CN107828402B - Improve deep viscous crude CO2Chemical additive for recovery ratio in gas flooding process - Google Patents
Improve deep viscous crude CO2Chemical additive for recovery ratio in gas flooding process Download PDFInfo
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Abstract
The invention discloses a method for improving deep thickened oil CO2The chemical additive for recovery of oil in the gas flooding process consists of a solubilizer and a viscosity reducer, wherein the weight ratio of the solubilizer to the viscosity reducer is 1-6: 1; wherein the solubilizer is a p-methoxybenzoate compound; the viscosity reducer is methacrylic acid long-chain ester-styrene-vinyl acetate copolymer. The chemical additive of the invention can enhance CO2The capability of mixing and dissolving in thick oil and reducing CO2Minimum miscible pressure between thickened oils, formation of CO2The miscible phase displacement can greatly reduce the viscosity of the thickened oil and improve the flow property of the thickened oil, thereby improving the recovery ratio of the thickened oil, having the advantages of high efficiency, strong economy, low energy consumption and the like, being particularly suitable for high-depth low-permeability oil reservoirs with high formation pressure, high crude oil viscosity and low permeability, and having wide application prospect.
Description
Technical Field
The invention relates to a method for improving deep thickened oil CO2Chemical additive for improving recovery ratio of gas flooding process and improving CO2The ability of dissolving in thick oil and reducing the viscosity of thick oil, belonging to the technical field of oil field development.
Background
The deep heavy oil refers to a heavy oil reservoir with large reservoir burial depth range (900-1300 m), compared with common shallow heavy oil, the deep heavy oil has the characteristics of large viscosity, poor underground fluidity and the like, and also has the unfavorable factors of high reservoir burial deep steam injection pressure, large steam injection heat loss, thin oil layer, strong reservoir sensitivity, loose cementation, large development mode selection difficulty and the like, and belongs to the heavy oil difficult to recover. Based on the factors, the problem of developing deep thick oil is always a difficult problem which troubles the oil exploitation work, the thick and poor fluidity of the crude oil causes very poor flow at the well bottom and near the well wall, and a lot of difficulties are brought to the oil exploitation work. The practical results show that the conventional crude oil extraction technology such as CO injection2Flooding, steam thermal recovery, chemical viscosity reduction, microbial flooding and the like are not ideal for exploiting deep thick oil. Therefore, the research and development of a novel thickened oil exploitation technology are needed to solve the problem of reducing the difficulty of thickened oil exploitation.
Currently, in the field of crude oil recovery, CO is injected2Gas drive and chemical viscosity reduction are two technologies with good prospects, and the two technologies have different action principles. Wherein, CO is injected2Flooding means that CO is removed2Compressed to a certain pressure and injected into the formation, during which process CO2Can be mixed and dissolved in crude oil, thereby expanding the volume of the crude oil, reducing the density and viscosity of the crude oil, forming a miscible effect and improving the fluidity of the crude oil. CO injection2Because of its low energy consumption and capability of fixing CO2Has attracted much attention for reducing the greenhouse effect. The chemical viscosity-reducing oil-displacing technology is characterized by that in the course of oil production the viscosity-reducing agent is injected into stratumThe plane overlapping and stacking structure between the asphaltene supermolecule and the colloid molecule is damaged, the spatial extensibility of the asphalt micelle is reduced, and the distribution of the asphalt micelle is more dispersed, so that the viscosity of the thickened oil is reduced, the flowability of the thickened oil is enhanced, and the recovery ratio of the thickened oil is improved. The viscosity reducers commonly used in the market at present can be divided into surfactant viscosity reducers and oil-soluble viscosity reducers. The practical result shows that the catalyst is CO2Gas flooding or chemical viscosity reduction, which is one of the techniques used alone, is not ideal in the recovery of heavy oil. At present, no relevant CO is found at home and abroad2The combination of gas drive and chemical viscosity reduction.
Disclosure of Invention
Aiming at the prior art, the invention provides a method for improving deep thickened oil CO2Chemical additive for improving recovery ratio in gas flooding process, which contains solubilizer and viscosity reducer and can enhance CO2The thick oil has the capability of dissolving in thick oil, reduces the viscosity of the thick oil and is suitable for exploiting deep thick oil.
The invention is realized by the following technical scheme:
improve deep viscous crude CO2The chemical additive for recovery of oil in the gas flooding process consists of a solubilizer and a viscosity reducer, wherein the weight ratio of the solubilizer to the viscosity reducer is 1-6: 1; the solubilizer is a p-methoxybenzoate compound (which can be purchased from conventional markets or prepared by conventional methods) capable of dissolving polar components and long-chain components of crude oil, contains ester groups, benzene rings and saturated alkyl chains, can dissolve the polar components in the crude oil, and promotes CO2Dissolving in crude oil to promote CO2-miscible development of the crude oil, forming miscible flooding, swelling the crude oil, reducing the density and viscosity of the crude oil, increasing the mobility of the crude oil in the formation; the relative molecular mass is 180.07-320.22, the structural formula is shown as the following, and in the structural formula, n is an integer of 2-12;
the viscosity reducer is methacrylic acid long-chain ester-styrene-vinyl acetate copolymer, and polar groups such as benzene rings, ester groups and the like contained in the viscosity reducer can effectively disperse macromolecular aggregates formed by stacking asphaltene and colloid molecule planes in the thickened oil, so that a spatial network structure formed by asphaltene colloid is destroyed, and the viscosity of the thickened oil is effectively reduced; the structural formula is as follows:
in the formula, R represents a saturated alkyl chain, and the number of C atoms is 12-20; j: k: 5 to 10: 2 to 8:1 to 3.
The methacrylic acid long-chain ester-styrene-vinyl acetate copolymer is prepared by the following method: taking methyl methacrylate, styrene and vinyl acetate as raw materials, wherein the molar ratio of the methyl methacrylate to the styrene to the vinyl acetate is (5-10) to (2-8) to (1-3), taking toluene as a solvent, adding an initiator azodiisobutyronitrile (the dosage is 5% of the total weight of the raw materials), and stirring and refluxing for 6-10 hours under the nitrogen atmosphere at 65-75 ℃ to obtain a terpolymer; heating to 80 +/-2 ℃, slowly adding concentrated sulfuric acid (the mass concentration is 98%) (the volume of the concentrated sulfuric acid is 1:1 in total weight of the raw materials, g: ml), adding saturated alkyl monohydric alcohol (the number of C atoms is 12-20) in an amount which is equimolar with that of methyl methacrylate, and carrying out ester exchange reaction for 4-6 hours in a nitrogen range to obtain a crude product; and transferring the crude product to ethanol for purification to obtain the methacrylic acid long-chain ester-styrene-vinyl acetate copolymer.
The invention improves deep thickened oil CO2The chemical additive for gas drive recovery can be injected into stratum by means of CO-injection or pre-injection to raise CO content2The capability of dissolving in thick oil reduces the viscosity of crude oil, thereby improving the recovery ratio of the crude oil. When injected in a companion injection mode, the total usage amount of the CO is CO used for oil displacement21-10% of the total amount; when the pre-slug injection is carried out, the total usage amount is CO in the pre-slug layer 25 to 30 percent of the total amount.
The invention converts CO into2The two technologies of gas drive and chemical viscosity reduction are combined, a composite huff and puff development mode is adopted, and a technology capable of promoting CO is designed and researched2Ability to dissolve in thickened oilAnd a chemical agent system effective in reducing viscosity of the thickened oil, which can enhance CO2The capability of mixing and dissolving in thick oil and reducing CO2Minimum miscible pressure between thickened oils, formation of CO2The miscible phase displacement can greatly reduce the viscosity of the thickened oil and improve the flow property of the thickened oil, thereby improving the recovery ratio of the thickened oil and having the advantages of high efficiency, strong economy, low energy consumption and the like.
The invention improves deep thickened oil CO2The chemical additive for recovery efficiency in the gas flooding process has good solubilization and viscosity reduction characteristics, is simple in injection mode, wide in stratum application range, especially suitable for high-depth low-permeability oil reservoirs with high formation pressure, high crude oil viscosity and low permeability, and has wide application prospects.
Drawings
FIG. 1: example 2A schematic structural view of an apparatus used therein, wherein 1 is CO2The device comprises a gas cylinder, an additive tank, a crude oil tank, a booster pump, a high-pressure infusion pump, a gas storage tank, a high-pressure phase equilibrium kettle, a pressure gauge, a pressure stabilizing valve, an emptying valve, a liquid phase collecting bottle, a gas phase collecting bottle and a mass flow meter, wherein the gas cylinder 2, the crude oil tank 3, the booster pump 4, the high-pressure infusion pump 5, the gas storage tank 6, the high-pressure phase equilibrium kettle.
Detailed Description
The present invention will be further described with reference to the following examples.
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 described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
EXAMPLE 1 preparation of chemical additives and determination of viscosity reducing Properties
The chemical additive consists of a solubilizer, namely p-methoxy propyl benzoate and a viscosity reducer, namely a lauryl methacrylate-styrene-vinyl acetate copolymer, wherein the mass ratio of the p-methoxy propyl benzoate to the viscosity reducer is 4: 1. And adding the solubilizer and the viscosity reducer into a beaker, and stirring for more than 1h at room temperature to fully and uniformly mix the solubilizer and the viscosity reducer to obtain the chemical additive.
The viscosity reducer AThe preparation method of the lauryl acrylate-styrene-vinyl acetate copolymer comprises the following steps: adding 80ml of toluene as a solvent into a 150ml three-necked bottle provided with a mechanical stirring and condensing tube, then sequentially adding 10g of methyl methacrylate, styrene and vinyl acetate in a molar ratio of 10:8:1 and 5% of initiator azodiisobutyronitrile by weight of the raw materials, and introducing N2After replacing the air in the bottle, stirring and refluxing the mixture at the temperature of 70 ℃ for 8 hours to react to obtain a terpolymer; then, at 80 ℃, 10ml of 98% concentrated sulfuric acid is slowly added by a constant pressure dropping funnel, n-dodecanol with the molar quantity equal to that of methyl methacrylate is added, and ester exchange reaction is carried out for 5 hours at 80 ℃ under the nitrogen atmosphere, thus obtaining the crude product of the lauryl methacrylate-styrene-vinyl acetate copolymer. And transferring the crude product to ethanol for purification to obtain a pure product.
The viscosity reduction rate of a prepared chemical additive system on thick oil is measured by a rotational viscometer method, wherein a thick oil sample is Luo 322 sand three-section thick oil, the four components of the thick oil sample are 23.6% of asphaltene, 30.1% of colloid, 35.2% of saturated component and 11.1% of aromatic component respectively, before an experiment, about 80g of the thick oil sample is taken in a 100m L beaker, an oil bath pot is used for stirring for 1 hour at constant temperature of 100 ℃ to fully mix the thick oil sample, the thick oil sample is taken out and placed at room temperature for natural cooling, the sample is placed in the oil bath pot and placed under a rotor of the rotational viscometer, the vertical height of the rotor is adjusted to extend into the thick oil, after a period of constant temperature, a rotational viscometer is started to measure, due to the characteristics of non-Newtonian fluid, the viscosity of the thick oil sample is closely related to the rotating speed, the model number of the rotor, the test time and the like during measurement, the rotating speed of the rotor is set to be 3min, the rotating speed of 5r/min, after each measurement, data is recorded, the influence of the temperature and the chemical additive addition amount of the viscosity reduction rate on the viscosity reduction rate can be measured by a chemical additive is considered, wherein after the constant temperature is 1h and the chemical additive is added into a chemical additive under the test result of a chemical additive under the test table after the chemical viscosity reduction rate is added under the test of the viscosity reduction rate of.
Table 1 results of testing viscosity and viscosity reduction rate with temperature before and after adding oil displacing additive
TABLE viscosity reduction Rate at 2100 deg.C test results with addition of chemical additives
Example 2 testing of chemical additives on CO promotion2Solubility in heavy oil
The apparatus used is shown in FIG. 1, and the chemical additives used are in accordance with example 1. Before the experiment, the air tightness of the instrument needs to be checked, and CO is introduced into the autoclave2The pressure was maintained at 25MPa for 2 hours, and if the pressure fluctuation was not more than 1%, the airtightness was considered to be good. In the experiment, 25g of thickened oil is weighed in a balance kettle, and CO is opened2A sample injection valve and a gas phase sampling valve, and the CO content is 100-200 ml/min2And (4) purging with air for 10min, discharging air in the kettle, and then closing all valves. Starting the thermostatic water bath, increasing the pressure to 15MPa, and stirring and balancing for more than 1h to ensure that the gas-liquid balance is achieved. And then, slightly opening a liquid phase sampling valve, taking out about 20mg of liquid phase sample, metering the released gas amount, and keeping the pressure in the kettle constant through a hand lever in the process. Each sampling is repeated at least twice to reduce random errors. The chemical additive is injected into the kettle through a high-pressure infusion pump, and the volume of the chemical additive needs to be corrected before each injection. Table 3 shows the CO after addition of various amounts of chemical additives2In the heavy oil, the mass percentage is obviously seen from the results, and the CO is increased along with the increase of the chemical additive2The dissolution amount in the thick oil is greatly increased, but the dissolution amount is basically not changed when the addition amount exceeds 5 percent.
TABLE 3 CO after addition of various amounts of chemical additives2Mass percent in thickened oil
Example 3 preparation of chemical additives and determination of their Properties
The chemical additive consists of a solubilizer, namely p-methoxy propyl benzoate and a viscosity reducer, namely octadecyl methacrylate-styrene-vinyl acetate copolymer, wherein the mass ratio of the p-methoxy propyl benzoate to the viscosity reducer is 4: 1. And adding the solubilizer and the viscosity reducer into a beaker, and stirring for more than 1h at room temperature to fully and uniformly mix the solubilizer and the viscosity reducer to obtain the chemical additive.
The preparation method of the viscosity reducer octadecyl methacrylate-styrene-vinyl acetate copolymer comprises the following steps: adding 80ml of toluene as a solvent into a 150ml three-necked bottle provided with a mechanical stirring and condensing tube, then sequentially adding 10g of methyl methacrylate, styrene and vinyl acetate in a molar ratio of 10:8:1 and 5% of initiator azodiisobutyronitrile by weight of the raw materials, and introducing N2After replacing the air in the bottle, stirring and refluxing the mixture at the temperature of 70 ℃ for 8 hours to react to obtain a terpolymer; then, at 80 ℃, 10ml of 98% concentrated sulfuric acid is slowly added by using a constant pressure dropping funnel, n-octadecyl alcohol with the same molar weight as methyl methacrylate is added, and ester exchange reaction is carried out for 5 hours at 80 ℃ under the nitrogen atmosphere, so as to obtain the stearyl methacrylate-styrene-vinyl acetate copolymer crude product. And transferring the crude product to ethanol for purification to obtain a pure product.
The viscosity reduction performance was measured by the same method as in example 1, and the result showed that the viscosity reduction rate was 83.9% when the chemical additive was added in an amount of 5% at 100 ℃.
Test chemical additive pair for CO promotion2The properties of the oil in the same manner as in example 2 are shown in Table 4, and the results show that CO is added with the chemical additives2The dissolution amount in the thick oil is greatly increased.
TABLE 4 CO after addition of various amounts of chemical additives2Mass percent in thickened oil
Example 4 preparation of chemical additives
The chemical additive consists of a solubilizer, namely propyloctyl p-methoxybenzoate and a viscosity reducer, namely cetyl methacrylate-styrene-vinyl acetate copolymer, wherein the mass ratio of the propyloctyl p-methoxybenzoate to the cetyl methacrylate-styrene-vinyl acetate copolymer is 1: 1. And adding the solubilizer and the viscosity reducer into a beaker, and stirring for more than 1h at room temperature to fully and uniformly mix the solubilizer and the viscosity reducer to obtain the chemical additive.
The preparation method of the viscosity reducer cetyl methacrylate-styrene-vinyl acetate copolymer comprises the following steps: adding 80ml of toluene as a solvent into a 150ml three-necked bottle provided with a mechanical stirring and condensing tube, then sequentially adding 10g of methyl methacrylate, styrene and vinyl acetate in a molar ratio of 5:2:3 and an initiator azobisisobutyronitrile with the total weight of 5% of the raw materials, introducing N2After replacing the air in the bottle, stirring and refluxing the mixture at the temperature of 70 ℃ for 8 hours to react to obtain a terpolymer; then, at 80 ℃, 10ml of 98% concentrated sulfuric acid is slowly added by a constant pressure dropping funnel, then n-hexadecanol with the same molar weight as the methyl methacrylate is added, and ester exchange reaction is carried out for 5 hours at 80 ℃ under the nitrogen atmosphere, thus obtaining the crude product of the hexadecyl methacrylate-styrene-vinyl acetate copolymer. And transferring the crude product to ethanol for purification to obtain a pure product.
EXAMPLE 5 preparation of chemical additives
The chemical additive consists of a solubilizer butyl p-methoxybenzoate and a viscosity reducer tetradecyl methacrylate-styrene-vinyl acetate copolymer, and the mass ratio of the solubilizer butyl p-methoxybenzoate to the viscosity reducer methyl methacrylate-styrene-vinyl acetate copolymer is 6: 1. And adding the solubilizer and the viscosity reducer into a beaker, and stirring for more than 1h at room temperature to fully and uniformly mix the solubilizer and the viscosity reducer to obtain the chemical additive.
The preparation method of the viscosity reducer methacrylic acid tetradecyl ester-styrene-vinyl acetate copolymer comprises the following steps: adding 80ml of toluene as a solvent into a 150ml three-necked bottle provided with a mechanical stirring and condensing tube, then sequentially adding 10g of methyl methacrylate, styrene and vinyl acetate in a molar ratio of 8:5:2 and 5% of initiator azodiisobutyronitrile by weight of the raw materials, and introducing N2After replacing the air in the bottle, stirring and refluxing the mixture at the temperature of 70 ℃ for 8 hours to react to obtain a terpolymer; then at 80 ℃, 10ml of 98% concentrated sulfuric acid is slowly added by using a constant pressure dropping funnel, and then normal with the same molar quantity as the methyl methacrylate is addedAnd (3) carrying out ester exchange reaction on tetradecanol at 80 ℃ for 5 hours in a nitrogen atmosphere to obtain a crude product of the tetradecyl methacrylate-styrene-vinyl acetate copolymer. And transferring the crude product to ethanol for purification to obtain a pure product.
Although the specific embodiments of the present invention have been described with reference to the examples, the scope of the present invention is not limited thereto, and those skilled in the art will appreciate that various modifications and variations can be made without inventive effort by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. Improve deep viscous crude CO2The chemical additive for recovery ratio in the gas flooding process is characterized in that: the viscosity reducer is composed of a solubilizer and a viscosity reducer, wherein the weight ratio of the solubilizer to the viscosity reducer is 1-6: 1; the solubilizer is a p-methoxybenzoate compound, and has the structural formula shown in the specification, wherein in the structural formula, n is an integer of 2-12;
the viscosity reducer is methacrylic acid long-chain ester-styrene-vinyl acetate copolymer, and the structural formula of the viscosity reducer is as follows:
in the formula, R represents a saturated alkyl chain, and the number of C atoms is 12-20; j: k: 5 to 10: 2 to 8:1 to 3.
2. The enhanced deep thickened oil CO of claim 12The chemical additive for recovery ratio in the gas flooding process is characterized in that: the weight ratio of the solubilizer to the viscosity reducer is 4: 1.
3. The enhanced deep thickened oil CO of claim 12Chemical additive for recovery of oil in gas flooding process, characterized in thatThe method comprises the following steps: the solubilizer is propyl p-methoxybenzoate.
4. The enhanced deep thickened oil CO of claim 12The chemical additive for recovery ratio in the gas flooding process is characterized in that: the viscosity reducer is a lauryl methacrylate-styrene-vinyl acetate copolymer.
5. Increasing deep thickened oil CO according to claim 1 or 42The chemical additive for recovery ratio in the gas flooding process is characterized in that: the methacrylic acid long-chain ester-styrene-vinyl acetate copolymer is prepared by the following method: taking methyl methacrylate, styrene and vinyl acetate as raw materials, taking toluene as a solvent, adding an initiator azobisisobutyronitrile, stirring and refluxing for 6-10 hours at 65-75 ℃ in a nitrogen atmosphere, and obtaining a terpolymer, wherein the molar ratio of the methyl methacrylate to the styrene to the vinyl acetate is (5-10): 2-8): 1-3; heating to 80 +/-2 ℃, slowly adding concentrated sulfuric acid, then adding saturated alkyl monohydric alcohol with the same molar amount as methyl methacrylate, wherein the C atom number of the saturated alkyl monohydric alcohol is 12-20, and carrying out ester exchange reaction for 4-6 h in a nitrogen range to obtain a crude product; and transferring the crude product to ethanol for purification to obtain the methacrylic acid long-chain ester-styrene-vinyl acetate copolymer.
6. The enhanced deep thickened oil CO of claim 52The chemical additive for recovery ratio in the gas flooding process is characterized in that: the dosage of the azodiisobutyronitrile is 5 percent of the total weight of the raw materials.
7. The enhanced deep thickened oil CO of claim 52The chemical additive for recovery ratio in the gas flooding process is characterized in that: the concentrated sulfuric acid is 98% in mass concentration, and the volume of the concentrated sulfuric acid is as follows: the total weight of the raw materials is 1:1, g: and (3) ml.
8. The enhanced deep thickened oil CO of claim 52The chemical additive for recovery ratio in the gas flooding process is characterized in that: the dropThe preparation method of the adhesive lauryl methacrylate-styrene-vinyl acetate copolymer comprises the following steps: adding 80ml of toluene as a solvent into a 150ml three-necked bottle provided with a mechanical stirring and condensing tube, then sequentially adding 10g of methyl methacrylate, styrene and vinyl acetate in a molar ratio of 10:8:1 and 5% of initiator azodiisobutyronitrile by weight of the raw materials, and introducing N2After replacing the air in the bottle, stirring and refluxing the mixture at the temperature of 70 ℃ for 8 hours to react to obtain a terpolymer; then, at the temperature of 80 ℃, 10ml of 98% concentrated sulfuric acid is slowly added by using a constant pressure dropping funnel, n-dodecanol with the molar weight equal to that of methyl methacrylate is added, ester exchange reaction is carried out for 5 hours at the temperature of 80 ℃ under the nitrogen atmosphere, a crude product is obtained, and the crude product is transferred to ethanol for purification, thus obtaining the product.
9. The method for improving deep thickened oil CO according to any one of claims 1 to 82Chemical additive for recovery of gas flooding process in deep heavy oil CO2The application in the gas drive process is characterized in that: injection into the formation is by satellite or pad injection.
10. Use according to claim 9, characterized in that: when injected in a companion injection mode, the total usage of the chemical additive is CO used for oil displacement21-10% of the total amount; when the front slug injection is carried out, the total usage amount of the chemical additive is CO in the front slug layer25 to 30 percent of the total amount.
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