CN112457836B - Sulfonated crude phenol Bola type surfactant and synthesis method and application thereof - Google Patents

Sulfonated crude phenol Bola type surfactant and synthesis method and application thereof Download PDF

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CN112457836B
CN112457836B CN202011480371.6A CN202011480371A CN112457836B CN 112457836 B CN112457836 B CN 112457836B CN 202011480371 A CN202011480371 A CN 202011480371A CN 112457836 B CN112457836 B CN 112457836B
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crude phenol
phenol
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张康
李旭红
王晨
李刚辉
杨晓武
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Shaanxi University of Science and Technology
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    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
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Abstract

The invention discloses a sulfonated crude phenol Bola type surfaceThe active agent and the synthesis method and the application thereof comprise: mixing the crude phenol after vacuum drying with a catalyst, slowly dropwise adding diisocyanate, heating to 60-100 ℃ under the protection of nitrogen, and carrying out vacuum pumping under reduced pressure to obtain an intermediate; adding concentrated H to the intermediate 2 SO 4 Reacting with a solvent at 70-80 ℃ to obtain a crude product; vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product, which was used as an oil-displacing agent. The sulfonated crude phenol Bola type surfactant solves the problems that the oil swept area of other surfactant stratums is small, crude phenol is toxic to oil products in coal tar and the utilization rate of the crude phenol is low. The crude phenol Bola type surfactant is prepared from phenols serving as raw materials through the bridge action of IPDI, and is applied to the field of heavy oil exploitation.

Description

Sulfonated crude phenol Bola type surfactant, and synthetic method and application thereof
Technical Field
The invention relates to a preparation method of a Bola type surfactant and an oil displacement technology thereof, in particular to a sulfonated crude phenol Bola type surfactant and a synthesis method and application thereof.
Background
Phenolics account for approximately 30% of coal tar and are harmful in oil products. But the phenol substance has extremely high utilization value as a chemical raw material, relatively rich yield and low price, and the phenol substance is used as the raw material to produce the surfactant and other products, and can improve the quality of the fuel oil. Therefore, with the increasing awareness of energy safety and the increasing emphasis on environmental issues, the effective utilization of phenolic substances is in the forefront. For the surfactant oil displacement technology, the traditional surfactant is composed of a hydrophobic chain and a hydrophilic polar head, the area of the surfactant on the surface of a solution is small, the area of the surfactant injected into an oil layer reaches the oil layer is small, and meanwhile, in the practical application, the surfactant oil displacement cost is high, and the thickened oil is difficult to recover. Therefore, the development of the novel functional surfactant with a synthetic structure and the oil displacement technology thereof by using the raw materials with low price has important significance for improving the economic benefit of oil field development, maintaining the stable yield of the oil field, increasing the yield and comprehensively utilizing the oil field.
Disclosure of Invention
In order to modify phenolic substances, the influence of sulfonation hydrolysis conditions on the structure-activity relationship of the structure and the performance of a crude phenol Bola type surfactant is researched, the influence rule on the stripping rate of coal tar is determined, and meanwhile, the problems that in the prior art, when the surfactant is used for oil displacement, because the area of the surfactant on the surface of a solution is small, the injection of the surfactant into an oil layer is small, the area of the surfactant to the oil layer is small, the consumption of the surfactant for oil displacement is high, the thick oil is difficult to extract, and crude phenol in the coal tar is toxic to oil products are solved. The invention relates to a sulfonated crude phenol Bola type surfactant, which solves the problems that the spread range of other surfactant stratum is smaller when meeting oil, crude phenol is toxic to oil products in coal tar and the utilization rate of the crude phenol is low.
The technical scheme adopted by the invention is as follows:
a sulfonated crude phenol Bola type surfactant having the following structural formula:
Figure BDA0002838045260000021
the synthesis method of the sulfonated crude phenol Bola type surfactant comprises the following steps:
adding a catalyst into the crude phenol, dropwise adding diisocyanate after mixing, heating to 60-100 ℃ under a protective atmosphere, reacting for 8-10 hours, and carrying out reduced pressure and vacuum pumping to obtain an intermediate;
the crude phenol is phenol, 2-methylphenol and 3-methylphenol in a molar ratio of 1.0:0.2: 0.7;
adding concentrated H to the intermediate 2 SO 4 And a solvent, and fully reacting at 70-80 ℃ to obtain a crude product;
carrying out post-treatment on the crude product to obtain a product;
as a further improvement of the invention, the diisocyanate is isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to crude phenol is 1 (2-2.1).
As a further development of the invention, the catalyst is dibutyltin dilaurate, added in an amount of 0.5% by weight based on the mass of the crude phenol.
As a further improvement of the invention, the intermediate is reacted with concentrated H 2 SO 4 In a molar ratio of 1: 2.05; concentrated H 2 SO 4 The mass fraction is 98%.
As a further improvement of the invention, the solvent is dichloromethane.
As a further improvement of the present invention, the post-treatment means: vacuum drying the crude product, dissolving in ethyl acetate, washing the ester layer with water and saturated saline solution, respectively, and anhydrous MgSO 4 Drying and distilling off ethyl acetate under reduced pressure.
The sulfonated crude phenol Bola type surfactant is applied as an oil displacement agent.
As a further improvement of the invention, the method comprises the following steps:
firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, and standing the coal tar of the rock core saturated reservoir at 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, injecting the sulfonated crude phenol Bola type surfactant flooding agent, and continuing the water flooding until the water content of the produced liquid reaches 98%, thus completing the oil flooding.
The concentration of the sulfonated crude phenol Bola type surfactant is 0.4%; the simulated formation temperature is 80 ℃.
Compared with the prior art, the invention has the following advantages:
the sulfonated crude phenol Bola type surfactant is formed by connecting and bonding two hydrophilic polar groups and a hydrophobic chain, is of a U-shaped structure, enables the area of molecules on the surface of a solution to be two times or more than the area occupied by the corresponding traditional surfactant under the same condition, and during oil displacement, the hydrophilic groups of the oil displacement agent enable the surface of rock to have hydrophilicity, so that the wettability of the surface of a core slice can be changed from strong oleophylicity to weak oleophylicity, the adhesion of coal tar and the surface of the rock is reduced, the coal tar is driven out of the stratum, the water-oil fluidity ratio is reduced, the water fingering phenomenon is reduced, the sweep capability is improved, and the recovery ratio of thick oil is further improved. The invention solves the problems that the spread range of other surfactant stratum is small when meeting oil, crude phenol is toxic to oil products in coal tar and the utilization rate of the crude phenol is low.
When the sulfonated crude phenol Bola type surfactant is prepared, phenolic substances extracted from medium-low temperature coal tar are used as basic raw materials, isophorone diisocyanate (IPDI) and dibutyltin dilaurate (DBTDL) are used as catalysts, phenolic hydroxyl groups are modified into carbamate groups, donor systems provide hydrophobic groups, and synthesized intermediates are sulfonated to prepare the sulfonated crude phenol Bola type surfactant. The sulfonated crude phenol Bola type surfactant is formed by connecting and bonding two hydrophilic polar groups and a hydrophobic chain, is of a U-shaped structure, enables the area of molecules on the surface of a solution to be twice or more than the area occupied by the corresponding traditional surfactant under the same condition, and during oil displacement, the hydrophilic groups of the oil displacement agent enable the surface of rock to have hydrophilicity, so that the wettability of the surface of a core slice can be changed from strong lipophilicity to weak lipophilicity, the adhesion force of coal tar and the surface of the rock is reduced, oil is driven out of the stratum, the water-oil fluidity ratio is reduced, the water fingering phenomenon is reduced, the sweep capability is improved, and the recovery ratio of thick oil is further improved. The invention solves the problems that the spread range of other surfactant stratum is small when meeting oil, crude phenol is toxic to oil products in coal tar and the utilization rate of the crude phenol is low. The crude phenol Bola type surfactant is prepared from phenols serving as raw materials through the bridge action of IPDI, and is applied to the field of heavy oil exploitation.
Drawings
FIG. 1 is a circuit diagram of the synthesis of a sulfonated crude phenol Bola type surfactant according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
The invention relates to a sulfonated crude phenol Bola type surfactant and a synthesis method and application thereof, wherein the sulfonated crude phenol Bola type surfactant has the following structural formula:
Figure BDA0002838045260000051
the principle is as follows: when the crude sulfonated phenol Bola type surfactant is prepared, phenolic substances extracted from medium-low temperature coal tar are used as basic raw materials, isophorone diisocyanate (IPDI) and dibutyltin dilaurate (DBTDL) are used as catalysts, phenolic hydroxyl groups are modified into carbamate groups, donor systems provide hydrophobic groups, and the synthesized intermediate is sulfonated to prepare the crude sulfonated phenol Bola type surfactant. The Bola type surfactant is formed by connecting and bonding two hydrophilic polar groups and a hydrophobic chain, and is of a U-shaped structure, so that the area of molecules on the surface of a solution is twice or more than that of the corresponding traditional surfactant under the same condition, and in the oil displacement process, the hydrophilic groups of the oil displacement agent enable the surface of rock to have hydrophilicity, so that the wettability of the surface of a core slice is changed from strong oleophylicity to weak oleophylicity, the adhesion of coal tar and the surface of the rock is reduced, oil is driven out of the stratum, the water-oil fluidity ratio is reduced, the fingering phenomenon of water is reduced, the sweep capability is improved, and the recovery ratio of thick oil is further improved. The synthetic mechanism is shown in figure 1.
Specifically, the synthesis method of the sulfonated crude phenol Bola type surfactant and the application of the sulfonated crude phenol Bola type surfactant as an oil displacement agent comprise the following steps:
(1) adding the crude phenol after vacuum drying into a flask, adding dibutyltin dilaurate for mixing, and slowly dropwise adding isophorone diisocyanate. Wherein the crude phenol must be dried under vacuum. The molar ratio of the isophorone diisocyanate to the crude phenol is 1 (2-2.1). The amount of dibutyltin dilaurate added was 0.5% by weight. And under the protection of nitrogen, heating to 60-100 ℃, reacting for 8-10 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
The crude phenol is phenol, 2-methylphenol and 3-methylphenol in a molar ratio of 1.0:0.2:0.7, the diisocyanate is isophorone diisocyanate (IPDI), and the molar ratio of isophorone diisocyanate (IPDI) to crude phenol is 1 (2-2.1); the catalyst is dibutyltin dilaurate (DBTDL), and the addition amount is 0.5 wt%.
(2) Mixing the intermediate obtained in the step one with concentrated H 2 SO 4 Flask with dichloromethane solvent added, intermediate and concentrated H 2 SO 4 In a molar ratio of 1:2.05, the solvent is dichloromethane, concentrated H 2 SO 4 The mass fraction of the crude product is 98%, the reaction temperature is 70-80 ℃, and the reaction time is 30 minutes to obtain the crude product.
The intermediate and concentrated H 2 SO 4 The molar ratio of (A) to (B) is 1: 2.05; concentrated H 2 SO 4 The mass fraction is 98%. The solvent is dichloromethane.
(3) Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product.
(4) Firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir at 80 ℃ for 24 hours to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, injecting the sulfonated crude phenol Bola type surfactant flooding agent, and continuing the water flooding until the produced liquid does not produce oil, so that the oil displacement is finished.
The concentration of the sulfonated crude phenol Bola type surfactant is 0.4%; the simulated formation temperature is 80 ℃.
The invention is further illustrated by the following specific examples:
example 1
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio of 1.0:0.2: 0.7) in a molar ratio of 1:2.05, and dibutyltin dilaurate in an amount of 0.5wt% was added to the flask, reacted at 60 ℃ for 8 hours under nitrogen protection, and then vacuum-pumped under reduced pressure to obtain an intermediate. GetIntermediate and concentrated H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 70 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2 to 3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar in a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 2
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio of 1.0:0.2: 0.7) in a molar ratio of 1:2.1, and dibutyltin dilaurate in an amount of 0.5wt% was added to a flask, reacted at 100 ℃ for 8 hours under nitrogen protection, and then vacuum-pumped under reduced pressure to obtain an intermediate. Taking the intermediate and concentrating H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 70 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. Ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 3
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio is 1.0:0.2: 0.7) in a molar ratio of 1:2.05, and dibutyltin dilaurate in an amount of 0.5wt% was added to the flask, reacted at 70 ℃ for 8 hours under nitrogen protection, and then vacuum was applied under reduced pressure to obtain an intermediate. Taking intermediate and concentrated H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 80 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. Ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2 to 3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 4
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio of 1.0:0.2: 0.7) in a molar ratio of 1:2.1, and dibutyltin dilaurate in an amount of 0.5wt% was added to a flask, reacted at 80 ℃ for 8 hours under nitrogen protection, and then vacuum-pumped under reduced pressure to obtain an intermediate. Taking intermediate and concentrated H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 70 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2-3.0 mu m 2 The artificial rock core is vacuumized to saturate underground water, then the rock core is saturated with reservoir coal tar, the temperature of the simulated formation is 80 DEG CThen, standing for 24 hours to fully age; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 5
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio of 1.0:0.2: 0.7) in a molar ratio of 1:2.05, and dibutyltin dilaurate in an amount of 0.5wt% was added to the flask, reacted at 90 ℃ for 8 hours under nitrogen protection, and then vacuum-pumped under reduced pressure to obtain an intermediate. Taking intermediate and concentrated H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 80 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 6
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio is 1.0:0.2: 0.7) in a molar ratio of 1:2.0, and dibutyltin dilaurate in an amount of 0.5wt% was added to the flask, and the mixture was reacted at 60 ℃ for 8 hours under nitrogen protection, and then the intermediate was obtained by vacuum evacuation under reduced pressure. Taking intermediate and concentrated H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 70 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, and collecting the ethyl acetate layerWashing with water, saturated brine respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 7
A mixture of isophorone diisocyanate and crude phenol (phenol: 2-methylphenol: 3-methylphenol molar ratio of 1.0:0.2: 0.7) in a molar ratio of 1:2.1, and dibutyltin dilaurate in an amount of 0.5wt% was added to a flask, reacted at 100 ℃ for 8 hours under nitrogen protection, and then vacuum-pumped under reduced pressure to obtain an intermediate. Taking the intermediate and concentrating H 2 SO 4 Adding dichloromethane solvent at a molar ratio of 1:2.05, and concentrating with concentrated H 2 SO 4 The mass fraction is 98 percent, and the reaction time is 30 minutes at 80 ℃ to obtain a crude product. Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product. The product is the sulfonated crude phenol Bola type surfactant. Firstly, the permeability is 1.2 to 3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
Example 8
(1) Adding the crude phenol after vacuum drying into a flask, adding dibutyltin dilaurate into the flask for mixing, and slowly dropwise adding isophorone diisocyanate. Wherein the crude phenol must be dried under vacuum. The molar ratio of isophorone diisocyanate to crude phenol was 1:2. The amount of dibutyltin dilaurate added was 0.5% by weight. Heating to 60 ℃ under the protection of nitrogen, reacting for 10 hours, and decompressing and vacuumizing to obtain an intermediate.
The crude phenol is phenol, 2-methyl phenol and 3-methyl phenol in a molar ratio of 1.0:0.2:0.7, the diisocyanate is isophorone diisocyanate (IPDI), and the molar ratio of isophorone diisocyanate (IPDI) to crude phenol is 1: 2; the catalyst is dibutyltin dilaurate (DBTDL), and the addition amount is 0.5 wt%.
(2) The intermediate obtained in the step one and concentrated H 2 SO 4 Flask with dichloromethane solvent addition, intermediate and concentrated H 2 SO 4 In a molar ratio of 1:2.05, the solvent is dichloromethane, concentrated H 2 SO 4 The mass fraction of (2) is 98%, the reaction temperature is 70 ℃, and the reaction time is 20 minutes to obtain a crude product.
(3) Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product.
(4) Firstly, the permeability is 1.2 to 3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
The concentration of the sulfonated crude phenol Bola type surfactant is 0.4%; the simulated formation temperature is 80 ℃.
Example 9
(1) Adding the crude phenol after vacuum drying into a flask, adding dibutyltin dilaurate for mixing, and slowly dropwise adding isophorone diisocyanate. Wherein the crude phenol must be dried under vacuum. The molar ratio of isophorone diisocyanate to crude phenol was 1: 2.05. Dibutyltin dilaurate was added in an amount of 0.5 wt%. And under the protection of nitrogen, heating to 70 ℃, reacting for 9 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
The crude phenol is phenol, 2-methylphenol and 3-methylphenol in a molar ratio of 1.0:0.2:0.7, the diisocyanate is isophorone diisocyanate (IPDI), and the molar ratio of isophorone diisocyanate (IPDI) to crude phenol is 1: 2.05; the catalyst is dibutyltin dilaurate (DBTDL), and the addition amount is 0.5 wt%.
(2) The intermediate obtained in the step one and concentrated H 2 SO 4 Flask with dichloromethane solvent addition, intermediate and concentrated H 2 SO 4 In a molar ratio of 1:2.05, the solvent is dichloromethane, concentrated H 2 SO 4 The mass fraction of (2) is 98%, the reaction temperature is 75 ℃, and the reaction time is 25 minutes to obtain a crude product.
(3) Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. Ethyl acetate was distilled off under reduced pressure to give the product.
(4) Firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
The concentration of the sulfonated crude phenol Bola type surfactant is 0.4%; the simulated formation temperature is 80 ℃.
Example 10
(1) Adding the crude phenol after vacuum drying into a flask, adding dibutyltin dilaurate for mixing, and slowly dropwise adding isophorone diisocyanate. Wherein the crude phenol must be dried under vacuum. The molar ratio of isophorone diisocyanate to crude phenol was 1: 2.1. Dibutyltin dilaurate was added in an amount of 0.5 wt%. And under the protection of nitrogen, heating to 100 ℃, reacting for 8 hours, and carrying out vacuum pumping under reduced pressure to obtain an intermediate.
The crude phenol is phenol, 2-methylphenol and 3-methylphenol in a molar ratio of 1.0:0.2:0.7, the diisocyanate is isophorone diisocyanate (IPDI), and the molar ratio of isophorone diisocyanate (IPDI) to crude phenol is 1: 2.1; the catalyst is dibutyltin dilaurate (DBTDL), and the addition amount is 0.5 wt%.
(2) The intermediate obtained in the step one and concentrated H 2 SO 4 Flask with dichloromethane solvent addition, intermediate and concentrated H 2 SO 4 In a molar ratio of 1:2.05, the solvent is dichloromethane, concentrated H 2 SO 4 The mass fraction of the crude product is 98 percent, the reaction temperature is 80 ℃, and the reaction time is 40 minutes to obtain the crude product.
(3) Vacuum drying the crude product, dissolving with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, respectively, anhydrous MgSO 4 And (5) drying. The ethyl acetate was distilled off under reduced pressure to give the product.
(4) Firstly, the permeability is 1.2 to 3.0 mu m 2 Vacuumizing the artificial rock core to saturate underground water, standing coal tar of a rock core saturated reservoir for 24 hours at the simulated formation temperature of 80 ℃ to fully age the coal tar; and (3) performing water flooding on the core of the saturated oil until the water content of the produced liquid reaches 98%, then injecting the sulfonated crude phenol Bola type surfactant oil displacement agent with the injection concentration of 0.4%, and then continuing the water flooding until the water content of the produced liquid reaches 98%, thus finishing the oil displacement.
The concentration of the sulfonated crude phenol Bola type surfactant is 0.4%; the simulated formation temperature is 80 ℃.
In order to characterize the interfacial tension of a sulfonated crude phenol Bola type surfactant as an oil displacement agent, the oil displacement agent synthesized in example 3 was subjected to surface tension and oil-water interfacial tension measurement at normal temperature using a TX-500D spinning drop interfacial tensiometer, and the test results are shown in table 1.
Table 1 interfacial tension test results
Figure BDA0002838045260000141
From the above results, it can be seen that as the concentration of the sulfonated crude phenol Bola type surfactant increases, the values of the solution surface tension and the oil-water interfacial tension both gradually decreaseWhen the concentration of the crude sulfonated phenol Bola type surfactant is 0.4%, the surface tension value is reduced to be below 25mN/m, and the oil-water interfacial tension value can reach 10 -3 mN/m order of magnitude, which shows that the sulfonated crude phenol Bola type surfactant has good interfacial activity.
In order to characterize the oil displacement efficiency of a sulfonated crude phenol Bola type surfactant as an oil displacement agent, an oil displacement experiment was performed on the oil displacement agent synthesized in example 3, and the results are shown in table 2.
TABLE 2 oil-displacing effect of sulfonated crude phenol Bola type surfactants with different concentrations
Figure BDA0002838045260000142
It can be seen from the table that the oil displacing agent has the best oil displacing effect when the concentration of the oil displacing agent is 0.4%.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.

Claims (8)

1. The method for synthesizing the sulfonated crude phenol Bola type surfactant is characterized by comprising the following steps of:
adding a catalyst into the crude phenol, dropwise adding diisocyanate after mixing, heating to 60-100 ℃ under a protective atmosphere, reacting for 8-10 hours, and performing reduced pressure and vacuum pumping to obtain an intermediate;
the crude phenol refers to the molar ratio of phenol to 2-methylphenol to 3-methylphenol of 1.0:0.2: 0.7;
adding concentrated H to the intermediate 2 SO 4 And a solvent, and fully reacting at 70-80 ℃ to obtain a crude product;
carrying out post-treatment on the crude product to obtain a product;
the diisocyanate is isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to crude phenol is 1 (2-2.1);
the catalyst is dibutyltin dilaurate, and the addition amount of the catalyst is 0.5wt% of the mass of the crude phenol.
2. The method for synthesizing the sulfonated crude phenol Bola-type surfactant according to claim 1, wherein the intermediate is reacted with concentrated H 2 SO 4 In a molar ratio of 1: 2.05; concentrated H 2 SO 4 The mass fraction is 98 percent.
3. The method for synthesizing the sulfonated crude phenol Bola-type surfactant according to claim 1, wherein the solvent is dichloromethane.
4. The method for synthesizing the sulfonated crude phenol Bola type surfactant according to claim 1, wherein the post-treatment is: vacuum drying the crude product, dissolving in ethyl acetate, washing the ester layer with water and saturated salt solution, respectively, and removing anhydrous MgSO 4 Drying and distilling off the ethyl acetate under reduced pressure.
5. The sulfonated crude phenol Bola type surfactant is characterized in that: prepared by the synthesis method of any one of claims 1 to 4.
6. Use of the sulfonated crude phenol Bola-type surfactant according to claim 5 as an oil-displacing agent.
7. The use according to claim 6, characterized in that it comprises the following steps:
firstly, the permeability is 1.2-3.0 mu m 2 Vacuumizing the artificial core to saturate underground water, and standing the coal tar of the core saturated reservoir at the formation temperature to fully age the coal tar; and performing water flooding until the water content reaches a set value, injecting the sulfonated crude phenol Bola type surfactant into an oil displacement system, and finishing oil displacement until the water flooding water content reaches the set value.
8. The use according to claim 7, characterized in that the sulfonated crude phenol Bola type surfactant concentration is 0.4%; the simulated formation temperature is 80 ℃.
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