Industrial fermentation defoaming agent and preparation method thereof

Abstract

The application discloses an industrial fermentation defoaming agent and a preparation method thereof. The defoaming agent comprises the following components in parts by weight: 5-10 parts of organic silicon active substance, 3-7 parts of polyether modified organosiloxane, 30-40 parts of polyether compound, 1-3 parts of emulsifier, 1-3 parts of thickening agent and 37-60 parts of deionized water. The organic silicon active substance comprises hydroxyl silicone oil, hydrogen-containing silicone oil, terpene olefin, vinyl silicone oil, MQ silicone resin, silicon dioxide and a catalyst. The polyether compound comprises at least one of fatty alcohol polyether, propylene glycol polyether, glycerol polyether and pentaerythritol polyether. The defoaming agent can inhibit product demulsification and keep the product performance stable before and after sterilization in the sterilization process of the industrial fermentation front end. The defoaming agent is compounded with different polyether turbidity precipitates, and is matched with silicon polyether, so that the emulsion emulsifier is complementary, and the organic silicon active substance is prevented from being precipitated. The preparation method of the industrial fermentation defoaming agent is simple in operation, raw materials are easy to obtain, and is suitable for large-scale production.

Description

Technical Field

[0001] This application relates to the field of fermentation defoamer technology, specifically to an industrial fermentation defoamer and its preparation method. Background Technology

[0002] Bio-fermentation is widely used in industries such as pharmaceuticals, food, energy, chemicals, and agriculture. However, foaming problems often occur during bio-fermentation, which may be caused by operational factors, the surrounding environment, or agitation. Foaming can lead to reduced fermentation yield, fermentation broth overflow and contamination, and a decrease in working volume. When the fermentation product is anionic surfactant, the foam produced during fermentation is more stable.

[0003] Fermentation is divided into aerobic and anaerobic fermentation, and both processes utilize defoamers to eliminate foam. Aerobic fermentation produces a large amount of foam, requiring defoamers with a certain foam-breaking ability. Furthermore, in some aerobic fermentation processes, residual foam is necessary, necessitating defoamers with foam-controlling capabilities. Anaerobic fermentation demands higher foam-suppressing capabilities from defoamers, requiring them to suppress foam for extended periods even at lower dosages. Regardless of whether it's aerobic or anaerobic fermentation, defoamers are sterilized before use. After high-temperature sterilization, many emulsion-type defoamers experience demulsification, leading to decreased performance. During fermentation, using demulsifying defoamers results in a large amount of viscous material forming on the reactor walls or sediment at the bottom, further degrading performance. Adding excessive thickeners and stabilizers to defoamers leads to excessively high emulsion viscosity, poor dispersibility, and hinders rapid foam breaking by the defoamer.

[0004] Chinese patent CN113750577B indicates that a compound of polyether-modified organosilicon, polyether-modified heptamethyltrisiloxane, and a solvent performs well in rhamnolipin surfactants, exhibiting excellent defoaming effects. However, it has almost no effect in actual fermentation liquids, resulting in huge consumption. The complex composition of rhamnolipin fermentation liquids leads to numerous factors affecting foam variation. Ethanol, isopropanol, and n-butanol cannot break the foam in the system, and small-molecule alcohols have certain antibacterial effects, impacting the final yield.

[0005] Chinese patent CN113750577B specifies the preparation of defoamers using only materials such as silicone paste, polyether, emulsifier, and glycerol fatty acid esters, but does not explicitly address the product's stability at high temperatures. This patent uses conventional emulsifiers to emulsify the defoamer, which carries a certain risk of high-temperature demulsification.

[0006] Therefore, there is a need for an industrial fermentation defoamer that can inhibit demulsification and has good defoaming properties. Summary of the Invention

[0007] In view of this, the purpose of this application is to provide an industrial fermentation defoamer and its preparation method. This defoamer, during the sterilization process at the front end of industrial fermentation, can inhibit product demulsification and maintain stable product performance before and after sterilization. This defoamer is compounded with different polyether cloud point precipitates and combined with polyether-modified organosiloxanes to complement the emulsion emulsifier, thereby ensuring that the organosilicon active substances do not precipitate.

[0008] To achieve, or at least partially achieve, the above objectives, this application provides the following technical solution:

[0009] In a first aspect, this application provides an industrial fermentation defoamer comprising the following components in parts by weight: 5-10 parts of organosilicon active ingredient, 3-7 parts of polyether-modified organosilicon, 30-40 parts of polyether compound, 1-3 parts of emulsifier, 1-3 parts of thickener, and 37-60 parts of deionized water.

[0010] The organosilicon active materials include hydroxyl silicone oil, hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, MQ silicone resin, silicon dioxide, and catalysts;

[0011] The polyether compound includes at least one of fatty alcohol polyether, propylene glycol polyether, glycerol polyether, and pentaerythritol polyether.

[0012] Secondly, this application provides a method for preparing the aforementioned industrial fermentation defoamer, comprising the following steps:

[0013] Step 1: Mix the organosilicon active material, polyether-modified organosiloxane, and emulsifier, stir, and heat to 50-80°C to obtain the first mixed solution;

[0014] Step 2: Add water and thickener to the first mixed solution in sequence, then adjust the pH value to 7, and repeat the above operation 2 to 3 times to obtain the second mixed solution;

[0015] Step 3: Keep the temperature of the second mixed solution at 50-80°C, add the polyether compound and mix, then let it cool naturally to room temperature to obtain the defoamer for industrial fermentation.

[0016] The industrial fermentation defoamer and its preparation method provided in this application have at least the following beneficial effects:

[0017] 1. Compared with the prior art, the industrial fermentation defoamer provided in this application has excellent defoaming ability. It can effectively control the foam generated during the fermentation process with only a small amount of dosage, and the defoaming speed is fast and the demulsification of the defoamer is inhibited.

[0018] 2. The raw materials used in the industrial fermentation defoamer provided in this application are mild. Due to the small amount added, it will be decomposed into carbon source components of the culture medium by fermentation bacteria in the later stage of fermentation. After use, there is no need to add an additional defoamer separation and removal process, which improves fermentation efficiency and reduces labor costs.

[0019] 3. The preparation method of the industrial fermentation defoamer provided in this application is simple to operate, the raw materials are readily available, and it is suitable for large-scale production. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0021] In this application, the term "terpenoid alkenes" refers to olefin compounds with a molecular formula that is an integer multiple of isoprene, with the general formula n(C5H8). Terpenoid alkenes are a class of naturally occurring hydrocarbons widely found in plants, particularly conifers; they are the main components of resins and turpentine derived from resins. Studies have also found large quantities of terpenoid alkenes extracted from marine organisms. Terpenoid alkenes are diverse, broadly classified into hemiterpenes (n=1, C5H8, meta-isoprene) and monoterpenes (n=2, C5H8, meta-isoprene). 10 H 16 Such as pinene, limonene, geraniol, camphene), sesquiterpenes (n=3, C 15 H 24 (e.g., gingerene), diterpenes (n=4, C 20 H 32 (e.g., camphorene) and polyterpenes (n=6, C 30 H 48 (such as squalene).

[0022] In this application text, the terms "first" and "second" are used to distinguish identical or similar items with essentially the same function and effect, solely for the purpose of clearly describing the technical solutions of the embodiments of this application, and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated.

[0023] In this application text, the term "normal temperature" refers to room temperature or general temperature, with a temperature range of 15 to 25°C.

[0024] In this application, the term "cloud point" refers to the cloud point, a characteristic constant of nonionic surfactants, which is affected by the surfactant's molecular structure and coexisting substances. Aqueous solutions of surfactants will become turbid with increasing temperature, as the surfactant changes from complete dissolution to partial dissolution; the temperature at which this transition occurs is the cloud point temperature. The cloud point (CP) is the temperature at which a homogeneous micelle solution of a nonionic surfactant (NS) undergoes phase separation, and is a very important physical parameter. It is the critical temperature at which a liquid sample begins to become turbid under standard conditions. In this application, the liquid sample refers to a polyether compound, including one or more combinations of fatty alcohol polyethers, propylene glycol polyethers, glycerol polyethers, and pentaerythritol polyethers. The cloud point of the polyether compound refers to the temperature at which the polyether solution begins to become turbid. This is because as the temperature increases, the movement of polyether molecules intensifies, leading to a weakening of the intermolecular forces, thus causing the solution to become turbid. This application does not explicitly define the cloud point testing method; it should be understood that existing publicly available techniques are used for cloud point testing.

[0025] To address the problems existing in the prior art, this application improves upon the composition of existing fermentation defoamer compositions, obtaining a novel industrial fermentation defoamer. This defoamer composition incorporates organosilicon active ingredients containing terpenes. Some terpenes possess hydrophilic groups, increasing hydrophilicity, and the plant-based terpenes accelerate the degradation rate of the compounds. Simultaneously, this industrial fermentation defoamer also introduces a polyether complex, composed of at least one or more polyethers with different cloud points selected from fatty alcohol polyethers, propylene glycol polyethers, glycerol polyethers, and pentaerythritol polyethers. The polyether complex consists of three polyethers with different cloud points: 5–20°C polyether, 21–30°C polyether, and 31–50°C polyether. The mass fractions of these three polyethers are 1–5 parts, 60–68 parts, and 27–39 parts, respectively. During high-temperature sterilization, the industrial fermentation defoamer containing the above-mentioned polyether compound replenishes the emulsifier in the defoamer due to the precipitation of the polyether compound. The precipitate is evenly dispersed in the emulsion, increasing its viscosity. Stirring during high-temperature sterilization further refines the emulsion, resulting in superior defoaming performance.

[0026] Based on this, embodiments of this application provide an industrial fermentation defoamer, comprising the following components in parts by weight: 5-10 parts of organosilicon active ingredient, 3-7 parts of polyether-modified organosiloxane, 30-40 parts of polyether compound, 1-3 parts of emulsifier, 1-3 parts of thickener, and 37-60 parts of deionized water; wherein the organosilicon active ingredient includes hydroxyl silicone oil, hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, MQ silicone resin, silica, and catalyst; wherein the polyether compound includes at least one of fatty alcohol polyether, propylene glycol polyether, glycerol polyether, and pentaerythritol polyether.

[0027] In this embodiment, the hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, hydroxyl silicone oil, and MQ silicone resin are the reaction components of the organosilicon active material, and silica is the defoaming particles in the organosilicon active material. The reaction components, defoaming particles, and catalyst together constitute the defoamer active material. In some embodiments, the molar ratio of the hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, and hydroxyl silicone oil in the reaction components of the organosilicon active material is 1:0.1-0.3:0.4-0.6:0.2-0.4. In some preferred embodiments, the molar ratio of the hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, and hydroxyl silicone oil in the reaction components of the organosilicon active material is 1:0.2:0.5:0.3.

[0028] In some embodiments, the hydrogen-containing silicone oil is an end-side hydrogen-containing silicone oil with a hydrogen content of 0.1% to 1%.

[0029] In some preferred embodiments, the terpene olefin is a sesquiterpene. In some more preferred embodiments, the terpene olefin is gingerene.

[0030] In some embodiments, the vinyl silicone oil is at least one of single-ended vinyl silicone oil, double-ended vinyl silicone oil, and end-sided vinyl silicone oil. In some preferred embodiments, the vinyl silicone oil is a double-ended vinyl silicone oil with a vinyl content of 0.1% to 0.5%.

[0031] In some embodiments, the hydroxyl silicone oil is at least one of monohydroxyl silicone oil and bihydroxyl-terminated silicone oil, and its D-type chain segment number is 10 to 1000. In some preferred embodiments, the hydroxyl silicone oil is bihydroxyl-terminated silicone oil.

[0032] In some embodiments, the M / Q value of the MQ silicone resin is 0.6 to 0.8:1, and the mass percentage of the MQ silicone resin in the reaction components is 1% to 10%, preferably 1% to 5%.

[0033] In some embodiments, the hydrophobicity of the silica is 30% to 70%, and the mass ratio of the silica to the reactant is 1 to 10:100. In some preferred embodiments, the mass ratio of the silica to the reactant is 1 to 5:100.

[0034] In some embodiments, the catalyst is selected from at least one of platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, isopropanol chloroplatinate solution, and platinum-vinyl complexes, and the catalyst is used to catalyze the polymerization reaction of the reaction components.

[0035] In some preferred embodiments, the catalyst is an isopropanol chloroplatinate solution.

[0036] In some embodiments, the amount of catalyst used, calculated based on platinum content, is 5 to 10 ppm of the total mass of the reaction components.

[0037] In some embodiments, the preparation method of the organosilicon active material includes: mixing hydrogen-containing silicone oil, terpene olefins, and MQ silicone resin; adding a catalyst for the first time and heating to 100-150°C for 30 minutes, then cooling to room temperature; then adding terminal vinyl silicone oil; adding a catalyst for the second time, the amount of which is 2-6 times that of the first addition; and heating to 100-150°C a second time for reaction; finally adding hydroxyl silicone oil and silica, stirring evenly, heating to 120°C for 4 hours, and then cooling to room temperature to obtain the organosilicon active material; wherein the catalyst is selected from at least one of platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, isopropanol chloroplatinate solution, and platinum-vinyl complexes.

[0038] In the embodiments of this application, the polyether-modified organosiloxane is a complex formed by the reaction of polyorganohydrosiloxane and unsaturated polyether under alkaline catalyst conditions.

[0039] In some embodiments, the general structural formula of the polyorganohydrosiloxane is (CH3)3SiO[Si(CH3)2O]. m (SiHCH3O) n Si(CH3)3, where m is an integer from 0 to 150 and n is an integer from 1 to 150.

[0040] In some embodiments, the unsaturated polyether structure has the general formula HO(EO). p (PO) q OH, where p is an integer from 1 to 10 and q is an integer from 2 to 10.

[0041] In some embodiments, the molar ratio of the organic hydrogen siloxane to the unsaturated polyether is 1:1 to 2.

[0042] In some embodiments, the alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, potassium silylate, sodium silylate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, β-hydroxyethyltrimethylamine, and tetramethylammonium hydroxide. In some preferred embodiments, the alkaline catalyst is potassium hydroxide, and its amount is 5 to 10 ppm of the total mass of the polyether-modified organosiloxane.

[0043] In some embodiments, the method for preparing the polyether-modified organosiloxane includes: mixing a polyorganohydrosiloxane, an unsaturated polyether, and an alkaline catalyst to obtain a mixed solution, then heating the mixed solution to 120–200°C and holding it at that temperature for 30 minutes, and then cooling it to room temperature.

[0044] In some embodiments, the polyether compound is composed of one or more polyethers selected from fatty alcohol polyether, propylene glycol polyether, glycerol polyether, and pentaerythritol polyether. The polyether compound is composed of three polyethers with different cloud points, namely a first polyether, a second polyether, and a third polyether. The cloud point range of the first polyether is 5–20°C, the cloud point range of the second polyether is 21–30°C, and the cloud point range of the third polyether is 31–50°C. The mass ratio of the first polyether, the second polyether, and the third polyether is 1–5:60–68:27–39.

[0045] In this embodiment, the main function of the emulsifier is to reduce the interfacial tension between the organosilicon active material and water, enabling the organosilicon active material to be stably dispersed in water for a long period. The emulsifiers used in this embodiment include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In some preferred embodiments, nonionic surfactants are selected as the emulsifier.

[0046] In some embodiments, the nonionic surfactant is a carbon chain emulsifier, including at least one of sorbitan monostearate (S-60), sorbitan monooleate (S-80), sorbitan tristearate (S-65), sorbitan monostearate (S-60), sorbitan monooleate polyoxyethylene ether ester (T-80), sorbitan tristearate polyoxyethylene ether ester (T-65), fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether ester, alkylphenol polyoxyethylene ether, and glyceryl monostearate.

[0047] In this embodiment, the thickener serves to enhance the stability of the emulsion. The thickener is categorized into natural and synthetic thickeners, and includes at least one of polyvinyl alcohol (PVA), sodium carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, guar gum, xanthan gum, nonionic polyurethane, and alkali-soluble acrylates. In some preferred embodiments, the thickener is an alkali-soluble acrylate.

[0048] During industrial fermentation, the fermentation broth usually contains inorganic salts or trace elements. Therefore, in this embodiment, deionized water is used as a component of the industrial fermentation defoamer to minimize the impact on the fermentation broth.

[0049] Based on this, this application embodiment also provides a method for preparing the aforementioned industrial fermentation defoamer, comprising: a first step: mixing organosilicon active material, polyether-modified organosiloxane, and emulsifier, stirring and heating to 50-80°C; obtaining a first mixed solution; a second step: sequentially adding water and thickener to the first mixed solution, then adjusting the pH value to 7, repeating the above operation 2-3 times to obtain a second mixed solution; a third step: maintaining the temperature of the second mixed solution at 50-80°C, adding polyether compound and mixing, and naturally cooling to room temperature to obtain the industrial fermentation defoamer.

[0050] The technical solution of this application and the technical effects achieved will be described in detail below through more specific embodiments.

[0051] Example 1

[0052] This embodiment provides a method for preparing an industrial fermentation defoamer, including the following steps:

[0053] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 100°C with isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components), and the mixture was heated to 150°C for further reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, and the mixture was heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X1.

[0054] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y1.

[0055] (3) Take 5g of organosilicon active material X1, 3g of polyether modified organosilicon Y1, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0056] (4) Keep the temperature of the mixed solution obtained in step (3) at 80°C, and add 30g of polyether compound, wherein the polyether compound includes a first polyether, a second polyether, and a third polyether, wherein the first polyether is a fatty alcohol polyether with a cloud point of 5°C and a mass of 0.3g, the second polyether is a propylene glycol polyether with a cloud point of 21°C and a mass of 18g, and the third polyether is a glycerol polyether with a cloud point of 50°C and a mass of 11.7g; cool to room temperature to obtain industrial fermentation defoamer Z1.

[0057] Example 2

[0058] This embodiment provides a method for preparing an industrial fermentation defoamer, including the following steps:

[0059] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.1 mol of gingerene, 0.4 mol of terminal vinyl silicone oil, and 0.2 mol of hydroxyl silicone oil (D-type chain segment number of 10); weigh MQ silicone resin (M / Q value of 0.6), whose mass is 3% of the reaction components; weigh silicon dioxide, whose mass is 3% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 120°C with isopropanol chloroplatinate solution (2 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (8 ppm of the total mass of the reaction components), and the mixture was heated to 100°C for further reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X2.

[0060] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 150 (SiHCH3O) 150 Si(CH3)3; Weigh out 0.1 mol of unsaturated polyether with the chemical formula HO(EO). 10(PO) 10 OH; add potassium hydroxide (10 ppm of the total mass of polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 200℃, keep warm for 30 min, and you will get polyether modified organosiloxane Y2.

[0061] (3) Take 8g of organosilicon active ingredient X2, 5g of polyether modified organosilicon Y2, 0.5g of dehydrated sorbitan monooleate (S-80), and 1g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 60℃. Add 15g of deionized water for emulsification. Add 0.33g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 15g of water for emulsification. Add 0.33g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 15g of water. Add 0.33g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0062] (4) Keep the temperature of the mixed solution obtained in step (3) at 50°C, and add 35g of polyether compound, wherein the polyether compound includes a first polyether, a second polyether, and a third polyether, wherein the first polyether is a fatty alcohol polyether with a cloud point of 20°C and a mass of 1.4g, the second polyether is a glycerol polyether with a cloud point of 30°C and a mass of 23.1g, and the third polyether is a pentaerythritol polyether with a cloud point of 31°C and a mass of 10.9g; cool to room temperature to obtain industrial fermentation defoamer Z2.

[0063] Example 3

[0064] This embodiment provides a method for preparing an industrial fermentation defoamer, including the following steps:

[0065] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.3 mol of gingerene, 0.6 mol of terminal vinyl silicone oil, and 0.4 mol of hydroxyl silicone oil (D-type chain segment number of 1000); weigh MQ silicone resin (M / Q value of 0.8), whose mass is 5% of the reaction components; weigh silicon dioxide, whose mass is 5% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 150°C with isopropanol chloroplatinate solution (1.5 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (6 ppm of the total mass of the reaction components), and the mixture was heated to 120°C for the second reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X3.

[0066] (2) The polyether-modified organosiloxane was prepared by weighing 0.1 mol of polyorganohydrosiloxane with the chemical formula SiHCH3OSi(CH3)3; weighing 0.2 mol of unsaturated polyether with the chemical formula HO(EO)(PO)2OH; adding potassium hydroxide (8 ppm of the total mass of polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heating to 150℃ and holding for 30 min to obtain polyether-modified organosiloxane Y3;

[0067] (3) Take 10g of organosilicon active ingredient X3, 7g of polyether modified organosilicon Y3, 1.5g of dehydrated sorbitan monooleate (S-80), and 1.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 60℃. Add 20g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 20g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0068] (4) Keep the temperature of the mixed solution obtained in step (3) at 70°C, and add 40g of polyether compound, wherein the polyether compound includes a first polyether, a second polyether, and a third polyether, wherein the first polyether is glycerol polyether with a cloud point of 15°C and a mass of 2g, the second polyether is glycerol polyether with a cloud point of 23°C and a mass of 27.2g, and the third polyether is glycerol polyether with a cloud point of 35°C and a mass of 10.8g; cool to room temperature to obtain industrial fermentation defoamer Z3.

[0069] Example 4

[0070] This embodiment provides a method for preparing an industrial fermentation defoamer, including the following steps:

[0071] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 400); weigh MQ silicone resin (M / Q value of 0.8), whose mass is 6% of the reaction components; weigh silicon dioxide, whose mass is 3% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 100°C with isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components), and the mixture was heated to 100°C for a second reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, and then heated to 120°C. After holding at this temperature for 4 hours, the mixture was cooled to room temperature to obtain organosilicon active material X4.

[0072] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 100 Si(CH3)3; Weigh 0.1 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (the mass of which is 6 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y4.

[0073] (3) Take 6g of organosilicon active material X4, 4g of polyether modified organosilicon Y4, 1g of dehydrated sorbitan monooleate (S-80), and 1.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 60℃. Add 13g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 14g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 15g of water. Add 1g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0074] (4) Keep the temperature of the mixed solution obtained in step (3) at 60°C, and add 35g of polyether compound, wherein the polyether compound includes a first polyether, a second polyether, and a third polyether, wherein the first polyether is propylene glycol polyether with a cloud point of 18°C ​​and a mass of 1.4g, the second polyether is glycerol polyether with a cloud point of 25°C and a mass of 23.1g, and the third polyether is pentaerythritol polyether with a cloud point of 40°C and a mass of 10.5g; cool to room temperature to obtain industrial fermentation defoamer Z4.

[0075] Comparative Example 1

[0076] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0077] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin, add isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) for the first time and heat up to 100℃, keep it at 30 min, and then cool down to room temperature; add terminal vinyl silicone oil and add isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components) for the second time and heat up to 150℃ for reaction; add hydroxyl silicone oil and silicon dioxide, mix evenly, heat up to 120℃, keep it at 4 h, and then cool down to room temperature to obtain organosilicon active material X5;

[0078] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y5.

[0079] (3) Take 5g of organosilicon active material X5, 3g of polyether modified organosilicon Y5, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0080] (4) Keep the temperature of the mixed solution obtained in step (3) at 80°C, and add 30g of polyether compound, wherein the polyether compound includes a first polyether, a second polyether, and a third polyether, wherein the first polyether is a fatty alcohol polyether with a cloud point of 5°C and a mass of 0.3g, the second polyether is a propylene glycol polyether with a cloud point of 21°C and a mass of 18g, and the third polyether is a glycerol polyether with a cloud point of 50°C and a mass of 11.7g; cool to room temperature to obtain industrial fermentation defoamer Z5.

[0081] Comparative Example 2

[0082] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0083] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 100°C with isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components), and the mixture was heated to 150°C for further reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, and the mixture was heated to 120°C and held for 4 hours before cooling to room temperature to obtain organosilicon active material X6.

[0084] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y6.

[0085] (3) Take 5g of organosilicon active material X6, 3g of polyether modified organosilicon Y6, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0086] (4) Cool the mixed solution obtained in step (3) to room temperature to obtain defoamer Z6 for industrial fermentation.

[0087] Comparative Example 3

[0088] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0089] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), its mass is 1% of the reaction components; weigh silicon dioxide, its mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene and MQ silicone resin, add isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) for the first time and heat up to 100℃, keep it at 30 min, and then cool down to room temperature; add terminal vinyl silicone oil and add isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components) for the second time, heat up to 150℃ for reaction; add hydroxyl silicone oil and silicon dioxide, mix evenly and heat up to 120℃, keep it at 4 h and then cool down to room temperature to obtain organosilicon active material X7.

[0090] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y7.

[0091] (3) Take 5g of organosilicon active material X7, 3g of polyether modified organosilicon Y7, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0092] (4) Cool the mixed solution obtained in step (3) to room temperature to obtain defoamer Z7 for industrial fermentation.

[0093] Comparative Example 4

[0094] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0095] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 100°C with isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components), and the mixture was heated to 150°C for further reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, and the mixture was heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X8.

[0096] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y8.

[0097] (3) Take 5g of organosilicon active material X8, 3g of polyether modified organosilicon Y8, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0098] (4) Keep the temperature of the mixed solution obtained in step (3) at 80°C, add 30g of fatty alcohol polyether with a cloud point of 5°C; cool to room temperature to obtain industrial fermentation defoamer Z8.

[0099] Comparative Example 5

[0100] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0101] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The reaction mixture was first heated to 100°C with isopropanol chloroplatinate solution (1 ppm of the total mass of the reaction components) and held at that temperature for 30 minutes, then cooled to room temperature. Then, terminal vinyl silicone oil was added, followed by a second addition of isopropanol chloroplatinate solution (4 ppm of the total mass of the reaction components), and the mixture was heated to 150°C for the second reaction. Finally, hydroxyl silicone oil and silica were added, mixed thoroughly, and the mixture was heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X9.

[0102] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether and potassium hydroxide), heat to 120℃, and keep warm for 30 min to obtain polyether-modified organosiloxane Y9.

[0103] (3) Take 5g of organosilicon active material X9, 3g of polyether modified organosilicon Y9, 0.5g of dehydrated sorbitan monooleate (S-80), and 0.5g of dehydrated sorbitan monooleate polyoxyethylene ether ester (T-80) and add them to a beaker. Stir and heat to 50℃. Add 12g of deionized water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7 and stir for 10min. Continue to add 12g of water for emulsification. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7. Emulsify with 12g of water. Add 0.5g of alkali-soluble acrylate. Then adjust the pH value to 7.

[0104] (4) Keep the temperature of the mixed solution obtained in step (3) at 80°C, add 30g of propylene glycol polyether, the cloud point is 21°C; cool to room temperature to obtain industrial fermentation defoamer Z9.

[0105] Comparative Example 6

[0106] This comparative example provides a method for preparing an industrial fermentation defoamer, comprising the following steps:

[0107] (1) Preparation of organosilicon active material: First, weigh the reaction components, including 1 mol of hydrogen-containing silicone oil with a hydrogen content of 0.1%, 0.2 mol of gingerene, 0.5 mol of terminal vinyl silicone oil, and 0.3 mol of hydroxyl silicone oil (D-type chain segment number of 350); weigh MQ silicone resin (M / Q value of 0.7), whose mass is 1% of the reaction components; weigh silicon dioxide, whose mass is 1% of the reaction components; and then mix the weighed hydrogen-containing silicone oil, gingerene, and MQ silicone resin. The mixture was first added to an isopropanol chloroplatinate solution (1 ppm of the total mass of the reactants), and the temperature was raised to 100°C and held for 30 minutes, then cooled to room temperature. Terminal-chain vinyl silicone oil was then added, followed by a second addition of an isopropanol chloroplatinate solution (4 ppm of the total mass of the reactants), and the temperature was raised to 150°C for the second reaction. Hydroxyl silicone oil and silica were then added, mixed thoroughly, and the mixture was heated to 120°C, held for 4 hours, and then cooled to room temperature to obtain organosilicon active material X. 10 ;

[0108] (2) Preparation of polyether-modified organosiloxane: The specific method is as follows: Weigh 0.1 mol of polyorganohydrosiloxane, whose chemical formula is (CH3)3SiO[Si(CH3)2O] 50 (SiHCH3O) 50 Si(CH3)3; Weigh 0.15 mol of unsaturated polyether, with the chemical formula HO(EO)5(PO)5OH; Add potassium hydroxide (5 ppm of the total mass of the polyorganohydrosiloxane, unsaturated polyether, and potassium hydroxide), heat to 120℃, and hold for 30 min to obtain polyether-modified organosiloxane Y. 10 ;

[0109] (3) Take 5g of organosilicon active material X 10 3g polyether-modified organosiloxane Y 10 0.5g of sorbitan monooleate (S-80) and 0.5g of sorbitan monooleate polyoxyethylene ether ester (T-80) were added to a beaker, stirred, and heated to 50°C. 12g of deionized water was added for emulsification, followed by the addition of 0.5g of alkali-soluble acrylate. The pH was then adjusted to 7, and the mixture was stirred for 10 minutes. Another 12g of water was added for emulsification, followed by the addition of 0.5g of alkali-soluble acrylate, and the pH was adjusted to 7.

[0110] (4) Keep the mixed solution obtained in step (3) at 80°C, add 30g of pentaerythritol polyether (cloud point 50°C), and cool to room temperature to obtain industrial fermentation defoamer Z. 10 .

[0111] The defoaming ability of the industrial fermentation defoamers prepared in Examples 1-4 and Comparative Examples 1-6 was tested. The specific method was as follows:

[0112] (1) High temperature resistance test: 100g of defoamer was added to the sterilization pressure cooker, the sterilization pressure cooker was heated to 120℃ and kept at that temperature for 4 hours, and then cooled to room temperature. 5% of the defoamer was taken out and dispersed in water to see if there was any oil floating.

[0113] (2) Performance test after sterilization: Take 1g of sterilized defoamer and add it to a 300ml sample bottle. Add 100g of sodium dodecylbenzenesulfonate solution with a mass fraction of 1% to the sample bottle. After filling the bottle, use an HVS-10M vertical shaker to shake at 450rpm / min for 30min and record the foam elimination time.

[0114] Industrial fermentation defoamers Z1-Z prepared in Examples 1-4 and Comparative Examples 1-6 10 The main differences in the preparation process and the comparison results of the final defoaming effect are shown in Table 1 below.

[0115] Table 1

[0116]

[0117]

[0118] As can be seen from the results in Table 1, the industrial fermentation defoamers Z1 to Z4 prepared in Examples 1 to 4 have the best defoaming effect, that is, no oil floats after high-temperature sterilization, and the defoaming speed is relatively fast, with the defoaming time all below 30 seconds. The reason for the above results is that the industrial fermentation defoamers prepared in the examples all incorporated terpenoids and polyether complexes with gradient cloud points. The terpenoids (such as gingerene) have hydrophilic groups, which increase hydrophilicity and accelerate the degradation of the compounds, thus achieving rapid defoaming. The reason for artificially setting the cloud point gradient of the polyether complex is that during high-temperature sterilization in the fermentation industry, the temperature rises from room temperature to 120-130°C. It is necessary to maintain the stability of the emulsion in different temperature ranges from room temperature to 120-130°C. This polyether complex with gradient cloud points forms an optimal hydrophilic-lipophilic balance (HLB) value, which greatly helps to maintain the stability of the emulsion and avoids demulsification after high-temperature sterilization, resulting in oil drift. Defoamers that only contain polyether complexes with a single cloud point range cannot achieve this effect.

[0119] Industrial fermentation defoamers Z5 and Z7 prepared in Comparative Examples 1 and 3, lacking terpene olefin components, exhibited longer defoaming times. Furthermore, Z7 lacked a polyether complex with a gradient cloud point, resulting in oil floating after high-temperature sterilization. Industrial fermentation defoamers Z6, Z8, Z9, and Z... prepared in Comparative Examples 2, 4, 5, and 6... 10 Polyether complexes lacking polyether compounds or possessing only a single cloud point cannot achieve the optimal hydrophilic-lipophilic balance (HLB) to maintain the stability of the defoamer. Therefore, oil floating may occur after high-temperature sterilization. Meanwhile, Z6, Z8, Z9, and Z... 10 The defoaming time is also longer than that of the industrial fermentation defoamers Z1 to Z4 prepared in the examples.

[0120] In summary, the industrial fermentation defoamer provided in this application embodiment can only achieve the optimal defoaming effect on the fermentation broth when it simultaneously possesses terpenoid olefins and polyether complexes with gradient cloud points.

[0121] The present application has been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of the present application. The descriptions of the embodiments above are only for the purpose of helping to understand the present application and its core ideas. It should be noted that those skilled in the art can make several improvements and modifications to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application.

Claims

1. An industrial fermentation defoamer, characterized in that, The product comprises the following components in parts by weight: 5-10 parts of organosilicon active ingredient, 3-7 parts of polyether-modified organosiloxane, 30-40 parts of polyether compound, 1-3 parts of emulsifier, 1-3 parts of thickener, and 37-60 parts of deionized water; wherein the organosilicon active ingredient includes hydroxyl silicone oil, hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, and MQ. The product comprises silicone resin, silica, and a catalyst. The polyether compound consists of three polyethers with different cloud points: a first polyether, a second polyether, and a third polyether. The cloud point range of the first polyether is 5–20°C, that of the second polyether is 21–30°C, and that of the third polyether is 31–50°C. The mass ratio of the first polyether, the second polyether, and the third polyether is 1–5:60–68:27–39. The molar ratio of the hydrogen-containing silicone oil, terpene olefins, vinyl silicone oil, and hydroxyl silicone oil in the reactive components of the organosilicon active material is 1:0.1–0.3:0.4–0.6:0.2–0.

4.

2. The industrial fermentation defoamer according to claim 1, characterized in that, The terpene olefins are sesquiterpenes.

3. The industrial fermentation defoamer according to claim 1, characterized in that, The catalyst is selected from platinum. At least one of the following: an alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, a platinum-ketone complex, an isopropanol solution of chloroplatinic acid, and a platinum-vinyl complex.

4. The industrial fermentation defoamer according to claim 1, characterized in that, The preparation method of the organosilicon active material includes: mixing hydrogen-containing silicone oil, terpene olefins, and MQ silicone resin; heating to 100-150°C for 30 minutes after the first addition of catalyst, and then cooling to room temperature; then adding terminal vinyl silicone oil, and adding catalyst a second time, the amount of which is 4 times that of the first addition, and heating to 100-150°C for the second reaction; finally adding hydroxyl silicone oil and silicon dioxide, stirring evenly, heating to 120°C for 4 hours, and then cooling to room temperature to obtain the organosilicon active material; the catalyst is selected from at least one of platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, isopropanol chloroplatinate solution, and platinum-vinyl complexes.

5. The industrial fermentation defoamer according to claim 1, characterized in that, The polyether-modified organosiloxane is a complex formed by the reaction of a polyorganohydrosiloxane and an unsaturated polyether under alkaline catalytic conditions; the general structural formula of the polyorganohydrosiloxane is (CH3)3SiO[Si(CH3)2O]. m (SiHCH3O) n Si(CH3)3, where m is an integer from 0 to 150 and n is an integer from 1 to 150; the general formula of the unsaturated polyether structure is HO(EO). p (PO) q OH, where p is an integer from 1 to 10 and q is an integer from 2 to 10; the molar ratio of the organic hydrogen-containing siloxane and the unsaturated polyether is 1:1 to 2.

6. The industrial fermentation defoamer according to claim 5, characterized in that, The alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, potassium silyl alcohol, sodium silyl alcohol, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, 2-hydroxyethyltrimethylamine, and tetramethylammonium hydroxide.

7. The industrial fermentation defoamer according to claim 1, characterized in that, The emulsifier includes at least one of the following: sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan monostearate, sorbitan monooleate polyoxyethylene ether ester, sorbitan tristearate polyoxyethylene ether ester, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether ester, alkylphenol polyoxyethylene ether, and glyceryl monostearate; the thickener includes at least one of the following: polyvinyl alcohol, sodium carboxymethyl cellulose, methylcellulose, hydroxyethyl cellulose, guar gum, xanthan gum, nonionic polyurethane, and alkali-soluble acrylate.

8. A method for preparing the industrial fermentation defoamer according to any one of claims 1 to 7, characterized in that, Includes the following steps: Step 1: Mix the organosilicon active material, polyether-modified organosiloxane, and emulsifier, stir, and heat to 50-80℃; to obtain the first mixed solution; Step 2: Add water and thickener to the first mixed solution in sequence, then adjust the pH value to 7, and repeat the above operation 2 to 3 times to obtain the second mixed solution; Step 3: Keep the temperature of the second mixed solution at 50~80℃, add the polyether compound and mix, and let it cool naturally to room temperature to obtain the defoamer for industrial fermentation.

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