A phenolic-based non-supporting meso-microporous carbon membrane and a preparation method and application thereof

Abstract

The application provides a phenolic-based non-supporting mesoporous-microporous carbon membrane and a preparation method and application thereof. The method comprises the following steps: reacting raw materials including phenolic compounds, amine compounds, aldehyde compounds and surfactants to obtain a resin precursor; performing low-temperature aging forming on the resin precursor to obtain an organic membrane; and performing high-temperature carbonization on the organic membrane. The application provides a fast, simple and efficient carbon membrane preparation method, and the prepared carbon membrane has uniform and adjustable pore structures.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of carbon membranes, in particular to a phenolic-based non-supported meso-microporous carbon membrane and a preparation method and application thereof. BACKGROUND

[0002] Porous carbon materials have been widely used in adsorption, catalysis, electrochemistry and energy environment due to their developed pore structure, good chemical stability, corrosion resistance and high electrical conductivity. Carbon membranes, as a new type of inorganic separation membrane, have high specific surface area, high thermal stability, biocompatibility and renewable advantages, and can distinguish gas molecular size due to their good pore structure, especially suitable for separating small molecules in gas mixture or separating isomers with smaller kinetic radius in isomer mixture, showing high separation selectivity and permeability.

[0003] With the increasing strictness of environmental protection and the need for green development, the permeability and selectivity of carbon membranes are also increasingly improved. Researchers have made every effort to improve the above two properties. For example, Kita et al. used porous aluminum with an average pore size of 1 um and a porosity of 50% as a support, coated phenolic resin solution on it, and then dried and carbonized to obtain carbon membranes. It was found that the coating times had a great influence on the gas permeability and selectivity, and the effect was better after coating 3 times. Centeno and Fuertes et al. coated phenolic resin solution on a carbon support with an average pore size of 0.5 um to prepare carbon membranes with molecular sieving effect. In addition, Kolar et al. used thermosetting phenolic resin as raw material to prepare a flat carbon support, and then coated phenolic resin solution on it, but there was no selectivity. It can be seen that it is still a great challenge to prepare porous carbon materials with specific pore structure and morphology.

[0004] Good permeability and selectivity are often closely related to regular and ordered mesoporous structure, so the research and preparation of ordered mesoporous carbon membranes are increasingly important and have attracted widespread attention from many scholars. Homogeneous carbon membranes have great research value and room for improvement due to their simple preparation process, controllable pore structure and relatively less research on non-supported carbon membranes. Flat carbon membranes are difficult to mass-produce, and the production cost is difficult to reduce, so it is still difficult to realize industrial application. In contrast, single-channel tube membranes, multi-channel tube membranes, capillary membranes and improved barrel membranes can be mass-produced and are expected to realize industrial application as soon as possible, so they have very attractive application prospects.

[0005] At present, the main methods for preparing carbon membranes are soft template method and hard template method. Compared with the hard template method, the soft template method uses soft structure molecules or molecular aggregates as template agents, such as cationic, anionic and non-ionic surfactants and their aggregates. First, micellar structures are formed in the synthesis solution, then under suitable acid or alkali conditions, the micellar structures form an intermediate phase with oxygen-containing carbon precursors through hydrogen bonding and / or coulomb force, and finally, the intermediate phase is carbonized by high-temperature heat treatment (also known as pyrolysis or calcination) to remove the template agent to form a pore structure, and finally a carbon membrane is obtained. It can be seen that the shape of the carbon membrane prepared by the soft template method is diverse and easy to construct, the operation is convenient, the process is simple, and the morphology of the carbon membrane can be controlled. Moreover, the carbon material has ordered pore channels, adjustable pore size, high thermal stability and high specific surface area, which is an ideal method for preparing carbon membranes.

[0006] In the preparation process of carbon membranes, the selection of raw materials is crucial. Phenolic resin (PFR) is an ideal precursor for preparing porous carbon membranes due to its wide source, low price and high carbon content.

[0007] Zhou and Centenod et al. (Functional Materials 2015 6:06026) both used PFR as a precursor, used the dip-coating method and the impregnation method, and used porous ceramic tubes or porous resin carbon materials as a support to prepare selective carbon membranes with developed pore structure, high specific surface area and few defects.

[0008] Chinese patent CN1821182A discloses a method for preparing mesoporous carbon materials. Zhao et al. prepared mesoporous carbon by solvent evaporation self-assembly. Although the precursor in the claim is one or more of phenolic resin, polyimide, polypyrrole, polyacrylamide, polyacrylonitrile or polyvinylpyridine, phenolic resin PFR is selected in all 17 preparation examples.

[0009] Therefore, with the in-depth study of the synthesis route and assembly mechanism of the soft template method, the use of PFR, which is inexpensive and easy to prepare, as a precursor for the preparation of non-supported carbon membranes by the soft template method will become a new research method or new preparation means for multifunctional carbon membranes. SUMMARY

[0010] In view of the defects of the existing preparation process, such as long synthesis time, high energy consumption, difficulty in surface chemical regulation, complicated carbon membrane forming, and poor permeability due to few mesopores, the present application provides a fast, simple and efficient phenolic-based non-supported mesoporous-microporous carbon membrane and a preparation method thereof.

[0011] The application adopts phenolic compounds, amine compounds and aldehyde compounds as raw materials, generates a crosslinked network of phenolic aldehyde resin, i.e. benzoxazine-phenolic aldehyde resin resin precursor, under the structure guiding effect of a template agent, wherein organic amine participates in catalytic copolymerization, promotes the formation of regular mesoporous structures, introduces nitrogen-containing functional groups, not only quickly forms (less than 30 minutes) regular mesoporous organic polymers (conventional methods need 10-100 hours), but also directly dries the obtained polymer in air, and through conventional high-temperature heat treatment (carbonization), mesoporous-microporous carbon membranes are obtained, thereby providing a brand-new fast, simple and efficient carbon membrane preparation method, and the prepared carbon membrane has uniform and adjustable pore structures.

[0012] One of the purposes of the application is to provide a preparation method of a phenolic aldehyde-based non-support mesoporous-microporous carbon membrane, comprising the following steps:

[0013] (1) reacting raw materials containing phenolic compounds, amine compounds, aldehyde compounds and surfactants to obtain a resin precursor;

[0014] (2) aging and forming the resin precursor at low temperature to obtain a porous organic membrane;

[0015] (3) carbonizing the organic membrane at high temperature to obtain a mesoporous-microporous carbon membrane.

[0016] In the preparation method, the phenolic compound is preferably at least one of phenol, m-dihydroxybenzene and m-trihydroxybenzene.

[0017] In the preparation method, the amine compound is preferably at least one of ethylenediamine, hexanediamine, propylenediamine and butanediamine.

[0018] In the preparation method, the surfactant is preferably at least one of F127, P123, F108 and B50.

[0019] In the preparation method, the aldehyde compound is preferably at least one of formaldehyde, polyformaldehyde and furfural.

[0020] In the preparation method, the molar ratio of the phenolic compound to the aldehyde compound is (1:1)-(1:3), and the preferred molar ratio is (1:1.5)-(1:3).

[0021] In the preparation method, the molar ratio of the phenolic compound to the amine compound is (1:0.005)-(1:0.05), and the preferred molar ratio is (1:0.005)-(1:0.01).

[0022] The molar ratio of the phenolic compound to the surfactant in the preparation method is (1:0.004)-(1:0.02), and the preferred molar ratio is (1:0.004)-(1:0.01).

[0023] The solvent in the preparation method is at least one selected from water and ethanol, and preferably a mixed solvent of water and ethanol.

[0024] In the preparation method, preferably, step (1) comprises:

[0025] (1-1) dissolving the phenolic compound in the solvent; (1-2) adding the surfactant and dissolving completely; (1-3) adding the amine compound; (1-4) quickly adding the aldehyde compound;

[0026] The order of step (1-3) and step (1-4) can be interchanged.

[0027] In the preparation method, preferably, in step (2), the sol-like mixed solution of the resin precursor obtained in step (1) is loaded into a mold and defoaming is performed, and then low-temperature aging is performed.

[0028] The mold is preferably any one of a single-channel tubular film mold, a multi-channel tubular film mold, a plate film mold, a barrel film mold, and a capillary film mold.

[0029] The defoaming method can be at least one selected from vibration, ultrasonic, and long-time static stop, and the selected defoaming method is ultrasonic defoaming.

[0030] In the preparation method, in step (2), the temperature for low-temperature aging is 60-110℃, and preferably 70-100℃; and the time for low-temperature aging is 15min-12h, and preferably 30min-8h.

[0031] In the preparation method, in step (2), after low-temperature aging and demolding, the step of drying the organic film can be further included.

[0032] In the preparation method, in step (3), high-temperature carbonization comprises the following steps: under the condition of inert gas, the temperature is increased from room temperature to 150-450℃ at a rate of 0.5-3℃ / min, the temperature is kept constant for 30min-2h, the temperature is continuously increased to 500-1000℃ at a rate of 1-5℃ / min, and the temperature is kept constant for 60min-5h.

[0033] The method utilizes phenolic compounds, amine compounds, and aldehyde compounds as raw materials, generates a cross-linked network mesoporous organic film of phenolic aldehyde resin under the guidance of a surfactant (soft template) in a solution, and prepares a non-supported mesoporous-microporous carbon film through high-temperature carbonization, so that a porous carbon film including mesoporous and microporous structures can be quickly, simply, and efficiently prepared.

[0034] The second object of the present application is to provide the phenolic-based non-supported meso-microporous carbon membrane prepared by the preparation method.

[0035] The meso-microporous carbon membrane of the present application contains a large amount of mesopores in terms of pore structure, thereby facilitating the improvement of the separation efficiency (flux) of the carbon membrane. The absolute amount of the mesopores is more than 50% of the total amount of meso-micropores.

[0036] The third object of the present application is to provide the application of the phenolic-based non-supported meso-microporous carbon membrane prepared by the preparation method in the separation of CO2 / N2.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] 1) The phenolic compound, amine compound and aldehyde compound are used as reactants, and the raw materials are conventional chemicals. In particular, the phenolic compound is widely available, low in price and easy to obtain.

[0039] 2) The non-supported carbon membrane is used, the forming process is greatly simplified, the production cycle is significantly shortened, and the large-scale industrial application is more possible.

[0040] 3) The aqueous solution system is selected, the solvent is simple and non-polluting, environmentally friendly, easy to scale up, and green production is easy to promote.

[0041] 4) The amine compound serves as a secondary amine source to assist the Mannich reaction and as an alkaline catalyst to promote the phenolic polycondensation reaction, forming a cross-linked network to ensure that the porous structure does not collapse.

[0042] 5) The resin precursor has good processability, and a hollow-shaped carbon membrane can be prepared.

[0043] The present application successfully prepares the carbon membrane in a particularly fast, simple and efficient manner, which can be in the form of a supporting body original membrane supplemented by a more finely controlled separation layer, and is applied to gas separation or separation of organic isomers. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 It is a side view photo of the non-supported mesoporous organic membrane precursor (polymer barrel membrane) obtained in Example 2.

[0045] Figure 2 It is a top view photo of the non-supported mesoporous organic membrane precursor (polymer barrel membrane) obtained in Example 2.

[0046] Figure 3 It is a side view photo of the non-supported mesoporous organic membrane precursor (polymer tube membrane) obtained in Example 6.

[0047] Figure 4Top view photograph of the non-supporting mesoporous organic film precursor (polymer tube film) obtained in Example 6. DETAILED DESCRIPTION

[0048] The following specific examples are provided to further illustrate the application. It is to be understood that the examples are merely illustrative of the present application and are not to be construed as limiting the scope of the application. Any modification of the application by one skilled in the art, which is not described expressly but which falls within the scope of the application, is intended to be included in the scope of the application.

[0049] The raw materials used in the examples and comparative examples are, if not specified otherwise, known in the art, for example commercially available or prepared according to known methods.

[0050] The present application adopts the technical solution as follows: using phenolic compounds, amine compounds and aldehyde compounds as raw materials, under the structure directing effect of surfactants, using aqueous solution as solvent, preparing cross-linked network copolymer, i.e. cross-linked copolymer of benzoxazine resin precursor and phenolic resin precursor, by low-temperature polymerization, which is a porous polymer rich in mesoporous channels.

[0051] According to a preferred embodiment of the present application, the preparation method can specifically include the following steps:

[0052] ① dissolving phenolic compounds in solvent,

[0053] ② adding surfactants (soft template agents) and stirring until uniform and completely dissolved,

[0054] ③ adding amine compounds and continuing to stir until uniform,

[0055] ④ quickly injecting all aldehyde compounds into the reaction solution, at this time the clear and transparent reaction solution can be seen to become white or golden gel within 30 minutes,

[0056] ⑤ after the system is stable, loading the above reaction mixture into selected mold and removing air bubbles,

[0057] ⑥ transferring to an environment with set temperature and uniform stability for low-temperature aging,

[0058] ⑦ after demolding and drying, obtaining non-supporting porous polymer film rich in mesoporous channels;

[0059] ⑧ high-temperature carbonization treatment.

[0060] According to a preferred embodiment of the present application, the phenolic compounds are one or a combination of phenol, resorcinol and phloroglucinol.

[0061] According to a preferred embodiment of the present application, the amine is any one or combination of ethylenediamine, hexanediamine, propylenediamine, butylenediamine.

[0062] According to a preferred embodiment of the present application, the surfactant is any one or combination of F127, P123, F108, B50.

[0063] According to a preferred embodiment of the present application, the aldehyde compound is any one or combination of formaldehyde, polyformaldehyde, furfural.

[0064] According to a preferred embodiment of the present application, the solvent is any one or combination of water and ethanol.

[0065] According to a preferred embodiment of the present application, the molar ratio of the phenolic compound to the aldehyde compound is (1:1)~(1:3), and specifically can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, etc.

[0066] According to a preferred embodiment of the present application, the molar ratio of the phenolic compound to the amine compound is (1:0.005)~(1:0.05), and specifically can be 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, etc.

[0067] According to a preferred embodiment of the present application, the molar ratio of the phenolic compound to the surfactant is (1:0.004)~(1:0.02), and specifically can be 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.010, 1:0.011, 1:0.012, 1:0.013, 1:0.014, 1:0.015, 1:0.016, 1:0.017, 1:0.018, 1:0.019, 1:0.02, etc.

[0068] According to a preferred embodiment of the present application, the molar ratio of the phenolic compound to water and / or alcohol is (1:20)~(1:300).

[0069] According to a preferred embodiment of the present application, the mass ratio of water to alcohol is (3:7)~(7:3).

[0070] In the above preparation method, after the aldehyde compound or the amine compound is added at the end, the reaction is completed in 10-30 minutes.

[0071] According to a preferred embodiment of the present application, the mixed solution is filled into a mold, which includes any of the following forms: a capillary, a single-channel tubular membrane, a multi-channel tubular membrane, a plate membrane, a barrel membrane, and the like.

[0072] According to a preferred embodiment of the present application, the bubbles are removed by any of the following methods or a combination thereof: vibration, ultrasonic, long-time static standing, and the like.

[0073] According to a preferred embodiment of the present application, the low-temperature aging temperature ranges from 60 to 110°C (preferably, 70 to 100°C), and the aging time ranges from 15 min to 12 h (preferably, 30 min to 8 h).

[0074] The drying method is conventional drying, and the humidity does not need to be specially controlled. According to a preferred embodiment of the present application, the drying is performed in an oven at 50 to 80°C for 4 to 24 h.

[0075] According to a preferred embodiment of the present application, the porous polymer with rich mesoporous channels prepared by the above method is placed in a carbonization furnace, and is heated at a rate of 0.5 to 3°C / min from room temperature to about 400°C under the protection of inert gas, is kept at the constant temperature for 30 min to 2 h, is continuously heated at a rate of 1 to 5°C / min to 500 to 1000°C, and is kept at the constant temperature for 60 min to 5 h, so as to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0076] The present application uses phenolic compounds, amine compounds and aldehyde compounds as raw materials, a surfactant such as F127 as a template agent, and an amine compound as a structure promoter. In an aqueous solution system, the precursors interact with the surfactant molecules, the organic amine and the phenol / aldehyde undergo Mannich reaction, and the precursors themselves undergo polycondensation reaction, so as to quickly form a cross-linked network structure, which ensures that the porous structure does not collapse during the carbonization process, and the mesoporous-microporous carbon membrane is efficiently prepared through high-temperature carbonization. The most remarkable feature of the present application is that the phenolic amine undergoes Mannich condensation reaction to form a heterocyclic benzoxazine monomer, and the monomer further undergoes thermal polymerization to form a benzoxazine resin, which, together with the self-assembly of the phenolic resin, forms a porous organic polymer (organic membrane) with rich mesopores. After further high-temperature carbonization, an inorganic carbon membrane with rich mesoporous-microporous is formed.

[0077] Example 1

[0078] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 0.55 g of surfactant P123 (0.095 mmol), 3.45 g (0.274 mmol) of surfactant F127, stir completely, then add 0.275 g (4.58 mmol) of ethylenediamine, quickly add 11.1 g (0.137 mol) of 37% formaldehyde solution, continue to stir, and after obtaining a white colloid, weigh 5.6 g of the above reaction solution into a cylindrical mold with a bottom thickness of 3.0 mm, a wall thickness of 1.8 mm, and a height of 40 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 95°C for 3 hours of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0079] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect it with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 1°C / min, keep it at a constant temperature for 60 minutes, continue to increase the temperature to 790°C at a rate of 1°C / min, keep it at a constant temperature for 300 minutes, and naturally cool it to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0080] Example 2

[0081] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, stir completely, then add 0.43 g (3.70 mmol) of hexanediamine, quickly add 18.4 g (0.227 mol) of 37% formaldehyde solution, continue to stir, and after obtaining a white colloid, weigh 5.6 g of the above reaction solution into the barrel-shaped mold of Example 1, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 90°C for 4 hours of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0082] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect it with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 1°C / min, keep it at a constant temperature for 60 minutes, continue to increase the temperature to 790°C at a rate of 1°C / min, keep it at a constant temperature for 300 minutes, and naturally cool it to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0083] Place the barrel membrane into an Instron universal mechanical property testing machine to measure the compressive strength of 14.2 MPa.

[0084] Example 3

[0085] Take 10 g (91 mmol) of resorcinol into a beaker, add 75 g of water and 25 g of ethanol, and stir at room temperature, after dissolution, add 10.8 g (1.86 mmol) of surfactant P123, stir completely, then add 0.275 g (4.58 mmol) of ethylenediamine, quickly add 22.1 g (0.273 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, take an appropriate amount of the above mixture to form a flat film with a thickness of about 2 mm on a flat plate, then transfer it to an oven set at 90°C, and perform 4h low-temperature aging, after demolding, take out and place in a 50°C oven to dry for 24h, to obtain a non-supported mesoporous organic film precursor.

[0086] Place the above organic film precursor in a carbonization furnace for heat treatment, protect with inert gas N2, heat from room temperature to 400°C at a rate of 0.6°C / min, maintain for 60 min; continue to heat to 790°C at a rate of 1°C / min, maintain for 300 min, and naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon film with uniform size and good morphology.

[0087] Example 4

[0088] Take 10 g (91 mmol) of resorcinol into a beaker, add 75 g of water and 25 g of ethanol, and stir at room temperature, after dissolution, add 10.8 g (1.86 mmol) of surfactant P123, stir completely, then add 0.275 g (4.58 mmol) of ethylenediamine, quickly add 22.1 g (0.273 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, refer to Example 3 to form a flat film, then transfer it to an oven set at 90°C, and perform 4h low-temperature aging, after demolding, take out the formed polymer and place it in a 50°C oven to dry for 24h, to obtain a non-supported mesoporous organic film precursor.

[0089] Place the above organic film precursor in a carbonization furnace for heat treatment, protect with inert gas N2, heat from room temperature to 400°C at a rate of 0.6°C / min, maintain for 60 min; continue to heat to 790°C at a rate of 1°C / min, maintain for 300 min, and naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon film with uniform size and good morphology.

[0090] Example 5

[0091] Resorcinol (10 g, 91 mmol) was weighed into a beaker, 40 g of water and 30 g of ethanol were added, and stirred at room temperature, after dissolution, 4.6 g (0.365 mmol) of surfactant F127 was added, after stirring completely, 0.22 g (1.89 mmol) of hexanediamine was added, 13.3 g (0.164 mol) of 37% formaldehyde solution was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed and loaded into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubble for 5 minutes, and then sealed and transferred into an oven with a set temperature of 90°C for 4 h low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0092] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, and kept at 400°C for 60 min; then heated to 790°C at a rate of 1°C / min, and kept at 790°C for 300 min, and then naturally cooled to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0093] The tubular membrane was placed in an Instron universal mechanical property testing machine, and the compressive strength was measured to be 14.5 MPa.

[0094] Example 6

[0095] Resorcinol (10 g, 91 mmol) was weighed into a beaker, 40 g of water and 30 g of ethanol were added, and stirred at room temperature, after dissolution, 4.6 g (0.365 mmol) of surfactant F127 was added, after stirring completely, 0.22 g (1.89 mmol) of hexanediamine was added, 13.3 g (0.164 mol) of 37% formaldehyde solution was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed and loaded into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubble for 5 minutes, and then sealed and transferred into an oven with a set temperature of 90°C for 4 h low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0096] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, and kept at 400°C for 60 min; then heated to 790°C at a rate of 1°C / min, and kept at 790°C for 300 min, and then naturally cooled to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0097] Example 7:

[0098] Take 10 g (91 mmol) of resorcinol into a beaker, add 40 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, 0.66 g (0.091 mmol) of surfactant B50, stir completely, then add 0.42 g (3.61 mmol) of hexanediamine, quickly add 13.3 g (0.164 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, weigh 8.8 g of the above reaction solution into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0099] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect it with inert gas N2, heat it from room temperature to 400°C at a rate of 0.8°C / min, keep it at this temperature for 60 min, continue to heat it to 790°C at a rate of 1°C / min, keep it at this temperature for 300 min, and then naturally cool it to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0100] Example 8:

[0101] Take 10 g (91 mmol) of resorcinol into a beaker, add 40 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, 0.66 g (0.091 mmol) of surfactant B50, stir completely, then add 0.42 g (3.61 mmol) of hexanediamine, quickly add 13.3 g (0.164 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, weigh 8.8 g of the above reaction solution into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0102] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect it with inert gas N2, heat it from room temperature to 400°C at a rate of 0.8°C / min, keep it at this temperature for 60 min, continue to heat it to 790°C at a rate of 1°C / min, keep it at this temperature for 300 min, and then naturally cool it to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0103] Example 9:

[0104] Take 10 g (91 mmol) of resorcinol into a beaker, add 40 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, stir completely, then add 0.32 g (3.63 mmol) of butanediamine, quickly add 13.3 g (0.164 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, weigh 8.8 g of the above reaction solution into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubble for 5 minutes, seal and transfer into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it into a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0105] Place the above organic membrane precursor into a carbonization furnace for heat treatment, protect with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 0.8°C / min, maintain the temperature for 60 min; continue to increase the temperature to 790°C at a rate of 1°C / min, maintain the temperature for 300 min, and naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0106] Example 10:

[0107] Take 10 g (91 mmol) of resorcinol into a beaker, add 40 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, stir completely, then add 0.32 g (3.63 mmol) of butanediamine, quickly add 13.3 g (0.164 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, weigh 8.8 g of the above reaction solution into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubble for 5 minutes, seal and transfer into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it into a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0108] Place the above organic membrane precursor into a carbonization furnace for heat treatment, protect with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 0.8°C / min, maintain the temperature for 60 min; continue to increase the temperature to 790°C at a rate of 1°C / min, maintain the temperature for 300 min, and naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0109] Example 11:

[0110] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, after stirring completely, add 0.064 g (0.551 mmol) of hexanediamine, quickly add 18.5 g (0.228 mol) of polyformaldehyde solution, continue to stir, after obtaining a white colloid, weigh 8.8 g of the above reaction solution into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubble for 5 minutes, seal and transfer into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0111] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect with inert gas N2, heat from room temperature to 400°C at a rate of 0.8°C / min, keep constant temperature for 60 min; continue to heat to 790°C at a rate of 1°C / min, keep constant temperature for 300 min, naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0112] Place the tubular membrane into an Instron mechanical property testing machine to measure the compressive strength of 16.5 MPa.

[0113] Example 12:

[0114] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, and stir at room temperature, after dissolution, add 4.6 g (0.365 mmol) of surfactant F127, after stirring completely, add 0.074 g (0.637 mmol) of hexanediamine, quickly add 18.5 g (0.228 mol) of 37% formaldehyde solution, continue to stir, after obtaining a white colloid, weigh 5.6 g of the above reaction solution into a cylindrical mold with a bottom thickness of 3.0 mm, a wall thickness of 1.8 mm, and a height of 40 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubble for 5 minutes, seal and transfer into an oven set at 90°C for 4 h of low-temperature aging, after demolding, take out the shaped polymer and place it in a 50°C oven for drying for 24 h, to obtain a non-supported mesoporous organic membrane precursor.

[0115] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect with inert gas N2, heat from room temperature to 400°C at a rate of 1°C / min, keep constant temperature for 60 min; continue to heat to 790°C at a rate of 1°C / min, keep constant temperature for 300 min, naturally cool to room temperature, to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0116] The tubular membrane was placed in an Instron universal mechanical property testing machine to measure the compressive strength of 16.3 MPa.

[0117] Example 13

[0118] 10 g (91 mmol) of resorcinol was weighed into a beaker, 30 g of water and 30 g of ethanol were added, and stirred at room temperature, after dissolution, 4.6 g (0.365 mmol) of surfactant F127 was added, after stirring completely, 0.085 g (0.731 mmol) of hexanediamine was added, 18.5 g (0.228 mol) of 37% formaldehyde solution was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, and then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubble for 5 minutes, and then sealed and transferred into an oven set at a temperature of 90°C for 4 hours of low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0119] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, kept at 400°C for 60 min; then heated to 790°C at a rate of 1°C / min, kept at 790°C for 300 min, and naturally cooled to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0120] Example 14

[0121] 10 g (91 mmol) of resorcinol was weighed into a beaker, 30 g of water and 30 g of ethanol were added, and stirred at room temperature, after dissolution, 4.6 g (0.365 mmol) of surfactant F127 was added, after stirring completely, 0.085 g (0.731 mmol) of hexanediamine was added, 18.5 g (0.228 mol) of 37% formaldehyde solution was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, and then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubble for 5 minutes, and then sealed and transferred into an oven set at a temperature of 90°C for 4 hours of low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0122] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, kept at 400°C for 60 min; then heated to 790°C at a rate of 1°C / min, kept at 790°C for 300 min, and naturally cooled to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0123] The tubular membrane was placed in an Instron mechanical property tester to measure the compressive strength of 16.1 MPa.

[0124] Example 15:

[0125] 10 g (91 mmol) of resorcinol was weighed into a beaker, 80 g of water and 60 g of ethanol were added, and stirred at room temperature, after dissolution, 5.75 g (0.456 mmol) of surfactant F127 was added, after stirring completely, 0.43 g (3.70 mmol) of hexanediamine was added, 26.2 g (0.272 mol) of furfural was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed and placed into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubbles for 5 minutes, and then sealed and transferred into an oven set at a temperature of 90°C for 4 hours of low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0126] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, kept at 400°C for 60 min, then heated to 790°C at a rate of 1°C / min, kept at 790°C for 300 min, and naturally cooled to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0127] Example 16:

[0128] 10 g (91 mmol) of resorcinol was weighed into a beaker, 80 g of water and 60 g of ethanol were added, and stirred at room temperature, after dissolution, 5.75 g (0.456 mmol) of surfactant F127 was added, after stirring completely, 0.43 g (3.70 mmol) of hexanediamine was added, 26.2 g (0.272 mol) of furfural was quickly added, and stirring was continued, after a white colloid was obtained, 8.8 g of the above reaction solution was weighed and placed into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then the mold containing the reaction solution was placed in an ultrasonic vibration tank to drive the bubbles for 5 minutes, and then sealed and transferred into an oven set at a temperature of 90°C for 4 hours of low-temperature aging, after demolding, the shaped polymer was taken out and placed in a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0129] The above organic membrane precursor was placed in a carbonization furnace for heat treatment, protected by inert gas N2, and heated from room temperature to 400°C at a rate of 0.8°C / min, kept at 400°C for 60 min, then heated to 790°C at a rate of 1°C / min, kept at 790°C for 300 min, and naturally cooled to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0130] Example 17:

[0131] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, stir at room temperature, dissolve, then add 4.6 g (0.365 mmol) of surfactant F127, stir completely, then add 18.4 g (0.227 mol) of 37% formaldehyde solution, quickly add 0.43 g (3.7 mmol) of hexanediamine, continue to stir, and after a white colloid is obtained, take 5.6 g of the above reaction solution and load it into the cylindrical mold of Example 1, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and then transfer it into an oven set at 90°C for 4 hours of low-temperature aging, open the cover, demold and take out the shaped polymer, and then place it into a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0132] Place the above organic membrane precursor into a carbonization furnace for heat treatment, protect it with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 1°C / min, keep the temperature constant for 60 minutes, continue to increase the temperature to 790°C at a rate of 1°C / min, keep the temperature constant for 300 minutes, and then naturally cool to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0133] Example 18:

[0134] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol, stir at room temperature, dissolve, then add 4.6 g (0.365 mmol) of surfactant F127, stir completely, then add 18.4 g (0.227 mol) of 37% formaldehyde solution, quickly add 0.43 g (3.7 mmol) of hexanediamine, continue to stir, and after a white colloid is obtained, take 5.6 g of the above reaction solution and load it into the cylindrical mold of Example 1, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and then transfer it into an oven set at 90°C for 4 hours of low-temperature aging, open the cover, demold and take out the shaped polymer, and then place it into a 50°C oven for drying for 24 hours, thereby obtaining a non-supported mesoporous organic membrane precursor.

[0135] Place the above organic membrane precursor into a carbonization furnace for heat treatment, protect it with inert gas N2, increase the temperature from room temperature to 400°C at a rate of 1°C / min, keep the temperature constant for 60 minutes, continue to increase the temperature to 790°C at a rate of 1°C / min, keep the temperature constant for 300 minutes, and then naturally cool to room temperature, thereby obtaining a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0136] Place the barrel membrane into an Instron mechanical property testing machine to measure the compressive strength, which is 16.1 MPa.

[0137] Example 19:

[0138] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol to stir at room temperature, after dissolution, add 4.2 g (0.333 mmol) of surfactant F127, stir completely, then add 14.8 g (0.182 mol) of 37% formaldehyde solution, quickly add 0.53 g (4.56 mmol) of hexanediamine, continue to stir, and after obtaining a white colloid, weigh 5.6 g of the above reaction solution into a cylindrical mold with a bottom thickness of 3.0 mm, a wall thickness of 1.8 mm, and a height of 40 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 90°C for 4 hours of low-temperature aging, then take out the shaped polymer after demolding, and place it in a 50°C oven for drying for 24 hours to obtain a non-supported mesoporous organic membrane precursor.

[0139] Place the above organic membrane precursor in a carbonization furnace for heat treatment, protect it with inert gas N2, heat it from room temperature to 400°C at a rate of 1°C / min, keep it at 400°C for 60 minutes, continue to heat it to 790°C at a rate of 1°C / min, keep it at 790°C for 300 minutes, and then naturally cool it to room temperature to obtain a non-supported mesoporous-microporous carbon membrane with uniform size and good morphology.

[0140] Place the barrel membrane into an Instron mechanical property testing machine to measure the compressive strength of 14.0 MPa.

[0141] Comparative Example 1:

[0142] Take 10 g (91 mmol) of resorcinol into a beaker, add 30 g of water and 30 g of ethanol to stir at room temperature, after dissolution, add 4.2 g (0.333 mmol) of surfactant F127, stir completely, then add 14.8 g (0.182 mol) of 37% formaldehyde solution, quickly add 0.53 g (4.56 mmol) of hexanediamine, continue to stir, and after obtaining a white colloid, weigh 5.6 g of the above reaction solution into a cylindrical mold with a bottom thickness of 3.0 mm, a wall thickness of 1.8 mm, and a height of 40 mm, then place the mold containing the reaction solution into an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it into an oven set at 90°C for 4 hours of low-temperature aging, then take out the shaped polymer after demolding, and place it in a 50°C oven for drying for 24 hours to obtain a non-supported mesoporous organic membrane precursor.

[0143] Comparative Example 2:

[0144] Take 10 g (91 mmol) of resorcinol into a beaker, add 35 g of water and 35 g of ethanol, stir at room temperature, dissolve, then add 11.4 g (0.91 mmol) of surfactant F127, stir until completely dissolved, then add 0.64 g (5.5 mmol) of hexanediamine, quickly add 14.8 g (0.182 mol) of 37% formaldehyde solution, continue to stir, and after a white colloid is obtained, take 8.8 g of the above reaction solution and load it into a tubular mold with a wall thickness of 1.8 mm and a height of 80 mm, then place the mold containing the reaction solution in an ultrasonic vibration tank to drive the bubbles for 5 minutes, seal it and transfer it to an oven set at a temperature of 90°C for 4 hours of low-temperature aging. After opening the cover, it was found that the polymer did not effectively polymerize and no tubular precursor was formed.

Claims

1. A method for preparing a non-supporting meso-microporous carbon membrane based on phenolic resin, comprising the following steps: (1) reacting raw materials including phenolic compounds, amine compounds, aldehyde compounds, and surfactants to obtain a resin precursor; (2) loading the resin precursor into a mold to perform low-temperature aging molding to obtain an organic membrane; and (3) high-temperature carbonization of the organic membrane; wherein the phenolic compounds are at least one of phenol, resorcinol, and phloroglucinol; the amine compounds are at least one of ethylenediamine, hexanediamine, propylenediamine, and butanediamine; the surfactants are at least one of F127, P123, F108, and B50; the aldehyde compounds are at least one of formaldehyde, polyformaldehyde, and furfural; the molar ratio of the phenolic compounds to the amine compounds is (1:0.005) to (1:0.01); the molar ratio of the phenolic compounds to the surfactants is (1:0.004) to (1:0.01); and the molar ratio of the phenolic compounds to the aldehyde compounds is (1:1) to (1:3); the mold is any one of a single-channel tubular membrane mold, a multi-channel tubular membrane mold, a barrel membrane mold, and a capillary membrane mold; and the method uses the phenolic compounds, the amine compounds, and the aldehyde compounds as raw materials, uses a water solution as a solvent, and uses the structure of the surfactants as a guide to prepare a crosslinked network copolymer of a benzoxazine resin precursor and a phenolic resin precursor by low-temperature polymerization, wherein the copolymer is a porous polymer rich in mesoporous channels, and the absolute amount of the mesopores is more than 50% of the total amount of mesopores and micropores. 2.The method for preparing a non-supporting meso-microporous carbon membrane according to claim 1, wherein the molar ratio of the phenolic compounds to the aldehyde compounds is (1:1.5) to (1:3). Step (1) comprises: (1-1) dissolving the phenolic compounds in a solvent; (1-2) adding the surfactants and dissolving completely; (1-3) adding the amine compounds; and (1-4) adding the aldehyde compounds. The order of steps (1-3) and (1-4) can be interchanged. 4.The method for preparing a non-supporting meso-microporous carbon membrane according to claim 1, wherein in step (2), the sol-like mixed solution of the resin precursor obtained in step (1) is loaded into the mold and deaerated, and then low-temperature aging is performed. 5.The method for preparing a non-supporting meso-microporous carbon membrane according to claim 4, wherein the deaeration method is at least one of vibration, ultrasonic, and long-time static standing. In step (2), the temperature for low-temperature aging is 60-110 ℃; and / or, the time for low-temperature aging is 15 min-12 h.

3. The method of claim 1, wherein 7.The method for preparing a non-supporting meso-microporous carbon membrane according to claim 6, wherein the temperature for low-temperature aging is 70-100 ℃; and / or, the time for low-temperature aging is 30 min-8 h. In step (3), ​ ​ ​ ​ ​ 6. The method of claim 1, wherein ​ ​ ​ ​ ​ ​ 8. The method of claim 1, wherein ​ High temperature carbonization includes under inert gas condition, from room temperature to 150-450℃ at 0.5-3℃ / min, constant temperature for 30min-2h, continue to 500-1000℃ at 1-5℃ / min, constant temperature for 60min-5h.

9. The phenolic-based unsupported meso-microporous carbon membrane obtained by the preparation method according to any one of claims 1-8.

10. The use of the phenolic-based unsupported meso-microporous carbon membrane obtained by the preparation method according to any one of claims 1-8 in CO2 / N2 separation.

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