CN115193271A - Pervaporation composite membrane with ultrathin separation active layer and preparation method thereof - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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Abstract
The invention discloses a pervaporation composite membrane with an ultrathin separation active layer and a preparation method thereof. The invention modifies the ceramic matrix by metal organic framework Materials (MOFs), thereby creating better reaction conditions for interfacial polymerization reaction to prepare the composite membrane. Compared with the prior art, the invention not only can effectively reduce the thickness of the effective separation skin layer of the pervaporation composite membrane so as to achieve the purposes of reducing membrane resistance and improving membrane performance, but also creates opportunities for carrying out interfacial polymerization reaction on a ceramic and other micron-sized macroporous substrate. The invention not only simplifies the preparation process of the thin film composite film, but also saves the preparation cost.
Description
Technical Field
The invention relates to a preparation method of an ultrathin active layer composite membrane, in particular to a preparation method of an MOFs modified middle layer on a ceramic base membrane, and then interfacial polymerization is carried out to generate an active layer.
Technical Field
In order to realize economic sustainable development, the Pervaporation (PV) technology has been considered as a new liquid mixture membrane separation technology rapidly developed in recent years, which has the advantages of high efficiency, energy saving, simple process, etc., compared to the conventional distillation, extraction and absorption separation technologies (Carbon, 123 (2017) 660-667, cn111036089a). The method is mainly used for removing the near-boiling residues, the constant-boiling residues, the trace water and the trace organic matters in the water which are difficult to treat in the traditional process. Pervaporation technology has been widely accepted due to its advantages in energy saving, environmental protection, etc., and is a chemical separation technology with great development prospects (j.membr.sci., 318 (2008), 5-37). The method is possible to replace the traditional operation technologies such as rectification adsorption crystallization with complex process and high energy consumption, and becomes one of the key points of novel separation technologies in the fields of future chemical engineering, environmental protection and the like (prog.polym.sci, 57 (2016) 1-31).
Inorganic membranes and organic membranes in membrane technology have advantages and disadvantages compared to each other (sep. Purif. Technol.,234 (2020), 116116). Although low cost is a significant advantage, organic pervaporation membranes generally have the disadvantages of poor stability and low flux in practical applications. The inorganic pervaporation membrane has complicated preparation process and high price due to difficult pore construction. In general, thin film composite membranes (TFCs) have been produced which have an inorganic ceramic-based membrane as the support and an organic active skin layer as the effective separation layer. TFC membranes are typically composed of a support and a polyamide layer (PA) (CN 104394968 a). Specifically, the ultra-thin polyamide selective layer provides a certain guarantee for effective membrane separation performance, and the porous support layer provides a certain guarantee for the operational stability of the membrane.
J. membr. Sci,448 (2013) 34-43, proposes deposition of polydopamine and polyethyleneimine on ceramic supports for improving the affinity of ceramic-based membranes and organic PA layers for the preparation of high performance isopropanol dehydrated TFC membranes (flux 6.0 kg/m) 2 h; separation factor: 1400).
J. Membr. Sci,576 (2019) 26-35, proposing the preparation of a titanium dioxide intermediate layer on a ceramic-based membrane for the preparation of TFC pervaporation membranes, the membrane prepared therein being excellent in isopropanol dehydration separation effect (flux of 6.4 kg/m) 2 h; separation factor: 12000).
The invention aims to utilize the characteristics of MOFs material porous structure and easy shape regulation and control based on the research contents to use the MOFs material porous structure as a middle layer modified material for preparing a TFC membrane on a ceramic base membrane.
Disclosure of Invention
The invention mainly aims to provide a pervaporation composite membrane with an ultrathin separation active layer and a preparation method thereof. The TFC membrane takes a macroporous ceramic base membrane as a support body and takes polyamide generated by interfacial polymerization as an active separation skin layer. The MOFs material is designed to be used as the middle layer of the support body and the active PA layer, and a good reaction environment is provided for the interfacial polymerization on the base film to generate the PA active layer. The purpose of the operation is to make the TFC membrane have the stability provided by the ceramic base membrane and the excellent separation performance provided by the ultrathin PA layer.
In order to achieve the purpose, the invention adopts the technical scheme that:
a pervaporation composite membrane with an ultrathin separation active layer is prepared from a ceramic membrane surface modification intermediate layer and a surface ultrathin effective separation layer; the middle layer is prepared from modified Metal Organic Frameworks (MOFs), and the ultrathin effective separation layer is a polyamide layer generated by interfacial polymerization.
According to the pervaporation composite membrane with the ultrathin separation active layer, the MOFs middle layer is modified through polymer modification or MOFs shape regulation.
Further, the modified Metal Organic Frameworks (MOFs) material is formed by directly carrying out in-situ growth on a ceramic base film by utilizing hydrophilic modification of an organic polymer material to serve as an intermediate layer and changing the hydrophilic modification into a sheet-shaped structure by regulating and controlling synthesis conditions, and is deposited on the ceramic base film by a vacuum filtration method.
The organic polymer material is polyvinyl alcohol, chitosan, sodium alginate or poly-p-styrene sulfonic acid.
According to the pervaporation composite membrane with the ultrathin separation active layer, the thickness of the polyamide selective layer is less than 500nm.
According to the pervaporation composite membrane with the ultrathin separation active layer, in the interfacial polymerization reaction, a water-phase active substance for generating a polyamide layer is a short-chain linear amine monomer (such as ethylenediamine, propylenediamine and the like), and an organic-phase active substance is trimesoyl chloride.
The invention also provides a preparation method of the pervaporation composite membrane with the ultrathin separation active layer, which takes a ceramic base membrane as a support body, an MOFs material as an intermediate layer and a surface interface polymeric polyamide layer as the structural characteristic of an effective separation skin layer, and comprises the following steps:
s1, preparing the cleaning of the ceramic hollow fiber base membrane and preparing MOFs synthetic solution by a phase inversion-sintering process coupling flow in a laboratory.
S2, interfacial growth (repeated growth by circularly dipping oil and water) of the MOFs middle layer on the ceramic base film or suction filtration and deposition process of the MOFs nanosheet on the ceramic base film.
S3, carrying out interfacial polymerization on the surface of the prepared MOFs intermediate layer to prepare an effective separation cortex, wherein in the preparation process, the water phase monomer is Ethylenediamine (EDA) or propylenediamine, and the oil phase monomer is trimesoyl chloride (TMC).
S4, after preparing the PA effective separation skin layer, placing the membrane in an air environment or a 75 ℃ oven for 5min to ensure that the interfacial polymerization reaction is complete and complete, thereby obtaining the pervaporation composite membrane with the MOFs middle layer ultrathin PA effective separation skin layer.
The preparation of the ligand solution of the MOFs, as described in step S2, depends on the synthesis method of the MOFs and the morphology of the MOFs required. The selected MOFs materials are ZIF series as an example, and the synthesis method comprises in-situ synthesis on the surface of the ceramic base film and synthesis of temperature-controlled ZIF nanosheets.
In the step S2, the solution preparation scheme for synthesizing the modified ZIF-8 on the surface of the in-situ ceramic-based membrane is as follows: dissolving zinc nitrate in the aqueous solution and adding poly (styrene-co-styrene) sulfonic acid (PSS) for modification (the concentration of the zinc nitrate solution is 8.6mg/ml, the concentration of the PSS is 10-200mg/ml, and the preferred concentration of the PSS is 35 mg/ml); 2-methylimidazole is dissolved in n-hexane solution and methanol and ethanol are added as a co-solvent (2-methylimidazole solution at 9.5mg/ml, methanol and ethanol concentration 1.0-5.0ml/100ml, preferably 2.5ml/100ml n-hexane).
In the step S2, the synthesis conditions of the ZIF nanosheet are as follows: preparing a zinc nitrate solution (29 mg/ml) and a 2-methylimidazole solution (68.4 mg/ml) in a room-temperature environment, then quickly adding the 2-methylimidazole solution into the zinc nitrate solution, stirring for 1 hour, repeatedly centrifuging the suspension (10000rpm, 10 minutes), washing with deionized water for 3 times, and vacuum-drying in an oven at 60 ℃ for 12 hours to obtain the ZIF-L nanosheets.
And S2, generating the modified ZIF-8 on the surface in-situ interface of the ceramic base film, immersing the ceramic base film in a zinc nitrate solution, taking out the ceramic base film, immersing the ceramic base film in a 2-methylimidazole solution, and reacting the two solutions to generate the modified ZIF-8.
In the step S2, the vacuum pressure is 10-30KPa, preferably 20KPa, in the process of carrying out suction filtration and deposition on the outer surface of the ceramic base film by the ZIF-L nano sheet.
In the step S3, when preparing the EDA solution, water is used as a solvent, and the concentration is 0.5-3.0wt%; when TMC solution is prepared, n-hexane is used as a solvent, and the concentration is 0.5-2.0wt%.
In the step S3, the interface polymerization process includes immersing the ceramic-based membrane with the MOFs intermediate layer in an amine monomer aqueous solution, taking out the ceramic-based membrane, and immersing the ceramic-based membrane in a TMC oil phase solution to form an ultrathin polyamide layer on the surface.
According to the pervaporation composite membrane with the ultrathin separation active layer, the organic polymer material is added into a ligand solution in a MOFs synthetic solution.
According to the pervaporation composite membrane with the ultrathin separation active layer, the MOFs nanosheet is of a sheet structure and serves as an intermediate layer, and good reaction conditions are provided for interfacial polymerization to generate the active layer.
The invention firstly proposes that the modified MOFs material is used as the intermediate layer of the pervaporation composite membrane, provides better generation conditions for the preparation of an ultrathin separation active layer on an inorganic support body, and particularly creates better conditions for preparing a TFC pervaporation membrane by interfacial polymerization on a ceramic support body.
Compared with other methods, the method has the following advantages:
(1) ZIF-8 is one of the MOFs materials that is most suitable for separating aqueous mixtures of ethanol because the pore size is reported in the literature to lie between the molecular dynamic diameters of water and ethanol.
(2) The construction of the intermediate layer provides possibility for generating an ultrathin effective active PA layer on the macroporous ceramic base film by direct interfacial polymerization.
(3) The protection of the polyamide ultrathin layer opens a potential development application type for MOFs materials in the field of liquid mixture membrane separation.
(4) The composite membrane organic PA selective layer modified by the middle MOFs and the ceramic inorganic support have better affinity (see attached figures 3 and 6).
(5) The invention not only simplifies the preparation process of the thin film composite film, but also saves the preparation cost.
It is inevitable that in practical applications, the intermediate MOFs layer will undergo partial hydrolysis, but because of the manufacturing process, a perfect separation skin layer is formed on the basis of the intermediate layer constructed from MOFs. Meanwhile, because the TFC membrane adopts an internal pressure type operation mode, the phenomenon that the membrane flux is slightly increased is possible, but the separation performance of the middle MOFs layer is not influenced by partial hydrolysis.
Description of the drawings:
FIG. 1 is a drawing of a ZIF-8 for surface growth modification of a ceramic-based membrane in pervaporation TFC composite membrane preparation.
FIG. 2 is a diagram of a process for preparing a PA layer on a ZIF-8 surface in situ formed by pervaporation TFC composite membranes.
FIG. 3 is a cross-sectional view of a pervaporation TFC membrane resulting from in situ generation of an intermediate layer of MOFs.
FIG. 4 is a drawing of a ceramic-based membrane surface suction filtration nanosheet in pervaporation TFC composite membrane preparation.
FIG. 5 is a diagram of a PA layer prepared on the surface of a vacuum filtration ZIF-L nanosheet by a pervaporation TFC composite membrane.
FIG. 6 is a cross-sectional view of a pervaporation TFC membrane obtained from MOFs nanosheets as the intermediate layer.
FIG. 7 is a graph comparing the dehydration performance of membrane pervaporation ethanol for different types of preparation methods.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is further described below with reference to the accompanying drawings and embodiments:
example 1
The preparation method of the TFC composite membrane with the in-situ synthesized modified ZIF-8 as the middle layer comprises the following steps:
s1, ultrasonically cleaning a hollow fiber composite membrane prepared in a laboratory by using deionized water, and drying the hollow fiber composite membrane in an oven for later use.
S2, preparing zinc nitrate and 2-methylimidazole ligand solution for synthesizing the modified ZIF-8. The preparation method comprises the following steps: zinc nitrate hexahydrate is added to deionized water and modified with a hydrophilic polymer, poly (p-styrenesulfonic acid), as an adherent. Weighing a proper amount of 2-methylimidazole, placing the 2-methylimidazole in a conical flask, adding a small amount of methanol (the concentration of each n-hexane is 2.5ml/100 ml) to dissolve the 2-methylimidazole, and adding an n-hexane solution to serve as an oil phase ligand solution.
S3, firstly, soaking the ceramic-based membrane in a polymer-modified zinc nitrate aqueous solution, and then soaking the ceramic-based membrane in a 2-methylimidazole n-hexane solution. So that the modified ZIF-8 particles are synthesized in situ on the outer surface of the ceramic base film. And drying the sample in an oven for 2 hours to obtain a layer of modified ZIF-8 attached sample surface, wherein the appearance is shown in an electron microscope picture 1.
And S4, carrying out interfacial polymerization on the surface of the sample in the S3 to prepare the ultrathin active layer TFC composite membrane. It was placed in an EDA solution (0.5-3.0 wt% concentration) and then in a TMC n-hexane solution (0.5-2.0 wt% concentration). The surface of the polyamide film is subjected to interfacial polymerization reaction to grow a PA separation layer, the appearance is shown as electron microscope pictures 2 (film surface) and 3 (film section), and the thickness of the polyamide layer is 117nm. The topography of the ceramic-based film is completely covered by the PA layer. And the prepared PA active layer is tightly attached to the surface of the ceramic base film, as shown in an electron microscope picture 3.
Example 2
The preparation method of the TFC composite membrane with the ZIF-L nanosheet as the middle layer comprises the following steps of:
s1, ultrasonically cleaning a hollow fiber composite membrane prepared in a laboratory by using deionized water, and drying the hollow fiber composite membrane in an oven for later use.
S2, preparing zinc nitrate and 2-methylimidazole ligand solution for synthesizing the ZIF-L nanosheet. The preparation method comprises the following steps: zinc nitrate hexahydrate was dissolved in deionized water to prepare a zinc nitrate solution (concentration: 29 mg/ml). 2-methylimidazole was weighed and added to deionized water to dissolve it as a 2-methylimidazole ligand solution (concentration: 68.4 mg/ml)
S3, adding the zinc nitrate solution into the 2-methylimidazole solution at room temperature, stirring for 1 hour, centrifuging at 10000rpm, washing with deionized water for three times, and drying in a vacuum oven. Obtaining the ZIF-L nano sheet.
And S4, re-dispersing the prepared ZIF-L nanosheets into an aqueous solution, and performing suction filtration on the ZIF-L nanosheets to the outer surface of the ceramic base film by using a suction filtration method under the pressure of a vacuum pump of 20KPa, wherein the morphology is as shown in an electron microscope picture 4.
And S5, carrying out interfacial polymerization on the surface of the sample in the S4 to prepare the ultrathin active layer TFC composite membrane. It was placed in an EDA solution (0.5-3.0 wt% concentration) and then in a TMC n-hexane solution (0.5-2.0 wt% concentration). A PA separation layer grows on the surface of the polyamide film, the appearance of the PA separation layer is shown as electron microscope pictures 5 and 6, and the thickness of the polyamide layer is 435nm. The topography of the ceramic-based film is completely covered by the PA layer. And the prepared PA active layer is tightly attached to the surface of the ceramic base film, as shown in an electron microscope picture 6.
FIG. 7 is a graph showing the comparison of the properties of a PA/Ceramic composite membrane prepared by interfacial polymerization without preparing a MOFs intermediate layer, a PA/ZIF-P/Ceramic membrane prepared by using a polymer modified ZIF material in example 1, and a PA/ZIF-L/Ceramic membrane prepared by suction filtration of a ZIF-L nanosheet prepared by morphology modification in example 2; as can be seen from the figure, the membrane flux after the MOFs intermediate layer is modified is slightly reduced, but the separation factor is almost improved by 4-6 times, and the performance is obviously improved.
Claims (10)
1. A pervaporation composite membrane with an ultrathin separation active layer is characterized by being prepared from a ceramic membrane surface modification intermediate layer and a surface ultrathin effective separation layer; the middle layer is prepared from modified Metal Organic Frameworks (MOFs), and the ultrathin effective separation layer is a polyamide layer generated by interfacial polymerization.
2. The pervaporation composite membrane with an ultrathin separation active layer according to claim 1, wherein the middle layer of the MOFs is modified by polymer modification or MOFs morphology control.
3. The pervaporation composite membrane with an ultrathin separation active layer according to claim 1, wherein the modified Metal Organic Frameworks (MOFs) material is directly grown in situ on a ceramic base membrane as an intermediate layer by hydrophilic modification of an organic polymer material and is deposited on the ceramic base membrane by a vacuum filtration method by changing the synthetic conditions into a sheet structure.
4. The pervaporation composite membrane with an ultrathin separation active layer according to claim 3, wherein the organic polymer material is polyvinyl alcohol, chitosan, sodium alginate or poly-p-styrenesulfonic acid.
5. A pervaporation membrane with an ultra thin separation active layer according to claim 1, wherein the thickness of the polyamide layer is below 500nm.
6. The pervaporation composite membrane with an ultrathin separation active layer according to claim 1, wherein in the interfacial polymerization reaction, the aqueous phase active substance for generating the polyamide layer is a short-chain linear amine monomer, and the organic phase active substance is trimesoyl chloride.
7. A method for preparing the pervaporation composite membrane with the ultrathin separation active layer according to any of claims 1 to 6, comprising the following steps:
s1, cleaning a ceramic hollow fiber base membrane prepared by a phase inversion-sintering process coupling flow in a laboratory and preparing an MOFs synthetic solution;
s2, in-situ growth of an interface of the MOFs middle layer on the ceramic base film or a suction filtration deposition process of the MOFs nanosheet on the ceramic base film;
s3, carrying out interfacial polymerization on the surface of the prepared MOFs intermediate layer to prepare an effective separation skin layer, soaking the ceramic base film with the MOFs intermediate layer in an amine monomer aqueous solution, taking out the ceramic base film and then soaking the ceramic base film in a TMC organic phase solution to generate an ultrathin polyamide layer on the surface; in the preparation process, the water-phase amine monomer is ethylenediamine or propylenediamine, and the organic monomer is trimesoyl chloride (TMC);
and S4, after preparing the PA effective separation skin layer, placing the membrane in an air environment or a baking oven to ensure that the interfacial polymerization reaction is complete and complete, thus obtaining the pervaporation composite membrane with the MOFs middle layer ultrathin PA effective separation skin layer.
8. The method for preparing a pervaporation composite membrane with an ultra-thin separation active layer according to claim 7, wherein in step S2, when an interfacial growth method is adopted, the solution formulation scheme for synthesizing the modified ZIF-8 is: dissolving zinc nitrate in the aqueous solution, and adding poly (styrene-co-styrene) sulfonic acid (PSS) for modification, wherein the concentration of the zinc nitrate solution is 8.6mg/ml, and the concentration of the PSS is 10-200mg/ml: dissolving 2-methylimidazole in n-hexane solution, and adding a small amount of methanol and ethanol as a cosolvent, wherein the concentration of the 2-methylimidazole solution is 9.5mg/ml, and the concentration of the methanol and the concentration of the ethanol are respectively 1.0-5.0ml/100ml of n-hexane;
in the step S2, when a ZIF nanosheet suction filtration method is adopted, the synthesis scheme of the ZIF nanosheet is as follows: preparing a zinc nitrate solution with the concentration of 29mg/ml and a 2-methylimidazole solution with the concentration of 68.4mg/ml in a room temperature environment, then quickly adding the 2-methylimidazole solution into the zinc nitrate solution, stirring, repeatedly centrifuging the suspension, washing with deionized water, and drying in a vacuum oven to obtain the ZIF-L nanosheet.
9. The method for preparing the pervaporation composite membrane with the ultrathin separation active layer according to claim 7, wherein in the step S2, the vacuum pressure is 10-30KPa during the process of performing suction filtration deposition on the ZIF-L nanosheet on the outer surface of the ceramic base membrane.
10. The method of claim 7, wherein in step S3, when preparing the EDA solution, water is used as the solvent, and the concentration of the solvent is 0.5-3.0wt%; when TMC solution is prepared, n-hexane is used as a solvent, and the concentration of the n-hexane is 0.5-2.0wt%.
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