JP2013094741A - Hollow fiber carbon membrane, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hollow fiber carbon membrane and a method for manufacturing the hollow fiber carbon membrane of high practicability combining high permeability and high selectivity when used as a separation membrane of a mixture, and securing flexibility required for modularization.SOLUTION: The hollow fiber carbon membrane includes a first hollow filiform carbon membrane, and a second carbon membrane provided on the outer surface of the first carbon membrane, and has a rupture elongation of 1-4%. The second carbon membrane is higher in compatibility with penetration components than the first carbon membrane. The method for manufacturing the hollow fiber carbon membrane includes steps of preparing a first precursor polymer which is a precursor polymer of the first carbon membrane, preparing a second precursor polymer which is a precursor polymer of the second carbon membrane, forming a hollow fiber carbon membrane precursor with the second precursor polymer installed on the outer surface of the first hollow filiform precursor polymer, and carrying out carbonization treatment of the hollow fiber carbon membrane precursor.

Description

  The present invention relates to a hollow fiber carbon membrane comprising a hollow fiber-like first carbon membrane and a second carbon membrane provided on the outer surface of the first carbon membrane, and a method for producing the same.

  From the viewpoint of environmental problems and energy saving in recent years, membrane separation methods have attracted attention in separation from mixtures such as various gases, and dehydration / purification processes of organic solvents. As the separation membrane to be used, polymer membranes such as polyimide membranes and polysulfone membranes have been proposed, but such polymer membranes have problems in heat resistance and solvent resistance. In addition, it is known to use a zeolite membrane, which is superior in heat resistance as compared with a polymer membrane, as a separation membrane, but the zeolite membrane has a problem of poor acid resistance.

  In recent years, carbon membranes have been developed as separation membranes excellent in heat resistance, solvent resistance, and acid resistance. Such carbon films are roughly classified into two types: a support-type carbon film formed on the surface of a support (porous substrate) and a self-supporting carbon film that does not use a support. Representative examples of the self-supporting carbon membrane include a flat membrane type and a hollow fiber type. Among them, a hollow fiber type (hollow fiber carbon membrane) is considered preferable because the membrane area per unit volume can be increased. ing.

  In order to form a dense and highly hydrophilic membrane structure in a self-supporting hollow fiber carbon membrane, it is known that it is effective to use a sulfonated polymer as a precursor. For example, Japanese Unexamined Patent Application Publication No. 2009-34614 (Patent Document 1) discloses a hollow fiber carbon membrane using a sulfonated polyphenylene oxide (SPPO) as a precursor.

  Moreover, as a subject of the carbon membrane, both high permeability and high selectivity can be mentioned from the viewpoint of membrane separation of the mixture. For example, in JP 2010-269229 A (Patent Document 2), dehydration from alcohol is studied, and the carbon film is hydrophilized by introducing excessive hydrophilic metal ions into the carbon film, and the alcohol By suppressing adsorption, we are trying to obtain high water permeability and selectivity.

  JP 2006-231095 (Patent Document 3) discloses a hollow fiber carbon membrane for gas separation using polyphenylene oxide (PPO) as a precursor.

  On the other hand, as a support-type carbon film, for example, in Japanese Patent No. 3647985 (Patent Document 4), a coating layer such as silica sol or alumina sol is formed on the surface of a ceramic porous body, and a carbon film adhered to the surface is formed. A molecular sieving carbon film is disclosed. JP 2010-510870 (Patent Document 5) discloses a first carbon film (carbon film underlayer) on the surface of a porous substrate and a surface of the first carbon film. A carbon membrane laminate including a second carbon membrane (carbon membrane separation layer) that is thinner than the carbon membrane and has a smaller average pore diameter is disclosed.

JP 2009-34614 A JP 2010-269229 A JP 2006-231095 A Japanese Patent No. 3647985 JP 2010-510870 A

  The present inventors tried to produce an SPPO hollow fiber carbon membrane according to the description in Patent Document 1. However, although the produced SPPO hollow fiber carbon membrane has a very dense membrane structure, the separation performance in the pervaporation separation method that removes water from the solvent is very good, but the entire membrane structure becomes dense, so The problem was that the performance would be low. In addition, in the SPPO hollow fiber carbon membrane disclosed in Patent Document 1, SPPO having a high degree of sulfonation (for example, the degree of sulfonation described as an example in Patent Document 1 of 45%) is due to the high hydrophilicity of the polymer. As a result of containing a large amount of moisture in the spinning process, the strength of the membrane is weakened, and the hollow fiber membranes are easily bonded to each other in the drying process, resulting in difficulty in handling in the mass production process.

  In the invention described in Patent Document 2, when a metal is introduced into the entire membrane, the affinity with water as a permeable material is improved, but the surface (upstream side) to the center portion to the back surface (downstream side) in the membrane cross section. Since the hydrophilicity increases in all cases, the selectivity of water on the surface (upstream side) is improved. However, the permeation flow rate is still low due to the adverse effects caused by diffusion at the center of the membrane and desorption to the outside of the membrane (downstream side). there were.

  In addition, the present inventors tried to produce a PPO hollow fiber carbon membrane according to the description in Patent Document 3. However, since the produced PPO hollow fiber carbon membrane is a carbon membrane having a relatively large pore diameter and high hydrophobicity in the pores, it has a structure that allows water molecules to easily permeate. When water is removed from a low solvent, water is not selectively permeated, resulting in poor separation performance. Further, since the permeation of water molecules is hindered by the low hydrophilic solvent molecules adsorbed in the membrane pores of the PPO hollow fiber carbon membrane, the total permeation amount is also reduced as a result. In addition, the PPO hollow fiber carbon membrane described in Patent Document 3 has a problem in that it is difficult to handle in the manufacturing process of the separation membrane module because it is poor in flexibility and easily broken.

  Further, in the support-type carbon membranes described in Patent Documents 4 and 5, since different materials such as ceramics that are not carbon are used for the porous base material, the thermal expansion coefficient differs between carbon and different materials such as ceramics. Therefore, there is a problem that cracks and peeling occur during firing or use. In addition, with respect to the carbon membrane laminate disclosed in Patent Document 5, the average pore size alone is insufficient to achieve both permeability and selectivity, and the affinity with the permeating substance is not considered. The selectivity was still low.

  The present invention has been made in order to solve the above-mentioned problems, and the object is to achieve both high permeability and high selectivity when used as a separation membrane for a mixture, and An object of the present invention is to provide a hollow fiber carbon membrane having high practicality and a method for producing the same, ensuring flexibility necessary for modularization.

  The hollow fiber carbon membrane of the present invention comprises a hollow fiber-shaped first carbon membrane and a second carbon membrane provided on the outer surface of the first carbon membrane, and the elongation at break is 1 to 4%. In addition, the second carbon film has a higher affinity with a permeable component than the first carbon film.

  In the hollow fiber carbon membrane of the present invention, the precursor polymer of the second carbon membrane is a repetition of a repeating unit A represented by the following formula (I) and a repeating unit B represented by the following formula (II): Has a structure,

In the formula (I) and the formula (II), m and n are each a natural number of 1 or more, and in the formula (II), R ¹ and R ² are each independently a hydrogen atom, or A sulfone group, a carboxyl group, and a phosphonic acid group which may be partially or wholly neutralized with a metal element; R ¹ and R ² do not simultaneously represent a hydrogen atom; the repeating unit A and the repeating unit B The ratio of the percentage of the number of repeating units B to the total number is preferably larger than 15% and smaller than 100%.

In the hollow fiber carbon membrane of the present invention, R ¹ and R ² in the formula (II) each independently represent —SO ₃ M, —SO ₃ H or a hydrogen atom, where M represents a metal element. Is preferred.

  In the hollow fiber carbon membrane of the present invention, the thickness of the first carbon membrane is preferably 5 to 100 μm, and the thickness of the second carbon membrane is preferably 0.05 to 20 μm.

The hollow fiber carbon membrane of the present invention preferably has a tensile elastic modulus of 5 GPa or more.
The permeation component of the hollow fiber carbon membrane of the present invention is preferably water. In this case, the hollow fiber carbon membrane of the present invention can be suitably used for separating the water from the volatile organic compound containing water.

  The hollow fiber carbon membrane of the present invention can also be suitably used for separating the volatile organic compound from the air containing the volatile organic compound.

  The present invention also includes a step of producing a first precursor polymer that is a precursor polymer of the first carbon film, and a second precursor polymer that is a precursor polymer of the second carbon film. A step, a step of forming a hollow fiber carbon membrane precursor in which a second precursor polymer is placed on the outer surface of the hollow fiber-like first precursor polymer, and a step of carbonizing the hollow fiber carbon membrane precursor A method for producing a hollow fiber carbon membrane is also provided.

  Also in the method for producing a hollow fiber carbon membrane of the present invention, the precursor polymer of the second carbon membrane includes a repeating unit A represented by the following formula (I) and a repeating unit represented by the following formula (II): Having a repeating structure with B,

In the formula (I) and the formula (II), m and n are each a natural number of 1 or more, and in the formula (II), R ¹ and R ² are each independently a hydrogen atom, or A sulfonic acid group, a carboxyl group, and a phosphonic acid group, which may be partially or wholly neutralized with a metal element, wherein R ¹ and R ² do not simultaneously represent a hydrogen atom, and the repeating unit A and the repeating unit The ratio of the percentage of the number of repeating units B to the total number of B is preferably larger than 15% and smaller than 100%.

Also in the method for producing a hollow fiber carbon membrane of the present invention, R ¹ and R ² in the formula (II) each independently represent —SO ₃ M, —SO ₃ H or a hydrogen atom, where M is a metal It is preferable to show an element.

  In the method for producing a hollow fiber carbon membrane of the present invention, it is preferable that the first precursor polymer is polyphenylene oxide and the second precursor polymer is sulfonated polyphenylene oxide.

  It is preferable that the method for producing a hollow fiber carbon membrane of the present invention further includes a step of subjecting the hollow fiber carbon membrane precursor to flame resistance treatment before the step of carbonizing.

  According to the present invention, the second carbon membrane having a high affinity with the permeation component is disposed on the front side, and the first carbon membrane having a low affinity with the permeation component is disposed on the back side. It becomes possible to achieve both transparency. In addition, the hollow fiber carbon membrane of the present invention is excellent in flexibility, is not easily damaged, is easily modularized, and has excellent practicality.

It is sectional drawing of the hollow fiber carbon membrane 10 of a preferable example of this invention. FIG. 2A is a front view of the hollow fiber carbon membrane 10 of the example shown in FIG. 1, and FIG. 2B is a partially enlarged view of FIG. It is a figure which shows typically the sample mount 21 used for the tension test. It is a figure which shows typically a pervaporation apparatus.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be specifically described. However, the present invention is not limited to the following embodiment, and is within the scope of the present invention without departing from the spirit of the present invention. It should be understood that design changes, improvements, and the like can be made as appropriate based on the knowledge.

  1 is a cross-sectional view of a preferred example of the hollow fiber carbon membrane 10 of the present invention, FIG. 2 (a) is a front view of the hollow fiber carbon membrane 10 of the example shown in FIG. 1, and FIG. 2 (b) is FIG. It is a figure which expands and shows (a) partially. The hollow fiber carbon membrane 10 of the present invention of the example shown in FIGS. 1 and 2 includes a hollow carbon-like first carbon membrane 1 and a second carbon membrane 2 provided on the outer surface of the first carbon membrane 1. And the second carbon film 2 has a higher affinity with a permeable component than the first carbon film 1.

  1 and 2 show an example in which the second carbon film 2 is provided on the outer surface of the first carbon film 1. In this case, the mixture containing the permeating component is brought into contact from the second carbon membrane 2 side which is the outer surface side of the hollow fiber. The second carbon film 2 in contact with the mixture containing the permeable component first selects the permeable component from the mixture and takes it into the second carbon film 2. The permeation component taken into the second carbon film 2 diffuses in the second carbon film 2, migrates into the first carbon film 1 below it, and diffuses into the first carbon film 1. After that, it is desorbed from the first carbon film 1 and permeates. Thus, in the hollow fiber carbon membrane of the present invention, different characteristics are required for the first carbon membrane 1 and the second carbon membrane 2.

  Here, as the first carbon film 1 and the second carbon film 2, a porous film containing carbon as a main component can be used. The first carbon film 1 and the second carbon film 2 may contain components other than carbon as long as they contain carbon as a main component. The carbon content in the first carbon film 1 and the second carbon film 2 is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably it is. In the present specification, the “main component” means a component having the largest content (% by mass) in the constituent components of the film. In addition, the structural component and its content of the hollow fiber carbon membrane 10 can be specified by, for example, energy dispersive X-ray spectroscopy (EDS).

  Furthermore, the present inventors have excellent gas separation performance and flexibility when the breaking elongation of the hollow fiber carbon membrane 10 is 1 to 4%, so that it is difficult to break and modularization is easy. It was found that a hollow fiber carbon membrane excellent in practicality can be provided. When the breaking elongation of the hollow fiber carbon membrane 10 is less than 1%, sufficient flexibility as the hollow fiber carbon membrane cannot be obtained and easily damaged, resulting in difficulty in handling during module production. Further, when it exceeds 4%, there is a problem that the acidification, the chemical resistance and the gas separation performance are not sufficient because the carbonization has not progressed sufficiently. That is, the elongation at break of the hollow fiber carbon membrane 10 is 1 for securing flexibility as the hollow fiber carbon membrane and improving the acid resistance, chemical resistance and gas separation performance as the carbon membrane. It is preferable to be within the range of 0.5 to 3.5%. The elongation at break of the hollow fiber carbon membrane 10 is, for example, a tensile tester technograph (TGI-200N or TG) in accordance with Japanese Industrial Standard “Testing Method for Tensile Properties of Carbon Fiber-Single Fiber” (JIS R7606). It can be measured by conducting a tensile test using -200NB Minebea Co., Ltd.).

  Further, the tensile elastic modulus of the hollow fiber carbon membrane 10 is preferably 5 GPa or more, and more preferably 10 GPa or more. When the tensile modulus of the hollow fiber carbon membrane 10 is less than 5 GPa, even if the elongation at break is high, the carbonization is not sufficiently advanced, so that the acid resistance, chemical resistance and gas separation performance are not sufficient. Because there is. If the carbonization proceeds too much, the elastic modulus of the carbon membrane increases, but the number of defects increases, resulting in a decrease in elongation.As a result, flexibility is lost, and further, the gas separation performance caused by the defects is reduced. Decline is likely to occur. For these reasons, the tensile elastic modulus of the hollow fiber carbon membrane 10 is preferably 50 GPa or less, and more preferably 30 GPa or less. The tensile modulus of the hollow fiber carbon membrane 10 is based on the tensile strength used for the measurement of the breaking elongation described above in accordance with the Japanese Industrial Standard “Testing Method for Tensile Properties of Carbon Fiber-Single Fiber” (JIS R7606: 2000). It can be measured using a testing machine. At this time, the measurement of the cross-sectional area of the hollow fiber carbon membrane in order to evaluate the tensile elastic modulus is the C method of Japanese Industrial Standard “Testing Method of Diameter and Cross-sectional Area of Carbon Fiber-Single Fiber” (JIS R7607: 2000). In conformity, the surface perpendicular to the fiber axis direction of the hollow fiber carbon membrane embedded in the resin piece was polished, and the cross section thereof was photographed with a scanning microscope (Scanning Electron Microscopy: SEM). This is possible by measuring the cross-sectional area and calculating the average value.

  The precursor polymer (first precursor polymer) of the first carbon film used in the present invention can function as a hollow fiber-like structure (support layer) even after the carbonization treatment. Strength and flexibility are required. Moreover, when the permeation | transmission component contained in a mixture is water, it is important to diffuse water efficiently and to discharge | emit it out of a 1st carbon film efficiently. For this reason, the first carbon film is required to have lower affinity for the permeable component than the second carbon film. Further, the molecular structure of the precursor polymer of the first carbon film is preferably a structure in which crosslinking with the structure of the precursor polymer of the second carbon film easily occurs during the heat treatment. Thereby, in a self-supporting hollow fiber carbon membrane, peeling of the interface between the first carbon membrane and the second carbon membrane formed of different materials can be made difficult to occur.

  As the first precursor polymer, for example, a known carbonizable polymer such as polyphenylene oxide, polyacrylonitrile, or polyethersulfone can be suitably used. Among these, polyphenylene oxide is more preferable because it has a high carbonization yield and is relatively inexpensive. The molecular weight of polyphenylene oxide is not particularly limited, but the weight average molecular weight is preferably in the range of 5,000 to 100,000 because it can be spun as a hollow fiber and can maintain the shape of the hollow fiber.

  In the second carbon membrane in the hollow fiber carbon membrane of the present invention, it is important to selectively work the permeation component from the mixture into the membrane, and high affinity with the permeation component is required. That is, when the permeation component contained in the mixture is water, it is preferable that the second carbon film has high affinity for water (hydrophilicity). Here, the characteristics of the carbon film reflect the characteristics of the precursor polymer before the carbonization treatment. Therefore, in order to increase the hydrophilicity of the second carbon film, the hydrophilicity of the precursor polymer (second precursor polymer) of the second carbon film is preferably high.

  The second precursor polymer having high hydrophilicity is not particularly limited, but includes a repeating unit A represented by the following formula (I) and a repeating unit B represented by the following formula (II). It preferably has a repeating structure.

  Here, in the formula (I) and the formula (II), m and n are each a natural number of 1 or more, and these are not particularly limited, but m is preferably in the range of 1 to 2000, more preferably Is in the range of 5 to 1000, and n is preferably in the range of 1 to 2000, more preferably in the range of 5 to 1000.

In the formula (II), R ¹ and R ² each independently represent a hydrogen atom or a sulfonic acid group, a carboxyl group, or a phosphonic acid group that may be partially or wholly neutralized with a metal element. R ¹ and R ² do not represent a hydrogen atom at the same time. R ¹ and R ² are each independently —SO ₃ M, —SO ₃ H or polyphenylene oxide representing a hydrogen atom from the viewpoint of not only high hydrophilicity but also high film-forming properties and structural controllability. It is particularly preferable to use it. Here, M represents a metal element, and examples thereof include one or more selected from monovalent metal elements such as lithium, sodium, and potassium, and divalent or higher metal elements such as calcium, magnesium, aluminum, and iron. Among these, sodium and / or potassium is preferable as the metal element, and sodium is particularly preferable from the viewpoint of easy availability and handling of the metal.

In the second precursor polymer used in the present invention, the ratio of the percentage of the number of repeating units B to the total number of repeating units A and B is greater than 15% and smaller than 100%. Is preferred. When the ratio (R ¹ and R ² independently represent —SO ₃ M, —SO ₃ H or a hydrogen atom, the degree of sulfonation (DS)) is 15% or less, the permeation component There is a tendency that affinity with is small. The ratio is more preferably greater than 30% and particularly preferably greater than 40% from the viewpoint of providing affinity with the permeation component. If the affinity is too high, it is more preferably less than 80%, and particularly preferably less than 60%, from the viewpoint of including moisture in the air and swelling.

  The second precursor polymer used in the present invention is also a sulfonated polyether sulfone having a repeating structure of a repeating unit C represented by the following formula (III) and a repeating unit D represented by the following formula (IV). (SPES) may be used. In this case, a ratio DS of the percentage of the number of repeating units D to the total number of repeating units C and D (degree of sulfonation: 100 × (number of repeating units D) / (total number of repeating units C and repeating units D) )) Is a sulfonated polyethersulfone containing a sulfonic acid group satisfying the relational expression of 15 <DS <100, preferably 30 <DS <100, more preferably 40 <DS <100. As the ratio DS of the percentage of the number of repeating units D to the total number of repeating units C and repeating units D of the sulfonated polyethersulfone increases, the hydrophilicity of the second carbon film 2 obtained through the carbonization treatment step described later is increased. Since the property increases, the water separation performance tends to increase.

  In the formula (III) and the formula (IV), k and l are each a natural number of 1 or more, and these are not particularly limited, but k is preferably in the range of 1 to 2000, more preferably It is in the range of 5-1000, and l is preferably in the range of 1-2000, more preferably in the range of 5-1000.

In the formula (IV), R ³ and R ⁴ are both sulfonic acid groups and represent —SO ₃ M or —SO ₃ H. Here, M represents a metal element, and examples thereof include one or more selected from monovalent metal elements such as lithium, sodium, and potassium, and divalent or higher metal elements such as calcium, magnesium, aluminum, and iron. Among them, when a hollow fiber carbon membrane is produced, the pore size of the carbon membrane suitable for pervaporation separation is obtained, and the hydrophilicity of the carbon membrane is increased, so that sodium and / or potassium is used as the metal element. Sodium is particularly preferred.

  The thickness T1 of the first carbon membrane 1 constituting the hollow fiber carbon membrane 10 of the present invention is not particularly limited, but is in the range of 5 to 100 μm from the viewpoint of both strength and flexibility. It is preferable that it is in the range of 5 to 50 μm, and it is particularly preferable that it is in the range of 5 to 30 μm.

  Further, the thickness T2 of the second carbon membrane 2 constituting the hollow fiber carbon membrane 10 of the present invention is not particularly limited, but it is preferable that the permeation component rapidly migrates to the first carbon membrane 1, It is preferable that the film thickness is thinner than the one carbon film 1. Specifically, the thickness T2 of the second carbon film 2 is preferably in the range of 0.05 to 20 μm, and more preferably in the range of 0.05 to 10 μm. If the thickness T2 of the second carbon film 2 is less than 0.05 μm, there is a high possibility that defects will occur in the second carbon film. This is because it tends to be difficult to shift to the carbon film 1.

  The total film thickness (T1 + T2) of the first carbon film 1 and the second carbon film 2 is preferably 1 to 50 μm. When the total film thickness (T1 + T2) of the first carbon film 1 and the second carbon film 2 of the hollow fiber carbon film 10 is less than 1 μm, sufficient flexibility as a self-supporting hollow fiber carbon film is obtained. This is because it tends to be damaged, and when it exceeds 50 μm, the permeation resistance of gas molecules becomes too large, so that a sufficient permeation flow rate as a gas separation membrane cannot be obtained. Because. That is, the total of the first carbon membrane 1 and the second carbon membrane 2 of the hollow fiber carbon membrane 10 is ensured because the flexibility as the hollow fiber carbon membrane is ensured and the permeation flow rate of gas separation is also secured. The film thickness (T1 + T2) is more preferably 5 to 20 μm.

  The outer diameter of the hollow fiber carbon membrane 10 is not particularly limited, but is preferably 50 to 500 μm. When the outer diameter of the hollow fiber carbon membrane 10 is less than 50 μm, it becomes difficult to produce in the spinning process of the precursor hollow fiber membrane, and the inner diameter of the hollow fiber carbon membrane 10 becomes too small, which may cause clogging with foreign matters. This is because it tends to occur. Further, when the outer diameter of the hollow fiber carbon membrane 10 exceeds 500 μm, the minimum bending radius at which the hollow fiber carbon membrane 10 breaks increases as the outer diameter of the hollow fiber carbon membrane 10 increases, and the handleability tends to deteriorate. Because it is in. That is, because of the ease of production, the provision of a sufficient space in the hollow portion 3 of the hollow fiber carbon membrane 10, and the sufficient flexibility as the hollow fiber carbon membrane 10 is ensured, the hollow fiber carbon membrane 10 The outer diameter is more preferably 100 to 400 μm.

  The thickness T1 of the first carbon film 1, the thickness T2 of the second carbon film 2, the total film thickness (T1 + T2) of the first carbon film 1 and the second carbon film 2, and hollow fiber carbon For the outer diameter of the membrane 10, for example, a method of evaluating the cross section of the hollow fiber carbon membrane embedded in the resin piece by SEM can be used.

  The hollow fiber carbon membrane of the present invention comprises (1) a step of producing a first precursor polymer, (2) a step of producing a second precursor polymer, and (3) a hollow fiber-like first precursor. By a method comprising a step of forming a hollow fiber carbon membrane precursor in which a second precursor polymer is disposed on the outer surface or inner surface of the polymer, and (4) a step of carbonizing the hollow fiber carbon membrane precursor It can manufacture suitably. The present invention also provides a method for producing a hollow fiber carbon membrane including the steps (1) to (4).

  Each process of the manufacturing method of the hollow fiber carbon membrane of this invention mentioned above can be suitably implemented by combining suitably the method conventionally used in this field | area. As a method of forming a hollow fiber carbon membrane precursor in which a second precursor polymer is installed on the outer surface of a hollow fiber-shaped first precursor polymer, for example, a first precursor polymer molded into a hollow fiber shape is used. An example is a dip coating method in which a solution obtained by dissolving the second precursor polymer is impregnated and then pulled up and dried. Since the membrane structure is easily controlled and the production process is simple, it is particularly suitable for forming a hollow fiber carbon membrane precursor.

  In this case, the method for forming the first precursor polymer into a hollow fiber shape is not particularly limited, but the breaking elongation of the hollow fiber carbon membrane after the carbonization treatment step described later is 1 to 4%, preferably 1 It is carried out by a method such that it becomes 5 to 3.5%. As such a method, for example, [1] a step of dissolving the first precursor polymer in an aprotic solvent (dissolution step), and [2] the first precursor polymer at a temperature-induced phase separation point or higher. A step of discharging from a spinning nozzle at a temperature to form a hollow fiber (discharge step); [3] a step of solidifying the hollow fiber-shaped first precursor polymer with water or a mixed solution of water and an organic solvent (coagulation step); [4] A method including a step (drying step) of drying the solidified hollow fiber-like first precursor polymer from a state containing water without performing a solvent replacement treatment can be suitably used. Hereinafter, a method including the steps [1] to [4] will be described.

[1] Dissolution Step First, for example, polyphenylene oxide (PPO) is dissolved in an aprotic solvent as the first precursor polymer. Solvents for PPO are, for example, benzene, toluene as summarized in known literature (G. Chowdhury, B. Kruczek, T. Matsuura, Polyphenylene Oxide and Modified Polyphenylene Oxide Membranes Gas, Vapor and Liquid Separation, 2001, Springer). , Chloroform such as chloroform has a large environmental load and is harmful to human body. On the other hand, for example, JP-A-3-65227 discloses that PPO is dissolved in an aprotic solvent having a relatively small environmental load at a temperature of about 100 ° C. or higher. As the aprotic solvent used in the present invention, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like are used. Among them, the solubility of PPO is particularly excellent. It is preferable to use methyl-2-pyrrolidone.

  When N-methyl-2-pyrrolidone is used as the aprotic solvent, N-methyl-2-pyrrolidone can uniformly dissolve PPO at a temperature of about 100 ° C. or higher. In addition, a desired poor solvent (for example, methanol, ethanol, acetone, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, etc.) is added to N-methyl-2-pyrrolidone as long as the solubility of the polymer is ensured. Thus, the pore size and pore size distribution of the membrane can be changed.

[2] Discharging Step In the subsequent step, a solution (spinning stock solution) in which the first precursor polymer is dissolved in an aprotic solvent as described above is discharged from a spinning nozzle to form a hollow fiber. The spinning type in the present invention is not particularly limited, and a conventionally known spinning method can be applied. However, from the viewpoint of precisely controlling the structure of the first carbon film 1 and from the viewpoint of ease of production. From the above, it is preferable to apply a dry and wet spinning method.

  In the discharging step, the spinning solution is discharged at a temperature equal to or higher than the temperature-induced phase separation point. Here, the “temperature-induced phase separation point” refers to a temperature at which solidification is not caused by temperature-induced phase separation, for example, a temperature-induced phase of a spinning dope in which PPO is dissolved in N-methyl-2-pyrrolidone (NMP). The separation point varies depending on the spinning dope concentration and the solvent composition, but is generally 80 ° C. (50 to 120 ° C.). Therefore, in this step, spinning is performed together with the internal liquid from a double cylindrical tube nozzle in a state of maintaining a uniform liquid state at a temperature of 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher. It should be noted that the temperature during the discharging step should be set to 200 ° C. or lower from the viewpoint that the viscosity of the stock solution for spinning is not too low and does not impair spinning stability. Is preferable, and it is more preferable to set it as 180 degrees C or less.

  The hollow fiber-shaped spinning dope discharged together with the inner liquid as described above is solidified by non-solvent induced phase separation from the inner liquid. As the internal solution, one that is discharged inside the spinning stock solution discharged in the form of a hollow fiber and can coagulate the spinning stock solution by non-solvent induced phase separation is preferably used. As such an internal solution, a solvent having a boiling point higher than that of water is suitably used when the spinning solution is discharged at 100 ° C. or higher as described above. Examples of such internal liquid include glycerin, ethylene glycol, diethylene glycol and the like. Among them, it is preferable to use ethylene glycol as the internal liquid because the subsequent water washing treatment becomes easy.

[3] Solidification step The spinning dope discharged in the discharge step described above is immersed in a solidification bath filled with a poor solvent in the subsequent solidification step. In addition, from the viewpoint of controlling the membrane structure, such as increasing the polymer concentration on the surface of the hollow fiber membrane and making the surface dense, the spinning dope formed into a hollow fiber after the discharge step is partially dried with a solvent. After that, it is preferable to use the solidification step. In the coagulation step, the spinning dope formed into a hollow fiber is solidified into a hollow fiber by non-solvent induced phase separation.

  As the poor solvent used in the coagulation step, water or a mixed solution of water and an organic solvent is used because it is possible to quickly coagulate the first precursor polymer in the spinning dope and it is easy to use. Is used. In the case of mixing an organic solvent, examples of the organic solvent include methanol, ethanol, glycerin, ethylene glycol, diethylene glycol, acetone, tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like. -Methyl-2-pyrrolidone is preferred.

  The temperature of the poor solvent when dipping the spinning dope is not particularly limited, but is preferably in the range of 0 to 50 ° C, more preferably in the range of 0 to 20 ° C. This is because when the temperature of the poor solvent is less than 0 ° C., the liquid in the coagulation bath freezes or the viscosity is too low, and the spinning stability tends to deteriorate, and the temperature of the poor solvent is 50. This is because when the temperature is higher than 0 ° C., the viscosity of the coagulation bath becomes too low, and the membrane structure tends to become unstable or the spinning stability tends to deteriorate. Further, the time for immersing the spinning dope in a poor solvent is not particularly limited, but it is in the range of 0.1 to 100 seconds from the viewpoint of sufficiently coagulating to maintain the hollow fiber shape and not wastefully lengthening the process. Is preferably within the range of 1 to 50 seconds.

[4] Drying Step After the solidification step described above, the solidified hollow fiber-like first precursor polymer is dried from a state containing water without performing a solvent replacement treatment. The hollow fiber-shaped first precursor polymer that has undergone phase separation in the coagulation step is preferably subjected to the drying step after sufficiently washing with water to remove the remaining solvent.

  “Solvent displacement treatment” not performed in the drying step is, for example, that a hollow fiber-like material containing water is gradually increased in solvent concentration to a solvent having a surface tension smaller than that of water, such as alcohol, and miscible with water. In this method, the solvent is finally completely replaced with the solvent. Moreover, the hollow fiber-like product substituted with alcohol may be substituted with a solvent having a smaller surface tension such as cyclohexane or n-hexane. The hollow fiber-like material dried from a state containing a solvent having a low surface tension is considered to easily maintain the initial pore structure. Further, as a method similar to solvent replacement, the same effect can be obtained when the poor solvent of the coagulation bath in the above-described discharge step is previously made to have a low surface tension, such as alcohol.

  However, such a solvent replacement process is not necessary in the drying step. According to the knowledge of the present inventors, even if such a solvent substitution process is performed, the hollow fiber formed from the discharged stock solution is melted in the porous structure in the flameproofing process and the carbonization process described later. This is because, when observed with a scanning electron microscope (SEM), the entire structure becomes a dense and uniform so-called homogeneous film structure. The hollow fiber carbon membrane 10 produced by performing the solvent replacement process becomes brittle and less flexible in spite of such a homogeneous membrane structure.

  On the other hand, the present inventors produced a hollow fiber carbon membrane 10 by drying a water-containing membrane without subjecting it to a solvent replacement treatment, and although a similar homogeneous membrane structure was obtained, Surprisingly, it has been revealed that the flexibility is very excellent as compared with the hollow fiber carbon membrane subjected to the solvent substitution treatment. Further, there was no significant difference in gas separation and permeability between the two. That is, it has been found that it is preferable to perform the drying process directly from a state containing water without performing the solvent replacement process in order to exhibit the excellent flexibility and gas separation performance of the hollow fiber carbon membrane.

  The outer diameter and thickness of the first carbon film 1 can be adjusted as appropriate by adjusting the shape of the double cylindrical tube nozzle.

  Next, a second precursor polymer is placed on the outer surface of the first precursor polymer formed into a hollow fiber shape. The step of placing the second precursor polymer on the outer surface of the hollow fiber-shaped first precursor polymer is not particularly limited. For example, the first precursor polymer formed into a hollow fiber shape is used as the second precursor polymer. After immersing in a dip solution containing a precursor polymer, it can be carried out by lifting and drying.

  The second precursor polymer is a ratio of the percentage of the number of repeating units B (or repeating units D) to the total number of repeating units A (or repeating units C) and repeating units B (or repeating units D) ( When the second precursor polymer is the above-described sulfonated polyphenylene oxide or sulfonated polyethersulfone, the solvent solubility varies depending on the degree of sulfonation (DS). For example, when the sulfonated polyphenylene oxide described above is used as the second precursor polymer, a known solvent such as dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, water, or a mixed solvent thereof is preferably used. be able to.

When R ¹ and R ² in the repeating unit B of the second precursor polymer (or R ³ and R ⁴ in the repeating unit D) are partially or wholly neutralized with the metal element described above, the metal element is The hollow fiber carbon film precursor obtained after the dip coating step may be introduced into the polymer solution raw material in the dip coating step, and a desired metal element is introduced by immersing the hollow fiber carbon membrane precursor in a solution containing metal ions. A method may be taken.

  In the dip coating step, the first precursor polymer formed into a hollow fiber shape is immersed in a dip solution of the second precursor polymer (for example, the sulfonated polyphenylene oxide described above), and then pulled up and dried. At this time, the concentration of the dip solution is preferably 1 to 50% by mass, more preferably 5 to 20% by mass. Hollow fiber carbon having a coat layer (second carbon film) having a desired thickness by applying a drying treatment while pulling up the hollow fiber-shaped first precursor polymer coated with the dip liquid at a predetermined pulling speed. A film precursor is prepared. Since the adhesion of dust to the hollow fiber-like first precursor polymer in the dip coating process becomes a defect of the carbon film, the hollow fiber carbon film precursor is preferably produced in an atmosphere with reduced dust. . In order to reduce coating unevenness and dust adhesion, a device such as immersion in a solvent as a pretreatment or dip coating may be performed a plurality of times.

  Using a triple cylindrical tube nozzle, a spinning stock solution containing the first precursor polymer, a spinning stock solution containing the second precursor polymer, and an internal solution for coagulating these spinning stock solutions were simultaneously extruded. The hollow fiber carbon membrane precursor may be formed using a dry spinning method, a wet spinning method, a dry wet spinning method, or the like.

  Next, the hollow fiber carbon membrane precursor can be carbonized to obtain the above-described hollow fiber carbon membrane of the present invention. Preferably, a flameproofing treatment is performed as a pretreatment for the carbonization treatment. The In the flameproofing treatment, the first precursor polymer and the first precursor polymer are heated by heating the hollow fiber carbon membrane precursor at 150 to 350 ° C., more preferably 200 to 300 ° C., for about 30 minutes to about 4 hours in an air atmosphere. The thermal crosslinking reaction of the second precursor polymer is promoted, the membrane structure after the carbonization treatment is strengthened, and it is advantageous for improving separation performance and flexibility. In addition, a strong hollow fiber carbon membrane that hardly peels between the first carbon membrane and the second carbon membrane due to thermal crosslinking occurring at the interface between the first precursor polymer and the second precursor polymer. Can be manufactured.

  As the carbonization treatment, a conventionally known appropriate method can be employed. Specifically, the hollow fiber carbon membrane precursor (preferably subjected to flameproofing treatment) is housed in a high-temperature furnace, and the inert gas atmosphere is replaced by a reduced-pressure atmosphere or helium, argon gas, nitrogen gas, or the like. The method of baking by heat-processing below can be mentioned. Further, there is a method for producing a hollow fiber carbon membrane in a continuous carbonization furnace that performs high-temperature treatment under an inert gas atmosphere while continuously conveying a hollow fiber carbon membrane precursor (preferably subjected to flameproofing treatment). May be. The heating conditions for the firing can be selected optimally depending on the type of polymer constituting the hollow fiber carbon membrane precursor, etc., but in an inert gas atmosphere at 400 to 1000 ° C. for 30 minutes to 4 hours. Firing is preferably performed under conditions of 500 to 800 ° C., and more preferably performed under conditions of 30 minutes to 2 hours. If the temperature during firing is less than 400 ° C, carbonization may be insufficient, and if the temperature during firing exceeds 1000 ° C, carbonization proceeds too much, There is a possibility that the obtained hollow fiber carbon membrane becomes brittle.

  The hollow fiber carbon membrane of the present invention can be suitably used for separating the water from an organic solvent containing water. Examples of the organic solvent include ethanol, isopropyl alcohol, acetone, ethyl acetate, acetic acid, dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and the like. It doesn't matter. Further, in performing the separation using the hollow fiber carbon membrane of the present invention, even when the organic solvent containing water is heated to a temperature lower than the boiling point and in a liquid state, it is heated to a temperature higher than the boiling point and in a vapor state. It doesn't matter.

  Of course, the use of the hollow fiber carbon membrane of the present invention is not limited to the above-mentioned use. For example, the hollow fiber carbon membrane of the present invention is used to separate the VOC from air containing a volatile organic compound (VOC). Can also be used.

Although the detail of the Example of this invention is shown below, this invention is not restrict | limited.
<Example 1>
(Production of second precursor polymer)
As a second precursor polymer, in a state where polyphenylene oxide (PPO) is dissolved in chloroform, a mixed solution of chlorosulfuric acid and chloroform is dropped at room temperature to advance the sulfonation reaction, followed by a drying treatment. Thus, sulfonated polyphenylene oxide (HSPPO) having a sulfonation degree DS of 43% was obtained.

(Production of hollow fiber-like first precursor polymer)
The first precursor is mixed in a mixed solvent prepared by mixing N-methyl-2-pyrrolidone and ethylene glycol at a mass ratio of 9: 1 so that the first precursor polymer concentration is 27.5% by mass. PPO (Poly (2,6-dimethyl-1,4-phenylene product No. 181781, manufactured by Aldrich)) as a polymer was added and stirred at 150 ° C. to obtain a uniform spinning solution.

  Subsequently, after the ethylene glycol as the internal liquid was extruded from the inside of the double cylindrical tube nozzle kept at 130 ° C., the above spinning stock solution was extruded from the outside and dried in the air gap, and then N-methyl-2- A spinning precursor solution was solidified in a coagulation bath filled with an N-methyl-2-pyrrolidone aqueous solution having a pyrrolidone concentration of 30% by mass to produce a first precursor polymer formed into a hollow fiber shape. Thereafter, the first precursor polymer formed into a hollow fiber shape was dried and wound up with a winder.

(Preparation of hollow fiber carbon membrane precursor)
What was dissolved by adding HSPPO (second precursor polymer) with DS = 43% to a polymer concentration of 10% by mass in a mixed solvent of methanol and dimethylacetamide having a mass ratio of 50/50 Is filled in the dip liquid bath, and the hollow fiber-shaped first precursor polymer is immersed therein, and then the drying process is performed while pulling up, so that the second surface is formed on the outer surface of the hollow fiber-shaped first precursor polymer. A hollow fiber carbon membrane precursor provided with a precursor polymer was obtained.

(Flame resistance treatment)
The resulting hollow fiber carbon membrane precursor was heated to 270 ° C. at a rate of 10 ° C./min in an air atmosphere in an electric furnace, heated at this temperature for 1 hour, and then allowed to cool to obtain a hollow fiber carbon membrane precursor. The body was thermally cross-linked.

(Carbonization treatment)
The hollow fiber carbon membrane precursor subjected to flame resistance treatment was subjected to carbonization treatment in a nitrogen atmosphere using a high temperature furnace. The temperature was raised to 650 ° C. at a rate of 10 ° C./minute, heated at this temperature for 1 hour, and then allowed to cool to obtain the hollow fiber carbon membrane 10 shown in FIG. The outer diameter of the film was 200 μm, the thickness T1 of the first carbon film 1 (support layer) was 9 μm, and the thickness T2 of the second carbon film 2 (surface layer) was 2 μm.

(Preparation of single film for water vapor adsorption measurement)
The first carbon membrane and the second carbon membrane in the hollow fiber carbon membrane obtained in Example 1 were evaluated for affinity with water. Water vapor in each of the first carbon membrane and the second carbon membrane alone It evaluated from the adsorption | suction measurement. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement.

(Production of single film of second carbon film)
Using DS = 43% HSPPO prepared in the same manner as in Example 1 (Preparation of second precursor polymer), HSPPO was dissolved in methanol at room temperature with stirring, and a spinning stock solution having a polymer concentration of 30% by mass was obtained. Was made. The spinning solution was extruded from a double cylindrical tube nozzle at the same time as the 35% ammonium nitrate aqueous solution as the inner solution, solidified on the inner layer of the membrane, dried in an air gap, and then filled with pure water. It was immersed in a coagulation tank. The wet hollow fiber was wound up with a winder. The wet hollow fiber material formed by using the obtained HSPPO alone was difficult to handle because it would be difficult to handle because it would adhere when bundled and dried, yielding in a state where single yarns cut to about 1 m were suspended one by one. A weight less than that of strength, that is, approximately 1 g, was attached, and dried while removing the internal liquid in the hollow fiber-like material. Next, the hollow fiber-like material after drying was subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 1 to obtain a single HSPPO hollow fiber carbon membrane. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

(Preparation of single film of first carbon film)
A PPO hollow fiber was prepared in the same manner as in Example 1 (Preparation of hollow fiber-shaped first precursor polymer), and subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 1. A PPO hollow fiber carbon membrane was obtained. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

<Example 2>
(Production of second precursor polymer)
As a second precursor polymer, in a state where polyphenylene oxide (PPO) is dissolved in chloroform, a mixed solution of chlorosulfuric acid and chloroform is dropped at room temperature to allow the sulfonation reaction to proceed. The reaction product washed with water is immersed in a 0.5 M aqueous sodium carbonate solution to neutralize the sulfonic acid group with sodium, then washed with water to completely remove the remaining sodium carbonate salt, followed by drying treatment, and the degree of sulfonation DS = 43% Na-substituted sulfonated polyphenylene oxide (NaSPPO) was obtained.

(Production of hollow fiber-like first precursor polymer)
A PPO hollow fiber product was obtained in the same manner as in Example 1.

(Preparation of hollow fiber carbon membrane precursor)
A solution in which NaSPPO (second precursor polymer) of DS = 43% is added to a mixed solvent of methanol and dimethylacetamide in a mass ratio of 50/50 so that the polymer concentration becomes 10% by mass and dissolved. Is filled in the dip liquid bath, and the hollow fiber-shaped first precursor polymer is immersed therein, and then the drying process is performed while pulling up, so that the second surface is formed on the outer surface of the hollow fiber-shaped first precursor polymer. A hollow fiber carbon membrane precursor provided with a precursor polymer was obtained.

(Flame resistance treatment)
The resulting hollow fiber carbon membrane precursor was heated to 270 ° C. at a rate of 10 ° C./min in an air atmosphere in an electric furnace, heated at this temperature for 1 hour, and then allowed to cool to obtain a hollow fiber carbon membrane precursor. The body was thermally cross-linked.

(Carbonization treatment)
The hollow fiber carbon membrane precursor subjected to flame resistance treatment was subjected to carbonization treatment in a nitrogen atmosphere using a high temperature furnace. The temperature was raised to 650 ° C. at a rate of 10 ° C./minute, heated at this temperature for 1 hour, and then allowed to cool to obtain the hollow fiber carbon membrane 10 shown in FIG. The outer diameter of the film was 200 μm, the thickness T1 of the first carbon film 1 (support layer) was 9 μm, and the thickness T2 of the second carbon film 2 (surface layer) was 2 μm.

(Preparation of single film for water vapor adsorption measurement)
The first carbon membrane and the second carbon membrane in the hollow fiber carbon membrane obtained in Example 2 were evaluated for affinity with water. Water vapor in each of the first carbon membrane and the second carbon membrane alone It evaluated from the adsorption | suction measurement. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement.

(Production of single film of second carbon film)
Using DS = 43% NaSPPO prepared in the same manner as in Example 2 (Preparation of second precursor polymer), NaSPPO was dissolved in methanol at room temperature with stirring, and a spinning stock solution having a polymer concentration of 30% by mass was obtained. Was made. The spinning solution was extruded from a double cylindrical tube nozzle at the same time as the 35% ammonium nitrate aqueous solution as the inner solution, solidified on the inner layer of the membrane, dried in an air gap, and then filled with pure water. It was immersed in a coagulation tank. The wet hollow fiber was wound up with a winder. The wet hollow fiber product formed by using NaSPPO alone was difficult to handle because it would be difficult to handle because it would adhere when bundled and dried, yielding in a state where single yarns cut to about 1 m were suspended one by one A weight less than that of strength, that is, approximately 1 g, was attached, and dried while removing the internal liquid in the hollow fiber-like material. Next, the dried hollow fiber-like material was subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 2 to obtain a single NaSPPO hollow fiber carbon membrane. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

(Preparation of single film of first carbon film)
A PPO hollow fiber was prepared in the same manner as in Example 1 (Preparation of hollow fiber-shaped first precursor polymer), subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 2, A PPO hollow fiber carbon membrane was obtained. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

<Example 3>
(Production of second precursor polymer)
As the second precursor polymer, a sulfonated polyethersulfone (SPES) comprising a combination of a repeating unit A and a repeating unit B each having the chemical structure represented by the above formulas (III) and (IV) is as follows: I prepared as follows. First, 3,3′-disulfo-4,4′-dichlorodiphenylsulfone disodium salt (abbreviation: S-DCDPS), 2,6-dichlorobenzonitrile (abbreviation: DCBN), 4,4′-biphenol, potassium carbonate , And molecular sieves were weighed into a four-necked flask and flushed with nitrogen. After adding N-methyl-2-pyrrolidone and stirring at 150 ° C. for 50 minutes, the reaction was continued by raising the reaction temperature to 195 to 200 ° C. and sufficiently increasing the viscosity of the system. Thereafter, the mixture was allowed to cool and then allowed to cool, and the precipitated molecular sieve was removed and the mixture was precipitated in water. The obtained polymer was washed in boiling water for 1 hour and then carefully washed with pure water to completely remove residual potassium carbonate. Then, the polymer after removing potassium carbonate was dried. This polymer was immersed in a 0.5 M aqueous sodium carbonate solution to neutralize sulfonic acid groups with sodium. And the sodium carbonate salt which remained in the reaction material was removed completely by washing the polymer after immersion in the sodium carbonate aqueous solution with water. Thereafter, the reaction product was dried to obtain NaSPES having a sulfonation degree DS = 60% as a target second precursor polymer.

(Production of hollow fiber-like first precursor polymer)
A PPO hollow fiber product was obtained in the same manner as in Example 1.

(Preparation of hollow fiber carbon membrane precursor)
To the dimethylacetamide solvent, DS = 60% NaSPES was added so that the polymer concentration was 8% by mass, the dissolved solution was filled in the dip liquid bath, and the support PPO hollow fiber membrane was immersed therein. Then, the hollow fiber carbon membrane precursor was obtained by performing a drying process while pulling up.

(Flame resistance treatment)
The resulting hollow fiber carbon membrane precursor was heated to 270 ° C. at a rate of 10 ° C./min in an air atmosphere in an electric furnace, heated at this temperature for 1 hour, and then allowed to cool to obtain a hollow fiber carbon membrane precursor. The body was thermally cross-linked.

(Carbonization treatment)
The hollow fiber carbon membrane precursor subjected to flame resistance treatment was carbonized in a nitrogen atmosphere using a high temperature furnace. The temperature was raised to 650 ° C. at a rate of 10 ° C./min, heated at this temperature for 1 hour, and then allowed to cool to obtain a hollow fiber carbon membrane as the target product. The outer diameter of the film was 200 μm, the thickness T1 of the first carbon film 1 (support layer) was 9 μm, and the thickness T2 of the second carbon film 2 (surface layer) was 3 μm.

(Preparation of single film for water vapor adsorption measurement)
The first carbon membrane and the second carbon membrane in the hollow fiber carbon membrane obtained in Example 3 were evaluated for their affinity with water. Water vapor in each of the first carbon membrane and the second carbon membrane alone was used. It evaluated from the adsorption | suction measurement. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement.

(Production of single film of second carbon film)
Using DS = 60% NaSPES prepared by the method described in Example 3 (Preparation of second precursor polymer), this NaSPES was added to N-methyl so that the concentration of NaSPES was 27.5% by mass. In addition to -2-pyrrolidone, the mixture was stirred at 150 ° C. to dissolve NaSPES in N-methyl-2-pyrrolidone to obtain a uniform spinning dope. Subsequently, an aqueous ammonium nitrate solution having a concentration of 15% by mass of ammonium nitrate as the inner liquid was extruded from the inside of the double cylindrical tube nozzle, and at the same time, the above spinning stock solution was extruded from the outside, dried in an air gap, and then filled with pure water. NaSPES formed into a hollow fiber shape was produced by solidifying the spinning solution in a coagulation bath. Thereafter, the wet NaSPES formed into a hollow fiber shape was wound with a winder. When the wet NaSPES formed into a hollow fiber shape was bundled and dried, the NaSPES was in close contact with each other and was difficult to handle. Therefore, each NaSPES was cut to a length of about 1 m and suspended one by one, and a weight of about 1 g was attached to each tip, and dried while removing the internal liquid in the hollow fiber-like NaSPES. Next, the dried hollow fiber-like product was subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 2 to obtain a single NaSPPES hollow fiber carbon membrane. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

(Preparation of single film of first carbon film)
A PPO hollow fiber was prepared in the same manner as in Example 1 (preparation of hollow fiber-shaped first precursor polymer), subjected to flameproofing treatment and carbonization treatment under the same conditions as in Example 3, A PPO hollow fiber carbon membrane was obtained. The outer diameter of the film was 200 μm, and the film thickness was 10 μm.

<Comparative Example 1>
(Production of second precursor polymer)
In the same manner as in Example 1, HSPPO (second precursor polymer) with DS = 43% was produced.

(Production of hollow fiber-like first precursor polymer)
Polyphenylene oxide (PPO) (Poly (2,6-dimethyl-1,4-phenylene product No. 181781, manufactured by Aldrich)) is added to chloroform so that the polymer concentration is 27.5% by mass, and the mixture is stirred at room temperature. The solution was dissolved to obtain a uniform spinning stock solution, and the spinning stock solution and the inner solution were simultaneously extruded with ethanol from a double cylindrical tube nozzle under normal temperature conditions, dried in an air gap, and filled with ethanol. The solid hollow fiber-like material that had been phase-separated by the above was dried and wound up to obtain a hollow fiber-like first precursor polymer.

(Preparation of hollow fiber carbon membrane precursor)
DS = 43% HSPPO was added to the dimethylacetamide solvent so that the polymer concentration was 8% by mass, and the dissolved solution was filled in the dip liquid bath, and the support PPO hollow fiber membrane (hollow fiber shape) The first precursor polymer) was dipped and then subjected to a drying treatment while being pulled up to obtain a hollow fiber carbon membrane precursor.

(Flame resistance treatment)
The treatment was performed under the same conditions as in Example 1.

(Carbonization treatment)
The treatment was performed under the same conditions as in Example 1 to obtain a hollow fiber carbon membrane. The outer diameter of the film was 200 μm, the thickness T1 of the first carbon film 1 (support layer) was 10 μm, and the thickness T2 of the second carbon film 2 (surface layer) was 2 μm.

(Preparation of single film for water vapor adsorption measurement)
The affinity evaluation of the first carbon membrane and the second carbon membrane with the water in the hollow fiber carbon membrane obtained in Comparative Example 1 was carried out using water vapor in each of the first carbon membrane and the second carbon membrane. It evaluated from the adsorption measurement. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement.

(Production of single film of second carbon film)
A single HSPPO hollow fiber carbon membrane was obtained in the same manner as described in Example 1 (Preparation of single membrane of second carbon membrane).

(Preparation of single film of first carbon film)
By performing the flameproofing treatment and the carbonization treatment of the PPO hollow fiber produced by the method described in Comparative Example 1 (Production of hollow fiber-shaped first precursor polymer) by the method described in Comparative Example 1. A single PPO hollow fiber carbon membrane was obtained.

<Comparative example 2>
(Production of second precursor polymer)
In the same manner as in Example 2, NaSPPO (second precursor polymer) with DS = 43% was produced.

(Production of hollow fiber-like first precursor polymer)
In the same manner as in Comparative Example 1, a hollow fiber-shaped first precursor polymer was obtained.

(Preparation of hollow fiber carbon membrane precursor)
NaSPPO with DS = 43% is added to the dimethylacetamide solvent so that the polymer concentration becomes 8% by mass, and the dissolved solution is filled in the dip liquid bath, and the support PPO hollow fiber membrane (hollow fiber shape) The first precursor polymer) was dipped and then subjected to a drying treatment while being pulled up to obtain a hollow fiber carbon membrane precursor.

(Flame resistance treatment)
The treatment was performed under the same conditions as in Example 2.

(Carbonization treatment)
The treatment was performed under the same conditions as in Example 2 to obtain a hollow fiber carbon membrane. The outer diameter of the film was 200 μm, the thickness T1 of the first carbon film 1 (support layer) was 10 μm, and the thickness T2 of the second carbon film 2 (surface layer) was 2 μm.

(About production of single film for water vapor adsorption measurement)
The affinity evaluation of the first carbon membrane and the second carbon membrane with the water in the hollow fiber carbon membrane obtained in Comparative Example 2 was carried out using water vapor in each of the first carbon membrane and the second carbon membrane alone. It evaluated from the adsorption | suction measurement. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement.

(Production of single film of second carbon film)
A single NaSPPO hollow fiber carbon membrane was obtained in the same manner as in Example 2 (Preparation of single membrane of second carbon membrane).

(Preparation of single film of first carbon film)
By performing the flameproofing treatment and the carbonization treatment on the PPO hollow fiber produced by the method described in Comparative Example 2 (Production of hollow fiber-shaped first precursor polymer), the method described in Comparative Example 2 A single PPO hollow fiber carbon membrane was obtained.

<Comparative Example 3>
By performing the flameproofing treatment and the carbonization treatment on the PPO hollow fiber produced by the method described in Example 1 (Production of hollow fiber-like first precursor polymer) by the method described in Example 1. A single PPO hollow fiber carbon membrane was obtained.

(Preparation of single film for water vapor adsorption measurement)
Since Comparative Example 3 has only the support layer, the PPO hollow fiber carbon membrane described in Comparative Example 3 was used as it was.

The evaluation methods of the hollow fiber carbon membranes obtained in the examples and comparative examples are as follows.
(Method for evaluating film shape and film thickness)
The outer diameter and film thickness of the cross-sections of the hollow fiber carbon membranes obtained in the examples and comparative examples were evaluated by a scanning electron microscope (SEM). The thickness of the second carbon membrane of the hollow fiber carbon membrane is based on the fact that there is a difference in contrast between the second carbon membrane on the surface layer side of the cross section of the hollow fiber carbon membrane and the first carbon membrane on the inner layer side. And evaluated.

(Water vapor adsorption measurement)
In the hollow fiber carbon membranes obtained in the examples and comparative examples, the first carbon membrane and the second carbon membrane have an affinity evaluation with water. The first carbon membrane and the second carbon membrane are each a single membrane. It evaluated from the water vapor | steam adsorption measurement in. That is, the first precursor polymer and the second precursor polymer were each independently formed, subjected to flameproofing treatment and carbonization treatment, and then subjected to water vapor adsorption measurement. Each manufacturing method condition was based on the manufacturing method of the 1st carbon film in an Example and a comparative example, and the flame resistance and carbonization used the conditions described in each Example and the comparative example.

  As a specific evaluation method, 50 mg of a sample was vacuum-dried at 150 ° C. for 24 hours, and then the adsorption of water vapor at 25 ° C. was performed using ASAP2020MC (manufactured by Micromeritics). The measurement conditions are shown below.

<Analysis conditions>
・ Dosing: Low Pressure incremental dose mode
・ Dose amount: 0.04461 mmol / g
・ Equilibrium interval: 5s
・ Po: 23.640mmHg
・ Temperature: 25 ° C
<Adsorption gas characteristics>
Density conversion factor: 0.0008055
Therm. Trans hardsphere diameter: 3.604Å
・ Molecular cross-section area: 0.108 nm ²
(Relative pressure P / Po = 0.03 is the water selectivity of the second carbon membrane with a low ratio contained in the mixture, and relative pressure P / Po = 0.9 is selected in the membrane. It was used as an index of how much moisture (high concentration) taken in by the first carbon film or the second carbon film is easily retained.

(Measurement of elongation at break and tensile modulus)
In accordance with JIS R7606: 2000, hollow fiber carbon membranes of Examples 1 to 3 and Comparative Examples 1 to 2 using a tensile tester technograph (TG-200NB, load cell type TT3D-10N, manufactured by Minebea Co., Ltd.) The tensile strength at break and the tensile modulus were evaluated by conducting a tensile test. The cross-sectional area of the hollow fiber carbon membrane sample was measured according to the JIS R7607: 2000 C method.

  Specifically, the samples 22 of the hollow fiber carbon membranes obtained in the examples and comparative examples are placed on both ends of the square frame-shaped mount 21 shown in FIGS. 3 (a) and 3 (b), respectively. Both ends of the sample 22 were bonded and fixed with a two-component epoxy resin 23, respectively. The end portions 25 of the mount 21 after the sample 22 was bonded as described above were each held and fixed to the chuck of the tensile tester. Subsequently, after disconnecting the connecting portion 24 of the mount 21 and the sample 22, the tensile test of the sample 22 of the hollow fiber carbon membrane was started. The length of the sample 22 was 25 mm, and the tensile speed was 5 mm / min. The average value was calculated assuming that the number of measurement in the tensile test was 20.

(Evaluation method of water-ethyl acetate separation performance)
In FIG. 4, the typical block diagram of the osmosis | evaporation separation apparatus used for evaluation of the water separation performance by the osmosis | evaporation separation method of the hollow fiber carbon membrane obtained by the Example and the comparative example and permeation | permeation performance is shown. A plurality of hollow fiber carbon membranes 10 obtained in Examples and Comparative Examples were bundled in the same number, and the opening at one end of the bundled hollow fiber carbon membranes 10 was sealed with an adhesive, and the other end was closed. The separation membrane module 20 was produced by opening the openings and fitting caps at both ends thereof. Then, the separation membrane module 20 produced in this way was attached to one end of the stainless tube 44 covered with the heat insulating tape 39 so as to keep an airtight state. A stop valve 40 was attached between the ends of the stainless tube 44.

  In addition, an ethyl acetate aqueous solution 32 having a water content of 3% by mass as a supply liquid was poured into the container 33, and a stirrer 35 was installed at the bottom of the container 33. And the container 33 was installed in the thermostat 34, the thermostat 34 was installed on the stirrer 31, and the thermometer 38 was inserted in the ethyl acetate aqueous solution 32. FIG. The stirrer 35 is rotated by the stirrer 31 while the ethyl acetate aqueous solution 32 is stirred by keeping the ethyl acetate aqueous solution 32 in the container 33 at a constant temperature by the thermostatic bath 34, and the separation membrane module 20 is immersed in the ethyl acetate aqueous solution 32. It was. This time, it set to 70 degreeC which is below the boiling point (77.1 degreeC) of ethyl acetate.

  Further, the other end of the stainless steel tube 44 was inserted in an airtight state into a cooling trap 36 cooled with liquid nitrogen 37 (−196 ° C.) together with one end of the other stainless steel tube 45. The other end of the stainless steel tube 45 was attached to the vacuum pump 43, and a pressure gauge 41 and a stop valve 42 were attached between the ends of the stainless steel tube 45 in this order from the cooling trap 36 side.

Then, the vacuum pump 43 was operated to set the pressure on the supply liquid side of the ethyl acetate aqueous solution 32 of the separation membrane module 20 to atmospheric pressure, and the pressure on the permeate side to 1 Pa. Then, after a predetermined time had passed since the evaluation was started, the permeation flux (kg · m ⁻² · h ⁻¹ ) was determined from the mass of the permeate trapped by the cooling trap 36 by the following formula. The results are shown in Table 1.

Permeation flux (kg · m ⁻² · h ⁻¹ ) = (mass of permeate (kg)) ÷ {area of hollow fiber carbon membrane (m ² ) × time (h)}
Further, the permeate trapped by the cooling trap 36 was analyzed by a TCD (Thermal Conductivity Detector) gas chromatograph to obtain the ethyl acetate concentration in the permeate and calculate the separation factor by the following formula.

Separation factor (water / ethyl acetate) = {water concentration in permeate (% by mass) / ethyl acetate concentration in permeate (% by mass)} ÷ {water concentration in feed (% by mass) / ethyl acetate in feed (mass%)}
Each evaluation result is shown in Table 1. As can be seen from Table 1, Examples 1, 2, and 3 according to the present invention have high performance in both permeation performance and separation performance, and have sufficient elongation at break for handling in the production of a separation membrane module. And has a tensile modulus.

  DESCRIPTION OF SYMBOLS 1 1st carbon membrane, 2nd 2nd carbon membrane, 10 hollow fiber carbon membrane, 21 sample mount, 22 samples, 23 epoxy resin, 24 connection part, 25 chuck holding part, 31 stirrer, 32 supply liquid, 33 container, 34 Thermostatic bath, 35 Stirrer, 36 Cooling trap, 37 Liquid nitrogen, 38 Thermometer, 39 Insulating tape, 40 Stop valve, 41 Pressure gauge, 42 Stop valve, 43 Vacuum pump.

Claims (13)

A hollow fiber-shaped first carbon membrane;
A second carbon film provided on the outer surface of the first carbon film,
The elongation at break is 1 to 4%,
The second carbon membrane is a hollow fiber carbon membrane having a higher affinity for a permeable component than the first carbon membrane. The precursor polymer of the second carbon film has a repeating structure of a repeating unit A represented by the following formula (I) and a repeating unit B represented by the following formula (II):

In the formula (I) and the formula (II), m and n are each a natural number of 1 or more, and in the formula (II), R ¹ and R ² are each independently a hydrogen atom, or R represents a sulfone group, a carboxyl group, or a phosphonic acid group that may be partially or wholly neutralized with a metal element, and R ¹ and R ² do not represent a hydrogen atom at the same time,
The hollow fiber carbon membrane according to claim 1, wherein a ratio of the percentage of the number of repeating units B to the total number of repeating units A and B is larger than 15% and smaller than 100%. The hollow fiber carbon according to claim 2, wherein R ¹ and R ² in formula (II) each independently represent -SO ₃ M, -SO ₃ H or a hydrogen atom, wherein M represents a metal element. film.   The hollow fiber carbon membrane according to any one of claims 1 to 3, wherein a thickness of the first carbon membrane is 5 to 100 µm, and a thickness of the second carbon membrane is 0.05 to 20 µm.   The hollow fiber carbon membrane according to any one of claims 1 to 4, wherein the tensile elastic modulus is 5 GPa or more.   The hollow fiber carbon membrane according to any one of claims 1 to 5, wherein the permeating component is water.   The hollow fiber carbon membrane according to claim 6, wherein the water can be separated from a volatile organic compound containing water.   The hollow fiber carbon membrane according to any one of claims 1 to 5, wherein the volatile organic compound can be separated from air containing the volatile organic compound. A method for producing the hollow fiber carbon membrane according to any one of claims 1 to 8,
Producing a first precursor polymer that is a precursor polymer of the first carbon film;
Producing a second precursor polymer that is a precursor polymer of the second carbon film;
Forming a hollow fiber carbon membrane precursor in which the second precursor polymer is installed on the outer surface of the hollow fiber-shaped first precursor polymer;
And a step of carbonizing the hollow fiber carbon membrane precursor. The second precursor polymer has a repeating structure of a repeating unit A represented by the following formula (I) and a repeating unit B represented by the following formula (II):

In the formula (I) and the formula (II), m and n are each a natural number of 1 or more, and in the formula (II), R ¹ and R ² are each independently a hydrogen atom, or R represents a sulfone group, a carboxyl group, or a phosphonic acid group that may be partially or wholly neutralized with a metal element, and R ¹ and R ² do not represent a hydrogen atom at the same time,
The method for producing a hollow fiber carbon membrane according to claim 9, wherein a ratio of a percentage of the number of repeating units B to a total number of repeating units A and B is larger than 15% and smaller than 100%. . The hollow fiber carbon according to claim 10, wherein R ¹ and R ² in the formula (II) each independently represent -SO ₃ M, -SO ₃ H, or a hydrogen atom, wherein M represents a metal element. A method for producing a membrane. The first precursor polymer is polyphenylene oxide;
The method for producing a hollow fiber carbon membrane according to claim 10 or 11, wherein the second precursor polymer is a sulfonated polyphenylene oxide.   The method for producing a hollow fiber carbon membrane according to any one of claims 9 to 12, further comprising a step of flameproofing the hollow fiber carbon membrane precursor prior to the carbonizing treatment.

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