CN115109204A - Organic silicon surface polymerization agent and application thereof in thickened oil recovery - Google Patents
Organic silicon surface polymerization agent and application thereof in thickened oil recovery Download PDFInfo
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Abstract
The invention discloses an organic silicon surface-gathering agent and application thereof in heavy oil recovery, and mainly relates to the technical field of chemical oil displacement in oil field oil recovery. The organosilicon polymer surfactant structurally contains alpha-olefine polymethylsiloxane monomers which have good lipophilicity, lower surface tension and excellent wetting and overturning capabilities, and the synthesized organosilicon polymer surfactant is easy to dissolve in water and difficult to hydrolyze and simultaneously has good thick oil emulsifying capability, lower oil-water interfacial tension and stronger wetting and overturning capabilities. Can be applied to products such as thick oil emulsification viscosity reducers, thick oil viscosity reduction oil displacement agents, hypotonic pressure reduction injection-increasing agents and the like.
Description
Technical Field
The invention relates to the technical field of chemical oil displacement in oil extraction of oil fields, in particular to an organic silicon surface-gathering agent and application thereof in heavy oil recovery.
Background
Along with the deepening of the exploitation degree of petroleum, the recoverable amount and the yield of conventional crude oil are continuously reduced, the crude oil becomes thick and heavy to become a worldwide irreversible trend, and the condition is particularly prominent in China. Therefore, the development of the thickened oil is also important in China. However, since the thick oil has a high viscosity and poor flow properties, its production and use are greatly limited.
At present, thick oil recovery methods researched at home and abroad can be divided into two methods of thermal recovery of thick oil and cold recovery of thick oil according to whether an oil layer is heated, and the methods developed at present are more for the thermal recovery of thick oil, but the methods have the defects of higher energy consumption and cost, lower heat energy utilization rate, incapability of developing thick oil reservoirs with thinner development layers and the like, so that the methods are greatly limited.
The cold production of heavy oil is to utilize the characteristics of oil reservoir, adopt proper technology, and do not raise temperature to achieve the purpose of viscosity reduction production, such as chemical flooding. Compared with steam-assisted heavy oil recovery, chemical flooding is widely applied to various large oil fields due to low energy consumption, low cost and high oil displacement efficiency. The surface active viscosity reducer is most applied at present, thick oil is formed into an oil-in-water emulsion, the apparent viscosity is only reduced, and the encapsulation of the oil-water emulsion in rock sometimes blocks pores, so that the viscosity reducing and displacing effects on the thick oil are very limited.
Disclosure of Invention
The invention aims to provide an organic silicon surface-gathering agent and application thereof in thickened oil exploitation, wherein the organic silicon surface-gathering agent is easy to dissolve in water and not easy to hydrolyze, and simultaneously has good thickened oil emulsifying capacity, lower oil-water interfacial tension and stronger wetting and overturning capacity.
In order to achieve the purpose, the invention is realized by the following technical scheme:
an organic silicon polyether agent, the structure of which is composed of 2-4 monomers of alpha-alkene polymethylsiloxane and acrylamide monomer, sodium acrylate monomer, 2-acrylamide-2-methyl sodium propyl sulfonate monomer and allyloxy nonyl phenol polyoxyethylene ether monomer, wherein the structural formula of the alpha-alkene polymethylsiloxane monomer is as follows:
wherein n is an integer of 3 to 8.
Preferably, the α -olefopolysiloxane monomer is prepared by the following method:
s1, adding polymethyl cyclosiloxane, end-capping agent trimethylethoxysilane and 0.01% tetramethylammonium hydroxide as catalysts into a reaction kettle, stirring and heating, and maintaining the reaction temperature at 80-90 ℃ for reaction for 2-3 h;
s2, adding vinyl dimethyl ethoxysilane into the reaction kettle, maintaining the reaction temperature of 80-90 ℃, and continuing to react for 2-3 h;
s3, reducing the vacuum degree to 20-50KPa, increasing the temperature to 110-120 ℃, and removing low-boiling-point substances in the reactants to obtain the alpha-olefin multi-methyl siloxane monomer.
Further, the polymethylcyclosiloxane includes: any one or combination of any several of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
Further, in step S1, the molar ratio of the polymethylcyclosiloxane to the capping agent trimethylethoxysilane is 1: 1.0-1.1;
and/or, in step S2, the molar ratio of the polymethylcyclosiloxane to the vinyldimethylethoxysilane is 1:1.1 to 1.2.
Preferably, the organosilicon surfactant has the structural formula:
further, the synthesis method comprises the following steps:
s1, adding alpha-olefin polymethyl siloxane into a reaction kettle, adding 2-4 monomers of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and allyloxy nonyl phenol polyoxyethylene ether, and controlling the concentration of the monomers to be 3-45% by adding ultrapure water;
s2, adding 1-5% of emulsifier into the reaction system, starting electric stirring, introducing nitrogen, adjusting the reaction temperature to 40-50 ℃, introducing nitrogen for 15min, adding 0.1-0.2% of initiator and sodium bisulfite, sealing the reaction kettle, stopping stirring, keeping the nitrogen pressure in the kettle at 0.2-0.3MPa, and reacting for 5-6 h;
and s3, after the reaction is finished, slicing, drying and granulating the gel product to obtain the organic silicon surface polymerization agent product.
Further, the modified acrylic acid is prepared by free radical polymerization of four monomers of alpha-olefepolymethylsiloxane, acrylamide, sodium acrylate and 2-acrylamide-2-methyl sodium propanesulfonate, wherein the molar ratio of the four monomers is 1-3: 60-90: 7-20: 1-4.
Further, the emulsifier comprises: any one or combination of any more of sodium dodecyl benzene sulfonate, dodecyl hydroxy sulfobetaine, octadecyl hydroxy sulfobetaine, span, tween, alpha olefin sodium sulfonate and fatty alcohol-polyoxyethylene ether sodium sulfate;
and/or, the initiator comprises: sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisoheptonitrile or the combination of any of them.
Further, the adding amount of the sodium bisulfite is 0.1-0.2% of the total mass of reactants.
The organic silicon polymer surface agent is applied as a thick oil emulsifying viscosity reducer, a thick oil viscosity-reducing oil-displacing agent or a low-permeability pressure-reducing injection-increasing agent in the thick oil exploitation.
Compared with the prior art, the invention has the beneficial effects that:
the structure of the surface polymerization agent contains an organic silicon oleophylic monomer of alpha-alkene polymethylsiloxane, and the monomer has good lipophilicity, lower surface tension and excellent wetting and overturning capacity, so that the surface polymerization agent has stronger emulsifying and dispersing capacity on thickened oil, and can emulsify the thickened oil into O/W emulsion, thereby reducing apparent viscosity. Due to the addition of the organic silicon oleophylic group, the product can reduce the oil-water interfacial tension to 0.1-1mN/m, thereby having certain oil displacement capability; the water phase wettability of the oil reservoir can be improved, so that the oil reservoir has certain imbibition and displacement capacity.
The organic silicon polymer surfactant product is a high molecular surfactant, has an oleophylic long carbon chain structure and a large number of hydrophilic groups, and can effectively improve the viscosity of injection liquid, thereby having certain profile control capability and effectively improving the sweep efficiency of the injection liquid. Meanwhile, the emulsion has the properties of emulsification, interface tension reduction and wetting turnover, and can be applied to products such as thick oil emulsification viscosity reducers, thick oil viscosity reduction oil displacement agents, seepage oil displacement agents and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the present application.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like in the following examples are all conventional experimental methods, detection methods, and the like in the prior art.
The surface polymerization agent is an organic silicon surface polymerization agent, and the structural formula of the surface polymerization agent is as follows:
the alpha-olefin polymethyl siloxane is an active oleophylic monomer, can reduce the surface tension and improve the wettability, and can ensure that a product can be quickly adsorbed and spread in oil reservoir pore canals, thereby improving the hydrophilicity of the oil reservoir pore canals and playing a role in imbibition and displacement of reservoir oil;
after acrylamide is polymerized, the molecular carbon chain can be made to have flexibility, and simultaneously, the acrylamide has good hydrophilicity, so that the viscosity of the water solution of the polyether surfactant can be improved, and the stability of the water solution of the polyether surfactant can be improved;
the sodium acrylate has strong hydrophilicity, can improve the hard water resistance and the thermal stability of the surface polymerization agent, has certain emulsifying capacity and can improve the emulsifying and viscosity reducing capacity of the product;
the 2-acrylamide-2-methyl sodium propanesulfonate can improve the calcium and magnesium ion resistance of the product and improve the stability of the polyepitometer agent in an oil reservoir with higher calcium and magnesium ion contents;
the allyloxy nonyl phenol polyoxyethylene ether has good thick oil emulsifying capacity, can obviously improve the emulsifying capacity of the poly surface agent to thick oil and super thick oil, and has certain interfacial activity to improve the spreadability of poly surface agent molecules on an oil-water interface.
The specific application can be used for multiple purposes, such as a thick oil emulsification viscosity reducer, a thick oil viscosity reduction oil displacement agent or a hypotonic oil absorbent, and the specific production and application examples are as follows.
Example 1: organic silicon surface polymerization agent and application thereof as viscosity reducer for thickened oil
The preparation method of the organic silicon polymer surface agent comprises the following specific steps:
(1) in a 1L stainless steel reactor, 163.24g of octamethylcyclotetrasiloxane, 71.58g of ethoxytrimethylsilane and 0.03g of tetramethylammonium hydroxide were charged. The reaction kettle is closed, the electric stirring is started, and the stirring speed is 60-70 rpm. The reaction temperature is stabilized at 80-85 ℃ and the reaction lasts for 3 h. 78.85g of vinyldimethylethoxysilane and 0.03g of tetramethylammonium hydroxide were added and the mixture was reacted at 80 to 85 ℃ for 3 hours. After the reaction is finished, a small amount of sample is taken and put into a beaker, the sample is dried for 2 hours at 105 ℃, and the solid content is detected to calculate the conversion rate. If the conversion rate reaches more than 98 percent, the temperature of the reaction kettle is raised to 110-120 ℃, the negative pressure of 20-50KPa is maintained, and low-boiling-point substances in the product are removed to obtain the alpha vinyl polymethylsiloxane monomer.
(2) Four monomers of alpha-olefine polymethylsiloxane, acrylamide, sodium acrylate and 2-acrylamide-2-methyl propyl sodium sulfonate are added into a 1L stainless steel reaction kettle according to the molar ratio of 1:80:20:2, and the addition amounts are 2.87g, 30.05g, 9.92g and 2.18g respectively. 943g of ultrapure water was added, 5g of sodium dodecylbenzenesulfonate and 7g of dodecylhydroxysultaine were added. The reaction kettle is sealed, electric stirring is started, the rotating speed is controlled at 110rpm, nitrogen is introduced, the reaction temperature is adjusted to 40-50 ℃, and 0.05g of sodium persulfate and 0.02g of sodium bisulfite are added after the nitrogen is introduced for 15 min. After the reaction is carried out for 1 hour, the stirring is stopped, the nitrogen pressure in the kettle is kept between 0.2 and 0.3MPa, and the reaction is continued for 5 hours. After the reaction is finished, the final viscous surface polymerization agent product is obtained.
(3) Product analysis
The performance of the heavy oil viscosity reducer is analyzed by using the heavy oil and the injection water of a pure beam oil extraction plant 822P2 well of the Shengli oil field according to the enterprise mark Q/SH 10201519-2016 of the Shengli oil field. The results are shown in the following table:
the product can be quickly dissolved by injected water, and is clear and transparent with slight viscosity after being prepared into a 1% solution. After active water is mixed with the thickened oil of 822P2 of pure Beam oil extraction factory in a ratio of 3:7, the thickened oil can be dispersed in water by slight stirring to form an oil-in-water emulsion. The viscosity reduction is rapid, and the viscosity reduction rate is more than 99%.
Example 2: organic silicon surfactant and application thereof as viscosity-reducing oil-displacing agent for thickened oil
The alpha-olefinopolymethylsiloxane prepared in example 1 was used as the silicone monomer.
Five monomers of alpha-allyl polymethyl siloxane, acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and allyloxy nonyl phenol polyoxyethylene ether are added into a 1L stainless steel reaction kettle according to the molar ratio of 1:50:30:3:2, and the addition amounts are 6.09g, 39.72g, 31.53g, 6.94g and 15.59g respectively. 900g of ultrapure water was added, emulsifier, 6g of sodium dodecylbenzenesulfonate, 14g of dodecylhydroxysultaine and 9g of octadecylhydroxysultaine were added. The reaction kettle is sealed, electric stirring is started, the rotating speed is controlled at 110rpm, nitrogen is introduced, the reaction temperature is adjusted to 40-50 ℃, and 0.05g of sodium persulfate and 0.02g of sodium bisulfite are added after the nitrogen is introduced for 15 min. After the reaction is carried out for 1 hour, the stirring is stopped, the nitrogen pressure in the kettle is kept between 0.2 and 0.3MPa, and the reaction is continued for 5 hours. After the reaction is finished, the final viscous surface polymerization agent product is obtained.
(3) Analysis of product Properties
And (3) carrying out performance analysis on the thick oil viscosity-reducing oil-displacing agent by using thick oil and injection water of a 6X20 well in an Dongxin oil extraction plant of the Shengli oil field according to the Hedgeli oil field enterprise mark Q/SLCG 0257-2018. The results are shown in the following table:
the product has good interfacial tension and oil washing capability while emulsifying and viscosity reducing, and can perform viscosity reducing on thick oil and perform displacement. Can effectively improve the recovery ratio of the thickened oil.
Example 3: surface modifying and flooding integrated polymer
(1) Into a 1L stainless steel reactor, 300g of decamethylcyclohexasiloxane, 40g of ethoxytrimethylsilane and 0.04g of tetramethylammonium hydroxide were charged. The reaction kettle is closed, the electric stirring is started, and the stirring speed is 60-70 rpm. The reaction temperature is stabilized at 80-85 ℃ and the reaction lasts for 3 h. 60g of vinyl dimethylethoxysilane and 0.04g of tetramethylammonium hydroxide are added and reacted at 80 to 85 ℃ for 3 hours. After the reaction is finished, a small amount of sample is taken and put into a beaker, the sample is dried for 2 hours at 105 ℃, and the solid content is detected to calculate the conversion rate. If the conversion rate reaches more than 98 percent, the temperature of the reaction kettle is raised to 110-120 ℃, the negative pressure of 20-50KPa is maintained, and low-boiling-point substances in the product are removed to obtain the alpha-olefine polymethine siloxane monomer.
(2) Adding four monomers of alpha-allyl polymethyl siloxane, acrylamide, 2-acrylamide-2-methyl sodium propane sulfonate and allyloxy nonyl phenol polyoxyethylene ether into a 1L stainless steel reaction kettle according to a molar ratio of 3:65: 5:5, 82.8g, 109.2g, 24.5g and 33.5g are added. 600g of ultrapure water was added, 6g of span 80 was added, 12g of sodium alpha olefin sulfonate was added, and 8g of octadecyl sultaine was added. The reaction kettle is sealed, electric stirring is started, the rotating speed is controlled at 110rpm, nitrogen is introduced, the reaction temperature is adjusted to 40-50 ℃, and 0.05g of sodium persulfate and 0.02g of sodium bisulfite are added after the nitrogen is introduced for 15 min. After the reaction is carried out for 1 hour, the stirring is stopped, the nitrogen pressure in the kettle is kept between 0.2 and 0.3MPa, and the reaction is continued for 5 hours. And after the reaction is finished, taking out the reactant, granulating and drying to obtain the final polymer surfactant product.
(3) Product analysis
The product is suitable for the integration of profile control and flooding with the mineralization degree less than or equal to 7000ppm and the viscosity of a crude oil stratum less than or equal to 120 mPa.s, and can play a role in oil displacement while profile control and water shutoff are carried out. Injecting water and dehydrated crude oil into a 15# station of a victory oil field island oil extraction plant for detection, preparing a 4000ppm solution by using injected water as a profile control and flooding integral polymer surfactant, and comparing the 4000ppm solution with a binary composite oil displacement system consisting of 1800ppm polymer and 4000ppm traditional oil displacement agent.
Compared with the traditional binary composite flooding system, the product has the characteristics of low usage amount, low interfacial tension, high oil washing efficiency and the like, and can reduce the chemical flooding cost of the high-water-content oil field to a certain extent.
Example 4: salt-resistant thick oil viscosity reducer
(1) In a 1L stainless steel reaction vessel, 200g of hexamethylcyclotrisiloxane, 106g of ethoxytrimethylsilane and 0.02g of tetramethylammonium hydroxide were charged. The reaction kettle is closed, the electric stirring is started, and the stirring speed is 60-70 rpm. The reaction temperature is stabilized at 80-85 ℃ and the reaction lasts for 3 h. 158.6g of vinyldimethylethoxysilane, and additionally 0.03g of tetramethylammonium hydroxide were added and reacted at 80-85 ℃ for 3 hours. After the reaction is finished, a small amount of sample is taken and put into a beaker, the sample is dried for 2 hours at 105 ℃, and the solid content is detected to calculate the conversion rate. If the conversion rate reaches more than 98 percent, the temperature of the reaction kettle is raised to 110-120 ℃, the negative pressure of 20-50KPa is maintained, and low-boiling-point substances in the product are removed to obtain the alpha-olefine polymethine siloxane monomer.
(2) Five monomers of alpha-allyl polymethyl siloxane, acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and allyloxy nonyl phenol polyoxyethylene ether are added into a 1L stainless steel reaction kettle according to the mol ratio of 1: 60: 25: 5: 1, 11.8g, 101.1g, 55.7g, 24.6g and 6.7 g. 600g of ultrapure water is added, and 10g of emulsifier dodecyl hydroxysulfobetaine, 8g of tween, 15g of alpha olefin sodium sulfonate and 5g of fatty alcohol-polyoxyethylene ether sodium sulfate are added. The reaction kettle is sealed, electric stirring is started, the rotating speed is controlled at 100 plus 110rpm, nitrogen is introduced, the reaction temperature is adjusted to 40-50 ℃, and 0.04g of sodium persulfate and 0.01g of sodium bisulfite are added after 15min of nitrogen introduction. After the reaction is carried out for 1 hour, the stirring is stopped, the nitrogen pressure in the kettle is kept between 0.2 and 0.3MPa, and the reaction is continued for 5 hours. And after the reaction is finished, taking out the reactant, granulating and drying to obtain the final polymer surfactant product.
(3) Product analysis
The product is suitable for reducing the viscosity of thick oil with the mineralization degree of more than or equal to 50000ppm and the crude oil viscosity of 10000-50000 mPas, and can emulsify the thick oil into O/W emulsion, thereby reducing the viscosity. Injecting water into 25 old stations of an oil extraction plant at the estuary of the Shengli oil field, wherein the mineralization degree is 67080 ppm; the viscosity of dehydrated raw oil is 13800 mPas, and the salt-resistant polymer surfactant is prepared into 500ppm solution by using injection water, and compared with 3000ppm of the traditional thick oil viscosity reducer.
| Item | Salt accumulation resisting agent | Traditional viscosity reducer for thick oil |
| Appearance of the product | Pale yellow solid particles | Homogeneous liquid without impurities |
| Solubility in water | Dissolving in water to form uniform transparent liquid | Dissolving in water to form uniform transparent liquid |
| pH value | 7-9 | 7.6 |
| Concentration of solution, ppm | 500 | 3000 |
| Viscosity reduction rate% | 99.5 | 99.5 |
| Stability (70 ℃, 30d) | The solution is stable and has no demixing | The solution is stable and has no demixing |
| Natural settling dehydration rate% | 82.3 | 84.7 |
| Organic chlorine content,% of | 0.0 | 0.0 |
Compared with the traditional thick oil viscosity reducer, the product has the characteristics of less dosage and high viscosity reduction efficiency, and can greatly reduce the cost of thick oil viscosity reduction exploitation on the premise of ensuring the application effect.
Claims (10)
1. An organic silicon polyether agent is characterized in that the structure of the organic silicon polyether agent is composed of 2-4 monomers of alpha-olefine polymethylsiloxane and acrylamide monomers, sodium acrylate monomers, 2-acrylamide-2-methyl sodium propyl sulfonate monomers and allyloxy nonyl phenol polyoxyethylene ether monomers, wherein the structural formula of the alpha-olefine polymethylsiloxane monomers is as follows:
wherein n is an integer of 3 to 8.
2. The silicone polyether according to claim 1, wherein the α -olefm polymethylsiloxane monomer is prepared by:
s1, adding polymethyl cyclosiloxane, end-capping agent trimethylethoxysilane and 0.01% tetramethylammonium hydroxide as catalysts into a reaction kettle, stirring and heating, and maintaining the reaction temperature at 80-90 ℃ for reaction for 2-3 h;
s2, adding vinyl dimethyl ethoxysilane into the reaction kettle, maintaining the reaction temperature of 80-90 ℃, and continuing to react for 2-3 h;
s3, reducing the vacuum degree to 20-50KPa, increasing the temperature to 110-120 ℃, and removing low-boiling-point substances in the reactants to obtain the alpha-olefin multi-methyl siloxane monomer.
3. The silicone polyether according to claim 2, wherein the polymethylcyclosiloxane comprises: any one or combination of any several of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
4. The silicone polyether polyol according to claim 2, wherein in step S1, the molar ratio of the polymethylcyclosiloxane to the capping agent trimethylethoxysilane is 1: 1.0-1.1;
and/or, in step S2, the molar ratio of the polymethylcyclosiloxane to the vinyldimethylethoxysilane is 1:1.1 to 1.2.
5. The silicone surfacing agent according to claim 1, having the formula:
6. the organosilicon polyether polyol according to claim 1, which is synthesized by the following method:
s1, adding alpha-olefin polymethyl siloxane into a reaction kettle, adding 2-4 monomers of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium salt and allyloxy nonyl phenol polyoxyethylene ether, and controlling the concentration of the monomers to be 3-45% by adding ultrapure water;
s2, adding 1-5% of emulsifier into the reaction system, starting electric stirring, introducing nitrogen, adjusting the reaction temperature to 40-50 ℃, introducing nitrogen for 15min, adding 0.1-0.2% of initiator and sodium bisulfite, sealing the reaction kettle, stopping stirring, keeping the nitrogen pressure in the kettle at 0.2-0.3MPa, and reacting for 5-6 h;
and s3, after the reaction is finished, slicing, drying and granulating the gel product to obtain the organic silicon surface polymerization agent product.
7. The organosilicon polyether polyol according to claim 6, wherein the monomer is prepared by free radical polymerization of four monomers of alpha-olefin polymethylsiloxane, acrylamide, sodium acrylate and 2-acrylamide-2-methyl propyl sodium sulfonate, and the molar ratio of the four monomers is 1-3: 60-90: 7-20: 1-4.
8. The silicone polyether polyol according to claim 6, wherein the emulsifier comprises: any one or combination of any more of sodium dodecyl benzene sulfonate, dodecyl hydroxysulfobetaine, octadecyl hydroxysulfobetaine, span, tween, alpha olefin sodium sulfonate and fatty alcohol polyoxyethylene ether sodium sulfate;
and/or, the initiator comprises: sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisoheptonitrile or the combination of any of them.
9. The silicone polyether polyol as claimed in claim 6, wherein the amount of sodium bisulfite added is 0.1-0.2% by mass of the total mass of the reactants.
10. The use of the silicone polyepithelizing agent as defined in any one of claims 1 to 9 as a thick oil emulsifying viscosity reducer, a thick oil viscosity reducing oil displacement agent or a hypotonic oil absorption agent in thick oil recovery.
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| CN115304771A (en) * | 2022-10-10 | 2022-11-08 | 山东诺尔生物科技有限公司 | Modified fracturing thickening agent and preparation method thereof |
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