CN109692505A - A kind of solid particulate matter mineral oil antifoam agent and preparation method thereof - Google Patents
A kind of solid particulate matter mineral oil antifoam agent and preparation method thereof Download PDFInfo
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- CN109692505A CN109692505A CN201910145485.6A CN201910145485A CN109692505A CN 109692505 A CN109692505 A CN 109692505A CN 201910145485 A CN201910145485 A CN 201910145485A CN 109692505 A CN109692505 A CN 109692505A
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- 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
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- 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
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Abstract
The invention belongs to defoaming agent technical fields, and in particular to a kind of solid particulate matter mineral oil antifoam agent and preparation method thereof.The mineral oil antifoam agent includes following raw material by mass percentage: mineral oil 64%~87%, alkyl modified silicon oil 10%~24%, hydrophobicity aerosil 0.5%~1.5%, polyethers 0.5~5% and emulsifier 1~6%.Wherein, the good alkyl modified silicon oil of solubility property in mineral oil is selected, and is mixed and made into silicon cream with silicon oil modified hydrophobicity aerosil at high temperature, the antifoaming performance and stability of defoaming agent can be significantly improved.This method does not need addition organic solvent, and preparation method is simple, and repeatability and controllability are good.By the particle size of hydrophobic silicic aerogels and the type of emulsifier and proportion of regulation addition, foam time needed for making the defoaming agent obtained is short, and the foam inhibition time is long, film without shrinkage cavity phenomenon, the fields such as coating, ink and papermaking with good application prospect.
Description
Technical field
The invention belongs to defoaming agent technical fields, and in particular to a kind of solid particulate matter mineral oil antifoam agent and its preparation side
Method.
Background technique
In pulping and paper-making, textile printing and dyeing, sewage treatment, biofermentation, oil exploitation and refining, building industry, adhesive
It in equal industrial processes, has used and has largely shown active material, during carrying out the mixture operation of material, with air
Entrance, a large amount of foams can be generated；In addition, can also generate a large amount of foams in the high speed harmonic process of material.These foams
The problems such as in the presence of will lead to production capacity reduction, wastage of material, extension reaction time, product quality decline.
The elimination of foam must add corresponding defoaming agent to complete in industrial process.The defoaming of traditional chemical defoaming agent
Mechanism is: spontaneous must all enter in liquid film first and sprawl rapidly, disperses on interface, then, change the interface characteristics of liquid film
Can, foam solution film strength is reduced, the rupture of film is finally resulted in.
Existing defoaming agent is broadly divided into organic silicon defoamer and mineral oil antifoam agent both types in the market.Organosilicon
Although defoaming agent defoaming is rapidly, it there is higher cost, easily tie the deficiencies of silicon spot, coating shrinkage cavity, cissing；Furthermore exist
In paper technology, when certain highly acids and strong alkali solution defoam, polyether silicone oil is decomposed rapidly, leads to the foam inhibition of silicon oil foam killer
Time strongly reduces, and is restricted its application.
Mineral oil antifoam agent has at low cost, the good dispersion in water-based system, does not influence the service performance of product, is resistant to
The advantages such as strong acid and strong base are widely used in field of industrial production.CN102120108A describes one kind based on polyethers, white carbon black
The mineral oil antifoam agent of substance is defoamed, but white carbon black is directly added into, haves the defects that product stability is poor.
CN101310814A describes a kind of mineral oil antifoam agent, joined silicone grease and improves antifoaming performance, but is used for water-based system
In can lead to the problem of coating shrinkage cavity, cissing.
Summary of the invention
In order to solve the above-mentioned technical problem, the primary purpose of the present invention is that providing a kind of solid particulate matter mineral oil defoaming
Agent.The defoaming agent efficiently solves the problems, such as the shrinkage cavity of organic silicon defoamer film, cissing, improves antifoaming performance and stable storing
Property.
Another object of the present invention is to provide the preparation methods of above-mentioned solid particulate matter mineral oil antifoam agent.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of solid particulate matter mineral oil antifoam agent, including following raw material by mass percentage: mineral oil 64%~
87%, alkyl modified silicon oil 10%~24%, hydrophobicity aerosil 0.5%~1.5%, polyethers 0.5~5% and emulsification
Agent 1~6%；Above-mentioned raw materials quality adds up to 100%；
The alkyl modified silicon oil is to replace the part methyl alkane sill of dimethyl silicone polymer, and grafting changes
Structure and obtain, structural formula is as follows:
Wherein R is the alkyl of carbon atom number 4~40, and m and n are 10~300 integers.
The mineral oil is the mixture of the refining liquid hydrocarbon obtained by petroleum, the cycloalkane and alkane being predominantly saturated
Mixture.
Preferably, kinematic viscosity of the mineral oil at 25 DEG C is 7~60mPas.
It is furthermore preferred that kinematic viscosity 15~60mPas of the mineral oil at 25 DEG C.
Preferably, the mineral oil is 5# white oil, 15# white oil, 26# white oil, 32# white oil, 68# white oil, atoleine
Or petroleum ether.
Preferably, the carbon atom number of the alkyl modified silicon oil is 10~20.At this point, alkyl modified silicon oil can be with mineral
Oil well dissolves each other.
It is furthermore preferred that the alkyl modified silicon oil is octyl, dodecyl or octadecyl modified silicone oil.
Preferably, kinematic viscosity of the alkyl modified silicon oil at 25 DEG C is 500~1000mPas.
The hydrophobicity aerosil is common inorganic hydrophobic substance, it has extremely strong antifoam performance, can
Greatly to enhance the antifoam performance of system.
Preferably, the hydrophobicity aerosil is silicon oil modified hydrophobicity aerosil or silazane
Modified hydrophobicity aerosil.
It is furthermore preferred that the hydrophobicity aerosil is Degussa R202 or R972.
Preferably, the specific surface area of the hydrophobicity aerosil is 100~200m2/g。
Preferably, the mass ratio of the hydrophobicity aerosil and alkyl modified silicon oil is 1:24~1:10.
The polyethers itself has defoaming and suds suppressing properties, can be with alkyl modified silicon oil, hydrophobicity aerosil
Generate synergistic effect.
Preferably, the polyethers is polyethylene glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PTMG).
Preferably, the molecular weight of the polyethers is 500~5000.
Preferably, the emulsifier is nonionic emulsifier.
It is furthermore preferred that the emulsifier is alkyl phenol polyoxyethylene ether class, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol are poly-
Ethylene oxide ether, fatty alcohol polyoxyethylene ether, aliphatic amine polyoxyethylene ether, polyoxyethylene stearic acid ester, sorbitan fatty acid
One or more of ester or polyoxyethylene sorbitan fatty acid ester.
It is further preferred that the sorbitan fatty acid ester is Span-20, Span-40, Span-60, Span-
One or more of 80 or Span-85.
It is further preferred that the polyoxyethylene sorbitan fatty acid ester be Tween-20, Tween-40,
One or more of Tween-60 or Tween-80.
It is further preferred that the emulsifier is compounded by Span80 and Tween80 according to mass ratio 5:1~7:2.
Preferably, the hydrophilic and oleophilic value of the emulsifier is 6~8.
The preparation method of above-mentioned solid particulate matter mineral oil antifoam agent, comprising the following steps:
(1) alkyl modified silicon oil and hydrophobicity aerosil are mixed and is reacted, silicon cream is made；
(2) mineral oil, silicon cream, polyethers and emulsifier are mixed and is reacted, mixture is prepared, then uses homogenizer
High speed dispersion to get arrive the solid particulate matter mineral oil antifoam agent.
Preferably, it is 300rpm that the condition of reaction described in step (1), which is low whipping speed, and reaction condition is 100
0.5~2.0h is reacted under conditions of~130 DEG C.
Preferably, it is 400~500rpm that the condition of reaction described in step (2), which is low whipping speed, and reaction temperature is
0.5~1.0h is reacted under conditions of 60~80 DEG C.
Preferably, with the when a length of 0.5h of homogenizer high speed dispersion described in step (2).
The mechanism of action of the invention is as follows:
Solid particulate matter defoaming agent is sprayed at the foam surface formed, and it is steady that solid particle destroys oil-water-air film
Qualitative, accelerate oil droplet runs through (needle point effect).Under the action of shock effect, rapid effect of breaking bubble is induced.With foam
Rupture, foamicide is finally dispersed in foam liquid.
Hydrophobic solid particles are directly entered liquid film in defoaming agent, form a bi-concave oily bridge, oil on liquid film surface
Bridge by oil-water it is gentle-effect of the uneven capillary pressure at liquid interface and radially gradually stretch, in oily bridge
Between form one layer of thin and unstable oil film, the rupture of last oil film causes entire liquid film to be perforated and ruptures.Hydrophobic granule object
Particle size directly determines the form and distribution of oily bridge, results in the length of foam inhibition time.The bridge formation of solid particulate matter ---
Mechanism is stretched, is the innovation in a mechanism relative to traditional chemical defoaming agent.
Solid particulate matter is dispersed in mineral oil, and since the density of the two has differences, particulate matter can be sent out in mineral oil
Raw sedimentation；Sedimentation time is related with the viscosity of mineral oil system with the partial size of particulate matter, density, the density of mineral oil system.Hair
In defoaming agent after raw sedimentation, upper layer is the supernatant of clear, and sinking is muddy object phase；The time of layering is used to distinguish
The shelf-life of defoaming agent.
Common precipitated silica partial size is bigger, and sedimentation layering occurs in a short period of time；Unmodified gas
Aerosil surface can be very big, and the partial size after reunion is big, and apparent layering occurs in several days time in mineral oil；Silicone oil changes
The nano fumed silica R202 product of property, 100~260m of specific surface area2/ g is kept for 3 months time not in mineral oil
It settles.
Compared with the existing technology, beneficial effects of the present invention are as follows:
(1) the good alkyl modified silicon oil of solubility property in mineral oil is selected, and is dredged at high temperature with silicon oil modified
Aqueous fumed silica is mixed and made into silicon cream, can significantly improve the antifoaming performance and stability of defoaming agent.
(2) technological operation of defoaming agent is simple, repeated and controllability is good, industrially easily realizes large-scale production,
Huge economic benefit can be brought.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 1 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: industry 5 is white
Oil 87%, alkyl modified silicon oil (carbon atom number in group R is 8, m=70, n=560) 10%, hydrophobicity gas phase titanium dioxide
Silicon 1%, polyethers (PPG5000) 1% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 5:1) 1%.
The preparation method is as follows:
(1) it takes 10g alkyl modified silicon oil and the hydrophobicity aerosil low whipping speed of 1g silazane modification is
300rpm, under the conditions of temperature is 100 DEG C, silicon cream is prepared in reaction time 0.5h.
(2) industrial No. 5 white oils of 87.0g, 11.0g silicon cream, 1.0g PPG5000 and 1.0g emulsifier are added in container,
Under conditions of temperature is 60 DEG C, 0.5h is reacted, mixture is obtained；After homogenizer high speed dispersion 0.5h, described consolidate is obtained
Body particulate matter mineral oil antifoam agent.
Embodiment 2
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 2 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: atoleine
64%, alkyl modified silicon oil (carbon atom number in group R is 8, m=60, n=600) 23.5%, hydrophobicity gas phase titanium dioxide
Silicon 1.5%, polyethers (PPG5000) 5% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 5:1) 6%.
(1) the hydrophobicity aerosil low whipping speed for taking 24g alkyl modified silicon oil silicon oil modified with 1g is
300rpm, under conditions of reaction temperature is 110 DEG C, the reaction time is that silicon cream is prepared in 1h.
(2) 64.0g atoleine, 25.0g silicon cream, 5.0g PPG5000 and 6.0g emulsifier are added in container,
Under conditions of temperature is 80 DEG C, 1.0h is reacted, mixture is obtained；With homogenizer high speed dispersion 0.5h, the solid is obtained
Grain object mineral oil antifoam agent.
Embodiment 3
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 3 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: industry 32 is white
Oil 86%, alkyl modified silicon oil (carbon atom number in group R is 12, m=70, n=560) 10%, hydrophobicity gas phase dioxy
SiClx 1%, polyethers (PPG5000) 0.5% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 5:1)
2.5%.
(1) 10g alkyl modified silicon oil (carbon atom number in group R is 12) and 1g silicon oil modified hydrophobicity gas phase are taken
Silica low whipping speed is that 300rpm reacts 2h, silicon cream is prepared under conditions of temperature is 120 DEG C.
(2) industrial No. 32 white oils of 86.0g, 11.0g silicon cream, 0.5g PPG5000 and 2.5g emulsifier are added to container
In, under conditions of temperature is 60 DEG C, 0.5h is reacted, mixture is obtained；With homogenizer high speed dispersion 0.5h, the solid is obtained
Particulate matter mineral oil antifoam agent.
Embodiment 4
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 4 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: atoleine
83.2%, alkyl modified silicon oil (carbon atom number in group R is 12, m=60, n=600) 10%, hydrophobicity gas phase dioxy
SiClx 0.8%, polyethers (PPG800) 3% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 5:1) 3%.
(1) hydrophobicity for taking 10g alkyl modified silicon oil (carbon atom number in group R is 12) modified with 0.8g silazane
Fumed silica low whipping speed is that 300rpm reacts 0.5h, be made to obtain silicon cream under conditions of temperature is 130 DEG C.
(2) 83.2g atoleine, 10.8g silicon cream, 3.0g PPG800 and 3.0g emulsifier are added in container, in temperature
Under conditions of degree is 60 DEG C, 0.5h is reacted, mixture is obtained；After homogenizer high speed dispersion 0.5h, the solid is obtained
Grain object mineral oil antifoam agent.
Embodiment 5
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 5 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: industry 68 is white
Oil 72.5%, alkyl modified silicon oil (carbon atom number in group R is 12, m=80, n=500) 15%, hydrophobicity gas phase two
Silica 1.5%, polyethers (PPG600) 5% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 7:2)
6%.
(1) 15g alkyl modified silicon oil (carbon atom number in group R is 12) and 1.5g silicon oil modified hydrophobicity gas are taken
Aerosil low whipping speed is that 300rpm reacts 1h, silicon cream is prepared under conditions of temperature is 100 DEG C.
(2) industrial No. 68 white oils of 72.5g, 16.5g silicon cream, 5.0g PPG600 and 6.0g emulsifier are added in container,
Under conditions of temperature is 80 DEG C, 1.0h is reacted, mixture is obtained；With homogenizer high speed dispersion 0.5h, the solid is obtained
Particulate matter mineral oil antifoam agent.
Embodiment 6
The present embodiment provides a kind of solid particulate matter mineral oil antifoam agents 6 and preparation method thereof.
The solid particulate matter mineral oil antifoam agent is made of following raw material by mass percentage: industry 68 is white
Oil 75.5%, alkyl modified silicon oil (carbon atom number in group R is 18, m=70, n=560) 15%, hydrophobicity gas phase two
Silica 0.5%, polyethers (PPG800) 3% and emulsifier (being compounded by Span80:Tween80 according to mass ratio 7:2)
6%.
(1) 15g alkyl modified silicon oil (carbon atom number in group R is 18) and 0.5g silicon oil modified hydrophobicity gas are taken
Aerosil low whipping speed is that 300rpm reacts 0.5h, silicon cream is prepared under conditions of temperature is 100 DEG C.
(2) industrial No. 68 white oils of 75.5g, 15.5g silicon cream, 3.0g PPG800 and 6.0g emulsifier are added in container,
Under conditions of temperature is 80 DEG C, 0.5h is reacted, mixture is prepared；With homogenizer high speed dispersion 0.5h, obtain described
Solid particulate matter mineral oil antifoam agent.
Defoaming agent performance test
1) 2.5g neopelex is taken, soluble in water, constant volume to 1000ml.
2) take the above-mentioned solution of 200ml into 1000ml graduated cylinder, ventilation makes bubble rise to 1000ml, and 0.2ml is added dropwise (about
0.2g) the defoaming agent prepared, time needed for recording bubble collapse are foam time；Open nitrogen valve, coutroi velocity 3L/
Min, the measurement bubble time required when reaching 1000ml is the foam inhibition time.
Test result is as follows:
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of solid particulate matter mineral oil antifoam agent, which is characterized in that including following raw material by mass percentage: mineral
Oil 64%~87%, alkyl modified silicon oil 10%~24%, hydrophobicity aerosil 0.5%~1.5%, polyethers 0.5~
5% and emulsifier 1~6%；Above-mentioned raw materials quality adds up to 100%；
The structural formula of the alkyl modified silicon oil is as follows:
Wherein R is the alkyl of carbon atom number 4~40, and m and n are 10~300 integers.
2. solid particulate matter mineral oil antifoam agent according to claim 1, it is characterised in that:
The hydrophobicity aerosil is modified hydrophobic of silicon oil modified hydrophobicity aerosil or silazane
Property fumed silica；
The alkyl modified silicon oil is octyl, dodecyl or octadecyl modified silicone oil；
The emulsifier is nonionic emulsifier.
3. solid particulate matter mineral oil antifoam agent according to claim 2, it is characterised in that:
The mineral oil is 5# white oil, 15# white oil, 26# white oil, 32# white oil, 68# white oil, atoleine or petroleum ether；
The polyethers is polyethylene glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PTMG)；
The emulsifier is alkyl phenol polyoxyethylene ether class, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, fat
Alcohol polyoxyethylene ether, aliphatic amine polyoxyethylene ether, polyoxyethylene stearic acid ester, sorbitan fatty acid ester or polyoxyethylene lose
One or more of water Span.
4. solid particulate matter mineral oil antifoam agent according to claim 3, it is characterised in that: the hydrophobicity gas phase two
The mass ratio of silica and alkyl modified silicon oil is 1:24~1:10.
5. solid particulate matter mineral oil antifoam agent according to claim 4, it is characterised in that:
Kinematic viscosity of the mineral oil at 25 DEG C is 7~60mPas；
The carbon atom number of the alkyl modified silicon oil is 10~20, and the kinematic viscosity at 25 DEG C is 500~1000mPas；
The specific surface area of the hydrophobicity aerosil is 100~200m2/g；
The molecular weight of the polyethers is 500~5000；
The hydrophilic and oleophilic value of the emulsifier is 6~8.
6. solid particulate matter mineral oil antifoam agent according to claim 5, it is characterised in that:
Kinematic viscosity 15~60mPas of the mineral oil at 25 DEG C；
The hydrophobicity aerosil is Degussa R202 or R972.
7. solid particulate matter mineral oil antifoam agent according to claim 6, it is characterised in that:
The sorbitan fatty acid ester is one in Span-20, Span-40, Span-60, Span-80 or Span-85
Kind is two or more；
The polyoxyethylene sorbitan fatty acid ester is in Tween-20, Tween-40, Tween-60 or Tween-80
One or more.
8. solid particulate matter mineral oil antifoam agent according to claim 7, it is characterised in that: the emulsifier by
Span80 and Tween80 is compounded according to mass ratio 5:1~7:2.
9. the preparation method of solid particulate matter mineral oil antifoam agent according to any one of claims 1 to 8, which is characterized in that packet
Include following steps:
(1) alkyl modified silicon oil and hydrophobicity aerosil are mixed and is reacted, silicon cream is made；
(2) mineral oil, silicon cream, polyethers and emulsifier are mixed and is reacted, mixture is prepared, then with homogenizer high speed
Disperse to get the solid particulate matter mineral oil antifoam agent is arrived.
10. the preparation method of solid particulate matter mineral oil antifoam agent according to claim 9, it is characterised in that:
The condition of reaction described in step (1) is that low whipping speed is 1000rpm, and the condition of reaction is anti-at 100~130 DEG C
Answer 0.5~2.0h；
The condition of reaction described in step (2) is that low whipping speed is 400~500rpm, the item that reaction temperature is 60~80 DEG C
0.5~1.0h is reacted under part；
With the when a length of 0.5h of homogenizer high speed dispersion described in step (2).
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| CN110465119A (en) * | 2019-08-28 | 2019-11-19 | 启东曦瑞新材料科技有限公司 | A kind of preparation method of mineral oil antifoam agent |
| CN110745898A (en) * | 2019-11-26 | 2020-02-04 | 广东沃泰环保有限公司 | Defoaming agent and preparation method thereof |
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| CN104479439A (en) * | 2014-12-08 | 2015-04-01 | 南京四新科技应用研究所有限公司 | Mineral oil defoaming agent |
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| 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 |
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| CN104284704A (en) * | 2012-05-07 | 2015-01-14 | 瓦克化学股份公司 | Defoamer formulations comprising organopolysiloxanes |
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| CN104479439A (en) * | 2014-12-08 | 2015-04-01 | 南京四新科技应用研究所有限公司 | Mineral oil defoaming agent |
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| CN110465119A (en) * | 2019-08-28 | 2019-11-19 | 启东曦瑞新材料科技有限公司 | A kind of preparation method of mineral oil antifoam agent |
| CN110745898A (en) * | 2019-11-26 | 2020-02-04 | 广东沃泰环保有限公司 | Defoaming agent and preparation method thereof |
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Application publication date: 20190430 |