CN109280546B - Viscosity stabilizer, preparation method thereof and polymer aqueous solution - Google Patents
Viscosity stabilizer, preparation method thereof and polymer aqueous solution Download PDFInfo
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- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The invention discloses a viscosity stabilizer, a preparation method thereof and a polymer aqueous solution, and belongs to the field of oilfield chemistry. The viscosity stabilizer comprises the following components in percentage by mass: 10-40% of reducing agent, 25-40% of polyhydroxy compound, 2-10% of dispersing agent and the balance of water. Active substances such as dissolved oxygen in the polymer water solution are reduced through the synergistic effect of the reducing agent and other components, and the oxidative degradation of the active substances such as the dissolved oxygen in the polymer oil-displacing agent is avoided. Under the synergistic effect of the polyhydroxy compound and other components, hydroxyl in the polyhydroxy compound and hydrogen atoms in the polymer oil-displacing agent are mutually associated to form a network, so that active substances such as dissolved oxygen are prevented from oxidizing and attacking hydrophobic carbon atoms in the polymer oil-displacing agent. The reducing agent and the polyhydroxy compound are uniformly dispersed in the polymer aqueous solution through the synergistic action of the dispersing agent and other components, so that the viscosity of the polymer aqueous solution is fully and efficiently stabilized, and the later efficient oil displacement is facilitated.
Description
Technical Field
The invention relates to the field of oilfield chemistry, and particularly relates to a viscosity stabilizer, a preparation method thereof and a polymer aqueous solution.
Background
In tertiary oil recovery, polymer flooding is mainly used to increase the recovery of crude oil. Polymer flooding refers to: a polymer oil displacement agent (such as polyacrylamide) is formulated with the oil well produced water as an aqueous polymer solution having a predetermined viscosity, which is then injected into the oil reservoir to displace the crude oil. Wherein, the smaller the flow rate ratio of the aqueous polymer solution with the predetermined viscosity to the crude oil, the larger the volume of the crude oil that the aqueous polymer solution can spread, and the better the effect of displacing the crude oil. However, the polymer aqueous solution is inevitably affected by chemical degradation of active substances such as dissolved oxygen in the produced water of the oil well or other factors, so that the viscosity is reduced, the flow rate ratio of the polymer aqueous solution to the crude oil is increased, and the later efficient oil displacement is not facilitated. The viscosity loss of the polymer aqueous solution can be reduced by adding the viscosity stabilizer into the polymer aqueous solution, so that the later-stage efficient oil displacement is facilitated. Based on the above, it is necessary to provide a viscosity stabilizer.
The prior art provides a viscosity stabilizer which is sodium thiosulfate. When used, 100mg of sodium thiosulfate was added to 2000mg/L of an aqueous polyacrylamide solution, and the mixed solution was then used to displace crude oil. The retention of the viscosity of the aqueous polyacrylamide solution by sodium thiosulfate over 50 days is 58.6%.
The inventor finds that the prior art has at least the following problems:
the viscosity stabilizing agent provided by the prior art has poor effect of stabilizing the viscosity of the polyacrylamide aqueous solution, and is not beneficial to efficient oil displacement in the later period.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide a viscosity stabilizer, a preparation method thereof and a polymer aqueous solution, and the problems that the effect of stabilizing the viscosity of the polymer aqueous solution is poor, the later efficient oil displacement is not facilitated and the like can be solved. The specific technical scheme is as follows:
in a first aspect, an embodiment of the present invention provides a viscosity stabilizer, where the viscosity stabilizer includes the following components in percentage by mass:
10-40% of reducing agent, 25-40% of polyhydroxy compound, 2-10% of dispersing agent and the balance of water.
In one possible design, the reducing agent is selected from at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, urea.
In one possible design, the polyol comprises: tetramethylolglycoluril and mannitol in a mass ratio of 4-6: 1-2.
In one possible design, the dispersant is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, isopropanol.
In one possible design, the viscosity stabilizer comprises the following components in percentage by mass:
10-40% of sodium thiosulfate, 20-30% of tetramethylolglycoluril, 5-10% of mannitol, 2-10% of a dispersing agent and the balance of water.
In one possible design, the viscosity stabilizer comprises the following components in percentage by mass:
15-35% of sodium thiosulfate, 22-28% of tetramethylolglycoluril, 6-9% of mannitol, 3-9% of sodium dodecyl benzene sulfonate and the balance of water.
In a second aspect, the embodiments of the present invention also provide a preparation method of the viscosity stabilizer, where the preparation method includes:
adding water, a reducing agent, a polyhydroxy compound and a dispersing agent into a reactor according to the mass percentage of each component, and stirring for a preset time to obtain the viscosity stabilizing agent.
In one possible design, the predetermined time is 50-70 min.
In a third aspect, embodiments of the present invention provide an aqueous polymer solution, wherein the aqueous polymer solution includes the viscosity stabilizer;
and each liter of the polymer aqueous solution contains 50-300 mg of the viscosity stabilizer.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
after the viscosity stabilizing agent provided by the embodiment of the invention is added into the polymer aqueous solution for displacing crude oil, on one hand, the reducing agent and other components act synergistically to reduce active substances such as dissolved oxygen in the polymer aqueous solution, so that the active substances such as dissolved oxygen are prevented from oxidizing and degrading the polymer oil displacement agent, and the viscosity of the polymer aqueous solution is stabilized. On the other hand, under the synergistic action of the polyhydroxy compound and other components, hydroxyl in the polyhydroxy compound and hydrogen atoms in the polymer oil-displacing agent are mutually associated to form a network, active substances such as dissolved oxygen are prevented from oxidizing and attacking hydrophobic carbon atoms in the polymer oil-displacing agent, and the viscosity of the polymer aqueous solution is further stabilized. The reducing agent and the polyhydroxy compound are conveniently and uniformly dispersed in the polymer aqueous solution through the synergistic action of the dispersing agent and other components, so that the viscosity of the polymer aqueous solution is fully and efficiently stabilized, and the later-stage efficient oil displacement is facilitated.
Detailed Description
Unless defined otherwise, all technical terms used in the examples of the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
In a first aspect, an embodiment of the present invention provides a viscosity stabilizer, where the viscosity stabilizer includes the following components in percentage by mass:
10-40% of reducing agent, 25-40% of polyhydroxy compound, 2-10% of dispersing agent and the balance of water.
After the viscosity stabilizing agent provided by the embodiment of the invention is added into the polymer aqueous solution for displacing crude oil, on one hand, the reducing agent and other components act synergistically to reduce active substances such as dissolved oxygen in the polymer aqueous solution, so that the active substances such as dissolved oxygen are prevented from oxidizing and degrading the polymer oil displacement agent, and the viscosity of the polymer aqueous solution is stabilized. On the other hand, under the synergistic action of the polyhydroxy compound and other components, hydroxyl in the polyhydroxy compound and hydrogen atoms in the polymer oil-displacing agent are mutually associated to form a network, active substances such as dissolved oxygen are prevented from oxidizing and attacking hydrophobic carbon atoms in the polymer oil-displacing agent, and the viscosity of the polymer aqueous solution is further stabilized. The reducing agent and the polyhydroxy compound are conveniently and uniformly dispersed in the polymer aqueous solution through the synergistic action of the dispersing agent and other components, so that the viscosity of the polymer aqueous solution is fully and efficiently stabilized, and the later-stage efficient oil displacement is facilitated.
Specifically, the reducing agent may be 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, etc. in mass%, the polyol may be 25%, 27%, 29%, 30%, 32%, 34%, 35%, 37%, 39%, 40%, etc. in mass%, the dispersant may be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. in mass%, with the balance being water. The above-mentioned mass percentages of the reducing agent, the polyhydroxy compound, the dispersant and the water can be combined at will, but the sum of the mass percentages of the four is required to be 100%. The components are set to be in the mass percentage, so that the reducing agent, the polyhydroxy compound, the dispersing agent and the water are subjected to synergistic action on the premise of saving cost, and the viscosity of the polymer aqueous solution is stabilized.
In the embodiment of the present invention, the water is distilled water or deionized water. Distilled water or deionized water is selected, so that other impurity ions can be prevented from being introduced into the viscosity stabilizer and the polymer aqueous solution.
Under the synergistic action of the reducing agent and other components, the reducing agent plays a role in reducing active substances such as dissolved oxygen in the polymer aqueous solution, and avoids oxidative degradation of the polymer oil-displacing agent. The reducing agent can be selected from a plurality of reagents with reducing function, and is selected from at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite and urea on the premise of low price, good compatibility with other components and good reducing effect. For example, the reducing agent may be selected from any one, two, three, or a mixture of all four of the above-mentioned four reducing agents. When the reducing agent is a mixture, the proportion of each component is not particularly limited, and the total mass percentage of the reducing agent mixture is 10-40%.
The polymer oil-displacing agent generally contains hydrophobic carbon atoms and hydrogen atoms, the polyhydroxy compound contains hydroxyl, the hydroxyl and the hydrogen and oxygen atoms in the polymer oil-displacing agent are easy to generate hydrogen bond association or other association effects, and a network is formed between the hydroxyl compound molecules and the polymer oil-displacing agent molecules, namely the hydroxyl compound molecules and the hydrogen atoms in the polymer oil-displacing agent form a protective layer similar to the hydrophobic carbon atoms, so that active substances such as dissolved oxygen in a polymer aqueous solution are prevented from oxidizing and degrading the hydrophobic carbon atoms, and the viscosity of the polymer aqueous solution is further stabilized.
The polyhydroxy compound can be selected from a plurality of compounds with hydroxyl groups, and on the premise of good compatibility with other components, low price and good antioxidant effect, the polyhydroxy compound comprises: tetramethylolglycoluril and mannitol in a mass ratio of 4-6: 1-2. For example, the mass ratio of tetramethylolglycoluril to mannitol can be 4:1, 4:2, 5:1, 5:2, 6:1, 6:2, and the like.
The weight ratio of the tetramethylol glycoluril to the mannitol is set, and under the synergistic effect of other components, the polymer oil displacement agent can be effectively prevented from being oxidized and degraded by active substances such as dissolved oxygen in a high-temperature environment (for example, 50-85 ℃) so as to stabilize the viscosity of the polymer aqueous solution in the high-temperature environment.
The dispersing agent can uniformly disperse other components in the aqueous polymer solution, so that the viscosity stabilizer provided by the embodiment of the invention can effectively and uniformly stabilize the viscosity of the aqueous polymer solution. The dispersing agent can be selected from a plurality of reagents with dispersing effect, and is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and isopropanol on the premise of low price, good intermiscibility and good dispersibility. For example, the dispersant may be selected from any one, two, or three of the above three dispersants. When the dispersant is a mixture, the proportion of each component is not particularly limited, and the total mass percent of the dispersant is 2-10%.
On the premise of low price, good effect of stabilizing polymer aqueous solution and long-term (1-120 days) suitability for high-temperature environment of oil wells, the viscosity stabilizer provided by the embodiment of the invention comprises the following components in percentage by mass:
10-40% of sodium thiosulfate, 20-30% of tetramethylolglycoluril, 5-10% of mannitol, 2-10% of a dispersant and the balance of water.
Further, in order to efficiently stabilize the viscosity of the polymer aqueous solution and further efficiently displace crude oil, the viscosity stabilizer provided by the embodiment of the invention comprises the following components in percentage by mass:
15-35% of sodium thiosulfate, 22-28% of tetramethylolglycoluril, 6-9% of mannitol, 3-9% of sodium dodecyl benzene sulfonate and the balance of water. For example, the mass percentage of sodium thiosulfate may be 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, etc., the mass percentage of tetramethylolglycoluril may be 22%, 23%, 24%, 25%, 26%, 27%, 28%, etc., the mass percentage of mannitol may be 6%, 7%, 8%, 9%, etc., the mass percentage of sodium dodecylbenzenesulfonate may be 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., and the balance may be water.
The viscosity stabilizer with the components has wide applicability, can be mutually soluble with various polymer aqueous solutions for displacing crude oil, and stabilizes the viscosity of the polymer aqueous solution.
In a second aspect, the embodiments of the present invention provide a preparation method of the above viscosity stabilizer, the preparation method includes:
adding water, a reducing agent, a polyhydroxy compound and a dispersing agent into a reactor according to the mass percentage of each component, and stirring for a preset time to obtain the viscosity stabilizing agent.
The preparation method is simple, the viscosity stabilizer can be prepared on site in a target operation area, and can also be transported to the target operation area after being prepared in other places, so that the application of the viscosity stabilizer is facilitated.
Wherein the stirring time is 50-70 min, such as 50min, 52min, 55min, 57min, 60min, 62min, 65min, 67min, 70min, etc.
The stirring time is short, the viscosity stabilizer is convenient to prepare, and the viscosity stabilizer is convenient to be adopted for stabilizing and maintaining the viscosity of the polymer aqueous solution in the later period.
In a third aspect, the embodiments of the present invention further provide an aqueous polymer solution, where the aqueous polymer solution includes the viscosity stabilizer;
the polymer aqueous solution (L) contains 50 to 300mg (mg) of a viscosity stabilizer, and may contain, for example, 50mg, 80mg, 100mg, 120mg, 150mg, 170mg, 200mg, 220mg, 250mg, 270mg, 300mg, and the like.
Wherein the mass concentration of the polymer oil-displacing agent in the polymer aqueous solution is 1900-2100 mg/L, and can be 1900mg/L, 1950mg/L, 2000mg/L, 2050mg/L, 2100mg/L and the like. In practical application, the method can also be described as adding 50-300 mg/L of viscosity stabilizer into 1900-2100 mg/L of polymer aqueous solution. That is, 50 to 300mg of a viscosity stabilizer is added to each L of an aqueous polymer solution having a mass concentration of 1900 to 2100 mg/L.
The application proves that the viscosity stabilizer added in each L of the polymer aqueous solution has the advantages of low mass and low use cost, can play a role in stabilizing and maintaining the viscosity of the polymer aqueous solution, and is convenient for efficient oil displacement in the later period.
The present invention will be further described below by way of specific examples.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Sodium thiosulfate was purchased from Bairun chemical Co., Tetramethylolglycoluril was purchased from Jinquan chemical Co., Ltd., mannitol was purchased from Jinnan Cheng Wang chemical Co., Ltd., sodium dodecylbenzenesulfonate was purchased from Glabrati chemical Co., Ltd., sodium dodecylsulfate was purchased from Guanyang chemical Co., Ltd., and isopropyl alcohol was purchased from Dongyi chemical Co., Ltd.
Example 1
This example provides a viscosity stabilizer prepared by the following method: according to the mass percent of each component, 25% of water, 40% of sodium thiosulfate, 20% of tetramethylolglycoluril, 10% of mannitol and 5% of sodium dodecyl benzene sulfonate are added into a reactor and stirred for 50min, so as to obtain the viscosity stabilizer provided by the embodiment.
Example 2
This example provides a viscosity stabilizer prepared by the following method: according to the mass percent of each component, 50 percent of water, 10 percent of sodium thiosulfate, 30 percent of tetramethylolglycoluril, 5 percent of mannitol and 5 percent of lauryl sodium sulfate are added into a reactor and stirred for 60min to obtain the viscosity stabilizer provided by the embodiment.
Example 3
This example provides a viscosity stabilizer prepared by the following method: according to the mass percent of the components, 40% of water, 20% of sodium thiosulfate, 20% of tetramethylolglycoluril, 10% of mannitol and 10% of isopropanol are added into a reactor and stirred for 70min to obtain the viscosity stabilizer provided by the embodiment.
Application example 1
The present application example evaluates the effect of the viscosity stabilizer provided in examples 1 to 3 on stabilizing the viscosity of the polymer aqueous solution. The specific evaluation process comprises the following steps: oil well produced water with the mineralization degree of 6726mg/L and the temperature of 58 ℃ is stirred and mixed with partially hydrolyzed polyacrylamide with the molecular weight of 2500 ten thousand and the model of BHHP-112 to prepare polymer aqueous solution with the concentration of 2000 mg/L. Selecting seven polymer aqueous solutions with the same mass, wherein one polymer aqueous solution is not added with a viscosity stabilizer, and the rest six polymer aqueous solutions are sequentially added with 50mg/L and 200mg/L of the viscosity stabilizer provided by example 1, 50mg/L and 200mg/L of the viscosity stabilizer provided by example 2, 50mg/L and 200mg/L of the viscosity stabilizer provided by example 3, uniformly stirring, and numbering as No. 1, No. 2, No. 3, No. 4, No. 5, No. 6 and No. 7 sequentially. And then respectively taking 20mL of No. 1-No. 7 polymer aqueous solution, respectively filling into 7 20mL vials, carrying out oxygen insulation treatment, sealing by a gland, then putting into an oven for aging, respectively detecting the viscosity of the No. 1-No. 7 polymer aqueous solution by a Bolifei DV-III type viscometer at 0 day, 30 days, 60 days, 90 days and 120 days, and calculating the viscosity retention rate of the No. 1-No. 7 mixed solution at 120 days by a formula (1), wherein the specific parameters are detailed in Table 1.
Wherein eta is the viscosity retention of the aqueous polymer solution, niThe viscosity of the aqueous polymer solution after 120 days of aging was determined as mPas, n0The initial viscosity of the aqueous polymer solution was expressed in mPas.
TABLE 1
As can be seen from Table 1, after the viscosity stabilizers provided in examples 1 to 3 were added, the viscosity retention of the polymer aqueous solution after aging for 30 to 120 days was significantly higher than that without the addition of the viscosity stabilizers, and when the viscosity stabilizer was added at 200mg/L, the viscosity retention of the polymer solution after aging for 120 days was 80.1% or more, which can meet the use requirements of tertiary oil recovery displacement sites.
Application example 2
The effect of the viscosity stabilizer provided in examples 1 to 3 on the stabilization of the viscosity of the aqueous polymer solution was evaluated in the following examples. The specific evaluation process comprises the following steps: oil well produced water with the mineralization degree of 29783mg/L and the temperature of 78 ℃ is stirred and mixed with hydrophobic association type polyacrylamide with the molecular weight of 1400 ten thousand and the model of AP-P7 to prepare polymer aqueous solution with the concentration of 2000 mg/L. Selecting seven parts of polymer aqueous solution with the same mass, wherein one part of the polymer aqueous solution is not added with the viscosity stabilizer, and the rest six parts of the polymer aqueous solution are sequentially added with 50mg/L and 300mg/L of the viscosity stabilizer provided by example 1, 50mg/L and 300mg/L of the viscosity stabilizer provided by example 2, 50mg/L and 300mg/L of the viscosity stabilizer provided by example 3, uniformly stirring, and sequentially numbering as a, b, c, d, e, f and g. Then respectively taking 20mL of a-g polymer aqueous solution, respectively filling the a-g polymer aqueous solution into 7 20mL vials, carrying out oxygen-insulating treatment, sealing the vials by a gland, then putting the vials into an oven for aging, respectively detecting the viscosity of the a-g polymer aqueous solution provided by a viscometer at 0 day, 30 days, 60 days, 90 days and 120 days, and calculating the viscosity retention rate of the a-g polymer aqueous solution at 120 days by a formula (1), wherein the specific parameters are detailed in Table 2.
TABLE 2
As can be seen from Table 2, after the viscosity stabilizers provided in examples 1 to 3 were added, the viscosity retention of the polymer aqueous solution after aging for 30 to 120 days was significantly higher than that without the addition of the viscosity stabilizers, and when the viscosity stabilizer was added at 300mg/L, the viscosity retention of the polymer solution after aging for 120 days was at least 64.1%, which was able to meet the use requirements of tertiary oil recovery displacement sites.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The viscosity stabilizer is characterized by comprising the following components in percentage by mass:
10-40% of reducing agent, 25-40% of polyhydroxy compound, 2-10% of dispersing agent and the balance of water;
the reducing agent is at least one selected from sodium thiosulfate, sodium sulfite, sodium bisulfite and urea;
the polyol comprises: tetrakis hydroxymethyl glycoluril and mannitol in a mass ratio of 4-6: 1-2;
the dispersing agent is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and isopropanol.
2. The viscosity stabilizer according to claim 1, wherein the viscosity stabilizer comprises the following components in percentage by mass:
10-40% of sodium thiosulfate, 20-30% of tetramethylolglycoluril, 5-10% of mannitol, 2-10% of a dispersing agent and the balance of water.
3. The viscosity stabilizer according to claim 1, wherein the viscosity stabilizer comprises the following components in percentage by mass:
15-35% of sodium thiosulfate, 22-28% of tetramethylolglycoluril, 6-9% of mannitol, 3-9% of sodium dodecyl benzene sulfonate and the balance of water.
4. A method for preparing a viscosity stabilizer according to any one of claims 1 to 3, comprising:
adding water, a reducing agent, a polyhydroxy compound and a dispersing agent into a reactor according to the mass percentage of each component, and stirring for 50-70 min to obtain the viscosity stabilizing agent.
5. An aqueous polymer solution comprising the viscosity stabilizer according to any one of claims 1 to 3;
and each liter of the polymer aqueous solution contains 50-300 mg of the viscosity stabilizer.
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Citations (2)
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| CN104311733A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Viscosity-maintaining polymer and preparation method thereof |
| CN105086978A (en) * | 2015-09-06 | 2015-11-25 | 华鼎鸿基采油技术服务（北京）有限公司 | Viscosity stabilizer and application thereof |
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| CN104311733A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Viscosity-maintaining polymer and preparation method thereof |
| CN105086978A (en) * | 2015-09-06 | 2015-11-25 | 华鼎鸿基采油技术服务（北京）有限公司 | Viscosity stabilizer and application thereof |
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| "疏水缔合聚丙烯酰胺溶液的稳定性研究";胡秋平;《应用化工》;20040830;第33卷(第4期);32-34 * |
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