CN107603584B - High-temperature foam stabilizer and preparation method and application thereof - Google Patents
High-temperature foam stabilizer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-temperature foam stabilizer and a preparation method and application thereof, and the high-temperature foam stabilizer comprises the following raw materials in percentage by weight: 20-30 wt.% of hydroxyethyl ethylenediamine, 15-25 wt.% of tetradecyl dihydroxyethyl ammonium oxide, 10-25 wt.% of residual oil sulfonate and the balance of water. The research of the invention shows that the foaming agent added with the foam stabilizer has good thermal stability under the high temperature condition of 300 ℃ and can keep the high-temperature foam stable.
Description
Technical Field
The invention relates to a high-temperature foam stabilizer, a preparation method and application thereof, in particular to a high-temperature foam stabilizer for preventing steam channeling in thickened oil steam flooding, a preparation method and application thereof, and belongs to the technical field of oil exploitation.
Background
After the heavy oil reservoir is subjected to multiple rounds of steam huff and puff, the oil-gas ratio begins to decrease, and the heavy oil recovery rate can be further improved only by switching to a steam flooding stage. However, with the increase of the steam injection amount and the extension of the steam injection time, the steam flooding process has the phenomena of steam overtopping and steam channeling which are more serious than those of the steam huff and puff process, namely, the steam suddenly enters in a single direction and the oil reservoir is not heated uniformly, so that the steam wave and volume are small, the heat efficiency is low and the economic benefit is reduced. In order to increase the total swept volume of steam flooding and the ultimate recovery of heavy oil reservoirs, effective measures must be taken to prevent steam breakthrough. Researches prove that in the steam flooding process, the sweep efficiency and the displacement efficiency of injected steam can be improved by injecting a high-temperature foaming agent along with the steam, and two key technical problems for restricting the application of the technology to the steam flooding are as follows: one is the high-temperature foaming property of the foaming agent, i.e., whether the foaming agent can be foamed at a high temperature of 300 ℃, and the other is the stability of the foam, i.e., whether the foam formed at a high temperature can be stably present. Among them, a high-temperature resistant foaming agent has been developed (Sun Jianfeng, Guo Dong hong, Xinhaochuan, etc. "synthesis and performance evaluation of JP series high-temperature foaming agent", oil drilling and production process, 2011,33(2), 117-. The initial foaming volume and the foam half-life period are two important parameters for measuring the performance of the foaming agent, one reflects the difficulty and the quantity of foaming, the other reflects the stability of the foam, and in order to comprehensively evaluate the static performance of the foaming agent, the influence of the initial foaming volume (maximum foaming volume) and the foam half-life period on the foam performance needs to be comprehensively considered.
In view of the above bottleneck problem and the deficiencies of the prior art, it is an urgent problem in the art to develop a high temperature foam stabilizer which has good thermal stability at a high temperature of 300 ℃ and can maintain high temperature foam stability.
Disclosure of Invention
In view of the actual need, it is an object of the present invention to provide a foam stabilizer to which a foaming agent having excellent thermal stability at a high temperature of 300 ℃ can be added and which can maintain a stable foam at a high temperature.
Another object of the present invention is to provide a process for producing the foam stabilizer.
It is a further object of the present invention to provide the use of the aforementioned foam stabilizers.
It is still another object of the present invention to provide a foaming agent comprising the foam stabilizer.
Therefore, in one aspect, the invention provides a foam stabilizer (which can be referred to as a high-temperature foam stabilizer) which comprises the following raw materials in percentage by weight: 20-30 wt.% of hydroxyethyl ethylenediamine, 15-25 wt.% of tetradecyl dihydroxyethyl ammonium oxide, 10-25 wt.% of residual oil sulfonate and the balance of water.
The experimental research of the invention shows that after the high-temperature foam stabilizer is introduced into the high-temperature foaming agent main agent which is conventional α -olefin sulfonate, the plugging performance of a high-temperature foam system is obviously improved, the foam stabilizing performance of the high-temperature foam stabilizer is obviously superior to that of the existing high-temperature foam stabilizer, after the high-temperature foam stabilizer of the invention is used,not only the stability of the high-temperature foam is obviously enhanced, but also the initial foaming amount of the foam system is not obviously reduced (generally, the initial foaming amount is reduced after the foam stabilizer is added). The molecular formula of the hydroxyethyl ethylenediamine is HO (CH)2)2NH(CH2)2NH2It is commercially available, for example from basf, germany.
The tetradecyl dihydroxyethyl ammonium oxide of the present invention is commercially available, for example, from Shanghai Nursen industries, Inc.
The residual oil sulfonate of the invention is a sulfonate surfactant obtained by sulfonating Daqing vacuum residual oil (fraction higher than 500 ℃) by sulfur trioxide and then neutralizing the sulfonated product by alkali liquor, and can be obtained commercially, for example, from an auxiliary agent factory of New technology company of Reid oil, Beijing.
As a specific embodiment of the present invention, preferably, the foam stabilizer is prepared as follows:
dividing the water into two parts, adding the hydroxyethyl ethylenediamine and the tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at the temperature of 30-40 ℃ to obtain a first solution; then adding the residual oil sulfonate into the other part of water at the temperature of 40-45 ℃, and stirring and dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the foam stabilizer.
The residual oil sulfonate is viscous, so that the residual oil sulfonate needs to be heated and fully stirred for dissolution, and the method can reduce energy consumption in the preparation process and save preparation time.
As described above, the present invention provides a method for producing the aforementioned foam stabilizer, which comprises the steps of:
dividing the water into two parts, adding the hydroxyethyl ethylenediamine and the tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at the temperature of 30-40 ℃ to obtain a first solution; then adding the residual oil sulfonate into the other part of water at the temperature of 40-45 ℃, and stirring and dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the foam stabilizer.
In a further aspect, the present invention provides the use of the foam stabilizers described above as additives in the preparation of blowing agents.
In another aspect, the present invention provides a foaming agent comprising the foam stabilizer of the present invention.
As a specific embodiment of the foregoing blowing agent, the blowing agent contains an alpha-olefin sulfonate. Preferably, the mass ratio of the foam stabilizer to the alpha-olefin sulfonate is 1:40 to 1:75, for example 1: 50. The foaming agent takes alpha-olefin sulfonate as a foaming main body, and the foam stabilizer is added into the foaming main body. It should be noted that the use of the alpha-olefin sulfonate as a blowing agent in the present invention is merely illustrative of whether the foam stabilizer has a stabilizing effect and is a commonly used foam stabilizer in the industry, and the foam stabilizer of the present invention is also applicable to other blowing agents without any evidence of contrary.
In another aspect, the invention provides the use of the aforementioned foaming agent in a process for producing heavy oil by steam flooding. Preferably, the foaming agent is injected as an aqueous solution having a mass concentration of 0.3% to 1.0% (e.g., 0.5%). The experiment of the invention shows that the foaming agent added with the foam stabilizer has good thermal stability under the high temperature condition of 300 ℃ and can keep the high-temperature foam stable. Due to the outstanding advantages of the foaming agent added with the high-temperature foam stabilizer, the steam channeling can be prevented and the swept volume of injected steam can be enlarged in the thick oil steam flooding process. Thereby achieving the purpose of improving the recovery ratio of the heavy oil reservoir.
In summary, the invention mainly provides a foam stabilizer and an application thereof, and a foaming agent added with the foam stabilizer has good thermal stability under the high-temperature condition of 300 ℃ and can keep high-temperature foam stable.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Hydroxyethylethylenediamine used in the following examples was purchased from basf, germany. The tetradecyldihydroxyethyl ammonium oxide used was purchased from Shanghai Nursen industries, Ltd. The residual oil sulfonate used was purchased from auxiliary agent factories of New technology company of Reid Petroleum, Beijing. The residual oil sulfonate is a sulfonate surfactant obtained by sulfonating Daqing vacuum residual oil (fraction higher than 500 ℃) by sulfur trioxide and then neutralizing by alkali liquor. The foaming agent alpha-olefin sulfonate used can be obtained commercially, the proportion and the content of industrial products produced by different manufacturers are basically consistent, the foaming agent alpha-olefin sulfonate generally refers to a sulfonated product of a mixture of C-14 alpha-olefin and C-16 alpha-olefin, and the foaming agent alpha-olefin sulfonate is obtained from Zhejiang Zanyan science and technology group, Inc.
Example 1
This example provides a high temperature foam stabilizer, which comprises the following raw materials, by taking the total weight of the high temperature foam stabilizer as 100%: 20% of hydroxyethyl ethylenediamine, 15% of tetradecyl dihydroxyethyl ammonium oxide, 25% of residual oil sulfonate and the balance of water. The high-temperature foam stabilizer is prepared by the following method: dividing a certain amount of water into two equal parts, adding 20% of hydroxyethyl ethylenediamine and 15% of tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at 30-40 ℃ to obtain a first solution; then adding 25% of residual oil sulfonate into the other part of water at the temperature of 40-45 ℃, and stirring and dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the finished product of the high-temperature foam stabilizer.
Mixing the obtained high-temperature foam stabilizer with conventional alpha-olefin sulfonate according to the weight ratio of 1:55 to obtain a high-temperature foaming agent system. And then dissolving the obtained high-temperature foaming agent system in water to prepare an aqueous solution with the mass concentration of 0.5% of alpha-olefin sulfonate, and measuring the half-life period of foam before and after aging, the initial foaming volume multiple and the resistance factor at high temperature. The foaming half-life and initial foaming times of the 0.5% aqueous solution before and after high-temperature aging were tested by the Waring Blender method. During the test, 100mL of the prepared 0.5% aqueous solution is poured into a Waring stirrer, the mixture is stirred for 1min at the rotating speed of 6500r/min, the foam is poured into a 1000mL measuring cylinder, and the initial foam volume and the time for half of the foam volume to decay are read, namely the half-life period. In the same manner, the half-life of an aqueous solution containing only 0.5% of the alpha-olefin sulfonate was measured, and the results are shown in Table 1.
The resistance factors of the 0.5% aqueous solution containing the alpha-olefin sulfonate and the high-temperature foam stabilizer and the 0.5% aqueous solution containing only the alpha-olefin sulfonate are respectively tested by adopting a dynamic evaluation experimental device, the device is a one-dimensional single-tube model, the model is horizontally placed in a constant temperature oven, and the core is 50.0cm long and 3.0cm in diameter. During the test, the rock core is saturated with water, the water phase permeability of the rock core is measured, then water and gas are simultaneously injected into the rock core according to a certain gas-liquid ratio, and when the pressure difference between two ends of the rock core is stable, the pressure difference between two ends of the rock core at the moment is recorded as the base pressure difference. And then injecting gas and a foaming agent under the same condition, and recording the pressure difference at the two ends of the core as a working pressure difference when the pressure difference at the two ends of the core is balanced. The drag factor is the ratio of the operating differential pressure to the base differential pressure. The resistance factor test conditions are as follows: the temperature is 200 ℃, the gas-liquid ratio is 1: 1, and the nitrogen pressure is 2.0 MPa. The above test methods refer to "performance study of high temperature channeling preventing agent for heavy oil thermal recovery" (guo dong red, xinhachuan, zui dong, etc.. performance study of high temperature channeling preventing agent for heavy oil thermal recovery [ J ]. fine petrochemical engineering progress, 2006, 7 (10): 1-3) and "high temperature foaming agent study for improving steam flooding effect" (guo dong red, xinhachuan, zuo dong. high temperature foaming agent study for improving steam flooding effect [ J ], fine and specialty chemicals, 2010,18 (11): 41-44), and the experimental results are shown in table 1:
table 10.5% aqueous solution various performance test results
Example 2
This example provides a high temperature foam stabilizer, which comprises the following raw materials, by taking the total weight of the high temperature foam stabilizer as 100%: 25% of hydroxyethyl ethylenediamine, 20% of tetradecyl dihydroxyethyl ammonium oxide, 15% of residual oil sulfonate and the balance of water. The high-temperature foam stabilizer is prepared by the following method: dividing a certain amount of water into two equal parts, adding 25% of hydroxyethyl ethylenediamine and 20% of tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at 30-40 ℃ to obtain a first solution; then taking another part of water, adding 15% of residual oil sulfonate at the temperature of 40-45 ℃, and stirring for dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the finished product of the high-temperature foam stabilizer.
Mixing the obtained high-temperature foam stabilizer with conventional alpha-olefin sulfonate according to the weight ratio of 1:55 to obtain a high-temperature foaming agent system. The obtained high-temperature foaming agent system is dissolved in water to prepare an aqueous solution with the mass concentration of alpha-olefin sulfonate of 0.5%, and the aqueous solution is subjected to initial foaming times before and after aging, foam half-life period and resistance factor test at high temperature, and the aqueous solution only containing 0.5% of alpha-olefin sulfonate is used as a reference, the test method is the same as that of example 1, and the test results are shown in table 2:
table 20.5% solution various performance test results
Example 3
This example provides a high temperature foam stabilizer, which comprises the following raw materials, by taking the total weight of the high temperature foam stabilizer as 100%: 30% of hydroxyethyl ethylenediamine, 15% of tetradecyl dihydroxyethyl ammonium oxide, 15% of residual oil sulfonate and the balance of water. The high-temperature foam stabilizer is prepared by the following method: dividing a certain amount of water into two equal parts, adding 30% of hydroxy ethylenediamine and 15% of tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at 30-40 ℃ to obtain a first solution; then taking another part of water, adding 15% of residual oil sulfonate at the temperature of 40-45 ℃, and stirring for dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the finished product of the high-temperature foam stabilizer.
Mixing the obtained high-temperature foam stabilizer with conventional alpha-olefin sulfonate according to the weight ratio of 1:55 to obtain a high-temperature foaming agent system. The obtained high-temperature foaming agent system is dissolved in water to prepare an aqueous solution with the mass concentration of alpha-olefin sulfonate of 0.5%, and the aqueous solution is subjected to initial foaming times before and after aging, foam half-life period and resistance factor test at high temperature, and the aqueous solution only containing 0.5% of alpha-olefin sulfonate is used as a reference, the test method is the same as that of example 1, and the test results are shown in table 3:
table 30.5% aqueous solution various performance test results
Comparative example 1
This comparative example tests the foam stabilizing effect of lauryl alcohol (lauryl alcohol), which is a conventionally used high-temperature foam stabilizer, and prepares a high-temperature foamer system by using only lauryl alcohol (lauryl alcohol), which is a high-temperature foam stabilizer obtained in example 1, in place of lauryl alcohol (lauryl alcohol), the rest of which is the same as in example 1, and the results are shown in Table 4:
TABLE 40.5% aqueous Performance test results
As can be seen from examples 1 to 3 and comparative example 1 described above:
(1) and (2) taking conventional alpha-olefin sulfonate as a high-temperature foaming agent main agent, and comparing before and after aging at 300 ℃ for 168h before introducing no high-temperature foaming stabilizer: the initial foaming amount before aging reaches more than 6.5 times, the half-life period of the foam reaches 6 hours, and the initial foaming amount after aging reaches 6 times, and the half-life period of the foam is only 3 hours. The resistance factor at 200 ℃ is 14.2-14.8; after the high-temperature foam stabilizer is introduced, comparison is carried out before and after aging for 168 hours at 300 ℃: the initial foaming amount before aging reaches more than 5.5 times, the foam half-life period reaches more than 15 hours, the initial foaming amount after aging reaches more than about 6 times, the foam half-life period can still reach more than 15 hours, and the resistance factor at 200 ℃ reaches more than 20, namely the resistance factor at high temperature after introducing the high-temperature foam stabilizer is improved by more than 35%, and the plugging performance of a high-temperature foam system is obviously improved. In contrast, it can be seen from the comparative example that the initial foaming amount after aging at high temperature was reduced from 6.0 times to 5.0 times and the foam half-life after aging was extended from 3.3 hours to 5.5 hours using lauryl alcohol (dodecanol), which is a conventional foam stabilizer. The resistance factor is 16.4, which is obviously lower than the resistance factor (more than 20 on average) when the foam stabilizer of the invention is used, and the foam stabilizing performance of the high-temperature foam stabilizer of the invention is obviously better than that of the existing high-temperature foam stabilizer.
(2) After the high-temperature foam stabilizer is used, the stability of high-temperature foam after high-temperature aging is obviously enhanced, and the initial foaming amount of a foam system after high-temperature aging is basically kept unchanged (the initial foaming amount is reduced after the foam stabilizer is added in a general case). The feature is that the prior high-temperature foam stabilizer does not have, and has great significance for enhancing the anti-channeling blocking performance.
It will be readily understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention.
Claims (10)
1. A foam stabilizer comprises the following raw materials in percentage by weight: 20-30 wt.% of hydroxyethyl ethylenediamine, 15-25 wt.% of tetradecyl dihydroxyethyl ammonium oxide, 10-25 wt.% of residual oil sulfonate and the balance of water.
2. The foam stabilizer according to claim 1, wherein the foam stabilizer is prepared by the following method:
dividing the water into two parts, adding the hydroxyethyl ethylenediamine and the tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at the temperature of 30-40 ℃ to obtain a first solution; then adding the residual oil sulfonate into the other part of water at the temperature of 40-45 ℃, and stirring and dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the foam stabilizer.
3. A process for the preparation of the foam stabilizer of claim 1 or 2, which comprises the steps of:
dividing the water into two parts, adding the hydroxyethyl ethylenediamine and the tetradecyl dihydroxyethyl ammonium oxide into one part of water, and stirring and dissolving at the temperature of 30-40 ℃ to obtain a first solution; then adding the residual oil sulfonate into the other part of water at the temperature of 40-45 ℃, and stirring and dissolving to obtain a second solution; and mixing the first solution and the second solution at 40-45 ℃, and fully stirring and uniformly mixing to obtain the foam stabilizer.
4. Use of the foam stabilizer according to claim 1 or 2 as an additive in the preparation of a blowing agent.
5. A blowing agent comprising the foam stabilizer of claim 1 or 2.
6. The blowing agent of claim 5 containing a blowing agent alpha olefin sulfonate.
7. The blowing agent according to claim 6, wherein the mass ratio of the foam stabilizer to the α -olefin sulfonate is from 1:40 to 1: 75.
8. Use of the foaming agent according to any one of claims 5 to 7 in a process for producing heavy oil by steam flooding.
9. The use of claim 8, wherein the foaming agent is used for preventing steam channeling and expanding the swept volume of injected steam in a heavy oil steam flooding process.
10. Use according to claim 8 or 9, wherein the foaming agent is formulated for injection as an aqueous solution with a foaming agent mass concentration of 0.3% to 1.0%.
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| CN102086389A (en) * | 2010-12-31 | 2011-06-08 | 上海大学 | Temperature-resistant salt-resistant composite foam oil displacement agent for tertiary oil recovery and preparation method thereof |
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| MX2014013981A (en) * | 2014-11-18 | 2016-05-17 | Inst Mexicano Del Petróleo | Multifunctional foaming composition with wettability modifying, corrosion inhibitory and mineral scale inhibitory/dispersants properties for high temperature and ultra high salinity. |
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