• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention provides a new flat and asymmetric polysulfone membrane capable of sequestering CO2from the atmosphere without the need to create a partial pressure difference between both faces of the membrane to capture the CO2contained in the air, under conditions of pressure and ambient temperature, and with improved flow velocity. Also, the invention provides a process for the preparation of the flat and asymmetric membrane of polysulfone and also provides an improved absorption system of CO2using said membrane. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2673492A1
    申请号:ES201631648
    申请日:2016-12-21
    公开日:2018-06-22
    发明作者:Ricard García Valls；Adrianna NOGALSKA；Tylkowsky BARTOSZ
    申请人:Centre Tecnologic de la Quimica De Catalunya；Centre Tecnologic de la Quim De Catalunya；Universitat Rovira i Virgili URV；
    IPC主号:
    专利说明:

    ASYMMETRIC MEMBRANE OF CO2 SEQUESTING POLYSULPHONE FROM THEATMOSPHERE, PROCEDURE FOR OBTAINING AND ABSORPTION SYSTEMOF CO2 USING THIS MEMBRANE
    The present invention relates to an asymmetric membrane of atmospheric CO2 sequestrant polysulfone comprising an essentially polysulfone structure or a polysulfone derivative, that is to say a chemically substantially homogeneous structure throughout its entire structure, and magnetic nanoparticles trapped therein. structure.
    The invention also relates to a process for the preparation of the CO2 sequestrant membrane and a CO2 absorption system using the membrane of the invention.
    Background of the invention
    Polysulfone membranes for separating gases from a gas mixture are known.
    In particular, the advantages of polysulfone polymers are known for their excellent thermal, mechanical properties, resistance to compaction and presence of chlorine, as well as for operating in a wide range of pHs.
    International patent application WO201570288 refers to a multilayer membrane prepared with different polymers to separate a target gas from a gas mixture. The membrane comprises a porous substrate having a first and second surface region between which the gas mixture flows, a polymeric sealant layer of different composition to the substrate that forms a continuous coating and is permeable to the gas mixture and a layer of selective polymer in the form of a covalently bonded macromolecular film and of greater permeability to the target gas than the other species present in the gas mixture. The selective polymer layer can incorporate solid nanoparticles into the polymer matrix. The example included in the patent application discloses Fe-dopamine organic-inorganic hybrid nanoparticles (Fig. 12).
    European patent EP259288 refers to membranes formed by chemically distinct polymers for separating gases from a gas mixture. The membranes obtained by the described method are free of macropores. According to EP259288, the presence of macropores is undesirable for gas separation, so that any defect is sealed with a silicone polymer or the like.
    International patent application WO2013169093 refers to a method for removing carbon dioxide from a mixture of hydrocarbons. The described method comprises contacting the hydrocarbon stream with a gas separation membrane composed of polysulfone to generate a hydrocarbon-rich gas stream (retained) and a carbon dioxide-rich gas stream (permeate); and passing one of the two currents retained or permeated through an absorption unit to generate a gas phase rich in hydrocarbons and an absorbent liquid phase containing carbon dioxide. The absorption unit comprises in its interior the membrane, which separates the gas flow from the flow of absorbent liquid, and which by partial pressure difference absorbs carbon dioxide in the flow of absorbent liquid. It is necessary to create a partial pressure difference for the separation of CO2 from the hydrocarbon mixture.

    On the other hand, the international patent application WO2009024973 refers to modified polysufone membranes, substituted in one or more of the phenyl rings by functional groups. The membranes are characterized by having a uniform pore structure across the entire membrane and have application in reverse osmosis, microfiltration (MF), nanofiltration and ultrafiltration (UF) to purify water, for example, in the treatment of wastewater, municipal , industrial or from agriculture. A membrane structure with a uniform pore size is necessary throughout the structure for proper separation of solute from water. The polysufone membranes are functionalized with functional groups and nanocavities are created using nanoparticles, which are distributed homogeneously through the polymer matrix with the aid of a magnetic field and then removed by the acid etching technique. These membranes require a partial pressure difference to achieve the separation of the solute from the water.
    In view of the state of the art it is necessary to use multilayer membranes formed by different materials, or membranes composed of different polymers to separate a gas from a gas mixture, whose preparation is of high complexity and high manufacturing costs, which also require a certain configuration to create a partial pressure difference between the two faces of the membrane in order to separate the target gas from the gas mixture.
    Therefore, there is still a need to provide a new membrane capable of sequestering CO2 from the atmosphere that does not require external pressure to separate CO2, whose manufacture is also simpler both in terms of the materials used and in the methodology for its preparation and, consequently, of lower manufacturing cost.
    Description of the invention
    The present invention has been made in view of the state of the art described above.
    The object of the present invention is to provide an asymmetric polysulfone membrane sequestrating CO2 from the atmosphere that operates simply and without the need to apply external pressure, and which also has other advantages that will be described later. Other objects of the present invention are also to provide a process for the preparation of the membrane and a CO2 absorption system employing the membrane of the invention without the need to create a partial pressure difference between the two faces of the membrane for transport. or subsequent reuse of CO2.
    To solve the problem posed in view of the state of the art, the present invention provides, in a first aspect, an asymmetric membrane of CO2 sequestrant polysulfone from the atmosphere, which is characterized by the fact that it consists of a structure chemically substantially homogeneous polysulfone or a polysulfone derivative comprising a first porous surface region interconnected with a second transport region that includes macroporos, and by the fact that the structure further comprises magnetic nanoparticles at a concentration between 0.01 and 35% by weight with respect to the total weight of the membrane, the magnetic nanoparticles being mostly distributed in the first surface region.
    In the CO2 sequestrant membrane, the first porous surface region includes pores of average pore size between 1.5 and 7 µm, and the second transport region includes macropores of average surface area comprised between 300 and 1300 µm2.

    The membrane of the invention is flat and of a thickness between 70 and 180 µm, and the polysulfone polymer or polysulfone derivative has an average molecular weight between 20,000 and 75,000 g / mol, preferably between 24,000 and 39,000, still more preferably around 35,000 g / mol.
    The membrane of the invention has the ability to sequester, at room temperature and pressure, the CO2 contained in the air without applying external pressure on any of the outer surfaces or faces of the membrane.
    It is believed that magnetic nanoparticles in the internal structure and / or membrane surface, on the one hand, locally increase the value of the surface ratio per unit volume, at least, in the membrane surface. This local increase in the surface to unit volume ratio generates areas with a higher affinity for CO2 on the outer surface or face of the membrane and, therefore, areas with higher CO2 adsorption than others. These areas with greater affinity for CO2 have been referred to in the present invention as "contactors" or "CO2 sequestering zones". Thus, these contactors or sequestering zones have the ability to spontaneously sequester CO2 from the air, allowing the membrane to operate without applying external pressure. In one embodiment, the membrane comprises magnetic nanoparticles at a concentration between 0.1 and 25%, preferably between 0.8 and 12%, by weight with respect to the total weight of the membrane.
    Surprisingly, the membrane structure defined in claim 1 exhibits superior surface uptake of CO2, that is, it exhibits greater adsorption of CO2 on the outer surface in contact with the atmosphere.
    Magnetic nanoparticles in the internal structure and / or membrane surface, in turn and due to the formation of contactors or sequestering zones on the outer surface of the membrane, modify the chemical potential of the membrane causing an increase in diffusion of the CO2 into the membrane, that is, they improve the transport speed of the CO2 molecule through the membrane. The transported CO2 is capable of being collected in a CO2 absorbing medium associated with the other external surface or opposite face of the membrane.
    Advantageously, the double effect generated by the magnetic nanoparticles in the chemically substantially homogeneous structure of the membrane in combination with the morphology of the membrane that includes the first porous surface region interconnected with the second transport region that includes macropores provides a membrane capable of capturing CO2 of the air with superior performance.
    Thus, the invention provides a membrane capable of spontaneously adsorbing CO2 from the air on the outer surface of the membrane, surface in contact with the first surface region, diffusing it through the second transport region, and releasing it through the external surface Opposite susceptible to be associated with a CO2 absorbing solution without creating a partial pressure difference between both outer surfaces of the membrane and despite containing the air a reduced concentration of CO2, usually less than 400ppm.
    In one embodiment, the magnetic nanoparticles (NPM) are ferrites. In another embodiment the magnetic nanoparticles may be functionalized with amino groups. Preferably, the magnetic nanoparticles are selected from one or more of the group consisting of CuFe2O4, Fe3O4, CoFe2O4, MnFe2O4, NiFe2O4, Fe2O3.

    In a preferred embodiment, the CO2 sequestrant membrane further comprises at least one enzyme selected from the group consisting of RuBisCo or a carbonic Anhydrase. Preferably, the carbonic Anhydrase enzyme is mostly distributed in the first surface region, and preferably, the RuBisco enzyme is mostly distributed in the second transport region.
    The additional presence of this type of enzymes makes it possible to further increase the adsorption of CO2 on the outer surface or face of the membrane that is in contact with the air, and / or further increase the rate of diffusion of CO2 through the membrane from the outer surface or face of the membrane in contact with the air to the outer surface
    or opposite face of the membrane capable of being associated with a CO2 absorbing medium.
    Surprisingly, with the membrane defined in the appended claims, CO2 can be sequestered from the air at a flow rate between 0.1 and 1.2 moles of CO2 per m2 of membrane surface per hour or more, which is up to 10 times higher to the flow of transmission of a leaf in its natural state.
    The membrane of the invention is a single layer of asymmetry between 3 and 15%. The morphology of the layer includes the two interconnected regions defined above. A cross section of the membrane shows from one face or outer surface of the membrane to the other outer surface or opposite face: a first surface region of less thickness and greater density interconnected with a second transport region of greater thickness and lower density, where both regions have been formed by phase inversion precipitation technology.
    In a second aspect, the present invention provides a process for the preparation of the membrane defined in the appended claims, based on the phase inversion precipitation technology, characterized by the fact that it comprises:
    - dissolve in a organic solvent a polysulfone polymer or polysulfone derivative at a concentration between 2 and 30%, preferably between 14 and 26%, by weight with respect to the weight of the organic solvent, and stir the resulting polymer solution;
    - let the polymer solution stand to degas it;
    - to the degassed polymer solution, add magnetic nanoparticles at a concentration between 0.01 and 35%, preferably between 0.8 and 12%, by weight with respect to the weight of the polymer solution, and stir to obtain a mixture of polymer solution and magnetic nanoparticles;
    - pour the obtained mixture into a support for this purpose, mold it with the use of a film bar and then immerse in a coagulation bath comprising a nosolvent, so that the precipitation of the polymer on the support takes place to form the membrane comprising magnetic nanoparticles in their structure;
    - remove from the bath, dry and separate the membrane from the support.
    In a preferred embodiment, the procedure defined above comprises in combination one or more of the following steps:
    - dissolve in an organic solvent selected from 1-Methyl-2-pyrrolidone (NMP, ACS), N, N-Dimethylformamide (DMF, 99%) and a polysulfone polymer or polysulfone derivative of average molecular weight between 25,000 and 75,000, and stir the resulting polymer solution for at least 2 days in a tightly closed container;
    5 -Let the polymer solution stand overnight to facilitate the exit of the gas formed during stirring;
    - To the degassed polymer solution, add magnetic nanoparticles at a concentration between 0.01 and 35% by weight with respect to the weight of the polymer solution, and stir for at least 45 minutes to obtain a solution mixture
    10 polymeric and magnetic nanoparticles;
    - pour the obtained mixture into a glass support, mold it with the use of a 150-300µm thick film bar and immediately immerse it in a coagulation bath comprising a non-solvent, preferably distilled water or an i-propanol solution in DMF, so that the membrane forms instantly
    15 by polymer precipitation;
    - remove the support and membrane from the bath, dry overnight under conditions of pressure and room temperature, and separate the membrane from the support for use.
    Advantageously, the membrane comprises at least one enzyme selected from RuBisCo and a carbonic Anhydrase. In this embodiment, the magnetic nanoparticles are
    20 magnetic nanoparticles functionalized with amino groups (-NH2), the amino group being the anchor site for the enzyme RuBisCo or Anhydrase.
    Once the membrane has been prepared with the magnetic nanoparticles as described above, where the magnetic nanoparticles have been functionalized with amino groups, the membrane can be incubated in a suspension that includes at least one enzyme
    25 selected from RuBisCo and a carbonic Anhydrase at a concentration between 0.025 and 1.2 mg / mg MNP-NH2.
    Next, the steps for this embodiment are included:
    1. In a suspension comprising at least one enzyme selected from RuBisCo and Carbonic Anhydrase at a concentration between 0.025 and 1.2 30 mg / mg of magnetic nanoparticles previously functionalized with an amino group (MNP-NH2), a precipitating reagent and , optionally, a nonionic surfactant incubate the membrane; Preferably, the precipitating reagent is ammonium sulfate at a concentration between 12.5 and 125 mmol / mg protein at 25 ° C. When the nonionic surfactant is present in the incubation medium, it is
    A concentration of between 0.01 and 5 mM is preferable. As an example, Triton X-100. The mixture was stirred gently, for example, at 30 rpm;
    2. After 5 minutes, add a solution of glutaraldehyde to the suspension and keep under stirring; preferably, the glutaraldehyde solution has a 2.5M concentration (final concentration between 0.01 and 500mM) and is
    40 keeps stirring for 1 to 24 hours;
    3. Reduce Schiff bases and unreacted aldehyde groups and wash the membrane for later use. Preferably, both Schiff bases and unreacted aldehyde groups are reduced for 2 hours at room temperature with rotational mixing in NaBH4 (0.75 mg / mg MNP-NH2) dissolved in

    100 mM bicarbonate / bicarbonate buffer, pH 10.0;
    Four. In order to minimize non-specific interactions, the membrane was washed for 10 min, first with 2M NaCl in PBS and then with 1% Triton X-100 (v / v) in PBS;
    5. The membrane was stored at 4 ° C in PBS for future use.
    In a third aspect, the present invention provides a CO2 absorption system from the atmosphere for subsequent transport or reuse of the CO2 sequestered with the membrane according to the first aspect of the invention.
    Thus, the CO2 absorption system of the atmosphere for transport or subsequent reuse is characterized by the fact that it comprises:
    - a CO2 absorbing solution, and
    - a membrane according to the first aspect of the invention, where the first porous surface region defines an outer surface or face of the membrane and is arranged in contact with the air of the atmosphere, and where the second transport region that includes macropores defines another outer surface or opposite face of the membrane and is associated with the CO2 absorbing solution,
    so that, at ambient pressure and temperature, the CO2 in the air in the atmosphere is spontaneously adsorbed on the outer surface of the membrane of the surface region, diffused through the membrane through the transport region to the other outer surface or opposite side of the membrane and absorbed in the absorbent solution for transport or subsequent reuse.
    Surprisingly, with the CO2 absorption system of the atmosphere according to the third aspect of the invention one can work at lower pHs, which is undoubtedly an added advantage of the system of the invention compared to the state CO2 absorption systems of the technique, which use very alkaline pHs.
    In a preferred embodiment, the absorbent solution is an alkaline aqueous solution of pH between 7 and 14, preferably between 8 and 9.
    Advantageously, the CO2 absorption system of the atmosphere according to the present invention is capable of transporting CO2 at a flow rate of 0.1 to 1.2 moles,
    or higher, of CO2 per m2 / h of the membrane.
    Therefore, the membrane defined in the appended claims is of special application for capturing CO2 from the air.
    Definitions
    In the present invention, the term "sequestrant" is understood to mean that the membrane has the property of sequestering CO2, that is, that it is capable of sequestering CO2 from the air without externally creating a partial pressure difference between the external surfaces of the membrane. The membrane of the invention has the property of sequestering CO2 from the air, at room temperature and pressure, similar to what occurs in a tree leaf. The air in the atmosphere has a CO2 concentration normally below 400ppm and, therefore, the membrane of the invention has special application as a CO2 sequestrant in the atmosphere.

    In the present invention, the term "magnetic nanoparticle (s) (MNP)" means a solid particle (s) of a size between 1 nm and 1 µm, more preferably between 1 nm and 100 nm , and of a material with magnetic character. A material with magnetic character means any element or compound diamagnetic, paramagnetic or ferromagnetic. Preferably, ferromagnetic that includes an element or compound comprising iron, cobalt or nickel. A value of Km (relative magnetic permeability) greater than or equal to 10 indicates that the element or compound is ferromagnetic. The nanoparticles can have any shape including cylindrical, triangular, cubic pyramidal, spherical, star-shaped or any combination, and can be functionalized with amino groups.
    In the present invention, the term "RuBisCo enzyme" means the oxygen enzyme Ribulose 1.5 bisphosphate Carboxylase-Oxygenase which is usually found in the chloroplast of autotrophic organisms and is also known by the name oxygenase. RuBisCO is capable of sequestering 3-4 molecules of carbon dioxide for each of oxygen.
    In the present invention, the term "carbonic Anhydrase enzyme" means any of the carbonic anhydrase enzymes α, β, γ, δ and ε. Carbonic anhydrase is an enzyme that belongs to a family of metalloenzymes, that is, enzymes that contain one or more metal atoms as a functional component of the enzyme. In plants, this enzyme helps raise the concentration of CO2 within the chloroplast to increase the carboxylation rate of the RuBisCO enzyme.
    In the present invention, the term "polysulfone" or "polysulfone derivative" means a thermoplastic polymer containing the aryl-SO2-aryl subunit, a distinctive characteristic of the sulfone group. The polysulfone polymer or polysulfone derivative selected has an average molecular weight between 20,000 and 75,000 g / mol, preferably between 24,000 and 39,000 g / mol.
    In the present invention, the term "asymmetric membrane" means a porous membrane with anisotropy in the structure of its pores, that is to say that the membrane does not have a uniformity of pore structure throughout its entire structure. Thus, for example, an asymmetry value of 5% indicates that 5% of the morphology has a different structure than the rest of the measured structure.
    In the present invention, by the term "chemically substantially homogeneous structure" it is understood that chemically the membrane is substantially homogeneous throughout its structure, that is, that the membrane has a chemical structure that is substantially homogeneous of polysulfone or a chemical structure that is substantially homogeneous of a polysulfone derivative.
    Brief description of the figures
    To better understand how much has been exposed, some drawings are attached in which, schematically and only by way of non-limiting example, a practical case of realization is represented.
    Figure 1 is an SEM photograph of the membrane cross section prepared in Example 1.
    Figure 2 is an SEM photograph of the cross section of the membrane prepared in the

    Example 4
    Figure 3 is a TEM photograph of CuFe2O4 MNP prepared according to the Example. 5.
    Figure 4 is a TEM photograph of MNP of Fe3O4-NH2 prepared according to Example 6.
    Examples
    Polysufone membrane preparation
    Example 1
    20.00 grams of polysulfone (Mw 35,000) were dissolved in 80.00 grams of N, N-Dimethylformamide as solvent. The solution was stirred at room temperature 25 ° C for 48 hours using a magnetic stirrer at 300 rpm. Then, the solution was allowed to stand overnight for degassing. Then, the solution was molded on a glass support by a film bar with a distance of 300 μm connected with a K paint applicator (R K Print Coat Instruments, Ltd., U.K.). Then, the molded film was coagulated in a bath containing 3000g of distilled water as a solvent. After separation and phase formation, the membrane was stored in water for 0.5h to ensure complete phase separation. This allowed to leach the water soluble membrane components. As a final stage, the membrane was dried by placing it between two sheets of filter paper for 24 h at room temperature.
    Characteristics of the membrane obtained:
    Thickness: 138 µm; Asymmetry: 11%; Porosity (ε): 65.32%; Average pore size: 5.33 µm; Macropores of average surface area: 832.67µm2; Contact angle: 60.17 °; CO2 absorption flow: 0.9208 mol / m2 · h;
    Example 2
    Example 1 was repeated, with the exception of the space of the film bar which in this example was 250 μm instead of 300 μm.
    Characteristics of the membrane obtained:
    Thickness: 90 µm; Asymmetry: 9%; Porosity (ε): 66.85%; Average pore size: 3.56 µm; Macropores of average surface area: 462.29µm2; Contact angle: 76.2 °; CO2 absorption flow: 0.4428 mol / m2 · h;
    Example 3
    This example was performed similarly to Example 2, except for the solvent that was 1-Methyl-2-pyrrolidone instead of N, N-Dimethylformamide.
    Characteristics of the membrane obtained:
    Thickness: 142 µm; Asymmetry: 12%; Porosity (ε): 77.42%; Average pore size: 4.56 µm; Macropores of average surface area: 609.89µm2; Contact angle: 66.13 °; CO2 absorption flow: 1.3627 mol / m2 · h;

    Example 4
    This example was performed similarly to Example 3, with the exception of the space of the film bar that was 200 μm instead of 250 μm.
    Characteristics of the membrane obtained:
    Thickness: 99 µm; Asymmetry: 5%; Porosity (ε): 72.87%; Average pore size: 1.83 µm; Macropores of average surface area: 350.85µm2; Contact angle: 62.58 °; CO2 absorption flow: 1,1507 mol / m2 · h;
    Preparation of magnetic nanoparticles
    Example 5
    4.01 grams of FeCl2 · 4H2O and 2.02 grams of CuCl2 · 2H2O were mixed in 100 grams of milliQ water at room temperature 25 ° C for 1h using a magnetic stirrer at
    1,100 rpm. Next, a 1M NaOH solution was added slowly until the CuFe2O4 nanoparticles precipitated. Then, it was decanted and rinsed with distilled water. Next, the CuFe2O4 nanoparticles were dried at 50 ° C for 72h.
    Example 6
    3.58 grams of FeCl2 · 4H2O and 9.73 grams of FeCl3 · 6H2O were mixed in 50 g of milliQ water at room temperature 25 ° C for 1 hour using a magnetic stirrer at 1,100 rpm. The homogeneous solution obtained was added dropwise to 450 mL of 1 M NH4OH under a nitrogen atmosphere. The nanoparticles obtained from Fe3O4-OH were collected by centrifugation, washed with 400 grams of distilled water and dried at 25 ° C in a desiccator for 24h. Next, 4 grams of Fe3O4-OH nanoparticles were mixed with 410 mL of a 2% aminopropyltriethoxy silane solution, vibrated by an orbital vibrator at 200 rpm and 70 ° C for 24 hours. Next, the black nanoparticles obtained from Fe3O4-NH2 were collected by centrifugation, washed with 500g of distilled water and dried at 25 ° C in a desiccator for 24h.
    Preparation of the polysulfone membrane with magnetic nanoparticles
    Example 8
    19 grams of polysulfone (Mw 35,000) were dissolved in 80.00 grams of N, N-Dimethylformamide as solvent. The solution was stirred at room temperature 25 ° C for 48 hours using a magnetic stirrer at 300 rpm. Then, 1 gram of the nanoparticles prepared in Example 6 was added gently. The solution was stirred for 1 h at room temperature 25 ° C using 110W ultrasound equipment (JP Selecta, Spain) and left overnight. for degassing Next, the solution was molded into a glass holder by using a 300 μm film stick connected to a K-type paint applicator (R K Print Coat Instruments, Ltd., U.K.). Then, the molded film was coagulated in a bath containing 3,000g of distilled water as a non-solvent. After separation and phase formation, the membrane was stored in water for 0.5h to ensure complete phase separation. This allowed the water soluble membrane components to be leached. As a final stage, the membrane was dried by placing it between two sheets of blotting paper for 24 h at room temperature.
    Characteristics of the membrane obtained:Thickness: 176 µm; Asymmetry: 12%; Porosity (ε): 72.97%; Average pore size: 2.17 µm;
    Macropores of average surface area: 1210.29µm2; Contact angle: 72.06 °; CO2 absorption flow: 0.2114 mol / m2 · h; Example 8 This example was performed similarly to Example 7, except for the bar space
    film that in this example was 250 μm instead of 300 μm. Characteristics of the membrane obtained:
    Thickness: 100 µm; Asymmetry: 4%; Porosity (ε): 71.24%; Average pore size: 4.88 µm; Macropores of average surface area: 587.13 µm2; Contact angle: 65.81 °; CO2 absorption flow: 0.536 mol / m2 · h;
    Example 9
    This example was performed similarly to Example 8, except for the solvent that was 1-Methyl-2-pyrrolidone instead of N, N-Dimethylformamide.
    Characteristics of the membrane obtained:
    Thickness: 123µm; Asymmetry: 6%; Porosity (ε): 71.25%; Average pore size: 5.00 µm; Macropores of average surface area: 588.76µm2; Contact angle: 70.04 °; CO2 absorption flow: 0.9344 mol / m2 · h;
    Example 10
    This example was performed similarly to Example 9, except for the space of the film bar that was 200 μm instead of 250 μm.
    Characteristics of the membrane obtained:
    Thickness: 92 µm; Asymmetry: 13%; Porosity (ε): 69.78%; Average pore size: 4.84 µm; Macropores of average surface area: 457.69µm2; Contact angle: 82.57 °; CO2 absorption flow: 0,3484 mol / m2 · h;
    Example 11
    This example was performed similarly to Example 7, except that 1 gram of Fe3O4 nanoparticles functionalized with amino groups (-NH2) prepared in Example 6 was used instead of 1 gram of CuFe2O4 nanoparticles.
    Example 12
    This example was performed similarly to Example 7, except that 2 grams of CuFe2O4 nanoparticles and 18 grams of polysulfone (dissolved in 80 grams of N, N-Dimethylformamide as solvent) were used.
    Polysulfone membrane preparation with magnetic nanoparticles and enzymes
    Example 13
    16 cm2 of the polysulfone membrane containing Fe3O4-NH2 nanoparticles prepared in Example 11 was incubated for 5 minutes in a solution containing: 0.01 grams of the RuBisCO enzyme; 0.017 grams of triton-x-100 surfactant; 1,000 grams of milliQ water. Next, 10.65 grams of ammonium sulfate was added and the solution was stirred using a magnetic stirrer at 300 rpm for 60h at room temperature 25 ° C. The membrane was then immersed in 500 mL of carbonate-bicarbonate buffer of pH 10 for 10 minutes. Then, 0.02 grams of sodium borohydrate was added to the mixture. The prepared mixture was stirred for 2h at room temperature 25 ° C using a magnetic stirrer at 300 rpm. Then, the pre-treated membrane was immersed for 5 minutes in 100 mL of a solution containing: 5 mL glutaraldehyde, 0.1 grams of triton-x-100 and 94.9 grams of milliQ water. Then, it was stirred with a magnetic stirrer for 24h at room temperature 25 ° C to give the polysulfone membrane
    15 modified with Fe3O4-NH-RuBisCO nanoparticles.
    Although reference has been made to a specific embodiment of the invention, it is apparent to one skilled in the art that the described membrane is susceptible to numerous variations and modifications, and that all the mentioned details can be replaced by other technically equivalent ones, without departing from the scope of protection
    20 defined by the appended claims.
    权利要求:
    Claims (15)
    [1]
    one. Asymmetric polysulfone membrane sequestering CO2 from the atmosphere, characterized by the fact that it consists of a chemically substantially homogeneous structure of polysulfone or a polysulfone derivative comprising a first porous surface region interconnected with a second transport region that includes macropores, and by the fact that the structure comprises magnetic nanoparticles at a concentration between 0.01 and 35% by weight with respect to the total weight of the membrane, the magnetic nanoparticles being mostly distributed in the first surface region.
    [2]
    2. CO2 sequestrant membrane according to claim 1, characterized in that the first porous surface region includes pores of average pore size between 1.5 and 7 µm, and the second transport region includes macropores of average surface area between 300 and 1300 µm2.
    [3]
    3. CO2 sequestrant membrane according to claim 1, characterized in that the membrane is flat and between 70 and 180 µm thick.
    [4]
    Four. CO2 sequestrant membrane according to claim 1, characterized in that the structure comprises at least one enzyme selected from the group consisting of RuBisCo or a carbonic Anhydrase.
    [5]
    5. CO2 sequestrant membrane according to claim 4, characterized in that the carbonic Anhydrase enzyme is mostly distributed in the first surface region.
    [6]
    6. CO2 sequestrant membrane according to claim 4, characterized in that the RuBisco enzyme is mostly distributed in the second transport region.
    [7]
    7. CO2 sequestrant membrane according to claim 1, characterized in that the magnetic nanoparticles are functionalized with amino groups.
    [8]
    8. CO2 sequestering membrane according to claim 1, characterized in that polysulfone or polysulfone derivative has an average molecular weight between 20,000 and 75,000 g / mol.
    [9]
    9. CO2 sequestrant membrane according to claim 1, characterized in that the membrane has an asymmetry comprised between 3 and 15%, and has been formed by phase inversion precipitation technology.
    [10]
    10. CO2 sequestrant membrane according to any one of claims 1 to 9, characterized in that, at room temperature and pressure, it is capable of sequestering CO2 from the atmosphere air at a flow rate of 0.1 to 1.2 moles of CO2 per m2 / h of the membrane or higher.
    [11]
    eleven. Process for the preparation of a membrane according to any one of claims 1 to 10, based on the phase inversion precipitation technology, characterized in that it comprises the following steps:
    - dissolve in an organic solvent of a polysulfone polymer or polysulfone derivative at a concentration between 2 and 30% by weight with respect to the weight of the organic solvent, and stir the resulting polymer solution;
    - let the polymer solution stand for degassing;
    - To the degassed polymer solution, add magnetic nanoparticles at a concentration between 0.01 and 35% by weight with respect to the weight of the polymer solution and stir to obtain a mixture of polymer solution and nanoparticles.
    5 magnetic;
    - pour the obtained mixture into a support for this purpose, mold it with the use of a film bar and then immerse in a coagulation bath comprising a nosolvent, so that the precipitation of the polymer on the support takes place to form the membrane comprising magnetic nanoparticles;
    10-remove from the bath, dry and separate the membrane from the support.
    [12]
    12. Method according to claim 11, characterized in that it comprises:
    - incubate the membrane in a previously prepared suspension that includes at least one enzyme selected from RuBisCo and a carbonic Anhydrase at a concentration
    15 comprised between 0.025 and 1.2 mg per mg of functionalized magnetic nanoparticle with amino groups in the membrane.
    [13]
    13. CO2 absorption system of the atmosphere for transport or subsequent reuse of CO2, characterized by the fact that it comprises:
    - a CO2 absorbing solution, and
    A membrane according to any one of claims 1 to 10, wherein the first porous surface region defines an outer surface or face of the membrane and is disposed in contact with the atmosphere air, and where the second transport region that includes macropores defines another outer surface or opposite face of the membrane and is associated with the CO2 absorbing solution,
    25 so that, at ambient pressure and temperature, the CO2 in the air in the atmosphere is spontaneously adsorbed on the outer surface of the membrane of the surface region, diffused through the membrane through the transport region to the other outer surface or opposite face of the membrane and absorbed in the absorbent solution for transport or subsequent reuse.
    14. The CO2 absorption system of the atmosphere according to claim 13, characterized in that the absorbent solution is an alkaline aqueous solution of pH between 8 and 9.
    [15]
    15. Atmospheric CO2 absorption system according to any of the claims
    13 and 14, characterized by the fact that the system is capable of transporting CO2 at a flow rate of 0.1 to 1.2 moles of CO2 per m2 / h of the membrane or higher.
    [16]
    16. Use of the membrane according to any one of claims 1 to 10 to capture CO2 from the air in the atmosphere.
    FIG. one
    FIG. 2
    FIG. 3
    FIG. 4
    类似技术:
    公开号 | 公开日 | 专利标题
    Xie et al.2019|Recent progress on fabrication methods of polymeric thin film gas separation membranes for CO2 capture
    Zhang et al.2016|High performance thin-film composite | forward osmosis | membrane fabricated on novel hydrophilic disulfonated poly | multiblock copolymer/polysulfone substrate
    ES2788169T3|2020-10-20|Selectively Permeable Graphene Oxide Membrane
    Ghanbari et al.2015|Synthesis and characterization of novel thin film nanocomposite | membranes embedded with halloysite nanotubes | for water desalination
    Lin et al.2016|Enhancement of polyethersulfone | membrane doped by monodisperse Stöber silica for water treatment
    Zhu et al.2014|Dual-layer polybenzimidazole/polyethersulfone | nanofiltration | hollow fiber membranes for heavy metals removal from wastewater
    He et al.2016|Concurrent removal of selenium and arsenic from water using polyhedral oligomeric silsesquioxane |–polyamide thin-film nanocomposite nanofiltration membranes
    ES2364041T3|2011-08-23|MEMBRANES TO FIND.
    El Badawi et al.2014|Novel carbon nanotube–cellulose acetate nanocomposite membranes for water filtration applications
    Hester et al.2002|Design and performance of foul-resistant poly | membranes prepared in a single-step by surface segregation
    Chen et al.2004|Preparation and performance of cellulose acetate/polyethyleneimine blend microfiltration membranes and their applications
    Guo et al.2020|Ultra-thin double Janus nanofiltration membrane for separation of Li+ and Mg2+:“Drag” effect from carboxyl-containing negative interlayer
    Cho et al.2011|Fouling-tolerant polysulfone–poly | random copolymer ultrafiltration membranes
    Blinova et al.2012|Functionalized polyaniline-based composite membranes with vastly improved performance for separation of carbon dioxide from methane
    Wang et al.2017|Recent progress on submicron gas-selective polymeric membranes
    Dai et al.2020|Constructing interlayer to tailor structure and performance of thin-film composite polyamide membranes: A review
    Lim et al.2019|Defect-free outer-selective hollow fiber thin-film composite membranes for forward osmosis applications
    Rastgar et al.2018|Highly-efficient forward osmosis membrane tailored by magnetically responsive graphene oxide/Fe3O4 nanohybrid
    Wang et al.2018|Dopamine incorporating forward osmosis membranes with enhanced selectivity and antifouling properties
    Zhang et al.2018|Polyphenol-assisted in-situ assembly for antifouling thin-film composite nanofiltration membranes
    Yong et al.2017|Nanoparticles embedded in amphiphilic membranes for carbon dioxide separation and dehumidification
    Stucki et al.2018|Porous polymer membranes by hard templating–a review
    Gui et al.2020|Ultrafast ion sieving from honeycomb-like polyamide membranes formed using porous protein assemblies
    Zhao et al.2019|Efficient removal of heavy metal ions based on the selective hydrophilic channels
    Xie et al.2020|Improved permeability and antifouling properties of polyvinyl chloride ultrafiltration membrane via blending sulfonated polysulfone
    同族专利:
    公开号 | 公开日
    ES2673492B2|2018-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20080060651A1|2006-09-08|2008-03-13|Drager Medical Ag & Co. Kg|Process and device for separating carbon dioxide from a breathing gas mixture by means of a fixed site carrier membrane|
    US20090152763A1|2007-12-12|2009-06-18|Chunqing Liu|Molecular Sieve/Polymer Asymmetric Flat Sheet Mixed Matrix Membranes|
    法律状态:
    2018-06-22| BA2A| Patent application published|Ref document number: 2673492 Country of ref document: ES Kind code of ref document: A1 Effective date: 20180622 |
    2018-10-31| FG2A| Definitive protection|Ref document number: 2673492 Country of ref document: ES Kind code of ref document: B2 Effective date: 20181031 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201631648A|ES2673492B2|2016-12-21|2016-12-21|ASYMMETRIC MEMBRANE OF ATMOSPHERE CO2 SEQUESTING POLYSULPHONE, PROCEDURE FOR OBTAINING AND CO2 ABSORPTION SYSTEM USING SUCH MEMBRANE|ES201631648A| ES2673492B2|2016-12-21|2016-12-21|ASYMMETRIC MEMBRANE OF ATMOSPHERE CO2 SEQUESTING POLYSULPHONE, PROCEDURE FOR OBTAINING AND CO2 ABSORPTION SYSTEM USING SUCH MEMBRANE|
    [返回顶部]