CN105126638A - Preparation method for back-diffusion in-situ self-assembled MOFs nanofiltration membrane - Google Patents
Preparation method for back-diffusion in-situ self-assembled MOFs nanofiltration membrane Download PDFInfo
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Abstract
The invention provides a preparation method for a back-diffusion in-situ self-assembled MOFs nanofiltration membrane, belonging to the field of separation of nanofiltration membranes. The method comprises the following steps: pretreating a porous base membrane so as to allow the surface of the porous base membrane to be charged; respectively placing a metal ion/polymer solution and an organic ligand solution at two sides of the base membrane, wherein the metal ion/polymer solution is located on the side where a compact layer is located, and the organic ligand solution is located on the side where a support layer is located; adjusting density difference, liquid level difference, precursor concentration and the like of the two sides of the base membrane so as to realize back diffusion of metal ions and organic ligand in the pores of the base membrane and contact of the metal ions and the organic ligand on the surface of the base membrane to produce MOFs particles, wherein a polymer is deposited on the surface of the base membrane at the same time, so a MOFs/polymer nanometer hybrid membrane grows in situ; and taking out the membrane and then drying the membrane at 20 DEG C to 150 DEG C for 0.1 to 2 h. The separation membrane prepared by using the method in the invention can effectively overcome the problems that agglomeration and uneven distribution of hybrid particles easily appear in the growth process of the MOFs hybrid membrane, MOFs have difficulty in heterogeneous nucleation, etc.
Description
Technical field
The present invention relates to a kind of method adopting diffuse in reverse direction primary reconstruction technology to prepare MOFs nano hybrid film, for Dye Removal, belong to NF membrane separation field.
Background technology
Membrane separation technique has that process is simple, non-secondary pollution, without phase transformation, the advantage such as efficient, energy-conservation, receive increasing concern at separation field.The key affecting membrane separating property is membrane material and membrane structure, therefore seeks novel membrane material and membrane structure construction method becomes key issue urgently to be resolved hurrily.Organic/inorganic hybrid membrane is the inorganic particle formation mixed substrate membrane containing nano-grade molecular sieve that adulterates in organic polymer, thus makes membrane material with the advantage of both organic polymer and inorganic particle, becomes study hotspot in recent years.The inorganic particulate that can be used for hydridization comprises metal oxide, molecular sieve, CNT, Graphene, metal-organic framework materials etc.Wherein, metal-organic framework materials (MOFs) is emerging in recent years a kind ofly to be formed by self assembly by metal ion or metal cluster and organic ligand, has the porous material of periodically infinite network structure.There is because of it features such as porosity is high, aperture is adjustable, size tunable, become one of focus developing direction in hybridized film field.
The preparation method of current MOFs hybridized film mainly contains physical blending process and in situ synthesis.Physical blending process is in the preparation process of hybridized film, directly inorganic particulate and mixed with polymers is formed casting solution, then prepares hybridized film, and the phenomenons such as uneven, the easy reunion of dispersion can appear in inorganic particulate in the polymer; In situ synthesis is in film forming procedure, and inorganic particulate is in-situ preparation in the polymer, can solve dispersion problem preferably.Based on this, the invention provides a kind of method adopting diffuse in reverse direction primary reconstruction technology to prepare MOFs hybridized film, the hybrid particle that the diffusion barrier prepared by the method effectively can overcome MOFs easily appearance in growth course is reunited and dispersion inequality, the not easily problem such as heterogeneous nucleation, and preparation process is simple, film formation time is short, hybrid particle uniform particle sizes, has broad application prospects in MOFs hybridized film field.
Summary of the invention
The object of this invention is to provide a kind of diffuse in reverse direction primary reconstruction technology prepares MOFs/ polymer hybrid separating layer method in membrane surface.The metal ion formed required for MOFs and organic ligand are dissolved in the both sides being placed in basement membrane in respective solvent respectively, and by dissolution of polymer in the mixed solution containing metal ion and additive ammoniacal liquor, metal ion and organic ligand pass through the fenestra diffuse in reverse direction of basement membrane under the effect of the driving forces such as basement membrane pressure at both sides difference, thus form MOFs particle in membrane surface by coordination self assembly; And organic polymer is comparatively large due to strand, cannot be spread by basement membrane fenestra, thus be deposited on membrane surface.Therefore, the hydridization separating layer of MOFs/ polymer can be formed in membrane surface original position, separating layer structure can be regulated and controled by the concentration, difference in height, diffusion time etc. that control basement membrane both sides solution, thus form MOFs nano hybrid film, for the NF membrane separation field of Dye Removal.
The method comprises the following steps:
(1) pretreatment is carried out to porous basement membrane, make its surface charge, make it to combine with metal ion by electrostatic interaction;
(2) metal ion and organic ligand are dissolved in respectively in respective solvent and stir, standing and defoaming;
(3) be dissolved in by organic polymer in step (2) metal ion solution and stir, standing and defoaming obtains metal ion/polymer solution;
(4) metal ion/polymer and organic ligand solution are placed in step (1) basement membrane both sides respectively, make metal ion/polymer solution be positioned at basement membrane compacted zone side, make organic ligand solution be positioned at basement membrane supporting layer side;
(5) at 20 DEG C ~ 120 DEG C, at basement membrane both sides metal ion and organic ligand the driving force of one or more in density contrast, liquid level difference, concentration difference etc. effect under there is diffuse in reverse direction, form MOFs particle in membrane surface by coordination self assembly; Organic polymer is comparatively large due to molecular weight, not by fenestra diffusion, is deposited on membrane surface, thus forms the hybridized film separating layer of MOFs/ polymer in membrane surface; Wherein preferably by adjustment density contrast, liquid level difference, one or more driving force in concentration difference, the actuating speed of organic ligand is made to be greater than the actuating speed of metal ion;
(6) MOFs hybridized film prepared by step (5) is put into rapidly 20 DEG C ~ 120 DEG C convection oven inner dryings;
(7) repeat (4) ~ (6) step 0-20 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
The metal ion that can synthesize MOFs described is in the present invention selected from: Zn
2+, Co
2+, Cu
2+, Zr
2+in one or more, organic ligand is selected from: one or more in benzimidazole, methylimidazole, trimesic acid, terephthalic acid (TPA), and the polymer selected is can be used for polyelectrolyte prepared by NF membrane and dissaving polymer.
The molar concentration rate of the metal ion that step (2) is used and organic ligand is 1:(1 ~ 100).
Solvent is preferably organic solvent.Equimolar ammoniacal liquor is also added in metal ion solution side.
In the present invention, the perforated membrane of described business is milipore filter, microfiltration membranes, ceramic membrane, membrane material is polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, aluminium oxide etc., and described porous-membrane module is flat, and described perforated membrane aperture is 1 nanometer ~ 100 micron.
The principle of technical solution of the present invention is: both sides MOFs presoma being placed in respectively film, liquid level difference, concentration difference poor by regulating density, makes precursor solution generation diffuse in reverse direction, generates MOFs particle by chemical bonding effect.The hybrid particle that the diffusion barrier prepared by the method effectively can overcome the easily appearance in growth course of MOFs hybridized film is reunited and dispersion inequality, and MOFs is not easy to the problems such as heterogeneous nucleation.
Compared with prior art, the present invention has following advantage:
One, in MOFs hybridized film field, significantly shorten film formation time and casting solution can be recycled repeatedly, saved time and resource.
Two, can regulate MOFs granular size and pattern by changing density contrast, liquid level difference, concentration difference etc., easy to operate, process is simple.
Three, the diffusion barrier that prepared by the inventive method effectively can overcome hybrid particle that MOFs hybridized film easily occurs in growth course and to reunite and dispersion is uneven, MOFs is not easy to the problems such as heterogeneous nucleation.This method preparation process is simple, is applied to nanofiltration field, has the features such as rejection is high, flux is large, can be widely used in water treatment field.
Accompanying drawing explanation
Fig. 1 is that the ESEM of ZIF-11/PAN hybridized film characterizes, and wherein a and b represents different multiplication factors.
The X-ray diffraction of Fig. 2: preparation ZIF-11/PAN hybridized film characterizes.
Fig. 3 is the embodiment of the present invention special U-shaped funnel device schematic diagram used;
1 glass ground joint plug A, 2 glass ground joint plug B, the circular funnel of 3 short straight tube ground processed, 4 funnel clips, the circular funnel of the U-shaped ground of the curved formula of 5 long system.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail, but the present invention is not limited to following examples.
The special U-shaped funnel device that the present invention adopts is shown in accompanying drawing 3.Comprise glass ground joint plug A (1), glass ground joint plug B (2), the circular funnel (3) of short straight tube ground processed, funnel clip (4), the circular funnel (5) of the curved formula ground of long system, the leakage neck of the circular funnel (3) of its short-and-medium straight tube ground processed is straight pipe type, and it is relatively short, leaking neck port is ground, and funnel cavity volume port is circular, the leakage neck of the circular funnel (5) of the curved formula ground of long system is curved, and relatively long, and leaking neck port is ground, and funnel cavity volume port is circular, the funnel cavity volume port of the circular funnel (5) of the curved formula ground of long system and the funnel cavity volume port of the circular funnel (3) of short straight tube ground processed connect, make the U-shaped structure of device utilizing diffuse in reverse direction legal system for Flat Membrane, when the funnel cavity volume port of the circular funnel (5) of the curved formula ground of long system and the funnel cavity volume port of the circular funnel (3) of short straight tube ground processed connect, funnel clip (4) is adopted to be fixed, glass ground joint plug A (1) and glass ground joint plug B (2) is sealed in the leakage neck port of the circular funnel (3) of short straight tube ground processed, another is sealed in the circular funnel (5) of the curved formula ground of long system and leaks neck port.
The funnel cavity volume port of the circular funnel (5) of the curved formula ground of long system and the funnel cavity volume port of the circular funnel (3) of short straight tube ground processed are ground.
During use, the joint of the funnel cavity volume port of the circular funnel (5) of the curved formula ground of long system and the funnel cavity volume port of the circular funnel (3) of short straight tube ground processed places flat perforated substrate, the funnel cavity volume port of the circular funnel (5) of the curved formula ground of long system and the funnel cavity volume port of the circular funnel (3) of short straight tube ground processed is fixed to clamp with funnel clip (4), then leak neck port to the circular funnel (3) of short straight tube ground processed and circular funnel (5) tubular type of the U-shaped ground of the curved formula of long system and pour a certain amount of metal ion solution and organic ligand solution respectively into, with glass ground joint plug A (1) and glass ground joint plug B (2) sealing orifice respectively., concentration difference, liquid level difference poor by regulating density come diffusion rate and the reaction rate of finely regulating molecule, thus at difference flat perforated substrate superficial growth MOFs particle.
Embodiment 1
Adopt commercialization perforated membrane to be polyacrylonitrile (PAN) material, form is flat-plate ultrafiltration membrane, and molecular cut off is 20,000, and membrane area is 12.5cm
2, selected presoma metal ion is zinc acetate, and organic ligand is benzimidazole, and organic polymer is dissaving polymer W3000, and selected solvent is toluene, ethanol, and additive is ammoniacal liquor.
The preparation method of MOFs hybridized film:
(1) adopt conventional hydrolyzed modified technology, first polyacrylonitrile ultrafiltration film to be dipped in the NaOH solution of the 2mol/L of 65 DEG C 30 minutes, to be modified as the milipore filter of surface band carboxyl;
(2) zinc acetate and dissaving polymer are dissolved in obtained solution A in the mixed solution of toluene, ethanol and ammoniacal liquor, benzimidazole is dissolved in obtained solution B in ethanol, its molar concentration rate is zinc acetate: benzimidazole: ammoniacal liquor=1:2:2, and the concentration of dissaving polymer W3000 is 0.5%;
(3) adopt special U-shaped funnel, pretreated polyacrylonitrile ultrafiltration film is placed in one, solution A is poured into polyacrylonitrile ultrafiltration film separating layer side, solution B is poured into polyacrylonitrile ultrafiltration film supporting layer side;
(4) make B solution comparatively solution A exceed 4cm, produce liquid level difference, allow two kinds of precursor solution diffuse in reverse direction 2h in fenestra, form MOFs particle, rear rapid taking-up;
(5) 90 DEG C of baking oven inner drying 1h are put into rapidly after being taken out by the film of step (4);
(6), after taking out film, at room temperature place 24h, prepare MOFs hybridized film;
(7) repeat (4) ~ (6) step 0 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
(8) by the methyl blue water solution system of the MOFs hybridized film of above-mentioned preparation for separating of 0.1g/L, when operating pressure is 0.5MPa, 97.0% and 166.4L/m are respectively to the rejection of methyl blue and flux
2hMPa.
Embodiment 2
Adopt commercialization perforated membrane to be polyacrylonitrile (PAN) material, form is flat-plate ultrafiltration membrane, and molecular cut off is 20,000, and membrane area is 12.5cm
2, selected presoma metal ion is zinc acetate, and organic ligand is benzimidazole, and organic polymer is dissaving polymer W3000, and selected solvent is toluene, ethanol, and additive is ammoniacal liquor.
The preparation method of MOFs hybridized film:
(1) adopt conventional hydrolyzed modified technology, first polyacrylonitrile ultrafiltration film to be dipped in the NaOH solution of the 2mol/L of 65 DEG C 30 minutes, to be modified as the milipore filter of surface band carboxyl;
(2) zinc acetate and dissaving polymer are dissolved in obtained solution A in the mixed solution of toluene, ethanol and ammoniacal liquor, benzimidazole is dissolved in obtained solution B in ethanol, its mol ratio is zinc acetate: benzimidazole: ammoniacal liquor=1:2:2, and dissaving polymer W3000 concentration is 0.5%;
(3) adopt special U-shaped funnel, pretreated polyacrylonitrile ultrafiltration film be placed in one, solution B is poured into polyacrylonitrile ultrafiltration film separating layer side, solution A is poured into polyacrylonitrile ultrafiltration film supporting layer side,
(4) make solution A comparatively B solution exceed 4cm, produce liquid level difference, allow two kinds of precursor solution diffuse in reverse direction 2h in fenestra, form MOFs particle, rear rapid taking-up;
(5) 90 DEG C of baking oven inner drying 1h are put into rapidly after being taken out by the film of step (4);
(6), after taking out film, at room temperature place 24h, prepare MOFs hybridized film;
(7) repeat (4) ~ (6) step 1 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
(8) by the methyl blue water solution system of the film of above-mentioned preparation for separating of 0.1g/L, when operating pressure is 0.5MPa, 99.0% and 176.64L/m are respectively to the rejection of methyl blue and flux
2hMPa.
Embodiment 3
Adopt commercialization perforated membrane to be polyacrylonitrile (PAN) material, form is flat-plate ultrafiltration membrane, and molecular cut off is 20,000, and membrane area is 12.5cm
2, selected presoma metal ion is zinc acetate, and organic ligand is benzimidazole, and organic polymer is polyacrylic acid (PAA), and selected solvent is toluene, ethanol, and additive is ammoniacal liquor.
The preparation method of MOFs hybridized film:
(1) adopt conventional hydrolyzed modified technology, first polyacrylonitrile ultrafiltration film to be dipped in the NaOH solution of the 2mol/L of 65 DEG C 30 minutes, to be modified as the milipore filter of surface band carboxyl;
(2) zinc acetate and polyacrylic acid are dissolved in obtained solution A in the mixed solution of toluene, ethanol and ammoniacal liquor, benzimidazole is dissolved in obtained solution B in ethanol, its mol ratio is zinc acetate: benzimidazole: ammoniacal liquor=1:2:2, and polyacrylic acid concentration is 0.5%;
(3) adopt special U-shaped funnel, pretreated polyacrylonitrile ultrafiltration film is placed in one, solution A is poured into polyacrylonitrile ultrafiltration film separating layer side, solution B is poured into polyacrylonitrile ultrafiltration film supporting layer side; (4) make B solution comparatively solution A exceed 4cm, produce liquid level difference, allow two kinds of precursor solution diffuse in reverse direction 2h in fenestra, form MOFs particle, rear rapid taking-up (5) puts into rapidly 90 DEG C of baking oven inner drying 1h after being taken out by the film of step (4);
(6), after taking out film, at room temperature place 24h, prepare MOFs hybridized film;
(7) repeat (4) ~ (6) step 0 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
(8) by the methyl blue water solution system of the film of above-mentioned preparation for separating of 0.1g/L, when operating pressure is 0.5MPa, 97.89%, 296.64L/m is respectively to the rejection of methyl blue and flux
2hMPa.
Embodiment 4
Adopt commercialization perforated membrane to be polyacrylonitrile (PAN) material, form is flat-plate ultrafiltration membrane, and molecular cut off is 20,000, and membrane area is 12.5cm
2, selected presoma metal ion is zinc acetate, and organic ligand is benzimidazole, and organic polymer is polymine (PEI), and selected solvent is toluene, ethanol, and additive is ammoniacal liquor.
The preparation method of MOFs hybridized film:
(1) adopt conventional hydrolyzed modified technology, first polyacrylonitrile ultrafiltration film to be dipped in the NaOH solution of the 2mol/L of 65 DEG C 30 minutes, to be modified as the milipore filter of surface band carboxyl;
(2) zinc acetate and polymine are dissolved in obtained solution A in the mixed solution of toluene, ethanol and ammoniacal liquor, benzimidazole is dissolved in obtained solution B in ethanol, its mol ratio is zinc acetate: benzimidazole: ammoniacal liquor=1:2:2, and polymine concentration is 0.25%;
(3) adopt special U-shaped funnel, pretreated polyacrylonitrile ultrafiltration film is placed in one, solution A is poured into polyacrylonitrile ultrafiltration film separating layer side, solution B is poured into polyacrylonitrile ultrafiltration film supporting layer side;
(4) make B solution comparatively solution A exceed 4cm, produce liquid level difference, allow two kinds of precursor solution diffuse in reverse direction 2h in fenestra, form MOFs particle, rear rapid taking-up;
(5) 90 DEG C of baking oven inner drying 1h are put into rapidly after being taken out by the film of step (4);
(6), after taking out film, at room temperature place 24h, prepare MOFs hybridized film;
(7) repeat (4) ~ (6) step 2 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
(8) by the methyl blue water solution system of the film of above-mentioned preparation for separating of 0.1g/L, when operating pressure is 0.5MPa, 98.21% and 224.24L/m are respectively to the rejection of methyl blue and flux
2hMPa.
Embodiment 5
Adopt commercialization perforated membrane to be polyacrylonitrile (PAN) material, form is flat-plate ultrafiltration membrane, and molecular cut off is 20,000, and membrane area is 12.5cm
2, selected presoma metal ion is cobalt acetate, and organic ligand is benzimidazole, and organic polymer is dissaving polymer W3000, and selected solvent is toluene, ethanol, and additive is ammoniacal liquor.
The preparation method of MOFs hybridized film:
(1) adopt conventional hydrolyzed modified technology, first polyacrylonitrile ultrafiltration film to be dipped in the NaOH solution of the 2mol/L of 65 DEG C 30 minutes, to be modified as the milipore filter of surface band carboxyl;
(2) cobalt acetate and dissaving polymer are dissolved in obtained solution A in the mixed solution of toluene, ethanol and ammoniacal liquor, benzimidazole is dissolved in obtained solution B in ethanol, its mol ratio is cobalt acetate: benzimidazole: ammoniacal liquor=1:2:2, and the concentration of dissaving polymer W3000 is 0.5%;
(3) adopt special U-shaped funnel, pretreated polyacrylonitrile ultrafiltration film is placed in one, solution A is poured into polyacrylonitrile ultrafiltration film separating layer side, solution B is poured into polyacrylonitrile ultrafiltration film supporting layer side;
(4) make B solution comparatively solution A exceed 4cm, produce liquid level difference, allow two kinds of precursor solution diffuse in reverse direction 2h in fenestra, form MOFs particle, rear rapid taking-up;
(5) 90 DEG C of baking oven inner drying 1h are put into rapidly after being taken out by the film of step (4);
(6), after taking out film, at room temperature place 24h, prepare MOFs hybridized film;
(7) repeat (4) ~ (6) step 0 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
(8) by the methyl blue water solution system of the MOFs hybridized film of above-mentioned preparation for separating of 0.1g/L, when operating pressure is 0.5MPa, 99.7% and 104.4L/m are respectively to the rejection of methyl blue and flux
2hMPa.
Claims (7)
1. a preparation method for diffuse in reverse direction primary reconstruction MOFs NF membrane, is characterized in that, comprise the following steps:
(1) pretreatment is carried out to porous basement membrane, make its surface charge, make it to combine with metal ion by electrostatic interaction;
(2) metal ion and organic ligand are dissolved in respectively in respective solvent and stir, standing and defoaming;
(3) be dissolved in by organic polymer in step (2) metal ion solution and stir, standing and defoaming obtains metal ion/polymer solution;
(4) metal ion/polymer and organic ligand solution are placed in step (1) basement membrane both sides respectively, make metal ion/polymer solution be positioned at basement membrane compacted zone side, make organic ligand solution be positioned at basement membrane supporting layer side;
(5) at 20 DEG C ~ 120 DEG C, at basement membrane both sides metal ion and organic ligand the driving force of one or more in density contrast, liquid level difference, concentration difference etc. effect under there is diffuse in reverse direction, form MOFs particle in membrane surface by coordination self assembly; Organic polymer is comparatively large due to molecular weight, not by fenestra diffusion, is deposited on membrane surface, thus forms the hybridized film separating layer of MOFs/ polymer in membrane surface; Wherein preferably by adjustment density contrast, liquid level difference, one or more driving force in concentration difference, the actuating speed of organic ligand is made to be greater than the actuating speed of metal ion;
(6) MOFs hybridized film prepared by step (5) is put into rapidly 20 DEG C ~ 120 DEG C convection oven inner dryings;
(7) repeat (4) ~ (6) step 0-20 time, form single or multiple lift MOFs hybridized film separating layer in porous membrane surface.
2. according to the method for claim 1, it is characterized in that, the metal ion of synthesis MOFs is selected from: Zn
2+, Co
2+, Cu
2+, Zr
2+in one or more, organic ligand is selected from: one or more in benzimidazole, methylimidazole, trimesic acid, terephthalic acid (TPA).
3. according to the method for claim 1, it is characterized in that, the polymer selected is can be used for polyelectrolyte prepared by NF membrane and dissaving polymer.
4. according to the method for claim 1, it is characterized in that, the molar concentration rate of the metal ion that step (2) is used and organic ligand is 1:(1 ~ 100).
5. according to the method for claim 1, it is characterized in that, solvent is preferably organic solvent.
6. according to the method for claim 1, it is characterized in that, in metal ion solution side, also add equimolar ammoniacal liquor.
7. according to the method for claim 1, it is characterized in that, perforated membrane is milipore filter, microfiltration membranes, ceramic membrane, and membrane material is polyacrylonitrile, polysulfones, polyether sulfone, Kynoar or aluminium oxide, described porous-membrane module is flat, described perforated membrane aperture is 1 nanometer ~ 100 micron.
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