CN113122208A - Ethylene tar-based water-in-oil type emulsion water shutoff agent and preparation method and application thereof - Google Patents

Ethylene tar-based water-in-oil type emulsion water shutoff agent and preparation method and application thereof Download PDF

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CN113122208A
CN113122208A CN202110396640.9A CN202110396640A CN113122208A CN 113122208 A CN113122208 A CN 113122208A CN 202110396640 A CN202110396640 A CN 202110396640A CN 113122208 A CN113122208 A CN 113122208A
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oil
ethylene tar
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shutoff agent
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裴海华
刘冬鑫
张贵才
张菅
郑家桢
蒋平
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China University of Petroleum East China
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    • C09K8/502—Oil-based compositions
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    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/82—Oil-based compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention provides an ethylene tar-based water-in-oil type emulsion water shutoff agent, and a preparation method and application thereof. The ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 1.0-2.0% of oil-soluble anionic surfactant, 1.0-2.0% of nonionic surfactant, 0.05-0.15% of cosurfactant, 1.0-2.0% of modified nano-particles, 30-45% of ethylene tar and the balance of water. The emulsion water shutoff agent not only ensures better shutoff effect of the water-in-oil type emulsion water shutoff agent, but also can improve the economic added value of ethylene tar and save the cost of the water-in-oil type emulsion water shutoff agent; and the prepared water-in-oil emulsion water shutoff agent has better high-temperature stability, better shutoff effect at high temperature and better scouring resistance effect.

Description

Ethylene tar-based water-in-oil type emulsion water shutoff agent and preparation method and application thereof
Technical Field
The invention relates to an ethylene tar-based water-in-oil emulsion water shutoff agent and a preparation method and application thereof, belonging to the technical field of oil well water shutoff.
Background
In the process of oilfield water injection development, due to the heterogeneity of the stratum, water can rush along the high-permeability layer, so that the water yield of an oil well is increased, and the low-middle permeability layer is driven to be low in use degree or not used. The water shutoff and profile control of the oil-water well is an important technical means for controlling water, stabilizing oil and improving water drive efficiency of a severe heterogeneous oil reservoir. In the oil-water well plugging adjusting technology, the oil well water plugging technology can be divided into two types: non-selective water plugging technology and selective water plugging technology. When the technical condition of the oil well casing becomes worse, the blocking operation can not be carried out, or the cement sheath of the oil well is damaged, so that the interlayer fluid channeling is caused, and the packer loses the function, the selective water plugging technology plays an important role.
For selective water shutoff, there are many types of water shutoff agents, such as gels, particles, precipitates, foams, emulsions, and the like. The emulsion plugging agent can be classified into an emulsified thick oil plugging agent, a reverse emulsion plugging agent and a water-in-oil type emulsion plugging agent. The emulsified thick oil plugging agent has the advantages that because water is an external phase, emulsion can enter a water layer preferentially, and a cationic emulsifier is easy to adsorb on the surface of negatively charged rock, so that the emulsion is broken, and high-viscosity thick oil is released, so that the flow resistance of water flow is increased, and the water outlet of the water layer is reduced; however, the water shutoff effect is influenced by the viscosity property of the thick oil, so that the application of the thick oil is limited. Chinese patent document CN106497531A provides an oil-in-water emulsion for water shutoff of horizontal wells. The emulsion mainly comprises thickened oil, deionized water, a water-soluble surfactant, an oil-soluble surfactant and a stabilizer. The emulsion disclosed by the invention is simple in preparation process, easy to inject, strong in selectivity and good in water plugging effect; however, the formation temperature of the test water well is 38-56 ℃, and the use in high-temperature formations is limited. The phase inversion emulsion plugging agent is characterized in that a phase inversion agent is used, an oil-in-water type emulsion with low viscosity is injected into a stratum, and then the phase inversion agent plays a role to form a water-in-oil type emulsion with high viscosity; however, because the stirring action in the stratum is very small, the thick oil is difficult to spontaneously form a water-in-oil emulsion, thereby limiting the application of the thick oil. Chinese patent document CN105154045A provides a thick oil emulsion phase inversion profile control water shutoff agent for plugging large gap rock stratum; its main components are active thick oil, water, lime powder, emulsifier, phase-transfer agent and stabilizer. The addition of the stabilizer and the lime powder is beneficial to increasing the stability and viscosity of the water-in-oil emulsion. However, no specific data are provided in this invention to demonstrate the plugging effect of the phase inversion plugging agent for thick oil emulsions, nor is it described whether the phase inversion agent exerts its effect, such that an oil-in-water emulsion is transformed into a water-in-oil emulsion.
The water plugging mechanism of the water-in-oil type emulsion plugging agent is that the high-viscosity water-in-oil type emulsion is used for plugging large pores of a water layer; in the oil flow pore channel, the emulsion is diluted by the crude oil and flows out together with the crude oil, and the device has the characteristics of water plugging and oil plugging. Chinese patent document CN102277143A reports an active thick oil plugging agent used for offshore oil fields. It is composed of internal phase water, thick oil and external phase water. The technology of wrapping the water-in-oil emulsion with high viscosity by the external phase water is adopted, and the water-in-oil emulsion has the advantages of good ground fluidity and low injection pressure. But the preparation process is complex and the cost is relatively high; and the high-temperature stability and the water plugging effect are not related. Chinese patent document CN112210357A discloses a W/O/W type multiple emulsion water shutoff system, which consists of a W/O type primary phase and an external water phase; the W/O type initial phase comprises an oil phase and an internal water phase, wherein the oil phase comprises an oil-soluble surfactant, nano silica sol and the balance of oil; the external aqueous phase comprises an emulsifier, a stabilizer and water. The W/O/W type multiple emulsion water plugging system is injected into an oil well, along with the gradual rise of the temperature from top to bottom in an oil reservoir oil well and the system entering a stratum, the W/O/W type multiple emulsion firstly plugs a water layer by using the Jamin effect of multiple interfaces, meanwhile, the emulsifier and the stabilizer of a water phase in the W/O/W type multiple emulsion are adsorbed on the surface of rock, the outer phase of the W/O/W type multiple emulsion loses stability, the W/O type emulsion with high viscosity is separated, and the water layer is further plugged. However, the W/O emulsion separated from the W/O/W type multiple emulsion provided by the invention can only be stabilized for 24 hours at room temperature, and cannot meet the requirement of long-time plugging on site.
In conclusion, most of the oil phases of the water-in-oil emulsion water shutoff agent used in the oil field are thick oil, so the cost is high; the preparation is complicated, and the cost is further increased; meanwhile, the long-time stability and the good plugging effect are difficult to maintain under the condition of a high-temperature stratum, and the scouring resistance effect is not good enough.
Disclosure of Invention
The invention aims to provide the water-in-oil type emulsion water shutoff agent based on the ethylene tar, and the preparation method and the application thereof, so that the better plugging effect of the water-in-oil type emulsion water shutoff agent is ensured, the economic added value of the ethylene tar can be improved, and the cost of the water-in-oil type emulsion water shutoff agent is saved; and the prepared water-in-oil emulsion water shutoff agent has better high-temperature stability, better shutoff effect at high temperature and better scouring resistance effect.
The technical scheme of the invention is as follows:
an ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 1.0-2.0% of oil-soluble anionic surfactant, 1.0-2.0% of nonionic surfactant, 0.05-0.15% of cosurfactant, 1.0-2.0% of modified nano-particles, 30-45% of ethylene tar and the balance of water.
According to the invention, the water-in-oil type emulsion water shutoff agent based on the ethylene tar preferably comprises the following components in percentage by weight: 2.0% of oil-soluble anionic surfactant, 1.0% of nonionic surfactant, 0.1% of cosurfactant, 1.0-2.0% of modified nano-particles, 30-40% of ethylene tar and the balance of water.
Preferably, the oil-soluble anionic surfactant is calcium dodecylbenzenesulfonate, calcium oleate or magnesium oleate.
According to the invention, the non-ionic surfactant is sorbitan monooleate Span-80, propylene glycol monolaurate or triethanolamine monooleate.
According to the invention, the preferable cosurfactant is polyoxyethylene sorbitan monostearate Tween-60, polyoxyethylene lauryl ether MOA-15 or polyoxyethylene octylphenol ether OP-15.
According to the invention, the modified nano-particles are hydrophobic nano-silica AEROSIL R812S with the average particle diameter of 7-10nm, the surface of the nano-particles is modified by hexamethyldisilazane, so that the nano-particles are easy to disperse in an oil phase, and the specific surface area is 195-245 m2/g。
Preferably, according to the invention, said ethylene tar has a density of 1.134g/cm at 20 ℃3，50℃、7.34s-1The viscosity is 156mPa & s, 80 ℃ and 7.34s-1The viscosity is 41 mPa.s, and the flash point is more than or equal to 80 ℃. The main components are alkane, arene and heterocyclic compound containing N, S, O.
The preparation method of the water-in-oil type emulsion water shutoff agent based on the ethylene tar comprises the following steps:
(1) sequentially adding an oil-soluble anionic surfactant, a nonionic surfactant and modified nanoparticles into ethylene tar, and fully dispersing and uniformly mixing to obtain activated ethylene tar;
(2) adding the cosurfactant into water, and fully mixing and dispersing uniformly to obtain a surfactant aqueous solution;
(3) and (3) dropwise adding the activated ethylene tar obtained in the step (1) into the surfactant aqueous solution obtained in the step (2), and fully and uniformly mixing to obtain the water-in-oil type emulsion water shutoff agent based on the ethylene tar.
According to the invention, the step (1) is preferably carried out at 60 to 80 ℃ to achieve thorough dispersive and uniform mixing.
The application of the water-in-oil type emulsion water shutoff agent based on the ethylene tar is used as the water shutoff agent for oil well water shutoff.
The invention has the following technical characteristics and beneficial effects:
1. the water-in-oil emulsion provided by the invention is prepared by taking industrial byproduct ethylene tar as a raw material, wherein the ethylene tar is a raw material of an ethylene cracking raw material in a cracking process and a high-temperature condensation product thereof, has the characteristics of high carbon-hydrogen ratio, low ash content and high aromaticity, and mainly comprises alkane and C8～C15Aromatic hydrocarbons, aromatic olefins and heterocyclic compounds containing N, S, O elements. The ethylene tar has high carbonization reaction activity, so the viscosity of the tar system rises quickly along with the reduction of the temperature. Currently, ethylene tar is mainly used for burning fuel, which not only results in low economic value, but also causes serious environmental problems such as carbon dioxide emission and global warming. Therefore, there is an urgent need to develop products with higher value from ethylene tar from both economic and environmental aspects. The invention adopts ethylene tar as the external phase of oil, prepares the water-in-oil type emulsion by the composite emulsifier and water, ensures the effective blocking property of the emulsion, reduces the cost of the water blocking agent, improves the economic added value of the ethylene tar and provides a new way for the reutilization of the ethylene tar.
2. The water plugging agent for the water-in-oil type emulsion is brown in appearance, the used emulsifier is formed by compounding a non-ionic surfactant and an anionic surfactant, and a cosurfactant is added for improving the stability of the emulsion. By adding the modified nano-particles, the modified nano-particles are adsorbed on the surface of the emulsion and have viscoelasticity; under high temperature, the modified nano particles can promote the adhesion of the liquid drops of the generated water-in-oil emulsion, and effectively improve the viscosity of the emulsion system; meanwhile, the nano particles are adsorbed on an oil-water interface, so that the stability of the emulsion can be obviously improved. Under the combined action of high viscosity and Jamin effect, the emulsion has strong plugging performance and can reduce the formation water yield. The components of the invention are taken as a whole to play a synergistic effect, so that the obtained water-in-oil type emulsion plugging agent has the characteristics of high viscosity and high stability, and simultaneously has high-temperature stability, can be stabilized for more than 30 days at 80 ℃, and has the viscosity retention rate of more than 80%. The water shutoff agent obtained by the invention has the characteristics of long-time stability and scouring resistance under the condition of high-temperature stratum. Meanwhile, the plugging agent shows a good plugging effect at high temperature, the plugging rate is more than 90%, and the plugging agent has a good selective plugging effect on oil and water.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The embodiments described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The density of the ethylene tar at 20 ℃ is 1.134g/cm3，80℃、7.34s-1The viscosity is 41 mPas, the flash point is more than or equal to 80 ℃, the main components are alkane, aromatic hydrocarbon, aromatic olefin and heterocyclic compounds containing N, S, O and the like, and the compound is sold by Yanshan petrochemical company of China.
Polyoxyethylene sorbitan monostearate Tween-60, polyoxyethylene lauryl ether MOA-15, polyoxyethylene octylphenol OP-15, which is sold by Heian petrochemical plants in Jiangsu province.
The nanosilicon dioxide is AEROSIL R812S, available from EVONIK-DEGUSSA, Germany.
Example 1
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 1.0 percent of nano-silica AEROSIL R812S 1.0, 58.9 percent of water and 37 percent of ethylene tar.
Wherein, the calcium dodecyl benzene sulfonate is an oil-soluble anionic surfactant; the sorbitan monooleate is an oil-soluble nonionic surfactant, and the polyoxyethylene sorbitan monostearate is a cosurfactant; the modified nano-particles are hydrophobic nano-silica AEROSIL R812S.
The preparation method comprises the following steps:
(1) adding oil-soluble surfactant calcium dodecyl benzene sulfonate, sorbitan monooleate and modified nano-particles R812S into ethylene tar, and stirring and mixing uniformly in a constant-temperature water bath at 70 ℃ to obtain activated ethylene tar;
(2) adding a cosurfactant polyoxyethylene sorbitan monostearate into water, and stirring and mixing uniformly to obtain a surfactant aqueous solution with certain viscosity;
(3) and (3) dropwise adding the activated ethylene tar obtained in the step (1) into the surfactant aqueous solution obtained in the step (2), and uniformly stirring and mixing to obtain the water-in-oil type emulsion water shutoff agent based on the ethylene tar.
Example 2
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 1.5 percent of nano-silica AEROSIL R812S 1.5, 58.4 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Example 3
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 2.0 percent of nano-silica AEROSIL R812S 2.0, 57.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Example 4
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium oleate, 1 percent of propylene glycol monolaurate, 0.1 percent of lauryl alcohol polyoxyethylene ether, 1.0 percent of nano-silica AEROSIL R812S 1.0, 58.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Example 5
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of magnesium oleate, 1 percent of triethanolamine monooleate, 0.1 percent of octylphenol polyoxyethylene ether, 1.0 percent of nano-silica AEROSIL R812S 1.0, 58.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Comparative example 1
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 1.0 percent of nano-silica AEROSIL R812S 1.0, 60.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Comparative example 2
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 0.1 percent of polyoxyethylene sorbitan monostearate, 1.0 percent of nano-silica AEROSIL R812S 1.0, 59.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Comparative example 3
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 1.0 percent of nano-silica AEROSIL R812S 1.0, 59 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Comparative example 4
An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 59.9 percent of water and 37 percent of ethylene tar.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the ethylene tar is obtained.
Comparative example 5
The water-in-oil type emulsion water shutoff agent based on the styrene tar comprises the following components in percentage by weight: 2 percent of calcium dodecyl benzene sulfonate, 1 percent of sorbitan monooleate, 0.1 percent of polyoxyethylene sorbitan monostearate, 1.0 percent of nano-silica AEROSIL R812S 1.0, 58.9 percent of water and 37 percent of styrene tar.
Wherein the styrene tar is at 80 ℃ for 7.34s-1The viscosity at room temperature was 13 mPas.
The preparation method is the same as that of example 1, and the water-in-oil type emulsion water shutoff agent based on the styrene tar is obtained.
Test examples
Experimental samples: the water-in-oil type emulsion water shutoff agent prepared in examples 1 to 5 and comparative examples 1 to 5.
(1) And (3) measuring the viscosity of the emulsion: the viscosity of the emulsion is measured at 80 ℃ by using a DV-II + Pro rotary viscometer, and the higher the viscosity of the emulsion is, the better the emulsifying effect of the emulsifier is.
(2) Determination of emulsion thermal stability: putting the water-in-oil type emulsion prepared from ethylene tar into a constant-temperature water bath kettle at the temperature of 80 ℃ for heat treatment for a certain time, taking out the emulsion, measuring the viscosity retention rate, wherein the calculation formula (1) of the viscosity retention rate is shown as follows:
Figure BDA0003018817690000061
in the formula: r-viscosity retention,%;
v1the initial viscosity of the emulsion, mPas;
v2-viscosity of the emulsion after heat treatment, mPa · s.
(3) Measurement of blocking Property of emulsion: the method comprises the steps of evaluating the water plugging performance of emulsion at 80 ℃ by adopting a physical simulation experiment device, filling a sand filling pipe model (the permeability is about 2000 mD) with quartz sand, injecting 0.3PV (PV means pore volume) emulsion and 0.3PV water displacement liquid into the sand filling pipe in a reverse direction at the flow rate of 1.0mL/min after formation water is saturated, driving water in a forward direction at the flow rate of 0.5mL/min, measuring the permeability after plugging, inspecting the water plugging performance of the emulsion, and taking the plugging rate as an evaluation index. 80
The calculation formula of the occlusion rate is shown in (2):
Figure BDA0003018817690000071
in the formula: rPlugging-plugging rate,%;
Kfront side-sand-packed pipe permeability before plugging, mD;
Krear end-permeability of sand filled pipe after plugging, mD.
The measurement results are shown in table 1.
Table 1 measurement results of each index
Figure BDA0003018817690000072
Figure BDA0003018817690000081
As can be seen from table 1, in the examples 1 to 3, under the conditions of similar water content, the viscosity of the water-in-oil emulsion increases with the increase of the mass concentration of the modified nanoparticles, and the viscosity retention rate after heat treatment also increases, which indicates that the modified nanoparticles form a viscoelastic film on the surface of the emulsion, and can promote the adhesion of the droplets of the generated water-in-oil emulsion at high temperature, thereby increasing the viscosity of the water-in-oil emulsion system; meanwhile, the modified nano particles are adsorbed on an oil-water interface, so that the stability of the emulsion can be obviously improved, and the viscosity retention rate is increased. Therefore, under the combined action of high viscosity and Jamin effect, the water-in-oil emulsion prepared by the invention has stronger plugging performance at high temperature, and the plugging rate is more than 90%; has high-temperature stability and shows better plugging effect when being applied to high-temperature stratum.
Compared with the examples 1-5, the viscosity of the emulsion is reduced, the stability can be stabilized for only 5 days, the viscosity retention rate is low, and the plugging effect is poor. The addition of the oil-soluble anionic surfactant calcium dodecyl benzene sulfonate is favorable for promoting the emulsification of the oil phase and the water phase and improving the viscosity and the stability of the emulsion.
Compared with the examples 1-5, the viscosity of the emulsion is reduced, the stability can be stabilized for only 10 days, the viscosity retention rate is low, and the plugging effect is poor. The addition of the oil-soluble nonionic surfactant sorbitan monooleate can generate a synergistic effect with the oil-soluble anionic surface active calcium dodecyl benzene sulfonate, and is favorable for improving the viscosity and the stability of the emulsion.
Compared with the examples 1-5, the viscosity of the emulsion is reduced, the stability is stable for 18 days, and the plugging effect is reduced in the comparative example 3. The addition of a small amount of cosurfactant polyoxyethylene sorbitan monostearate is favorable for promoting the adsorption of the oil-soluble surfactant on the interface, thereby being favorable for improving the viscosity and the stability of the emulsion.
Compared with the examples 1-5, the emulsion of the comparative example 4 has the advantages of obviously reduced viscosity, stable stability for 15 days, small viscosity retention rate and obviously reduced plugging rate. The addition of the modified nano silicon dioxide particles can obviously improve the viscosity of water-in-oil formation, and meanwhile, the modified nano particles are adsorbed on an oil-water interface to improve the interfacial film viscoelasticity, so that oil drops are not easy to coalesce, and the aim of improving the emulsion stability is fulfilled.
Compared with the examples 1-5, the emulsion stability of the comparative example 5 is close, but the blocking rate is lower. This is because the styrene tar used in comparative example 5 was at 80 ℃ for 7.34s-1The viscosity is only 13 mPas, while the ethylene tar is 7.34s at 80 deg.C-1The viscosity was 41 mPas. Since the viscosity of the water-in-oil type emulsion is related to the type and viscosity of the oil phase, the higher the viscosity of the oil phase is, the higher the viscosity of the formed emulsion is. Therefore, in the same case, the viscosity of the water-in-oil emulsion formed by emulsifying the styrene tar and water in comparative example 1 is greatly different from that of the emulsion formed by the ethylene tar in example 1. Therefore, the plugging effect of the water-in-oil type emulsion water plugging agent prepared by adopting the styrene tar instead of the ethylene tarIs poor.
Compared with the prior art, the ethylene tar-based water-in-oil type emulsion water shutoff agent provided by the invention has the advantages of high viscosity, high thermal stability, stability for more than 30 days at 80 ℃, viscosity retention rate of more than 80% and shutoff rate of more than 90%. Therefore, the water shutoff agent provided by the invention has the advantages of long-time stability under the condition of high-temperature stratum, good scouring resistance and good shutoff effect at high temperature, and can effectively prolong the effective period of water shutoff of a high-temperature oil reservoir.
The above embodiments are merely illustrative of the present invention, and should not be construed as limiting the scope of the present invention, and all designs identical or similar to the present invention are within the scope of the present invention. The parts of the embodiment not specifically described are all common general knowledge and common knowledge in the art, and are not described in detail herein.

Claims (10)

1. An ethylene tar-based water-in-oil type emulsion water shutoff agent comprises the following components in percentage by weight: 1.0-2.0% of oil-soluble anionic surfactant, 1.0-2.0% of nonionic surfactant, 0.05-0.15% of cosurfactant, 1.0-2.0% of modified nano-particles, 30-45% of ethylene tar and the balance of water.
2. The ethylene tar-based water-in-oil emulsion water shutoff agent according to claim 1, wherein the ethylene tar-based water-in-oil emulsion water shutoff agent comprises the following components in percentage by weight: 2.0% of oil-soluble anionic surfactant, 1.0% of nonionic surfactant, 0.1% of cosurfactant, 1.0-2.0% of modified nano-particles, 30-40% of ethylene tar and the balance of water.
3. The water-in-oil emulsion plugging agent based on ethylene tar of claim 1, wherein the oil-soluble anionic surfactant is calcium dodecylbenzenesulfonate, calcium oleate or magnesium oleate.
4. The water-in-oil emulsion plugging agent based on ethylene tar according to claim 1, wherein the nonionic surfactant is sorbitan monooleate Span-80, propylene glycol monolaurate or triethanolamine monooleate.
5. The water-in-oil emulsion plugging agent based on ethylene tar as claimed in claim 1, wherein the cosurfactant is polyoxyethylene sorbitan monostearate Tween-60, polyoxyethylene lauryl ether MOA-15 or polyoxyethylene octylphenol OP-15.
6. The ethylene tar-based water-in-oil emulsion water shutoff agent according to claim 1, wherein the modified nanoparticles are hydrophobic nano-silica AEROSIL R812S, the average particle diameter is 7-10nm, the surface of the nanoparticles is modified by hexamethyldisilazane, and the specific surface area is 195-245 m2/g。
7. The water-in-oil emulsion plugging agent based on ethylene tar of claim 1, wherein said ethylene tar has a density of 1.134g/cm at 20 ℃3，50℃、7.34s-1The viscosity is 156mPa & s, 80 ℃ and 7.34s-1The viscosity is 41 mPa.s, and the flash point is more than or equal to 80 ℃.
8. The process for the preparation of a water-in-oil emulsion water shutoff agent based on ethylene tar as claimed in any of claims 1 to 7, comprising the steps of:
(1) sequentially adding an oil-soluble anionic surfactant, a nonionic surfactant and modified nanoparticles into ethylene tar, and fully dispersing and uniformly mixing to obtain activated ethylene tar;
(2) adding the cosurfactant into water, and fully mixing and dispersing uniformly to obtain a surfactant aqueous solution;
(3) and (3) dropwise adding the activated ethylene tar obtained in the step (1) into the surfactant aqueous solution obtained in the step (2), and fully and uniformly mixing to obtain the water-in-oil type emulsion water shutoff agent based on the ethylene tar.
9. The method for preparing a water-in-oil emulsion plugging agent based on ethylene tar according to claim 8, wherein the step (1) of thoroughly dispersing and uniformly mixing is performed at 60-80 ℃.
10. Use of the ethylene tar-based water-in-oil emulsion water shutoff agent according to any of claims 1 to 7 as a water shutoff agent for oil well water shutoff.
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