CN104151585A - Preparation method of hydrophobic nano-grade calcium carbonate filled polyurethane pervaporation membrane - Google Patents
Preparation method of hydrophobic nano-grade calcium carbonate filled polyurethane pervaporation membrane Download PDFInfo
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- CN104151585A CN104151585A CN201410394289.XA CN201410394289A CN104151585A CN 104151585 A CN104151585 A CN 104151585A CN 201410394289 A CN201410394289 A CN 201410394289A CN 104151585 A CN104151585 A CN 104151585A
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Abstract
The invention discloses a preparation method of a hydrophobic nano-grade calcium carbonate filled polyurethane pervaporation membrane. The method comprises the steps of: (1) dried nano-grade calcium carbonate is added into deionized water; a modifying agent is added, and a reaction is carried out while stirring; the material is repeatedly washed by using a solvent n-hexane, such that superfluous modifying agent is removed; the material is dried under vacuum and is ground, such that hydrophobic nano-grade calcium carbonate is obtained; (2) hydroxyl-terminated polybutadiene and toluene-2,4-diisocyanate are mixed and dissolved into a xylene solvent; a catalyst dibutyltin dilaurate is added; a prepolymer is obtained after a reaction; a proper amount of the hydrophobic nano-grade calcium carbonate is added, and diphenylmethane diamine is gradually dropped in; and a casting liquid is obtained after a reaction; and (3) the casting liquid is allowed to stand such that the casting liquid is de-aerated; the casting liquid is cast into a film on a polytetrafluoroethylene plate; the film is naturally air-dried under a normal temperature and is then vacuum dried, such that the pervaporation membrane is obtained. The method provided by the invention has the advantages of simple production steps, convenient operation, and low production cost. The film has good separation effect upon low-concentration butanol/water. The method and the film have good industrial application prospect.
Description
Technical field
The present invention relates to a kind of preparation method who preferentially sees through the calcium carbonate-filled urethane infiltrating and vaporizing membrane of organic dewatering nano for infiltration evaporation, belong to infiltrating and vaporizing membrane separation technology field.
Background technology
Affected by energy dilemma, rise in oil price, more and more comes into one's own as the butanols of the new bio energy.Biological fermentation process is prepared in the product of butanols (ABE fermentation) main containing acetone, butanols and ethanol, and three's ratio is 3:6:1.Mainly be subject to the restraining effect of product butanols, in fermented liquid, total solvent concentration can only reach about 20gL
-1, throughput is lower.In order to address the above problem, scientist attempts some separation methods, infiltration evaporation (PV), absorption, liquid-liquid extraction, air lift and reverse osmosis etc., the original position that is directly coupled to realize butanols with fermenting process separates, alleviate the restraining effect of butanols to microorganism, improve ferment strength and raw material availability.
In numerous separation methods, infiltration evaporation (pervaporation, PV) can realize with low energy consumption the separation task that the traditional methods such as distillation, extraction, absorption have been difficult to, be particularly suitable for separating the separation of nearly boiling point, constant boiling mixture and isomers, to minor amount of water in organic solvent and mixed solvent remove and waste water in the separation of a small amount of organic pollutant there is significantly technical and advantage economically.
The infiltrating and vaporizing membrane that is applied at present ABE fermenting process Separation Research is mainly high molecular polymerization film, be mainly used in the preferential infiltration vaporization separation film material of alcohol thoroughly and have organosilicon polymer (PDMS, PTMSP), as fluorinated polymkeric substance (PTFE, PVDF) and other polymkeric substance (PDMS/PVDF, PEBA) etc., as Srinivasan carries out infiltration evaporation separation with the pvdf membrane of silicone grease modification to the butanol solution of 7.5wt%, under 50 DEG C of conditions, total flux is 3.42 kgm
-2h
-1separation 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).Liu makes thickness 100 μ m polymeric membrane with PEBA to the separating effect of binary system (acetone-water, butanols-water, alcohol-water) is: separation factor
α acetone=4.2,
α butanols=8.2 Hes
α 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 is better, self film-forming properties, bad mechanical property, although the fluorinated polymkeric substance hydrophobic nature good because contain fluorine atoms has, selectivity is bad, and high cost, composite membrane preparation technology relative complex.
The urethane (PU) that the present invention adopts is a kind of important macromolecular material, there is good physical strength, to the simple hydrophobically modified of nano-calcium carbonate process, be filled in conventional urethane and be prepared into infiltrating and vaporizing membrane, significantly improve the hydrophobic performance of film, improve film to organic selectivity, the further physical strength of reinforcing membrane of while, with low cost, industrial applications is worth high, has a extensive future.
Summary of the invention
The object of the invention is to for above-mentioned key technical problem, a kind of preparation method of the preferential calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano by butanols is provided.
For achieving the above object, the technical solution used in the present invention is: the preparation method of the calcium carbonate-filled urethane infiltrating and vaporizing membrane of this dewatering nano comprises the following steps:
(1) prepare dewatering nano calcium carbonate: under the condition stirring, dried nano-calcium carbonate is added in 10 times of deionized waters, under 80 DEG C of conditions, stirring makes dispersed, after add properties-correcting agent, stirring reaction 1-12h at 80 DEG C, filter, repeatedly clean nano-calcium carbonate with solvent normal hexane afterwards, remove unnecessary properties-correcting agent, be placed in 80 DEG C of vacuum drying ovens and dry, after grinding, obtain dewatering nano calcium carbonate; Described properties-correcting agent is the one in oleic acid and stearic acid, and described properties-correcting agent and nano-calcium carbonate mass ratio are 0.01～0.1:1;
(2) prepare film-casting liquid: in the reactor that nitrogen protection, mechanical stirring and condensing reflux are housed, add dimethylbenzene as solvent, by hydroxy-terminated polybutadienes and Toluene-2,4-diisocyanate, 4-vulcabond is mixed into mixture, after be dissolved in xylene solvent, and add catalyzer dibutyl tin laurate, stir, after reacting 1～3h at 60-70 DEG C, be cooled to room temperature, synthetic performed polymer, after add dewatering nano calcium carbonate, and dropwise add diphenylmethanediamiand, and be warming up to 50 DEG C of stirring reaction 1h, obtain film-casting liquid; The molecular-weight average of described hydroxy-terminated polybutadienes is 2500～3000; Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and hydroxy-terminated polybutadienes is 2～8:1; The mass ratio of mixture and xylene solvent is 1:0.5～4; The mass ratio of dibutyl tin laurate and hydroxy-terminated polybutadienes is 0.0005～0.001:1; The mass ratio of described dewatering nano calcium carbonate and hydroxy-terminated polybutadienes is 0.01～0.05:1; The mol ratio of described diphenylmethanediamiand and hydroxy-terminated polybutadienes is 1～2.5:1;
(3) prepare infiltrating and vaporizing membrane: by film-casting liquid standing and defoaming, after on polyfluortetraethylene plate casting film-forming, naturally after drying under normal temperature, be placed in 60～100 DEG C of vacuum drying oven vacuum-drying 6～12h, obtain the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano.
Compared with prior art, first the present invention carries out hydrophobically modified to nano-calcium carbonate, then be filled in polybutadiene polyurethane, the infiltrating and vaporizing membrane of preparing not only has good physical strength, and have good hydrophobic surface, improved the selectivity of film to low-concentration organic, and this film is not polluted by fermented feed liquid, be applicable to and fermenting process coupling, realize original position and separate.Preparation technology of the present invention is simple, easy to operate, and material composition is cheap, has a extensive future.
Embodiment
Below in conjunction with specific examples, technical scheme of the present invention is described further.
Embodiment 1:
(1) prepare dewatering nano calcium carbonate: take the dried nano-calcium carbonate of 10g, add in 100g deionized water, under 80 DEG C of conditions, stirring makes dispersed, after add 0.5g oleic acid, stirring reaction 4h at 80 DEG C, filters, repeatedly clean nano-calcium carbonate with solvent normal hexane afterwards, remove unnecessary oleic acid, be placed in 80 DEG C of vacuum drying ovens and dry, after grinding, obtain dewatering nano calcium carbonate;
(2) prepare film-casting liquid: in the reactor that nitrogen protection, mechanical stirring and condensing reflux are housed, add dimethylbenzene as solvent, by hydroxy-terminated polybutadienes and Toluene-2,4-diisocyanate, 4-vulcabond is mixed into mixture, after be dissolved in xylene solvent, and add catalyzer dibutyl tin laurate, stir, after reacting 3h at 60 DEG C, be cooled to room temperature, synthetic performed polymer, after add dewatering nano calcium carbonate, and dropwise add diphenylmethanediamiand, and be warming up to 50 DEG C of stirring reaction 1h, obtain film-casting liquid; The molecular-weight average of described hydroxy-terminated polybutadienes is 2500; Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and hydroxy-terminated polybutadienes is 2:1; The mass ratio of mixture and xylene solvent is 1:0.5; The mass ratio of dibutyl tin laurate and hydroxy-terminated polybutadienes is 0.0005:1; The mass ratio of described dewatering nano calcium carbonate and hydroxy-terminated polybutadienes is 0.01:1; The mol ratio of described diphenylmethanediamiand and hydroxy-terminated polybutadienes is 1:1;
(3) prepare infiltrating and vaporizing membrane: by film-casting liquid standing and defoaming, after on polyfluortetraethylene plate casting film-forming, after naturally drying under normal temperature, be placed in 80 DEG C of vacuum drying oven vacuum-drying 10h, obtain the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano.
The infiltrating and vaporizing membrane of the present embodiment gained is carried out to infiltration evaporation separating experiment to 0.6wt% butanol/water mixing solutions, 40 DEG C of temperature, under the vacuum tightness 1.3KPa condition of film downstream, permeation flux is that separation factor is 120.5gm
-2h
-1, separation factor is 29.6.
Embodiment 2:
(1) prepare dewatering nano calcium carbonate: take the dried nano-calcium carbonate of 10g, add in 100g deionized water, under 80 DEG C of conditions, stirring makes dispersed, after add 0.8g stearic acid, stirring reaction 8h at 80 DEG C, filters, repeatedly clean nano-calcium carbonate with solvent normal hexane afterwards, remove unnecessary stearic acid, be placed in 80 DEG C of vacuum drying ovens and dry, after grinding, obtain dewatering nano calcium carbonate;
(2) prepare film-casting liquid: in the reactor that nitrogen protection, mechanical stirring and condensing reflux are housed, add dimethylbenzene as solvent, by hydroxy-terminated polybutadienes and Toluene-2,4-diisocyanate, 4-vulcabond is mixed into mixture, after be dissolved in xylene solvent, and add catalyzer dibutyl tin laurate, stir, after reacting 1h at 70 DEG C, be cooled to room temperature, synthetic performed polymer, after add dewatering nano calcium carbonate, and dropwise add diphenylmethanediamiand, and be warming up to 50 DEG C of stirring reaction 1h, obtain film-casting liquid; The molecular-weight average of described hydroxy-terminated polybutadienes is 3000; Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and hydroxy-terminated polybutadienes is 4:1; The mass ratio of mixture and xylene solvent is 1:1; The mass ratio of dibutyl tin laurate and hydroxy-terminated polybutadienes is 0.0008:1; The mass ratio of described dewatering nano calcium carbonate and hydroxy-terminated polybutadienes is 0.02:1; The mol ratio of described diphenylmethanediamiand and hydroxy-terminated polybutadienes is 1.5:1;
(3) prepare infiltrating and vaporizing membrane: by film-casting liquid standing and defoaming, after on polyfluortetraethylene plate casting film-forming, after naturally drying under normal temperature, be placed in 90 DEG C of vacuum drying oven vacuum-drying 10h, obtain the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano.
The infiltrating and vaporizing membrane of the present embodiment gained is carried out to infiltration evaporation separating experiment to 0.6wt% butanol/water mixing solutions, 40 DEG C of temperature, under the vacuum tightness 1.3KPa condition of film downstream, permeation flux is that separation factor is 110.4gm
-2h
-1, separation factor is 30.1.
Embodiment 3:
(1) prepare dewatering nano calcium carbonate: take the dried nano-calcium carbonate of 10g, add in 100g deionized water, under 80 DEG C of conditions, stirring makes dispersed, after add 0.5g oleic acid, stirring reaction 4h at 80 DEG C, filters, repeatedly clean nano-calcium carbonate with solvent normal hexane afterwards, remove unnecessary oleic acid, be placed in 80 DEG C of vacuum drying ovens and dry, after grinding, obtain dewatering nano calcium carbonate;
(2) prepare film-casting liquid: in the reactor that nitrogen protection, mechanical stirring and condensing reflux are housed, add dimethylbenzene as solvent, by hydroxy-terminated polybutadienes and Toluene-2,4-diisocyanate, 4-vulcabond is mixed into mixture, after be dissolved in xylene solvent, and add catalyzer dibutyl tin laurate, stir, after reacting 2h at 70 DEG C, be cooled to room temperature, synthetic performed polymer, after add dewatering nano calcium carbonate, and dropwise add diphenylmethanediamiand, and be warming up to 50 DEG C of stirring reaction 1h, obtain film-casting liquid; The molecular-weight average of described hydroxy-terminated polybutadienes is 2500; Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and hydroxy-terminated polybutadienes is 6:1; The mass ratio of mixture and xylene solvent is 1:3; The mass ratio of dibutyl tin laurate and hydroxy-terminated polybutadienes is 0.001:1; The mass ratio of described dewatering nano calcium carbonate and hydroxy-terminated polybutadienes is 0.03:1; The mol ratio of described diphenylmethanediamiand and hydroxy-terminated polybutadienes is 2:1;
(3) prepare infiltrating and vaporizing membrane: by film-casting liquid standing and defoaming, after on polyfluortetraethylene plate casting film-forming, after naturally drying under normal temperature, be placed in 100 DEG C of vacuum drying oven vacuum-drying 7h, obtain the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano.
The infiltrating and vaporizing membrane of the present embodiment gained is carried out to infiltration evaporation separating experiment to 0.6wt% butanol/water mixing solutions, 40 DEG C of temperature, under the vacuum tightness 1.3KPa condition of film downstream, permeation flux is that separation factor is 104.8gm
-2h
-1, separation factor is 31.2.
Claims (1)
1. a preparation method for the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano, is characterized in that the method comprises the following steps:
(1) prepare dewatering nano calcium carbonate: under the condition stirring, dried nano-calcium carbonate is added in 10 times of deionized waters, under 80 DEG C of conditions, stirring makes dispersed, after add properties-correcting agent, stirring reaction 1-12h at 80 DEG C, filter, repeatedly clean nano-calcium carbonate with solvent normal hexane afterwards, remove unnecessary properties-correcting agent, be placed in 80 DEG C of vacuum drying ovens and dry, after grinding, obtain dewatering nano calcium carbonate; Described properties-correcting agent is the one in oleic acid and stearic acid, and described properties-correcting agent and nano-calcium carbonate mass ratio are 0.01～0.1:1;
(2) prepare film-casting liquid: in the reactor that nitrogen protection, mechanical stirring and condensing reflux are housed, add dimethylbenzene as solvent, by hydroxy-terminated polybutadienes and Toluene-2,4-diisocyanate, 4-vulcabond is mixed into mixture, after be dissolved in xylene solvent, and add catalyzer dibutyl tin laurate, stir, after reacting 1～3h at 60-70 DEG C, be cooled to room temperature, synthetic performed polymer, after add dewatering nano calcium carbonate, and dropwise add diphenylmethanediamiand, and be warming up to 50 DEG C of stirring reaction 1h, obtain film-casting liquid; The molecular-weight average of described hydroxy-terminated polybutadienes is 2500～3000; Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and hydroxy-terminated polybutadienes is 2～8:1; The mass ratio of mixture and xylene solvent is 1:0.5～4; The mass ratio of dibutyl tin laurate and hydroxy-terminated polybutadienes is 0.0005～0.001:1; The mass ratio of described dewatering nano calcium carbonate and hydroxy-terminated polybutadienes is 0.01～0.05:1; The mol ratio of described diphenylmethanediamiand and hydroxy-terminated polybutadienes is 1～2.5:1;
(3) prepare infiltrating and vaporizing membrane: by modification film-casting liquid standing and defoaming, after on polyfluortetraethylene plate casting film-forming, naturally after drying under normal temperature, be placed in 60～100 DEG C of vacuum drying oven vacuum-drying 6～12h, obtain the calcium carbonate-filled urethane infiltrating and vaporizing membrane of dewatering nano.
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