WO2022267968A1 - 一种有机-无机纳米复合凝胶封堵剂的合成及油基钻井液 - Google Patents

一种有机-无机纳米复合凝胶封堵剂的合成及油基钻井液 Download PDF

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WO2022267968A1
WO2022267968A1 PCT/CN2022/099052 CN2022099052W WO2022267968A1 WO 2022267968 A1 WO2022267968 A1 WO 2022267968A1 CN 2022099052 W CN2022099052 W CN 2022099052W WO 2022267968 A1 WO2022267968 A1 WO 2022267968A1
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organic
drilling fluid
oil
parts
based drilling
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French (fr)
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谢刚
汪若兰
黄进军
罗玉婧
范莉
陈宇
曹少帅
黄国豪
谷硕
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西南石油大学
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Definitions

  • the invention relates to the technical field of oil and gas field drilling, in particular to an organic-inorganic nano composite gel plugging agent and an oil-based drilling fluid containing the nano plugging agent.
  • Organic-inorganic nanocomposite gel plugging agent is a nano-scale plugging material that can deform into nanopores under pressure. It has the function of filling tiny pores and cracks, so as to realize the multi-purpose plugging function of one dose, and its lipophilic group can make it well dispersed in oil-based drilling fluid.
  • the present invention provides an organic-inorganic nanocomposite gel plugging agent with a particle size of nanometers. It can effectively seal the nano-scale pores and fractures in the shale formation, so as to achieve the purpose of stabilizing the borehole wall. And a new type of nano plugging oil-based drilling fluid suitable for shale formations has been developed, which can solve the problems of wellbore stability and reservoir pollution.
  • an organic-inorganic nanocomposite gel plugging agent and its oil-based drilling fluid The raw material of the organic-inorganic nanocomposite gel sealing agent comprises molybdenum disulfide, 2-ethylacrylic acid, N,N-dimethylacrylamide, the preparation of the organic-inorganic nanocomposite gel sealing agent Proceed as follows:
  • the added amount of the modified nano molybdenum disulfide is 5-15% of the total weight of 2-ethylacrylic acid and N,N-dimethylacrylamide;
  • the weight ratio of the 2-ethylacrylic acid to N,N-dimethylacrylamide is 1:1-2.5;
  • N,N-methylenebisacrylamide 1%-3%
  • the added amount of the ammonium persulfate is 1%-3%.
  • Another object of the present invention is to provide an oil-based drilling fluid, which is added with the organic-inorganic nanocomposite gel plugging agent of the present invention.
  • the composition of the drilling fluid is as follows: 70-100 parts of white oil, 0.5-1 part of main emulsifier, 1-3 parts of auxiliary emulsifier, 5-10 parts of fluid loss control agent, 2-5 parts of organic soil, 1- 5 parts of quicklime, 10-30 parts of CaCl 2 (concentration 20-25%) brine, 0.5-2 parts of wetting agent, 10-50 parts of barite, and 1-5 parts of organic-inorganic nanocomposite gel plugging agent.
  • the white oil in the oil-based drilling fluid is 3# white oil
  • the main emulsifier is one of OME, WO-NT, HIEMUL and HW Pmul-1
  • the auxiliary emulsifier is OME-2, HICOAT and HW Smul- One of 1
  • the wetting agent is HW Wet-1
  • the fluid loss control agent is one of oxidized bitumen, YJ-2 and HWTrol-101
  • the organic soil is HW Gel-3
  • the density of barite is 4.2 g/cm 3 .
  • the pH of the oil-based drilling fluid is 8.5-10.
  • the oil-based drilling fluid has a density of 1.55 g/cm 3 when no organic-inorganic nanocomposite gel plugging agent is added.
  • the particle size distribution of the organic-inorganic nanocomposite gel prepared by the present invention is between 50-200nm, which can effectively block the nanoscale pores and cracks in the shale formation, thereby achieving the effect of stabilizing the well wall; the present invention
  • the oil-based drilling fluid used has good rheological properties, stability and plugging performance under shale formation conditions.
  • Fig. 1 is the particle size distribution figure of organic-inorganic nanocomposite gel in embodiment one;
  • Fig. 2 is a particle size distribution diagram of the organic-inorganic nanocomposite gel in Example 2.
  • Nano-molybdenum disulfide place nano-molybdenum disulfide in a vacuum drying oven at 75°C for 12 hours, accurately weigh 2g of dried nano-molybdenum disulfide, add it to 40mL ethanol/water dispersion, and disperse by ultrasonic for 45 minutes , then add 2.5g KH550 dropwise while stirring, react at 75°C for 9h, wash with ethanol, repeat 4 times, and finally place it in a vacuum oven at 58°C for 10h to obtain modified nanomolybdenum disulfide.
  • Nano-molybdenum disulfide place nano-molybdenum disulfide in a vacuum drying oven at 80°C for 12 hours, accurately weigh 2.5g of dried nano-molybdenum disulfide, add it to 45mL ethanol/water dispersion, and ultrasonically disperse 50min, then add 3g KH550 dropwise while stirring, react at 80°C for 8h, wash with ethanol, repeat 5 times, and finally place it in a vacuum oven at 60°C for 9h to obtain modified nano molybdenum disulfide.
  • organic-inorganic nanocomposite gel add 0.65g modified nanomolybdenum disulfide to the reactor, add 50ml ultrapure water for ultrasonic dispersion for 15min; add 3g comonomer 2-ethylacrylic acid and 3.5gN,N -Dimethacrylamide, 0.05g of cross-linking agent N,N-methylenebisacrylamide, keep stirring rapidly until dissolved, blow nitrogen for 30min; raise the temperature of the reaction system to 60°C, keep stirring, add 0.08g of persulfuric acid Ammonium was added to the mixed system, and the reaction was carried out at constant temperature for 4 hours; after the reaction was completed, the reaction system was lowered to 25°C, and the prepared samples were washed with distilled water until neutral, and then dried in an oven at 70°C.
  • Example 1 In order to further illustrate the effect of the organic-inorganic nanocomposite gel plugging agent and oil-based drilling fluid of the present invention, the performance of the organic-inorganic nanocomposite gel plugging agent and oil-based drilling fluid prepared in Example 1 and Example 2 were carried out. test.
  • the particle size test results of the organic-inorganic nanocomposite gel plugging agent prepared in the two examples are respectively As shown in Figure 1 and Figure 2.
  • the particle size distribution of the organic-inorganic nanocomposite gel plugging agent of the present invention is between 50-200nm, and the average particle diameter is 125nm, indicating that the plugging agent synthesized by the present invention is of nanometer size, and the plugging agent has a wide distribution range , can effectively block nanopores of different nanometer sizes.
  • the present invention mainly illustrates the application of the organic-inorganic nanocomposite gel plugging agent with the following specific formula.
  • the composition of the drilling fluid is as follows: 0.5-1 parts of main emulsifier, 1-3 parts of auxiliary emulsifier, 5-10 parts of fluid loss reducer, 2-5 parts of organic soil, 1-5 parts of quicklime, 10-30 parts of CaCl 2 (concentration 20-25%) brine, 0.5-2 parts of wetting agent, 10-50 parts of barite, 1-5 parts of organic-inorganic nanocomposite gel for plugging agent.
  • AV apparent viscosity
  • PV plastic viscosity
  • YP dynamic shear force
  • API normal temperature medium pressure filtration loss
  • HTHP High temperature and high pressure filtration loss, the unit is mL.
  • Drilling fluid aged at 150°C for 16 hours as the amount of organic-inorganic nanocomposite gel plugging agent increases, the high-temperature and high-pressure fluid loss gradually decreases, and when the dosage is 12 parts by mass, the high-temperature and high-pressure fluid loss The amount is the smallest, indicating that the organic-inorganic nanocomposite gel plugging agent has good rheological properties and water loss wall-building properties, can effectively reduce the high-temperature and high-pressure filtration loss of drilling fluid, and can also provide better plugging in high-temperature environments performance, effectively prevent the filtrate from entering the formation, and improve the stability of the borehole wall.
  • Use artificial cores to simulate formations with nano-micron pores and fractures, measure the average flow rate of the drilling fluid system in the artificial cores, and use Darcy's formula to calculate the penetration of artificial cores before and after adding organic-inorganic nanocomposite gel plugging agents Rate K Q ⁇ l/(A ⁇ P), so as to calculate the plugging rate of the organic-inorganic nanocomposite gel plugging agent on the artificial core, and evaluate its plugging performance.
  • Table 2 shows the recording table of the plugging effect of the organic-inorganic nanocomposite gel on the artificial core. Plugging rate (initial permeability-permeability after plugging)/initial permeability ⁇ 100%.
  • Drilling fluid name Core permeability/10 -3 mD Blocking rate% 1 Base slurry 1.56 - 2 Drilling fluid 1 0.38 75.40 3 Drilling fluid 2 0.20 87.20 4 Drilling fluid 3 0.12 92.00 5 Drilling fluid 4 0.07 95.50
  • the core length is 5cm and the diameter is 2.5cm.

Abstract

本发明公开了一种有机-无机纳米复合凝胶封堵剂及油基钻井液。该油基钻井液所用封堵剂为有机-无机纳米复合凝胶，所述有机-无机纳米复合凝胶合成原料包括二硫化钼，2-乙基丙烯酸，N,N-二甲基丙烯酰胺，N,N-亚甲基双丙烯酰胺；所述钻井液包含有本发明的有机-无机纳米复合凝胶。本发明的有机-无机纳米复合凝胶作为纳米封堵剂，其粒径分布在50-200nm之间，可以有效阻止钻井液滤液侵入地层，防止井壁坍塌等事故的发生，特别适用于页岩地层的纳米封堵，其制备方法原理可靠，具有广阔的市场前景。

Description

一种有机-无机纳米复合凝胶封堵剂的合成及油基钻井液 技术领域
本发明涉及油气田钻井技术领域，具体涉及一种有机-无机纳米复合凝胶封堵剂及其包含有该纳米封堵剂的油基钻井液。
背景技术
在石油与天然气资源开发的过程中，深层页岩气的开采一直是研究人员的研究热点。对于一些层理和微孔缝发育的硬脆性和破碎性地层，油基钻井液滤液的侵入会带来地层的不稳定因素。此外，水力压力通过微孔缝传递也会导致井壁失稳，因此，必须加强油基钻井液对微孔缝的封堵性。目前，油基钻井液的封堵剂种类少，使用的封堵材料多是仅具亲水性能的桥塞类材料，在油基钻井液中的适应性差，粒径匹配能力不足。同时，井筒压力的变化将引起孔缝大小的变化，孔缝动态变形会对封堵层造成破坏，非弹性封堵剂形成的封堵层不能适应孔缝变形，这将影响封堵效果；弹性封堵剂能够更好地适应孔缝变形，封堵效果稳定。同时，上提钻柱时，由于抽汲作用使井内液柱压力降低，当封堵材料对井壁的吸附性不强时，孔缝中的封堵材料有可能在抽汲压力的作用下被驱替出来，因此，研究了一种有机-无机纳米复合凝胶封堵剂的合成及油基钻井液。
有机-无机纳米复合凝胶封堵剂是一种纳米级别的封堵材料，能够在压力下变形进入纳米孔缝，刚性内核可以起到支撑架桥的作用，柔性聚合物外壳可以发生形变，起到填充微小孔缝的作用，从而实现一剂多用的封堵功能，其亲油基团能使其很好的分散在油基钻井液中。
发明内容
针对目前常规封堵剂无法有效封堵页岩中的纳米孔缝而导致的井壁失稳问题，本发明提供了一种有机-无机纳米复合凝胶封堵剂，其粒径为纳米级，能够有效对页岩地层中的纳米级孔缝进行封堵，从而达到稳定井壁的目的。且研制了一种能适用于页岩地层的新型纳米封堵油基钻井液能够解决井壁稳定、储层污染等问题。
为实现上述目的，本发明的技术方案为：一种有机-无机纳米复合凝胶封堵剂及其油基钻井液。所述有机-无机纳米复合凝胶封堵剂的原料包括为二硫化钼，2-乙基丙烯酸，N,N-二甲基丙烯酰胺，所述有机-无机纳米复合凝胶封堵剂的制备步骤如下：
(1)纳米二硫化钼的改性：将纳米二硫化钼置于75-80℃真空干燥箱中干燥10-12h，准确称取干燥后的纳米二硫化钼2-3g，加入到40-50mL乙醇/水的分散液中，超声分散40-50min，然后边搅拌边滴加2-3gKH550，在75-80℃反应8-10h后，用乙醇洗涤，反复3-5次，最后置于55-60℃真空干燥箱中干燥8-10h得到改性纳米二硫化钼。
(2)有机-无机纳米复合凝胶的制备:
①向反应器中加入改性后的纳米二硫化钼，加超纯水超声分散10-15min；
②加入共聚单体2-乙基丙烯酸和N,N-二甲基丙烯酰胺，交联剂N,N-亚甲基双丙烯酰胺，保持快速搅拌至溶解，通入氮气20-30min；
③将反应体系升温至55-60℃，保持搅拌，将过硫酸铵加入到混合体系内，恒温反应3-4h；
④反应完毕后，将反应体系降至20-25℃，制备得的样品用蒸馏水洗涤至中性，接着在烘箱中60-70℃干燥；
⑤将烘干的样品进行研磨，然后密封保存。
所述改性后的纳米二硫化钼的加量为2-乙基丙烯酸与N,N-二甲基丙烯酰胺总重量的5-15％；
所述2-乙基丙烯酸的加量为3-3.5g；
所述2-乙基丙烯酸与N,N-二甲基丙烯酰胺的重量比为1:1-2.5；
所述N,N-亚甲基双丙烯酰胺的加量为1％-3％；
所述过硫酸铵的加量为1％-3％。
本发明的另一种目的是提供一种油基钻井液，所述钻井液添加有本发明所述的一种有机-无机纳米复合凝胶封堵剂。
所述钻井液的组成如下：70-100份的白油，0.5-1份主乳化剂，1-3份辅乳化剂，5-10份降滤失剂，2-5份有机土，1-5份生石灰，10-30份CaCl 2(浓度20-25％)盐水，0.5-2份润湿剂，10-50份重晶石，1-5份有机-无机纳米复合凝胶封堵剂。
所述油基钻井液中的白油为3#白油，主乳化剂为OME、WO-NT、HIEMUL和HW Pmul-1中的一种，辅乳化剂为OME-2、HICOAT和HW Smul-1中的一种，润湿剂为HW Wet-1，降滤失剂为氧化沥青、YJ-2和HWTrol-101中的一种，有机土为HW Gel-3，重晶石的密度为4.2g/cm 3。
所述油基钻井液的pH为8.5-10。
所述油基钻井液在不加有机-无机纳米复合凝胶封堵剂时的密度为1.55g/cm 3。
本发明有益效果如下：
本发明所制备的有机-无机纳米复合凝胶的粒径分布在50-200nm之间，能够有效的对页岩地层中的纳米级别孔缝进行封堵，从而达到稳定井壁的效果；本发明所使用的油基钻井液在页岩地层条件下的流变性、稳定性以及封堵性等方面性能良好。
附图说明
图1为实施例一中有机-无机纳米复合凝胶的粒径分布图；
图2为实施例二中有机-无机纳米复合凝胶的粒径分布图。
具体实施方式
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
一、有机-无机纳米复合凝胶的合成：
实施例1：
纳米二硫化钼的改性：将纳米二硫化钼置于75℃真空干燥箱中干燥12h，准确称取干燥后的纳米二硫化钼2g，加入到40mL乙醇/水的分散液中，超声分散45min，然后边搅拌边滴加2.5gKH550，在75℃反应9h后，用乙醇洗涤，反复4次，最后置于58℃真空干燥箱中干燥10h得到改性纳米二硫化钼。
有机-无机纳米复合凝胶的制备:向反应器中加入0.3g改性后的纳米二硫化钼，加50ml超纯水超声分散12min；加入3g共聚单体2-乙基丙烯酸和3gN，N-二甲基丙烯酰胺，0.04g交联剂N,N-亚甲基双丙烯酰胺，保持快速搅拌至溶解，通入氮气25min；将反应体系升温至55℃，保持搅拌，0.06g过硫酸铵加入到混合体系内，恒温反应3h；反应完毕后，将反应体系降至22℃，制备得的样品用蒸馏水洗涤至中性，接着在烘箱中65℃干燥。
实施例2：
纳米二硫化钼的改性：将纳米二硫化钼置于80℃真空干燥箱中干燥12h，准确称取干燥后的纳米二硫化钼2.5g，加入到45mL乙醇/水的分散液中，超声分散50min，然后边搅拌边滴加3gKH550，在80℃反应8h后，用乙醇洗涤，反复5次，最后置于60℃真空干燥箱中干燥9h得到改性纳米二硫化钼。
有机-无机纳米复合凝胶的制备:向反应器中加入0.65g改性后的纳米二硫化钼，加50ml超纯水超声分散15min；加入3g共聚单体2-乙基丙烯酸和3.5gN，N-二甲基丙烯酰胺，0.05g交联剂N,N-亚甲基双丙烯酰胺，保持快速搅拌至溶解，通入氮气30min；将反应体系升温至60℃，保持搅拌，将0.08g过硫酸铵加入到混合体系内，恒温反应4h；反应完毕后，将反应体系降至25℃，制备得的样品用蒸馏水洗涤至中性，接着在烘箱中70℃干燥。
为了进一步说明本发明有机-无机纳米复合凝胶封堵剂以及油基钻井液的效果，对实施例1、实施例2制备的有机-无机纳米复合凝胶封堵剂以及油基钻井液进行性能测试。
二、性能测试
1、有机-无机纳米复合凝胶封堵剂粒径测试
利用美国布鲁克海文仪器公司生产的BI-200SM型激光散射仪对纳米微乳液封堵剂进行粒径测试，两个实施例中制备的有机-无机纳米复合凝胶封堵剂粒径测试结果分别如图1、图2所示。本发明有机-无机纳米复合凝胶封堵剂的粒径分布在50-200nm之间，平均粒径为125nm，说明本发明合成的封堵剂是纳米尺寸的，且该封堵剂分布范围宽，能有效封堵不同纳米尺寸的纳米孔缝。
2.钻井液流变性能和失水造壁性能测试
本发明主要以以下具体配方对有机-无机纳米复合凝胶封堵剂的应用方式进行说明。以100质量份的白油为基准，所述钻井液的组成如下：0.5-1份主乳化剂，1-3份辅乳化剂，5-10份降滤失剂，2-5份有机土，1-5份生石灰，10-30份CaCl 2(浓度20-25％)盐水，0.5-2份润湿剂，10-50份重晶石，1-5份有机-无机纳米复合凝胶封堵剂。
三、油基钻井液的配置：
将1.80g的主乳化剂HW Pmul-1、4.50g辅乳HW Smul-1、2.40g润湿剂HW Wet-1直接称取在高搅杯中；量取240mL 3#白油导入高搅杯中，将高搅杯置于高搅机上，以12000rpm高速搅拌，搅拌10min；用玻璃纸称取9g有机土HW Gel-3，在高搅状态下，将有机土HW Gel-3缓慢加入到高搅杯中，防止飞溅，高搅10min；在高搅状态下，量取60mL浓度为25％的CaCl 2水溶液加入到高搅杯中，防止飞溅，高搅10min；在高搅状态下，将9g生石灰HW-pH缓慢加入到高搅杯中，高搅10min；在高搅杯状态下，将24g的滤失剂HW Trol-101缓慢加入到高搅杯中，搅拌10min，期间取下高搅杯刮壁；在高搅状态下，将295g重晶石缓慢加入到高搅杯中，继续搅拌30min，期间取下高搅杯再次刮壁。
搅拌均匀后，分别向5份油基钻井液基浆中加入0、4g、8g、12g、16g上述方式制备的有机-无机纳米复合凝胶封堵剂，制得含有机-无机纳米复合凝胶封堵剂添加量不同的五种钻井液，分别命名为基浆、钻井液1、钻井液2、钻井液3和钻井液4，其中基浆不含有机-无机纳米复合凝胶封堵剂，作为空白实验组。
依据中华人民共和国国家标准GB/T 16783.2-2012《石油天然气工业钻井液现场测试第2部分：油基钻井液》，分别对步骤配制好的钻井液进行老化前后钻井液流变性和失水造壁性进行测试，结果记录在表1中。
表1钻井液流变性能及滤失性能记录表
Figure PCTCN2022099052-appb-000001
注∶AV—表观黏度，单位为mPa·s；PV—塑性黏度，单位为mPa·s；YP—动切力，单位为Pa；API—常温中压滤失量，单位为mL；HTHP—高温高压滤失量，单位为mL。
由表1所示的结果可以看出，与不加有机-无机纳米复合凝胶封堵剂的钻井液相比，当有机-无机纳米复合凝胶在钻井液中加量为4-16质量份时，钻井液性能未受到明显的影响，表明该钻井液封堵剂具有良好的配伍性能。随着有机-无机纳米复合凝胶封堵剂加量的增加，在同一实验条件下钻井液的表观黏度、塑性黏度逐渐增大，对切力的影响较小。在150℃下老化16h后的钻井液，随着有机-无机纳米复合凝胶封堵剂加量的增加，高温高压滤失量逐渐减小，且在加量为12质量份时高温高压滤失量最小，说明有机-无机纳米复合凝胶封堵剂具有良好的流变性能和失水造壁性能，能有效降低钻井液高温高压滤失量，在高温环境下也能提供较好的封堵性能，有效阻止滤液进入地层，提高井壁稳定性。
3、钻井液封堵性能测试
使用人造岩芯模拟地层纳微米孔缝地层，通过测量钻井液体系在人造岩芯中的平均流量，通过达西公式，计算加入有机-无机纳米复合凝胶封堵剂前后，人造岩芯的渗透率K＝Qμl/(AΔP)，从而计算得到有机-无机纳米复合凝胶封堵剂对人造岩芯的封堵率，评价其封堵性能。表2所示为有机-无机纳米复合凝胶对人造岩芯封堵效果记录表。封堵率为(初始渗透率-封堵后渗透率)/初始渗透率×100％。
表2人造岩芯封堵性的评价实验数据表
岩芯 钻井液名称 岩芯渗透率/10 -3mD 封堵率％
1 基浆 1.56 -
2 钻井液1 0.38 75.40
3 钻井液2 0.20 87.20
4 钻井液3 0.12 92.00
5 钻井液4 0.07 95.50
注∶岩芯长度为5cm，直径为2.5cm。
由表2所表示的结果可知，与不加有机-无机纳米复合凝胶封堵剂的基浆相比，加入不同比例有机-无机纳米复合凝胶封堵剂后，对岩芯的封堵率增加了，且当加入有机-无机纳米复合凝胶封堵剂为12g时，对岩芯的封堵率均达到92％，这表明有机-无机纳米复合凝胶封堵剂可以对微孔缝实现有效的封堵，进而阻止钻井液进入岩芯。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (7)

  1. 一种有机-无机纳米复合凝胶封堵剂，其特征在于，所述一种有机-无机纳米复合凝胶的原料为二硫化钼(20nm)，2-乙基丙烯酸，N,N-二甲基丙烯酰胺，采用步骤如下制备而成：
    (1)纳米二硫化钼的改性：将纳米二硫化钼置于75-80℃真空干燥箱中干燥10-12h，准确称取干燥后的纳米二硫化钼2-3g，加入到40-50mL乙醇/水的分散液中，超声分散40-50min，然后边搅拌边滴加3-氨丙基三乙氧基硅烷(KH550)2-3g，在75-80℃反应8-10h后，用乙醇洗涤，反复3-5次，最后置于55-60℃真空干燥箱中干燥8-10h得到改性纳米二硫化钼；
    (2)有机-无机纳米复合凝胶的制备:
    ①向反应器中加入改性后的纳米二硫化钼，加超纯水超声分散10-15min；
    ②加入共聚单体2-乙基丙烯酸和N,N-二甲基丙烯酰胺，交联剂N,N-亚甲基双丙烯酰胺，保持快速搅拌至溶解，通入氮气20-30min；
    ③将反应体系升温至55-60℃，保持搅拌，将过硫酸铵加入到混合体系内，恒温反应3-4h；
    ④反应完毕后，将反应体系降至20-25℃，制备得的样品用蒸馏水洗涤至中性，接着在烘箱中60-70℃干燥；
    ⑤将烘干的样品进行研磨，然后密封保存。
  2. 根据权利要求1所述的一种有机-无机纳米复合凝胶封堵剂，其特征在于，所述改性后的纳米二硫化钼的加量为2-乙基丙烯酸和N,N-二甲基丙烯酰胺总重量的5-15％；所述2-乙基丙烯酸的加量为3-3.5g，2-乙基丙烯酸与N,N-二甲基丙烯酰胺的重量比为1：1-1.5，N,N-亚甲基双丙烯酰胺的加量为1％-3％，过硫酸铵的加量为1％-3％。
  3. 一种油基钻井液，其特征在于，所述钻井液中添加有权利要求1-2任一项所述的有机-无机纳米复合凝胶封堵剂。
  4. 根据权利要求3所述的油基钻井液，其特征在于，所述钻井液包括以下组分：70-100份的白油，0.5-1份主乳化剂，1-3份辅乳化剂，5-10份降滤失剂，2-5份有机土，0.5-5份生石灰，10-30份浓度为20-25％的CaCl 2盐水，0.5-2份润湿剂，10-30份重晶石，1-5份有机-无机纳米复合凝胶封堵剂。
  5. 根据权利要求4所述的油基钻井液，其特征在于，白油为3#白油，主乳化剂为OME、HIEMUL和HWPmul-1中的一种，辅乳化剂为OME-2、HICOAT和HWSmul-1中的一种，润湿剂为HWWet-1，降滤失剂为氧化沥青、YJ-2和HWTrol-101中的一种，有机土为HWGel-3，重晶石的密度为4.2g/cm 3。
  6. 根据权利要求4所述的油基钻井液，其特征在于，所述油基钻井液的pH为8.5-10。
  7. 根据权利要求4所述的油基钻井液，其特征在于，所述油基钻井液在不加有机-无机纳米复合凝胶封堵剂时的密度为1.20-2.20g/cm 3。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117165270A (zh) * 2023-10-31 2023-12-05 新疆春华石油科技有限责任公司 一种钻井液用封堵防塌剂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113337261B (zh) * 2021-06-22 2022-04-22 西南石油大学 一种有机-无机纳米复合凝胶及油基钻井液
CN114350330B (zh) * 2022-01-24 2023-02-21 西南石油大学 一种高强度强吸附封堵剂及油基钻井液
CN115319647B (zh) * 2022-08-09 2024-01-19 河南科技大学 干凝胶及制备方法、有机-无机复合结合剂、刚玉磨具及制备方法
CN116751573B (zh) * 2023-08-21 2023-11-14 大庆科讯油田技术服务有限公司 一种石油纳米解堵剂及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5792727A (en) * 1990-05-16 1998-08-11 Jacobs; Norman Laurie Lubricant compositions
CN105924599A (zh) * 2016-05-11 2016-09-07 中国石油大学(北京) 改性的二氧化硅纳米颗粒及其制备方法和钻井液
CN110066645A (zh) * 2018-01-22 2019-07-30 中国石油化工股份有限公司 一种钻井液润滑剂及其制备方法
CN111218261A (zh) * 2020-02-28 2020-06-02 中国石油天然气股份有限公司 一种有机/无机复合内刚外柔凝胶堵漏剂及其制备方法
CN111334265A (zh) * 2020-04-13 2020-06-26 西南石油大学 一种粘土矿物纳米水凝胶封堵剂及水基钻井液
CN111363106A (zh) * 2020-03-24 2020-07-03 四川大学 一种高强高韧纳米复合水凝胶及其制备方法和应用
CN113337261A (zh) * 2021-06-22 2021-09-03 西南石油大学 一种有机-无机纳米复合凝胶及油基钻井液

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045400A (en) * 1975-05-14 1977-08-30 Vasily Vladimirovich Korshak Antifriction self-lubricating material
DE2530002A1 (de) * 1975-07-04 1977-01-27 Dow Corning Gmbh Verfahren zur verbesserung der schmiereigenschaften von festschmierstoffen
JPS58142942A (ja) * 1982-02-19 1983-08-25 Central Glass Co Ltd ポリマ−被覆フッ化黒鉛の製造方法
US4708821A (en) * 1985-03-27 1987-11-24 Hoechst Gosei Kabushiki Kaisha Process for preparing aqueous gel and use thereof
JP3830341B2 (ja) * 2000-05-30 2006-10-04 Ｎｏｋ株式会社 ブチルゴム組成物
WO2014197834A1 (en) * 2013-06-06 2014-12-11 Halliburton Energy Services, Inc. Fluid loss well treatment
CN105862426B (zh) * 2016-04-26 2017-11-17 复旦大学 一种纳米片层二硫化钼增强型碳纤维上浆剂及其制备方法
CN108913279A (zh) * 2018-07-26 2018-11-30 界首市鑫全龙粮食机械购销有限公司 一种高分散的改性纳米二硫化钼润滑剂及其制备方法
CN110452677B (zh) * 2019-08-08 2021-10-15 河南郸城顺兴石油助剂有限公司 一种基于改性MoS2制备减阻剂的方法
CN110982369B (zh) * 2019-12-17 2021-10-12 武汉工程大学 一种二硫化钼改性丙烯酸乳液及利用其制备的水性防火涂料
CN112266780B (zh) * 2020-10-13 2022-12-20 宁波锋成先进能源材料研究院有限公司 一种改性纳米稳泡剂及其制备方法与应用
CN112940836B (zh) * 2021-02-09 2022-10-18 鞍钢股份有限公司 一种高分散性纳米二硫化钼水基轧制液及其制备方法
CN113004472B (zh) * 2021-02-23 2022-05-20 中国石油大学(北京) 一种纳米减阻剂及其制备方法与滑溜水压裂液

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5792727A (en) * 1990-05-16 1998-08-11 Jacobs; Norman Laurie Lubricant compositions
CN105924599A (zh) * 2016-05-11 2016-09-07 中国石油大学(北京) 改性的二氧化硅纳米颗粒及其制备方法和钻井液
CN110066645A (zh) * 2018-01-22 2019-07-30 中国石油化工股份有限公司 一种钻井液润滑剂及其制备方法
CN111218261A (zh) * 2020-02-28 2020-06-02 中国石油天然气股份有限公司 一种有机/无机复合内刚外柔凝胶堵漏剂及其制备方法
CN111363106A (zh) * 2020-03-24 2020-07-03 四川大学 一种高强高韧纳米复合水凝胶及其制备方法和应用
CN111334265A (zh) * 2020-04-13 2020-06-26 西南石油大学 一种粘土矿物纳米水凝胶封堵剂及水基钻井液
CN113337261A (zh) * 2021-06-22 2021-09-03 西南石油大学 一种有机-无机纳米复合凝胶及油基钻井液

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117165270A (zh) * 2023-10-31 2023-12-05 新疆春华石油科技有限责任公司 一种钻井液用封堵防塌剂及其制备方法
CN117165270B (zh) * 2023-10-31 2024-01-09 新疆春华石油科技有限责任公司 一种钻井液用封堵防塌剂及其制备方法

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