WO2021218019A1 - 纳米驱油剂及其制备方法、应用 - Google Patents

纳米驱油剂及其制备方法、应用 Download PDF

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WO2021218019A1
WO2021218019A1 PCT/CN2020/118019 CN2020118019W WO2021218019A1 WO 2021218019 A1 WO2021218019 A1 WO 2021218019A1 CN 2020118019 W CN2020118019 W CN 2020118019W WO 2021218019 A1 WO2021218019 A1 WO 2021218019A1
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nano
oil
displacing agent
water
modified
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PCT/CN2020/118019
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French (fr)
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张欢乐
王金剑
俞波
王耀国
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宁波锋成纳米科技有限公司
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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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Definitions

  • the application relates to a nano oil-displacing agent and a preparation method and application thereof, and belongs to the technical field of oil field exploitation.
  • nano-displacing agent As a new type of oil-displacing agent, nano-displacing agent has great advantages compared with traditional chemical oil-displacing agent, such as high specific surface area, excellent biocompatibility, and high oil recovery.
  • the general functional nanomaterial itself has a certain charge, and it is easy to flocculate and precipitate in a high-salt environment, making it impossible to inject.
  • amphiphilic graphene oxide as a functional nanomaterial, has a good oil displacement effect, but its high-temperature salt resistance stability is extremely poor.
  • the electrical spatial repulsion formed by the adsorbed PSS molecules on the surface of amphiphilic graphene oxide exceeds the attraction effect, thereby stabilizing the stability of amphiphilic graphene oxide in salt water.
  • the amount of PSS used to stabilize nanomaterials is extremely large, which is 100 times the amount of nanomaterials; the salinity (salinity) of the system is increased, and the amount of PSS needs to be increased; the sulfonic acid group in PSS has A large amount of electric charge is easily adsorbed on the inlet end of the core (similar to surfactants), making it difficult for nanomaterials to stabilize. In some cases, they cannot play a role in deep formations. In severe cases, nanomaterials aggregate and block the ports; there is no oil displacement related data, and the effect unknown.
  • a nano oil-displacing agent is provided.
  • the nano-oil-displacing agent is a temperature- and salt-tolerant oil-displacing agent, which ensures that the functional nano-dispersion is not in a certain temperature and salinity range. Flocculation and precipitation; and the water-soluble polymer can slowly decompose under the conditions of high temperature and high salt, and at the same time release the nano material, so that the functional nano material can play a role.
  • a nano oil-displacing agent comprising: nano material, surfactant, water-soluble polymer and solvent;
  • the water-soluble polymer is wrapped around the nano material.
  • the water-soluble polymer presents a disordered network structure in water, and nanomaterials are filled therein.
  • the network structure prevents the nanomaterials from moving freely and prevents them from coagulating under salt water conditions and blocking the core ports.
  • a nano oil-displacing agent is composed of a nano material, a surfactant, a water-soluble polymer and a solvent; the water-soluble polymer is coated around the nano material.
  • the content of each component is:
  • the solvent is water.
  • the nano material is selected from any one of modified graphene oxide, modified nano silica, modified titanium dioxide, and modified bentonite.
  • the modified graphene oxide includes nano amphiphilic graphene oxide.
  • Modified graphene oxide refers to grafting different groups on the surface of graphene oxide to achieve different effects.
  • the nano amphiphilic graphene oxide is grafted with a hydrophobic group on one side of the graphene oxide and a hydrophilic group on the other side (or no group, because the graphene oxide itself has a large number of hydrophilic groups).
  • the modified nano-silica is nano-silica modified by fatty alcohol and its derivatives
  • the modified titanium dioxide is modified titanium dioxide modified by fatty alcohol and its derivatives
  • the modified bentonite is bentonite modified by fatty alcohol and its derivatives
  • the fatty alcohol and its derivatives include any one of carboxylic acid compounds, amine compounds, ethoxy compounds, amide compounds, fatty acid methyl ester compounds, and glycolipid compounds.
  • the surfactant is selected from any one of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • the anionic surfactant is selected from any one of sulfonate anionic surfactants and sulfate anionic surfactants;
  • the cationic surface activity is selected from any one of quaternary ammonium salt type cationic surfactants, heterocyclic type cationic surfactants, and amine salt type cationic surfactants;
  • the nonionic surfactant is selected from any one of polyoxyethylene type nonionic surfactants and polyol type nonionic surfactants;
  • amphoteric surfactant is selected from any one of betaine type surfactants and amino acid type surfactants.
  • the water-soluble polymer includes acrylic acid polymer, acrylamide polymer, acrylic acid and acrylamide copolymer, 2-acrylamido-2-methylpropanesulfonic acid polymer, xanthan gum, hydroxyethyl cellulose, hard At least one of glucose.
  • a preparation method of a nano oil-displacing agent comprising the following steps:
  • the purpose of adding a surfactant is to improve the surface charge of the nanomaterial dispersion so that it is not easy to flocculate and precipitate in the polymer.
  • step b) the purpose of adding polymer is to increase the steric hindrance between the amphiphilic graphene oxide and prevent its flocculation.
  • step a) a surfactant is added to the nanomaterial dispersion liquid, and the mixture is stirred and mixed I to obtain the mixed solution;
  • the mass ratio of the surface active agent to the nanomaterial in the nanomaterial dispersion is 1-100:1-20.
  • the conditions of the stirring and mixing I are: rotating speed 100-500 r/min; time 1-30 min.
  • the upper limit of the rotation speed is independently selected from 200r/min, 300r/min, 400r/min, 500r/min; the lower limit of the rotation speed is independently selected from 100r/min, 200r/min, 300r/min, 400r/min.
  • the upper limit of the stirring time is independently selected from 5min, 10min, 15min, 20min, 30min, 40min, 50min; the lower limit of the stirring time is independently selected from 1min, 5min, 10min, 15min, 20min, 30min, 40min.
  • step b) the water-soluble polymer is added to the solvent to obtain a mother liquor containing the water-soluble polymer, and the concentration of the mother liquor is 500-50000 mg/L.
  • the upper limit of the mother liquor concentration is independently selected from 1000 mg/L, 5000 mg/L, 10000 mg/L, 20000 mg/L, 30000 mg/L, 40000 mg/L, and 50000 mg/L;
  • the lower limit of the mother liquor concentration is independently selected from 500 mg/L , 1000mg/L, 5000mg/L, 10000mg/L, 20000mg/L, 30000mg/L, 40000mg/L.
  • step c) adding the mother liquor to the mixed solution, stirring and mixing II, to obtain the nano oil-displacing agent;
  • the mass ratio of the mother liquor to the mixed solution is 50-5000:1-10.
  • the conditions of the stirring and mixing II are: time 3-60 min; rotation speed 100-1000 r/min.
  • the upper limit of the stirring time is independently selected from 5min, 10min, 15min, 20min, 30min, 40min, 50min, 60min; the lower limit of the stirring time is independently selected from 3min, 5min, 10min, 15min, 20min , 30min, 40min, 50min.
  • the upper limit of the speed is independently selected from 200r/min, 300r/min, 400r/min, 500r/min, 700r/min, 900r/min, 1000r/min; the lower limit of the speed is independently selected from 100r/min , 200r/min, 300r/min, 400r/min, 500r/min, 700r/min, 900r/min.
  • an oil displacement method which uses a nano oil displacement agent for oil displacement
  • the nano oil-displacing agent is selected from any one of the nano-oil-displacing agent described in any one of the above or the nano-oil-displacing agent obtained by the preparation method of any one of the above.
  • the nano-oil-displacing agent is diluted and stirred to obtain a treated nano-oil-displacing agent
  • the treated nano-oil-displacing agent is injected into the oil layer for oil-displacing.
  • the dilution and stirring treatment includes: diluting the concentration of the nano-oil-displacing agent to 100-5000 mg/L; mechanical stirring under the condition of 100-1000 r/min for 1-60 min.
  • the temperature-resistant salt-resistant nano-oil-displacing agent provided by this application guarantees that the functional nano-dispersed liquid will not flocculate and precipitate within a certain temperature and salinity range (temperature ⁇ 90°C, total salinity: ⁇ 100000ppm);
  • the water-soluble polymer itself has a certain viscosity, which can increase the oil-water two-phase fluidity ratio, and expand the spread area is beneficial to improve the oil-displacing effect.
  • the material is carried into deeper and smaller pores, making it easier for functional nanomaterials to function.
  • Fig. 1 is a schematic diagram of the structure of a nano-oil-displacing agent and a schematic diagram of its action process in an embodiment of this application;
  • Figure 2 is a scanning electron micrograph of a nano-oil-displacing agent solution in an embodiment of the application
  • FIG. 3 is a scanning electron micrograph of the nano-oil-displacing agent in a solid deposition state in an embodiment of the application
  • Figure 4 is a graph showing the stability of the nano-oil-displacing agent in one embodiment of the application in a high-temperature and high-salt (70°C, 10% wt. NaCl, 1% wt. CaCl 2 ) state for 24 hours;
  • Figure 5 is a photo of the stability of the nano oil-displacing agent in one embodiment of the application under high temperature and high salt (70°C, 1% wt. NaCl, 0.1% wt. CaCl 2 ) for 5 days, 10 days, and 30 days;
  • Fig. 6 is a diagram of core displacement data of nano-oil displacement agent in an embodiment of this application.
  • step 3 Add 1-100 parts of the polymer mother liquor obtained in step 3 to the intermediate mixture of step 2, at a speed of 100-1000 revolutions per minute, and stir for 3-60 minutes to obtain a high-temperature, salt-tolerant nano-oil-displacing agent (addition The purpose of the polymer: to increase the steric hindrance between the amphiphilic graphene oxide and prevent its flocculation).
  • the functional nanomaterial in step one can be nano amphiphilic graphene oxide, modified nano silica, modified titanium dioxide, nano bentonite, etc.
  • the surfactant in step one can be an anionic surfactant, cationic surfactant, nonionic surfactant or amphoteric surfactant.
  • the water-soluble polymer in step two includes acrylic acid polymer, acrylamide polymer, copolymer of acrylic acid and acrylamide, 2-acrylamido-2-methylpropanesulfonic acid polymer, xanthan gum, hydroxyethyl At least one of cellulose and hard glucose.
  • the preparation method of the modified graphene oxide nanosheets adopts the preparation method commonly used in the prior art, and a common preparation method is introduced below: see references: Luo D, Zhang F, Zheng H, et al. Electrostatic-attraction-induced high internal phase emulsion for large-scale synthesis of amphiphilic Janus nanosheets[J].Chemical Communications,2019.;
  • the preparation method of modified titanium dioxide adopts the preparation method commonly used in the prior art.
  • a common preparation method is introduced below: see references: Feng Xiaoyu, Hou Jirui, Cheng Tingting, et al. Preparation and flooding of oleic acid-modified nano-TiO2 Oil performance evaluation[J]. Oilfield Chemistry, 2019..
  • the preparation method of modified silica adopts the preparation method commonly used in the prior art.
  • a common preparation method is introduced below: see reference: Wang Wei. Preparation and modification of nano silica for flooding [D ].China University of Petroleum).
  • modified bentonite adopts the preparation method commonly used in the prior art, and a common preparation method is introduced below: see reference: Sun Hongliang, Zhu Lizhong. Cetyl trimethyl quaternary ammonium salt-ethyl mercaptan ammonium salt Study on the adsorption performance of composite modified bentonite[J].Acta Scientiae Circumstantiae,2010,30(5):1037-1042.
  • modified graphene oxide nanosheets are grafted with different groups on the surface of graphene oxide to achieve different effects.
  • Amphiphilic graphene oxide only represents the grafting of hydrophobic groups on one side of graphene oxide and grafting on the other side. Graft hydrophilic groups (or not graft groups, because graphene oxide itself has a large number of hydrophilic groups). Therefore, the modified graphene oxide nanosheets contain nano amphiphilic graphene oxide.
  • step 3 Add 1000 parts by mass of the polymer mother liquor obtained in step 2 to 1 part by mass of the mixed solution in step 1, at a speed of 500 revolutions per minute, and stir for 30 minutes to obtain a high-temperature salt-tolerant nano-oil-displacing agent, which is recorded as a sample 1#.
  • sample 1# the ratio of the mass fractions of nano-material nanometer amphiphilic graphene oxide, anionic surfactant sodium lauryl sulfate, and polyacrylamide is 1:5:10.
  • step 3 Add 2000 parts by mass of the polymer mother liquor obtained in step 2 to 1 part by mass of the mixed solution in step 1, at a speed of 500 rpm, stirring for 30 minutes, to obtain a high-temperature salt-tolerant nano-oil-displacing agent, which is recorded as a sample 2#.
  • sample 2# the ratio of mass fractions of nano-material modified nano-silica, cationic surfactant cetyltrimethylammonium bromide, and water-soluble sodium polystyrene sulfonate is 1:10:12.
  • step 3 Take 1000 parts by mass of the polymer mother liquor obtained in step 2 and add it to 1 part by mass of the mixed solution in step 1, at a speed of 500 revolutions per minute, and stir for 30 minutes to obtain a high-temperature, salt-tolerant nano-oil-displacing agent, which is recorded as a sample 3#.
  • sample 3# the ratio of mass fractions of nano-material modified nano-titanium dioxide, non-ionic surfactant octylphenol polyoxyethylene ether, and water-soluble polymer polyacrylamide is 2:5:20.
  • FIG. 1 The schematic diagram of the structure of the nano-oil-displacing agent provided by the present application is shown in Fig. 1. It can be seen from Fig. 1 that under the action of the surfactant, the water-soluble polymer is coated around the nano-material. It can also be seen from Figure 1 that under the action of high temperature and high salt, the polymer coated on the outermost layer of the nano-oil-displacing agent slowly degrades. During this period, the presence of the polymer can expand the spread and improve the oil recovery efficiency.
  • the functional nanomaterials and surfactants can move freely, and the hydrophobic groups of the surfactants can carry the functional nanomaterials to search for oil droplets spontaneously, and the surfactants are enriched in the oil-water interface , Which can reduce the interfacial tension of the oil and water phases, and at the same time, the functional nanomaterials are fully in contact with the oil droplets to further play the oil displacement effect.
  • the SEM image of sample 1# in the solution state is shown in Fig. 2, and the SEM image of sample 1# in the solid deposition state is shown in Fig. 3. From Figures 2 and 3, it can be seen that the water-soluble polymer has a disordered network structure in water, and nanomaterials are filled in it. The network structure hinders the free movement of the nanomaterials. Large steric hindrance to prevent flocculation of nanomaterials.
  • the performance tests were performed on the samples 1# to 3# in the above-mentioned embodiments, and the test conditions were 70° C., 10% wt. NaCl, and 1% wt. CaCl 2.
  • Samples 1# ⁇ 3# are all at 70°C, 1%wt.NaCl, 0.1%wt.CaCl 2 salinity, the nano dispersion does not flocculate and precipitate.
  • sample 1# As a typical representative, the test results are shown in Fig. 4. It can be seen from Fig. 4 that sample 1 has basically no flocculation and particle growth tendency under high temperature and high salt for 24 hours.
  • Viscosity performance test was carried out on samples 1# ⁇ 3# in the above-mentioned examples.
  • the test conditions before adding polymer were: temperature 70°C and pure water preparation; after adding polymer, the test conditions were: temperature 70°C, 0.5%wt.NaCl Simulate water preparation.
  • test results show that the viscosity increases significantly after adding the polymer, and the nano-oil displacement agent can expand the spread during the oil displacement process, thereby improving the oil recovery.
  • the performance test was performed on the sample 1# in the above-mentioned embodiments, and the test conditions were 70° C., 1% wt. NaCl, and 0.1% wt. CaCl 2.
  • test result It can be seen from Figure 5 that sample 1# is very stable within 5 days without any flocculation and precipitation at 70°C, 1% wt. NaCl, and 0.1% wt. CaCl 2 salinity. After 10 days, the The polymer slowly degrades, and there is a very small amount of particles suspended in the sample. After 30 days, the polymer is almost completely degraded and the nanoparticles are released. However, because there is no oil phase, the nanoparticles all sink under the action of gravity. bottom.
  • Sample 1# was diluted with oilfield mineralized water to 1000mg/L, and mechanically stirred at 500r/min for 60min to obtain a treated nano-oil-displacing agent.
  • the treated nano-oil-displacing agent was injected into a natural sandstone core with a permeability of 200mD for testing.
  • the specific data is shown in Figure 6. It can be seen from Figure 6 that after 1PV nano-oil-displacing agent flooding and squeezing the pressure for 7 days, followed by 2PV follow-up water flooding, the recovery factor can be comprehensively increased by 20.54%.

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Abstract

本申请公开了一种纳米驱油剂以及制备方法、应用。一种纳米驱油剂，其特征在于，所述纳米驱油剂包括：纳米材料、表面活性剂、水溶性聚合物和水；所述水溶性聚合物包覆在所述纳米材料的周围。该纳米驱油剂为一种耐温耐盐型驱油剂，在一定温度、矿化度范围内，保证功能型纳米分散液不絮凝沉淀；且水溶性聚合物可在高温高盐条件下缓慢分解，同时释放出纳米材料，使功能型纳米材料发挥作用。

Description

纳米驱油剂及其制备方法、应用 技术领域
本申请涉及一种纳米驱油剂及其制备方法、应用，属于油田开采技术领域。
背景技术
石油产业是我国能源产业的根基，随着国内石油需求的不断提升，我国也由往日的石油出口国转变为石油进口大国，石油已经成为制约我国经济增长的"瓶颈"。为了有效提升石油采收率，新型驱油剂也是层出不穷，但是收效甚微。
纳米驱油剂作为新型的驱油剂，相较于传统的化学驱油剂有很大的优势，如高的比表面积、出色的生物相容性、高采收率等。但是一般功能型纳米材料本身带有一定电荷，在高盐环境下极易絮凝沉淀，导致无法注入。
现有技术中，双亲氧化石墨烯作为一种功能型的纳米材料，具有较好的驱油的效果，但高温抗盐稳定性极差。Dan Luo,Feng Wang,et al.Poly(sodium 4-styrenesulfonate)Stabilized Janus Nanosheets in Brine with Retained Amphiphilicity[J].Langmuir 2018,34,3694-3700，文章中将PSS(聚苯乙烯磺酸钠)吸附在双亲氧化石墨烯表面，吸附的PSS分子在双亲氧化石墨烯表面的形成的电空间排斥作用超过吸引作用，从而稳定了双亲氧化石墨烯在盐水中的稳定性。但是，在该报道中，用以稳定纳米材料的PSS用量极大，是纳米材料用量的100倍；体系的矿化度(盐度)提高，需要PSS用量也提高；PSS中的磺酸基带有大量电荷，容易吸附在岩心入口端(与表活剂类似)，导致纳米材料难以稳定，轻则无法在地层深处发挥作用，重则纳米材料聚集，堵住端口；无驱油相关数据，效果未知。
发明内容
根据本申请的一个方面，提供了一种纳米驱油剂，该纳米驱油剂为一种耐温耐盐型驱油剂，在一定温度、矿化度范围内，保证功能型纳米分散液不絮凝沉淀；且水溶性聚合物可在高温高盐条件下缓慢分解，同时释放出纳米材料，使功能型纳米材料发挥作用。
一种纳米驱油剂，所述纳米驱油剂包括：纳米材料、表面活性剂、水溶性聚合物和溶剂；
所述水溶性聚合物包覆在所述纳米材料的周围。
水溶性聚合物与纳米材料之间未形成化学键。
本申请中，水溶性聚合物在水中呈无序网状结构，纳米材料填充其中，网状结构阻碍了纳米材料自由移动，防止其在盐水条件下发生聚沉，而堵住岩心端口。
可选地，一种纳米驱油剂，所述纳米驱油剂由纳米材料、表面活性剂、水溶性聚合物和溶剂组成；所述水溶性聚合物包覆在所述纳米材料的周围。
可选地，在所述纳米驱油剂中，各组分的含量为：
纳米材料1～20质量份；
表面活性剂1～100质量份；
水溶性聚合物10～500质量份。
可选地，溶剂为水。
可选地，所述纳米材料选自改性氧化石墨烯、改性纳米二氧化硅、改性二氧化钛、改性膨润土中的任一种。
可选地，所述改性氧化石墨烯包括纳米双亲氧化石墨烯。
改性氧化石墨烯是指在氧化石墨烯表面接枝不同的基团，以达到不同的效果。
所述纳米双亲氧化石墨烯为在氧化石墨烯一面接枝疏水基团，另一面接枝亲水基团(或者不接枝基团，因为氧化石墨烯本身带有大量亲水基团)。
可选地，所述改性纳米二氧化硅为经脂肪醇及其衍生物改性的纳米二氧化硅；
所述改性二氧化钛为经脂肪醇及其衍生物改性的改性二氧化钛；
所述改性膨润土为经脂肪醇及其衍生物改性的膨润土；
其中，所述脂肪醇及其衍生物包括羧酸类化合物、胺类化合物、乙氧基化合物、酰胺类化合物、脂肪酸甲酯类化合物、糖脂类化合物中的任一种。
可选地，所述表面活性剂选自阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂中的任一种。
具体地，阴离子表面活性剂选自磺酸盐阴离子型表面活性剂、硫酸酯盐阴离子型表面活性剂中的任一种；
阳离子表面活性选自季铵盐型阳离子表面活性剂、杂环类阳离子表面活性剂、胺盐型阳离子表面活性剂中的任一种；
非离子表面活性剂选自聚氧乙烯型非离子表面活性剂和多元醇型非离子表面活性剂中的任一种；
两性表面活性剂选自甜菜碱型表面活性剂、氨基酸型表面活性剂中的任一种。
所述水溶性聚合物包括丙烯酸聚合物、丙烯酰胺聚合物、丙烯酸与丙烯酰胺共聚物、2-丙烯酰胺基-2-甲基丙磺酸聚合物、黄原胶、羟乙基纤维素、硬葡萄糖中的至少一种。
根据本申请的另一方面，还提供了一种纳米驱油剂的制备方法，所述制备方法包括以下步骤：
a)获得含有纳米材料和表面活性剂的混合溶液；
b)获得含有水溶性聚合物的母液；
c)将所述母液加入所述混合溶液中，得到所述纳米驱油剂。
具体地，在步骤a)中，加表面活性剂的目的：改善纳米材料分散液的表面电荷，使其在聚合物中不易絮凝沉淀。
在步骤b)中，加聚合物的目的：增大双亲氧化石墨烯间的空间位阻，阻止其絮凝。
可选地，在步骤a)中，将表面活性剂加入纳米材料分散液中，搅拌混合Ⅰ，得到所述混合溶液；
其中，所述表面活性剂与纳米材料分散液中的纳米材料的质量份数比为1～100：1～20。
可选地，所述搅拌混合Ⅰ的条件为：转速100～500r/min；时间1～30min。
具体地，在搅拌混合Ⅰ中，转速的上限独立地选自200r/min、300r/min、400r/min、500r/min；转速的下限独立地选100r/min、200r/min、300r/min、400r/min。
在搅拌混合Ⅰ中，搅拌时间的上限独立地选自5min、10min、15min、20min、30min、40min、50min；搅拌时间的下限独立地选自1min、5min、10min、15min、20min、30min、40min。
可选地，在步骤b)中，将所述水溶性聚合物加入溶剂中，得到含有水溶性聚合物的母液，所述母液的浓度为500～50000mg/L。
具体地，母液浓度的上限独立地选自1000mg/L、5000mg/L、10000mg/L、20000mg/L、30000mg/L、40000mg/L、50000mg/L；母液浓度的下限独立地选自500mg/L、1000mg/L、5000mg/L、10000mg/L、20000mg/L、30000mg/L、40000mg/L。
可选地，在步骤c)中，将所述母液加入所述混合溶液，搅拌混合Ⅱ，得到所述纳米驱油剂；
所述母液与混合溶液的质量份数比为50～5000：1～10。
可选地，所述搅拌混合Ⅱ的条件为：时间3～60min；转速100～1000r/min。
具体地，在搅拌混合Ⅱ中，搅拌时间的上限独立地选自5min、10min、15min、20min、 30min、40min、50min、60min；搅拌时间的下限独立地选自3min、5min、10min、15min、20min、30min、40min、50min。
在搅拌混合Ⅱ中，转速的上限独立地选自200r/min、300r/min、400r/min、500r/min、700r/min、900r/min、1000r/min；转速的下限独立地选100r/min、200r/min、300r/min、400r/min、500r/min、700r/min、900r/min。
根据本申请的又一方面，还提供了一种驱油方法，所述驱油方法采用纳米驱油剂进行驱油；
所述纳米驱油剂选自上述任一项所述的纳米驱油剂或上述任一项所述的制备方法得到的纳米驱油剂中的任一种。
可选地，将纳米驱油剂进行稀释搅拌处理，得到处理纳米驱油剂；
将所述处理纳米驱油剂注入油层中进行驱油。
可选地，所述稀释搅拌处理包括：将所述纳米驱油剂的浓度稀释至100～5000mg/L；在100～1000r/min的条件下机械搅拌1～60min。
本申请能产生的有益效果包括：
1)本申请所提供的耐温耐盐纳米驱油剂，在一定温度、矿化度范围(温度＜90℃，总矿化度：＜100000ppm内)，保证功能型纳米分散液不絮凝沉淀；
2)本申请所提供的耐温耐盐纳米驱油剂，水溶性聚合物与功能型纳米材料作用，形成较大的空间位阻，从而防止纳米材料絮凝，无需特别考虑盐度与温度；
3)本申请所提供的耐温耐盐纳米驱油剂，油藏条件下(高温高盐)，纳米材料会在一定时间内释放，既能保证纳米材料的可注入性，也可使纳米材料发挥驱油的作用；
4)本申请所提供的耐温耐盐纳米驱油剂，水溶性聚合物本身具有一定的粘度，可提高油水两相流度比，扩大波及面积有利于提升驱油效果，同时也可将纳米材料携带入更深更小的孔隙中，使功能型纳米材料更容易发挥作用。
附图说明
图1为本申请一种实施方式中纳米驱油剂的结构示意图及其作用过程示意图；
图2为本申请一种实施方式中纳米驱油剂溶液状态下扫描电镜图；
图3为本申请一种实施方式中纳米驱油剂固体沉积状态下扫描电镜图；
图4为本申请一种实施方式中纳米驱油剂在高温高盐(70℃，10％wt.NaCl，1％wt.CaCl 2)状态下放置24h的稳定性趋势图；
图5为本申请一种实施方式中纳米驱油剂分别在高温高盐下(70℃，1％wt.NaCl，0.1％wt.CaCl 2)5天，10天，30天后的稳定性照片；
图6为本申请一种实施方式中纳米驱油剂岩心驱替数据图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
下面介绍可能的实施方式
1、取功能型纳米材料分散液(换算成干粉质量为1-20份)，加入1-100份表面活性剂，搅拌混合1-30min(转速100-500转/分钟)。加表面活性剂的目的：改善功能型纳米材料分散液的表面电荷，使其在聚合物中不易絮凝沉淀。
2、将水溶性聚合物溶于纯水中，配制成浓度为500-50000mg/L的母液。
3、将步骤三得到的聚合物母液取1-100份加入到步骤二的中混合液中，转速100-1000转/分钟，搅拌3-60min，即制得高温耐盐纳米驱油剂(加聚合物的目的：增大双亲氧化石墨烯间的空间位阻，阻止其絮凝)。
4、将高温耐盐纳米驱油剂用油田矿化水稀释至使用浓度(100-5000mg/L)机械搅拌1-60min(转速：100-1000转/分钟)，即可进行使用。
5、步骤一中的功能型纳米材料可以为纳米双亲氧化石墨烯、改性纳米二氧化硅、改性二氧化钛、纳米膨润土等。
6、步骤一中的表面活性剂可以是阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂或两性表面活性剂。
7、步骤二中的水溶性聚合物包括丙烯酸聚合物、丙烯酰胺聚合物、丙烯酸与丙烯酰胺共聚物、2-丙烯酰胺基-2-甲基丙磺酸聚合物、黄原胶、羟乙基纤维素、硬葡萄糖中的至少一种。
下面介绍本申请中的改性纳米材料的制备方法：
改性氧化石墨烯纳米片的制备方法采用现有技术中常用的制备方法，下面介绍一种常见的制备方式：见参考文献：Luo D,Zhang F,Zheng H,et al.Electrostatic-attraction-induced high internal phase emulsion for large-scale synthesis of amphiphilic Janus nanosheets[J].Chemical Communications,2019.；
改性二氧化钛的制备方法，采用现有技术中常用的制备方法，下面介绍一种常见的制备方式：见参考文献：冯晓羽,侯吉瑞,程婷婷,et al.油酸改性纳米TiO2的制备及其驱油性能评价[J].油田化学,2019.。
改性二氧化硅的制备方法，采用现有技术中常用的制备方法，下面介绍一种常见的制备方式：见参考文献：王维.驱油用纳米二氧化硅的制备及改性研究[D].中国石油大学(华东)。
改性膨润土的制备方法，采用现有技术中常用的制备方法，下面介绍一种常见的制备方式：见参考文献：孙洪良,朱利中.十六烷基三甲基季铵盐-乙硫醇铵盐复合改性膨润土吸附性能研究[J].环境科学学报,2010,30(5):1037-1042。
本申请中，改性氧化石墨烯纳米片是在氧化石墨烯表面接枝部不同的基团以达到不同的效果，双亲氧化石墨烯仅代表在氧化石墨烯一面接枝疏水基团，另一面接枝亲水基团(或者不接枝基团，因为氧化石墨烯本身带有大量亲水基团)。所以说，改性氧化石墨烯纳米片包含纳米双亲氧化石墨烯。
如无特别说明，本申请的实施例中的原料均通过商业途径购买。
实施例1
1、取纳米双亲氧化石墨烯分散液(换算成干粉质量为1份)，加入5份阴离子表面活性剂(具体为十二烷基硫酸钠)，搅拌混合30min(转速100转/分钟)，得到混合溶液。
2、将聚丙烯酰胺(阴离子型，分子量为1600万)溶于纯水中，配制成浓度为10000mg/L的母液。
3、将步骤2得到的聚合物母液取1000质量份加入到1质量份步骤1中的混合溶液中，转速500转/分钟，搅拌30min，即制得高温耐盐纳米驱油剂，记作样品1#。
在样品1#中，纳米材料纳米双亲氧化石墨烯、阴离子表面活性剂十二烷基硫酸钠、聚丙烯酰胺的质量分数之比为1:5:10。
实施例2
1、取改性纳米二氧化硅分散液(换算成干粉质量为1份)，加入10份阳离子表面活性剂(具体为十六烷基三甲基溴化铵)，搅拌混合20min(转速300转/分钟)， 得到混合溶液。
2、将羟乙基纤维素(购自阿拉丁，分子量为25万)溶于纯水中，配制成浓度为6000mg/L的母液。
3、将步骤2得到的聚合物母液取2000质量份加入到1质量份步骤1中的混合溶液中，转速500转/分钟，搅拌30min，即制得高温耐盐纳米驱油剂，记作样品2#。
在样品2#中，纳米材料改性纳米二氧化硅、阳离子表面活性剂十六烷基三甲基溴化铵、水溶性聚苯乙烯磺酸钠的质量分数之比为1:10:12。
实施例3
1、取改性纳米二氧化钛分散液(换算成干粉质量为2份)，加入5份非离子表面活性剂(具体为辛基酚聚氧乙烯醚)，搅拌混合30min(转速100转/分钟)，得到混合溶液。
2、将聚丙烯酰胺(非离子型，分子量为800万)溶于纯水中，配制成浓度为20000mg/L的母液。
3、将步骤2得到的聚合物母液取1000质量份加入到1质量份步骤1中的混合溶液中，转速500转/分钟，搅拌30min，即制得高温耐盐纳米驱油剂，记作样品3#。
在样品3#中，纳米材料改性纳米二氧化钛、非离子表面活性剂辛基酚聚氧乙烯醚、水溶性聚合物聚丙烯酰胺的质量分数之比为2:5:20。
实施例4 纳米驱油剂的结构表征
分别对上述实施例中的样品1#～3#进行扫描电镜测试，测试结果表明，水溶性聚合物包覆在纳米材料的周围。
本申请所提供的纳米驱油剂的结构示意图见图1，由图1可以看出，在表面活性剂的作用下，水溶性聚合物包覆在所述纳米材料的周围。从图1中也可以看出纳米驱油剂在高温高盐作用下，包覆在最外层的聚合物慢慢降解，在此期间聚合物的存在能扩大波及，提高采油效率。当聚合物降解至一定程度，功能型纳米材料与表面活性剂可自由移动，表面活性剂的疏水基团可带着功能型纳米材料自发地去寻找油滴，表面活性剂富集到油水界面中，可降低油水两相的界面张力，同时功能型纳米材料充分与油滴接触，进一步起到驱油效果。
样品1#的溶液状态下扫描电镜图如图2所示，样品1#的固体沉积状态下扫描电镜图如图3所示。由图2和图3可以看出水溶性聚合物在水中呈无序网状结构，纳米材 料填充其中，网状结构阻碍了纳米材料自由移动，即水溶性聚合物与功能型纳米材料作用，形成较大的空间位阻，从而防止纳米材料絮凝。
实施例5 纳米驱油剂的性能测试
分别对上述实施例中的样品1#～3#进行性能测试，测试条件70℃，10％wt.NaCl，1％wt.CaCl 2。
测试结果：样品1#～3#均在70℃、1％wt.NaCl，0.1％wt.CaCl 2矿化度下，纳米分散液不絮凝沉淀。
以样品1#为典型代表，测试结果如图4所示，由附图4可以看出样品1在高温高盐下24h基本无絮凝以及颗粒长大的趋势。
实施例6 纳米驱油剂的性能测试
分别对上述实施例中的样品1#～3#进行粘度性能测试，加聚合物前测试条件：温度70℃，纯水配制；加聚合物后测试条件为：温度70℃，0.5％wt.NaCl模拟水配制。
测试结果见下表。
样品 加聚合物前粘度/mPa·s 加聚合物前粘度/mPa·s
样品1 0.7 3.1
样品2 0.6 2.0
样品3 0.6 4.2
以样品1#为典型代表，测试结果表明加入聚合物后粘度明显增大，纳米驱油剂可在驱油过程中可起到扩大波及的作用，从而提高原油采收率。
实施例7 纳米驱油剂的性能测试
分别对上述实施例中的样品1#进行性能测试，测试条件70℃，1％wt.NaCl，0.1％wt.CaCl 2。
测试结果：由附图5可以看出样品1#在70℃、1％wt.NaCl，0.1％wt.CaCl 2矿化度下，在5天内十分稳定无任何絮凝沉淀等现象，10天后随着聚合物慢慢降解，样品中出现了极少量的颗粒悬浮，在30天后，聚合物基本完全降解，释放出了纳米粒子，但由于没有油相的存在，纳米粒子在重力作用下，全部沉于底部。
实施例8 纳米驱油剂的应用
将样品1#用油田矿化水稀释至1000mg/L，在500r/min的条件下机械搅拌60min，得到处理纳米驱油剂。
将该处理纳米驱油剂注入渗透率200mD的天然砂岩心中测试，具体数据见附图6。由图6可以看出经过1PV纳米驱油剂驱并憋压焖井7天，再接续2PV后续水驱后，可综合提高采收率20.54％。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (13)

  1. 一种纳米驱油剂，其特征在于，所述纳米驱油剂包括：纳米材料、表面活性剂、水溶性聚合物和溶剂；
    所述水溶性聚合物包覆在所述纳米材料的周围。
  2. 根据权利要求1所述的纳米驱油剂，其特征在于，在所述纳米驱油剂中，各组分的含量为：
    纳米材料1～20质量份；
    表面活性剂1～100质量份；
    水溶性聚合物10～500质量份。
  3. 根据权利要求1所述的纳米驱油剂，其特征在于，所述纳米材料选自改性氧化石墨烯、改性纳米二氧化硅、改性二氧化钛、改性膨润土中的任一种。
  4. 根据权利要求3所述的纳米驱油剂，其特征在于，
    所述改性纳米二氧化硅为经脂肪醇及其衍生物改性的纳米二氧化硅；
    所述改性二氧化钛为经脂肪醇及其衍生物改性的改性二氧化钛；
    所述改性膨润土为经脂肪醇及其衍生物改性的膨润土；
    其中，所述脂肪醇的衍生物包括羧酸类化合物、胺类化合物、乙氧基化合物、酰胺类化合物、脂肪酸甲酯类化合物、糖脂类化合物中的任一种。
  5. 根据权利要求1所述的纳米驱油剂，其特征在于，所述表面活性剂选自阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂中的任一种。
  6. 根据权利要求1所述的纳米驱油剂，其特征在于，所述水溶性聚合物包括丙烯酸聚合物、丙烯酰胺聚合物、丙烯酸与丙烯酰胺共聚物、2-丙烯酰胺基-2-甲基丙磺酸聚合物、黄原胶、羟乙基纤维素、硬葡萄糖中的至少一种。
  7. 一种纳米驱油剂的制备方法，其特征在于，所述制备方法包括以下步骤：
    a)获得含有纳米材料和表面活性剂的混合溶液；
    b)获得含有水溶性聚合物的母液；
    c)将所述母液加入所述混合溶液中，得到所述纳米驱油剂。
  8. 根据权利要求7所述的制备方法，其特征在于，在步骤a)中，将表面活性剂加入纳米材料分散液中，搅拌混合Ⅰ，得到所述混合溶液；
    其中，所述表面活性剂与纳米材料分散液中的纳米材料的质量份数比为1～100：1～20。
  9. 根据权利要求7所述的制备方法，其特征在于，在步骤b)中，将所述水溶性聚合物加入溶剂中，得到含有水溶性聚合物的母液，所述母液的浓度为500～50000mg/L。
  10. 根据权利要求7所述的制备方法，其特征在于，在步骤c)中，将所述母液加入所述混合溶液，搅拌混合Ⅱ，得到所述纳米驱油剂；
    所述母液与混合溶液的质量份数比为50～5000：1～50。
  11. 一种驱油方法，其特征在于，所述驱油方法采用纳米驱油剂进行驱油；
    所述纳米驱油剂选自权利要求1至6中任一项所述的纳米驱油剂或权利要求7至10中任一项所述的制备方法得到的纳米驱油剂中的任一种。
  12. 根据权利要求11所述的驱油方法，其特征在于，将纳米驱油剂进行稀释搅拌处理，得到处理纳米驱油剂；
    将所述处理纳米驱油剂注入油层中进行驱油。
  13. 根据权利要求12所述的驱油方法，其特征在于，所述稀释搅拌处理包括：将所述纳米驱油剂的浓度稀释至100～5000mg/L；在100～1000r/min的条件下机械搅拌1～60min。
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