CN104151585B - A kind of preparation method of the calcium carbonate-filled polyurethane infiltrating and vaporizing membrane of dewatering nano - Google Patents
A kind of preparation method of the calcium carbonate-filled polyurethane infiltrating and vaporizing membrane of dewatering nano Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the calcium carbonate-filled polyurethane infiltrating and vaporizing membrane of dewatering nano, and its step is：(1) dried nano-calcium carbonate is added in deionized water, adds modifying agent, stirring reaction, after cleaned repeatedly with solvent hexane, remove unnecessary modifying agent, vacuum drying, grinding obtains dewatering nano calcium carbonate；(2) it is dissolved in after mixing end hydroxy butadiene, the diisocyanate of toluene 2,4 in xylene solvent, and adds catalyst dibutyltin dilaurylate, react after performed polymer, appropriate dewatering nano calcium carbonate is added, and diphenylmethanediamiand is added dropwise, reaction obtains casting solution；（3）Casting solution is carried out to be dried in vacuo after drying naturally under casting film-forming, normal temperature on polyfluortetraethylene plate after standing and defoaming, infiltrating and vaporizing membrane is obtained.The inventive method production stage is simple, and easy to operate, production cost is low, and film has good separating effect to the butanol/water of low concentration, and prospects for commercial application is wide.
Description
Technical field
Preferentially oozed the present invention relates to a kind of for infiltration evaporation through the calcium carbonate-filled polyurethane of dewatering nano of organic matter
The preparation method of vaporization film, belongs to infiltration evaporation technical field of membrane separation thoroughly.
Background technology
Influenceed, rise in oil price, be increasingly taken seriously as the butanol of the new bio energy by energy crisis.It is biological
Fermentation method prepares butanol（ABE ferments）Product in mainly contain acetone, butanol and ethanol, and three ratio be 3:6:1.Mainly
By the inhibitory action of product butanol, total solvent concentration can only achieve about 20gL in zymotic fluid-1, production capacity is relatively low.In order to solve
Above mentioned problem, scientist is attempted some separation methods, infiltration evaporation（PV）, absorption, liquid-liquid extraction, air lift and counter-infiltration etc.,
Directly separated with fermentation process coupling with the original position for realizing butanol, mitigate inhibitory action of the butanol to microorganism, improve fermentation strong
Degree and raw material availability.
In numerous separation methods, infiltration evaporation（Pervaporation, PV）Can be distilled, extracted with low energy consumption realization,
The conventional methods such as absorption are difficult to the separation task completed, are particularly suitable for separating nearly boiling point, constant boiling point mixture and isomer
Separation, the separation of a small amount of organic pollution has obvious in the removing and waste water to organic solvent and in the mixed solvent minor amount of water
Technical and advantage economically.
The infiltrating and vaporizing membrane applied to ABE fermentation process Separation Research is mainly high-molecular polymerization membrane at present, main application
There is organosilicon polymer in the infiltration vaporization separation film material of preferential alcohol thoroughly（PDMS、PTMSP）, such as fluorinated polymer（PTFE、
PVDF）And other polymers（PDMS/PVDF、PEBA）Deng the pvdf membrane being modified such as Srinivasan with silicone grease is to 7.5wt%
Butanol solution is carried out under the conditions of infiltration evaporation separation, 50 DEG C, and total flux is 3.42 kgm-2h-1, separation factor is 4.88
（Srinivasan, K., K. Palanivelu, and A.N. Gopalakrishnan, Recovery of 1-
butanol from a model pharmaceutical aqueous waste by pervaporation. Chemical
Engineering Science, 2007. 62(11): p. 2905-2914）.The polymerization of 100 μm of thickness is made with PEBA by Liu
Film is to binary system（Acetone-water, butanol-water, alcohol-water）Separating effect be：Separation factorα Acetone=4.2,α Butanol=
8.2 andα Ethanol=2.4, corresponding total permeation flux is respectively 27.4 gm-2h-1、65.3 gm-2h-1And 37.2gm-2h-1（Liu,
FF; Liu, L; Feng, XS. Separation of acetone–butanol–ethanol (ABE) from dilute
aqueous solution by pervaporation[J]. Sep. Purif. Technol. 2005, 42(3): 273-
282）.Though organosilicon polymer separating effect preferably, itself film forming, bad mechanical property, although fluorinated polymer because containing
Fluorine atom and with good hydrophobicity, but selectivity is bad, and cost is too high, and composite membrane preparation technology is relative complex.
The polyurethane that the present invention is used（PU）It is a kind of important high polymer material, with excellent mechanical strength, to receiving
Rice calcium carbonate passes through simple hydrophobically modified, and filling is prepared into infiltrating and vaporizing membrane into conventional polyurethane, significantly improves dredging for film
Aqueous energy, improves the selectivity to organic matter of film, while the mechanical strength of film can be further enhanced, with low cost, industry
Change application value high, have a extensive future.
The content of the invention
It is an object of the invention to for above-mentioned key technical problem, there is provided a kind of preferential dewatering nano carbon by butanol
The preparation method of sour calcium filled polyurethane infiltrating and vaporizing membrane.
To achieve the above object, the technical solution used in the present invention is：The calcium carbonate-filled polyurethane of the dewatering nano oozes
The preparation method of vaporization film comprises the following steps thoroughly：
（1）Prepare dewatering nano calcium carbonate：Under conditions of stirring by dried nano-calcium carbonate addition 10 times go from
In sub- water, stirring makes dispersed under the conditions of 80 DEG C, and stirring reaction 1-12h at modifying agent, 80 DEG C is added afterwards, filters, afterwards with molten
Agent n-hexane cleans nano-calcium carbonate repeatedly, removes unnecessary modifying agent, is placed in 80 DEG C of vacuum drying ovens and dries, is dredged after grinding
Water nano-calcium carbonate；The modifying agent is one kind in oleic acid and stearic acid, and the modifying agent is with nano-calcium carbonate mass ratio
0.01~0.1:1；
（2）Prepare casting solution：Dimethylbenzene is added protecting equipped with nitrogen, in the reactor of mechanical agitation and condensing reflux to make
For solvent, by end hydroxy butadiene and Toluene-2,4-diisocyanate, 4- diisocyanate is mixed into mixture, after be dissolved in xylene solvent,
And catalyst dibutyltin dilaurylate is added, stir, reacted at 60-70 DEG C and room temperature is cooled to after 1~3h, synthesize pre-polymerization
Body, it is rear to add dewatering nano calcium carbonate, and diphenylmethanediamiand is added dropwise, 50 DEG C of stirring reaction 1h are warming up to, are cast
Film liquid；The mean molecule quantity of described end hydroxy butadiene is 2500~3000；Toluene-2,4-diisocyanate, 4- diisocyanate and terminal hydroxy group
The mol ratio of polybutadiene is 2~8:1；The mass ratio of mixture and xylene solvent is 1:0.5~4；Di lauric dibutyl
The mass ratio of tin and end hydroxy butadiene is 0.0005~0.001:1；The dewatering nano calcium carbonate and terminal hydroxy group polybutadiene
The mass ratio of alkene is 0.01~0.05:1；The mol ratio of the diphenylmethanediamiand and end hydroxy butadiene is 1~2.5:
1；
（3）Prepare infiltrating and vaporizing membrane：By casting solution standing and defoaming, after on polyfluortetraethylene plate under casting film-forming, normal temperature
Naturally after drying, 6~12h of vacuum drying in 60~100 DEG C of vacuum drying ovens is placed in, the calcium carbonate-filled polyurethane of dewatering nano is obtained
Infiltrating and vaporizing membrane.
Compared with prior art, the present invention carries out hydrophobically modified to nano-calcium carbonate first, is subsequently filled to the poly- ammonia of fourth hydroxyl
In ester, the infiltrating and vaporizing membrane prepared not only has excellent mechanical strength, and possesses preferable hydrophobic surface, improves film
To the selectivity of low-concentration organic, and the film is not polluted by fermented feed liquid, is adapted to couple with fermentation process, realizes in situ point
From.Preparation technology of the present invention is simple and convenient to operate, and material composition is cheap, is had a extensive future.
Embodiment
Technical scheme is described further below in conjunction with instantiation.
Embodiment 1：
（1）Prepare dewatering nano calcium carbonate：The dried nano-calcium carbonates of 10g are weighed, are added in 100g deionized waters, 80
Stirring makes dispersed, rear to add stirring reaction 4h at 0.5g oleic acid, 80 DEG C, filtering under the conditions of DEG C, after it is anti-with solvent hexane
Nano-calcium carbonate is cleaned again, unnecessary oleic acid is removed, and is placed in 80 DEG C of vacuum drying ovens and is dried, dewatering nano carbonic acid is obtained after grinding
Calcium；
（2）Prepare casting solution：Dimethylbenzene is added protecting equipped with nitrogen, in the reactor of mechanical agitation and condensing reflux to make
For solvent, by end hydroxy butadiene and Toluene-2,4-diisocyanate, 4- diisocyanate is mixed into mixture, after be dissolved in xylene solvent,
And catalyst dibutyltin dilaurylate is added, stir, reacted at 60 DEG C and room temperature is cooled to after 3h, synthesize performed polymer, after
Dewatering nano calcium carbonate is added, and diphenylmethanediamiand is added dropwise, 50 DEG C of stirring reaction 1h is warming up to, obtains casting solution；
The mean molecule quantity of described end hydroxy butadiene is 2500；Toluene-2,4-diisocyanate, 4- diisocyanate and end hydroxy butadiene
Mol ratio is 2:1；The mass ratio of mixture and xylene solvent is 1:0.5；Dibutyl tin laurate and terminal hydroxy group polybutadiene
The mass ratio of alkene is 0.0005:1；The mass ratio of the dewatering nano calcium carbonate and end hydroxy butadiene is 0.01:1；It is described
The mol ratio of diphenylmethanediamiand and end hydroxy butadiene is 1:1；
（3）Prepare infiltrating and vaporizing membrane：By casting solution standing and defoaming, after on polyfluortetraethylene plate under casting film-forming, normal temperature
Naturally after drying, it is placed in 80 DEG C of vacuum drying ovens and is dried in vacuo 10h, obtains the calcium carbonate-filled polyurethane infiltration evaporation of dewatering nano
Film.
Infiltrating and vaporizing membrane obtained by the present embodiment is subjected to infiltration evaporation separation to 0.6wt% butanol/waters mixed solution real
Test, 40 DEG C of temperature, permeation flux is that separation factor is 120.5gm under the conditions of film downstream vacuum degree 1.3KPa-2h-1, separation factor
For 29.6.
Embodiment 2：
（1）Prepare dewatering nano calcium carbonate：The dried nano-calcium carbonates of 10g are weighed, are added in 100g deionized waters, 80
Stirring makes dispersed, rear to add stirring reaction 8h at 0.8g stearic acid, 80 DEG C, filtering under the conditions of DEG C, after use solvent hexane
Nano-calcium carbonate is cleaned repeatedly, unnecessary stearic acid is removed, and is placed in 80 DEG C of vacuum drying ovens and is dried, dewatering nano carbon is obtained after grinding
Sour calcium；
（2）Prepare casting solution：Dimethylbenzene is added protecting equipped with nitrogen, in the reactor of mechanical agitation and condensing reflux to make
For solvent, by end hydroxy butadiene and Toluene-2,4-diisocyanate, 4- diisocyanate is mixed into mixture, after be dissolved in xylene solvent,
And catalyst dibutyltin dilaurylate is added, stir, reacted at 70 DEG C and room temperature is cooled to after 1h, synthesize performed polymer, after
Dewatering nano calcium carbonate is added, and diphenylmethanediamiand is added dropwise, 50 DEG C of stirring reaction 1h is warming up to, obtains casting solution；
The mean molecule quantity of described end hydroxy butadiene is 3000；Toluene-2,4-diisocyanate, 4- diisocyanate and end hydroxy butadiene
Mol ratio is 4:1；The mass ratio of mixture and xylene solvent is 1:1；Dibutyl tin laurate and end hydroxy butadiene
Mass ratio be 0.0008:1；The mass ratio of the dewatering nano calcium carbonate and end hydroxy butadiene is 0.02:1；Described two
The mol ratio of phenylmethane diamines and end hydroxy butadiene is 1.5:1；
（3）Prepare infiltrating and vaporizing membrane：By casting solution standing and defoaming, after on polyfluortetraethylene plate under casting film-forming, normal temperature
Naturally after drying, it is placed in 90 DEG C of vacuum drying ovens and is dried in vacuo 10h, obtains the calcium carbonate-filled polyurethane infiltration evaporation of dewatering nano
Film.
Infiltrating and vaporizing membrane obtained by the present embodiment is subjected to infiltration evaporation separation to 0.6wt% butanol/waters mixed solution real
Test, 40 DEG C of temperature, permeation flux is that separation factor is 110.4gm under the conditions of film downstream vacuum degree 1.3KPa-2h-1, separation factor
For 30.1.
Embodiment 3：
（1）Prepare dewatering nano calcium carbonate：The dried nano-calcium carbonates of 10g are weighed, are added in 100g deionized waters, 80
Stirring makes dispersed, rear to add stirring reaction 4h at 0.5g oleic acid, 80 DEG C, filtering under the conditions of DEG C, after it is anti-with solvent hexane
Nano-calcium carbonate is cleaned again, unnecessary oleic acid is removed, and is placed in 80 DEG C of vacuum drying ovens and is dried, dewatering nano carbonic acid is obtained after grinding
Calcium；
（2）Prepare casting solution：Dimethylbenzene is added protecting equipped with nitrogen, in the reactor of mechanical agitation and condensing reflux to make
For solvent, by end hydroxy butadiene and Toluene-2,4-diisocyanate, 4- diisocyanate is mixed into mixture, after be dissolved in xylene solvent,
And catalyst dibutyltin dilaurylate is added, stir, reacted at 70 DEG C and room temperature is cooled to after 2h, synthesize performed polymer, after
Dewatering nano calcium carbonate is added, and diphenylmethanediamiand is added dropwise, 50 DEG C of stirring reaction 1h is warming up to, obtains casting solution；
The mean molecule quantity of described end hydroxy butadiene is 2500；Toluene-2,4-diisocyanate, 4- diisocyanate and end hydroxy butadiene
Mol ratio is 6:1；The mass ratio of mixture and xylene solvent is 1:3；Dibutyl tin laurate and end hydroxy butadiene
Mass ratio be 0.001:1；The mass ratio of the dewatering nano calcium carbonate and end hydroxy butadiene is 0.03:1；The hexichol
The mol ratio of methylmethane diamines and end hydroxy butadiene is 2:1；
（3）Prepare infiltrating and vaporizing membrane：By casting solution standing and defoaming, after on polyfluortetraethylene plate under casting film-forming, normal temperature
Naturally after drying, it is placed in 100 DEG C of vacuum drying ovens and is dried in vacuo 7h, obtains the calcium carbonate-filled polyurethane infiltration evaporation of dewatering nano
Film.
Infiltrating and vaporizing membrane obtained by the present embodiment is subjected to infiltration evaporation separation to 0.6wt% butanol/waters mixed solution real
Test, 40 DEG C of temperature, permeation flux is that separation factor is 104.8gm under the conditions of film downstream vacuum degree 1.3KPa-2h-1, separation factor
For 31.2.
Claims (1)
1. a kind of preparation method of the calcium carbonate-filled polyurethane infiltrating and vaporizing membrane of dewatering nano, it is characterised in that this method include with
Lower step：
（1）Prepare dewatering nano calcium carbonate：Dried nano-calcium carbonate is added into 10 times of deionized waters under conditions of stirring
In, stirring makes dispersed under the conditions of 80 DEG C, and stirring reaction 1-12h at modifying agent, 80 DEG C is added afterwards, filters, after with solvent just
Hexane cleans nano-calcium carbonate repeatedly, removes unnecessary modifying agent, is placed in 80 DEG C of vacuum drying ovens and dries, hydrophobic receive is obtained after grinding
Rice calcium carbonate；The modifying agent is one kind in oleic acid and stearic acid, and the modifying agent is 0.01 with nano-calcium carbonate mass ratio
~0.1:1；
（2）Prepare casting solution：Dimethylbenzene is added as molten being protected equipped with nitrogen, in the reactor of mechanical agitation and condensing reflux
Agent, by end hydroxy butadiene and Toluene-2,4-diisocyanate, 4- diisocyanate is mixed into mixture, after be dissolved in xylene solvent, and add
Enter catalyst dibutyltin dilaurylate, stir, reacted at 60-70 DEG C and room temperature is cooled to after 1~3h, synthesize performed polymer,
Dewatering nano calcium carbonate is added afterwards, and diphenylmethanediamiand is added dropwise, and is warming up to 50 DEG C of stirring reaction 1h, is obtained casting film
Liquid；The mean molecule quantity of described end hydroxy butadiene is 2500~3000；Toluene-2,4-diisocyanate, 4- diisocyanate gathers with terminal hydroxy group
The mol ratio of butadiene is 2~8:1；The mass ratio of mixture and xylene solvent is 1:0.5~4；Dibutyl tin laurate
Mass ratio with end hydroxy butadiene is 0.0005~0.001:1；The dewatering nano calcium carbonate and end hydroxy butadiene
Mass ratio be 0.01~0.05:1；The mol ratio of the diphenylmethanediamiand and end hydroxy butadiene is 1~2.5:1；
（3）Prepare infiltrating and vaporizing membrane：Will modified casting solution standing and defoaming, after on polyfluortetraethylene plate under casting film-forming, normal temperature
Naturally after drying, 6~12h of vacuum drying in 60~100 DEG C of vacuum drying ovens is placed in, the calcium carbonate-filled polyurethane of dewatering nano is obtained
Infiltrating and vaporizing membrane.
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| EP3178873A1 (en) | 2015-12-08 | 2017-06-14 | ETH Zurich | Waterproof and breathable, porous membranes |
| CN105367733B (en) * | 2015-12-16 | 2018-02-06 | 合肥工业大学 | A kind of preparation method and purposes based on benzoic anhydride polyester polyol aqueous polyurethane film |
| CN106632970A (en) * | 2016-10-20 | 2017-05-10 | 合肥创想能源环境科技有限公司 | Preparation method of polyurethane pervaporation membrane |
| CN106606934A (en) * | 2016-12-02 | 2017-05-03 | 中国石油大学(华东) | Polyurethane pervaporation recovered solvent membrane and preparation method thereof |
| CN109077344A (en) * | 2018-09-01 | 2018-12-25 | 王婧婧 | A kind of preparation method of milk-taste essence |
| CN112516813B (en) * | 2019-09-18 | 2022-10-28 | 中国石油化工股份有限公司 | Graphene-polyurethane composite filtering membrane for oil-water separation and preparation method thereof |
| CN112574551A (en) * | 2019-09-27 | 2021-03-30 | 常州碳酸钙有限公司 | Modified nano calcium carbonate-polyurethane-polyamide foam and preparation method thereof |
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