A high foam suppression defoamer and preparation method thereof

Abstract

The present application relates to the field of defoaming technology, and specifically discloses a high-foam-suppressing defoamer and a preparation method thereof. A high-foam-suppressing defoamer comprises the following raw materials in parts by weight: 100-150 parts of silicone oil; 10-20 parts of capric triglyceride; 10-20 parts of modified quercetin; 5-10 parts of nano silicon dioxide; 1-5 parts of surfactant; 1-5 parts of dispersant; 1-5 parts of emulsifier; 30-50 parts of micro-nano bubble water; 30-50 parts of deionized water; the modified quercetin is obtained by modifying quercetin with ethylene oxide. The defoamer of the present application can be used for defoaming treatment in a variety of industrial applications, and it has efficient defoaming performance and foam suppression performance.

Description

Technical Field

[0001] The present application relates to the field of defoaming technology, and more specifically, to a high-antifoaming defoaming agent and a preparation method thereof. Background Art

[0002] The raw gas of natural gas and petroleum processing industry (such as catalytic dry gas, coking dry gas, cracking gas, liquefied gas, etc.) contains a certain amount of H2S and organic sulfur (such as CS2, COS, RSH, RS-R', etc.), which must be removed before transportation and processing. Methyldiethanolamine is a solvent used in desulfurization and decarbonization processes. It can be used to treat acidic gases with different H2S concentrations. It can remove sulfides and CO2 at the same time, and can also remove H2S and organic sulfur with high selectivity. It has the advantages of low energy consumption, low circulation volume, and low operating costs. However, in practical applications, the surface tension of methyldiethanolamine is large, and it is easy to produce foam under reaction operating conditions. The formation of foam will not only reduce the desulfurization efficiency, but also increase the operating load and energy consumption of the equipment. Therefore, the use of defoaming agents becomes crucial.

[0003] In the related art, most of the defoamers used in the desulfurization process are silicone series defoamers. Although silicone series defoamers have good foam breaking ability, the silicone defoamers of a single system have low foam suppression ability, so the consumption is large, resulting in high production costs. Therefore, it is urgent to provide a defoamer with strong foam suppression ability. Summary of the invention

[0004] In order to enhance the antifoaming performance of a defoaming agent, the present application provides a high antifoaming defoaming agent and a preparation method thereof.

[0005] The present application provides a high-foam suppression defoamer adopts the following technical solution:

[0006] A high foam suppression defoamer, comprising the following raw materials in parts by weight:

[0007] 100-150 parts of silicone oil;

[0008] Capric triglyceride 10-20 parts;

[0009] 10-20 parts of modified quercetin;

[0010] 5-10 parts of nano silicon dioxide;

[0011] 1-5 parts of surfactant;

[0012] Dispersant 1-5 parts;

[0013] Emulsifier 1-5 parts;

[0014] 30-50 portions of micro-nano bubble water;

[0015] 30-50 parts of deionized water;

[0016] The modified quercetin is obtained by modifying quercetin with ethylene oxide.

[0017] By adopting the above technical scheme, silicone oil is used as one of the main components of the defoamer, and the silicone oil has good foam breaking ability, which can effectively destroy the formed foam. Capric triglyceride, as an auxiliary component, helps to enhance the anti-foaming ability of the defoamer. Capric triglyceride can also improve the dispersibility and stability of the defoamer in the system, thereby prolonging the action time of the defoamer. The addition of nano-silica can enhance the physical stability of the defoamer and prevent it from stratification or precipitation during use. At the same time, nano-silica can also improve the wettability and permeability of the defoamer, which helps to better contact the foam surface and destroy its structure. The structure of modified quercetin contains lipophilic and hydrophilic groups, which enables it to play a good dispersing and stabilizing role at the oil-water interface. At the same time, since the modified quercetin has a long polymer chain, a protective film can be formed on the foam surface to prevent the generation of new foam, thereby enhancing the anti-foaming ability of the defoamer.

[0018] Optionally, the modified quercetin is prepared by the following method:

[0019] A. Add quercetin, aluminum triisopropoxide and ethanol into the reactor, control the pressure in the reactor to 0.3-0.5 MPa, raise the temperature to 120-150°C and keep it for 1-2 hours;

[0020] B. After the insulation is completed, ethylene oxide is added to the reactor for the first time. When the pressure in the reactor is increased to 1.0 MPa, an induction reaction is carried out. When the pressure in the reactor drops, ethylene oxide is added to the reactor for the second time, and the temperature is raised to 180-200°C for reaction. When the pressure in the reactor drops again, the temperature in the reactor is lowered to room temperature and the material is discharged to obtain modified quercetin.

[0021] By adopting the above technical scheme, aluminum triisopropoxide can selectively catalyze the reaction of quercetin with ethylene oxide to ensure that the ether bond in the quercetin molecule reacts with ethylene oxide. Through the modification reaction, the epoxy group of ethylene oxide is introduced into the quercetin molecule. These newly introduced functional groups change the chemical structure and properties of quercetin, making it have a stronger balance of hydrophilicity and lipophilicity. This balance enables the modified quercetin to play a more effective role at the oil-water interface and improve the anti-foaming ability of the defoamer. The modification reaction may also lead to the optimization of the molecular structure of quercetin, such as the extension of the molecular chain, the increase of the branch chain, etc. These structural changes enable the modified quercetin to form a more stable dispersion system in the defoamer to prevent agglomeration and precipitation. At the same time, the optimized molecular structure also helps to improve the adsorption capacity and stability of the defoamer on the foam surface, thereby further enhancing the anti-foaming ability.

[0022] Optionally, in step A, the mass ratio of quercetin, aluminum triisopropoxide and ethanol is 1:0.5:(1-3).

[0023] Optionally, in step B, the mass of ethylene oxide added for the first time is 1%-5% of the mass of quercetin; the mass of ethylene oxide added for the second time is 30%-50% of the mass of quercetin.

[0024] Optionally, the micro-nano bubble water is micro-nano carbon dioxide bubble water, and the bubble particle size of the micro-nano bubble water is 1-50nm.

[0025] By adopting the above technical solution, the bubble particle size of micro-nano bubble water is extremely small (within the range of 1-50nm). In the early stage of foam formation, the presence of micro-nano bubble water can interfere with the normal arrangement of the liquid-gas interface. Usually, foam is formed by a liquid film wrapping a gas. When micro-nano bubbles exist, they will occupy part of the liquid-gas interface, which hinders the normal foam formation process. Because foam formation requires liquid to form a continuous film around the gas, the interference of micro-nano bubbles will make it difficult for the liquid to form a regular film, thereby inhibiting the generation of foam. At the same time, micro-nano bubble water also has extremely high surface tension. When it comes into contact with foam, it can quickly adsorb on the foam surface and reduce its surface tension, thereby destroying the stability of the foam. In addition, micro-nano bubble water can also cooperate with silicone oil and modified quercetin in the defoamer to form a more stable defoaming system, further improving the defoaming ability of the defoamer. Micro-nano carbon dioxide bubbles have a weak negative charge on the surface and have a repulsive force between each other, so they are more stable and not easy to aggregate and break. This allows micro-nano carbon dioxide bubble water to stay in the system for a long time and continue to play a defoaming role. Thereby enhancing the durability of the defoaming agent in suppressing foam.

[0026] Optionally, the surfactant is any one of polyethylene glycol octylphenyl ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate.

[0027] Optionally, the dispersant is any one of sodium polyacrylate, polycarboxylate and polyethylene glycol.

[0028] The present application also provides a method for preparing a high-foam-suppressing defoamer, which adopts the following technical solution:

[0029] A method for preparing a high-foam-suppressing defoamer comprises the following steps:

[0030] S1. Mix silicone oil, capric triglyceride, modified quercetin, nano silicon dioxide, dispersant, micro-nano bubble water and deionized water, and stir at 50-60° C. for 1-3 min to obtain a premix;

[0031] S2. After the premix and the emulsifier are mixed and emulsified for 2-3 hours, the mixture is allowed to stand for 1-2 hours to obtain a highly anti-foaming defoamer.

[0032] In summary, this application has the following beneficial effects:

[0033] 1. The silicone oil in the defoamer of the present application has good foam breaking ability, and capric triglyceride can also improve the dispersibility and stability of the defoamer in the system, thereby extending the action time of the defoamer. The addition of nano-silicon dioxide can enhance the physical stability of the defoamer and prevent it from stratification or precipitation during use. At the same time, nano-silicon dioxide can also improve the wettability and permeability of the defoamer. By adding modified quercetin, the structure of the modified quercetin contains lipophilic and hydrophilic groups, which enables it to play a good dispersing and stabilizing role at the oil-water interface. At the same time, since the modified quercetin has a longer polymer chain, a protective film can be formed on the foam surface to prevent new foam from being generated, thereby enhancing the anti-foaming ability of the defoamer.

[0034] 2. The present application can selectively catalyze the reaction of quercetin and ethylene oxide through aluminum triisopropoxide, ensuring that the ether bond in the quercetin molecule reacts with ethylene oxide. Through the modification reaction, the epoxy group of ethylene oxide is introduced into the quercetin molecule. These newly introduced functional groups change the chemical structure and properties of quercetin, making it have a stronger balance of hydrophilicity and lipophilicity. This balance enables the modified quercetin to play a more effective role at the oil-water interface and improve the foam suppression ability of the defoamer. The modification reaction may also lead to the optimization of the molecular structure of quercetin, such as the extension of the molecular chain, the increase of the side chain, etc. These structural changes enable the modified quercetin to form a more stable dispersion system in the defoamer to prevent agglomeration and precipitation. At the same time, the optimized molecular structure also helps to improve the adsorption capacity and stability of the defoamer on the foam surface, thereby further enhancing the foam suppression ability.

[0035] 3. Micro-nano bubble water is added to the defoamer of the present application, and the micro-nano bubble water can quickly penetrate into the foam and destroy its structure. At the same time, the micro-nano bubble water also has extremely high surface tension. When it comes into contact with the foam, it can quickly adsorb on the foam surface and reduce its surface tension, thereby destroying the stability of the foam. In addition, the micro-nano bubble water can also cooperate with the silicone oil and modified quercetin in the defoamer to form a more stable defoaming system, further improving the defoaming ability of the defoamer. DETAILED DESCRIPTION

[0036] The present application is further described in detail below with reference to the embodiments.

[0037] The main component of the organic silicone oil is dimethyl silicone oil. In this embodiment, the organic silicone oil is No. 201 dimethyl silicone oil purchased from Shandong Shuntai New Materials Co., Ltd.

[0038] Preparation example of modified quercetin

[0039] Preparation Example 1

[0040] The modified quercetin is prepared by the following method:

[0041] A. Add 10 kg of quercetin, 5 kg of aluminum triisopropoxide and 10 kg of ethanol into the reactor, control the pressure in the reactor to 0.3 MPa, and heat it to 120 °C for 1 hour;

[0042] B. After the insulation is completed, 0.1 kg of ethylene oxide is added to the reactor for the first time. When the pressure in the reactor is increased to 1.0 MPa, an induction reaction is carried out. When the pressure in the reactor drops, 3 kg of ethylene oxide is added to the reactor for the second time, and the temperature is raised to 180°C for reaction. When the pressure in the reactor drops again, the temperature in the reactor is lowered to room temperature for discharging to obtain modified quercetin.

[0043] Preparation Example 2

[0044] The modified quercetin is prepared by the following method:

[0045] A. Add 10 kg of quercetin, 5 kg of aluminum triisopropoxide and 20 kg of ethanol into the reactor, control the pressure in the reactor to 0.4 MPa, and heat it to 130 ° C for 1.5 hours;

[0046] B. After the insulation is completed, 0.3 kg of ethylene oxide is added to the reactor for the first time. When the pressure in the reactor is increased to 1.0 MPa, an induction reaction is carried out. When the pressure in the reactor drops, 4 kg of ethylene oxide is added to the reactor for the second time, and the temperature is raised to 190°C for reaction. When the pressure in the reactor drops again, the temperature in the reactor is lowered to room temperature for discharging to obtain modified quercetin.

[0047] Preparation Example 3

[0048] The modified quercetin is prepared by the following method:

[0049] A. Add 10 kg of quercetin, 5 kg of aluminum triisopropoxide and 30 kg of ethanol into the reactor, control the pressure in the reactor to 0.5 MPa, and heat it to 150 ° C for 2 hours;

[0050] B. After the insulation is completed, 0.5 kg of ethylene oxide is added to the reactor for the first time. When the pressure in the reactor is increased to 1.0 MPa, an induction reaction is carried out. When the pressure in the reactor drops, 5 kg of ethylene oxide is added to the reactor for the second time, and the temperature is raised to 200°C for reaction. When the pressure in the reactor drops again, the temperature in the reactor is lowered to room temperature and the material is discharged to obtain modified quercetin.

[0051] Preparation Example 4

[0052] The modified quercetin is different from Preparation Example 3 in that in step A, an equal amount of zinc hexacyanocobaltate is used instead of aluminum triisopropoxide as a catalyst.

[0053] Preparation Example 5

[0054] The modified quercetin is different from Preparation Example 3 in that the ethylene oxide added for the first and second times in step B is replaced by an equal amount of propylene oxide.

[0055] Example

[0056] Example 1

[0057] A highly anti-foaming defoamer, whose raw material components and dosages are shown in Table 1, wherein the modified quercetin is the modified quercetin prepared in Preparation Example 1; the surfactant is polyethylene glycol octylphenyl ether; the dispersant is sodium polyacrylate; the emulsifier is lecithin; the micro-nano bubble water is micro-nano carbon dioxide bubble water, and the bubble particle size of the micro-nano bubble water is 1-50 nm.

[0058] A method for preparing a high-foam-suppressing defoamer comprises the following steps:

[0059] S1. Mix silicone oil, capric triglyceride, modified quercetin, nano-silica, dispersant, micro-nano bubble water and deionized water, and stir at 50° C. for 3 min to obtain a premix;

[0060] S2. The premix and the emulsifier are mixed and emulsified for 2 hours, and then allowed to stand for 1 hour to obtain a high-foam-suppressing defoamer.

[0061] Example 2

[0062] A highly anti-foaming defoamer, whose raw material components and dosages are shown in Table 1, wherein the modified quercetin is the modified quercetin prepared in Preparation Example 1; the surfactant is polyoxyethylene sorbitan monolaurate; the dispersant is polycarboxylate; the emulsifier is lecithin; the micro-nano bubble water is micro-nano carbon dioxide bubble water, and the bubble particle size of the micro-nano bubble water is 1-50 nm.

[0063] A method for preparing a high-foam-suppressing defoamer comprises the following steps:

[0064] S1. Mix silicone oil, capric triglyceride, modified quercetin, nano-silica, dispersant, micro-nano bubble water and deionized water, and stir at 55° C. for 2 min to obtain a premix;

[0065] S2. The premix and the emulsifier are mixed and emulsified for 2.5 hours, and then allowed to stand for 1.5 hours to obtain a high-foam-suppressing defoamer.

[0066] Example 3

[0067] A highly anti-foaming defoamer, whose raw material components and dosages are shown in Table 1, wherein the modified quercetin is the modified quercetin prepared in Preparation Example 1; the surfactant is polyoxyethylene sorbitan monostearate; the dispersant is polyethylene glycol; the emulsifier is lecithin; the micro-nano bubble water is micro-nano carbon dioxide bubble water, and the bubble particle size of the micro-nano bubble water is 1-50 nm.

[0068] A method for preparing a high-foam-suppressing defoamer comprises the following steps:

[0069] S1. Mix silicone oil, capric triglyceride, modified quercetin, nano-silica, dispersant, micro-nano bubble water and deionized water, and stir at 60° C. for 1 min to obtain a premix;

[0070] S2. The premix and the emulsifier are mixed and emulsified for 3 hours, and then allowed to stand for 2 hours to obtain a high-foam-suppressing defoamer.

[0071] Table 1 Raw material components and dosage of defoaming agent in Examples 1-3 (g)

[0072]

[0073] Example 4

[0074] A high foam suppression defoamer, which is different from Example 3 in that the modified quercetin in this example is the modified quercetin prepared in Preparation Example 2.

[0075] Example 5

[0076] A high foam suppression defoamer, which is different from Example 3 in that the modified quercetin in this example is the modified quercetin prepared in Preparation Example 3.

[0077] Example 6

[0078] A high foam suppression defoamer, which is different from Example 3 in that the modified quercetin in this example is the modified quercetin prepared in Preparation Example 4.

[0079] Comparative Example

[0080] Comparative Example 1

[0081] The organosilicon defoamer was prepared according to Example 1 in the patent document with publication number CN110314417B and titled “An organosilicon defoamer”.

[0082] Comparative Example 2

[0083] A high foam suppression defoamer, which is different from Example 3 in that the modified quercetin in this example is the modified quercetin prepared in Preparation Example 5.

[0084] Comparative Example 3

[0085] A high foam suppression defoamer, which is different from Example 3 in that an equal amount of deionized water is used instead of micro-nano bubble water in this example.

[0086] Performance testing

[0087] Test 1 Defoaming performance test

[0088] Test subjects: defoamers in Examples 1-6 and Comparative Examples 1-3.

[0089] Foaming solution: 1.20% sodium dodecylbenzenesulfonate aqueous solution.

[0090] Test method: A 100 mL stoppered measuring cylinder containing 50 mL of 1.20% sodium dodecylbenzene sulfonate aqueous solution was shaken up and down 10 times at a speed of 2 times / s, and then a defoaming agent was added. The defoaming time was measured by pressing a stopwatch. The time taken for the foam to drop to 60 mL was the defoaming time. The test results are shown in Table 2.

[0091] Test 2: Antifoaming performance test

[0092] Test subjects: defoamers in Examples 1-6 and Comparative Examples 1-3.

[0093] Foaming solution: 1.20% sodium dodecylbenzenesulfonate aqueous solution.

[0094] Test method: add 100mL of 1.20% sodium dodecylbenzene sulfonate aqueous solution into the cylinder, then add 1g of defoamer, then bubble with nitrogen, control the nitrogen flow rate to 3L / min, and the time when the foam height reaches the 200mL mark is the foam suppression time. The test results are shown in Table 2.

[0095] Table 2 Test results of Examples 1-6 and Comparative Examples 1-3

[0096]

[0097] The defoaming time of Examples 1-5 is between 13.2 seconds and 13.7 seconds, showing similar excellent defoaming performance. It shows that in the technical solution provided in the present application, the synergistic effect of the components such as modified quercetin, silicone oil, capric triglyceride, nano-silica and micro-nano bubble water in the defoamer is significant, and jointly promotes the acceleration of the defoaming speed. The defoaming time of Examples 1-5 is between 55.2 minutes and 55.8 minutes, showing similar excellent defoaming performance. It shows that the synergistic effect of the components of the defoamer provided in the present application not only improves the defoaming speed, but also enhances the defoaming ability.

[0098] The defoaming time of Example 6 was 18.3 seconds, and the foam suppression time was 45.6 minutes, which were lower than those of Examples 1 to 5. This indicated that the modified quercetin prepared by using zinc hexacyanocobaltate as a catalyst had a lower promoting effect on the defoaming and foam suppression performance of the defoamer.

[0099] The defoaming time of comparative example 1 is 27.5 seconds, which is significantly longer than that of examples 1-5, further indicating that the defoaming performance of the defoamer provided in the present application is good. The antifoaming time of comparative example 1 is 24.6 minutes, which is significantly shorter than that of the examples, indicating that its antifoaming performance is weak. It further indicates that the modified quercetin used in the present application scheme has a strong promoting effect on the defoaming performance and antifoaming performance of the defoamer.

[0100] The defoaming time of Comparative Example 2 is 24.3 seconds, which is shorter than that of Comparative Example 1, but still longer than that of the example, indicating that the modified quercetin prepared by using propylene oxide instead of ethylene oxide in Preparation Example 5 has a reduced defoaming performance. The antifoaming time of Comparative Example 2 is 32.2 minutes, which is longer than that of Comparative Example 1, but still shorter than that of the example, indicating that the modified quercetin prepared by using propylene oxide instead of ethylene oxide in Preparation Example 5 also has a reduced antifoaming performance.

[0101] The defoaming time of Comparative Example 3 is 21.3 seconds, which is between Example 6 and Comparative Example 2. This may be because deionized water is used instead of micro-nano bubble water in Comparative Example 3, resulting in a decrease in defoaming performance, but it is still better than Comparative Examples 1 and 2, indicating that micro-nano bubble water has a certain effect in improving the defoaming speed. The anti-foaming time of Comparative Example 3 is 40.8 minutes, which is between Example 6 and Comparative Example 2. This may be because deionized water is used instead of micro-nano bubble water in Comparative Example 3, resulting in a decrease in anti-foaming performance, but it is still better than Comparative Examples 1 and 2, further illustrating the importance of micro-nano bubble water in improving anti-foaming ability.

[0102] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A high foam suppression defoamer, characterized in that: The invention comprises the following raw materials in parts by weight: 100-150 parts of silicone oil; Capric triglyceride 10-20 parts; 10-20 parts of modified quercetin; 5-10 parts of nano silicon dioxide; 1-5 parts of surfactant; Dispersant 1-5 parts; Emulsifier 1-5 parts; 30-50 portions of micro-nano bubble water; 30-50 parts of deionized water; The modified quercetin is prepared by the following method: A. Add quercetin, aluminum triisopropoxide and ethanol into the reactor, control the pressure in the reactor to 0.3-0.5 MPa, raise the temperature to 120-150°C and keep it for 1-2 hours; B. After the insulation is completed, ethylene oxide is added to the reactor for the first time. When the pressure in the reactor is increased to 1.0 MPa, an induction reaction is carried out. When the pressure in the reactor drops, ethylene oxide is added to the reactor for the second time, and the temperature is raised to 180-200°C for reaction. When the pressure in the reactor drops again, the temperature in the reactor is lowered to room temperature and the material is discharged to obtain modified quercetin.

2. A high foam suppression defoamer according to claim 1, characterized in that: In step A, the mass ratio of quercetin, aluminum triisopropoxide and ethanol is 1:0.5:(1-3).

3. A high foam suppression defoamer according to claim 1, characterized in that: In step B, the mass of ethylene oxide added for the first time is 1%-5% of the mass of quercetin; the mass of ethylene oxide added for the second time is 30%-50% of the mass of quercetin.

4. A high foam suppression defoamer according to claim 1, characterized in that: The micro-nano bubble water is micro-nano carbon dioxide bubble water, and the bubble particle size of the micro-nano bubble water is 1-50nm.

5. A high foam suppression defoamer according to claim 1, characterized in that: The surfactant is any one of polyethylene glycol octylphenyl ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate.

6. A high foam suppression defoamer according to claim 1, characterized in that: The dispersant is any one of sodium polyacrylate, polycarboxylate and polyethylene glycol.

7. A method for preparing a high foam suppression defoamer according to any one of claims 1 to 6, characterized in that: The steps include: S1. Mix silicone oil, capric triglyceride, modified quercetin, nano silicon dioxide, dispersant, micro-nano bubble water and deionized water, and stir at 50-60° C. for 1-3 min to obtain a premix; S2. After the premix and the emulsifier are mixed and emulsified for 2-3 hours, the mixture is allowed to stand for 1-2 hours to obtain a highly anti-foaming defoamer.

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