CN112057906A - Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof - Google Patents
Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof Download PDFInfo
- Publication number
- CN112057906A CN112057906A CN202010876699.3A CN202010876699A CN112057906A CN 112057906 A CN112057906 A CN 112057906A CN 202010876699 A CN202010876699 A CN 202010876699A CN 112057906 A CN112057906 A CN 112057906A
- Authority
- CN
- China
- Prior art keywords
- castor oil
- parts
- oil
- amino silicone
- epoxy castor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0495—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Activated Sludge Processes (AREA)
Abstract
The invention belongs to the technical field of chemical assistants, and particularly discloses a low COD defoaming agent for a water body, which is nontoxic to microorganisms, and a preparation method thereof. The defoaming agent comprises the following components in parts by weight: 10-20 parts of polydimethylsiloxane, 20-40 parts of mineral oil, 20-40 parts of amino silicone oil modified epoxy castor oil, 1-10 parts of hydrophobic white carbon black, 0.5-5 parts of defoaming auxiliary agent and 0.1-10 parts of emulsifier; adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst, stirring and reacting for 8-12 hours at the temperature of 60-80 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the organic solvent to obtain the base silicone oil modified epoxy castor oil. The defoaming agent has the advantages of good chemical stability, small using amount, high defoaming speed, long foam inhibition time, high efficiency, no toxicity to microorganisms, easy dispersion in sewage, reduction of the surface tension of a foam film, rapid elimination of foam and capability of solving the problem of foam generated by biochemical sewage treatment.
Description
Technical Field
The invention relates to the technical field of chemical additives, in particular to a low COD defoaming agent for a water body which is nontoxic to microorganisms and a preparation method thereof.
Background
The biochemical water treatment method is commonly adopted in large cities to treat industrial sewage. The biochemical waste water treatment process comprises a biological membrane, activated sludge and the like. The biological sewage treatment can remove organic matters in the sewage, convert organic pollutants into gas, liquid products and solid products rich in the organic matters, and carry out solid-liquid separation through a sedimentation tank. However, in the biochemical sewage treatment process, the problem of foaming is easily caused. The cause of foaming in biochemical sewage treatment is mainly related to abnormal growth of microorganisms in activated sludge. Foams generated by abnormal growth of microorganisms in the activated sludge can be accumulated on the water surface, and are gathered and floated on the water surface, so that organic matters and suspended solids are increased, the water quality is deteriorated, and the progress of the whole water treatment is influenced. When the biochemical sewage treatment meets the foaming problem, the foaming problem can be quickly solved by adding a chemical agent, and the operation is simple. The common chemical additive is the biochemical sewage treatment defoaming agent. However, the general antifoaming agent easily affects the activity of microorganisms in the activated sludge. Therefore, the performance of the defoaming agent for treating the biochemical sewage is required to be higher.
Most of the defoaming agents used in the biochemical sewage treatment at present are polyether defoaming agents, the largest advantage is high foam inhibition capability, but the defoaming agent has the fatal defect of low foam breaking rate, and once a large amount of foam is generated, the defoaming agent cannot be effectively extinguished at once, but the defoaming agent has good defoaming and foam inhibition capabilities only by adding a large amount of defoaming agents.
Compared with polyether defoaming agents, the polyorganosiloxane defoaming agent has stable chemical properties, small side effects, and good defoaming capability and lasting foam inhibition capability at a low dosage. Chinese patent CN101422712A discloses a defoaming agent composition, which is prepared by crosslinking trimethyl siloxanyl terminated polydimethylsiloxane, hydroxyl terminated polydimethylsiloxane and organic resin under the action of a catalyst, and then treating the crosslinked polydimethylsiloxane and white carbon black; the defoaming agent has a fast defoaming performance, but the defoaming agent has a fast defoaming speed in a nonionic system, and organic resin is used in the defoaming agent and is used for treating foam in sewage, so that the COD content of a water body is increased.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a low COD defoaming agent for water body which has a fast defoaming speed, a long foam inhibition time, a low consumption and is non-toxic to microorganisms, and a preparation method thereof.
In order to achieve the above objects and other related objects, in one aspect, the present invention provides a low COD defoamer for water bodies, which is non-toxic to microorganisms, comprising the following components in parts by weight: 10-20 parts of polydimethylsiloxane, 20-40 parts of mineral oil, 20-40 parts of amino silicone oil modified epoxy castor oil, 1-10 parts of hydrophobic white carbon black, 0.5-5 parts of defoaming auxiliary agent and 0.1-10 parts of emulsifier, wherein the preparation method of the amino silicone oil modified epoxy castor oil comprises the following steps:
adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
Optionally, the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Alternatively, the amount of the basic catalyst required for adding 1mol of the epoxidized castor oil to react with the aminosilicone oil is 0.5-1.0 mL.
Optionally, the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide.
Optionally, the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Further, the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
Optionally, the molar ratio of formic acid or acetic acid to hydrogen peroxide to castor oil is 3: 8-10: 6-8.
Optionally, the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Alternatively, the acid catalyst is concentrated sulfuric acid, and the amount of concentrated sulfuric acid required for adding 1mol of formic acid or acetic acid is 0.3-0.5 mL.
Optionally, the mass fraction of the concentrated sulfuric acid is 95-98%.
Optionally, the mineral oil is at least one selected from white oil, liquid paraffin and alkylbenzene.
Optionally, the defoaming auxiliary agent is selected from at least one of polyether, triethanolamine, n-octanol and isooctanol.
Optionally, the emulsifier is selected from at least one of span 20, tween 20, span 60, tween 60, span 80, tween 80 or polyoxyethylene 40 stearate.
In another aspect, the present invention provides a method for preparing the low COD antifoaming agent for water body having no toxicity to microorganisms, comprising the following steps:
(1) adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain amino silicone oil modified epoxy castor oil;
(2) sequentially adding polydimethylsiloxane, mineral oil, amino silicone oil modified epoxy castor oil, hydrophobic white carbon black, a defoaming auxiliary agent and an emulsifier into a reaction kettle according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Optionally, in the step (1), the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Alternatively, in the step (1), the amount of the basic catalyst required for adding 1mol of the epoxidized castor oil to react with the aminosilicone is 0.5-1.0 mL.
Optionally, in the step (1), the alkaline catalyst is at least one selected from sodium hydroxide and potassium hydroxide.
Optionally, in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Further, in the step (1), the preparation method of the epoxidized castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
Optionally, the molar ratio of formic acid or acetic acid to hydrogen peroxide to castor oil is 3: 8-10: 6-8.
Optionally, the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Alternatively, the acid catalyst is concentrated sulfuric acid, and the amount of concentrated sulfuric acid required for adding 1mol of formic acid or acetic acid is 0.3-0.5 mL.
Optionally, the mass fraction of the concentrated sulfuric acid is 95-98%.
As described above, the low COD defoaming agent for water bodies and the preparation method thereof have the following beneficial effects:
the novel low COD defoaming agent for the water body is prepared by compounding polydimethylsiloxane, mineral oil, amino silicone oil modified epoxy castor oil, hydrophobic white carbon black, a defoaming auxiliary agent and an emulsifier, has the advantages of good chemical stability, small using amount, high defoaming speed, long foam inhibition time, high efficiency and the like, has no influence on microorganisms in the water treatment process, is easy to disperse in sewage, can reduce the surface tension of a foam membrane, quickly eliminates foam, can solve various stubborn foams in the biochemical sewage treatment process, can be applied to circulating sewage treatment of various industries, various industrial sewage, domestic and chemical sewage, water treatment defoaming of all normal temperature and partial alkali systems and the like.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a low COD defoaming agent for a water body, which is nontoxic to microorganisms and comprises the following components in parts by weight: 10-20 parts of polydimethylsiloxane, 20-40 parts of mineral oil, 20-40 parts of amino silicone oil modified epoxy castor oil, 1-10 parts of hydrophobic white carbon black, 0.5-5 parts of defoaming auxiliary agent and 0.1-10 parts of emulsifier.
Wherein the mineral oil is at least one selected from white oil, liquid paraffin and alkylbenzene.
Wherein the defoaming auxiliary agent is at least one selected from polyether, triethanolamine, n-octanol and isooctanol.
Wherein the emulsifier is at least one selected from span 20, Tween 20, span 60, Tween 60, span 80, Tween 80 or polyoxyethylene 40 stearate.
The preparation method of the low COD defoaming agent for the water body comprises the following steps:
(1) under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain epoxy castor oil; and then adding the epoxy castor oil and the amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain a supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
(2) Sequentially adding polydimethylsiloxane, mineral oil, amino silicone oil modified epoxy castor oil, hydrophobic white carbon black, a defoaming auxiliary agent and an emulsifier into a reaction kettle according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Wherein in the step (1), the molar use ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8.
Wherein in the step (1), the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Wherein, in the step (1), the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL. Concentrated sulfuric acid is used as a catalyst to facilitate the formation of peroxy acid, but the use amount of the concentrated sulfuric acid is too small, the catalytic effect is not strong, the required reaction time is long, the epoxy bonds of the obtained epoxy castor oil are few, and the improvement of the defoaming performance is not facilitated; however, if the amount is too large, the castor oil may be carbonized.
Wherein in the step (1), the mass fraction of the concentrated sulfuric acid is 95-98%.
In the step (1), the molar use ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Wherein, in the step (1), the amount of the basic catalyst required by adding 1mol of epoxy castor oil to react with the amino silicone oil is 0.5-1.0 mL.
Wherein, in the step (1), the alkaline catalyst is at least one of sodium hydroxide and potassium hydroxide.
Wherein, in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Castor, a plant of the genus ricinus of the family euphorbiaceae, mainly produced in india, brazil and china, is a herbaceous plant growing for one or more years, with oval seeds and an oil content of 40-48%, and is used for preparing biodegradable lubricating oils, coal dyes, drugs, etc. Castor oil derived from castor is a natural fatty acid triglyceride, 90% of fatty acids are ricinoleic acid (9-alkenyl-12-hydroxyoctadecanoic acid), and 10% of fatty acids are oleic acid and linoleic acid without hydroxyl, are the only vegetable oil containing hydroxyl in nature, have certain defoaming performance, and can be used as a component of a defoaming agent. However, vegetable oils such as castor oil have poor hydrophilicity due to the long carbon chain structure, and are difficult to disperse in the water phase quickly and effectively, and have poor defoaming performance, so that the vegetable oils are not suitable for being directly added into a defoaming agent for a water body.
According to the invention, the double bonds of the castor oil are epoxidized, the surface activity of the castor oil can be greatly increased by hydrophilic epoxy bonds, so that the dispersing power of the castor oil at the interface of water bubbles is improved, the defoaming performance of the castor oil is improved, and the epoxy castor oil is further subjected to graft modification by amino silicone oil to obtain amino silicone oil modified epoxy castor oil, so that the ratio of lipophilic groups to hydrophilic groups in the castor oil is changed, the surface tension of the castor oil is further reduced, and the hydrophilicity and defoaming capability of the castor oil are improved.
The amino silicone oil modified epoxy castor oil is compounded with mineral oil, polydimethylsiloxane, hydrophobic white carbon black, a defoaming auxiliary agent and an emulsifier to obtain the novel defoaming agent for water bodies, the defoaming agent has the advantages of good chemical stability, small using amount, high defoaming speed, long foam inhibition time, high efficiency and the like, has no influence on microorganisms in the water treatment process, is easy to disperse in sewage, can reduce the surface tension of a foam membrane, quickly eliminates foam, can solve various stubborn foams in the biochemical sewage treatment process, can be applied to circulating sewage treatment in various industries, various industrial sewage, domestic and chemical sewage, water treatment defoaming of all normal temperature and partial alkali systems and the like.
Specific examples are given below to further illustrate the preparation of the present invention. The reagents used in the following examples are all commercially available.
Example 1
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 6 formic acid, hydrogen peroxide and castor oil into a reaction kettle, adding concentrated sulfuric acid (0.3 mL of concentrated sulfuric acid needs to be added correspondingly to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:3) into N, N dimethyl formamide, adding sodium hydroxide (0.5 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 12 hours at 60 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Sequentially adding 20 parts of polydimethylsiloxane, 40 parts of white oil, 40 parts of amino silicone oil modified epoxy castor oil, 5 parts of hydrophobic white carbon black, 0.5 part of polyether and 801 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 70 ℃, stirring for 2 hours, keeping the temperature for 2 hours, cooling to 40 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Example 2
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 10: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 70 ℃, reacting for 3 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 8-12 hours at 60-80 ℃, centrifuging to obtain supernatant, and removing the N, N dimethyl formamide through rotary evaporation to obtain the amino silicone oil modified epoxy castor oil.
(2) Sequentially adding 10 parts of polydimethylsiloxane, 20 parts of liquid paraffin, 20 parts of amino silicone oil modified epoxy castor oil, 5 parts of ethylene bis stearamide, 1 part of hydrophobic white carbon black, 5 parts of triethanolamine and 8010 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the defoaming agent.
Example 3
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.4 mL of concentrated sulfuric acid needs to be correspondingly added for 1mol of formic acid), heating to 70 ℃, reacting for 5 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:4) into N, N dimethyl formamide, adding sodium hydroxide (0.6 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 15 parts of polydimethylsiloxane, 25 parts of alkylbenzene, 30 parts of amino silicone oil modified epoxy castor oil, 3 parts of hydrophobic white carbon black, 3 parts of triethanolamine and 603 parts of tween into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 2 hours, then preserving heat for 1 hour, cooling to 40 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the defoaming agent.
Example 4
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 9: placing 7 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.4 mL of concentrated sulfuric acid needs to be added correspondingly to 1mol of formic acid), heating to 60 ℃, reacting for 4 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:3) into N, N dimethyl formamide, adding sodium hydroxide (0.8 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 8 hours at 80 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Sequentially adding 20 parts of polydimethylsiloxane, 20 parts of white oil, 30 parts of amino silicone oil modified epoxy castor oil, 5 parts of hydrophobic white carbon black, 5 parts of polyether and 805 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 70 ℃, stirring for 2 hours, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the defoaming agent.
Example 5
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Sequentially adding 20 parts of polydimethylsiloxane, 40 parts of white oil, 30 parts of amino silicone oil modified epoxy castor oil, 8 parts of hydrophobic white carbon black, 4 parts of polyether and 808 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Example 6
The preparation method of the low COD defoaming agent for the water body in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 acetic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 15 parts of polydimethylsiloxane, 25 parts of liquid paraffin, 30 parts of amino silicone oil modified epoxy castor oil, 8 parts of hydrophobic white carbon black, 4 parts of triethanolamine and 208 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Comparative example 1
The preparation method of the defoaming agent in the comparative example is as follows:
(1) mixing the components in a molar ratio of 3: 8: placing 8 acetic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain the epoxy castor oil.
(2) Sequentially adding 15 parts of polydimethylsiloxane, 25 parts of liquid paraffin, 30 parts of modified epoxy castor oil, 8 parts of hydrophobic white carbon black, 4 parts of triethanolamine and 208 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Comparative example 2
The preparation method of the defoaming agent in the comparative example is as follows:
sequentially adding 15 parts of polydimethylsiloxane, 25 parts of liquid paraffin, 8 parts of hydrophobic white carbon black, 4 parts of triethanolamine, 8 parts of hydrophobic white carbon black and 208 parts of span into a reaction kettle, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Comparative example 3
The preparation method of the defoaming agent in the comparative example is as follows:
adding 15 parts of polydimethylsiloxane, 8 parts of hydrophobic white carbon black, 4 parts of triethanolamine and 208 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the defoaming agent.
Testing of defoaming agent Performance
The defoaming agents of examples 1 to 6 and comparative examples 1 to 3 were tested for defoaming performance and compared with the defoaming performance of two commercially available defoaming agents (a, german BYK-023 silicone defoaming agent, B, defoaming agent for wastewater treatment of hill material). The specific test method is as follows:
a TX-10 aqueous solution with the mass percent of 1 percent is used as a foaming medium and is tested by a shake flask method. The test method is as follows: adding 50mL of the foaming medium into a 100mL measuring cylinder with a plug, then adding 0.01g of defoaming agent, shaking the measuring cylinder for 50 times at the amplitude of 30-40cm at the frequency of 100 plus 120 times/min in the vertical direction, then standing the measuring cylinder, recording the time of foam elimination until the liquid level appears, namely the defoaming time, and then shaking for 50 times to record the defoaming time until the total shaking times reaches 400 times. The shorter the defoaming time is, the better the defoaming and foam inhibiting effect of the defoaming agent is. The results are shown in Table 1.
TABLE 1 defoaming time of defoamers in examples 1 to 6 and comparative examples 1 to 3 and commercially available defoamers
As can be seen from the test results in Table 1, the defoaming agents prepared in examples 1 to 6 of the present invention are superior in defoaming performance to those of comparative examples 1 to 3 and two defoaming agents commercially available, which indicates that the defoaming agent of the present invention has a strong defoaming ability against foams generated in sewage treatment.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The low COD defoaming agent for the water body which is nontoxic to microorganisms is characterized by comprising the following components in parts by weight: 10-20 parts of polydimethylsiloxane, 20-40 parts of mineral oil, 20-40 parts of amino silicone oil modified epoxy castor oil, 1-10 parts of hydrophobic white carbon black, 0.5-5 parts of defoaming auxiliary agent and 0.1-10 parts of emulsifier, wherein the preparation method of the amino silicone oil modified epoxy castor oil comprises the following steps:
adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
2. The low COD defoamer for water bodies according to claim 1, wherein: the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5;
and/or, the amount of the basic catalyst required by adding 1mol of epoxy castor oil to react with the amino silicone oil is 0.5-1.0 mL.
3. The low COD defoamer for water bodies according to claim 1, wherein: the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide;
and/or the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
4. The low COD defoamer for water bodies according to claim 1, wherein: the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
5. The low COD defoamer for water bodies according to claim 4, wherein: the molar ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8;
and/or the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours;
and/or the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL;
and/or the mass fraction of the concentrated sulfuric acid is 95-98%.
6. The low COD defoamer for water bodies according to claim 1, wherein: the mineral oil is at least one of white oil, liquid paraffin and alkylbenzene;
and/or the defoaming auxiliary agent is selected from at least one of polyether, triethanolamine, n-octanol and isooctanol;
and/or the emulsifier is at least one selected from span 20, tween 20, span 60, tween 60, span 80, tween 80 and polyoxyethylene 40 stearate.
7. The method for preparing a low COD antifoaming agent for a water body that is non-toxic to microorganisms according to any one of claims 1 to 6, wherein: the method comprises the following steps:
(1) adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain amino silicone oil modified epoxy castor oil;
(2) sequentially adding polydimethylsiloxane, mineral oil, amino silicone oil modified epoxy castor oil, hydrophobic white carbon black, a defoaming auxiliary agent and an emulsifier into a reaction kettle according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the defoaming agent.
8. The method of claim 7, wherein: in the step (1), the molar use ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5;
and/or, in the step (1), the amount of the basic catalyst required by the reaction of 1mol of epoxy castor oil and amino silicone oil is 0.5-1.0 mL;
and/or, in the step (1), the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide;
and/or in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N-dimethylformamide, tetrahydrofuran, benzene and toluene.
9. The method of claim 7, wherein: in the step (1), the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
10. The method of claim 9, wherein: the molar ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8;
and/or the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours;
and/or the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL;
and/or the mass fraction of the concentrated sulfuric acid is 95-98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876699.3A CN112057906A (en) | 2020-08-27 | 2020-08-27 | Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876699.3A CN112057906A (en) | 2020-08-27 | 2020-08-27 | Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112057906A true CN112057906A (en) | 2020-12-11 |
Family
ID=73660355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010876699.3A Pending CN112057906A (en) | 2020-08-27 | 2020-08-27 | Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112057906A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113350833A (en) * | 2021-05-12 | 2021-09-07 | 深圳市点石源水处理技术有限公司 | Defoaming agent and preparation method thereof |
| CN114011117A (en) * | 2021-11-29 | 2022-02-08 | 淄博爱迪毅环保技术有限公司 | Defoaming agent and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083998A (en) * | 1998-04-24 | 2000-07-04 | Betzdearborn Inc. | Defoamer and methods of use thereof |
| US20100292380A1 (en) * | 2009-05-15 | 2010-11-18 | Kemira Chemicals, Inc. | Polymeric defoamer additive |
| WO2014179127A1 (en) * | 2013-04-28 | 2014-11-06 | Ecolab Usa Inc. | Biodiesel-based emulsion defoamer and method for making the same |
| CN106621478A (en) * | 2016-11-23 | 2017-05-10 | 北京麦尔化工科技有限公司 | Light-colored mineral oil de-foaming agent and preparation method thereof |
| CN107551609A (en) * | 2017-09-29 | 2018-01-09 | 西安三业精细化工有限责任公司 | Contain organic-silicon-modified castor oil defoamer and preparation method in a kind of production for PVA |
| CN109663886A (en) * | 2019-02-24 | 2019-04-23 | 湖南七纬科技有限公司 | A kind of die cast metal release agent and preparation method thereof |
| CN109893885A (en) * | 2019-02-28 | 2019-06-18 | 常州市天宁区鑫发织造有限公司 | A kind of weaving preparation method of defoaming agent |
| CN110075573A (en) * | 2019-05-22 | 2019-08-02 | 江苏长丰有机硅有限公司 | A kind of silicate-containing oil and the defoaming agent of epoxidized soybean oil and preparation method thereof |
| CN111117691A (en) * | 2019-12-26 | 2020-05-08 | 安徽遨信网络科技有限公司 | Mineral oil defoaming auxiliary agent for water-based paint and preparation method thereof |
-
2020
- 2020-08-27 CN CN202010876699.3A patent/CN112057906A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083998A (en) * | 1998-04-24 | 2000-07-04 | Betzdearborn Inc. | Defoamer and methods of use thereof |
| US20100292380A1 (en) * | 2009-05-15 | 2010-11-18 | Kemira Chemicals, Inc. | Polymeric defoamer additive |
| WO2014179127A1 (en) * | 2013-04-28 | 2014-11-06 | Ecolab Usa Inc. | Biodiesel-based emulsion defoamer and method for making the same |
| CN106621478A (en) * | 2016-11-23 | 2017-05-10 | 北京麦尔化工科技有限公司 | Light-colored mineral oil de-foaming agent and preparation method thereof |
| CN107551609A (en) * | 2017-09-29 | 2018-01-09 | 西安三业精细化工有限责任公司 | Contain organic-silicon-modified castor oil defoamer and preparation method in a kind of production for PVA |
| CN109663886A (en) * | 2019-02-24 | 2019-04-23 | 湖南七纬科技有限公司 | A kind of die cast metal release agent and preparation method thereof |
| CN109893885A (en) * | 2019-02-28 | 2019-06-18 | 常州市天宁区鑫发织造有限公司 | A kind of weaving preparation method of defoaming agent |
| CN110075573A (en) * | 2019-05-22 | 2019-08-02 | 江苏长丰有机硅有限公司 | A kind of silicate-containing oil and the defoaming agent of epoxidized soybean oil and preparation method thereof |
| CN111117691A (en) * | 2019-12-26 | 2020-05-08 | 安徽遨信网络科技有限公司 | Mineral oil defoaming auxiliary agent for water-based paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 祝韵: "大豆油的改性及在消泡剂中的应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113350833A (en) * | 2021-05-12 | 2021-09-07 | 深圳市点石源水处理技术有限公司 | Defoaming agent and preparation method thereof |
| CN113350833B (en) * | 2021-05-12 | 2022-12-06 | 深圳市点石源水处理技术有限公司 | Defoaming agent and preparation method thereof |
| CN114011117A (en) * | 2021-11-29 | 2022-02-08 | 淄博爱迪毅环保技术有限公司 | Defoaming agent and preparation method thereof |
| CN114011117B (en) * | 2021-11-29 | 2023-03-14 | 淄博爱迪毅环保技术有限公司 | Defoaming agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112057906A (en) | Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof | |
| He et al. | Comparison of membrane extraction with traditional extraction methods for biodiesel production | |
| CN107551609B (en) | Organic silicon-containing modified castor oil defoaming agent for PVA production and preparation method thereof | |
| CN103768834A (en) | Defoaming agent composition | |
| BR112021001025A2 (en) | PURIFICATION OF RECYCLED AND RENEWABLE ORGANIC MATERIAL | |
| CN107837795B (en) | Microbial-loaded resin adsorbent capable of degrading oil stains and preparation method thereof | |
| CN112661361B (en) | Oily sewage treatment method, treatment system and construction method of treatment system | |
| Hamdi et al. | Comparison between anaerobic filter and anaerobic contact process for fermented olive mill wastewaters | |
| CN112057907A (en) | Water-oil universal mineral oil defoaming agent and preparation method thereof | |
| JP2018130697A (en) | Biogas production promoter, and biogas production promoting method, organic waste treating method, and treating device using the same | |
| CN110964755B (en) | Method for treating foam in microbial fermentation process | |
| CN104014165A (en) | Compound-type de-foaming agent and preparation method thereof | |
| CN109550282B (en) | High-temperature-resistant integral power plant desulfurization defoaming agent and preparation method thereof | |
| WO2013146853A1 (en) | Method for treating fat-containing wastewater | |
| RU2009133479A (en) | THE PROCESS OF CHANGING THE VISCOSITY OF RAW OIL | |
| CN110627970B (en) | Process method for preparing polyester antistatic agent by using pentaerythritol tetraacrylate wastewater | |
| CN111921492A (en) | Traditional Chinese medicine residue activated carbon and preparation method and application thereof | |
| CN115109204B (en) | Organosilicon surface-accumulating agent and application thereof in thickened oil exploitation | |
| JP2012210585A (en) | Method and apparatus for anaerobic treatment of kraft pulp wastewater | |
| CN112495000A (en) | Novel organic silicon defoaming agent for landfill leachate treatment and preparation method thereof | |
| CN109589650B (en) | Polymer long-acting defoaming agent and preparation method thereof | |
| Tang et al. | Efficient heterogeneous catalyst for biodiesel production from soybean oil over modified CaO | |
| CN112717479A (en) | Polyether defoaming agent and preparation method thereof | |
| CN111875066A (en) | Immobilized microorganism particles for degrading grease in kitchen wastewater, preparation method and application | |
| CN102020769A (en) | Application of silica copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |