CN103669108B - A kind of paper industry silicone defoaming agent and preparation method thereof - Google Patents
A kind of paper industry silicone defoaming agent and preparation method thereof Download PDFInfo
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- CN103669108B CN103669108B CN201310687969.6A CN201310687969A CN103669108B CN 103669108 B CN103669108 B CN 103669108B CN 201310687969 A CN201310687969 A CN 201310687969A CN 103669108 B CN103669108 B CN 103669108B
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Abstract
The present invention discloses a kind of paper industry silicone defoaming agent and preparation method thereof, obtained through emulsification by organosilicon defoaming composition, organosilicon defoaming composition comprises active compound, emulsifying agent and auxiliary agent, and described active compound comprises polysiloxanes, polyether modified silicon oil, hydrophobic type gas-phase silica and MQ silicon resin particle; When polysiloxanes is 25 DEG C, viscosity is methyl-silicone oil or the hydroxy silicon oil of 10000-500000mPas; The structural formula of polyether modified silicon oil is R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
2-(PO) (EO)
a(PO)
br and/or R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
3; The particle diameter of MQ silicon resin particle is 5-20 μm, and the specific area of hydrophobic type gas-phase silica is 100 ~ 300m
2/ g, the present invention also provides the preparation method of defoamer.The defoamer that the present invention is prepared through special technique by organosilicon and hydrophobic type gas-phase silica, MQ silicon resin particle, have excellent defoaming effectiveness and defoaming activity persistence, and product is deposited with dilution stability good.
Description
Technical field
The present invention relates to defoamer technical field, relate to a kind of paper industry silicone defoaming agent and preparation method thereof, particularly relate to a kind of silicone defoaming agent for slurrying in papermaking and copy paper operation froth breaking and preparation method thereof.
Technical background
In most industrial processes, a large amount of bubble produced can make troubles, such as, affect production efficiency, cause device damage, even cause production to carry out time serious.Such as, in the pulping process of paper technology, the aliphatic acid contained in pulping raw material, the natural materials such as resin acid, with the caustic soda added, the chemicalss such as akali sulphide react generation fatty acid soaps, the foamers such as resin acid soaps, and containing polymer substances such as celluloses, there is steady bubble effect in raw material, make slurry stream send with mixed process in produce foam stable in a large number, to subsequent wash, conveying, the operations such as bleaching bring very large difficulty, and cause laitance and pulp quality is reduced, simultaneously, pulping process washs the fatty acid soaps of black liquor also containing high concentration obtained, resin acid soaps etc. are bubbled and are surely steeped material, the generation of foam is unfavorable for carrying out alkali collection to black liquor.Thus, generally need in paper industry to carry out froth breaking, to enhance productivity.
Paper industry debubbling method generally adopts chemical froth breaking method, defoamer is added in foaming system and carry out froth breaking and press down bubble, existing defoamer comprises aliphatic acid and derivative, polyethers, organosilicon etc., wherein silicone defoaming agent is owing to having chemical inertness, physiological inertia, pollution-free, antifoam performance is good, heat-resisting, cold-resistant, weather-proof and ageing-resistant performance is given prominence to, flexibility and the feature such as greasy property is good and furtherd investigate.Disclosed in US4639489, organosilicon defoaming activity thing is by methyl-silicone oil, filler, organic siliconresin and catalyst heat obtained at 50-300 DEG C, disclosed in US4395352, foam control composition comprises dimethyl siloxane, the organic siliconresin of filler particles and modification, and add base catalyst to improve the froth breaking stability of composition, JP45-2613 (23, 613/70) disclosed defoamer comprises dimethyl polysiloxane, silicone resin and white carbon, in US5153258, organosilicon crosslinked thing and silicone grease are mixed to get the defoaming activity thing that suds suppressing properties is improved, defoaming activity thing disclosed in US6207722 is by methyl MQ resin or the methyl MQ resin and the methyl-silicone oil that contain part vinyl, white carbons etc. are prepared through pyroreaction, disclosed in CN100408138C, active defoaming composition is primarily of organosiloxane, silicones, solid inorganic oxides particle, water repellent agent forms.
Above-mentioned defoamer of the prior art in preparation process by adding coupling agent or base catalyst to strengthen the adhesion between organosilicon and inorganic oxide particles, thus improve the froth breaking speed of defoamer particle and extend the defoaming activity duration, and the adaptive capacity to harsh conditions such as high temperature highly basic, but the adhesion that interpolation coupling agent obtains improves limited efficiency, and the addition of base catalyst is difficult to control, organosilicon time excessive, is easily caused to lose defoaming activity.
Summary of the invention
For above-mentioned prior art Problems existing, the invention provides a kind of paper industry silicone defoaming agent and preparation method thereof, wherein defoamer has that antifoaming speed is fast, froth breaking suds suppressing properties excellent and the advantage that froth breaking persistence is outstanding, and preparation method is simple, and cost is low.
Object of the present invention is achieved through the following technical solutions:
A kind of paper industry silicone defoaming agent, obtained through emulsification by organosilicon defoaming composition, described organosilicon defoaming composition comprises active compound, emulsifying agent and auxiliary agent, and described active compound comprises polysiloxanes, polyether modified silicon oil, hydrophobic type gas-phase silica and MQ silicon resin particle;
When described polysiloxanes is 25 DEG C, viscosity is methyl-silicone oil or the hydroxy silicon oil of 10000-500000mPas;
The structural formula of described polyether modified silicon oil is
R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
2-(PO) (EO)
a(PO)
br and/or R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
3, wherein, R Wei – H, – CH
3huo – COCH
3;
The particle diameter of described MQ silicon resin particle is 5-20 μm, and the specific area of described hydrophobic type gas-phase silica is 100 ~ 300m
2/ g; Described auxiliary agent comprises tributyl phosphate and/or polypropylene glycol.
In the structural formula of described polyether modified silicon oil, EO represents that structural formula is-OCH
2cH
2-construction unit, PO represents that structural formula is-OCH
2cH (CH
3)-construction unit.Preferably, described polyether modified silicon oil is 100-5000mPas the viscosity of 25 DEG C, and cloud point is 35 ~ 75 DEG C.
Preferred, described polyether modified silicon oil is 3000-5000mPas the viscosity of 25 DEG C.
Preferably, when described polysiloxanes is 25 DEG C, viscosity is methyl-silicone oil or the hydroxy silicon oil of 200000-500000mPas.
Described MQ silicon resin particle is solid powder particle, and preferably, the M/Q value of described MQ silicon resin particle is 0.3-0.9.
Preferably, in active compound quality for 100%, described active compound comprises following component by mass percentage:
Described emulsifying agent comprises compound emulsifying agent, preferably, described compound emulsifying agent is two or more the composition in sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan mono-laurate, polyoxyethylene 20 sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate, fatty alcohol polyglycol ether, polyoxyethylene stearic acid ester, and its HLB value is 7-10.
Preferably, described emulsifying agent comprises assistant for emulsifying agent further, and assistant for emulsifying agent is one or more in n-butanol, ethylene glycol, propylene glycol, glycerine, polyglycerol ester, and its quality accounts for 8% ~ 16% of emulsifying agent quality.
Described polypropylene glycol is used as floating oil improver, and preferably, it is one or more in the polypropylene glycol of 1000,2000,4000 that described polypropylene glycol is selected from molecular weight.
Preferably, in organosilicon defoaming composition quality for 100%, described organosilicon defoaming composition comprises following component by mass percentage:
Active compound 70%-85%
Emulsifying agent 12%-25%
Auxiliary agent 1%-5%.
A preparation method for paper industry silicone defoaming agent, comprises following operating procedure:
It is 5-20 μm that MQ silicones is ground to particle diameter, obtains MQ silicon resin particle;
Preparation latex A:
By polysiloxanes, hydrophobic type gas-phase silica, the mixing of MQ silicon resin particle, be heated to 210-250 DEG C, stirring reaction 2-6 hour, then stir and be cooled to less than 80 DEG C, obtain active compound A; Mix after emulsifying agent heat fused with active compound A, then add auxiliary agent, stir, obtain defoaming composition A; In defoaming composition A, add decentralized medium carry out emulsification, obtain latex A;
Preparation emulsion B:
Polyether modified silicon oil is mixed with hydrophobic type gas-phase silica, is heated to 80-150 DEG C, stirring reaction 0.5-1 hour, then stir and be cooled to less than 45 DEG C, obtain active compound B; Mix after emulsifying agent heat fused with active compound B, then add decentralized medium and carry out emulsification, obtain emulsion B;
Described decentralized medium is water or the aqueous solution containing thickener;
Latex A is mixed with emulsion B, obtains paper industry silicone defoaming agent.
Preferably, in latex A, in the quality of hydrophobic type gas-phase silica and emulsion B, the mass ratio of hydrophobic type gas-phase silica is (0.1-0.62): 1.
Preferably, in the step of preparation latex A, the quality of emulsifying agent accounts for 24% ~ 57% of emulsifying agent gross mass.
Preferably, preparation latex A and emulsion B step in, described thickener is at least one in hydroxyethylcellulose, Carboxymethyl Cellulose, Sodium Tvlose or xanthan gum, and the mass concentration containing the aqueous solution of thickener is 0.5 ‰-6 ‰.
Preferably, in described latex A, the mass percent of decentralized medium is 75-85%, and in described emulsion B, the mass percent of decentralized medium is 75-85%.
The invention has the beneficial effects as follows: silicone defoaming agent of the present invention prepares primarily of organosilicon material and hydrophobic type gas-phase silica, wherein organosilicon material comprises the MQ silicon resin particle with particular particle size, and through special processing method, organosilicon material and inorganic oxide particles are combined closely and forms stable defoamer particle, press down in bubble process at froth breaking and not easily occur to be separated and to come off, thus effectively improve the diffusion rate of silicone defoaming agent, defoaming effectiveness and defoaming activity persistence, and product is deposited with dilution stability good, not easily breakdown of emulsion, not floating oil, can not have a negative impact to paper product quality for paper industry froth breaking, simultaneously in preparation process without the need to adding any catalyst, simple to operate, cost is low.
Detailed description of the invention
The present invention is by following embodiment further instruction, but embodiment is not limiting the scope of the invention.
The polyether modified silicon oil used in following examples can be commercially available prod, or prepare with reference to existing method, 80-120 DEG C is warming up to as mixed in inert environments with allyl polyether by hydrogen containing siloxane, add platinum catalyst reaction 2-5 hour, decompression removing low-boiling-point substance, obtains polyether modified silicon oil, by selecting the raw material that is suitable for and reaction condition, prepare the polyether modified silicon oil of different viscosities and turbidity, reaction equation is as follows:
H(Me
2SiO)
mSiHMe
2+2R(PO)
b(EO)
aOCH
2CH=CH
2→
R(PO)
b(EO)
a(PO)–(Me
2SiO)
mSiMe
2–(PO)(EO)
a(PO)
bR;
H(Me
2SiO)
mSiMe
3+R(PO)
b(EO)
aOCH
2CH=CH
2→
R(PO)
b(EO)
a(PO)–(Me
2SiO)
mSiMe
3
Wherein, EO represents that structural formula is-OCH
2cH
2-construction unit, PO represents that structural formula is-OCH
2cH (CH
3)-construction unit, R Wei – H, – CH
3huo – COCH
3, You Xuan Wei – H.
Embodiment 1
The preparation method of paper industry silicone defoaming agent, comprises following operating procedure:
By M/Q value be 0.9 MQ silicones to be ground to particle diameter be 5-20 μm, obtain MQ silicon resin particle;
Preparation latex A:
Be methyl-silicone oil, the 7g specific area of 500000mPas by 300g viscosity at 25 DEG C be 238m
2(Guangzhou Ji Bisheng manufactures the hydrophobic type gas-phase silica of/g, HB-630), 25.5gMQ silicon resin particle mixing, be uniformly mixed under the low speed of 300rpm, be heated to 230 DEG C, react 2 hours under the high-speed stirred of 6000rpm, be brown to mixed material, close to brown, be considered as reaction and complete, stop heating, stir under 300rpm low speed and be cooled to less than 80 DEG C, obtain active compound A;
7g sorbitan monostearate, 7.5g polyoxyethylene 20 sorbitan monostearate are mixed with 1.5g ethylene glycol, obtain emulsifying agent, wherein sorbitan monostearate and polyoxyethylene 20 sorbitan monostearate form compound emulsifying agent, and HLB value is 7.23; Mix after emulsifying agent heat fused with 40g active compound A, add the polypropylene glycol that 2g molecular weight is 2000, mixing and stirring, obtain defoaming composition A;
Defoaming composition A is heated to 65 DEG C, and adding 180g mass concentration is that the aqueous solution of the sodium carboxymethylcellulose of 4 ‰ carries out emulsification, obtains latex A.
Preparation emulsion B:
Be 3000mPas by 300g viscosity at 25 DEG C, cloud point is that (structural formula is H (PO) for the polyether modified silicon oil of 45 DEG C
b(EO)
a(PO) – (Me
2siO)
msiMe
2– (PO) (EO)
a(PO)
bh) with 6.5g specific area be 238m
2/ g(Guangzhou Ji Bisheng manufactures, HB-630) mix under the low speed of 200rpm, be heated to 120 DEG C, stirring reaction 1 hour under the high speed of 1200rpm, react rear stopping heating, stirred under 400rpm low speed and be cooled to less than 45 DEG C, obtain active compound B;
By 2.7g sorbitan monopalmitate, 1.5g polyoxyethylene 20 sorbitan monostearate, 1.3g fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix, sorbitan monopalmitate, polyoxyethylene 20 sorbitan monostearate and fatty alcohol polyglycol ether form compound emulsifying agent, its HLB value is 9.22, after being heated fusing, mix with 19g active compound B, control temperature is 65 DEG C, adding 138g mass concentration is again that the aqueous solution of the sodium carboxymethylcellulose of 4 ‰ carries out emulsification, obtains emulsion B.
By 60g latex A and 140g emulsion B mixing and stirring, obtain paper industry silicone defoaming agent.
Embodiment 2
The preparation method of paper industry silicone defoaming agent, comprises following operating procedure:
By M/Q value be 0.4 MQ silicones to be ground to particle diameter be 5-20 μm, obtain MQ silicon resin particle;
Preparation latex A:
Be hydroxy silicon oil, the 4g specific area of 300000mPas by 200g viscosity at 25 DEG C be 150m
2(Guangzhou Ji Bisheng manufactures the hydrophobic type gas-phase silica of/g, HB-630), 18.8gMQ silicon resin particle mixing, be uniformly mixed under the low speed of 250rpm, be heated to 210 DEG C, react 2 hours under the high-speed stirred of 5500rpm, be brown to mixed material, close to brown, be considered as reaction and complete, stop heating, stir under 300rpm low speed and be cooled to less than 80 DEG C, obtain active compound A;
By 8g sorbitan monooleate, 4g polyoxyethylene 20 sorbitan monostearate and 5g fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix, obtain emulsifying agent, wherein sorbitan monooleate, polyoxyethylene 20 sorbitan monostearate and fatty alcohol polyglycol ether form compound emulsifying agent, and its HLB value is 8.4; Mix after emulsifying agent heat fused with 36g active compound A, add the polypropylene glycol that 3g molecular weight is 2000, mixing and stirring, obtain defoaming composition A;
Defoaming composition A is heated to 65 DEG C, and adding 310g mass concentration is that the aqueous solution of the sodium carboxymethylcellulose of 0.6 ‰ carries out emulsification, obtains latex A.
Preparation emulsion B:
Be 1600mPas by 300g viscosity at 25 DEG C, cloud point is that (structural formula is H (PO) for the polyether modified silicon oil of 70 DEG C
b(EO)
a(PO) – (Me
2siO)
msiMe
3) with 12.3g specific area be 238m
2/ g(Guangzhou Ji Bisheng manufactures, HB-630) mix under the low speed of 250rpm, be heated to 100 DEG C, stirring reaction 1 hour under the high speed of 1500rpm, react rear stopping heating, stirred under 350rpm low speed and be cooled to less than 45 DEG C, obtain active compound B;
By 3g sorbitan monostearate, 1.5g polyoxyethylene 20 sorbitan monooleate, 1.5g polyoxyethylene stearic acid ester (Hai'an petrochemical industry, SG-6) mix, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene stearic acid ester form compound emulsifying agent, and its HLB value is 8.35; After being heated fusing, mix with 27.6g active compound B, control temperature is 60 DEG C, then to add 170g mass concentration be that the aqueous solution of the sodium carboxymethylcellulose of 0.6 ‰ carries out emulsification, obtains emulsion B.
By 70g latex A and 130g emulsion B mixing and stirring, obtain paper industry silicone defoaming agent.
Embodiment 3
The preparation method of paper industry silicone defoaming agent, comprises following operating procedure:
By M/Q value be 0.9 MQ silicones to be ground to particle diameter be 5-20 μm, obtain MQ silicon resin particle;
Preparation latex A:
Be methyl-silicone oil, the 4.5g specific area of 300000mPas by 200g viscosity at 25 DEG C be 260m
2hydrophobic type gas-phase silica (the Degussa manufacture of/g, AerosilR-812), 33gMQ silicon resin particle mixing, be uniformly mixed under the low speed of 250rpm, be heated to 250 DEG C, react 2 hours under the high-speed stirred of 5000rpm, be brown to mixed material, close to brown, be considered as reaction and complete, stop heating, stir under 300rpm low speed and be cooled to less than 80 DEG C, obtain active compound A;
By 5.9g sorbitan monopalmitate, 3g polyoxyethylene 20 sorbitan monooleate, 1.2g polyoxyethylene stearic acid ester (Hai'an petrochemical industry, SG-6) mix with 0.9g n-butanol, obtain emulsifying agent, wherein sorbitan monopalmitate, polyoxyethylene 20 sorbitan monooleate and polyoxyethylene stearic acid ester form compound emulsifying agent, its HLB value is 8.55, mix after emulsifying agent heat fused with 21.5g active compound A, add the polypropylene glycol that 2g molecular weight is 4000, mixing and stirring, obtains defoaming composition A;
Defoaming composition A is heated to 65 DEG C, and adding 143g mass concentration is that the aqueous solution of the sodium carboxymethylcellulose of 2 ‰ carries out emulsification, obtains latex A.
Preparation emulsion B:
Be 1000mPas by 300g viscosity at 25 DEG C, cloud point is that (structural formula is H (PO) for the polyether modified silicon oil of 52 DEG C
b(EO)
a(PO) – (Me
2siO)
msiMe
3) with 16g specific area be 260m
2/ g(Degussa manufactures, AerosilR-812) mix under the low speed of 250rpm, be heated to 100 DEG C, stirring reaction 1 hour under the high speed of 1000rpm, react rear stopping heating, stirred under 400rpm low speed and be cooled to less than 45 DEG C, obtain active compound B;
By 3g sorbitan monostearate, 1.5g polyoxyethylene 20 sorbitan monostearate, 1g fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monostearate and fatty alcohol polyglycol ether form compound emulsifying agent, its HLB value is 7.73, after being heated fusing, mix with 27.6g active compound B, control temperature is 60 DEG C, adding 138g mass concentration is again that the aqueous solution of the sodium carboxymethylcellulose of 2 ‰ carries out emulsification, obtains emulsion B.
By 80g latex A and 120g emulsion B mixing and stirring, obtain paper industry silicone defoaming agent.
Embodiment 4
The preparation method of paper industry silicone defoaming agent, comprises following operating procedure:
By M/Q value be 0.7 MQ silicones be ground to particle diameter and be less than 20 μm, obtain MQ silicon resin particle;
Preparation latex A:
Be hydroxy silicon oil, the 21.5g specific area of 200000mPas by 400g viscosity at 25 DEG C be 300m
2(Guangzhou Ji Bisheng manufactures the hydrophobic type gas-phase silica of/g, HL-300), 42.5gMQ silicon resin particle mixing, be uniformly mixed under the low speed of 200rpm, be heated to 210 DEG C, react 4 hours under the high-speed stirred of 6000rpm, be brown to mixed material, close to brown, be considered as reaction and complete, stop heating, stir under 300rpm low speed and be cooled to less than 80 DEG C, obtain active compound A;
By 1g sorbitan monostearate, 1.4g polyoxyethylene 20 sorbitan monostearate and 0.6g fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix, obtain emulsifying agent, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monostearate and fatty alcohol polyglycol ether form compound emulsifying agent, and its HLB value is 8.85; Mix after emulsifying agent heat fused with 26g active compound A, add 1.2g tributyl phosphate and 3g molecular weight is the polypropylene glycol of 1000, mixing and stirring, obtain defoaming composition A;
Defoaming composition A is heated to 65 DEG C, and adding 132g mass concentration is that the aqueous solution of the xanthan gum of 4 ‰ carries out emulsification, obtains latex A.
Preparation emulsion B:
Be 2100mPas by 300g viscosity at 25 DEG C, cloud point is that (structural formula is H (PO) for the polyether modified silicon oil of 42 DEG C
b(EO)
a(PO) – (Me
2siO)
msiMe
2– (PO) (EO)
a(PO)
bh) with 26g specific area be 260m
2/ g(Guangzhou Ji Bisheng manufactures, HL-300) mix under the low speed of 250rpm, be heated to 150 DEG C, stirring reaction 0.5 hour under the high speed of 1500rpm, react rear stopping heating, stirred under 400rpm low speed and be cooled to less than 45 DEG C, obtain active compound B;
By 2g sorbitan monostearate, 1g polyoxyethylene 20 sorbitan monolaurate, 0.5g polyoxyethylene stearic acid ester (Hai'an petrochemical industry, SG-6) mix, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monolaurate and polyoxyethylene stearic acid ester form compound emulsifying agent, its HLB value is 7.14, after being heated fusing, mix with 19g active compound B, control temperature is 70 DEG C, adding 127g mass concentration is again that the aqueous solution of the xanthan gum of 4 ‰ carries out emulsification, obtains emulsion B.
By 60g latex A and 140g emulsion B mixing and stirring, obtain paper industry silicone defoaming agent.
Embodiment 5
The preparation method of paper industry silicone defoaming agent, comprises following operating procedure:
By M/Q value be 0.8 MQ silicones to be ground to particle diameter be 5-20 μm, obtain MQ silicon resin particle;
Preparation latex A:
Be the hydroxy silicon oil of 15000mPas by 50kg viscosity at 25 DEG C, 680g specific area is that (Guangzhou Ji Bisheng manufactures for the hydrophobic type gas-phase silica of 238 ㎡/g, HL-300), 3070gMQ silicon resin particle mixing, be uniformly mixed under the low speed of 200rpm, be heated to 230 DEG C, react 3 hours under the high-speed stirred of 6000rpm, be brown to mixed material, close to brown, be considered as reaction and complete, stop heating, stir under 300rpm low speed and be cooled to less than 80 DEG C, obtain active compound A;
By 5100g sorbitan monostearate, 2300g polyoxyethylene 20 sorbitan monostearate, 1000g fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix with 1600g ethylene glycol, obtain emulsifying agent, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monostearate and fatty alcohol polyglycol ether form compound emulsifying agent, and its HLB value is 7.15; Mix after emulsifying agent heat fused with 19kg active compound A, add 1500g tributyl phosphate and 3300g molecular weight is the polypropylene glycol of 2000, mixing and stirring, obtain defoaming composition A;
Defoaming composition A is heated to 65 DEG C, and adding 120kg mass concentration is that the aqueous solution of the sodium carboxymethylcellulose of 6 ‰ carries out emulsification, obtains latex A.
Preparation emulsion B:
Be 3000mPas by 80kg viscosity at 25 DEG C, cloud point is that (structural formula is H (PO) for the polyether modified silicon oil of 37 DEG C
b(EO)
a(PO) – (Me
2siO)
msiMe
2– (PO) (EO)
a(PO)
bh) with 3000g specific area be 238m
2/ g(Guangzhou Ji Bisheng manufactures, HL-300) mix under the low speed of 250rpm, be heated to 120 DEG C, stirring reaction 1 hour under the high speed of 1000rpm, react rear stopping heating, stirred under 400rpm low speed and be cooled to less than 45 DEG C, obtain active compound B;
By 3.5kg sorbitan monostearate, 1kg polyoxyethylene 20 sorbitan monostearate, 4.5kg fatty alcohol polyglycol ether (Hai'an petrochemical industry, O-15) mix, wherein sorbitan monostearate, polyoxyethylene 20 sorbitan monostearate, fatty alcohol polyglycol ether form compound emulsifying agent, its HLB value is 9.89, after being heated fusing, mix with 30kg active compound B, control temperature is 70 DEG C, adding 128kg mass concentration is again that the aqueous solution of the sodium carboxymethylcellulose of 6 ‰ carries out emulsification, obtains emulsion B.
By 60kg latex A and 140kg emulsion B mixing and stirring, obtain paper industry silicone defoaming agent.
Performance test embodiment
The paper industry silicone defoaming agent prepare embodiment 1 ~ 5 and commercially available black liquid defoamer (being designated as contrast defoamer) carry out froth breaking speed, the test of froth breaking persistence, the respective performances of the silicone defoaming agent prepared of testing example and contrast defoamer respectively in black liquor of pulp making, black liquor of pulp making is wheat straw sulfate pulping black liquor, solid content is 130g/L, and total alkali 28g/L(is with Na
2o counts), pH value is 12.Performance test methods is as follows:
Cancellation infusion sample respectively configuration quality concentration is the defoamer solution of 1.5 ‰;
Get 100g black liquid to add in the conical flask of with a scale and ground stopper, be heated to 85 DEG C, fiercely to shake 50 times up and down fast, shake high foam, dropwise add defoamer solution 5;
Continue to add 2g defoamer solution again, fierce to shake 50 times up and down fast, shake high foam, record foam height V(ml) and foam disappear time t(s completely clean) (hereinafter referred to as foam time), be designated as 1# data;
Conical flask is put into 85 DEG C of baking ovens to be incubated, carry out once identical concussion every 0.5h operate and record foam height V(ml) and foam time t(s), carry out 10 times altogether, be designated as 2# ~ 11# data, foam height less explanation defoamer suds suppressing properties is better, and foam time shorter explanation defoamer antifoam performance is better; Meanwhile, if foam time is greater than 30s, think that defoamer loses defoaming activity, foam time is better lower than more the speak more froth breaking persistence of bright defoamer of the number of times of 30s;
Once shake again when conical flask temperature retention time in 85 DEG C of baking ovens reaches 48h and operate and record foam height V and foam time t, be designated as 12# data, foam height less explanation defoamer suds suppressing properties is better, foam time shorter explanation defoamer antifoam performance is better, and froth breaking persistence is better simultaneously.
The foam time data of each defoamer sample are in table 1, and data unit is s, and the foam height data of each defoamer sample are in table 2, and data unit is ml.
Table 1
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Contrast defoamer |
| 1# | 4.3 | 4.1 | 4.6 | 4.3 | 4.4 | 9.4 |
| 2# | 4.5 | 4.2 | 4.9 | 4.6 | 4.8 | 10.7 |
| 3# | 4.5 | 4.4 | 5.1 | 4.7 | 4.9 | 12.4 |
| 4# | 5.2 | 4.9 | 5.4 | 5.0 | 5.5 | 15.5 |
| 5# | 5.7 | 5.5 | 5.8 | 5.3 | 5.6 | 17.8 |
| 6# | 6.2 | 6.0 | 6.6 | 5.9 | 6.3 | 20.2 |
| 7# | 7.8 | 7.0 | 7.9 | 6.8 | 7.6 | 24.5 |
| 8# | 8.4 | 7.7 | 8.8 | 7.7 | 8.9 | 26.6 |
| 9# | 10.4 | 9.3 | 10.9 | 9.6 | 11.7 | 29.4 |
| 10# | 14.7 | 13.5 | 13.8 | 13.8 | 15.6 | 34.7 |
| 11# | 17.9 | 16.7 | 17.1 | 18.0 | 19.2 | 40.1 |
| 12# | 28.4 | 26.7 | 28.2 | 32.4 | 30.7 | 62.3 |
Table 2
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Contrast defoamer |
| 1# | 120 | 123 | 127 | 125 | 121 | 140 |
| 2# | 123 | 125 | 128 | 126 | 125 | 145 |
| 3# | 125 | 126 | 130 | 128 | 126 | 146 |
| 4# | 128 | 130 | 133 | 132 | 131 | 149 |
| 5# | 132 | 135 | 134 | 136 | 133 | 151 |
| 6# | 133 | 138 | 139 | 141 | 136 | 153 |
| 7# | 141 | 143 | 142 | 141 | 142 | 155 |
| 8# | 142 | 146 | 143 | 145 | 144 | 156 |
| 9# | 147 | 152 | 149 | 147 | 150 | 165 |
| 10# | 152 | 156 | 150 | 154 | 153 | 167 |
| 11# | 153 | 155 | 154 | 157 | 153 | 175 |
| 12# | 158 | 160 | 169 | 158 | 164 | 189 |
From table 1 table 2 data, compare with contrast defoamer, silicone defoaming agent of the present invention has outstanding froth breaking suds suppressing properties, in the data group of identical numbering concussion first practical after the foam time of defoamer and foam height significantly lower than contrast defoamer, black liquid simultaneously containing defoamer carries out more than 10 rear foam times of concussion test still lower than 30s at the temperature of 85 DEG C, do not lose defoaming activity, and the foam time after shaking when reaching 48h standing time is about 30s, significantly lower than contrast defoamer, show that defoamer of the present invention can tolerate high ph-values and hot conditions, froth breaking excellent durability, and preparation method is simple, have a extensive future.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (7)
1. a paper industry silicone defoaming agent, obtained through emulsification by organosilicon defoaming composition, it is characterized in that, described organosilicon defoaming composition comprises active compound, emulsifying agent and auxiliary agent, and described active compound comprises polysiloxanes, polyether modified silicon oil, hydrophobic type gas-phase silica and MQ silicon resin particle;
When described polysiloxanes is 25 DEG C, viscosity is methyl-silicone oil or the hydroxy silicon oil of 10000-500000mPas;
The structural formula of described polyether modified silicon oil is
R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
2-(PO) (EO)
a(PO)
br and/or R (PO)
b(EO)
a(PO)-(Me
2siO)
msiMe
3, wherein, R Wei – H, – CH
3huo – COCH
3;
The particle diameter of described MQ silicon resin particle is 5-20 μm, and the specific area of described hydrophobic type gas-phase silica is 100 ~ 300m
2/ g; Described auxiliary agent comprises tributyl phosphate and/or polypropylene glycol;
Described paper industry silicone defoaming agent is prepared by the method comprising following operating procedure:
It is 5-20 μm that MQ silicones is ground to particle diameter, obtains MQ silicon resin particle;
Preparation latex A:
By polysiloxanes, hydrophobic type gas-phase silica, the mixing of MQ silicon resin particle, be heated to 210-250 DEG C, stirring reaction 2-6 hour, then stir and be cooled to less than 80 DEG C, obtain active compound A; Mix after emulsifying agent heat fused with active compound A, then add auxiliary agent, stir, obtain defoaming composition A; In defoaming composition A, add decentralized medium carry out emulsification, obtain latex A;
Preparation emulsion B:
Polyether modified silicon oil is mixed with hydrophobic type gas-phase silica, is heated to 80-150 DEG C, stirring reaction 0.5-1 hour, then stir and be cooled to less than 45 DEG C, obtain active compound B; Mix after emulsifying agent heat fused with active compound B, then add decentralized medium and carry out emulsification, obtain emulsion B;
Described decentralized medium is water or the aqueous solution containing thickener;
Latex A is mixed with emulsion B, obtains paper industry silicone defoaming agent.
2. paper industry silicone defoaming agent as claimed in claim 1, it is characterized in that, described polyether modified silicon oil is 100-5000mPas the viscosity of 25 DEG C, and cloud point is 35 ~ 75 DEG C.
3. paper industry silicone defoaming agent as claimed in claim 1, it is characterized in that, the M/Q value of described MQ silicon resin particle is 0.3-0.9.
4. the paper industry silicone defoaming agent as described in any one of claims 1 to 3, is characterized in that, in active compound quality for 100%, described active compound comprises following component by mass percentage:
5. the paper industry silicone defoaming agent as described in any one of claims 1 to 3, is characterized in that, in organosilicon defoaming composition quality for 100%, described organosilicon defoaming composition comprises following component by mass percentage:
Active compound 70%-85%
Emulsifying agent 12%-25%
Auxiliary agent 1%-5%.
6. the paper industry silicone defoaming agent as described in any one of claims 1 to 3, it is characterized in that, described emulsifier package is containing compound emulsifying agent, described compound emulsifying agent is two or more the composition in sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan mono-laurate, polyoxyethylene 20 sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate, fatty alcohol polyglycol ether, polyoxyethylene stearic acid ester, and its HLB value is 7-10.
7. paper industry silicone defoaming agent as claimed in claim 1, it is characterized in that, in described latex A, the quality of emulsifying agent accounts for 24 ~ 57% of emulsifying agent gross mass.
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| CN107130459B (en) * | 2017-05-19 | 2018-12-21 | 山东佑震化工有限公司 | A kind of black liquid defoaming agent and its preparation method and application |
| CN107126729B (en) * | 2017-06-22 | 2019-04-12 | 江苏赛欧信越消泡剂有限公司 | A kind of graphene oxide modified organic silicon defoaming agent and preparation method thereof |
| CN109647009A (en) * | 2019-01-10 | 2019-04-19 | 济南航晨生物科技有限公司 | A kind of dedicated defoaming agent of bacillus subtilis liquid fermentation and preparation method |
| CN110280051B (en) * | 2019-07-09 | 2021-07-09 | 四川省蜀爱新材料有限公司 | Low-silicon defoaming agent |
| CN110559696A (en) * | 2019-08-29 | 2019-12-13 | 安徽銮威化工科技开发有限公司 | Defoaming agent with high defoaming speed and preparation method thereof |
| CN113512902B (en) * | 2020-04-09 | 2023-04-07 | 江苏四新科技应用研究所股份有限公司 | Organic silicon composite emulsion type defoaming agent for papermaking industry and preparation method thereof |
| CN114225477B (en) * | 2021-12-16 | 2023-02-28 | 杭州崇耀科技发展有限公司 | Composite water-based organic silicon defoaming agent and preparation method thereof |
| CN114191853A (en) * | 2021-12-29 | 2022-03-18 | 杭州撒拉弗科技有限公司 | Preparation method of modified silane papermaking wastewater defoaming agent |
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