A quick-acting defoaming agent, a preparation method and application thereof

Abstract

This invention relates to the fields of oil and gas field development and applied chemistry, and particularly to a fast-acting defoamer, its preparation method, and its application. The raw material components of the fast-acting defoamer include, by mass percentage: 1%-3% emulsifier, 0.5%-1.0% stabilizer, 5%-10% polyether-modified silicone oil, 2%-5% silicone paste, and the remainder being water. The high-efficiency fast-acting defoamer prepared by this invention possesses excellent defoaming performance and stability, achieving rapid and stable defoaming in water-based emulsion defoaming processes.

Description

Technical Field

[0001] This invention relates to the fields of oil and gas field development and applied chemistry, and particularly to a fast-acting defoamer, its preparation method, and its application. Background Technology

[0002] In oil and gas extraction processes, such as surfactant-assisted oil and gas recovery, foam drainage gas recovery, and unblocking and dewatering, the addition of large amounts of surfactant components can cause foaming in the produced fluid and flowback fluid. Failure to promptly eliminate this foam will lead to unnecessary problems in production and subsequent fluid treatment.

[0003] Currently, the most widely used defoamers are silicone defoamers. These defoamers primarily use polydimethyl silicone oil and its modified materials as the core defoaming components, characterized by rapid defoaming speed and long foam suppression time. However, their emulsification problem under water-based conditions is the biggest obstacle limiting their use. Polyethers or polyether-modified siloxanes have good dispersibility in water, but their defoaming performance is significantly reduced compared to polydimethyl silicone oil. Therefore, increasing the stability of silicone in emulsions is key to improving defoamer performance.

[0004] The content of the main components "organopolysiloxane, polyether-modified silicone oil, silicone resin, emulsifier, and dispersant / thickener" in the preparation of organosilicon defoamer described in Chinese patent CN 104069654 A is approximately 32% at the upper limit and more than 25% at the lower limit, indicating that the amount of main components used in this patent is relatively high, resulting in higher costs.

[0005] With the continuous updating of relevant standards, the performance requirements for defoamers are gradually increasing. For example, in the process of foam drainage gas production, the defoaming time of defoamers is increased to 20 seconds, and they need to be stable for 24 hours after dispersion. Existing products cannot meet the production needs of oil and gas fields, which undoubtedly poses new challenges to the organosilicon defoamer system. Summary of the Invention

[0006] To address the problems of slow defoaming speed and poor stability of defoamers in oil and gas extraction, this invention provides a fast-acting defoamer, its preparation method, and its application.

[0007] This invention provides the following technical solution:

[0008] This invention provides a fast-acting defoamer, the raw material components of which, by mass percentage, are: 1%-3% emulsifier, 0.5%-1.0% stabilizer, 5%-10% polyether-modified silicone oil, 2%-5% silicone paste, and the remainder being water.

[0009] Further, the emulsifier is one or more selected from the following: Span-60, Tween-60, polyoxyethylene alkylphenol ether, fatty alcohol polyoxyethylene ether, glyceryl monostearate, sodium lauryl sulfate, and sodium lauryl benzoate.

[0010] Further, the emulsifier is one or more selected from Span-60, Tween-60, polyoxyethylene alkylphenol ether, fatty alcohol polyoxyethylene ether, and glyceryl monostearate.

[0011] Furthermore, the stabilizer is a mixture of a thickener, a bactericide, and a synergist, wherein,

[0012] The mass ratio of thickener, bactericide, and synergist is 1:(0.1-0.5):(0.5-2.0).

[0013] Furthermore, the thickener is a cellulose polysaccharide;

[0014] The bactericide is an isothiazolinone;

[0015] The synergist is a propylene glycol derivative.

[0016] Furthermore, the raw materials for preparing silicone paste include dimethyl silicone oil and hydrophobic nano-silica, wherein,

[0017] The mass ratio of dimethyl silicone oil to hydrophobic nano silica is 1:(0.01-0.1).

[0018] Further, the emulsifier and stabilizer are added to water, stirred and dispersed evenly at a predetermined temperature, then polyether-modified silicone oil and silicone paste are added, and stirring is continued until evenly mixed to obtain a fast-acting defoamer.

[0019] Furthermore, the predetermined temperature is 50-70°C.

[0020] Furthermore, the method for preparing the silicone paste includes:

[0021] Dimethyl silicone oil and hydrophobic nano-silica are simmered at 110-150℃ for 4-8 hours to obtain silicone paste, wherein the mass ratio of dimethyl silicone oil to hydrophobic nano-silica is 1:0.01-0.1.

[0022] It also provides the application of the aforementioned fast-dissolving defoamer in the oil and gas extraction process.

[0023] The technical effects and advantages of this invention are as follows:

[0024] The high-efficiency, fast-acting defoamer prepared by this invention has the advantages of fast defoaming speed and high dispersion stability.

[0025] 1. The present invention preferably uses an emulsification system and prepares a high-efficiency and fast-acting defoamer with polyether modified silicone oil and silicone paste as the main raw materials, which solves the problems of slow defoaming speed and poor stability of defoamers in the oil and gas extraction process.

[0026] 2. The raw materials used in this invention have been industrially produced and are readily available. The reaction process is simple and can be completed under general chemical conditions. The preparation conditions are mild, the reaction conditions are easy to control, and the reaction process is safe.

[0027] 3. The high-efficiency, fast-acting defoamer prepared by this invention is stable and can be stored stably for a long time at room temperature and pressure.

[0028] 4. The high-efficiency, fast-dissolving defoamer prepared by this invention has good compatibility with other water-based systems and can maintain stability for more than 48 hours after dispersion.

[0029] 5. The high-efficiency, fast-acting defoamer prepared by this invention has excellent defoaming performance, with the fastest defoaming time as low as 3.2 seconds.

[0030] 6. The high-efficiency, fast-acting defoamer prepared by this invention can be used for defoaming of produced fluids and backflow fluids during oil and gas extraction, and can significantly improve oil and gas extraction efficiency.

[0031] In summary, the high-efficiency, fast-acting defoamer prepared by this invention has good defoaming performance and stability, and can achieve rapid and stable defoaming effect in the defoaming process of water-based emulsions.

[0032] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures pointed out in the description and the drawings. Attached Figure Description

[0033] Figure 1 This is a flowchart of the preparation method of the fast-dissipating defoamer provided in the embodiments of this application;

[0034] Figure 2 This is a physical image of the white, viscous, emulsion-like, fast-dissolving defoamer provided in the embodiments of this application. Detailed Implementation

[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] To address the shortcomings of existing technologies, this invention discloses a fast-dissipating defoamer, which is a white, viscous, emulsion-like liquid. The raw material components of the fast-dissipating defoamer include, by mass percentage, 1%-3% emulsifier, 0.5%-1.0% stabilizer, 5%-10% polyether-modified silicone oil, 2%-5% silicone paste, and the remainder being water.

[0037] In one specific embodiment of the present invention, the emulsifier is one or more selected from the following: P-20, Span-60, Tween-60, polyoxyethylene alkylphenol ether (OP-10), fatty alcohol polyoxyethylene ether (S185), glyceryl monostearate (GMS), sodium lauryl sulfate (K12), and sodium dodecyl benzoate (SDS). Preferably, the emulsifier is one or more selected from the following: Span-60, Tween-60, polyoxyethylene alkylphenol ether, fatty alcohol polyoxyethylene ether, and glyceryl monostearate.

[0038] In one specific embodiment of the present invention, the stabilizer is specially formulated by physically mixing a thickener, a bactericide, and a synergist. The mass ratio of the thickener, bactericide, and synergist is 1:(0.1-0.5):(0.5-2.0). The thickener is a cellulose polysaccharide, including carboxymethyl cellulose (molecular weight 15000). Hydroxypropyl cellulose The fungicide is an isothiazolinone, including methylisothiazolinone, 5-chloro-2-methylisothiazolin-3-one, N-octyl-4-isothiazolin-3-one, or n-butyl-1,2-isothiazolin-3-one; the synergist is a propylene glycol derivative, including polyethylene glycol (molecular weight 5000) and methylpropylene glycol.

[0039] The polyether-modified silicone oil is a commercially available industrial-grade raw material, such as polyether-modified heptamethyltrisiloxane (molecular weight 300-400).

[0040] The silicone paste is prepared by simmering dimethyl silicone oil and hydrophobic nano-silica at 110-150℃ for 4-8 hours. The ratio of dimethyl silicone oil to hydrophobic nano-silica is 1:0.01-0.1 (g:g).

[0041] This invention also provides a method for preparing a fast-acting defoamer, such as... Figure 1 As shown, the method includes:

[0042] Emulsifiers and stabilizers are added to water and stirred until evenly dispersed at 50-70℃. Then, polyether-modified silicone oil and silicone paste are added, and stirring is continued until homogeneous. The resulting white, viscous emulsion is the fast-acting defoamer. The high-efficiency, fast-acting defoamer prepared by this invention has excellent defoaming performance and stability, achieving rapid and stable defoaming in water-based emulsion defoaming processes.

[0043] The present invention also provides the application of the aforementioned fast-dissolving defoamer in the oil and gas extraction process.

[0044] The high-efficiency, fast-acting defoamer prepared by this invention has good defoaming performance and stability, and can achieve rapid and stable defoaming effect in the defoaming process of water-based emulsions.

[0045] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0046] Example 1

[0047] In a reactor, 1g of emulsifier (1g S-60) and 0.5g of stabilizer (stabilizers include carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone, and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) were added to 91.5g of water and stirred and dispersed at 60℃. After the system was homogeneous and stable, 5g of polyether-modified silicone oil (polyether-modified heptamethyltrisiloxane, molecular weight 300-400) and 2g of silicone paste were added. After stirring and dispersing, and after the system was homogeneous and stable, the following was obtained: Figure 2 The white, viscous emulsion is a highly efficient, fast-acting defoamer.

[0048] Example 2

[0049] The preparation method is the same as described in Example 1, except that the emulsifier is replaced with OP-10.

[0050] Example 3

[0051] In a reactor, 2g of emulsifier (1g S-60, 1g S185) and 0.6g of stabilizer (stabilizers include carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) are added to 87.4g of water and stirred and dispersed at 60℃. After the system is uniform and stable, 8g of polyether modified silicone oil and 2g of silicone paste are added, stirred and dispersed, and the system is stirred and stabilized. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0052] Example 4

[0053] The preparation method is the same as described in Example 3, except that the amount of stabilizer is increased to 0.8g and the amount of water is 87.2g.

[0054] Example 5

[0055] In a reactor, 2g of emulsifier (1g S185, 1g GMS) and 0.8g of stabilizer (stabilizers include carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) were added to 87.4g of water and stirred and dispersed at 60℃. After the system was uniform and stable, 10g of polyether modified silicone oil and 2g of silicone paste were added, stirred and dispersed, and the system was stirred and dispersed until it was uniform and stable. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0056] Example 6

[0057] The preparation method is the same as described in Example 5, except that the amount of polyether-modified silicone oil used is 8g and the amount of silicone paste used is 4g.

[0058] Example 7

[0059] In the reactor, add 3g of emulsifier (1g S-60, 1g S185, 1g...) GMS Add 1g of stabilizer, which includes carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5, to 85g of water, stir and disperse at 60℃, and after the system is uniform and stable, add 8g of polyether modified silicone oil and 3g of silicone paste, stir and disperse, and after the system is uniform and stable, the resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0060] Example 8

[0061] In the reactor, add 3g of emulsifier (1g S-60, 1g S185, 1g...) GMS ) and 1g of stabilizer (the stabilizer includes carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5). ) Add 81g of water and stir to disperse at 60℃. After the system is uniform and stable, add 10g of polyether modified silicone oil and 5g of silicone paste. Stir to disperse and then wait for the system to become uniform and stable. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0062] Example 9

[0063] In a reactor, 1g of emulsifier (1g S185) and 1g of stabilizer (stabilizers include carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) are added to 88g of water and stirred and dispersed at 60℃. After the system is uniform and stable, 8g of polyether modified silicone oil and 2g of silicone paste are added, stirred and dispersed, and the system is uniform and stable. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0064] Example 10

[0065] In a reactor, 2.5g of emulsifier (1g T-60, 1g OP-10, 0.5g S-60) and 0.7g of stabilizer (stabilizers include carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) were added to 83.8g of water and stirred and dispersed at 60℃. After the system was uniform and stable, 9g of polyether modified silicone oil and 4g of silicone paste were added, stirred and dispersed, and the system was stirred and dispersed until it was uniform and stable. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0066] Example 11

[0067] In the reactor, add 3g of emulsifier (1g S-60, 1g S185, 1g...) GMS Add 1g of stabilizer (the stabilizer includes carboxymethyl cellulose (molecular weight 15000), methylisothiazolinone and polyethylene glycol (molecular weight 5000), in a ratio of 1:0.1:0.5) to 85g of water, stir and disperse at 60℃. If there are no obvious particles, it indicates that the system is mixed evenly and stably. Then add 8g of polyether modified silicone oil and 3g of silicone paste, stir and disperse for 2-4 hours. If there are no obvious particles, it indicates that the system is mixed evenly and stably. The resulting white viscous emulsion is the high-efficiency fast-acting defoamer.

[0068] Comparative Example 1

[0069] The reference describes a mineral oil defoamer prepared from white oil, silicone paste, and polyether. Reference: Zhu Liqiang. Preparation of silicone paste from long-chain alkyl silicone oil and its application in mineral oil defoamers [D]. South China University of Technology, Guangzhou, Guangdong, 2020.

[0070] Comparative Example 2

[0071] The polyether-modified silicone oil defoamer prepared in Example 1 of patent document CN 106215465 A.

[0072] Comparative Example 3

[0073] The organosilicon defoamer prepared in Example 1 of patent document CN 106215468 A.

[0074] The corrosion inhibition and foaming liquid carrying capacity of Examples 1-11 and Comparative Examples 1-3 were evaluated.

[0075] The defoaming performance and stability of the defoamer were evaluated in accordance with GB / T 26527-2024 "Organic Silicone Defoamers" and Q / SY 17001-2022 "Defoamer for Foam Drainage and Gas Extraction - Organosilicone Emulsion". The experimental results are shown in Table 1.

[0076] The evaluation methods and experimental procedures are as follows:

[0077] 1. Storage stability

[0078] Take two 10mL centrifuge tubes, add 8mL of defoaming agent to each, place them symmetrically in a centrifuge, and centrifuge at 3000r / min for 15min. After centrifugation, remove the centrifuge tubes and immediately read the volume of the layered liquid. The result is the arithmetic mean of the two measurements.

[0079] Storage stability was measured by the volume of the stratified layer after centrifugation, with an index of ≤0.5mL. Table 1 shows the comparative data of the Example and Comparative Example 1, using the number of days until the stratified layer reached 0.5mL as the index.

[0080] 2. Dilution stability

[0081] Weigh 40g (accurate to 0.01g) of defoamer into a 250mL beaker. Measure 160mL of distilled water using a graduated cylinder and add it to the beaker. Stir at 300rpm for 5min. Let stand in a sealed container at room temperature for 24h, observing the results visually under natural light. Actual procedures should follow the standard. Standard requirement: ≥24h.

[0082] 3. Defoaming performance

[0083] Measure 100 mL of foaming solution into a 250 mL stoppered graduated cylinder and seal it tightly. Manually shake vigorously up and down (or use a reciprocating shaker) until the foam reaches or exceeds the 250 mL mark. Open the stopper and immediately use a pipette (or pipette tip) to inject 5 mL of defoaming solution into the center of the graduated cylinder. Quickly stopper the cylinder and invert it once, then observe for 2 seconds. Start a stopwatch from the moment the defoaming solution contacts the foam, and record the time it takes for the foam to disappear until it reaches the 100 mL mark. Repeat this process at least three times, with each measurement differing by less than or equal to 2 seconds. Take the average of the multiple measurements as the defoaming time. In practice, follow the standard procedure, using 0.3% cocamidopropyl betaine (CAB) as the foaming agent. The standard requirement is ≤20 seconds.

[0084] Table 1. Defoaming performance and stability of different defoamers

[0085]

[0086]

[0087] Note: The data in Comparative Examples 1-3 are derived from the original records in the relevant literature, or converted from the original data.

[0088] As can be seen from the data in Table 1, the high-efficiency, fast-acting defoamer prepared by this invention meets the relevant performance standards within the experimental range: defoaming time ≤ 20s, dispersion stability ≥ 24h.

[0089] Comparing Examples 1 and 2, the performance indicators of the prepared products did not change significantly when only the type of emulsifier was changed. This may be because the screened emulsifiers could form relatively stable emulsions, so the product performance was mainly affected by the organosilicon content.

[0090] Comparing Examples 3 and 4, the product prepared by increasing only the stabilizer content exhibited better defoaming properties. This is likely because increasing the amount of stabilizer within a certain range allows for more complete emulsification of the system, thus improving the product's performance.

[0091] Comparing Examples 5 and 6, increasing the amount of silicone paste while keeping the silicone content constant resulted in a decrease in the performance of the prepared product. This may be because the silicone paste is extremely hydrophobic, and within the experimental range, the emulsion particles after emulsification are larger, thus reducing the product's performance. This situation was also observed in Comparative Examples 7 and 8.

[0092] Examples 9 and 10 were prepared randomly within the range of material types and proportions selected in the invention, and the performance of the prepared products met the requirements of the relevant implementation standards.

[0093] Comparing Examples 3 and 9, when the content of each component in the system does not change significantly, the performance indicators of the prepared product do not change significantly.

[0094] Based on the above implementation examples, defoamers with an organosilicon content of around 10% offer better cost-effectiveness.

[0095] Comparative Examples 1-3 are all silicone-based defoamers used in the field. The high-efficiency, fast-dissipating defoamers prepared in the embodiments of this invention have better performance than Comparative Examples 1-3, and have better defoaming performance and stability.

[0096] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; these ranges or thresholds should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and individual point values, and individual point values ​​can be combined to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A fast-acting defoamer, characterized in that, The raw material components of the fast-acting defoamer include, by mass percentage, 1%-3% emulsifier, 0.5%-1.0% stabilizer, 5%-10% polyether-modified silicone oil, 2%-5% silicone paste, and the remainder being water.

2. The quick-dissipating defoamer according to claim 1, characterized in that, The emulsifier is one or more of the following: Pingpingjia, Span-60, Tween-60, polyoxyethylene alkylphenol ether, fatty alcohol polyoxyethylene ether, glyceryl monostearate, sodium lauryl sulfate, and sodium lauryl benzoate.

3. The quick-dissipating defoamer according to claim 1, characterized in that, The emulsifier is one or more of Span-60, Tween-60, polyoxyethylene alkylphenol ether, fatty alcohol polyoxyethylene ether, and glyceryl monostearate.

4. The quick-dissipating defoamer according to claim 1, characterized in that, The stabilizer is a mixture of thickener, bactericide, and synergist, wherein, The mass ratio of thickener, bactericide, and synergist is 1:(0.1-0.5):(0.5-2.0).

5. The quick-dissipating defoamer according to claim 4, characterized in that, The thickener is a cellulose polysaccharide; The bactericide is an isothiazolinone; The synergist is a propylene glycol derivative.

6. The quick-dissipating defoamer according to claim 1, characterized in that, The raw materials for preparing silicone paste include dimethyl silicone oil and hydrophobic nano-silica, among which, The mass ratio of dimethyl silicone oil to hydrophobic nano silica is 1:(0.01-0.1).

7. A method for preparing a fast-acting defoamer, characterized in that, The method includes: Emulsifier and stabilizer are added to water and stirred and dispersed evenly at a predetermined temperature. Then, polyether-modified silicone oil and silicone paste are added and stirred evenly to obtain a fast-acting defoamer.

8. The method for preparing the quick-dissipating defoamer according to claim 7, characterized in that, The predetermined temperature is 50-70℃.

9. The method for preparing the quick-dissipating defoamer according to claim 7, characterized in that, The method for preparing the silicone paste includes: Dimethyl silicone oil and hydrophobic nano-silica are simmered at 110-150℃ for 4-8 hours to obtain silicone paste, wherein the mass ratio of dimethyl silicone oil to hydrophobic nano-silica is 1:0.01-0.

1.

10. The application of the quick-dissolving defoamer as described in any one of claims 1-6 in the oil and gas extraction process.

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