component segments are truncated destroyed. 在人工裂缝区之上,可能存在气顶,因为气体分流井的液态石油组分,所以气顶将对井生产造成损害。 On artificial fracture zone a gas cap may exist as components of liquid petroleum gas diversion well, so well production gas cap will cause damage.

[0004] 为了使生产井处理流体更均匀地分配到多个待处理井段中的每一个中,已开发出了用于使处理流体转向到渗透性和/或注入能力较低的井段中的方法和材料。 [0004] In order to produce a well treatment fluid more uniformly distributed to each of the plurality of interval to be treated, it has been developed a process for turning the fluid to a lower permeability and / or injectivity of the well section methods and materials. 然而,常规转向技术可能昂贵和/或可能仅取得非常有限的成果。 However, conventional steering technology can be costly and / or may be made only very limited success. 在这点上,机械转向技术通常复杂且昂贵。 In this regard, mechanical steering techniques typically complex and expensive. 此外,机械转向方法通常局限于下套管井的情况且依赖于足够的用于实现转向的水泥和设备隔离物。 In addition, mechanical steering method is generally limited to the case where the well casing and is dependent on sufficient for achieving a steering device and cement spacers.

[0005] 因此,多年来在井增产处理中始终难以有效地处理延伸垂直段并同时处理多组孔目艮。 [0005] Thus, for many years in well stimulation process it has always been difficult to efficiently handle section and extends perpendicularly simultaneous multi-purpose set of apertures Gen. 许多处理转向方法(例如油溶性I丐阜、硫酸和Dowell的“Fixafrac”(石灰、煤油、分级氯化I丐阜和胶凝剂的混合物)和Dowell的FLAX-2™(如Harrison在他的Journal ofPetroleumTechnology的综述,pp. 593-598 (1972)中所述)已以不同效率用于处理多个区。许多种化学型转向剂已经尝试用于堵塞地层开口且使处理流体转向到地层的其他区。例如,已使用蜡珠作为转向剂。然而,蜡珠具有有限的熔点:约138 °F到约192 °F,这使得其在地层温度超过其熔点时失效。 Many process to process (e.g. a mixture of "Fixafrac" (lime, kerosene, chlorinated grade I Hack Fu oil-soluble gelling agent and I Hack Fu, sulfuric acid, and Dowell), and Dowell's FLAX-2 ™ (Harrison as his Summary of other Journal ofPetroleumTechnology, pp. 593-598 (1972) in the) have been used to efficiently process a plurality of different regions. many chemical agents have been attempted for type steering clogging the formation and opening the process fluid is turned into the formation the district example, wax beads have been used as diverting agents However, the wax beads have limited melting point: about 138 ° F to about 192 ° F, which makes its fail when the formation temperature above its melting point.

[0006] 还描述了萘(卫生球(moth ball))和氯化钠颗粒可用作有效转向剂。 [0006] Also described naphthyl (mothball (moth ball)) and sodium chloride particles may be used as effective diverting agents. 萘颗粒易溶于油中,而在约180 °FT熔融,因此限制了其在较低温度地层中的应用。 Naphthalene particles soluble in oil, but melt at about 180 ° FT, thus limiting their use in low temperature formation. 氯化钠的熔点为约1,470 °F,可在高温下使用,但需要在处理地层之后用水或稀酸清洗井,以便完全除去氯化钠颗粒。 Sodium chloride melting point of about 1,470 ° F, can be used at high temperatures, but require well washed with water or dilute acid after the formation process, so as to completely remove sodium chloride particles. 此外,由于形成不溶性沉淀物可能阻挡井眼而带来一定问题,氯化钠不能与氢氟酸一起用于处理地下井。 Further, due to the formation of insoluble precipitates may block certain problems brought wellbore, sodium chloride can not be used together with hydrofluoric acid treating a subterranean well.

[0007] 或者,在同时处理多个具有不同注入能力的井段时,已使用了转向剂,例如聚合物、悬浮固体物质和/或泡沫体。 [0007] Alternatively, when handling multiple injection wells segments have different capabilities, diverting agents have been used, such as polymers, suspended solids and / or foam. 通常在泵送井处理流体之前,将这类转向剂泵送入地层中,以便封堵渗透性较高的井段并使井处理流体转向到渗透性较低的井段。 Generally well treatment fluid prior to pumping, this type of steering agent pumped into the formation so that plugging and high permeability interval well treatment fluid to the lower permeability steering interval. 然而,这类转向剂的转向作用经常难以预测和监控,且不能成功地使处理流体转向到所有所要的井段中。 However, such a steering action of the steering agents is often difficult to predict and monitor, and the process fluid can not successfully diverted into all desired interval. 这些问题在裸眼完井,特别是具有大面积对井眼开口的地层的高度倾斜完井中尤其严重。 These problems in open-hole completions, especially having a large area highly inclined wellbore completion of the formation of the opening is particularly serious. 天然裂缝的存在也可使得转向更加困难。 Presence of natural fractures may also makes it more difficult to turn. [0008] 多年来已进行了许多解决井眼内不同渗透性区域的问题的努力。 [0008] Over the years many efforts have been made to solve the problem of different permeability zones within the wellbore. 授予Hower的美国专利第2,803,306号提供了一种增加具有数个不同渗透性区域的地层的渗透性的方法。 U.S. Patent No. 2,803,306 granted Hower provides a method of increasing the permeability of the formation having a plurality of regions of different permeabilities. 所描述的步骤包括向井眼中引入含有盐酸的处理流体,油溶性颗粒分散于所述处理流体中,该材料选自黑浙青、萘、对二氯苯、蒽及β_萘酚。 The steps described include introducing treatment fluid containing hydrochloric acid soluble particles dispersed in the treatment fluid to the wellbore, the material is selected from Zhejiang Green black, naphthalene, para-dichlorobenzene, anthracene, and β_ naphthol. 在处理时,颗粒使地层的高渗透性区域部分堵塞,让处理流体进入低渗透性区域。 When processing, the particles of the high permeability zones of the formation plugging portion, so that the treatment fluid enters the low permeability zones.

[0009] 转让给Halliburton的美国专利第3,797,575号公开了由溶于溶剂(例如甲醇或异丙醇)中的相对水不溶性固体材料组成的转向形成添加剂。 [0009], assigned to Halliburton U.S. Patent No. 3,797,575 discloses a steering dissolved in a solvent (e.g. methanol or isopropanol) are relatively water-insoluble solid material forming additives. 当该添加剂与含水处理流体混和时,溶于添加剂中的固体材料在含水处理流体中沉淀形成细碎形式,其随后充当转向齐U。 When the additive is mixed with an aqueous treatment fluid, the solid material was dissolved in the additive-containing treatment fluid formation of a precipitate in finely divided form, which then acts as a steering homogeneous U. 同样转让给Halliburton的美国专利第3,724,549号描述了一种用于使含水处理流体转向到渗透性渐差的地层中的转向剂材料。 Similarly U.S. Patent No. 3,724,549, assigned to Halliburton describes a diverting agent material for making water-containing fluid diverted into the permeable formation become worse. 该材料由载液和熔点为约200 0F的具有约20个至约1,400个碳原子的环状或直链烃类树脂的分级颗粒组成。 The particulate material is graded by a carrier fluid and a melting point of about 200 0F cyclic or linear hydrocarbon resin having about 20 to about 1,400 carbon atoms. 这种材料被描述为基本上不溶于水和酸,但可溶于油,使得树脂可在完成油处理操作之后由产出油除去。 This material is described as being substantially insoluble in water and acids, but soluble in oil, such that the resin can be removed from the oil after completion of the oil output processing operation.

[0010] Knight等在美国专利第3,872,923号中已描述了使用辐射诱导型聚合物作为暂时或永久转向剂。 [0010] Knight et al U.S. Pat. No. 3,872,923 has been described the use of radiation-induced polymers as temporary or permanent diverting agents. 根据该说明书,渗透性的暂时或永久降低可通过注入水溶性聚合物的水溶液来得到,所述水溶性聚合物通过丙烯酰胺和/或甲基丙烯酰胺与丙烯酸、甲基丙烯酸和/或这类酸的碱金属盐的辐射诱导聚合得到。 According to the specification, temporary or permanent reduction of the permeability can be obtained by injecting an aqueous solution of water-soluble polymer, the water soluble polymer by acrylamide and / or methacrylamide and acrylic acid, methacrylic acid and / or such radiation-induced polymerization of an alkali metal salt of the acid obtained. 所得聚合物转向剂具有例如温度和PH稳定性的性质,以便有效地降低多孔介质渗透性。 The resultant polymeric diverting agent has properties such as temperature and PH stability, so as to effectively reduce the permeability of the porous medium. 地层内的渗透性可通过随后用化学品(例如次氯酸肼溶液或强无机酸)处理以分解聚合物来恢复。 Permeability within the formation can be treated to decompose the polymer is then recovered by chemical (e.g. hydrazine hypochlorite solution or strong mineral acid).

[0011] Scheffel等的美国专利第3,954,629号和第4,005,753号提供了聚合物转向剂和分别用这类聚合物转向剂处理地层的方法。 [0011] Scheffel et U.S. Patent Nos. 3,954,629 and No. 4,005,753 provides a polymeric diverting agents and methods of using such polymeric diverting agents, respectively, the formation process. 据描述所述聚合物组合物包含聚乙烯、乙烯-乙酸乙烯酯共聚物、聚酰胺和例如长链脂族二酰胺的软化剂的均质混合物的固体颗粒。 It is described that the polymer composition comprises polyethylene, ethylene - vinyl acetate copolymer, polyamide softening agent and solid particles e.g. long chain aliphatic diamides homogeneous mixture. 据报道这种聚合物转向剂适用于地层温度等于或大于350 0F的地层中。 Polymeric diverting agents are reported to have applied to or greater than the formation temperature is equal to 350 0F in the formation.

[0012] Dill等在美国专利第4,527,628号中描述了使用包含含水载液的转向材料和包含固体偶氮组分和亚甲基(methylenic)组分的转向剂暂时堵塞地层的方法。 [0012] Dill et al describe a method of using an aqueous liquid carrier comprising a solid material and a steering azo component and a methylene group (methylenic) steering component temporary clogging agent in the formation of U.S. Patent No. 4,527,628 . 转向剂优选为Hansa Yellow G(Fanchon YellowYH-5707 颜料)或Fast Yellow 4RLF 染料,两者都具 Diverting agent is preferably Hansa Yellow G (Fanchon YellowYH-5707 pigment) or Fast Yellow 4RLF dyes, with both

有偶氮组分和亚甲基组分且具有熔点为至少332. 6 °F,在约200至约425 0F的温度下在水 Azo component and the methylene component and having a melting point of at least 332. 6 ° F, in water at a temperature of from about 200 to about 425 0F to

中具有一定溶解度且在约200 0F到约425 0F的温度下在煤油中具有一定溶解度的特征。 Having some solubility and having a degree of solubility in kerosene at a temperature of about 200 0F to 425 0F to about features.

[0013] Purvis等在美国专利第6,367,548号中描述了通过使井处理流体转向到多个井段中使地下井中的多个井段增产的方法和组合物。 [0013] Purvis et al describe the well treatment fluid by the steering manipulation to a plurality of well sections plurality interval subterranean well stimulation methods and compositions of U.S. Patent No. 6,367,548. 根据该说明书,这通过交替地从井眼的环形区转移转向剂到地层中且从油管柱转移处理流体到地层中来实现。 According to this specification, which are alternately transferred from the wellbore annulus diverter and transferred into the formation treatment fluid from the tubing string into the formation is achieved. [0014] 使压裂处理转向的其他方法包括LaGrone等,SPE 530, pp. 695-702(1963)描述的限流量法(limited-entry technique)和Dingxiang 等,SPE 30816,80-86 页(1988)提出的使用转向剂(TMFUD)压裂的多压裂法,后者展示每个井平均采油量提高15. Ot/d,总产量提高340. 3X 104吨。 [0014] Other methods to make the fracturing process to include other LaGrone, SPE 530, pp. 695-702 (1963) limit flow method (limited-entry technique) described Dingxiang and the like, SPE 30816,80-86 (1988 ) proposed the use of diverting agents (TMFUD) multiple fracturing the fracturing, the latter showing improved average oil production for each well 15. Ot / d, improve production 340. 3X 104 tons. 还描述了用于酸化增产的基于粘弹性表面活性剂的转向剂(Alleman,D.等,SPE 80222 (2003)),其为VES凝胶(polyQuat),其特征在于在高pH下稳定且在约250 °F热稳定的独特泡囊结构。 Also described for acid stimulation based on viscoelastic surfactant diverter (Alleman, D., Etc., SPE 80222 (2003)), which is a VES gel (polyQuat), characterized in that at high pH and stable at about 250 ° F unique thermally stable vesicle structure. 通常,在泵送井增产流体之前,将这种凝胶型转向剂泵送入地层中以便封堵渗透性高的井段且使井处理流体转向到渗透性低的井段。 Typically, prior to pumping the well stimulation fluid, such gel-type steering agent pumped into the formation in order to block high permeability interval and the well treatment fluid into the low permeability steering interval.

[0015] 根据所有这些进展和新技术,转向剂的转向作用经常难以预测和监控,且不能成功地使处理流体转向到所有所要的井段中,因此未能最大程度地发挥压裂方法的优势。 [0015] According to all these developments and new technologies, turning the steering role of agents is often difficult to predict and monitor, and can not be successfully steering the treatment fluid into the well to be in all segments, and therefore failed to maximize the advantages of fracturing method . 这些问题在裸眼完井,特别是具有大面积对井眼开口的地层的高度倾斜完井中可进尤其严重。 These problems in open-hole completions, especially in highly inclined wellbore completion large opening into the formation can be particularly severe. 地层内存在的天然裂缝还可使转向更具挑战性。 Natural fractures existing in the formation of the steering may also more challenging. 因此,存在对于使井处理流体转向到地层内多个不同渗透性的井段中的新组合物和方法的需要。 Accordingly, a need exists for steering the well treatment fluid compositions and methods of the new hole section in a plurality of different permeability within the formation.

[0016] 发明概述 [0016] Summary of the Invention

[0017] 本发明提供了一种在地层中使用具有可溶性外涂层的颗粒作为转向剂的方法。 [0017] The present invention provides a method of using particles having a soluble outer coating as diverting agents in the formation process. 在标准井下压裂流体和破胶剂组合物存在下,在井下温度和压力下经过所要时间之后,可溶性外涂层将溶解。 In the standard downhole fracturing fluids and breaker compositions exist at the downhole temperatures and pressures for a time after the soluble outer coating will dissolve. 可溶性外涂层的实例包括胶原蛋白、聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇、聚内酯、聚丙烯酸酯、胶乳、聚酯、第I或II族的硅酸盐聚合物或其混合物。 Examples of the soluble outer coating include collagen, poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate / polyvinyl alcohol, polylactone, polyacrylate, latex, polyester, group I or II silicate polymer or mixtures thereof.

[0018] 本发明提供了作为转向剂的水溶性聚合物涂覆的支撑剂和使用这类转向剂处理地层的方法。 [0018] The present invention provides a water-soluble polymer coated proppant diverting agent of methods and using such a steering treated formation. 转向剂和载液一起被引入地层中。 And diverting agent carrier fluid is introduced into the formation together. 载液流进地层内的裂缝和/或井段中。 Carrier stream into the cracks and / or in the formation interval. 这些裂缝或井段表现不同程度的渗透性。 These cracks or interval at different degrees of permeability. 根据本发明的方法,载液与转向剂一起首先流向渗透性最高的井段。 The method according to the present invention, the highest permeability first flow interval with the steering carrier liquid agent. 地层的温度将致使转向剂的水溶性聚合物涂层软化并溶胀,由此堵塞裂缝。 Temperature of the formation will cause the water soluble polymer coating of the diverting agent to soften and swell, thereby plugging the fracture.

[0019] 在一个实施方案中,描述了适于使井处理流体转向到单个或多个井段中的转向齐U,其中该转向剂由微粒基体和水溶性外层组成。 [0019] In one embodiment, it is described that the well treatment fluid is adapted to turn into single or multiple wells steering homogeneous segments U, wherein the diverting agent by the matrix particles and water-soluble outer layer. 这类水溶性外层聚合物的实例有(不限于)胶原蛋白、聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇、聚合内酯、水溶性丙烯酸类、胶乳、聚酯、第I或II族的硅酸盐聚合物及其混合物。 Examples of such polymers are the water-soluble layer (not limited to) collagen, poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate / polyvinyl alcohol, caprolactone polymerised silicate polymers and mixtures thereof, water-soluble acrylics, latex, polyester, group I or II.

[0020] 在另一个实施方案中,描述了适于使井处理流体转向到单个或多个井段中的转向齐U,其中该转向剂由微粒基体、中间水不溶性层及水溶性聚合物外层组成。 [0020] In another embodiment, the outer described well treatment fluid adapted to turn into single or multiple wells steering homogeneous segments U, wherein the particulate diverting agent by the matrix, the intermediate layer is a water-insoluble and water-soluble polymer layer. 水溶性外层聚合物的实例有(不限于)胶原蛋白、聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇、聚合内酯、水溶性丙烯酸类、胶乳、聚酯、第I族或第II族的硅酸盐聚合物及其混合物。 Examples of water soluble polymers have an outer layer (not limited to) collagen, poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate / polyvinyl alcohol, the polymerization esters, water-soluble acrylics, latex, polyester, group I or group II silicate polymers and mixtures thereof. 水不溶性中间层的实例有可溶可熔酚醛聚合物和可溶酚醛聚合物。 Examples of the water-insoluble intermediate layer with a novolak polymer and a resole polymers.

[0021 ] 在另一个实施方案中,描述了适于使井处理流体转向到井眼内的单个或多个井段中的转向剂,其中该转向剂主要为水溶性聚合物颗粒,例如胶原蛋白珠;或聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇、聚合内酯、水溶性丙烯酸类、胶乳、聚酯、第I或II族的硅酸盐聚合物或其混合物的粒状颗粒。 [0021] In another embodiment, there is described that the well treatment fluid is adapted to turn into a single or multiple interval within a wellbore steering agent, wherein the primary agent is a water soluble polymer steering particles, such as collagen beads; or a poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate / polyvinyl alcohol, polymeric lactones, water-soluble acrylics, latex, polyester, first group I or II silicate polymer granular particles or mixtures thereof.

[0022] 在另一个实施方案中,公开了使地层的单一井段增产的方法,该方法包括以下步骤:将其外层上具有水溶性组分的转向剂与低粘度流体或压裂流体组合引入井眼内管中;将转向剂和压裂流体转移到地层中,让转向剂逐渐堵塞部分正处理的地层;和根据需要重复该过程,在压裂操作期间将转向剂加入段塞中的载液中。 [0022] In another embodiment, a method is disclosed that the formation of a single stimulation interval, the method comprising the steps of: diverting agent having a water-soluble component and a low viscosity fluid or a fracturing fluid composition on the outer layer thereof introducing tube within a wellbore; the diverting agent and fracturing fluid transfer into the formation, so that the steering agent is gradually clogged portion of the formation being processed; and the process is repeated as necessary, during the fracturing operation is added to the steering of the slug carrier liquid.

[0023] 附图简述 [0023] BRIEF DESCRIPTION

[0024] 以下附图成为本说明书的一部分且参阅这些附图以进一步说明本发明的某些方面。 [0024] The following drawings form part of this specification and the drawings to refer to these further demonstrate certain aspects of the present invention. 参考一个或多个附图以及本文所提供的具体实施方案的详细描述可更好地理解本发明。 Reference to one or more of the drawings and the detailed description of specific embodiments provided herein may be better understood with the present invention.

[0025] 图I展示具有垂直套管和单个处理井段的地层的井下部分的正面剖视图,其中正根据本发明公开的一个方面将多种涂覆的转向剂注入含烃类地层中。 [0025] Figure I shows a front portion of a downhole formation having a vertical casing and a single treatment interval is a sectional view, wherein n in accordance with one aspect of the present invention will be disclosed more coated diverting agents are injected into the hydrocarbon containing formation.

[0026] 图2说明图I的地层的正面剖视图,其中正将支撑剂注入已注入本发明的转向剂的含烃类地层中。 [0026] FIG 2 illustrates a front sectional view of the formation of the I, wherein n has been injected is injected proppant diverting agents containing hydrocarbon formation according to the present invention.

[0027] 图3展示具有垂直套管和多个处理井段58、60和62的井,且正根据本发明公开的一个方面将多种涂覆的转向剂注入。 [0027] FIG 3 shows a well having a vertical sleeve 58, 60 and 62 and a plurality of processing interval, and timing in accordance with an aspect of the present invention will be disclosed more coated diverting agents injection.

[0028] 定义 [0028] defined

[0029] 提供以下定义以帮助本领域的技术人员理解发明的详述。 [0029] The following definitions are provided to aid those skilled in the art in understanding the detailed description.

[0030] 本文使用的术语“载液”是指能够移动悬浮状态的颗粒(例如支撑剂)的基于油或水的液体。 [0030] As used herein, the term "liquid carrier" refers to oil-based or aqueous liquid suspension capable of moving particles (e.g., proppants) is. 低粘度载液具有较小的载流能力且颗粒可能受重力影响,因此如果颗粒密度比液体小则颗粒上升,或如果颗粒密度比液体密度大则颗粒下沉。 Low viscosity carrier fluid have less carrying capacity and the particles may be affected by gravity, so if the particle density is smaller than the liquid particles rise, or if the particle density greater than the density of the liquid particles from sinking. 高粘度液体可运载沉降或上升程度较小的颗粒,因为粘度克服了重力效应。 High viscosity liquid carrier can increase the degree of sedimentation or small particles, since the viscosity overcomes gravity effects.

[0031] 本文使用的术语“交联剂(crosslinker, cross-linking agent) ”是指那些用于共价改性蛋白质(例如胶原蛋白)的化合物,且包括含有两个相同活性基团的同双官能交联剂和含有两个不同活性基团的杂双官能交联剂。 [0031] As used herein, the term "crosslinking agent (crosslinker, cross-linking agent)" refers to those compounds used to covalently-modified protein (e.g. collagen), and comprises two identical with the bis-reactive groups containing functional and heterobifunctional crosslinkers contain two different reactive groups of the crosslinking agent.

[0032] 本文使用的术语“转向剂”意思指且通常是指用以暂时或永久地防止液体流动到通常位于地层中的特定位置的试剂,其中该试剂用来密封该位置,由此致使液体“转向”到不同位置。 [0032] As used herein, the term "diverting agent" means and refers generally to temporarily or permanently preventing liquid flow into the reagent layer typically located in a specific position, wherein the agent used to seal this position, thereby causing the liquid "steering" to a different location.

[0033] 本文使用的术语“支撑剂”是指那些用于井修井和处理(例如水力压裂操作)中以在处理后保持裂缝开口的定尺寸颗粒。 [0033] As used herein, the term "support" refers to those sized particles for well workover and processing (e.g. hydraulic fracturing operation) to hold the fracture open after the treatment. 这类定尺寸颗粒经常与压裂流体混合以在水力压裂处理或类似井下井处理之后保持裂缝开口。 Such sized particles are often mixed with fracturing fluid to hold the fracture after hydraulic fracturing treatment or similar downhole well treatment openings. 除天然存在的砂粒和坚果壳外,术语“支撑齐IJ”还包括人造或具体设计的支撑剂,例如树脂涂覆的砂粒或高强度的陶瓷材料,如烧结铝矾土。 In addition to naturally occurring sand grains and nut hulls, the term "support Qi IJ" further comprises a proppant or an artificial particular design, for example, sand or resin-coated high-strength ceramic material such as sintered bauxite. 树脂涂覆的支撑剂以涂覆有可溶可熔酚醛聚合物或可溶酚醛聚合物的支撑剂为代表。 Resin-coated proppant is coated with a novolak polymer or a novolac polymer proppant represented. 通常,但不必然地,支撑剂材料按尺寸和球形仔细分类以提供用于使生产流体从储层到井眼的有效管道。 Typically, but not necessarily, proppant materials classified by size and spherical carefully to provide efficient conduit for production fluids from the reservoir to the wellbore.

[0034] 在本文所述和公开的实施方案中,使用的术语“引入”包括使用本领域中已知的任何合适方式在井、井眼或地层内泵送、注入、倾入、释放、转移、加样、循环或另外放置流体或材料。 [0034] In the embodiment disclosed herein and embodiments, the term "introducing" encompasses any suitable manner known in the art pumping within the well, a wellbore or formation, injected, poured, released, transferred , loading, cycling, or otherwise placing a fluid or material. 同样,本文使用的术语“混和”、“接触”和“施加”包括以足以使材料、化合物或组分之间存在至少部分反应或其他相互作用的方式使两种或多种材料、化合物或组分混和、接触或使其在一起的任何已知的合适方法。 Likewise, the term "mixture" as used herein, "contacting" and "applying" include sufficient material is present between the at least partially reacted compounds or components, or other manner of interaction of two or more materials, compounds, or the group mixing points, or make contact with any suitable method known in together. [0035] 本文使用的术语“水溶性”是指在地面环境条件下稳定(不溶解)但在被置于地下环境中在既定时间(通常经数小时或数天)后变得可溶的树脂、聚合物或涂层。 [0035] As used herein, the term "water-soluble" refers to a stable (does not dissolve) under ambient conditions, but the floor is placed in the subterranean environment in a given time (usually several hours or days) after the resin becomes soluble , or a polymer coating.

[0036] 本文使用的术语“处理”是指在井下、井眼或储层上或井下、井眼或储层内的多种操作中的任一种,包括但不限于修井型处理;增产型处理,例如水力压裂处理或酸处理;隔离处理;控制储层流体处理或其他被执行以改善总体井操作和生产力的补救型处理。 [0036] As used herein, the term "treatment" refer to or downhole, wellbore, or any of a variety of operations within the reservoir, including but not limited to a workover type of treatment downhole, wellbore or reservoir; stimulation type process, for example, a hydraulic fracturing treatment or an acid treatment; isolation process; controlling the fluid reservoir or other processing is performed to improve the overall remediation process type well operation and productivity. [0037] 本文使用的术语“增产”是指作为用以使井生产力或寿命增加和/或达到最大的水力压裂、酸压裂、基岩酸化、砂粒处理或其他类型处理的结果的井生产力提高或再生操作,这经常通过产生高传导性储层流动路径来实现。 [0037] As used herein, the term "yield" refers to the well as a result of increased longevity or productivity and / or the maximum hydraulic fracturing, acid fracturing, matrix acidizing, sand treatment, or other types of processing of well productivity increase or reproducing operation, which is often achieved by creating highly conductive reservoir flow paths.

[0038] 发明详述 [0038] DETAILED DESCRIPTION

[0039] 在所公开的转向剂的实施方案中,地层的单个和多个井段可通过持续引入包含微粒基体和缓慢溶于水的外涂层的转向剂来分段处理或增产,其中所述缓慢溶于水的外涂层包含胶原蛋白或胶原蛋白与缓慢溶于水的非胶原蛋白材料的混合物。 [0039] In the disclosed embodiments of the diverting agent, single and multiple interval of the formation by continued introduction of particulate diverting agent comprising a substrate and a slowly water-soluble overcoat layer to increase or segmentation process, wherein said slow water-soluble overcoat layer comprises a mixture of collagen or collagen and non-collagenous material slowly dissolved in water.

[0040] 本发明提供了包含含有胶原蛋白的可溶性材料涂层的颗粒组合物以及制备这类组合物的方法。 [0040] The present invention provides a coating material comprising a soluble collagen containing particulate compositions and methods for preparing such compositions. 这类组合物可用于地层中以在水力压裂操作期间使井处理流体在单个井段中转向以增加裂缝长度或在具有不同渗透性和/或注入能力的地层的多个井段中转向。 Such compositions can be used in the formation to the well during a hydraulic fracturing operation in a single treatment fluid steering interval to increase the fracture length or having a different permeability and / or the formation of a plurality of injection wells segments steering capability. 在压裂过程使用本发明转向剂的过程中,涂覆有缓慢溶于水的涂层(例如单独的胶原蛋白或胶原蛋白与非胶原蛋白水溶性塑料涂层材料混合物的基体)的支撑剂(或微粒基体)用以使裂缝转向,因为支撑剂上的涂层充当初始裂缝的限定边界。 During the fracturing process of the present invention a steering agent, coated with a slowly water-soluble coating (e.g., collagen alone or a mixture of the matrix material non-collagenous soluble collagen coated plastic) proppant ( or particulate substrate) for causing steering crack, because the coating on the proppant to act as a boundary defining the initial cracks. 在压裂处理之后,由于涂层的缓慢溶解特性,涂层可被除去,余留的高渗透性支撑剂流进裂缝中,发挥其支撑剂的作用。 After the fracturing treatment, due to the slow dissolution properties of the coating, the coating can be removed, high permeability proppant remaining flows into the fracture, proppants play its role.

[0041] 虽然用“包含/包括”各种组分或步骤来描述组合物和方法,但组合物和方法还可基本上由各种组分或步骤组成或由各种组分或步骤组成。 [0041] Although the use of "including / comprising" various components or steps, the compositions and methods described, the compositions and methods may also consist essentially or of various components or steps of various components or steps.

[0042] A.基体 [0042] A. matrix

[0043] 适用于本发明的微粒材料(本文中还称为基体材料)包括可用于井下操作的已知为合适或可能合适的支撑剂的多种微粒材料。 [0043] The particulate materials suitable for the present invention (also referred to herein as base material) comprising a downhole known to be useful for the proper operation or may be more suitable proppant particulate material. 根据本发明,可使用的微粒材料(或基体材料)包括本领域已知的适于水力压裂的任何支撑剂。 According to the present invention, the particulate material (or matrix material) include any known in the art suitable for hydraulic fracturing proppant may be used. 这类微粒材料的实例包括但不限于天然材料、二氧化硅支撑剂、陶瓷支撑剂、金属支撑剂、合成有机支撑剂、其混合物等。 Examples of such particulate materials include, but are not limited to, natural materials, silica proppants, ceramic proppants, metallic proppants, synthetic organic proppants, mixtures thereof and the like.

[0044] 适合用作支撑剂的天然产物包括但不限于坚果壳,例如胡桃、巴西果和澳洲坚果;以及果核,例如桃核、杏核、橄榄核;及这些产物的任何树脂浸溃或树脂涂覆的型式。 [0044] Suitable natural products used as proppants include, but are not limited to, nut shells such as walnut, brazil nut, and macadamia nuts; and pyrenes, e.g. Peach, almond, olive pits; and any of these products impregnated resin or resin-coated type. 典型的树脂涂层或浸溃物包括双酚、双酚均聚物、双酚均聚物与酚-醛聚合物的共混物、双酚-醛树脂和/或聚合物、酚-醛聚合物及均聚物、改性和未改性的可溶酚醛树脂、酚类物质(包括芳基酚、烷基酚、烷氧基酚及芳氧基酚)、间苯二酚树脂、环氧树脂、可溶可熔酚醛聚合物树脂、可溶可熔双酚-醛聚合物及蜡以及这类树脂涂层的预固化或固化型式。 Typical resin coatings or impregnated include bisphenols, bisphenol homopolymers, homopolymers of bisphenol and phenol - formaldehyde polymer blend of bisphenol - aldehyde resins and / or polymers, phenol - formaldehyde polymerization and homopolymers thereof, modified and unmodified resol resins, phenolics (including arylphenols, alkylphenols, alkoxylated phenols and aryloxy phenol), resorcinol resins, epoxy resins, phenol novolak polymer resins, bisphenol novolac - a pre-cured polymer and an aldehyde resin, wax, and such coatings or curing type.

[0045] 适用于本发明的二氧化娃支撑剂包括但不限于玻璃球和玻璃微球、玻璃珠、二氧化硅石英砂和所有类型的砂粒,例如白色或褐色的砂粒。 [0045] wa dioxide proppants useful in the present invention include, but are not limited to, glass spheres and glass microspheres, glass beads, silica quartz sand, and all types of sand, for example, white or brown sand. 适合使用的典型二氧化硅砂粒包括Northern White Sands(Fairmount Minerals, Chardon, OH)、Ottawa、Jordan、Brady、Hickory、Arizona、St. Peter、Wonowoc和Chalfort以及这些砂粒的任何树脂涂覆的型式。 Typical silica sands suitable for use include Northern White Sands (Fairmount Minerals, Chardon, OH), Ottawa, Jordan, Brady, Hickory, Arizona, St. Peter, Wonowoc and Chalfort and any of these types of resin-coated sand. 在使用氧化硅纤维的情况下,纤维可为直线、曲线、卷曲或螺旋状的,且可具有任何等级,例如E-级、S-级和AR-级。 In the case of silica fibers, the fibers may be straight, curved, curled or spiral, and may have any level, for example level E-, S- and AR- grade level. 用于本发明的合适树脂涂覆的二氧化硅支撑剂的实例包括可变形的支撑剂,例如FLEXSAND LS™ 和FLEXSAND MS™(自BJ Services, Inc.,Houston, TX 购得);和Tempered HS®、Tempered LC ®、TemperedDC ® 和Tempered TF ® 回火支撑剂,全部自Santrol, Fresno, TX 购得。 Examples of the silica proppants suitable for the present invention resin-coated proppant comprising a deformable, e.g. FLEXSAND LS ™ and FLEXSAND MS ™ (from BJ Services, Inc., Houston, TX available); and Tempered HS ®, tempered LC ®, TemperedDC ® and tempered TF ® tempered proppants, all from Santrol, Fresno, TX available.

[0046] 适用于本发明的方法的陶瓷支撑剂包括但不限于陶瓷珠;废流体-裂化催化剂(FCC),例如美国专利第6,372,378号中描述的那些催化剂,该专利全文结合到本文中;超轻质多孔陶瓷;经济型轻质陶瓷,例如“EC0N0PR0P™” (Carbo Ceramics, Inc.,Irving,TX);轻质陶瓷,例如“CARBOLITE™”;中等强度陶瓷,例如“CARBOPROP™” (自Carbo Ceramics,Inc. , Irving, TX 购得);高强度陶瓷,例如“CARB0HSP™” 和“Sintered Bauxite”(CarboCeramics, Inc.,Irving TX)和HYPERPROP G2™、DYNAPROP G2™ 或OPT I PROP G2™ 封装的可固化陶瓷支撑剂(自Santrol,FreSno,TX购得)以及这些陶瓷支撑剂(例如上所述)的任何树脂涂覆或树脂浸溃的型式。 [0046] The method of the present invention suitable for ceramic proppants include, but are not limited to, ceramic beads; waste fluid - cracking catalyst (the FCC), such as those described in U.S. Patent No. 6,372,378 the catalyst described in this patent is incorporated into the herein; ultra lightweight porous ceramics; economical, lightweight ceramics such as "EC0N0PR0P ™" (Carbo ceramics, Inc., Irving, TX); lightweight ceramics such as "CARBOLITE ™"; medium strength ceramics such as "CARBOPROP ™ "(. from Carbo ceramics, Inc, Irving, TX available); high-strength ceramics such as" CARB0HSP ™ "and" Sintered Bauxite "(CarboCeramics, Inc., Irving TX) and HYPERPROP G2 ™, DYNAPROP G2 ™ or OPT I PROP G2 ™ package curable ceramic proppants (from Santrol, FreSno, TX commercially available) and the ceramic proppants (Example as described above) of any resin-coated or resin impregnated type.

[0047] 适用于本发明的实施方案的金属支撑剂包括但不限于铝丸、铝粒、铝针、铝线、铁丸、钢丸等以及这些金属支撑剂的任何树脂涂覆的型式。 [0047] For metal proppant embodiment of the present invention include, but are not limited to any type of resin-coated balls to aluminum, aluminum particles, aluminum needles, aluminum wire, iron shot, steel shot and the like of these metals proppant.

[0048] 合成支撑剂同样适用于本发明。 [0048] Synthetic proppants are equally applicable to the present invention. 合适的合成支撑剂的实例包括但不限于塑料颗粒或珠、尼龙珠、尼龙粒、SDVB(苯乙烯二乙烯基苯)珠、碳纤维(例如自Zoltek Corporation (Van Nuys, CA)购得的PANEX™ 碳纤维)和类似于“FLEXSAND MS™” (BJServices Company, Houston, TX)的树脂聚结颗粒及其树脂涂覆的型式。 Examples of suitable synthetic proppants include, but are not limited to, plastic particles or beads, nylon beads, nylon particles, SDVB (styrene divinyl benzene) beads, carbon fibers (e.g. from Zoltek Corporation (Van Nuys, CA) commercially available PANEX ™ carbon fibers) and the like "FLEXSAND MS ™" (BJServices Company, Houston, TX) and the resin particles coalesced resin-coated type.

[0049] 另外,同样预想适合用作支撑剂的可溶性材料可用于本发明的方法中。 [0049] In addition, also contemplated for use as soluble proppant material used in the process according to the present invention. 例如,置于所产生的孔眼的通道中的可溶性支撑剂包括但不限于大理石或石灰石屑或任何其他合适的碳酸盐微粒。 For example, soluble proppants placed in a passage aperture produced include but are not limited to marble or limestone chips or any other suitable carbonate particulates. 另外,通过与处理化学品接触而变得可溶解的或自裂缝回流的可熔融的涂覆或未涂覆的蜡、塑料或树脂颗粒适合用作本发明的支撑剂。 Further, by contacting the treatment chemical from the cracks become soluble or meltable reflux wax coated or uncoated, plastic or resin suitable for use as proppant particles of the present invention.

[0050] 本发明合适的支撑剂通常的使用浓度为约I到约18磅/加仑(约120g/L到约2,160g/L)压裂流体组合物,但按需要也可使用更高或更低的浓度。 [0050] Suitable concentrations commonly used proppants of the present invention is from about I to about 18 lbs / gallon (120g / L to about 2,160g / L) of fracturing fluid composition, but may also be used as desired or higher lower concentration.

[0051] 同样,适用于本发明的微粒基体的粒径在美国标准试验筛孔目数约4到约200的范围内(即,约O. 18英寸到约0.003英寸的筛孔)。 [0051] Similarly, the particulate substrate suitable for the present invention is in the range of a particle size sieve U.S. Standard Test number from about 4 to about 200 (i.e., from about O. 18 inches to about 0.003 inch mesh). 更详细地讲,适用于本发明的微粒基体的尺寸包括约4网目(4750微米)到约200网目(75微米)的尺寸范围。 More specifically, the matrix size of the particles suitable for use in the present invention comprises from about 4 mesh (4750 microns) to about 200 mesh (75 micron) size range. 同样适用于本发明的是具有以下尺寸标记的微粒材料或支撑剂:6/12、8/16、12/18、12/20、16/20、16/30、20/40,30/50,40/70和70/140,不过可使用任何所要的尺寸分布,例如10/40,14/20,14/30、14/40、18/40等,以及其任何组合(例如,10/40和14/40的混合物)。 Also useful in the present invention is a particulate material or proppant tagged with the following dimensions: 6 / 12,8 / 16,12 / 18, 12 / 20,16 / 20,16 / 30,20 / 40,30 / 50, 40/70 and 70/140, but may be any desired size distribution, e.g., any combination thereof and 10 / 40,14 / 20,14 / 30,14 / 40,18 / 40, (e.g., 10/40 and mixture of 14/40). 根据本发明,优选的网目尺寸为20/40网目。 According to the present invention, the preferred mesh size of 20/40 mesh.

[0052] B.可溶件涂层 [0052] B. Soluble Coating member

[0053] 根据本发明使用的可溶性涂层可为经一段时间在井下、地层中可缓慢溶解的许多已知的可溶性试剂。 [0053] Many of the known agent may be soluble in a period of time downhole, the formation may be slowly soluble soluble coatings according to the present invention. 可用于本发明的可溶性聚合物材料应在井下、地层条件下可溶于(也就是说能够溶于)盐水、水、油、有机溶剂、酸或酸性介质和/或PH为约I到约14的流体以及其混合物中。 Soluble polymeric materials may be used in the present invention should downhole formation conditions are soluble (i.e. soluble in), brine, water, oil, organic solvents, acid or acidic media, and / or PH of from about I to about 14 fluids and mixtures thereof.

[0054] 可溶性涂层优选为结构蛋白,例如胶原蛋白或去端肽胶原蛋白(atelocollagen);植物蛋白,例如小麦、玉米、燕麦或杏仁中存在的植物蛋白;或来源于海洋环境的胶原蛋白。 [0054] The soluble coating is preferably a structural protein, such as collagen or protein atelocollagen (atelocollagen); vegetable proteins, such as wheat, corn, oat or almond protein present in a plant; or collagen derived from the marine environment. 后一类型的胶原蛋白可从鱼类、藻类、浮游生物、微浮游生物等中提取。 The latter type of collagen can be extracted from fish, algae, plankton, micro-plankton, and the like. 可溶性涂层更优选为胶原蛋白,包括I型胶原蛋白、II型胶原蛋白、III型胶原蛋白、IV型或V型胶原蛋白以及其组合。 More preferably the soluble coating is collagen, including type I collagen, type II collagen, type III collagen, IV or V collagen, and combinations thereof. 根据本发明,可溶性涂层最优选为I型胶原蛋白或去端肽胶原蛋白。 According to the present invention, a soluble coating and most preferably type I collagen or atelocollagen protein. [0055] 根据本发明适合用作可溶性涂层的I型胶原蛋白或去端肽胶原蛋白为那些含有至少一个羟基脯氨酸残基的胶原蛋白。 [0055] According to the present invention is suitable for use as a coating soluble type I collagen or atelocollagen collagen protein are those containing at least one hydroxyproline residue. 这类I型胶原蛋白或去端肽胶原蛋白包括肌腱、皮肤、骨骼、疤痕组织等中存在的胶原蛋白(例如原胶原蛋白)以及来源于胶原蛋白的受控、酶促或化学还原的产物。 Such type I collagen or atelocollagen proteins include collagen present in tendons, skin, bone, scar tissue, etc. (e.g., procollagen) and the controlled, enzymatic or chemical reduction of collagen derived product. 这类胶原蛋白的分子量优选为约10,000道尔顿到约500,000道尔顿,更优选为约100,000道尔顿到约300,000道尔顿。 Such collagen preferably a molecular weight from about 10,000 daltons to about 500,000 daltons, more preferably from about 100,000 daltons to about 300,000 daltons. 合适的分子量为约100,000道尔顿、125,000道尔顿、150,000道尔顿、175,000道尔顿、200,000道尔顿、225,000道尔顿、250,000道尔顿、275,000道尔顿、300,000道尔顿以及这些值中的任何两个之间的分子量,例如分子量为约225,000到约275,000道尔顿的胶原蛋白。 Suitable molecular weight of about 100,000 daltons, 125,000 daltons, 150,000 daltons, 175,000 daltons, 200,000 daltons, 225,000 daltons, 250,000 daltons, 275,000 daltons, and a molecular weight between any two of these values, 300,000 Daltons, e.g. a molecular weight of from about 225,000 to about collagen 275,000 Daltons. 例如,适用于本发明的优选I型胶原蛋白为Milligans and Higgins, Inc. (Johnstown, NY)供应的分子量为约250,000的原胶原蛋白。 For example, the present invention is preferably suitable for type I collagen molecular Milligans and Higgins, Inc. (Johnstown, NY) is supplied procollagen about 250,000.

[0056] 适用于本发明的胶原蛋白的勃鲁姆强度(Bloom strength)为约IOOpsi到约900psi,更优选为约300psi到约700psi。 Bloom strength (Bloom strength) [0056] The present invention is applicable to collagen is from about IOOpsi to about 900psi, and more preferably from about 300psi to about 700psi. 适用于本发明的胶原蛋白的勃鲁姆强度为约400psi到约600psi。 Suitable for the present invention are collagen bloom strength of about 400psi to about 600psi. 根据本发明,合适的勃鲁姆强度为约400psi、约410psi、约420psi、约430psi、约440psi、约450psi、约460psi、约470psi、约480psi、约490psi、约500psi、约510psi、约520psi、约530psi、约540psi、约550psi、约560psi、约570psi、约580psi、约590psi和约600psi以及在这些值中的任何两个之间的勃鲁姆强度,例如约400psi到约520psi,例如512psiο According to the present invention, suitable bloom strength of about 400 psi, about 410psi, about 420psi, about 430 psi, about 440psi, about 450 psi, about 460psi, about 470 psi, about 480psi, about 490 psi, about 500 psi, about 510psi, about 520psi, about 530psi, about 540psi, about 550 psi, about 560 psi, about 570 psi, about 580 psi, about 600psi to about 590psi, and any of these bloom strength between the two values, for example from about 400psi to about 520psi, e.g. 512psiο

[0057] 本文使用的勃鲁姆强度是指根据标准化勃鲁姆试验方法(例如BS757 : 1975,GMIATesting Standard B5757、用于试验粘性动物胶的International Standard IS09665 或如“Official Methods of Analysis ofAOAC INTERNATIONAL(OMA) ”中所述的类似标准)测量由在恒定温度下保持特定时间的确定浓度的标准溶液形成的凝胶物质(例如胶原蛋白)的强度和/或刚度的测量值。 [0057] bloom strength herein refers Bloom according to standardized test methods (e.g., BS757: 1975, GMIATesting Standard B5757, the test for tack or glue as the International Standard IS09665 "Official Methods of Analysis ofAOAC INTERNATIONAL (OMA ) measurement value "according to similar criteria in) strength of the gel material (e.g. collagen) formed was measured by standard solution to determine the concentration of a specific retention time at constant temperature and / or stiffness. 勃鲁姆强度值的单位通常为“磅/平方英寸”(Psi)或克,反映了降低样品表面所选区域4_的距离所需的力。 Unit bloom strength value is generally "pounds / square inch" (the Psi) or grams, reflecting the force required to reduce the surface area of ​​the selected sample distance of 4_. 在典型方法中,凝胶产物(例如胶原蛋白或明胶)以具体稠度(例如6和2/3%溶液)形成且在10°C恒温浴的恒温下保持18小时。 In a typical process, the gel product (e.g., collagen or gelatin) to form a specific consistency (e.g., 6, and 2/3% solution) and maintained at a constant temperature bath at 10 ° C for 18 hours. 随后采用称作质地分析仪(例如TA. ΧΤ2Ϊ质地分析仪,Scarsdale,NY)的装置测量,将具有锋利下边缘的标准AOAC ® [Associateion of OfficialAnalytical Chemists (官方分析化学师协会)]凝胶强度计活塞降低4_到凝胶中或者将可用作活塞的具有底边缘的BS活塞转向0. 4mm半径所需的重量(克)(或压力,psi)。 Then using a texture analyzer device measures referred to (e.g. TA. ΧΤ2Ϊ Texture Analyzer, Scarsdale, NY), and having a sharp lower edge of the standard AOAC ® [Associateion of OfficialAnalytical Chemists (Association of Official Analytical Chemists)] Gel strength meter 4_ reduced piston into the gel or the BS may be used as a piston with a piston bottom edge turning radius needed to 0. 4mm by weight (g) (or pressure, psi). 例如,如果这种方法需要200克来降低活塞,那么明胶的勃鲁姆强度为200。 For example, if this method requires to lower the piston 200 g, then the strength of the gelatin is 200 Bloom.

[0058] 适用于本发明的I型胶原蛋白的筛孔分布/尺寸标记为6/12、8/16、12/18、12/20、16/20、16/30、20/40、30/50、40/70和70/140以及在这些标记中的任何两个之间的筛孔分布,不过可使用任何所要的尺寸分布,例如8/40、10/40、14/20、14/30、14/40、18/40等以及其任何组合(例如10/40和14/40混合物)。 [0058] Type I collagen suitable for the present invention, the distribution of mesh / size flag is 6 / 12,8 / 16,12 / 18, 12 / 20,16 / 20,16 / 30,20 / 40,30 / 50, 40/70 and 70/140, and any of these markers in distribution between two mesh, but may be distributed in any desired size, for example 8 / 40,10 / 40,14 / 20,14 / 30 , 14 / 40,18 / 40, and any combination thereof (e.g., a mixture of 10/40 and 14/40). 根据本发明,优选的网目尺寸为8/40网目。 According to the present invention, the preferred mesh size of 8/40 mesh.

[0059] 本文用作可溶性涂层的胶原蛋白可为交联的、未交联的或两者的组合,交联的类型和程度取决于基于胶原蛋白的可溶性涂层的具体应用。 [0059] The soluble coatings used herein as collagen may be crosslinked, the uncrosslinked or a combination of both, the type and degree of crosslinking depends upon the particular application of the collagen-based soluble coating is. 存在4种固定胶原蛋白材料和由加工的胶原蛋白纤维或纯化的胶原蛋白建造的材料的基本策略。 There are four fixing material and the collagen material of the basic strategy built by collagen fibers or purified collagen processing. 这些策略包括使用利用胶原蛋白纤维体系中的目标反应性部分和交联分子本身共价偶合邻近胶原蛋白纤维的试剂进行外源性化学交联;通过天然存在的反应性氨基酸侧链共价连接胶原蛋白纤维的物理化学交联技术,例如光氧化、微波照射、脱水和脱氢热处理;在胶原蛋白纤维上的氨基酸侧链之间化学催化分子内交联;和聚合与胶原蛋白装配混合的化合物并形成不与胶原蛋白纤维化学反应的聚合非共价或共价相互作用[Koob, TJ , “Collagen Fixation”,在Encyclopedia of Biomaterials andBiomedical Engineering 中,Wnek, G. Ε·, Bowlin,GL,Eds.,2004]。 These strategies include the use of reagent-reactive moiety and a target molecule cross-linked collagen fibers in the system itself covalently coupled adjacent collagen fibers is exogenous chemical crosslinking; connected by a reactive amino acid side chain of collagen is covalently naturally occurring physical chemical crosslinking techniques of protein fibers, such as photo-oxidation, microwave irradiation, dehydration and dehydrogenation heat treatment; the catalyzed intramolecular chemical crosslinks between amino acid side chains on the collagen fibers; and a polymerizable compound mixed with collagen and assembly are formed do not interact [Koob, TJ, "collagen Fixation" polymerization covalent or non-covalent chemical reaction of collagen fibers, in the Encyclopedia of Biomaterials andBiomedical Engineering, Wnek, G. Ε ·, Bowlin, GL, Eds., 2004]. 根据本发明,用作可溶性涂层的胶原蛋白优选使用化学交联技术交联。 According to the present invention, the collagen used as a soluble coating is preferably chemical crosslinking using crosslinking techniques. 这些技术包括但不限于基于醛的交联技术、基于多聚环氧化合物的交联技术、使用异氰酸酯、碳化二亚胺交联和基于酰基叠氮的交联。 These techniques include, but are not limited to, aldehyde-based crosslinking techniques, techniques based on crosslinked polymeric epoxy compound, isocyanate, carbodiimide crosslinking, and acyl azide based crosslinking of. 胶原蛋白更优选使用基于醛的交联技术交联,例如使用戊二醛或甲醛交联。 More preferably collagen crosslinked using aldehyde-based crosslinking techniques, for example using glutaraldehyde or formaldehyde cross-linking.

[0060] 基于醛的交联技术包括那些使用含有两个用以在邻近胶原蛋白(特别是胶原蛋白中赖氨酸残基的ε -氨基)之间形成共价交联的反应性醛基的试剂的技术[Khor,E.,Biomaterials, Vol. 18 :pp. 95-105 (1997)]。 [0060] The aldehyde-based crosslinking techniques include those containing two to adjacent collagen (especially collagen lysine residue ε - amino) forming reactive aldehyde groups covalently cross-linked between the technical reagent [Khor, E., Biomaterials, Vol 18:.. pp 95-105 (1997)]. 适用于本发明的醒包括但不限于戍二醒、甲醒、丙醛和丁醛。 Wake useful in the present invention include, but are not limited to two Shu wake, wake A, propionaldehyde and butyraldehyde.

[0061] 基于多聚环氧化物的交联技术和试剂包括使用例如以反应性环氧化物官能团为端基的短支链聚合物的化合物。 [0061] The reaction of the compound used, for example an epoxide functional group-terminated short-chain branched polymer-based crosslinking techniques and reagents include poly epoxides. 适合用作本发明的交联剂的多聚环氧化合物包括但不限于甘油醚、乙二醇和甘油多缩水甘油醚。 Suitable crosslinking agents of the present invention as the polyepoxy compounds include, but are not limited to glycerol ethers, glycol and glycerol polyglycidyl ether.

[0062] 异氰酸酯同样适合用作本发明的交联剂。 [0062] Also suitable isocyanate crosslinking agents used according to the present invention. 通常,使异氰酸酯(R-NCO)与伯胺反应以形成脲键(RH-CO-NH-R);因此双官能异氰酸酯能够通过其赖氨酸侧链与胶原蛋白交联。 Typically, the isocyanate (R-NCO) react with primary amines to form a urea bond (RH-CO-NH-R); thus difunctional isocyanates with lysine side chain can be crosslinked by its collagen. 适合用作本发明的交联剂的异氰酸酯优选为二异氰酸酯,包括联苯基二异氰酸酯、二甲氧基-4,4'-联苯基二异氰酸酯、二甲基_4,4'-联苯基二异氰酸酯、1,3_双(异氰酸根甲基)苯、苯基二异氰酸酯、甲苯二异氰酸酯(toluenediisocyanate)、甲苯二异氰酸酯(tolylene diisocyanate)、二异氰酸根己烧、二异氰酸根辛烧、二异氰酸根丁烧、异佛尔酮二异氰酸酯、二甲苯二异氰酸酯、、1,8_辛二异氰酸酯、苯二异氰酸酯和聚(1,6_己二异氰酸酯)。 The present invention suitable for use as the isocyanate crosslinking agents is preferably diisocyanates, including biphenyl diisocyanate, dimethoxy-4,4'-biphenyl diisocyanate, biphenyl dimethyl _4,4'- yl diisocyanate, 1,3_-bis (isocyanatomethyl) benzene, phenyl diisocyanate, toluene diisocyanate (toluenediisocyanate), toluene diisocyanate (tolylene diisocyanate), diisocyanato-hexyl burn-diisocyanato-octyl burning, burn-diisocyanato-butoxy, isophorone diisocyanate, xylylene diisocyanate ,, suberic 1,8_ diisocyanate, phenylene diisocyanate, and poly (hexamethylene diisocyanate 1,6_). 用作本发明的胶原蛋白分子的交联剂的异氰酸酯优选为1,6_己二异氰酸酯。 The present invention is used as a crosslinking agent collagen molecules isocyanate 1,6_ preferably hexamethylene diisocyanate.

[0063] 在本发明的范围内还可使用碳化二亚胺交联剂和技术。 [0063] The crosslinking agent may be used and carbodiimide technology within the scope of the present invention. 使这类试剂与胶原蛋白内的天冬氨酸和谷氨酸侧链的羧基反应以形成异酰基脲衍生物/异肽键[Khor,E.,出处同上]。 So that such a side chain carboxyl group of aspartic acid and glutamic reaction in the reagent to form a heterologous collagen acylurea derivatives / iso-peptide bonds [Khor, E., Ibid.]. 适合用作本发明的胶原蛋白的交联剂的碳化二亚胺包括但不限于N,N' -二环己基碳化二亚胺(DCC) ;N,N' - 二异丙基碳化二亚胺(DIC) ;N,N' -二叔丁基碳化二亚胺;I-乙基-3-(3-二甲基氨基丙基)碳化二亚胺(EDC5EDAC);水溶性EDC(WSC) ;1_叔丁基_3_乙基碳化二亚胺;I-(3- 二甲基氨基丙基)-3-乙基碳化二亚胺;双(三甲基甲硅烷基)-碳化二亚胺;1,3_双(2, 2-二甲基-I, 3-二氧杂环戍烧-4-基甲基)碳化二亚胺(BDDC,如美国专利第5,602, 264号所述);N-环己基-N' -(2-吗啉-4-基乙基)碳化二亚胺;N,N' -二乙基碳化二亚胺(DEC) ; I-环己基-3-(2-吗啉-4-基乙基)碳化二亚胺甲基-对甲苯磺酸盐[例如,Sheehan, JC等,J. Org. Chem. , Vol. 21 :ρρ· 439-441 (1956)];低聚烧基环己基碳化二亚胺,例如Zhang等描述的那些低聚烧基环己基碳化二亚胺[J. Org. Chem. ,Vol. 69 :pp. 8340-8344(2004)];聚合物键合的DCC Suitable crosslinking agents as collagen of the present invention include, but are not limited to carbodiimide to N, N '- dicyclohexyl carbodiimide (DCC); N, N' - diisopropyl carbodiimide (DIC); N, N '- di-tert-butyl-carbodiimide; the I-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC5EDAC); water-soluble EDC (WSC); 1_ _3_-tert-butyl-ethylcarbodiimide; I- (3- dimethylaminopropyl) -3-ethylcarbodiimide; bis (trimethyl-silyl) - carbodiimide amine; 1,3_-bis (2,2-dimethyl -I, 3- dioxol-4-ylmethyl burning Shu) carbodiimide (BDDC, as described in U.S. Patent No. 5,602 264 of a); N-cyclohexyl--N '- (2- morpholin-4-yl-ethyl) carbodiimide; N, N' - diethyl carbodiimide (DEC); I- cyclohexyl - ... 3- (2-morpholin-4-yl-ethyl) carbodiimide methyl - p-toluenesulfonate [e.g., Sheehan, JC like, J Org Chem, Vol 21: ρρ · 439-441. (1956)]; oligomeric burning cyclohexyl carbodiimide, such as those oligomeric Zhang et burning cyclohexyl carbodiimide described [J. Org Chem, Vol 69:.... pp 8340-8344 ( 2004)]; polymer-bonded DCC ;和聚合物键合的EDC,例如JANDAJEL™的交联N-乙基-N' -(3- 二甲基氨基丙基)碳化二亚胺。 ; And polymer-bound EDC, e.g. JANDAJEL ™ crosslinked N- ethyl -N '- (3- dimethylaminopropyl) carbodiimide. 另外,N-羟基琥珀酰亚胺(NHS)、I-羟基-7-氮杂苯并三唑(HOAt)或类似试剂可连同碳化二亚胺一起使用以使活化异酰基脲衍生物的内部重排减到最少且提供更有效的交联。 Further, N- hydroxysuccinimide (NHS), I- hydroxy-7-azabenzotriazole (of HOAt), or similar reagents may be used in conjunction with the activated carbodiimide to urea derivatives isobutyl group internal weight row minimized and provide more efficient cross-linking.

[0064] 如碳化二亚胺处理一样,酰基叠氮交联剂在天冬氨酸和谷氨酸的羧酸侧链与胶原蛋白的赖氨酸的ε-氨基之间生成共价键[Petit, H.等,J. Biomed. Mater. Res. , Vol. 24 :PP. 179-187(1990)]。 [0064] The process as carbodiimide, acyl azide crosslinking agent between lysine side chains of aspartic acid and glutamic acid and ε- amino group of collagen form a covalent bond [Petit ..., H. et, J Biomed Mater Res, Vol 24:... PP 179-187 (1990)]. 在羧基酯化(其中将甲基加入酸中)之后,将生物材料用肼处理以形成相应酰肼;随后加入氮化钠,使其与酰肼反应且形成酰基叠氮。 After the esterified carboxy group (wherein the acid is added methyl), the biological material by treatment with hydrazine to form the corresponding hydrazide; followed by addition of sodium azide, and reacting it with the hydrazide form an acyl azide. 本领域已知的许多肼可用于这种方法中,包括马来酰亚胺基丙酰肼(MPH)。 Many hydrazines known in the art may be used in this process, including maleimido propionyl hydrazide (MPH).

[0065] 适用于本发明以提供充当支撑剂颗粒上的可溶性涂层的交联胶原蛋白分子的其他化学交联剂包括但不限于同双官能交联剂,例如BMME、BS0C0ES, DSP (硫代-可裂解的交联剂)、DSS、EGS、水溶性EGS和SATA ;以及杂双官能交联剂,包括GMB、MBS、PMPI、SMCC,SPDP和MPH(马来酰亚胺基丙酰肼)、MCH、EMCH(马来酰亚胺基癸酰肼)、KMUH(N-(k-马来酰亚胺基i^一烷)酰肼)和MPBH(4-(4-N-马来酰亚胺基苯基)丁酰肼),全部自Interchim(Cedex, France)购得。 [0065] The present invention is suitable for providing a soluble coating on the proppant particles function as other chemical crosslinking agent the collagen molecules include but are not limited to homobifunctional crosslinkers such as BMME, BS0C0ES, DSP (thio - cleavable cross-linking agent), the DSS, EGS, water-soluble EGS, and the SATA; and hetero bifunctional crosslinking agents including GMB, MBS, PMPI, SMCC, SPDP, and the MPH (maleimido propionyl hydrazide) , MCH, EMCH (dec maleimido hydrazide), KMUH (N- (k- i ^ a maleimido alkyl) hydrazide), and MPBH (4- (4-N- maleimidomethyl sub-aminophenyl) butyric acid hydrazide), all from Interchim (Cedex, France) are commercially available.

[0066] 适于交联胶原蛋白纤维以供可溶性支撑剂涂层用的其他技术包括但不限于脱水、在254nm下UV照射、结合UV照射的葡萄糖介导交联(糖基化)和生物交联。 [0066] suitable for crosslinking the collagen fibers for use in other techniques using soluble proppant coatings include but are not limited to dehydration, UV radiation at 254nm, UV irradiation binding glucose-mediated crosslinking (glycation) and biological deposit Union. 后一技术包括使用天然产物,例如京尼平(genipin)及其相关环烯醚職类化合物,其自桅子属植物(桅子(Gardenia jasminoides))的果实分离,其为二醒水溶液,因此可与邻近胶原蛋白分子的赖氨酸侧链上的ε-氨基反应以提供交联。 The latter technique includes using natural products such as genipin (genipin) and its related iridoid compounds category, which is isolated from the fruit of gardenia plant genus (gardenia (Gardenia jasminoides)), which is a two wake solution, thus ε- amino group may react with the lysine side chain adjacent collagen molecules to provide crosslinking. 适用于本发明的其他生物交联体系包括自杂酚油灌木分离的儿茶酚-醌鞣体系,例如3,4- 二羟基酪胺和去甲二氢愈创木酸(NDGA),其通过NDGA 上的两个儿茶酌■充当交联剂[Koob, TJ,Comp. Biochem. Physiol.,PartA, Vol. 133 :pp.1171-1192(2002)]。 The present invention is applicable to other biological systems include self-crosslinking creosote bush isolated catechol - quinone tanning systems, such as 3,4-dihydroxy-dihydro-tyramine and norepinephrine nordihydroguaiaretic acid (of NDGA), by NDGA on two catechu discretion ■ acts as a crosslinking agent [Koob, TJ, Comp Biochem Physiol, PartA, Vol 133:.... pp.1171-1192 (2002)].

[0067] 根据本发明公开,微粒基体上的缓慢溶于水的涂层还可为非胶原蛋白物质,例如缓慢溶于水的合成聚合物。 [0067] According to the present disclosure, the slow water-soluble coating on the particulate substrate may be a non-collagenous material, such as a slow water-soluble synthetic polymers. 这类非胶原蛋白物质包括但不限于:聚环氧乙烷、聚环氧丙烷、聚己酸内酯;聚乙烯/聚丙烯和polycaprolene的接枝物;聚乙烯/聚环氧丙烧和聚己酸内酯的接枝物;水可溶或水可还原的丙烯酸类;水可还原的苯氧基树脂;胶乳;聚酯;可溶性嵌段共聚物;聚乙烯醇(PVA)和聚乙酸乙烯酯的接枝物;聚交酯和聚乳酸的衍生物•'聚乙醇酸(PGA);聚乙醇酸乳酸(polyglycoliclactic acid, PGLA)。 Such non-collagenous materials include, but are not limited to: polyethylene oxide, polypropylene oxide, polycaprolactone; polyethylene / polypropylene and the graft polycaprolene; polyethylene / polypropylene and polyethylene propan burn polycaprolactone graft; acrylic water-soluble or water-reducible; water reducible phenoxy resin; latex; polyesters; soluble block copolymers; polyvinyl alcohol (PVA) and polyvinyl acetate ester graft; polylactide and polylactic acid derivatives • 'polyglycolic acid (the PGA); polyglycolic acid (polyglycoliclactic acid, PGLA). 也可用于水溶性涂层的是元素周期表第I或II族(碱金属或碱土金属)的硅酸盐聚合物,例如S0L0SIL™(FosecoInternational, Ltd. , Great Britain), 一种娃酸钠聚合物。 Water soluble coating can be used is a Group I or II of the periodic table (alkali metal or alkaline earth metal) silicate polymers, e.g. S0L0SIL ™ (FosecoInternational, Ltd., Great Britain), a sodium baby polymerization thereof.

[0068] C.使用方法 [0068] C. Use

[0069] 在所公开方法的实施方案中,地层的单个或多个井段可通过持续将本发明的转向剂引入地层中,接着将井处理流体引入地层中来分段处理或增产。 [0069] In an embodiment of the disclosed method, single or multiple interval by continuing the formation of the present invention, the diverting agent introduced into the formation, the well treatment fluid is then introduced into the formation or to increase fragmentation process. 本文使用的“井眼”包括井的下套管段和/或裸眼井段,应了解井眼可为垂直的、水平的或其组合。 As used herein, "wellbore" includes cased section of the well and / or open hole, as should be understood that the wellbore may be vertical, horizontal, or combinations thereof. 术语“管道柱”是指适于放置和运输流体到井眼的任何管道,包括但不限于油管、工作管柱、钻管、螺旋油管等。 The term "tubing string" refers to any conduit suitable for placement and transportation of fluids into the wellbore, including but not limited to, tubing, work string, drill pipe, coil tubing and the like. 此外,应理解本发明公开的益处在于所公开的转向剂和转向处理技术适用于任何类型的井处理流体,包括但不限于酸处理、凝结水处理、水力压裂处理等。 Further, it should be understood that the benefits of the invention disclosed in the steering agents disclosed steering and processing techniques are applicable to any type of well treatment fluid including, but not limited to acid treatment, condensate treatment, hydraulic fracturing treatment. 此外,应理解所公开的方法和组合物的益处可由在地层的压裂压力处、在压裂压力下或压裂压力以上进行的井处理实现。 Moreover, it should be understood that the benefits of the disclosed methods and compositions may be in the fracturing pressure of the formation, the well treatment performed above the fracture pressure or fracture pressure of at implemented.

[0070] 第一:井眼用途:在本发明的这个方面中,公开了在井眼中完全水溶性的颗粒(例如胶原蛋白或其他水溶性聚合物塑料或其混合物)使流体流动自一个区域转向到另一区域的用途,完全水溶性的颗粒随后溶解。 [0070] First: wellbore Use: In this aspect of the present invention, discloses a fully water-soluble particles (such as collagen or other water soluble polymer plastics or mixtures thereof) in the wellbore fluid to flow from a region of the deflection the use of another region, completely water-soluble particles are then dissolved. 胶原蛋白(呈未交联形式和交联形式)和可溶性塑料可用于使流体的流动在井中转向。 Collagen (in the form of uncrosslinked and crosslinked form) and soluble plastics can be used to turn the flow of fluid in the well. 这类转向材料应在1-100网目尺寸,优选4-50网目尺寸的范围内且可与其他添加剂或塑料材料组合使用以通过使流体的流动从一个区域转向到另一区域来提高性能。 Such materials should be turned and may be used by the flow of fluid diverted from a region to another to improve the performance of other additives in combination with a plastic material or in the range of 1-100 mesh size, preferably 4-50 mesh size .

[0071] 这些材料已用作转向堵塞球,但近来试验展示这种材料可用作转向剂以阻挡流体流进一个区域和流进另一孔隙压力较高或渗透性较低的区域。 [0071] These materials have been used as diverting ball clogging, but recently such a material may be used as the test shows diverting agent to block fluid flow into a higher region and further flows into the pore pressure or lower permeability region.

[0072] 本发明提供了一种处理下套管井眼以使流体的流动从一个区域转向到另一区域的方法。 [0072] The present invention provides a wellbore casing such that the flow of processing fluid from one region to the steering method of another region. 该方法涉及将转向流体泵送入井眼中,该转向流体由具有分散于其中的微粒形式的水溶性聚合物的含水载液构成,其中微粒聚合物的密度大于或小于载液的密度。 The method involves steering fluid pumped into the wellbore, the fluid steering aqueous carrier liquid consists of water-soluble polymer having dispersed therein in particulate form, wherein the density of the polymer particles is greater or less than the density of the carrier liquid. 在转向流体被泵送入井眼中时,微粒聚合物沉降到井眼区域,由此使处理流体的流动从一个区域转向到另一区域。 When steering fluid is pumped into the wellbore, the polymer particles settle to the wellbore region, thereby turning the flow of process fluid from one region to another. 通常,使处理流体转向或阻挡其流进孔隙压力较高或渗透性较低的区域中。 Typically, the process or barrier fluid which flows into the steering higher pore pressure or lower permeability region.

[0073] 在本发明关于井眼使用的方法中,水溶性微粒聚合物为胶原蛋白、聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇、聚内酯、聚丙烯酸酯、胶乳、聚酯、元素周期表第I或II族(碱金属或碱土金属)的硅酸盐聚合物或其混合物。 [0073] In the method of using the wellbore on the present invention, the water-soluble particulate polymer is collagen, poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate / polyvinylalcohol, polylactone, polyacrylate, latex, polyester, group I or II of the periodic table (alkali metal or alkaline earth metal) silicate polymers or mixtures thereof. 通常,存在于载液中的微粒聚合物的量为约O. 001磅/加仑到约10磅/加仑载液。 Typically, the amount of particulate polymer present in the carrier liquid is from about O. 001 lb / gal to about 10 lb / gallon of carrier fluid. 有利的是微粒聚合物具有大于或小于载液密度的不同密度。 Advantageously the particulate polymer having different densities greater or less than the density of the carrier liquid. 通常,载液为水、盐水、酸水溶液或胶凝酸溶液。 Typically, the carrier liquid is water, brine, aqueous acid solutions, or gelled acid.

[0074] 第二:产生的裂缝用途:在本发明的这个方面中,可将采用涂覆颗粒的各种支撑剂(涂覆有完全可溶性胶原蛋白或聚合塑料材料或可溶性与不可溶胶原蛋白或聚合塑料材料的混合物)泵送入压裂地层中以防止裂缝从生产区中转向。 [0074] Second: the use of cracks generated: In this aspect of the present invention, the proppant may be coated using a variety of particles (coated with a totally soluble collagen or polymeric plastic material, or a soluble protein or with a non-collagenolytic polymeric plastics material mixture) was pumped into the fracture to prevent the fracture from the formation from the production zone shift. 例如,具有可溶性或部分可溶性涂层的致密烧结铝矾土颗粒将降落到裂缝底部且使裂缝从较低岩层或含水区中转向。 For example, a dense sintered bauxite particle with a soluble or partially soluble coating would fall to the bottom of the fracture and that the crack diverted from the lower strata or a water zone. 同样,具有可溶性或部分可溶性涂层的低密度胡桃壳将在裂缝内上升以使裂缝从向上生长转向到含气体或含水区。 Similarly, soluble or partially soluble coating having a low density walnut shell will rise so that the fracture from upward growth into a gas-containing or aqueous steering within the fracture zone. 涂层可具有完全或部分可溶性,因为支撑剂将保持置于裂缝中且在压裂作业完成之后在裂缝中提供传导性。 Coating can have a fully or partially soluble since the proppant will remain placed in the fracture and provide conductivity in the fracture after the fracturing operation is completed. 支撑剂上的一些涂层应可以溶解,但有利的是可溶性与不可溶性塑料或胶原蛋白的混合物以防止支撑剂在裂缝中移动。 Some coatings on proppant can be dissolved, but advantageously is a mixture of soluble and insoluble plastics or collagen to prevent movement in the fracture proppant.

[0075] 在裂缝中使用的转向剂为用可溶性或部分可溶性涂层(使用胶原蛋白和/或聚合塑料涂层材料或这些材料的任何混合物)涂覆的支撑剂。 [0075] The diverting agent for use in the fracture is coated with a soluble or partially soluble (the collagen and / or polymeric plastic coating material or any mixture of these materials) coated proppant. 通过使用这些在作为初始裂缝的限定边界的支撑剂上的可溶性涂层而使裂缝转向。 By turning the crack using these soluble coatings on proppants as the defining boundaries of the initial fracture of. 压裂处理之后,涂层将消失且先前涂覆的颗粒将恢复为正常的支撑剂,其具有高渗透性。 After the fracturing treatment, the coating would disappear and the previously coated particles would return to normal proppant, which has a high permeability. 多种密度支撑剂上的涂层能在压裂过程初期产生裂缝边界,因为低粘度流体将使高密度涂覆的支撑剂沉降或降落在裂缝内,以得到较低的裂缝边界并使裂缝从井眼中转向,从而使裂缝变长且增加井的生产力。 More coatings on the initial density of the proppant can boundary cracks during fracturing, because a high density low viscosity fluid would coated proppant settling within the fracture or land, to give a lower boundary fracture and crack from steering a wellbore, the fracture becomes long and thereby increase the productivity of the well. 同样,低密度涂覆的支撑剂将上升到生长裂缝的上部以形成顶部边界,并使生长裂缝转向远离可损害井生产的上部区域。 Similarly, a low density coated proppant fracture growth will rise to the upper portion to form a top border, and the upper region remote from the steering crack growth can impair well production. 在顶部和底部含有裂缝的情况下,裂缝能向外生长且所含的较长裂缝将提高井的潜在生产力。 In the case where the top and bottom containing cracks, fracture can grow outward and a longer contained fracture would improve the well potential productivity.

[0076] 图I说明将根据本发明公开的一个实施方案进行处理的具有垂直下套管井眼段和单个井段地层的井。 [0076] FIG. I illustrates the well will be a vertical cased wellbore section and a single interval formation process according to an embodiment of the present disclosure. 图I的井10具有从井头11延伸其至少一部分长度的套管12,在外部用水泥护层14粘合以就地固定套管12,隔离渗透的地层或井段。 FIG 10 is well I have at least part of the length of the cannula which extends from the wellhead 11 12, the adhesive in the outer sleeve 12 is fixed in situ, or isolated permeable formation interval 14 by cement sheath. 水泥护层14在套管12之外与井眼内壁之间的环状空间中,自井眼底部向上延伸到至少高于生产岩层/含烃类地层18处。 Cement sheath 14 in the annular space between the inner wall of the eye outside the well casing 12, extending upwardly from the bottom of the borehole to at least above the production formation / 18 hydrocarbon containing formation. 包括这种护层的原因有许多,但主要是水泥护层14有助于保证井眼的完整性(即,因此其不坍陷)或隔离具体不同的地质区(即,隔离含油区与(不合需要的)出水区)。 Such reasons include many protective layer, but mainly the cement sheath 14 helps to ensure the integrity of the wellbore (i.e., so it does not collapse), or isolated from different geological regions specific (i.e., the oil isolation region (sub required) water area). 井眼任选还装备有套管或衬管鞋16,以便帮助引导套管柱12在其置于井眼中期间越过岩礁或阻碍物。 Optionally further equipped with a wellbore casing or liner shoe 16, to help guide the casing string 12 past the obstruction during rocks or placed in the wellbore. 对于在生产岩层18中有待生产的烃类来说,必须在生产岩层18与套管12内部之间建立流体通道。 For the production formation 18 to be produced hydrocarbons, the fluid channel must be established between the production formation 18 and the interior of the sleeve 12. 这通过借助本领域的技术人员已知的工具钻透套管12和水泥护层14的孔眼15实现。 This is achieved by means of perforations skilled in the art known tools 12 to drill through the casing and cement sheath 14 to 15 achieved. 这类工具包括但不限于射孔枪、聚能射孔弹装置(shapedcharge device)和phase charge装置,例如美国专利第6,755,249号、第5,095,099号和第5,816,343号中所述的那些装置;水平定向射孔体系(HOPS),例如那些由Owen Oil Tubes, Inc. (Ft. Worth,TX)制造的体系;机械射孔装置,例如可横向移动的打眼器(美国专利第2,482,913号)、针刺射孔器和齿轮射孔器(例如美国专利第4,220,201号描述的那些射孔器);和剪切塞(例如美国专利第4,498,543号中所述者)。 Such tools include, but are not limited to, perforation guns, shaped charge means (shapedcharge device) and phase charge devices, for example, U.S. Pat. Nos. 6,755,249, 5,095,099 and No. 5,816, those in the apparatus 343; horizontally-oriented perforating system (HOPS), such as those system consisting Owen Oil Tubes Inc. (Ft Worth, TX.) manufactured; mechanical perforation means, for example laterally displaceable drilling device (U.S. Pat. No. 2,482,913), and the gear needle perforating gun perforating gun (such as those perforator U.S. Patent No. 4,220,201 described above); and shear Qiese (e.g. U.S. Pat. No. 4,498,543 the person). 孔眼15形成流体自地层流到套管12和从套管12流到地层的路径。 Aperture 15 formed in the formation fluid from the flow path of the sleeve 12 and the sleeve 12 flows from the formation.

[0077] 从生产岩层18通过孔眼15流出且流进套管12内部的烃类可通过生产油管20运输到地面。 [0077] produced from the formation 18 flows through the perforations 15 and the interior of the sleeve 12 into the hydrocarbon fluid through the production tubing may be 20 to ground transportation. 生产封隔器22可任选安装在生产油管20的下端附近且在最高孔眼15以上,以便实现生产油管20与套管12之间的压力密封。 Production packer 22 can be optionally mounted in the vicinity of the lower end of the production tubing 20 and above the highest aperture 15, 20 and the production tubing in order to achieve a pressure seal between the sleeve 12. 根据本发明,任选且同样可接受地,并非必须使用生产油管20,而在这样的情况下,套管12的全部体积均被用来引导烃类至陆地表面。 According to the present invention, and likewise optionally an acceptable manner, not essential to use the production tubing 20, and in this case, the entire volume of the sleeve 12 are for guiding the hydrocarbons to the land surface.

[0078] 在井处理操作期间需要转向时,使用高比重支撑转向剂26a和/或低比重支撑转向剂26b(两者都主要用本发明的可溶性涂层涂覆)(即具有含胶原蛋白的涂层)基本密封生产岩层18的上下段。 [0078] if desired well treatment during a steering operation, using a high specific gravity steering support 26a and / or the low specific gravity of the proppant diverting agents 26b (both soluble primary coating applied by the present invention) (i.e., having a collagen-containing coating) substantially sealed upper and lower sections of the producing strata 18. 当在处理期间在预定时间将暂时转向剂26a和/或26b引入套管12中时,存在这种基本密封或边界地层。 When the steering temporarily during processing at a predetermined time agents 26a and / or 26b are introduced into the casing 12, or the presence of such substantially sealed boundary formation. 当将转向剂26a和/或26b引入套管12的射孔部分的流体上游时,其通过处理流体24流动运载流下生产油管20或套管12。 When the diverting agents 26a and / or 26b introducing fluid upstream portion 12 of the casing perforation, by the processing flow of the fluid stream 24 carrying the production tubing 20 or casing 12. 一旦处理流体24到达套管中的有孔井段,其将从孔眼15表面流过,并流进待处理的岩层18中。 Once the processing fluid 24 reaches the sleeve hole interval, which flows through the perforations 15 from the surface, and into the formation to be treated 18. 流经孔眼15的处理流体24运载暂时转向剂26a和/或26b经过孔眼且进入岩层18中。 Treatment fluid flowing through the perforations 24 carries the temporary diverting agents 15, 26a and / or 26b through the perforations and into the formation 18. 此时,密度大于处理流体24的高比重支撑转向剂26a沉降到人工裂缝的底部(如箭头所示),在裂缝和例如砂粒、页岩或粘土层19或其他区域(需要自生产岩层封堵)之间形成暂时的“下边界”。 At this time, the processing fluid 24 is greater than the density of the high specific gravity support diverting agents 26a settle to the bottom of the created fracture (as indicated by an arrow), and cracks 19 or other areas such as sand, shale or clay layer (from the production formation requires closure forming a temporary "lower border" between). 同样,密度小于处理流体24的低比重支撑转向剂26a上升到人工裂缝的顶部(如箭头所示),由此在裂缝和不合需要的层(例如页岩或岩层的粘土层)之间形成另一暂时的“上边界”。 Similarly, low specific gravity and density is less than the process fluid diverting agents 26a of the support 24 rises to the top of the created fracture (as indicated by an arrow), thereby forming a crack and the other between the layers (e.g. clay or shale formations) undesirable a temporary "on the border."

[0079] 图2说明本发明的这个方面的下一步。 [0079] Figure 2 illustrates the next step of this aspect of the present invention. 一旦暂时转向剂26a和26b分别落在人工裂缝的顶部和/或底部,含有规则支撑剂颗粒28的处理流体24的流体流动速率和粘度就会增加。 Once the temporary diverting agents 26a and 26b, respectively, falls on top of the created fracture and / or bottom, containing proppant particles Rule 28 of the treatment fluid flow rate and viscosity of the fluid 24 will increase. 以这种方式,裂缝能远离井眼(沿箭头方向)向外生长,在这种情况下,裂缝的总长度增加,因此有助于增加井的增产和/或寿命。 In this manner, the fracture can be remote from the wellbore (direction of arrow) outgrowth, in this case, the total length of the cracks increases, and thus contribute to increased yield and / or life of the well. 在完成井处理的情况下,暂时转向剂26a和26b上的可溶性涂层将溶解,让剩余支撑剂颗粒与处理流体24 —起经孔眼15除去,或保留且在支撑打开裂缝岩层的过程中充当另外的支撑剂。 In the case where the completion of the well treatment, the soluble coating on the temporary steering agents 26a and 26b will dissolve, allowing the remaining proppant particles treated with fluid 24 - Process removed from 15 via perforations, or retained and open a fracture in the formation of the support act as Further proppant.

[0080] 图3说明本发明的另一个实施方案。 [0080] Figure 3 illustrates another embodiment of the present invention. 与图I所示类似,井50具有垂直套管井眼和水泥护层56,其中所述垂直套管井眼具有从井头52延伸至少一部分井眼长度的套管54,所述水泥护层56在套管54外部和井眼内壁之间的环状空间中自井眼底部向上延伸到至少高于现有岩层处。 Similar to that shown in Fig. I, a vertical well 50 having a wellbore casing and cement sheath 56, wherein said vertical wellbore casing extends from a wellhead 52 having a length of at least a portion of the well casing 54, the cement sheath 56 an annular space between an inner wall of the eye 54 and the outer casing from the bottom of the well borehole extends upwardly to at least higher than the prior formation. 在井眼的裸眼井段内暴露的是具有多个处理井段58、60和62的地层。 Exposed at the open hole wellbore formation has a plurality of processing sections 58, 60 and 62 wells. 虽然在图3中说明了3个单独的井段,但是应理解本发明公开的益处在于可使用本发明公开的方法和组合物处理从两个处理井段到许多个处理井段的任何数量的井段。 Although described three separate well section in FIG. 3, it should be understood that the benefits of the present invention may be used is that disclosed methods and compositions of the present invention disclosed handle any number from two to a plurality of processing the processing interval of the interval Well section. 此外,应理解这些处理井段可连续布置而并非一定是由相对不可渗透区域(例如页岩夹层)分隔。 Moreover, it should be understood that these sections may be continuously arranged in the treatment well and are not necessarily separated by relatively impermeable areas (e.g. shales). 虽然图3说明了完全下套管的井眼,但是还应理解所公开的处理方法可用于几乎所有类型的井眼整体情形。 While Figure 3 illustrates a fully cased wellbore, it should be understood that disclosed treatment methods may be used for the entire wellbore almost all types of situations. 例如,所公开的方法可有利地用于处理以下井结构,包括但不限于垂直井眼、完全下套管井眼、水平井眼、具有多底井的井眼和共用这些特征的一个或多个的井眼。 For example, the disclosed methods may be advantageously used to treat the well structure, including but not limited to a vertical wellbore, the wellbore is completely horizontal wellbore casing, a bottom having a plurality of wells and wellbores sharing one or more of these features wellbore. [0081] 在图3中,处理井段58、60和62代表已确定处理的地层的确定井段。 [0081] In FIG. 3, the processing sections 58, 60 and 62 represents the well interval to determine the formation process has been determined. 在这点上,可如此确定存在于地层中的许多井段或仅仅其一部分。 In this regard, a number of thus determined may be present in the formation interval or only a portion thereof. 或者,这类井段还可代表下套管井眼中的有孔井段。 Alternatively, cased hole wellbore interval may be the interval representative of this type. 如图3所示,孔眼66由本领域已知的工具延伸通过套管54和水泥护层56,在这种情况下形成流体从地层流到套管54和从套管54流到地层的路径。 3, perforations 66 known in the art means extending through the casing 54 and cement sheath 56, formed from a formation fluid flow path of the sleeve 54 and the sleeve 54 flows from the formation in this case.

[0082] 从处理井段58、60和62中的生产岩层18通过孔眼66流出且流进套管内部的烃类可通过生产油管64运输到地面。 [0082] from the processing sections 58, 60 and 62 in the well production formation 18 through the perforations 66 and the effluent flows into the interior of the sleeve may be a hydrocarbon production tubing 64 to the ground through the transport. 此外,如图3所说明,生产封隔器68可任选安装在基本接近生产油管64的下端且在最高孔眼66以上,以便实现生产油管64与套管54之间的压力密封。 Further, as illustrated in FIG. 3, a production packer 68 can be optionally installed substantially near the lower end of the production tubing 64 and perforations 66 above the highest, in order to achieve a pressure between the production tubing 64 and casing 54 sealed. 并非总是需要使用生产油管64,在这样的情况下,套管54的全部内部体积被用来引导烃类至地面至井头52。 It is not always necessary to use the production tubing 64, in this case, all of the internal volume of the casing 54 is used to guide the hydrocarbons to the surface to wellhead 52.

[0083] 在井处理期间需要转向时,使用转向剂72基本密封一些孔眼66。 When the [0083] need to move during a well treatment, diverting agents 72 using a number of perforations 66 is substantially sealed. 在通过孔眼66的流量显著降低时发生基本密封,通常由转向剂72阻挡一个或多个孔眼66所引起的井底压力的增加所指示。 Sealing occurs at substantially significantly reduced flow through the aperture 66, increasing the bottomhole pressure barrier typically one or more apertures 66 caused by the diverting agents 72 indicated. 根据本发明的这个方面,转向剂72优选主要呈球形,不过可使用其他几何形状。 According to this aspect of the present invention, diverting agents 72 preferably predominantly spherical, but other geometries may be used. 使用本发明的转向剂72堵塞一些孔眼66通过在处理期间在预定时间将转向剂72引入套管12来实现。 Using diverting agents 72 of the present invention is blocked by a number of apertures 66 during the turning treatment agent introduced into the sleeve 72 12 is achieved at a predetermined time. 当将转向剂72引入套管12的有孔部分¢6)的流体上游时,其靠流动压裂流体70运载流下生产油管64或套管12。 When the steering fluid agent into the sleeve 12 ¢. 6 upstream hole portion) 72, which is carried by the flow of fracturing fluid 70 flows down the production tubing 64 or casing 12. 一旦压裂流体70到达套管中的有孔井段,其将从孔眼66的表面流过,并流进待处理的处理井段58、60和62中。 Once the fracture fluid 70 in the sleeve reaches the hole interval, from the surface of the aperture 66 flows, and flows into the processing interval to be processed 58, 60 and 62. 流经孔眼66的压裂流体70向孔眼66运载转向剂72,使转向剂72落在孔眼66上。 Fracturing fluid flowing through the eyelet 66 to the eyelet 70 of the carrier 66 diverter 72, 72 falls on the aperture 66 of the upper steering agent. 一旦落在孔眼66上,转向剂72就由套管54的内侧和套管54外侧的处理井段58、60和62之间存在的流体压差固定在孔眼66上。 Once he landed eyelet 66, diverting agents 72 of the fluid pressure differential exists between the inner sleeve 58, 60 and 54, 62 and 54 outside the processing interval casing is fixed to the eyelet 66. 当转向剂72落在孔眼66上时,转向剂72的尺寸优选基本密封孔眼66。 When the diverting agents 72 falls on the aperture 66, the size of the steering agent 72 preferably substantially sealing the aperture 66. 因此,坐落的转向剂72用以有效封闭那些孔眼66,直到压差反转且转向剂释放或转向剂72由于其环境改变(例如引入水)而经一段时间溶解。 Thus, the diverter 72 is located for effectively closing those perforations 66 until pressure is released or reversed and the diverting agents diverter 72 changes due to its environment (e.g., the introduction of water) was dissolved over a period of time.

[0084] 转向剂72将首先密封压裂流体70最快速流过的孔眼66。 [0084] The diverting agents 72 will first fracture fluid 70 sealed fastest flowing through perforations 66. 优先封闭高流速孔眼66以平衡处理整个有孔井段上的处理井段58、60和62。 Priority blocking high flow rate perforations 66 has to process the entire balance in the process interval hole sections 58, 60 and 62 wells. 为使转向剂72最有效地落在孔眼66上,在井下有孔区域的温度和压力条件下,转向剂72的密度应小于井眼内处理流体70的密度。 In order to most effectively diverting agent 72 falls on the aperture 66, with a downhole temperature and pressure conditions at the hole region, the steering agents 72 should be less than the density of the density of the process fluid within the wellbore 70. 通常,且根据本发明的这个方面,转向剂72应至少具有由胶原蛋白或胶原蛋白混合物组成的相当大的外表面。 Typically, and in accordance with this aspect of the present invention, diverting agents 72 should have at least a substantial outer surface of the collagen or collagen protein mixtures thereof. 在修井或井处理期间所需的转向剂72的数量取决于单井的客观情况和特征以及待使用的增产处理,且可由本领域的技术人员确定。 Required during workover or well treatment depends diverter number of individual wells 72 and objective conditions wherein stimulation treatment to be used as well, and is determined by one skilled in the art.

[0085] 在实施所公开的方法的过程中,所使用的适于实现使流体转向到已确定的处理井段的转向剂或介质为本发明的转向剂,其包含微粒基体和缓慢溶于水的胶原蛋白外层。 [0085] In the course of the method disclosed in the embodiments, adapted to be used to divert the fluid to achieve steering or medium for the determined processing interval diverting agent of the present invention, microparticles comprising water soluble base and slow collagen layer. 在一个实施方案中,可使用这种含胶原蛋白转向体系的中性浮力变体,以便降低转向剂和微粒转向剂载液离析的机会。 In one embodiment, can be used neutrally buoyant variation of this collagen-containing steering system, in order to reduce opportunities for steering and a fine particulate diverting agent carrier fluid isolated. “中性浮力”转向体系为以下体系,其中微粒转向剂悬浮在具有产生混合物的足够封闭密度或特定重力的载液中,并且在静止条件下转向剂的固体组分在体系中基本上不沉降或上升。 "Neutral buoyancy" steering system, the following system, wherein the particulate diverting agent is suspended in a carrier liquid to produce a mixture having a sufficient density or specific gravity of the closure, and the diverting agent in the solid component under substantially static conditions do not settle in the system or rise. 这类离析可引起(例如)转向剂在井眼中的一个或多个位置堆积和管道柱停留(sticking)在井眼段内。 Such segregation can cause (e.g.) diverting agents in a wellbore or a plurality of stacking positions and dwell tubing string (sticking) within the wellbore section. 此外,由于转向剂移动远离待处理的并段,所以离析可引起转向作用丧失。 Further, since the diverter and moved away from the segment to be treated, so that segregation can cause loss of steering action. 中性浮力转向体系在高度倾斜或水平井中可具有特殊优势,其中由于例如转向剂在井眼的高度倾斜或水平段中向上或向下迁移,非中性浮力转向体系的重力离析可能妨碍有效堵塞或降低暴露于井眼中的地层面整个圆周的渗透性。 Neutral buoyancy steering system highly deviated or horizontal wellbore may have special advantages, since, for example, downward migration of diverting agent upwards or in a highly inclined or horizontal wellbore sections, gravity segregation of a non-neutrally buoyant steering system may prevent efficient blockage in or exposure to reduce the permeability of the wellbore to the level of the entire circumference.

[0086] 可使用的转向剂包括单独或与任何适于使后续处理流体转向到具有较低注入能力的井段中的转向剂(例如油溶性、酸溶性等)组合的具有缓慢溶于水的外涂层的本发明转向剂。 [0086] which may be used alone or in combination with a steering agents include any means suitable for subsequent processing into the fluid steering interval having a lower injectability steering agents (e.g., oil soluble, acid soluble, etc.) in combination with a slow water-soluble the present invention is a steering overcoat agent. 本发明的一种合适的转向剂为基本上为胶原蛋白的转向剂。 Suitable one inventive agent is substantially steering collagen diverting agents. 可与本发明的转向剂组合的合适转向剂的实例包括但不限于苯甲酸薄片、腊(例如自BJ Services购得的"Divert VI”)、水泥级黑浙青或硬浙青、聚合物(包括但不限于天然聚合物,例如瓜尔胶;或合成聚合物,例如聚丙烯酸酯)、石盐等。 Examples of suitable diverting agent may be combined with the diverting agent of the present invention include, but are not limited to benzoic acid flakes, wax (e.g., commercially available from BJ Services "Divert VI"), cement grade green or black Zhejiang Zhejiang green hard polymer ( including but not limited to, natural polymers such as guar gum; or synthetic polymers such as polyacrylate), rock salt. 可使用的其他类型的合适转向剂包括但不限于酸溶性转向剂,例如美国专利第3,353,874号描述的那些酸溶性转向剂;和酞酰亚胺颗粒,例如美国第4,444,264号中描述的那些酞酰亚胺颗粒。 May be used other types of suitable diverting agents include, but are not limited to, acid soluble diverting agents such as described in U.S. Patent No. 3,353,874, those acid soluble diverting agents; and phthalimide particles of e.g. U.S. 4,444, those phthalimide particles 264 described herein.

[0087] 在本发明的一个实施方案中,可使用具有适于形成中性浮力转向体系的任何类型的载液,包括天然或合成盐水(例如KCl水溶液等)和包括胶凝剂(例如普通或合成聚合物)或本领域已知的其他增重材料的载液。 [0087] In one embodiment of the present invention may be used with any type of carrier liquid to form a neutral buoyancy adapted to the steering system, including synthetic or natural brine (e.g., KCl aqueous solution) and comprises a gelling agent (e.g., normal or synthetic polymers) or other weighting liquid carrier materials known in the art. 水泥级黑浙青(亦称“Uintate”)为被压碎且分成多种尺寸的颗粒的天然品种的浙青。 Zhejiang cement grade black cyan (also known as "Uintate") is crushed and classified into various particle sizes Zhejiang natural green varieties. 这种转向剂组合物可在油井位置与用以分散黑浙青的经特定化学改性的新鲜水(例如含有约O. 05%-约1%湿润表面活性剂的水)和任选地用于调整密度和/或控制地层-粘土的增重剂(包括但不限于盐,例如KCl、NH4C1、NaCl、CaCl2等)和用于调整粘度和/或减小阻力的胶凝剂(聚合物,例如瓜尔胶、羟基丙基瓜尔胶、羧基甲基羟基丙基瓜尔胶、羧基甲基羟乙基纤维素、黄原胶、羧甲基纤维素等)混合。 This shift of fresh water in a composition may be dispersed through the well to a position with a specific chemical modification of black cyan Zhejiang (e.g. containing about O. 05% - to about 1% water wetting surfactant) and optionally with to adjust the density and / or controlling formation - clay weighting agent (including but not limited to salts, such as KCl, NH4C1, NaCl, CaCl2, etc.) for adjusting the viscosity and / or gelling agents reduce drag (polymer, such as guar gum, hydroxypropyl guar, carboxymethyl hydroxypropyl guar, carboxymethyl hydroxyethyl cellulose, xanthan gum, carboxymethyl cellulose, etc.) were mixed.

[0088] 本发明的转向剂优选以约O. 001磅/加仑到约10磅/加仑载液的浓度存在于载液中,但也可使用超出这个范围的浓度。 [0088] The diverting agent of the present invention is preferably from about O. 001 lb / gal to a concentration of about 10 lbs / gallon of the carrier liquid in the carrier liquid, the concentration may also be used beyond this range. 转向剂的最优选浓度为约O. 01到约6磅/加仑载液。 The most preferred concentration is about diverting agent O. 01 to about 6 pounds / gallon of carrier fluid. 当以在油井位置处通常采用的载液体积使用时,小于约O. 001磅/加仑的转向剂浓度将不易堵塞地层。 When the volume of carrier liquid to the well at a position generally employed to use, less than about O. 001 lb / gal concentration of the steering clogging the formation. 在浓度小于0.001磅/加仑的情况下,将需要逐渐增大体积的载液以产生足够的地层堵塞。 At concentrations less than 0.001 lb / gal, you will need to gradually increase the volume of carrier liquid to generate sufficient formation plugging.

[0089] 大于约10磅/加仑的转向剂浓度不会明显地增加处理流体的转向,因此在实施本发明的过程中不特别合乎需要。 [0089] greater than about 10 lbs / gallon steering concentration does not significantly increase the fluid steering process, it is not particularly desirable in the practice of the present invention.

[0090] 载液通常由水、盐水、酸水溶液或胶凝酸溶液组成。 [0090] The carrier liquid is typically composed of water, brine, aqueous acid solutions, or gelled acid. 酸溶液可用纤维素、树胶、多糖、聚丙烯酰胺、烷氧基化脂肪胺及其混合物胶凝。 Acid solution may be cellulose, gums, polysaccharides, polyacrylamides, alkoxylated fatty amines and mixtures thereof gel.

[0091] 转向剂可在处理开始时加入载液中,在处理流体泵送入井眼时连续加入载液中,或可在处理期间不时地加入载液中。 [0091] The diverting agent may be added to the carrier liquid when the process is started, when the treatment fluid is pumped into the wellbore continuously added to the carrier liquid, or may be added to the carrier liquid from time to time during processing. 例如,在酸化过程中,可将转向剂连续加入酸化液中。 For example, in the acidification process, diverting agents may be added continuously acidified solution. 因此,转向剂将逐渐堵塞部分待处理地层,由此阻止酸仅流到渗透性最大的部分地层中的趋势,代之以产生均匀酸化的地层。 Thus, the diverting agent will progressively plug the formation parts to be treated, thereby preventing the acid to flow only trend permeable portion of the formation is the greatest, acidified instead produce a uniform formation. 当处理流体分段泵送时,第一阶段后面有大量由载液(通常含有桥堵剂的胶凝或乳化的水或酸)组成的转向材料。 When the process fluid pumping segment, after the first stage of a large steering liquid carrier material (generally contain bridging agent gelled or emulsified water or acid) composition. 转向剂封堵由第一阶段处理流体渗透的部分地层。 Diverter block processed by the first stage portion of the formation fluid permeable. 接着将第二阶段处理流体泵送入另一部分地层中。 The second stage of the treatment fluid is then pumped into another portion of the formation. 交替量的处理流体和转向材料可继续提供均匀酸化的地层。 The amount of treatment fluid and alternate materials may continue to provide a uniform steering acidified formation. 虽然对于压裂处理可使用在载液中连续引入转向剂的相同方法,但是通常在压裂操作期间将转向剂加入段塞中的载液中。 Although for fracturing treatment may be used in the same manner as in the carrier liquid is continuously introduced diverting agent, but is usually in the steering operation during the fracturing agent is added to the carrier in the slug liquid.

[0092] 已知压裂液优先流进最易于接受该液体的部分地层中。 [0092] Known fracturing fluid flows preferentially into the portion of the formation of the most receptive to liquid. 在这部分地层被压裂之后,可将桥堵剂加到压裂液中,从而其将堵塞地层的已压裂部分。 After this portion of the formation is fractured, the bridging agent may be added to the fracturing fluid, so that it will plug the already fractured portion of the formation. 因为压裂流体优先流进压裂区,因此其将运载桥堵剂。 Because the fracturing fluid is preferentially flowing into the fracture zone, so it will carry the bridging agent. 因此压裂区被堵塞且压裂流体转向到仍接受流体的地层的渗透性最大的部分中。 Thus fracturing the fracturing fluid region is blocked and still receive fluid diverted to the formation of the maximum permeability section.

[0093] 在本发明的一个方面中,可重复这种压裂和转向的方法以得到多个裂缝。 [0093] In one aspect of the present invention, a method of fracturing and this may be repeated to obtain a plurality of steering fractures. [0094] 可借助使转向剂升华或用产出流体使转向剂溶解而从地层中除去转向剂。 [0094] The agent may be by sublimation, or by steering of the steering output fluid diverting agent is dissolved is removed from the formation. 增加地层温度产生更大的转向剂溶解或升华速率。 Increasing the temperature of the formation of a greater steering dissolved or sublimation rate. 例如,已经发现在约250 °FT,大约80%重量的稍微溶于水的胶原蛋白在24小时内升华,而在300 °F下,约95%重量在24小时内升华,在约400 0F的温度下,约99%的稍微溶于水的胶原蛋白在约24小时内升华/溶解。 For example, it has been found that at about 250 ° FT, about 80% by weight of the slightly water-soluble collagen sublimates in 24 hours, while at 300 ° F, about 95% by weight sublimates in 24 hours, at about 400 0F to temperature, about 99% of the slightly water-soluble collagen sublimation / dissolution within about 24 hours. 由此可见转向剂的升华/溶解速率随地层温度增加而增加。 Thus diverting agent sublimation / dissolution rate increases with the temperature of the formation.

[0095] 包括以下实施例以说明本发明的优选实施方案。 [0095] The following examples are included to demonstrate preferred embodiments of the present invention. 本领域的技术人员应了解实施例中公开的技术仍代表本发明人所发现的在实施本发明中具有良好效果的技术,因此可认为这些技术构成实施本发明的优选方式。 Those skilled in the art will appreciate that embodiments disclosed in the examples representative of the present technology still has a good effect in the practice of the present invention found that these techniques can thus constitute preferred embodiments of the present invention. 然而,根据本发明,本领域的技术人员应了解,在不脱离本发明的范围的情况下可对所公开的具体实施方案进行许多改变,这些改变仍得到相似或类似的结果。 However, according to the present invention, those skilled in the art will appreciate that many changes may be made in the specific embodiments disclosed without departing from the scope of the present invention, these changes are still obtain a like or similar result.

[0096] 实施例 [0096] Example

[0097] 实施例I :预示件实施例 [0097] Example I: Example indicating member

[0098] 以下预示性实施例描述了本发明在支撑剂上的可溶性涂层可如何用于使裂缝生长转向且使裂缝延伸到油或气井的生产区中的方法。 [0098] The following prophetic example describes how the soluble coating on the proppant of the present invention may be used to crack growth and extending the steering to a method of producing oil or gas in the fracture zone. 可溶性涂覆的支撑剂的主要目的是在液压产生垂直裂缝中限定上下边界,从而使主要生长方向在远离井眼的长度方向上向外继续延伸。 The main purpose of the soluble coated proppant is a vertical hydraulic fracture in the upper and lower boundaries defined so that the main direction of growth continues to extend outward in the longitudinal direction away from the wellbore. 这种传导裂缝的额外长度有助于引流生产层的补充区,由于裂缝长度更长,让油、气和/或水回收生产力提高且得到更大的流速。 This additional length of the conductive fracture zone helps to replenish drainage layer is produced, due to the longer fracture length, so that the oil, gas and / or water recovery and improved productivity greater flow rate.

[0099] 使用本发明可溶性涂覆的支撑剂材料,可遵循以下步骤。 [0099] The use of soluble coated proppant materials of the present invention, the following steps may follow.

[0100] I.用低粘度压裂流体确定裂缝注入速率。 [0100] I. fracture injection rate is determined with a low viscosity fracturing fluid.

[0101] 2.可溶性涂覆的支撑剂(例如用交联的胶原蛋白涂覆的胡桃壳、用交联的胶原蛋白涂覆的铝矾土或两者的组合)在混合管处加入以形成压裂流体浆液。 [0101] 2. A soluble coated proppant (e.g. coated with collagen crosslinked walnut shells, or by a combination of both bauxite collagen-coated cross-linked) were added at the mixing tube to form fracturing fluid slurry.

[0102] 3.将含有可溶性涂覆的支撑剂的压裂流体泵送至井下。 [0102] 3. The fracturing fluid containing the soluble coated proppant is pumped downhole. 第一部分浆液进入接受大部分流体的初始裂纹中。 Receiving a first portion of the slurry enters the initial crack most fluid. 在这种情况下,由于使用在该流体中缓慢软化且溶胀的可溶性转向剂(例如胶原蛋白),浆液缓慢堵塞人工裂缝的边界。 In this case, since the slow swelling and softening in the fluid steering soluble agent (e.g. collagen), the slurry was slowly clogging artificial boundary fracture.

[0103] 4. 一旦流速在第一裂纹中变缓或明显降低,压力就会增大,直至另一流动路径、裂纹或区域开始接受含有可溶性涂覆的支撑剂的浆液。 [0103] 4. Once the flow rate slowed or decreased in the first crack, the pressure will increase, until another flow path, crack, or zone begins to accept the slurry containing the soluble coated proppant is.

[0104] 5.在裂缝的顶部和底部都需要含有可溶性涂覆的支撑剂的情况下,优选使用两种不同的支撑剂密度。 [0104] 5. In the case of the top and bottom of the fracture need containing the soluble coated proppant, preferably using two different proppant densities. 例如,将高密度铝矾土颗粒用可溶性胶原蛋白涂层涂覆,当其在裂缝中落到垂直人工裂缝的底部时其缓慢软化且溶涨。 For example, a high density bauxite particle is coated with a coating soluble collagen, that slowly softens when it falls vertical hydraulic fracture in the fracture and a bottom swelling. 为了使在垂直裂缝中向上生长变缓,将低密度的第二支撑剂(例如可溶性涂覆的胡桃壳)加入注入流体中。 In order to slow the growth upwards in the vertical fracture, a second proppant of low density (e.g., a soluble-coated walnut shells) in the injection fluid was added. 在注入流体进入地层中时,低密度可溶性材料涂覆的支撑剂在垂直裂缝中上升且减缓了使流体损耗和向上方向的生长。 , Low-density soluble material coated proppant rises and slows down fluid loss and growth in an upward direction perpendicular to the fracture during injection of fluid into the formation.

[0105] 6.在裂缝仍在高于压裂速率和压力下注入流体时,裂缝继续远离井眼生长且通过控制压裂流体的流速来维持控制裂缝生长。 [0105] 6. If the injection fluid in the fracture is still higher than the fracturing pressure and rate, the fracture continues to grow away from the wellbore by controlling the flow rate of the fracturing fluid and to maintain control of crack growth. 继续注入,直到规则的支撑剂装填裂缝,压力达到预定界限或直到注入总计划量。 Injection continues until the regular proppant filled fracture, pressure reaches a predetermined limit, or until the total planned amount of injection.

[0106] 7. 一旦顶部和底部生长均减小,则将标准不溶性涂覆的支撑剂(例如OttawaSand(20/40))、陶瓷或许多树脂涂覆的支撑剂)注入地层中。 [0106] 7. Once the top and bottom growth are reduced, then the insoluble standard coated proppants (e.g. OttawaSand (20/40)), or a plurality of resin-coated ceramic proppant) into the formation. 继续泵送直到全部数量的指定支撑剂处于人工裂缝中。 Pumping continued until all of the specified number of artificial proppant in the fracture. [0107] 8.关闭井且移除泵送设备。 [0107] 8. A closed well and pumping equipment is removed.

[0108] 9.使井恢复生产,且在地层中的水随时间而溶解支撑剂上的可溶性涂层时,胡桃壳或铝矾土上的可溶性胶原蛋白涂层被除去。 When [0108] 9. Allow the well to resume production, and the water in the formation dissolves the soluble coating over time on the proppant, soluble collagen coating on the walnut shell or bauxite is removed.

[0109] 实施例2 :确定聚合物的溶解速率和溶解度的方法 2 [0109] Example: The method of determining the rate of dissolution and the solubility of the polymer

[0110] 将砂粒基体用多种水溶性聚合物涂覆: [0110] The sand substrate coated with a plurality of water-soluble polymers:

[0111] [0111]

Figure CN101146888BD00181

[0112] 此后,使用以下试验方法确定溶解速率和溶解度: [0112] Thereafter, it is determined using the following test methods solubility and dissolution rate:

[0113] 用正规LOI方法确定砂粒上聚合物的总质量。 [0113] determining the total mass of the polymer on the sand by regular LOI method. 在I升水中加入500克涂覆的砂粒。 500 g of the coated grit in I liter of water. 取400mm滤纸且在分析天平上将其称重至小数点后4位。 Take 400mm filter paper and weighed in on an analytical balance to 4 decimal places. 通过使用400mm滤纸、有孔陶瓷漏斗、2升具有通过橡皮管与真空泵连接的侧孔的锥形烧瓶制备真空过滤装置。 By using 400mm filter paper, perforated ceramic funnel, 2 liters Preparation vacuum filtration apparatus having a conical flask with a vacuum pump through a side hole hose connection. 在每一分钟间隔之后通过400_滤纸过滤涂覆的砂粒和水浆。 After each minute intervals by 400 angstroms filter paper coated sand and water slurry. 须将“滤过”水中的涂覆砂粒加回滤纸上。 Shall "filtered" water is added back-coated sand on filter paper. 在过滤完成之后从有孔漏斗中移出滤纸,且通过将其保持在干燥器中使其干燥。 After the completion of the filter funnel was removed from the porous filter paper, and by holding and dried in a desiccator. 将滤纸称重。 The filters were weighed. 这为溶解的聚合物和滤纸的总重量,因此其应大于在将滤纸用于过滤过程之前滤纸的重量。 This total weight of the polymer and the filter paper dissolved, thus it should be greater than the weight of the filter paper before the filter paper for filtration. 通过使用以下公式计算被溶解聚合物的% : % Of the polymer is dissolved is calculated by using the following equation:

[0114] X = ((CB)/A)) XlOO [0114] X = ((CB) / A)) XlOO

[0115]其中, [0115] wherein,

[0116] X=被溶解聚合物的百分比 [0116] X = the percentage of dissolved polymer

[0117] A =在砂粒上的聚合物的质量(g) [0117] A = mass of the polymer on the sand grains (g)

[0118] B =在过滤过程之前滤纸的质量(g) [0118] B = mass of the filter paper before filtration (g)

[0119] C =在过滤过程之后滤纸的质量(g) [0119] C = mass of filter paper after filtration (g)

[0120] [0120]

Figure CN101146888BD00182

胶原蛋白I IWSRN750 Collagen I IWSRN750

胶原蛋白2 PLA6551-D Collagen 2 PLA6551-D

PLA5600 PLA5600

[0121] 这个试验方法的结果是:聚环氧乙烧(自Dow Chemical购得的WSR 80)在80 0F下在约300分钟内达到完全溶解,在150 °FT,其需要约180分钟,在200 °FT,其需要约90分钟。 [0121] The results of this test method is: burning polyethylene oxide (commercially available from Dow Chemical WSR 80) at 80 0F complete dissolution was achieved in about 300 minutes, at 150 ° FT, which requires about 180 minutes, 200 ° FT, which requires about 90 minutes.

[0122] 使用另一聚合物进行相同试验。 [0122] The same experiment using another polymer. 这些结果表明聚环氧丙烷聚合物(自DowChemicals购得的WSRN 750)在80 °F下在约390分钟内达到完全溶解,在150 °FT,其需要约320分钟,在200 0F下,其需要约245分钟达到完全溶解。 These results show that polypropylene oxide polymer (available from DowChemicals WSRN 750) to achieve complete dissolution at 80 ° F in about 390 minutes at 150 ° FT, which requires about 320 minutes at 200 0F, which requires about 245 minutes to reach complete dissolution.

[0123] 溶胀的聚合物在30分钟内展示100%的溶解度,但显微镜分析展示由于溶胀而不是溶解而保留在滤纸上。 [0123] swollen polymer showing a solubility of 100% in 30 minutes, but microscopic analysis shows instead of being dissolved and swelling due retained on the filter paper. 形成胶凝物质和砂粒/水浆体积显著增加表明聚合物溶胀而不是聚合物溶解。 Forming a gel substance and a sand / water slurry indicate a significant increase in the volume of polymer swelling instead of polymer dissolution.

[0124] 根据本发明公开,可制备或实施本文所公开和要求保护的所有组合物、方法和/或工艺,而无需过度的实验。 [0124] The present disclosure can be prepared or embodiments herein disclosed and claimed All of the compositions, methods and / or processes, without undue experimentation according to. 虽然已经根据优选实施方案描述了本发明的组合物和方法,但是本领域的技术人员应显而易见在不脱离本发明的原则和范围的情况下,可对本文所述的组合物、方法和/或工艺和方法的步骤或步骤的顺序施加各种变化。 While there have been described methods and compositions of the present invention according to preferred embodiments, those skilled in the art should be apparent without departing from the spirit and scope of the present invention, it may be of the compositions described herein, methods, and / or various changes applied to the sequence of steps or processes and methods. 更具体地讲,显然可用化学和生理学相关的某些试剂替代本文所述的试剂,而将实现相同或类似的结果。 More specifically, obviously chemically and physiologically usable certain agents substituted for the agents described herein while the same or similar results achieved. 认为所有这些对于本领域的技术人员显而易见的类似替代和修改都在本发明的范围和原则之内。 For all such apparent to those skilled in the art and similar substitutes and modifications are within the scope of the principles of the invention.

Claims (28)

1. 一种转向流体,所述转向流体用于通过将所述转向流体装入限定与处理井段流体连通的孔的井眼中来暂时密封处理井段的上下部分,所述转向流体包含(a)基本上由水组成的含水载液, (b)分散于所述含水载液中的第一转向剂微粒,所述第一转向剂微粒包含具有水溶性聚合物涂层的第一支撑微粒基体,所述第一转向剂微粒的密度大于所述含水载液的密度,所述转向流体含有足够的第一转向剂微粒以基本上密封处理井段的下面部分,和(C)分散于所述含水载液中的第二转向剂微粒,所述第二转向剂微粒包含具有水溶性聚合物涂层的第二支撑微粒基体,所述第二转向剂微粒的密度小于所述含水载液的密度,所述转向流体含有足够的第二转向剂微粒以基本上密封处理井段的上面部分。 1. A steering fluid, the fluid steering for steering a wellbore fluid charged with the aperture defined in fluid communication processing interval to temporarily seal the upper and lower part of the processing by the interval, the steering fluid comprises (a ) an aqueous carrier liquid essentially consisting of water, (b) in the aqueous dispersion of first particulate diverting agent carrier fluid, the particulate diverting agent comprising a first support a first water-soluble polymer having a particulate base coating the first steering agent particles a density greater than the density of the aqueous carrier liquid, said first steering fluids contain a sufficient steering agent particles to a substantially lower portion of the sealing treatment interval, and (C) dispersed in the the aqueous carrier liquid in the second steering agent particles, the second support comprises a second steering agent particles having a particulate water-soluble polymer base coating layer, the second steering agent particles density less than the density of the aqueous liquid carrier the second steering fluid contains sufficient steering agent particles to substantially seal the upper portion of the processing interval.
2.权利要求I的转向流体,其中所述第一转向剂微粒的密度足够大于所述载液的密度,致使从井眼装入处理井段的第一转向剂微粒可下沉到处理井段的底部,从而形成暂时的下边界,所述下边界基本上密封处理井段防止液体流过该下边界;并且其中所述第二转向剂微粒的密度足够小于所述载液的密度,致使从井眼装入处理井段的第二转向剂微粒可同时上升到处理井段的顶部,从而形成暂时的上边界,所述上边界在形成的同时基本上密封处理井段防止液体流过该上边界。 2. The steering fluid as claimed in claim I, wherein the density of the first steering agent particles is sufficiently greater than the density of the carrier liquid, so that charged particulate treatment agent first steering shaft section from the wellbore interval can be sunk into the process bottom, thereby forming a temporary lower boundary, the lower boundary interval is substantially sealed to prevent fluid flow through the lower boundary; and wherein the density of said second steering agent particles is sufficiently smaller than the density of the carrier liquid, resulting from load handling wellbore interval second steering agent particles can rise to the top while the processing interval to form a temporary upper boundary, the upper boundary is formed at the same interval substantially sealed to prevent the flow of liquid through the boundary.
3.权利要求2的转向流体,其中所述载液为水、盐水和酸水溶液和胶凝酸溶液中的至少一种。 Steering fluid of claim 2, wherein the carrier liquid is water, brine, and at least one acid and a gelling aqueous acid solution.
4.权利要求3的转向流体,其中所述第一转向剂微粒的支撑微粒基体选自二氧化硅支撑剂、密度大于含水载液密度的陶瓷支撑剂、金属支撑剂、大理石屑、石灰石屑、除大理石屑和石灰石屑之外的碳酸盐微粒以及它们的混合物,而所述第二转向剂微粒的支撑微粒基体选自密度小于含水载液密度的天然材料、密度小于含水载液密度的陶瓷支撑剂、塑料颗粒或珠、碳纤维、树脂聚结颗粒以及它们的混合物。 Steering fluid of claim 3, wherein said first steering particulate support matrix agent particles selected from silica proppant, a density greater than the density of the aqueous carrier liquid ceramic proppants, metallic proppants, chips of marble, limestone dust, in addition to limestone and marble chips particulate debris carbonates, and mixtures thereof, and supporting the second steering matrix microparticles agent particles is selected from a density less than the density of the aqueous carrier liquid natural material, a density less than the density of the aqueous carrier liquid ceramic proppant, plastic particles or beads, carbon fibers, the resin coalesced particles, and mixtures thereof.
5.权利要求4的转向流体,其中所述的天然材料选自坚果壳、果核及其混合物。 Steering fluid of claim 4, wherein said natural material is selected from nut shells, fruit pits, and mixtures thereof.
6.权利要求5的转向流体,其中第一转向剂微粒和第二转向剂微粒中的至少一种的支撑微粒基体为树脂涂覆的支撑剂。 Steering fluid of claim 5, wherein the first and second steering agent particles of at least one steering proppant particulate support matrix microparticles agent is a resin-coated.
7.权利要求6的转向流体,其中所述树脂涂覆的支撑剂被选自以下的至少一种水不溶性树脂涂覆:双酚均聚物、酚-醛聚合物、芳基酚聚合物、烷基酚聚合物、烷氧基酚聚合物、芳氧基酚聚合物、间苯二酚树脂、环氧树脂及蜡。 Steering fluid of claim 6, wherein said resin-coated proppant is selected from at least one water-insoluble resin coated: bisphenol homopolymer, a phenol - formaldehyde polymer, phenolic polymer aryl, alkylphenol polymer, a phenolic polymer alkoxy, aryloxy polymeric phenols, resorcinol resins, epoxy resins and waxes.
8.权利要求4的转向流体,其中在第一转向剂微粒和第二转向剂微粒上的水溶性聚合物涂层独立地选自包括去端肽胶原蛋白在内的胶原蛋白、植物蛋白、合成聚合物、碱金属硅酸盐聚合物和碱土金属硅酸盐聚合物。 Steering fluid of claim 4, wherein the water-soluble polymer coating on the first steering agent particles and the second particles are independently selected from the diverting agent comprising collagen atelocollagen including protein, vegetable protein, synthesized polymers, polymeric alkali metal silicate and alkaline earth metal silicate polymer.
9.权利要求8的转向流体,其中在第一转向剂微粒和第二转向剂微粒上的水溶性聚合物涂层为胶原蛋白。 9. A steering fluid as claimed in claim 8, wherein the water-soluble polymer coating on the first steering the steering agent and a second agent particles collagen microparticles.
10.权利要求9的转向流体,其中在第一转向剂微粒和第二转向剂微粒中的至少一种上的胶原蛋白涂层为交联的。 10. The steering fluid of claim 9, wherein the collagen coating on at least one first particle and the second diverter diverting agent microparticles are crosslinked.
11.权利要求2的转向流体,其中在第一转向剂微粒和第二转向剂微粒上的水溶性聚合物涂层独立地选自包括去端肽胶原蛋白在内的胶原蛋白、植物蛋白、合成聚合物、碱金属硅酸盐聚合物和碱土金属硅酸盐聚合物。 11. The steering fluid as claimed in claim 2, wherein the water-soluble polymer coating on the first steering agent particles and the second particles are independently selected from the diverting agent comprising collagen atelocollagen including protein, vegetable protein, synthesized polymers, polymeric alkali metal silicate and alkaline earth metal silicate polymer.
12.权利要求11的转向流体,其中在第一转向剂微粒和第二转向剂微粒上的水溶性聚合物涂层为胶原蛋白。 12. The steering fluid of claim 11, wherein the water-soluble polymer coating on the first steering the steering agent and a second agent particles collagen microparticles.
13.权利要求12的转向流体,其中在第一转向剂微粒和第二转向剂微粒中的至少一种上的胶原蛋白涂层为交联的。 Steering fluid of claim 12, wherein the collagen on at least one first and second steering steering agent particles in a coating agent particles is crosslinked.
14.权利要求7的转向流体,其中所述树脂涂覆的支撑剂被选自以下的至少一种树脂涂覆:可溶可熔酚醛聚合物树脂和可溶酚醛聚合物树脂。 14. A steering fluid as claimed in claim 7, wherein said at least one resin-coated resin-coated proppant is selected from the following: novolak resin and a resole polymer polymer resin.
15. 一种在压裂处理期间处理地层以便使地层增产的方法,所述方法包括: 将权利要求I的转向流体泵送入地层中; 使载液渗透到地层中以便运载转向材料到地层中;和使转向材料堵塞地层的多孔部分,因此使处理流体的流动转向到地层的渗透性低的部分中。 15. A method of treating a subterranean formation during fracturing treatment so as to increase the formation, the method comprising: I claim steering fluid pumped into the formation; carrier liquid to permeate into the formation in the carrier material is turned into the formation ; steering portion and the porous material clogging the formation, thus steering the flow of treatment fluid to the low permeability of the formation portion.
16.权利要求15的方法,其中地层的所述处理为压裂处理,且其中所述增产是由于裂缝长度的增加所致。 16. The method of claim 15, wherein said process is the formation fracturing treatment, and wherein said increase is due to increased fracture length caused.
17.权利要求15的方法,其中所述第一和第二转向剂的支撑微粒基体各自独立选自天然材料支撑剂、二氧化硅支撑剂、陶瓷支撑剂、金属支撑剂、合成有机支撑剂及其混合物。 17. The method of claim 15, wherein the base support particles first and second steering agent each independently selected proppant natural materials, silica proppants, ceramic proppants, metallic proppants, synthetic organic agents support mixtures thereof.
18.权利要求15的方法,其中至少一种转向剂的支撑微粒基体为树脂涂覆的支撑剂。 18. The method of claim 15, wherein the at least one particulate support matrix agent steering resin coated proppant.
19.权利要求15的方法,其中所述第一和第二转向剂的水溶性聚合物各自独立选自胶原蛋白、聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚内酯、聚丙烯酸酯、聚酯、碱金属的硅酸盐聚合物、碱土金属的硅酸盐聚合物及其混合物。 19. The method of claim 15, wherein said first and second steering agent is a water soluble polymer is independently selected from collagen, poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, poly vinyl alcohol, polylactone, polyacrylate, polyester, polymer alkali metal silicates, alkaline earth metal, silicate polymers and mixtures thereof.
20.权利要求15的方法,其中所述第一和第二转向剂的支撑微粒基体各自的粒径为3网目到200网目。 20. The method of claim 15, wherein the base support particles first and second diverter respective particle size of 3 mesh to 200 mesh.
21.权利要求15的方法,其中所述第一和第二转向剂的水溶性聚合物各自独立选自I型胶原蛋白、II型胶原蛋白、III型胶原蛋白、IV型胶原蛋白、V型胶原蛋白及其混合物。 21. The method of claim 15, wherein said first and second steering agent is a water soluble polymer is independently selected from type I collagen, type II collagen, type III collagen, IV collagen, V collagen protein and mixtures thereof.
22.权利要求21的方法,其中至少所述第一或第二转向剂的水溶性胶原蛋白采用选自醛、碳化二亚胺、异氰酸酯及酰基叠氮的交联剂进行交联。 22. The method of claim 21, wherein at least the first or the second steering agent soluble collagen employed is selected from an aldehyde, carbodiimide, isocyanate, acyl azide crosslinking agents and crosslinking.
23.权利要求15的方法,所述第一和第二转向剂中的至少一种还包括非水溶性聚合物。 23. The method of claim 15, said first and second diverter further comprising at least one non-water soluble polymer.
24.权利要求23的方法,其中所述非水溶性聚合物为可溶可熔酚醛聚合物和可溶酚醛聚合物。 24. The method of claim 23, wherein said water-insoluble polymer is a novolac polymer and a phenolic-soluble polymer.
25.权利要求15的方法,其中所述第一和第二转向剂中的至少一种中的水溶性聚合物为聚(亚烷基)氧化物、聚(乳酸)、聚乙酸乙烯酯、聚乙烯醇、聚乙酸乙烯酯/聚乙烯醇接枝聚合物或其混合物。 25. The method as claimed in claim 15, at least one water-soluble polymer wherein said first and second steering agent is a poly (alkylene) oxide, poly (lactic acid), polyvinyl acetate, poly vinyl alcohol, polyvinyl acetate / polyvinyl alcohol graft polymers, or mixtures thereof.
26.权利要求25的方法,其中所述聚(亚烷基)氧化物为聚环氧乙烷、聚环氧丙烷、聚(环氧乙烷)-聚(环氧丙烷)嵌段共聚物或其混合物。 Poly (propylene oxide) block copolymer, or - 25 Method of polypropylene oxide, poly (ethylene oxide) as claimed in claim 26, wherein said poly (alkylene) oxide is polyethylene oxide, mixtures thereof.
27.权利要求15的方法,其中存在于载液中的转向材料的量为O. 001磅/加仑到10磅/加仑载液。 27. The method of claim 15, wherein the amount of the steering material in the carrier liquid is O. 001 lb / gallon to 10 lb / gal carrier liquid.
28.权利要求15的方法,其中所述载液为水、盐水、酸水溶液或胶凝酸溶液。 28. The method of claim 15, wherein the carrier liquid is water, brine, aqueous acid solutions, or gelled acid.
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