CN109777393B - Foam oil displacement agent - Google Patents

Foam oil displacement agent Download PDF

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Publication number
CN109777393B
CN109777393B CN201910210546.2A CN201910210546A CN109777393B CN 109777393 B CN109777393 B CN 109777393B CN 201910210546 A CN201910210546 A CN 201910210546A CN 109777393 B CN109777393 B CN 109777393B
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foam
oil
water
foam oil
sulfopropyl
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CN109777393A (en
Inventor
刘宝增
赵海洋
何龙
刘中云
周福建
任波
丁保东
王建海
焦保雷
李亮
秦飞
冯一波
杨利萍
李海霞
李婷婷
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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Abstract

The invention provides a foam oil displacement agent suitable for a high-temperature high-salinity oil reservoir, which comprises 0.3-0.8% of foaming agent, 0.5-2.0% of foam stabilizer and the balance of water in percentage by weight. The foam oil displacement agent has strong stability and long half-life period under the condition of high temperature and high salinity, and can obviously improve the recovery ratio of a high-temperature and high-salinity oil reservoir.

Description

Foam oil displacement agent
Technical Field
The invention belongs to the field of oilfield chemistry, and particularly relates to a foam oil-displacing agent, and more particularly relates to a polymer soft particle reinforced foam oil-displacing agent suitable for a high-temperature high-salinity oil reservoir.
Background
The reserves of the high-temperature high-salinity fracture-cavity oil reservoir in China are rich, but the reservoir structure of the oil reservoir mainly comprises fractures and karst caves, the space connectivity is special, the saturation degree of residual oil after water flooding is high, and part of the residual oil in the fracture-cavity oil reservoir exists in the form of attic oil. Because the gas has the characteristic of low density, the gas can effectively spread to high-position attic oil of the fracture-cavity unit, thereby improving the recovery ratio of the fracture-cavity oil reservoir. However, due to the density and viscosity difference among water, oil and gas, gas channeling is easily generated at the top of the oil reservoir in the gas flooding process, so that the saturation of the residual oil in the middle of the oil reservoir is higher. For a conventional oil reservoir, the foam density can be adjusted by adjusting the gas-liquid ratio, so that the aims of plugging the top gas channeling of the oil reservoir and displacing residual oil in the middle of the oil reservoir are fulfilled. However, the foam is taken as a thermodynamically unstable system, gravity drainage, Laplace drainage, Ostwald curing and other processes are aggravated under the condition of high temperature and high salt, and the foam stability is reduced. Taking a tower river oil field fracture-cave type oil reservoir as an example, the temperature is as high as 130 ℃, the mineralization degree is as high as 220000mg/L, and the conventional foam is difficult to maintain better stability in the stratum environment. Therefore, in order to improve the recovery ratio of the high-temperature and high-salinity fracture-cavity oil reservoir, it is urgently needed to develop a foam system suitable for the high-temperature and high-salinity conditions.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polymer soft particle reinforced foam oil displacement agent suitable for high-temperature and high-salinity oil reservoirs.
The technical scheme of the invention is as follows:
a foam oil displacement agent comprises 0.3-0.8% of foaming agent, 0.5-2.0% of foam stabilizer and the balance of water in percentage by weight.
Further, the foaming agent is 0.4-0.6% by weight, the foam stabilizer is 0.8-1.5% by weight, and the balance is water.
Further, the water is simulated water.
Further, the foaming agent comprises sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to the weight ratio of 2: 1-1: 3.
Further, the foaming agent comprises sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to the weight ratio of 1: 1-1: 2.
Further, the molecular formula of the sulfopropyl polyoxyethylene dodecyl alcohol ether is C12H25O(CH2CH2O)n(CH2)3SO3M, wherein n is an integer of 10 to 15, and M is H+Or Na+
Further, the foam stabilizer is polyethylene glycol.
Further, the relative molecular mass of the polyethylene glycol is 12000-20000.
Further, the half-life period of the foam oil displacement agent is 4-5 hours.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the foam stabilizer used in the invention is low molecular weight polyethylene glycol (with a molecular weight of 12000-20000), and due to the low molecular weight, the foam stabilizer has good stability and slow degradation speed under high temperature and high salt conditions, and can ensure the foam stabilizing capability under the high temperature and high salt conditions.
(2) The foam stabilizer polyethylene glycol used in the invention can be self-assembled with the foaming agent to form soft particles with surface activity, and the soft particles are adsorbed on a gas-liquid interface to further enhance the stability of a liquid film, thereby enhancing the foam stability.
(3) The foaming agent has excellent stability under the conditions of high temperature and high salt (130 ℃, 220000mg/L and 1MPa), the half-life period of the foam measured by a bubbling method is up to 4-5 h, and in addition, indoor flow experiments show that the recovery ratio of the foaming agent is improved by 14.2-22%.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
In order to develop a foam system suitable for high-temperature and high-salt conditions, a foaming agent and a foam stabilizer can be used. For the foaming agent, the inventor researches and discovers that polyoxyethylene ether sulfonate surfactants and betaine surfactants can still maintain good foaming performance under high-temperature and high-salt conditions, but a simple foaming agent cannot maintain good foaming performance under the high-temperature and high-salt conditions, and because foams generated by the simple foaming agent are poor in stability under the high-temperature and high-salt conditions, a foam stabilizer is needed to improve the stability of the foams under the high-temperature and high-salt conditions.
For the foam stabilizer, there are two types of foam stabilizers commonly used at present: polymers and solid particles. The polymer can enhance the viscosity of the foam liquid film due to the high molecular weight characteristic, thereby reducing the liquid discharge speed of the liquid film and further improving the foam stability. However, high molecular weight polymers are susceptible to degradation under high temperature and high salt conditions, resulting in a decrease in foam stabilizing ability. Another type of foam stabilizer is a particulate foam stabilizer, such as nano-silica particles, fly ash particles, clay particles, and the like. Mechanisms for stabilizing the foam include: desorption energy theory, particle aggregate theory, particle arrangement hindering liquid discharge theory, and maximum capillary pressure theory. However, the particles are easy to agglomerate and precipitate under the condition of high temperature and high salt, and the foam stabilizing capability is reduced. Therefore, the currently used polymer and particle foam stabilizers can not better improve the stability of foam under high-temperature and high-salt conditions, so that the foam stability under the high-temperature and high-salt conditions is poor, and the effect of improving the crude oil recovery efficiency by foam flooding is poor.
Through research, the inventor creatively compounds sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to a specific proportion to serve as a foaming agent, and adopts low-molecular-weight polyethylene glycol as a foam stabilizer, so that the polymer soft particle reinforced foam oil displacement agent suitable for high-temperature and high-salt oil reservoir conditions (the temperature is not lower than 130 ℃, and the mineralization degree is not lower than 220000mg/L) is provided, and the recovery ratio of the high-temperature and high-salt fracture-cavity oil reservoir is improved.
The foam oil displacement agent comprises 0.3-0.8% of foaming agent, 0.5-2.0% of foam stabilizer and the balance of water in percentage by weight. Preferably, the foam oil displacement agent comprises 0.4-0.6% of foaming agent, 0.8-1.5% of foam stabilizer and the balance of water in percentage by weight.
The water may be simulated water, and the mineralization degree of the simulated water is determined according to the mineralization degree of the oil reservoir to which the foam oil displacement agent of the present invention is applied, and is not specifically limited herein.
Preferably, the foaming agent is prepared by compounding sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to the weight ratio of 2: 1-1: 3. More preferably, the foaming agent is prepared by compounding sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to the weight ratio of 1: 1-1: 2.
Wherein the molecular formula of the sulfopropyl polyoxyethylene dodecyl alcohol ether is C12H25O(CH2CH2O)n(CH2)3SO3M, wherein n is an integer of 10 to 15, and M is H+Or Na+
Wherein the oleamide hydroxysultaine has the formula C17H33CONH(CH2)3N+(CH3)2CH2CH(OH)CH2SO3 -
Preferably, the foam stabilizer is a low molecular weight polyethylene glycol. The relative molecular weight of the polyethylene glycol is preferably 12000-20000.
The invention compounds sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine according to a specific proportion to be used as a foaming agent, and adopts polyethylene glycol with low molecular weight as a foam stabilizer. On one hand, the sulfopropyl polyoxyethylene dodecyl alcohol ether and the oleamide hydroxysulfobetaine generate a synergistic effect between the two surfactants, so that the surface expansion modulus of a gas-liquid interface is improved, and the foam stability is further improved; on the other hand, polyethylene glycol, because of its large number of ether oxygen atoms in the molecule, readily neutralizes H in aqueous solutions+The combination of the surface active agent and the polyethylene glycol leads the surface active agent to be provided with certain positive electricity, so that the polyethylene glycol is assembled with the surface active agent under the electrostatic action and the hydrophobic action to form aggregate soft particles, and the soft particles have certain surface activity, so that the soft particles are easily adsorbed on a gas-liquid interface, the mechanical strength of the gas-liquid interface is improved, and the foam stability is further improved.
The substances used in the present invention are commercially available, for example, sulfopropyl polyoxyethylene lauryl alcohol ether is available from Qingdao Chang Huadong Co., Ltd, oleamide hydroxysulfobetaine is available from Linyi LvSen science and technology Co., Ltd, and polyethylene glycol is available from Haian petrochemical plant.
The foam oil displacement agent can be prepared by uniformly mixing by adopting a common method. For example, the foam concentrate is obtained by mixing and stirring the sulfopropyl polyoxyethylene lauryl alcohol ether, the oleamide hydroxysulfobetaine and the polyethylene glycol with water according to the proportion.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Method for testing half-life of foam oil displacement agent in the following examples: placing 100mL of foam oil displacement agent in a foam instrument at 130 ℃ and 1MPa, carrying out foam generation by adopting a bubbling method, and recording the change of the foam volume along with timeAnd then calculating the foam half-life tfSpecifically, the foam half-life is the time at which the foam volume is reduced to half the original foam volume.
The method for testing the influence of the foam oil displacement agent on the core recovery ratio in the embodiment comprises the following steps: and (4) investigating the influence of the foam oil displacement agent on the core recovery ratio through an indoor core flow experiment.
Example 1:
0.2g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.2g of oleamide hydroxysulfobetaine, 0.5g of polyethylene glycol and 99.1g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.06h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 14.6 percent.
Example 2:
0.2g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.2g of oleamide hydroxysulfobetaine, 0.8g of polyethylene glycol and 98.8g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.68h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 18.2 percent.
Example 3:
0.4g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.4g of oleamide hydroxysulfobetaine, 1.2g of polyethylene glycol and 98g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to reach 5h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 22 percent.
Example 4:
0.1g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.2g of oleamide hydroxysulfobetaine, 0.8g of polyethylene glycol and 98.9g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.4 hours at the temperature of 130 ℃ and under the condition of 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery ratio by 16 percent.
Example 5:
0.1g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.3g of oleamide hydroxysulfobetaine, 0.8g of polyethylene glycol and 98.8g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.0h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 14.2 percent.
Example 6:
0.2g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.1g of oleamide hydroxysulfobetaine, 0.8g of polyethylene glycol and 98.9g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.2h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery ratio by 15 percent.
Example 7:
0.3g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.3g of oleamide hydroxysulfobetaine, 0.8g of polyethylene glycol and 98.6g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.8h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 19.8 percent.
Example 8:
0.2g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.4g of oleamide hydroxysulfobetaine, 1.5g of polyethylene glycol and 97.9g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to be 4.85h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery ratio by 20.2%.
Example 9:
0.2g of sulfopropyl polyoxyethylene dodecyl alcohol ether, 0.2g of oleamide hydroxysulfobetaine, 2.0g of polyethylene glycol and 98g of simulated water with the mineralization degree of 220000mg/L are added into a beaker and fully stirred to obtain a foam oil displacement agent, and the foam half-life period of the foam system is measured to reach 4.98h under the conditions of 130 ℃ and 1MPa by a foam instrument bubbling method. Indoor core flow experiments show that the system improves the recovery rate by 21.2 percent.
The present invention has been disclosed in the foregoing in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all changes and substitutions equivalent to those of the embodiments are intended to be included within the scope of the claims of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined in the claims.

Claims (7)

1. A foam oil displacement agent is characterized by comprising 0.3 to 0.8 weight percent of foaming agent, 0.5 to 2.0 weight percent of foam stabilizer and the balance of water;
the foaming agent comprises sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine in a weight ratio of 2: 1-1: 3;
the foam stabilizer is polyethylene glycol, and the relative molecular mass of the polyethylene glycol is 12000-20000.
2. The foam oil-displacing agent according to claim 1, which comprises 0.4-0.6% of foaming agent, 0.8-1.5% of foam stabilizer and the balance of water in percentage by weight.
3. The foam oil-displacing agent according to claim 1, wherein the water is simulated water.
4. The foam oil-displacing agent according to claim 2, wherein the water is simulated water.
5. The foam oil-displacing agent according to claim 1, wherein the foaming agent comprises sulfopropyl polyoxyethylene dodecyl alcohol ether and oleamide hydroxysulfobetaine in a weight ratio of 1: 1-1: 2.
6. The foam oil-displacing agent according to claim 5, wherein the formula of the sulfopropyl polyoxyethylene dodecyl alcohol ether is C12H25O(CH2CH2O)n(CH2)3SO3M, wherein n is an integer of 10 to 15, and M is H+Or Na+
7. The foam oil-displacing agent according to any one of claims 1 to 6, wherein the half-life of the foam oil-displacing agent is 4 to 5 hours.
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CN111218267B (en) * 2020-01-19 2022-05-13 成都华阳兴华化工有限公司 Foam scrubbing agent with low foam water content and preparation method thereof
CN115216284B (en) * 2021-04-15 2024-03-26 中国石油天然气股份有限公司 Three-phase foam system suitable for regulation and control of deep clastic rock oil reservoir gas channeling
CN114437703B (en) * 2021-12-27 2023-09-05 河南天祥新材料股份有限公司 Efficient composite foaming cleanup additive for fracturing and preparation method thereof

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