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CN103073873A - Novel material pressure-out ball used in staged fracturing pitching slide sleeve opening - Google Patents

Novel material pressure-out ball used in staged fracturing pitching slide sleeve opening Download PDF

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Publication number
CN103073873A
CN103073873A CN2011103282519A CN201110328251A CN103073873A CN 103073873 A CN103073873 A CN 103073873A CN 2011103282519 A CN2011103282519 A CN 2011103282519A CN 201110328251 A CN201110328251 A CN 201110328251A CN 103073873 A CN103073873 A CN 103073873A
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pressure
ball
weight
new material
fracturing
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CN103073873B (en
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吴姬昊
姚辉前
尹慧博
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92561Time, e.g. start, termination, duration or interruption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92904Die; Nozzle zone

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

本发明为多级滑套分段压裂投球打开式滑套提供了一种以聚苯并咪唑、聚醚醚酮为主体材料的新材料憋压球。该憋压球的主要作用就是快速、可靠的实现憋压密封,从而打开投球滑套,实现压裂。它具有以下几个显著的特点:①以其密度低,其密度为1.5-1.6g/cm3,能够提高憋压球在水平状态下快速向前移动的能力,并且易于返排;②采用聚苯并咪唑、聚醚醚酮为主体的复合材料,具有较高的抗冲击强度,保证憋压球在前移的过程中磨损小,能够可靠的密封;③耐压能力强,试验表明在70MPa的高压下,无损伤;④节省了时间、降低了施工风险。The invention provides a new pressure-suppressing ball with polybenzimidazole and polyether ether ketone as the main materials for the multi-stage sliding sleeve segmental fracturing pitching open sliding sleeve. The main function of the pressure holding ball is to quickly and reliably realize pressure holding sealing, thereby opening the ball sliding sleeve and realizing fracturing. It has the following notable features: ①With its low density, its density is 1.5-1.6g/cm3, which can improve the ability of the pressure-holding ball to move forward quickly in a horizontal state, and it is easy to flow back; ②Using polystyrene The composite material with imidazole and polyetheretherketone as the main body has high impact strength, which ensures that the pressure holding ball has less wear and tear during the forward movement and can be reliably sealed; Under high pressure, there is no damage; ④ saves time and reduces construction risks.

Description

一种用于分段压裂投球滑套打开的新材料憋压球A new material pressure-suppressing ball for the opening of the staged fracturing pitching sleeve

技术领域 technical field

本发明涉及一种在水平井分段压裂技术中用于打开投球滑套的新材料憋压球,属石油勘探领域。The invention relates to a pressure-suppressing ball of a new material used for opening a ball-throwing sliding sleeve in the staged fracturing technology of a horizontal well, belonging to the field of petroleum exploration.

背景技术 Background technique

憋压球主要用于石油勘探开发领域水平井分段压裂技术中投球滑套的打开,具体使用过程如下:在施工过程中投入憋压球,泵送至压裂开关滑套上,并与滑套密封,以增大油管中的压力,直到与阀座起到密封憋压的作用,当压力升高,剪断剪钉,从而打开滑套,憋压球与滑套一起下行,关闭下部已压裂完成的油层,开始对上部油层实施压裂。现有的憋压球通常采用钢球或普通低密度球,在水平井进行压裂时采用钢球或普通低密度球存在如下缺陷:由于钢球密度大,在水平井中不易移动,同时由于钢球通常采用空心形式,由于钢制憋压球壁薄,在高压作用下易变形,变形后球与阀座不易密封且密封不可靠;而普通低密度球的抗冲击能力差,在液流的冲击下易磨损破碎,同样也不能实现可靠密封。The pressure holding ball is mainly used to open the ball sliding sleeve in the staged fracturing technology of horizontal wells in the field of petroleum exploration and development. The sliding sleeve is sealed to increase the pressure in the oil pipe until it is sealed with the valve seat and holds the pressure. When the pressure rises, the shear nail is cut to open the sliding sleeve, and the pressure holding ball goes down together with the sliding sleeve to close the lower part. After fracturing the oil layer, start fracturing the upper oil layer. Existing pressure-holding balls usually use steel balls or ordinary low-density balls. When using steel balls or ordinary low-density balls for fracturing in horizontal wells, there are the following defects: due to the high density of steel balls, they are not easy to move in horizontal wells; The ball usually adopts a hollow form. Because the wall of the steel pressure-holding ball is thin, it is easy to deform under high pressure. After deformation, the ball and the valve seat are not easy to seal and the seal is not reliable; It is easy to wear and break under impact, and it cannot achieve reliable sealing.

发明内容 Contents of the invention

本发明的目的在于解决上述现有技术中存在的难题,提供一种用于分段压裂投球滑套打开的新材料憋压球具有抗冲击、耐压、密度低和易于顶替到位的优点,能快速到达指定阀座,与阀座形成有效密封,顺利打开滑套,为水平井分段压裂投球滑套的打开提供有效的技术保障。为投球滑套提供了一种密度低、耐冲击、耐压,且易于推动能够实现可靠密封的新材料憋压球。The purpose of the present invention is to solve the problems existing in the above-mentioned prior art, and to provide a pressure-suppressing ball of a new material used for opening the segmental fracturing pitching sleeve, which has the advantages of impact resistance, pressure resistance, low density and easy replacement in place. It can quickly reach the designated valve seat, form an effective seal with the valve seat, and open the sliding sleeve smoothly, providing effective technical support for the opening of the sliding sleeve for staged fracturing of horizontal wells. A low-density, impact-resistant, pressure-resistant, and easy-to-push new material pressure-suppressing ball that can achieve reliable sealing is provided for the pitching sleeve.

本发明一种用于分段压裂投球滑套打开的新材料憋压球,制备该憋压球的新材料的配比如下:聚苯并咪唑(PBI)35.2-37.8%(重量),聚醚醚酮(PEEK)37.8-39.5%(重量),酚醛树脂13.4-15.2%(重量),碳纤维4.0-6.0%(重量),碳素纳米管0.9-1.5%(重量),填充料0.4-1.0%(重量),聚乙烯0-3.2%(重量)。所述的填充料(胶结剂)为酚醛-环氧胶结剂。The present invention is a new material pressure-suppressing ball used for segmental fracturing pitching sliding sleeve opening, and the proportion of the new material for preparing the pressure-suppressing ball is as follows: polybenzimidazole (PBI) 35.2-37.8% (weight), poly Ether ether ketone (PEEK) 37.8-39.5% (weight), phenolic resin 13.4-15.2% (weight), carbon fiber 4.0-6.0% (weight), carbon nanotube 0.9-1.5% (weight), filler 0.4-1.0 % (weight), polyethylene 0-3.2% (weight). The filler (bonding agent) is a phenolic-epoxy cementing agent.

本发明一种用于分段压裂投球滑套打开的新材料憋压球的制备方法,采用注射成型或挤出成型的方法;所述的注射成型方法采用螺杆式注塑机或柱塞式注塑机加工成型,注塑机须满足的条件为:①料筒要能升温至400~500℃;②料筒内没有熔料死角;③喷嘴不需要加断流阀;④模具温度应保持在160~200℃或任选将得到的注射成型制品在200℃热处理1h;The invention discloses a preparation method of a pressure-suppressing ball of a new material used for segmental fracturing pitching sleeve opening, which adopts injection molding or extrusion molding; the injection molding method adopts a screw type injection molding machine or a plunger type injection molding For machining molding, the injection molding machine must meet the following conditions: ①The barrel must be able to heat up to 400-500°C; ②There is no dead corner of molten material in the barrel; ③The nozzle does not need to add a shut-off valve; ④The mold temperature should be kept at 160-500°C; 200°C or optionally heat-treat the obtained injection molded product at 200°C for 1 hour;

所述的挤出成型方法中组成憋压球新材料的主要组分聚苯并咪唑、聚醚醚酮的热稳定性好,在加工过程中易形成凝胶,导致形成砂砾状表面,在挤出薄片过程中采用2层38μm(400目)不锈钢网筛,对形成的凝胶进行有效地分离;同时为降低制品的表面粗糙度,所使用模具的模口温度应保持在(380±2)℃。In the extrusion molding method described above, polybenzimidazole and polyetheretherketone, which are the main components of the new pressure-suppressing ball material, have good thermal stability and tend to form gels during processing, resulting in the formation of a gravel-like surface. Two layers of 38μm (400 mesh) stainless steel mesh sieves are used to effectively separate the formed gel during the flake-out process; at the same time, in order to reduce the surface roughness of the product, the die temperature of the mold used should be kept at (380±2) ℃.

由于该新材料主体材料为聚苯并咪唑、聚醚醚酮都属于工程塑料,根据其性能特点可采用下列制备成形方法:Since the main material of this new material is polybenzimidazole and polyether ether ketone, both of which are engineering plastics, the following preparation and forming methods can be adopted according to their performance characteristics:

(1)注射成型:采用螺杆式或柱塞式注塑机加工成型,注塑机须满足的条件为:①料筒可升温至400--500℃;②料筒内没有熔料死角。由于PBI,PEEK熔体粘度高,不会自动流淌,所以喷嘴不需要加断流阀。为确保PBI,PEEK具有良好的注塑特性及在成型过程中形成高度结晶,注射成型时,模具温度应保持在160~200℃。这样即使不再对聚苯并咪唑、聚醚醚酮制品进行热处理也能得到性能很好的制品。如模具温度无法达到要求,可将制品在200℃热处理1h。(1) Injection molding: It is processed by a screw type or plunger type injection molding machine. The conditions that the injection molding machine must meet are: ①The barrel can be heated to 400--500°C; ②There is no dead angle of molten material in the barrel. Due to the high viscosity of PBI and PEEK melt, it will not flow automatically, so the nozzle does not need to add a stop valve. In order to ensure PBI, PEEK has good injection molding properties and forms a high degree of crystallization during the molding process. During injection molding, the mold temperature should be kept at 160-200 °C. In this way, products with good performance can be obtained even if the polybenzimidazole and polyetheretherketone products are no longer subjected to heat treatment. If the mold temperature cannot meet the requirements, the product can be heat treated at 200°C for 1 hour.

(2)挤出成型:聚苯并咪唑、聚醚醚酮的热稳定性非常好,但在加工过程中会形成凝胶,导致形成砂砾状表面。网筛可以有效地分离这些凝胶,在挤出薄片时应使用2层38μm(400目)不锈钢网筛。为降低制品的表面粗糙度,模口温度应维持在(380±2)℃。(2) Extrusion molding: polybenzimidazole and polyether ether ketone have very good thermal stability, but gel will form during processing, resulting in the formation of a gritty surface. Mesh screens can effectively separate these gels, and two layers of 38 μm (400 mesh) stainless steel mesh screens should be used when extruding flakes. In order to reduce the surface roughness of the product, the die temperature should be maintained at (380±2)°C.

与现有技术相比,本发明的有益效果是:Compared with prior art, the beneficial effect of the present invention is:

1)本发明新材料憋压球的密度低:密度在1.5-1.6/cm3之间,在相同流量的液流冲击下,以其低密度,质量轻的优点能够提高憋压球在水平状态下向前移动的能力,在压裂完成后,因其密度低也易于返排,这样节省了时间、降低了施工风险。1) The density of the pressure-suppressing ball of the new material of the present invention is low: the density is between 1.5-1.6/cm 3 , under the impact of the liquid flow of the same flow rate, the advantage of its low density and light weight can improve the pressure-suffocating ball in a horizontal state. After the fracturing is completed, it is easy to flow back due to its low density, which saves time and reduces construction risks.

2)本发明新材料憋压球的刚性高、韧性好,耐压能力高,抗冲击强度高:在高压作用下不易变形,试验表明在70MPa的高压下,本发明憋压球无损伤;能够承受在高压作用下的冲击,保证憋压球在前移的过程中磨损小、不易破碎,可以实现安全可靠的密封。2) The pressure holding ball of the new material of the present invention has high rigidity, good toughness, high pressure resistance, and high impact strength: it is not easily deformed under high pressure, and the test shows that the pressure holding ball of the present invention has no damage under the high pressure of 70MPa; it can Withstand the impact under high pressure to ensure that the pressure holding ball has little wear and is not easy to break during the forward movement process, and can realize safe and reliable sealing.

3)本发明新材料憋压球具有优良的耐摩擦和耐磨损性能:在液流的作用下长距离前行时,不会因不断的冲击碰撞而磨损,从而实现了与憋压座的有效密封。3) The pressure holding ball of the new material of the present invention has excellent friction resistance and wear resistance: when it travels a long distance under the action of the liquid flow, it will not be worn due to continuous impact and collision, thus realizing the connection with the pressure holding seat Effective seal.

4)本发明所用新材料的加工性能较好:可挤出和压力注塑,且成型效率较高,同时易于切削成形。4) The new material used in the present invention has better processing performance: it can be extruded and pressure-injected, and the molding efficiency is high, and it is easy to cut and shape.

具体实施方式 Detailed ways

下面对本发明作进一步详细描述:The present invention is described in further detail below:

实施例Example

本发明的憋压球采用的新材料的组分配比,剩余组分为聚乙烯。分别如表1所示。The composition ratio of the new material used in the pressure holding ball of the present invention is that the remaining components are polyethylene. They are shown in Table 1 respectively.

表1Table 1

本发明憋压球的工作原理为:在施工过程中通过投球器投入新材料低密度憋压球,并泵送至压裂投球滑套上,并与阀座密封,增大油管中压力,直到与阀座密封起到憋压的作用,当压力升高,剪断剪钉,从而打开滑套,憋压球与滑套一起下行,关闭下部已压开油层,开始压裂。待压裂完成后,将憋压球随压裂液返排,完成压裂作业。The working principle of the pressure-suppressing ball of the present invention is as follows: during the construction process, a low-density pressure-suppressing ball of new material is put into the ball feeder, and pumped to the fracturing ball sliding sleeve, and sealed with the valve seat to increase the pressure in the oil pipe until The seal with the valve seat plays the role of pressure suppression. When the pressure rises, the shear pin is cut to open the sliding sleeve, and the pressure holding ball and the sliding sleeve go down together, closing the lower part to open the oil layer, and fracturing begins. After the fracturing is completed, the pressure holding ball is flowed back with the fracturing fluid to complete the fracturing operation.

试验测试结果:Experimental test results:

Figure BDA0000102083790000041
Figure BDA0000102083790000041

与现有空心钢球相比试验效果对比Compared with the existing hollow steel ball, the test effect comparison

Figure BDA0000102083790000042
Figure BDA0000102083790000042

对比两种憋压球试验结果,本发明新材料憋压球具有密度低,在液压力作用下快速达到工作位置,并易于返排;同时其具有较高的抗压能力,在最高工作压力70MPa时,无磨损、无变形,密封可靠。Comparing the test results of the two pressure-holding balls, the new material pressure-holding ball of the present invention has low density, can quickly reach the working position under the action of hydraulic pressure, and is easy to flow back; at the same time, it has high compression resistance, and the maximum working pressure is 70MPa , no wear, no deformation, and reliable sealing.

本发明的低密度憋压球自研制以来,已经完成样件的加工和地面试验,各项技术参数均与设计相符。随着非常规油气资源开采力度的加大,开采页岩气和低渗透产层的定向井、水平井的压裂增产改造也越来越多,而多级滑套分段压裂工具是油气层多级压裂改造的关键技术,投球滑套的打开与否,憋压球能否顺利到位,都直接关系着水平井的多级压裂改造的顺利进行。本发明的低密度球以其特有的优势解决了定向井、水平井分段压裂改造中的难题,降低了风险,节约了成本,具有巨大的推广应用前景。Since the development of the low-density pressure-suffocating ball of the present invention, sample processing and ground tests have been completed, and all technical parameters are consistent with the design. With the increasing exploitation of unconventional oil and gas resources, more and more directional wells and horizontal wells are used for fracturing and stimulation in shale gas and low-permeability production layers. The key technology of multi-stage fracturing, whether the ball sliding sleeve is opened or not, and whether the pressure-holding ball can be put in place are all directly related to the smooth progress of multi-stage fracturing of horizontal wells. The low-density ball of the present invention solves the difficult problems in staged fracturing reconstruction of directional wells and horizontal wells with its unique advantages, reduces risks, saves costs, and has great prospects for popularization and application.

上述技术方案只是本发明的一种实施方式,对于本领域内的技术人员而言,在本发明公开了应用方法和原理的基础上,很容易做出各种类型的改进或变形,而不仅限于本发明上述具体实施方式所描述的方法,因此前面描述的方式只是优选的,而并不具有限制性的意义。The above-mentioned technical solution is only an embodiment of the present invention. For those skilled in the art, on the basis of the application methods and principles disclosed in the present invention, it is easy to make various types of improvements or deformations, and is not limited to The methods described in the above specific embodiments of the present invention, therefore, the above-described methods are only preferred and not limiting.

Claims (4)

1.一种用于分段压裂投球滑套打开的新材料憋压球,其特征在于,制备该憋压球的新材料的配比如下:聚苯并咪唑35.2-37.8%(重量),聚醚醚酮37.8-39.5%(重量),酚醛树脂13.4-15.2%(重量),碳纤维4.0-6.0%(重量),碳素纳米管0.9-1.5%(重量),填充料0.4-1.0%(重量),聚乙烯0-3.2%(重量)。1. A new material pressure-suppressing ball for segmental fracturing pitching sliding sleeve to open, it is characterized in that, the proportioning of the new material of preparing this pressure-suffocating ball is as follows: polybenzimidazole 35.2-37.8% (weight), Polyether ether ketone 37.8-39.5% (weight), phenolic resin 13.4-15.2% (weight), carbon fiber 4.0-6.0% (weight), carbon nanotube 0.9-1.5% (weight), filler 0.4-1.0% ( weight), polyethylene 0-3.2% (weight). 2.根据权利要求1所述的用于分段压裂投球滑套打开的新材料憋压球,其特征在于,制备该憋压球的新材料,其中的填充料为酚醛-环氧胶结剂。2. The new material pressure-holding ball for the opening of the staged fracturing pitching sleeve according to claim 1, characterized in that, the new material of the pressure-holding ball is prepared, and the filler therein is a phenolic-epoxy cement . 3.权利要求1-2之一用于分段压裂投球滑套打开的新材料憋压球的制备方法,其特征在于,采用注射成型或挤出成型的方法;所述的注射成型方法采用螺杆式注塑机或柱塞式注塑机加工成型,注塑机须满足的条件为:①料筒要能升温至400~500℃;②料筒内没有熔料死角;③喷嘴不需要加断流阀;④模具温度应保持在160~200℃或任选将得到的注射成型制品在200℃热处理1h;3. one of claim 1-2 is used for the preparation method of the new material holding back pressure ball that segmental fracturing pitching sleeve is opened, is characterized in that, adopts the method for injection molding or extrusion molding; Described injection molding method adopts Screw type injection molding machine or plunger type injection molding machine processing molding, the injection molding machine must meet the following conditions: ① barrel must be able to heat up to 400 ~ 500 ℃; ② there is no dead corner of molten material in the barrel; ③ nozzle does not need to add a shut-off valve ; ④ The mold temperature should be kept at 160-200°C or optionally heat-treat the obtained injection molded product at 200°C for 1 hour; 所述的挤出成型方法中组成憋压球新材料的主要组分聚苯并咪唑、聚醚醚酮的热稳定性好,在加工过程中易形成凝胶,导致形成砂砾状表面,在挤出薄片过程中采用2层38μm(400目)不锈钢网筛,对形成的凝胶进行有效地分离;同时为降低制品的表面粗糙度,所使用模具的模口温度应保持在(380±2)℃。In the extrusion molding method described above, polybenzimidazole and polyetheretherketone, which are the main components of the new pressure-suppressing ball material, have good thermal stability and tend to form gels during processing, resulting in the formation of a gravel-like surface. Two layers of 38μm (400 mesh) stainless steel mesh sieves are used to effectively separate the formed gel during the flake-out process; at the same time, in order to reduce the surface roughness of the product, the die temperature of the mold used should be kept at (380±2) ℃. 4.权利要求1-2之一用于分段压裂投球滑套打开的新材料憋压球在水平井分段压裂技术中的应用。4. The application of the new material pressure-holding ball used for opening the staged fracturing ball sliding sleeve according to one of claims 1-2 in the staged fracturing technology of horizontal wells.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096833A (en) * 2014-07-09 2014-10-15 徐梓辰 Dissoluble metal material for downhole construction
CN105134155A (en) * 2015-08-11 2015-12-09 苏州固韧纳米材料技术有限公司 Fracturing ball of double-layer structure used for fracturing oil and gas well and preparation method thereof

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CN1898753A (en) * 2003-09-30 2007-01-17 通用电气公司 Electrically conductive compositions, methods of manufacture thereof and articles derived from such compositions
CN101194324A (en) * 2005-06-10 2008-06-04 通用电气公司 Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom

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US5139863A (en) * 1989-04-13 1992-08-18 Hoechst Celanese Corporation Molded polybenzimidazole/polyaryleneketone articles and method of manufacture
CN1898753A (en) * 2003-09-30 2007-01-17 通用电气公司 Electrically conductive compositions, methods of manufacture thereof and articles derived from such compositions
CN101194324A (en) * 2005-06-10 2008-06-04 通用电气公司 Thermoplastic long fiber composites, methods of manufacture thereof and articles derived therefrom

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096833A (en) * 2014-07-09 2014-10-15 徐梓辰 Dissoluble metal material for downhole construction
CN105134155A (en) * 2015-08-11 2015-12-09 苏州固韧纳米材料技术有限公司 Fracturing ball of double-layer structure used for fracturing oil and gas well and preparation method thereof
CN105134155B (en) * 2015-08-11 2018-01-12 苏州固韧纳米材料技术有限公司 Double-decker well fracturing pressure break ball and preparation method thereof

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