WO2018157615A1 - 一种低密度、高强度、可降解暂堵剂及其制备方法与应用 - Google Patents

一种低密度、高强度、可降解暂堵剂及其制备方法与应用 Download PDF

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WO2018157615A1
WO2018157615A1 PCT/CN2017/108470 CN2017108470W WO2018157615A1 WO 2018157615 A1 WO2018157615 A1 WO 2018157615A1 CN 2017108470 W CN2017108470 W CN 2017108470W WO 2018157615 A1 WO2018157615 A1 WO 2018157615A1
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agent
temporary
blocking agent
temporary blocking
starch
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French (fr)
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吕宝强
慕立俊
赵振峰
陆红军
卜向前
齐银
李建山
赵伯平
李向平
李建辉
杨立安
卜军
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose

Definitions

  • the invention relates to a low-density, high-strength, degradable temporary plugging agent, a preparation method and application thereof, and belongs to the technical field of oilfield chemical engineering.
  • Temporary plugging and fracturing technology is to add temporary plugging agent in the fracturing process, temporarily block the old seam or the sand crack, and turn the fluid through the change of the cracking pressure and the crack extension pressure to create a new seam.
  • the temporary plugging agent and its action principle in the crack are: the internal steering material developed based on the principle of the bridge of the granular material.
  • the solid particle size of the temporary plugging agent When it is larger than 1/3-2/3 of the dynamic width of the crack, the solid particles of the temporary plugging agent will form a bridge at this place, and block the road of the subsequent temporary plugging agent particles to form a pile, and continue to join with the subsequent temporary plugging agent.
  • More and more temporary blocking agent particles are generated and bridged, and a certain thickness and length of the blocking zone is formed in the main channel of the crack, which hinders and limits the continued extension and development of the crack, and the crack volume between the wellbore and the plugging zone Subsequently, the continued addition of the sand-carrying fluid continues, and the net pressure of the crack increases continuously. When the net pressure in the crack reaches the micro-crack opening pressure or the new seam breaking pressure, the micro-crack or new seam will open, with the subsequent sand-carrying liquid. Continue to join, micro cracks or new seams will extend and expand into new branch cracks.
  • the Chinese Patent Application No. 201610227808.2 discloses a temporary plugging agent and a preparation method thereof.
  • the temporary plugging agent forms a filter cake in contact with water to prevent the liquid from flowing to the oil layer.
  • the crude oil can dissolve the filter cake plugging agent to restore the oil layer.
  • the permeability of the plugging agent is used in oil well sandblasting construction operations.
  • the blocking agent component is mainly composed of a modified oil-soluble resin, a crosslinking agent and a temperature-resistant salt ultra-high molecular weight polymer.
  • Chinese patent CN103409121A discloses a water-soluble fracturing steering temporary blocking agent, which is composed of plant starch, a high polymer, a swelling agent and a curing agent, wherein the plant starch is high.
  • the mass ratio of the polymer, the expansion agent and the curing agent was 4.5:3.5:0.5:1.5.
  • the temporary plugging mode is to determine the breakthrough pressure by forming a filter cake in the water by a plugging agent.
  • Cisoka patent CN102653673A discloses a biodegradable temporary plugging agent, which is lowered by biological a composition of a decomposing agent, an organic swelling material and a thickener, wherein the biodegrading agent is a mixture of particles of soybean and corn in an amount of 60-85% by weight, and the weight ratio of soybean to corn in the mixture of particles
  • the particle size is from 1:2 to 2:1, and the particle size is from 2 to 3 times the particle size of the sand.
  • the traditional temporary plugging and fracturing in this field is mainly based on the filter cake plugging mode in which the plugging agent forms the filter cake in the crack, which provides a low density and high strength for enriching the temporary plugging mode of temporary plugging and fracturing.
  • the degradable temporary blocking agent and its preparation method and application have become technical problems to be solved in the field.
  • the object of the present invention is to provide a low density, high strength, degradable temporary blocking agent, and a preparation method and application thereof.
  • the present invention provides a low-density, high-strength, degradable temporary blocking agent, which comprises 60% by weight to 85% by weight of polylactic acid, and 5% by weight, based on the total weight of the temporary blocking agent. 20 wt% starch, 5 wt%-10 wt% polycaprolactone, 2 wt%-5 wt% solubilizer, 2 wt%-5 wt% toughening agent.
  • the weight ratio of the starch to the polycaprolactone is from 1:1 to 2:1.
  • the polylactic acid in the temporary plugging agent, preferably, has a molecular weight of 900 to 11 million, a melting point of 175 ° C, and a tensile strength of more than 70 MPa.
  • the starch is a soluble starch.
  • the soluble starch comprises one or a combination of corn starch, rice starch, millet starch, tapioca starch and potato starch.
  • the toughening agent comprises styrene-butadiene rubber, polybutylene succinate, polybutylene adipate, chitin and One of chitosan.
  • the styrene-butadiene rubber used is an industrial grade product, which can increase the toughness of the temporary plugging agent product under pressure.
  • the solubilizing agent comprises one of glycerin, water, polyvinyl alcohol, polyethylene glycol, and tetrabutyl titanate.
  • glycerin is an industrial grade product, which is a solubilizing agent when polylactic acid, starch, polycaprolactone and styrene-butadiene rubber are blended.
  • the temporary plugging agent particles have a particle size of from 1 to 4 mm.
  • the particle size of the temporary plugging agent particles can be selected according to the difference of the dynamic crack width of the target well.
  • the temporary plugging agent particles have a density of from 1.1 to 1.3 g/cm 3 and a compressive strength of greater than 52 MPa.
  • the invention also provides a preparation method of the temporary plugging agent, which comprises the following steps:
  • the polylactic acid, the solubilizing agent, the toughening agent, the starch and the polycaprolactone are blended, and then extruded to obtain the temporary plugging agent.
  • the preparation method specifically comprises the steps of: blending polylactic acid, a solubilizing agent, a toughening agent, a starch and a polycaprolactone to obtain a mixture; and then injecting the mixture into the double Extruding the screw extruder to obtain the temporary plugging agent;
  • the twin-screw extruder has an extrusion temperature of 140-160 ° C and a screw rotation speed of 100-300 r/min.
  • the order of adding the raw materials polylactic acid, solubilizing agent, toughening agent, starch and polycaprolactone is not specifically required.
  • the invention also provides the application of the temporary plugging agent in the temporary plugging and fracturing of oil wells or gas wells.
  • the specific preparation process of the temporary plugging agent is: in the blending materials of polylactic acid, starch, solubilizer, polycaprolactone and toughening agent, the polylactic acid is a continuous mother phase, and the starch is smaller in size and cost.
  • the most important problem in the blending system of polylactic acid and starch is that the interface bonding force between the hydrophobic polylactic acid and the hydrophilic starch is too weak, that is, the compatibility between the two is poor, therefore, the improved blending compound
  • the material compatibility method is to introduce a third phase solubilizing agent to reduce the interface energy, promote diffusion, and improve the adhesion between the polylactic acid and the starch; and the polycaprolactone used is a biodegradable polymer, and the degradation rate thereof Slower, polycaprolactone combined with starch can regulate the degradation rate of the temporary plugging system.
  • the temperature of the reservoir of the oil field is between 30 and 90 °C.
  • the degrading process of the temporary plugging agent provided by the invention is: the temporary plugging agent absorbs and swells under the formation temperature, loses the mechanical strength, increases with time, and finally degrades into water and carbon dioxide.
  • the temporary blocking agent provided by the invention has the following technical effects:
  • the low-density, high-strength, degradable temporary plugging agent provided by the invention is a rigid temporary plugging agent, which can form a bridge in the existing crack, and the temporary plugging and boosting is obvious; according to SY/T5108-2006 "Fracturing"
  • the proppant performance index and the test recommendation method are tested on the temporary plugging agent provided by the invention, and the test results show that:
  • the temporary plugging agent has a density (30 ° C) of 1.1-1.3 g/cm 3 and a bearing strength of more than 52 MPa; it loses mechanical strength within 48 hours under reservoir temperature conditions, and the final degradation time is 168 hours (60 ° C anaerobic) Natural degradation); suitable temperature 30 ° C to 90 ° C reservoir
  • the preparation method of the temporary plugging agent is simple, the process requirement is low, and industrial production can be realized.
  • the temporary plugging agent provided by the invention is applied to temporary plugging and fracturing, under the condition of formation, it can be completely degraded within a certain period of time, does not cause secondary damage to the reservoir, and can avoid the temporary plugging agent to the formation pollution and The occurrence of a card pump accident.
  • FIG. 2 is a construction curve diagram of a G123-162 oil well in an application example of the present invention.
  • the present embodiment provides a low-density, high-strength, degradable temporary blocking agent, wherein the temporary blocking agent comprises 60% by weight of polylactic acid and 20% by weight of corn starch, based on 100% by weight of the total weight of the temporary blocking agent. , 10 wt% of polycaprolactone, 5 wt% of glycerin, 5 wt% of styrene butadiene rubber;
  • the above temporary plugging agent is prepared by the following steps:
  • the temperature setting 1 area is 140 ° C
  • the 2 area is 155 ° C
  • the 3 area is 160 ° C
  • the 4 area is 160 ° C
  • the 5 area is 155 ° C
  • the screw rotation speed is 100 r / min; extrusion molding, the temporary plugging agent is obtained.
  • the embodiment provides a low-density, high-strength, degradable temporary blocking agent, wherein the temporary blocking agent comprises 75 wt% of polylactic acid and 11 wt% of rice starch, based on 100 wt% of the total weight of the temporary plugging agent. , 8 wt% of polycaprolactone, 4 wt% of water, 2 wt% of polybutylene succinate;
  • the above temporary plugging agent is prepared by the following steps:
  • the present embodiment provides a low-density, high-strength, degradable temporary blocking agent, wherein the temporary blocking agent comprises 85 wt% of polylactic acid and 5 wt% of millet starch, based on 100 wt% of the total weight of the temporary plugging agent. , 5 wt% of polycaprolactone, 2.5 wt% of polyvinyl alcohol, 2.5 wt% of polybutylene adipate;
  • the above temporary plugging agent is prepared by the following steps:
  • the present embodiment provides a low-density, high-strength, degradable temporary blocking agent, wherein the temporary blocking agent comprises 81% by weight of polylactic acid and 10% by weight of tapioca starch, based on 100% by weight of the total weight of the temporary blocking agent. , 5 wt% of polycaprolactone, 2 wt% of polyethylene glycol, 2 wt% of chitin;
  • the above temporary plugging agent is prepared by the following steps:
  • the present embodiment provides a low-density, high-strength, degradable temporary blocking agent, wherein the temporary blocking agent comprises 65 wt% of polylactic acid and 15 wt% of potato starch, based on 100 wt% of the total weight of the temporary plugging agent. 10 wt% of polycaprolactone, 5 wt% of tetrabutyl titanate, 5 wt% of chitosan;
  • the above temporary plugging agent is prepared by the following steps:
  • the low-density, high-strength, degradable temporary plugging agent obtained in Example 1-5 was tested by SY/T5108-2006 "Fracturing proppant performance index and test recommendation method", and the test results show that the present invention provides the temporary
  • the blocking agent has the following characteristics:
  • the plugging agent loses mechanical strength within 48 hours under the condition of reservoir temperature, and the final degradation time is 168 hours (60 ° C anaerobic natural degradation);
  • This application example provides the application of the temporary blocking agent in the temporary plugging and fracturing of the oil well in Changqing Oilfield, which includes the following steps:
  • Test well 1 G125-164, temporary plugging agent filling conditions: construction displacement is 2.0m 3 /min, sand ratio is 227kg/m 3 , and temporary plugging agent (Example 1) is 150kg, temporarily blocked The agent addition speed is 20-50kg/min; the G125-164 oil well construction curve is shown in Figure 1. It can be seen from Figure 1 that after the temporary plugging agent perforation hole, the wellhead construction pressure is raised from 28MPa to 40MPa. It has risen by 12 MPa (after the temporary plugging agent is used to pass through the perforation, it accumulates in the cracks in the formation, and the static pressure causes the static pressure to rise). From the pressure rise, it can be judged that there is a crack in the process.
  • test well 2 test well 2, G123-162, temporary plugging agent filling conditions: construction displacement is 2.0m 3 /min, sand ratio is 180kg / m 3 , plus temporary blocking agent (Example 1) amount is 200kg, temporary blocking The agent addition speed is 20-50kg/min.
  • the construction curve of the G123-162 oil well is shown in Figure 2. It can be seen from Figure 2 that after the temporary plugging agent perforation hole, the wellhead construction pressure rises from 34.5MPa to 37.5. MPa, increased by 3MPa.
  • the temporary plugging agent was used to complete the field test of 13 wells in Changqing Oilfield.
  • the test results show that the single well production increased from 0.97t to 2.62t in the initial stage of the measure, and the average daily oil increase of the single well was 1.65t.
  • the current effective rate is 92.3%
  • the cumulative oil increase is 2331.11 tons.

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Abstract

本发明提供一种低密度、高强度、可降解暂堵剂及其制备方法与应用。以该暂堵剂的总重量为100wt％计，其包括60wt％-85wt％的聚乳酸，5wt％-20wt％的淀粉，5wt％-10wt％的聚己内酯，2wt％-5wt％的增溶剂，2wt％-5wt％的增韧剂。本发明所提供的该暂堵剂为一种刚性暂堵剂，其能在已有裂缝中形成桥堵，暂堵升压明显。同时，该暂堵剂的制备方法简单，工艺要求低，可以实现工业化生产。将本发明所提供的暂堵剂应用于暂堵压裂，在地层条件下，一定时间内，其可完全降解，不会对储层造成二次伤害，并可避免暂堵剂对地层污染及卡泵事故的发生。

Description

一种低密度、高强度、可降解暂堵剂及其制备方法与应用 技术领域
本发明涉及一种低密度、高强度、可降解暂堵剂及其制备方法与应用，属于油田化工技术领域。
背景技术
暂堵压裂技术是在压裂过程中实时加入暂堵剂，暂堵老缝或已加砂裂缝，通过破裂压力、裂缝延伸压力的变化使流体发生转向，从而造出新缝。暂堵剂及其在裂缝内的作用原理是：以颗粒材料桥堵原理为依据开发的缝内转向材料，在重复压裂施工中加入暂堵剂后，由于水力压裂裂缝在井筒附近动态缝宽最大，距离井越远裂缝宽度越来越小，当暂堵剂和支撑剂同时以一定比例进入压裂裂缝后，在支撑剂和暂堵剂的共同作用下，暂堵剂固体颗粒粒径大于裂缝动态宽度的1/3-2/3时，暂堵剂固体颗粒就会在该处形成桥堵，并挡住后续暂堵剂颗粒前进的道路形成堆积，随着后续暂堵剂的继续加入，产生桥堵和堆积的暂堵剂颗粒越来越多，在裂缝主通道形成一定厚度和长度的堵塞带，阻碍和限制了裂缝的继续延伸和发展，处于井筒和堵塞带之间的裂缝体积随后续携砂液的继续加入，裂缝净压力不断升高，当裂缝内净压力达到微裂缝开启压力或新缝破裂压力时，微裂缝或新缝就会开启，随着后续携砂液的继续加入，微裂缝或新缝就会延伸和扩展，成为新的支裂缝。
针对压裂过程中暂堵剂的研究，国内外已经开展了一定的研究工作。
申请号为201610227808.2的中国专利公开了一种暂堵剂及其制备方法，该暂堵剂遇水形成滤饼，阻止措施液流向油层，措施结束后原油可将该滤饼状堵剂溶解恢复油层的渗透性，该堵剂是用在油井冲砂施工作业。堵剂成分主要由改性油溶树脂、交联剂和温抗盐超高分子量聚合物等组成。
中国专利CN103409121A公开了一种水溶性压裂转向暂堵剂，该水溶性压裂转向暂堵剂是由植物淀粉、高聚物、膨胀剂和固化剂组成的，其中，所述植物淀粉、高聚物、膨胀剂和固化剂的质量比为4.5:3.5:0.5:1.5。其暂堵模式为由堵剂在水中形成滤饼评价其突破压力。
中国专利CN102653673A公开了一种能生物降解的暂堵剂，该暂堵剂由生物降 解剂、有机膨胀材料和增稠剂组成，其中，以重量百分比计，所述生物降解剂为黄豆和玉米的颗粒混合物，用量为60-85％，该颗粒混合物中，黄豆和玉米的重量比例为1:2至2:1，颗粒粒径为出砂粒径的2至3倍。
由此可见，本领域传统暂堵压裂均以堵剂在裂缝内形成滤饼的滤饼封堵模式为主，为丰富暂堵压裂的暂堵模式，提供一种低密度、高强度、可降解暂堵剂及其制备方法与应用已经成为本领域亟需解决的技术问题。
发明内容
为解决上述技术问题，本发明的目的在于提供一种低密度、高强度、可降解暂堵剂及其制备方法与应用。
为实现上述目的，本发明提供了一种低密度、高强度、可降解暂堵剂，以该暂堵剂的总重量为100wt％计，其包括60wt％-85wt％的聚乳酸，5wt％-20wt％的淀粉，5wt％-10wt％的聚己内酯，2wt％-5wt％的增溶剂，2wt％-5wt％的增韧剂。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述淀粉和聚己内酯的重量比为1:1-2:1。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述聚乳酸的分子量为900-1100万，熔点为175℃，拉伸强度大于70MPa。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述淀粉为可溶性淀粉。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述可溶性淀粉包括玉米淀粉、大米淀粉、小米淀粉、木薯淀粉及马铃薯淀粉中的一种或几种的组合。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述增韧剂包括丁苯橡胶、聚丁二酸丁二醇酯、聚己二酸丁二醇酯、甲壳素及壳聚糖中的一种。其中，所用丁苯橡胶为工业级产品，其可以增加该暂堵剂产品承压时的韧性。
根据本发明具体实施方案，在所述的暂堵剂中，优选地，所述增溶剂包括甘油、水、聚乙烯醇、聚乙二醇及钛酸四丁酯中的一种。其中，甘油为工业级产品，其为聚乳酸、淀粉、聚己内酯和丁苯橡胶共混时的增溶剂。
根据本发明具体实施方案，优选地，该暂堵剂颗粒的粒径为1-4mm。其中，在本申请具体实施方式中可以根据目标井动态裂缝宽度的不同来选择暂堵剂颗粒的粒径。
根据本发明具体实施方案，优选地，该暂堵剂颗粒的密度为1.1-1.3g/cm3，承压 强度大于52MPa。
本发明还提供了所述暂堵剂的制备方法，其包括以下步骤：
将聚乳酸、增溶剂、增韧剂、淀粉及聚己内酯共混后，再经挤塑成型，得到所述暂堵剂。
根据本发明具体实施方案，优选地，该制备方法具体包括以下步骤：将聚乳酸、增溶剂、增韧剂、淀粉及聚己内酯进行共混，得到混合料；再将该混合料注入双螺杆挤出机进行挤塑成型，得到所述暂堵剂；
其中，所述双螺杆挤出机挤出温度为140-160℃，螺杆转速为100-300r/min。
本申请对暂堵剂制备过程中，原料聚乳酸、增溶剂、增韧剂、淀粉及聚己内酯的加入顺序不作具体要求。
本发明还提供了所述暂堵剂在油田油井或气井暂堵压裂中的应用。
该暂堵剂的具体制备过程为：在聚乳酸、淀粉、增溶剂、聚己内酯和增韧剂等的共混材料中，聚乳酸是连续母相，而淀粉由于颗粒较小、成本较低，常在共混体系内作为填充剂，并且淀粉组成分子为多羟基化合物，具有极强的吸水特性，其在一定温度下可快速吸水膨胀，进而起到降解促进剂的作用。但是，聚乳酸与淀粉共混体系中最主要的问题是疏水性的聚乳酸与亲水性的淀粉之间的界面结合力太弱，即两者相容性较差，因此，改进共混复合材料相容性的方法是引入第三相增溶剂，以减少界面能量，促进扩散，提高聚乳酸和淀粉两相间的粘合力；而所用聚己内酯为生物可降解高分子，其降解速率较慢，聚己内酯与淀粉配合使用可调控暂堵剂体系的降解速率。
根据本发明具体实施方案，在所述应用中，优选地，所述油田的储层的温度为30-90℃。
应用过程中，本发明所提供的暂堵剂的降解过程为：该暂堵剂在地层温度下吸水膨胀开裂，失去力学强度，随时间增加，最终降解为水和二氧化碳。
与现有技术相比，本发明提供的暂堵剂具有如下技术效果：
本发明所提供的低密度、高强度、可降解暂堵剂为一种刚性暂堵剂，其能在已有裂缝中形成桥堵，暂堵升压明显；根据SY/T5108-2006《压裂支撑剂性能指标及测试推荐方法》对本发明所提供的该暂堵剂进行测试，测试结果表明：
该暂堵剂的密度(30℃)为1.1-1.3g/cm3，承压强度大于52MPa；其在储层温度条件下48小时内失去力学强度，最终降解时间为168小时(60℃无氧自然降解)； 适宜温度30℃至90℃储层
该暂堵剂的制备方法简单，工艺要求低，可以实现工业化生产。
将本发明所提供的暂堵剂应用于暂堵压裂，在地层条件下，一定时间内，其可完全降解，不会对储层造成二次伤害，并可避免暂堵剂对地层污染及卡泵事故的发生。
附图说明
图1为本发明应用例中G125-164油井的施工曲线图；
图2为本发明应用例中G123-162油井的施工曲线图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，以下将通过具体的实施例详细地说明本发明的实施过程和产生的有益效果，旨在帮助阅读者更好地理解本发明的实质和特点，但是不作为对本案可实施范围的限定。
实施例1
本实施例提供了一种低密度、高强度、可降解暂堵剂，其中，以该暂堵剂的总重量为100wt％计，该暂堵剂包括60wt％的聚乳酸，20wt％的玉米淀粉，10wt％的聚己内酯，5wt％的甘油，5wt％的丁苯橡胶；
上述暂堵剂是通过以下步骤制备得到的：
将聚乳酸、甘油、丁苯橡胶、玉米淀粉及聚己内酯按上述重量百分含量加入到高速混料机中充分搅拌均匀，得到混合料；再将该混合料注入双螺杆挤出机，温度设置1区为140℃、2区为155℃、3区为160℃、4区为160℃、5区为155℃，螺杆转速为100r/min；挤塑成型，得到所述暂堵剂。
实施例2
本实施例提供了一种低密度、高强度、可降解暂堵剂，其中，以该暂堵剂的总重量为100wt％计，该暂堵剂包括75wt％的聚乳酸，11wt％的大米淀粉，8wt％的聚己内酯，4wt％的水，2wt％的聚丁二酸丁二醇酯；
上述暂堵剂是通过以下步骤制备得到的：
将聚乳酸、水、聚丁二酸丁二醇酯、大米淀粉及聚己内酯按上述重量百分含量加入到高速混料机中充分搅拌均匀，得到混合料；再将该混合料注入双螺杆挤出机，温度设置1区为140℃、2区为155℃、3区为160℃、4区为160℃、5区为155℃，螺 杆转速为150r/min；挤塑成型，得到所述暂堵剂。
实施例3
本实施例提供了一种低密度、高强度、可降解暂堵剂，其中，以该暂堵剂的总重量为100wt％计，该暂堵剂包括85wt％的聚乳酸，5wt％的小米淀粉，5wt％的聚己内酯，2.5wt％的聚乙烯醇，2.5wt％的聚己二酸丁二醇酯；
上述暂堵剂是通过以下步骤制备得到的：
将聚乳酸、聚乙烯醇、聚己二酸丁二醇酯、小米淀粉及聚己内酯按上述重量百分含量加入到高速混料机中充分搅拌均匀，得到混合料；再将该混合料注入双螺杆挤出机，温度设置1区为140℃、2区为155℃、3区为160℃、4区为160℃、5区为155℃，螺杆转速为200r/min；挤塑成型，得到所述暂堵剂。
实施例4
本实施例提供了一种低密度、高强度、可降解暂堵剂，其中，以该暂堵剂的总重量为100wt％计，该暂堵剂包括81wt％的聚乳酸，10wt％的木薯淀粉，5wt％的聚己内酯，2wt％的聚乙二醇，2wt％的甲壳素；
上述暂堵剂是通过以下步骤制备得到的：
将聚乳酸、聚乙二醇、甲壳素、木薯淀粉及聚己内酯按上述重量百分含量加入到高速混料机中充分搅拌均匀，得到混合料；再将该混合料注入双螺杆挤出机，温度设置1区为140℃、2区为155℃、3区为160℃、4区为160℃、5区为155℃，螺杆转速为250r/min；挤塑成型，得到所述暂堵剂。
实施例5
本实施例提供了一种低密度、高强度、可降解暂堵剂，其中，以该暂堵剂的总重量为100wt％计，该暂堵剂包括65wt％的聚乳酸，15wt％的马铃薯淀粉，10wt％的聚己内酯，5wt％的钛酸四丁酯，5wt％的壳聚糖；
上述暂堵剂是通过以下步骤制备得到的：
将聚乳酸、钛酸四丁酯、壳聚糖、马铃薯淀粉及聚己内酯按上述重量百分含量加入到高速混料机中充分搅拌均匀，得到混合料；再将该混合料注入双螺杆挤出机，温度设置1区为140℃、2区为155℃、3区为160℃、4区为160℃、5区为155℃，螺杆转速为300r/min；挤塑成型，得到所述暂堵剂。
测试例
采用SY/T5108-2006《压裂支撑剂性能指标及测试推荐方法》对实施例1-5得到的低密度、高强度、可降解暂堵剂进行测试，测试结果表明，本发明所提供该暂堵剂具有如下特性：
(1)密度(30℃)：1.1-1.3g/cm3；
(2)承压强度大于52MPa；
(3)该堵剂在储层温度条件下48小时内失去力学强度，最终降解时间为168小时(60℃无氧自然降解)；
(4)适宜温度30℃至90℃的储层。
应用例
本应用例提供了暂堵剂在长庆油田油井暂堵压裂中的应用，其包括以下步骤：
1、试验井1，G125-164，暂堵剂加注条件：施工排量为2.0m3/min，砂比为227kg/m3，加暂堵剂(实施例1)量为150kg，暂堵剂加入速度为20-50kg/min；该G125-164油井施工曲线图如图1所示，从图1中可以看出，暂堵剂过射孔孔眼后，井口施工压力由28MPa上升到40MPa，上升了12MPa(所用暂堵剂过射孔孔眼后，其在地层裂缝中聚集，限流引起静压力升高)，从压力上升可以判断措施过程有裂缝转向。
2、试验井2，G123-162，暂堵剂加注条件：施工排量为2.0m3/min，砂比为180kg/m3，加暂堵剂(实施例1)量为200kg，暂堵剂加入速度为20-50kg/min，该G123-162油井施工曲线图如图2所示，从图2中可以看出，暂堵剂过射孔孔眼后，井口施工压力由34.5MPa上升到37.5MPa，上升了3MPa。
采用该暂堵剂在长庆油田完成13口井的现场试验，试验结果表明：措施初期单井产量由0.97t提高至2.62t，平均单井日增油1.65t，目前措施井平均单井产量为2.02t，目前措施有效率为92.3％，累计增油2331.11吨。
以上仅为本发明的较佳实施例，并非仅限于本发明的实施范围，凡依本发明专利范围的内容所做的等效变化和修饰，都应为本发明的技术范畴。

Claims (14)

  1. 一种暂堵剂，其特征在于，以该暂堵剂的总重量为100wt％计，其包括60wt％-85wt％的聚乳酸，5wt％-20wt％的淀粉，5wt％-10wt％的聚己内酯，2wt％-5wt％的增溶剂，2wt％-5wt％的增韧剂。
  2. 根据权利要求1所述的暂堵剂，其特征在于，所述淀粉和聚己内酯的重量比为1:1-2:1。
  3. 根据权利要求1所述的暂堵剂，其特征在于，所述聚乳酸的分子量为900-1100万，熔点为175℃，拉伸强度大于70MPa。
  4. 根据权利要求1所述的暂堵剂，其特征在于，所述淀粉为可溶性淀粉。
  5. 根据权利要求4所述的暂堵剂，其特征在于，所述可溶性淀粉包括玉米淀粉、大米淀粉、小米淀粉、木薯淀粉及马铃薯淀粉中的一种或几种的组合。
  6. 根据权利要求1所述的暂堵剂，其特征在于，所述增韧剂包括丁苯橡胶、聚丁二酸丁二醇酯、聚己二酸丁二醇酯、甲壳素及壳聚糖中的一种。
  7. 根据权利要求1所述的暂堵剂，其特征在于，所述增溶剂包括甘油、水、聚乙烯醇、聚乙二醇及钛酸四丁酯中的一种。
  8. 根据权利要求1-7任一项所述的暂堵剂，其特征在于，该暂堵剂颗粒的粒径为1-4mm。
  9. 根据权利要求1-7任一项所述的暂堵剂，其特征在于，该暂堵剂颗粒的密度为1.1-1.3g/cm3，承压强度大于52MPa。
  10. 权利要求1-9任一项所述暂堵剂的制备方法，其包括以下步骤：
    将聚乳酸、增溶剂、增韧剂、淀粉及聚己内酯共混后，再经挤塑成型，得到所述暂堵剂。
  11. 根据权利要求10所述的制备方法，其特征在于，该制备方法具体包括以下步骤：将聚乳酸、增溶剂、增韧剂、淀粉及聚己内酯进行共混，得到混合料；再将该混合料注入双螺杆挤出机进行挤塑成型，得到所述暂堵剂；
    其中，所述双螺杆挤出机挤出温度为140-160℃，螺杆转速为100-300r/min。
  12. 权利要求1-9任一项所述暂堵剂在油田油井或气井暂堵压裂中的应用。
  13. 根据权利要求12所述的应用，其特征在于，所述油田的储层的温度为 30-90℃。
  14. 根据权利要求12或13所述的应用，其特征在于，所述暂堵剂的加注条件为：
    施工排量2-4m3/min，砂比180-327kg/m3，单级加暂堵剂量100-200kg，暂堵剂加入速度20-50kg/min。
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