CN109011726A - Acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind and preparation method thereof - Google Patents

Acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind and preparation method thereof Download PDF

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Publication number
CN109011726A
CN109011726A CN201811120840.6A CN201811120840A CN109011726A CN 109011726 A CN109011726 A CN 109011726A CN 201811120840 A CN201811120840 A CN 201811120840A CN 109011726 A CN109011726 A CN 109011726A
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defoaming agent
preparation
high temperature
temperature resistant
resistant type
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CN201811120840.6A
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Inventor
张金娜
李富华
吴敬礼
王迪
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Tianjin Changlu Haijing Group Co Ltd
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Tianjin Changlu Haijing Group Co Ltd
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Priority to CN201811120840.6A priority Critical patent/CN109011726A/en
Publication of CN109011726A publication Critical patent/CN109011726A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of acidproof resistance to high temperature resistant type defoaming agents with high salt and preparation method thereof, and the group that the defoaming agent includes is divided into polyether modified silicon oil, silicon cream, emulsifier, thickener K and water;Preparation method includes the following steps: the preparation of (I) polyethers;The preparation of (II) polyether modified silicon oil;The preparation of (III) silicon cream;(IV), which emulsifies, is made defoaming agent.The characteristics of defoaming agent of the present invention can adapt to high-temperature bittern, stability is good, can have stronger and lasting defoaming and foam inhibition effect in the environment of strong acid, with high salt, high temperature;Preparation method passes through specific polyether-modified, promote that solubility can be reduced in the range of EO/PO is maintained at 0.2 ~ 08 in polyether structure, improve the performance of defoaming agent, the mode that the mode connected in the preparation of polyethers simultaneously is Si-C, not facile hydrolysis can be reached, the good feature of stability, the features such as carrying out compound emulsion by silicone oil after polyether-modified and silicon cream, can be improved the high temperature resistant of organic silicon defoaming agent.

Description

Acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind and preparation method thereof
Technical field
The invention belongs to a kind of defoaming agents and preparation method thereof, and in particular to a kind of acidproof resistance to high temperature resistant type defoaming agent with high salt And preparation method thereof.
Background technique
The generation of foam is to compare distinct issues in an influence brine Chemical Manufacture, acid, with high salt due to brine Characteristic and production process high temperature condition be to influence the important factor in order of most defoaming agent effects, it is therefore, right Higher ask is proposed in the selection of defoaming agent.
With the increase of production requirement, more and more people start the defoaming agent being applicable under valuing researches extreme condition, have Provided in research it is a kind of be used in compounding with organosiloxane using polyether modified siloxane, improve lotion to reach and defoam The performance of agent, but defoaming agent made from this method not can solve siloxanes and easily occur in extreme strong acid, strong alkali environment The problem of chain rupture, stability are poor.Simultaneously there are also defoaming agent of the starch as stabilizer is used, the property of acid and alkali-resistance is greatly improved Can, but stabiliser content is larger in defoaming agent, therefore has seriously affected the suds suppressing properties of defoaming agent, while the defoaming agent is in height Stability under temperature is poor.A kind of organic silicon modified by polyether oxygen alkane is proposed in research and silicon composition is multiple in addition, also having The defoaming agent matched greatly improves antifoam performance of the defoaming agent under the extreme conditions such as strong acid, highly basic, improves defoaming agent Stability, but the effective performance for not being described the high temperature resistant of the defoaming agent etc..
Summary of the invention
The present invention is to overcome the disadvantage that defoaming effect is undesirable under conditions of strong acid, with high salt and high temperature in the prior art And propose, the purpose is to provide acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind and preparation method thereof.
The technical scheme is that
A kind of acidproof resistance to high temperature resistant type defoaming agent with high salt, the mass percent of component and each component that the defoaming agent includes are as follows:
Polyether modified silicon oil 5% ~ 30%;
Silicon cream 10% ~ 50%;
Emulsifier 2% ~ 10%;
Thickener 0.1% ~ 2%;
Water 20% ~ 30%.
The emulsifier is octyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene stearic acid ester, fatty alcohol In any one or any a variety of mixture.
The thickener is any one or two kinds in cellulose ethers or natural polymer and its derivative species Mixture;The cellulose ethers are any one in methylcellulose, sodium carboxymethylcellulose or hydroxypropyl cellulose;Institute It states natural polymer and its derivative species is any one in gelatin, sodium alginate, chitosan, gum arabic or xanthan gum Kind.
The polyether modified silicon oil mixes generation graft copolymerization with silicon oil of low hydrogen content by polyethers and is made;The polyethers It is that the propylene glycol block polyether to be formed is reacted by block copolymerization with ethylene oxide, propylene oxide by glycerol.
The silicon cream be mixed as dimethicone with fumed silica obtained by.
A kind of preparation method of acidproof resistance to high temperature resistant type defoaming agent with high salt, comprising the following steps:
The preparation of (I) polyethers
Under basic catalyst effect block copolymerization is occurred for glycerol with ethylene oxide, propylene oxide to react to form propylene glycol block Polyethers;
The preparation of (II) polyether modified silicon oil
Polyethers obtained by step (I) and silicon oil of low hydrogen content are blended in generation graft copolymerization under the catalytic condition of catalyst to be made Polyether modified silicon oil;
The preparation of (III) silicon cream
Dimethicone and fumed silica are blended under certain reaction temperature after held for some time, system is cooled to room temperature Obtain silicon cream;
(IV), which emulsifies, is made defoaming agent
Polyether modified silicon oil, emulsifier, thickener and water obtained by silicon cream, step (II) obtained by step (III) are mixed in proportion It emulsifies afterwards and defoaming agent is made.
Basic catalyst in the step (I) is KOH;EO/PO in polyether structure after control is reacted in the step (I) Range be 0.2 ~ 0.8.
Catalyst in the step (II) is chloroplatinic acid;The catalytic condition specifically: reaction temperature is 100 DEG C, instead It is 6h between seasonable;The molar ratio of Si-H and C-C in the polyethers and silicon oil of low hydrogen content mixture are 1:1.1 ~ 1.3;It is described low The hydrogen content of hydrogen silicone oil is 0.05% ~ 0.1%.
The mass ratio of dimethicone and fumed silica is 10 ~ 12.5:1 in the step (III);The step Reaction temperature in (III) is 150 DEG C, soaking time 3h.
The specific method emulsified in the step (IV) is first by polyethers obtained by silicon cream obtained by step (III) and step (II) For modified silicon oil under the conditions of 75 DEG C, stirring promotes silicon cream to disperse, and adds emulsifier for mixing heating 1h ~ 3h, stops heating, then Thickener and water are added, 20min is stirred under conditions of 1000r/min using emulsification pretreatment machine, after obtaining white emulsification Defoaming agent.
The beneficial effects of the present invention are:
The present invention provides a kind of acidproof resistance to high temperature resistant type defoaming agents with high salt and preparation method thereof, and anti-foam product can be extreme Strong acid, there is under conditions of with high salt and high temperature stronger stability, reduce foam time, improve the persistence of defoaming, solve The undesirable problem of defoaming effect under conditions of strong acid, with high salt and high temperature;Preparation method mainly pass through it is specific polyether-modified, Promote that solubility can be reduced in the range of EO/PO is maintained at 0.2 ~ 08 in polyether structure, improve the performance of defoaming agent, gathers simultaneously The mode connected in the preparation of ether is the mode of Si-C, can reach not facile hydrolysis, the good feature of stability, by polyether-modified Silicone oil and silicon cream afterwards carries out compound emulsion, can be improved the feature of high temperature resistant of organic silicon defoaming agent etc..
Specific embodiment
Acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind of the invention and preparation method thereof is carried out below with reference to embodiment detailed It describes in detail bright:
A kind of acidproof resistance to high temperature resistant type defoaming agent with high salt, the mass percent of component and each component that the defoaming agent includes are as follows:
Polyether modified silicon oil 5% ~ 30%;
Silicon cream 10% ~ 50%;
Emulsifier 2% ~ 10%;
Thickener 0.1% ~ 2%;
Water 20% ~ 30%.
The emulsifier is octyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene stearic acid ester, fatty alcohol In any one or any a variety of mixture.
The thickener is any one or two kinds in cellulose ethers or natural polymer and its derivative species Mixture;The cellulose ethers are any one in methylcellulose, sodium carboxymethylcellulose or hydroxypropyl cellulose;Institute It states natural polymer and its derivative species is any one in gelatin, sodium alginate, chitosan, gum arabic or xanthan gum Kind.
The polyether modified silicon oil mixes generation graft copolymerization with silicon oil of low hydrogen content by polyethers and is made;The polyethers It is that the propylene glycol block polyether to be formed is reacted by block copolymerization with ethylene oxide, propylene oxide by glycerol.
The silicon cream be mixed as dimethicone with fumed silica obtained by.
A kind of preparation method of acidproof resistance to high temperature resistant type defoaming agent with high salt, comprising the following steps:
The preparation of (I) polyethers
Under basic catalyst effect block copolymerization is occurred for glycerol with ethylene oxide, propylene oxide to react to form propylene glycol block Polyethers;
The preparation of (II) polyether modified silicon oil
Polyethers obtained by step (I) and silicon oil of low hydrogen content are blended in generation graft copolymerization under the catalytic condition of catalyst to be made Polyether modified silicon oil;
The preparation of (III) silicon cream
Dimethicone and fumed silica are blended under certain reaction temperature after held for some time, system is cooled to room temperature Obtain silicon cream;
(IV), which emulsifies, is made defoaming agent
Polyether modified silicon oil, emulsifier, thickener and water obtained by silicon cream, step (II) obtained by step (III) are mixed in proportion It emulsifies afterwards and defoaming agent is made.
Basic catalyst in the step (I) is KOH;EO/PO in polyether structure after control is reacted in the step (I) Range be 0.2 ~ 0.8.
Catalyst in the step (II) is chloroplatinic acid;The catalytic condition specifically: reaction temperature is 100 DEG C, instead It is 6h between seasonable;The molar ratio of Si-H and C-C in the polyethers and silicon oil of low hydrogen content mixture are 1:1.1 ~ 1.3;It is described low The hydrogen content of hydrogen silicone oil is 0.05% ~ 0.1%.
The mass ratio of dimethicone and fumed silica is 10 ~ 12.5:1 in the step (III);The step Reaction temperature in (III) is 150 DEG C, soaking time 3h.
The specific method emulsified in the step (IV) is first by polyethers obtained by silicon cream obtained by step (III) and step (II) For modified silicon oil under the conditions of 75 DEG C, stirring promotes silicon cream to disperse, and adds emulsifier for mixing heating 1h ~ 3h, stops heating, then Thickener and water are added, 20min is stirred under conditions of 1000r/min using emulsification pretreatment machine, after obtaining white emulsification Defoaming agent.
Embodiment 1
Acidproof, resistance to high salt and high temperature modification defoaming agent of one kind and preparation method thereof, wherein raw material forms: 5% polyether modified silicon oil F, 30% silicon cream I, 2% emulsifier J, 0.1% thickener K and water.
The step of specific preparation method, is as follows:
It reacts to form third firstly, block copolymerization occurs in the catalytic condition of KOH with ethylene oxide B, propylene oxide C using glycerol A Diol block polyethers D, the range of EO/PO is 0.2 in polyether structure after control reaction, then, using polyethers D and silicon oil of low hydrogen content E is using chloroplatinic acid as catalyst, and temperature is to react 6 hours to be made at 100 DEG C, the wherein molar ratio control of the Si-H in raw material and C-C System is in 1:1.1.
Then, dimethicone G is uniformly mixed with fumed silica H with mass ratio for 10, is protected under the conditions of 150 DEG C After warm 3h, it is cooled to room temperature and obtains silicon cream I.
Finally, stirring promotes silicon cream to disperse by silicon cream I and polyether modified silicon oil E under the conditions of 75 DEG C, emulsifier is added Agitating and heating 1h is stopped heating, then adds thickener and water, stirred under conditions of 1000r/min using emulsification pretreatment machine 30min is mixed, the defoaming agent (I) after obtaining white emulsification.
Embodiment 2
Acidproof, resistance to high salt and high temperature modification defoaming agent of one kind and preparation method thereof, wherein raw material forms: 30% polyether modified silicon oil F, 10% silicon cream I, 10% emulsifier J, 1% thickener K and water.
The step of specific preparation method, is as follows:
It reacts to form third firstly, block copolymerization occurs in the catalytic condition of KOH with ethylene oxide B, propylene oxide C using glycerol A Diol block polyethers D, the range of EO/PO is 0.5 in polyether structure after control reaction, then, using polyethers D and silicon oil of low hydrogen content E is using chloroplatinic acid as catalyst, and temperature is to react 6 hours to be made at 100 DEG C, the wherein molar ratio control of the Si-H in raw material and C-C System is in 1:1.2.
Then, dimethicone G is uniformly mixed with the mass ratio of fumed silica H for 11, is protected under the conditions of 150 DEG C After warm 3h, it is cooled to room temperature and obtains silicon cream I.
Finally, stirring promotes silicon cream to disperse by silicon cream I and polyether modified silicon oil E under the conditions of 75 DEG C, emulsifier is added Agitating and heating 2h is stopped heating, then adds thickener and water, stirred under conditions of 1000r/min using emulsification pretreatment machine 30min is mixed, the defoaming agent (II) after obtaining white emulsification.
Embodiment 3
Acidproof, resistance to high salt and high temperature modification defoaming agent of one kind and preparation method thereof, wherein raw material forms: 20% polyether modified silicon oil F, 30% silicon cream I, 5% emulsifier J, 0.5% thickener K and water.
The step of specific preparation method, is as follows:
Block copolymerization is occurred in the catalytic condition of KOH using glycerol A and ethylene oxide B, propylene oxide C and reacts that form propylene glycol embedding Section polyethers D, the range of EO/PO is 0.8 in polyether structure after control reaction, then, uses polyethers D and silicon oil of low hydrogen content E with chlorine Platinic acid is catalyst, and temperature is to react 6 hours to be made at 100 DEG C, and wherein the molar ratio of the Si-H in raw material and C-C is controlled 1: 1.3
Dimethicone G is uniformly mixed with the mass ratio of fumed silica H for 12, it is cold after keeping the temperature 3h under the conditions of 150 DEG C But silicon cream I is obtained to room temperature.
Finally, stirring promotes silicon cream to disperse by silicon cream I and polyether modified silicon oil E under the conditions of 75 DEG C, emulsifier is added Agitating and heating 2h is stopped heating, then adds thickener and water, stirred under conditions of 1000r/min using emulsification pretreatment machine 30min is mixed, the defoaming agent (III) after obtaining white emulsification.
The performance test of defoaming agent:
To same temperature (120 DEG C), the defoaming agent that addition prepares in the acid brine (pH=2) of same blistering degree, record disappears Time and foam inhibition time are steeped, while being compared with certain defoaming agent in the market, the results are shown in Table 1:
As shown in Table 1: the defoaming agent I, defoaming agent II and the defoaming agent III that are prepared by this method and certain defoaming agent pair in the market It is better than in the market in terms of foam time, foam inhibition time and centrifugal stability than can be seen that defoaming agent made from this method Defoaming agent, the results showed that, anti-foam product made from this method can be used for strong acid, condition with high salt and high temperature, improve Stability, the performance of defoaming and foam inhibition of defoaming agent under extreme condition.

Claims (10)

1. a kind of acidproof resistance to high temperature resistant type defoaming agent with high salt, it is characterised in that: the component and each component that the defoaming agent includes Mass percent are as follows:
Polyether modified silicon oil 5% ~ 30%;
Silicon cream 10% ~ 50%;
Emulsifier 2% ~ 10%;
Thickener 0.1% ~ 2%;
Water 20% ~ 30%.
2. the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 1, it is characterised in that: the emulsifier is Octyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene stearic acid ester, in fatty alcohol any one or it is any A variety of mixtures.
3. the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 1, it is characterised in that: the thickener is The mixture of any one or two kinds in cellulose ethers or natural polymer and its derivative species;The cellulose ethers For any one in methylcellulose, sodium carboxymethylcellulose or hydroxypropyl cellulose;The natural polymer and its derivative Species are any one in gelatin, sodium alginate, chitosan, gum arabic or xanthan gum.
4. the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 1, it is characterised in that: described polyether-modified Silicone oil mixes generation graft copolymerization with silicon oil of low hydrogen content by polyethers and is made;The polyethers is by glycerol and epoxy second Alkane, propylene oxide react the propylene glycol block polyether to be formed by block copolymerization.
5. the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 1, it is characterised in that: the silicon cream is logical It crosses dimethicone and mixes gained with fumed silica.
6. a kind of preparation method of acidproof resistance to high temperature resistant type defoaming agent with high salt, it is characterised in that: the following steps are included:
The preparation of (I) polyethers
Under basic catalyst effect block copolymerization is occurred for glycerol with ethylene oxide, propylene oxide to react to form propylene glycol block Polyethers;
The preparation of (II) polyether modified silicon oil
Polyethers obtained by step (I) and silicon oil of low hydrogen content are blended in generation graft copolymerization under the catalytic condition of catalyst to be made Polyether modified silicon oil;
The preparation of (III) silicon cream
Dimethicone and fumed silica are blended under certain reaction temperature after held for some time, system is cooled to room temperature Obtain silicon cream;
(IV), which emulsifies, is made defoaming agent
Polyether modified silicon oil, emulsifier, thickener and water obtained by silicon cream, step (II) obtained by step (III) are mixed in proportion It emulsifies afterwards and defoaming agent is made.
7. the preparation method of the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 6, it is characterised in that: institute Stating the basic catalyst in step (I) is KOH;The range of EO/PO is in polyether structure after control reaction in the step (I) 0.2~0.8。
8. the preparation method of the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 6, it is characterised in that: institute Stating the catalyst in step (II) is chloroplatinic acid;The catalytic condition specifically: reaction temperature is 100 DEG C, reaction time 6h; The molar ratio of Si-H and C-C in the polyethers and silicon oil of low hydrogen content mixture are 1:1.1 ~ 1.3;The low hydrogen silicone oil it is hydrogeneous Amount is 0.05% ~ 0.1%.
9. the preparation method of the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 6, it is characterised in that: institute Stating the mass ratio of dimethicone and fumed silica in step (III) is 10 ~ 12.5:1;Reaction in the step (III) Temperature is 150 DEG C, soaking time 3h.
10. the preparation method of the acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind according to claim 6, it is characterised in that: The specific method emulsified in the step (IV) is first by polyether modified silicon oil obtained by silicon cream obtained by step (III) and step (II) It is dispersed with stirring under the conditions of 75 DEG C, adds emulsifier for mixing heating 1h ~ 3h, stop heating, then add thickener and water, 20min is stirred under conditions of 1000r/min using emulsification pretreatment machine, the defoaming agent after obtaining white emulsification.
CN201811120840.6A 2018-09-26 2018-09-26 Acidproof resistance to high temperature resistant type defoaming agent with high salt of one kind and preparation method thereof Pending CN109011726A (en)

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CN110393953A (en) * 2019-07-11 2019-11-01 北京三聚环保新材料股份有限公司 A kind of Compounded Antifoamer and its preparation method and application
CN110964755A (en) * 2019-12-06 2020-04-07 鹤山市东古调味食品有限公司 Method for treating foam in microbial fermentation process
CN111151033A (en) * 2020-01-17 2020-05-15 广东轻工职业技术学院 Preparation method of novel polyether modified organic silicon defoaming agent
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CN112744886A (en) * 2021-01-14 2021-05-04 南京英伟莱新材料有限公司 Defoaming agent for wastewater zero-discharge process and preparation method thereof
CN113082785A (en) * 2021-04-09 2021-07-09 广东中联邦精细化工有限公司 Organosilicon emulsion defoaming agent and preparation method thereof
CN113577840A (en) * 2021-08-09 2021-11-02 杭州撒拉弗科技有限公司 Preparation method of high-temperature-resistant and alkali-resistant organic silicon defoaming agent
CN114307262A (en) * 2022-01-11 2022-04-12 江西蓝星星火有机硅有限公司 Defoaming agent for steam boiler and application thereof
CN115054953A (en) * 2022-08-05 2022-09-16 山东圣佑高科新材料有限公司 High-efficiency energy-saving organic silicon defoaming agent

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CN110393953A (en) * 2019-07-11 2019-11-01 北京三聚环保新材料股份有限公司 A kind of Compounded Antifoamer and its preparation method and application
CN110964755A (en) * 2019-12-06 2020-04-07 鹤山市东古调味食品有限公司 Method for treating foam in microbial fermentation process
CN110964755B (en) * 2019-12-06 2020-11-20 鹤山市东古调味食品有限公司 Method for treating foam in microbial fermentation process
CN111151033A (en) * 2020-01-17 2020-05-15 广东轻工职业技术学院 Preparation method of novel polyether modified organic silicon defoaming agent
CN111760333A (en) * 2020-06-18 2020-10-13 浙江新安化工集团股份有限公司 Defoaming agent composition and preparation method and application thereof
CN111760333B (en) * 2020-06-18 2021-10-08 浙江新安化工集团股份有限公司 Defoaming agent composition and preparation method and application thereof
CN112744886A (en) * 2021-01-14 2021-05-04 南京英伟莱新材料有限公司 Defoaming agent for wastewater zero-discharge process and preparation method thereof
CN113082785A (en) * 2021-04-09 2021-07-09 广东中联邦精细化工有限公司 Organosilicon emulsion defoaming agent and preparation method thereof
CN113577840A (en) * 2021-08-09 2021-11-02 杭州撒拉弗科技有限公司 Preparation method of high-temperature-resistant and alkali-resistant organic silicon defoaming agent
CN114307262A (en) * 2022-01-11 2022-04-12 江西蓝星星火有机硅有限公司 Defoaming agent for steam boiler and application thereof
CN115054953A (en) * 2022-08-05 2022-09-16 山东圣佑高科新材料有限公司 High-efficiency energy-saving organic silicon defoaming agent
CN115054953B (en) * 2022-08-05 2024-04-02 山东圣佑高科新材料有限公司 Efficient energy-saving organic silicon defoamer

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Application publication date: 20181218