JP2011016119A - Adsorption filter membrane module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hollow fiber membrane module effectively suppressing the lowering of the degree of effective utilization of adsorption capacity accompanying scaling-up and high-degree integration.SOLUTION: The hollow fiber membrane module 12 includes an adsorption filter membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed to the pore surface of a porous membrane and the effective membrane length of the adsorption filter membrane is 10 cm or above.

Description

  The present invention relates to an adsorption filtration membrane module.

Conventionally, as a means for separating a substance dissolved in a liquid phase, a substance separation technique using an adsorption method has been widely used in various fields.
For example, adsorptive substance separation techniques are used in various fields such as biotechnology, genetic engineering, pharmaceutical industry, chemical industry, beverage industry, food industry, environmental protection, and resource recycling.
In addition, the substance to be adsorbed in the substance separation technology to which the adsorption method is applied varies depending on the field of use, for example, biological molecules, proteins, enzymes, viruses, ionic substances, metal ions, noble metal ions, heavy metal ions, etc. It spans.

Column chromatography is known as a general apparatus as an adsorptive substance separation apparatus for industrially separating the adsorbed substance efficiently.
Column chromatography has a configuration in which a porous resin having selective adsorptivity is packed.
Adsorption to column chromatography is the principle of diffusion in which the adsorbed substance contained in the liquid phase moves into the pores of the porous resin by diffusion and contacts and adsorbs the functional groups present on the surface of the pores. Based on.
Therefore, when the specific surface area of the porous resin increases, there is an advantage that the amount of adsorption increases correspondingly, but the adsorption capacity is affected by diffusion rate limiting, so the adsorption capacity decreases as the processing speed is increased. Has the disadvantages.

On the other hand, as an adsorptive substance separation apparatus in which the adsorption capacity does not decrease even if the processing speed is increased, an apparatus using an adsorption membrane is known.
The adsorption membrane refers to a filtration membrane having selective adsorption performance, and an adsorption membrane module having a structure in which the adsorption membrane is housed in a predetermined outer cylinder is used in the field of the purification process.
In the adsorption membrane constituting this adsorption membrane module, a forced flow is generated in the pores using the filtration differential pressure acting on the porous filtration membrane as a driving force. It is based on the principle of forced flow.
For this reason, the specific surface area of the adsorption film is smaller than that of the column chromatography described above, and the amount of adsorption is small, but on the other hand, there is an advantage that even if the treatment speed is increased, the adsorption capacity does not decrease.

A protein adsorption membrane is mentioned as a specific example of the adsorption membrane which comprises the said adsorption membrane module.
In this method, even when a protein-containing aqueous solution is passed at a high flow rate, the protein is adsorbed and effective for rapid processing, but the protein is adsorbed only on the membrane surface. The amount depends on the specific surface area, and the amount of adsorption is significantly lower than that of column chromatography using the porous resin (see, for example, Patent Documents 1 and 2).

On the other hand, a technique for achieving both the rate of adsorption of protein to the porous membrane and the amount of adsorption has also been studied. A porous material in which a functional group is fixed to a graft chain and the graft chain is fixed to a porous substrate. A membrane is disclosed (for example, see Non-Patent Documents 1 to 3).
In such a porous membrane, since a large number of functional groups are fixed to one graft chain, proteins adsorb three-dimensionally not only on the surface of the porous membrane but also in the pores, as described above. Compared with the case where adsorption is performed only on the surface, the amount of adsorption is greatly increased.

Special table 2003-532746 Special table 2002-537106 gazette

Journal of Chromatography A, 689 (1995) 212-218 Biotechol. Prog. 1994, 10, 76-81 Biotechol. Prog. 1997, 13, 89-95

In recent years, in the various fields described above, there is an increasing demand for the processing capacity of the adsorptive substance separation device.
In particular, in the purification process of antibody pharmaceuticals, an adsorption filtration membrane module with higher capacity is desired because of the growing expectation for a technique for achieving both mass processing and high-speed processing. The following describes means for achieving mass processing as well as high speed processing.

First, as a means for achieving mass processing, a method for increasing the volume of the adsorption membrane in the adsorption filtration membrane module can be considered. Specifically, means for increasing the outer cylinder diameter and outer cylinder length of the adsorption filtration membrane module and means for increasing the integration of the adsorption membrane in the outer cylinder can be considered. However, when the outer cylinder diameter and outer cylinder length are increased, the difficulty of forming the adsorption membrane module is extremely increased, it becomes difficult to fit in the indoor volume of the purification site, and handling work becomes difficult. There is an upper limit to the dimensional increase.
On the other hand, when the filling rate of the adsorption membrane is increased or when the outer cylinder length is increased, the fluid flow path structure in the adsorption membrane module is thin and long, so that the pressure loss increases. Regardless of whether the shape of the adsorption filtration membrane module is a flat membrane type or a hollow fiber type, if pressure loss increases, the distribution of locations with high and low membrane differential pressure locally in the longitudinal direction of the fluid flow path Will increase.

  Next, as a means for achieving high-speed processing, a highly integrated method for reducing the film thickness of the adsorption film and increasing the water permeation speed per film area can be considered. However, the increase in the water permeation rate increases the pressure loss in the longitudinal direction of the adsorption membrane module, and this occurs in both the flat membrane module and the hollow fiber membrane module. On the other hand, as a problem peculiar to the hollow fiber membrane module, in order to keep the total membrane volume in the module high and maintain the strength that can withstand the pressure load, the size of the hollow fiber membrane is reduced while keeping the ratio of the inner and outer diameters constant. It will be necessary. In this case, the hollow fiber membrane inevitably has a small inner diameter, and as a result, extremely high pressure loss occurs.

  That is, taking the above-mentioned means of increasing the size or increasing the integration to achieve a large-scale process or a high-speed process acts in the direction of increasing the pressure loss inside the adsorption filtration membrane module. Due to this increase in pressure loss, the adsorption filtration membrane module causes a distribution in the degree of progress of adsorption in the longitudinal direction of the liquid flow. As a result, in an extreme example, the local area where adsorption has just started and the local area where adsorption has progressed and leakage of the substance to be adsorbed exist at the same time. In this case, the adsorption capacity of the entire module does not increase as expected. become.

  Therefore, the means for increasing the size and integration of the adsorption filtration membrane module leads to an undesirable result that the adsorption capability inherent to the adsorption filtration membrane cannot be sufficiently exhibited, that is, the utilization of the adsorption capability is reduced. In view of this situation, an object of the present invention is to provide an adsorption filtration membrane module that effectively suppresses a decrease in the effective utilization of adsorption capacity associated with an increase in size and integration.

As a result of earnest research, the present inventors have effectively reduced the effective utilization of the adsorption capacity associated with the increase in size and integration by using an adsorption filtration membrane having a function of reducing FLUX as the adsorption proceeds. Based on this finding, the present inventors have found that the present invention can be suppressed.
That is, the present invention relates to a hollow fiber membrane module in which the decrease in the effective utilization of the adsorption capacity accompanying the increase in size and integration is small.
[1] An adsorption filtration comprising an adsorption filtration membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed on the pore surface of a porous membrane, and the effective membrane length of the adsorption filtration membrane is 10 cm or more Membrane module
[2] The weak electrolytic ion exchange group is any one or more selected from the group consisting of a tertiary amino group, a secondary amino group, a primary amino group, a carboxylic acid group, and a phosphoric acid group. Adsorption filtration membrane module
[3] The adsorption filtration membrane module according to [1] or [2], wherein the weakly electrolytic ligand is a diethylamino group.
[4] The adsorption filtration membrane module according to any one of [1] to [3], wherein the graft polymer chain has a non-crosslinked structure.
[5] The adsorption filtration membrane module according to any one of [1] to [4], wherein an effective membrane length of the adsorption filtration membrane is 10 cm or more and 20 cm or less, and an inner diameter of the hollow fiber is 0.28 mm or more.
[6] The adsorption filtration according to any one of [1] to [4], wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 20 cm and within 50 cm, and an inner diameter of the hollow fiber is 0.43 mm or more. Membrane module
[7] The adsorption filtration according to any one of [1] to [4], wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 50 cm and within 100 cm, and an inner diameter of the hollow fiber is 0.60 mm or more. Membrane module
[8] The adsorption filtration according to any one of [1] to [4], wherein an effective membrane length of the adsorption filtration membrane is in a range of more than 100 cm and within 150 cm, and an inner diameter of the hollow fiber is 0.76 mm or more. Membrane module
[9] The adsorptive filtration according to any one of [1] to [4], wherein an effective membrane length of the adsorptive filtration membrane is in a range exceeding 150 cm and within 200 cm, and an inner diameter of the hollow fiber is 0.86 mm or more. Membrane module
[10] The adsorption filtration membrane module according to any one of [1] to [9], wherein the adsorption filtration membrane is a hollow fiber membrane.

  ADVANTAGE OF THE INVENTION According to this invention, the hollow fiber membrane module by which the fall of the adsorption capability accompanying enlargement and high integration was suppressed effectively is obtained.

The schematic block diagram of an example of the hollow fiber membrane module in this embodiment is shown. The schematic block diagram of the 2nd example of the hollow fiber membrane module in this embodiment is shown. The schematic block diagram of the 3rd example of the hollow fiber membrane module in this embodiment is shown. The schematic block diagram of the 4th example of the hollow fiber membrane module in this embodiment is shown. The schematic block diagram of the 5th example of the hollow fiber membrane module in this embodiment is shown. The schematic block diagram of the 6th example of the hollow fiber membrane module in this embodiment is shown. The graph which shows the condition of adsorption | suction and a pressure change of the adsorption filtration membrane which has the graft | grafting polymer chain which has a weak electrolysis ion exchange group in this embodiment on the pore surface. The graph which shows the condition of adsorption | suction and the pressure change of the adsorption filtration membrane which has the graft polymer chain which has a weakly electrolyzed ion exchange group of this embodiment on the pore surface A graph showing the state of adsorption and pressure change of an adsorption filtration membrane having a graft polymer chain having a strong electrolytic anion exchange group on the pore surface of a comparative example A graph showing the state of adsorption and pressure change of an adsorption filtration membrane having a graft polymer chain having a strong electrolytic cation exchange group on the pore surface of a comparative example

A mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described with reference to the drawings.
The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.
In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawings unless otherwise specified, and the dimensional ratio in the drawing is not limited to the illustrated ratio.

[Adsorption filtration membrane module]
The form of the adsorption filtration membrane module of the present embodiment is not particularly limited, and may be a filtration membrane module made of a hollow fiber membrane, a pleated filtration module made of a flat membrane, or a spiral made of a flat membrane. It may be a filter membrane module.

  About the adsorption filtration membrane module in this embodiment, the structure is demonstrated using FIGS. 1-6 by making a hollow fiber membrane type adsorption filtration membrane module into an example. Moreover, the shape of a figure is a representative example and does not limit the scope of the present invention.

  When the adsorption filtration membrane module of this embodiment is a hollow fiber membrane type adsorption filtration membrane module, both ends or one end of the hollow fiber membrane are either directly by a predetermined sealing resin, or via a predetermined indirect member or fixing jig. Indirectly, it is desirable to be fixed to an outer cylinder or an external pipe connecting material.

(First configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 1, both ends of the hollow fiber membrane 2 are directly fixed to the outer cylinder 1 by a predetermined sealing resin 3, and the opening is exposed at the bonding end surface 5. Is open.
The opening of the hollow fiber membrane 2 is connected to a pipe connecting member 9 via a fixing jig 10 and communicates with an external pipe (not shown).

(Second configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 2, one end of the hollow fiber membrane 2 is directly fixed to the outer cylinder 1 with a predetermined sealing resin 3, and the opening is exposed at the bonding end surface 5. The part is open. The opening of the hollow fiber membrane 2 is connected to a pipe connecting member 9 via a fixing jig 10 and communicates with an external pipe (not shown).
The other one end is in a state where the adhesive end surface 6 is closed by the sealing resin 4 and is not fixed to the outer cylinder 1. Here, the hollow fiber bundle of the bonding end surface 6 needs to be closed by the sealing resin 4, but the bundle may be bundled and fixed by the sealing resin 4. Each thread may be in a disjoint state.

(Third configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 3, one end of the hollow fiber membrane 2 is directly fixed to the outer cylinder 1 by a predetermined sealing resin 3, and the opening is exposed at the bonding end surface 5. The part is open. The opening of the hollow fiber membrane 2 is connected to a pipe connecting member 9 via a fixing jig 10 and communicates with an external pipe (not shown).
At the other one end, the adhesion end face 6 is closed by the sealing resin 3, is fixed to the outer cylinder 1, and the hollow portion is closed.

(Fourth configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 4, one end of the hollow fiber membrane 2 is directly fixed to the outer cylinder 1 by a predetermined sealing resin 3, and an opening is exposed at the bonding end surface 5. The part is open. The opening of the hollow fiber membrane 2 is connected to a pipe connecting member 9 via a fixing jig 10 and communicates with an external pipe (not shown).
The other end of the hollow fiber membrane 2 is directly fixed to the outer cylinder 1 with a predetermined sealing resin 3, and the bonded end face 6 is closed.
In the bonding end face 6, a slit 7 that penetrates the sealing resin 3 that bundles the bundle of hollow fiber membranes 2 is provided. The liquid can also be supplied from the lower inlet of the hollow fiber membrane module 12 through the slit 7.

(Fifth configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 5, the hollow fiber membranes 2 are bundled with the sealing resin 4, the opening is exposed at the bonding end surface 5, and the hollow portion is open. . The sealing resin 4 and the outer cylinder 1 are not fixed, and the hollow fiber membrane 2 is fixed to the indirect member 11 by the sealing resin 4, and the indirect member 11 is provided detachably from the outer cylinder 1. ing.
The opening of the hollow fiber membrane 2 is connected to a pipe connecting member 9 via a fixing jig 10 and communicates with an external pipe (not shown).
At the other one end, the adhesive end surface 6 is closed by the sealing resin 4. The outer cylinder 1 is not fixed.

(Sixth configuration example)
In the hollow fiber membrane module 12 having the configuration shown in FIG. 6, the hollow fiber membrane 2 is bundled with a sealing resin 4, the opening is exposed at the bonding end face 5, and the hollow member is opened to the indirect member 11. It is fixed. The indirect member 11 communicates with an external pipe (not shown) on the bonding end surface 5 via the fixing jig 10.
At the other one end, the adhesive end surface 6 is closed by the sealing resin 4. Note that there is no outer cylinder, and the hollow fiber membrane 2 is immersed directly in the liquid tank 8.
On the adhesion end face 6 side, a slit 7 that penetrates the sealing resin 4 is provided.
Through this slit 7, the liquid is also supplied from the lower side of the hollow fiber membrane module 12 in FIG. 6.

In the hollow fiber membrane module of this embodiment, either an internal pressure filtration system or an external pressure filtration system can be selected.
There is no difference in the adsorption capacity in any of the above methods, but it is preferable to select the internal pressure filtration method when there is a concern about membrane deformation due to the differential pressure of filtration.

The advantage of the hollow fiber membrane module having the configuration shown in FIG. 1 is that when an internal pressure filtration method is selected, a cross-flow type stock solution can be supplied, and there are impurities and contaminants that easily accumulate on the membrane surface in the stock solution. If it is, it is advantageous to function.
In addition, both ends can be supplied when the internal pressure filtration method is used, and both ends can be discharged when the external pressure filtration method is used.
The advantage of the hollow fiber membrane module having the configuration shown in FIGS. 5 and 6 is that the outer cylinder 1 or the tank 8 and the hollow fiber membrane 2 can be separated from each other. It is a point that reduction can be achieved.
In the hollow fiber membrane module having the configuration shown in FIGS. 4 and 6, the slits 7 are provided in the sealing resins 3 and 4, and when using an external pressure filtration method, air bubbles are supplied from below through the slits 7. It is convenient for vibrating the hollow fiber membrane by the movement of bubbles and scraping off foreign matter deposited on the outer surface of the hollow fiber membrane by aeration. Such a slit structure can be employed in addition to the hollow fiber membrane module having the structure shown in FIGS.
Each of the hollow fiber membrane modules shown in FIGS. 1 to 6 is a specific configuration example, and the present invention is not limited to these.

(Outer cylinder)
Examples of the material of the outer cylinder 1 include resins such as polysulfone, polycarbonate, vinyl chloride, ABS, fluorocarbon resins such as Teflon (registered trademark) and PVDF, metals such as SUS, and glasses. And can be selected according to usage and cost.
In particular, when a physical load such as a temperature load, a chemical load, a use pressure or vibration is generated depending on the use application, a material suitable for each use is selected.

(Sealing resin)
The sealing resins 3 and 4 are not particularly limited, and known sealing resins conventionally used for hollow fiber membrane modules can be used. For example, epoxy resin, polyurethane resin, and silicon rubber can be used as the curable injection resin. Examples of the thermoplastic resin include thermoplasts such as polypropylene.
In addition, when a physical load such as a temperature load, a chemical load, a use pressure or vibration is generated depending on the use application, it is necessary to select a material suitable for each use.

(Adsorption filtration membrane)
In the adsorption filtration membrane, graft polymer chains having weakly electrolytic ion exchange groups are formed on the pore surfaces of the porous membrane.
Here, the weakly electrolytic ion exchange group includes a weakly electrolytic cation exchange group and a weakly electrolytic anion exchange group, specifically, a primary amino group, a secondary amino group, a tertiary amino group, In addition to carboxylic acid groups, phosphoric acid groups, and the like, chelate type functional groups such as imidinoacetic acid groups can be used. Examples of the secondary amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, a phenylamino group, and an arylamino group. Tertiary amino groups include, for example, dimethylamino, secondary ethylamino, dipropylamino, diisopropylamino, dibutylamino, secondary phenylamino, diarylamino, ethylmethylamino, propylmethylamino, isopropyl Examples include methylamino group, butylmethylamino group, phenylmethylamino group, arylmethylamino group, propylethylamino group, isopropylethylamino group, butylmethylethyl group, phenylethylamino group, arylethylamino group and the like. Examples of the carboxylic acid group include a carboxylic acid group and a benzoic acid group. Examples of the phosphate group include a phosphate group as well as a phosphate group. Among these weakly electrolytic ion exchange groups, carboxylic acids, primary amino groups, secondary amino groups, and tertiary amino groups that can be easily introduced into the graft polymer chain are preferable. In the case of a carboxylic acid group, it is preferable in that it can be obtained directly by polymerizing a graft chain using acrylic acid or methacrylic acid as a monomer for a filtration membrane. In the case of primary amino group, secondary amino group and tertiary amino group, it can be easily obtained by first introducing a vinyl monomer having an epoxy group into a filtration membrane and then converting the epoxy group to an amino group. Is possible.

  The adsorptive filtration membrane of this embodiment has the property of being able to adsorb ionic species and reducing FLUX with the adsorption of ionic species.

  Here, the ionic chemical species refers to a chemical species that is dissociated in an aqueous solution and is in a charged state. Specifically, monoatomic ions such as metal ions, polyatomic ions consisting of multiple atomic groups such as metal oxide ions, complex ions such as metal complex ions, acetic acid, ammonia, amino acids, and ionic interfaces Examples thereof include low molecular weight organic substances that dissociate in a solution as in an active agent, and high molecular weight organic substances that dissociate in a solution in a charged state, such as proteins, viruses, DNA, and ionic polymers. That is, it is sufficient that it is dissolved in an aqueous solution and dissociated to be in a charged state, and the size is not limited here.

  In the adsorption filtration membrane of this embodiment, the amount of filtrate per unit time gradually decreases under operating conditions with a constant pressure. The same applies to an adsorption membrane in which the filtration pressure gradually increases under operating conditions with a constant filtration rate. However, the decrease in the filtrate volume and the increase in pressure are limited to those caused by adsorption of ionic species that are smaller than the pore size of the filtration membrane. For example, the filtrate is caused by suspension or viscous clogging of the membrane surface. A distinction must be made between volume reduction and pressure increase.

  A specific FLUX behavior when using an adsorption filtration membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed on the pore surface of the porous membrane of this embodiment will be described.

  Cattle which is a protein that is negatively charged in a buffer solution of pH 8, for example, against an adsorption filtration membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed on the pore surface of the porous membrane When serum albumin (BSA) or lysozyme, which is a positively charged protein, is subjected to adsorption filtration under a constant pressure operating condition, the amount of adsorption increases with the progress of filtration, and FLUX gradually decreases. In addition, when adsorption filtration is performed under an operation condition with a constant filtration rate, the amount of adsorption increases with the progress of filtration, and at the same time, the filtration pressure increases.

  As described above, the reason why FLUX decreases with the adsorption of ionic species in an adsorption filtration membrane in which graft polymer chains having weakly electrolytic ion-exchange groups are formed on the pore surface is considered as follows. Can do.

  First, the relationship between the type of ion exchange group and the form of the graft polymer chain will be described. The ion exchange group on the graft polymer chain affects the shape of the graft polymer chain due to repulsion between the ion exchange groups. This repulsion is thought to originate from the steric repulsion of the hydrated water group surrounding the ion exchange group.

  In order to increase the adsorption capacity of the adsorption filtration membrane, it is necessary to increase the ion exchange group density. Here, when a strong electrolytic ion exchange group is used as the ion exchange group, almost all of the ion exchange groups are used in a wide pH range. Since the ion exchange groups are in a dissociated state, the ion exchange groups having hydrated water are present at a high density. As a result, the steric repulsion within the graft polymer chain on the pore surface and between adjacent graft polymer chains inevitably increases, resulting in the graft polymer chain in an extended state.

  On the other hand, when a weakly electrolytic ion exchange group is used as the ion exchange group, even if the ion exchange group density is increased for the purpose of increasing the adsorption capacity of the adsorption filtration membrane, it is in a dissociated state near neutral pH. Since there are few ion exchange groups, the steric repulsion is small as a result, and the graft polymer on the pore surface is in a relatively contracted state.

  Next, the change in the shape of the graft polymer chain when the graft polymer chain having a weak electrolytic ion exchange group adsorbs the adsorbed substance will be described. When a liquid containing an ionic species is filtered at a constant pressure against a filtration membrane having a graft polymer chain having a weakly electrolytic ion-exchange group on the pore surface, the weakly electrolytic ion-exchange group as the filtration process proceeds Ionic chemical species are taken into the graft polymer chain having Since ionic species have bulky hydrated water groups or are themselves bulky particles, the graft polymer chains that were in a relatively contracted state before adsorption gradually become adsorbed within the graft chain. Further, the steric repulsion between adjacent graft chains is increased, and the graft polymer chain is eventually extended.

  As described above, in an adsorption filtration membrane in which a graft polymer chain having a weakly electrolytic ion-exchange group is formed on the pore surface, the graft polymer chain expands as the ionic species are adsorbed. Since the pores are blocked, it can be considered that FLUX gradually decreases (or the filtration pressure increases).

  Conventionally, such a feature that FLUX gradually decreases was considered to be simply disadvantageous as the performance of the adsorption filtration membrane.

  The problem to be solved by the present invention is to solve the undesirable result that the effective utilization of the adsorption capacity decreases due to “upsizing” and “high integration” of the adsorption membrane module. The inventors have surprisingly found that this problem can be improved by using, as a constituent member, an adsorption filtration membrane having a characteristic that FLUX decreases as the adsorption proceeds as described above.

  In other words, in the conventional technology, as described above, “upsizing” and “high integration” in the adsorption filtration membrane module are, in an extreme example, the local area where adsorption has just started and the adsorption progresses and the leakage of the adsorbed substance begins. In this case, since the capacity of the entire module does not increase as expected, there is a limit to “upsizing” and “high integration”. However, by using “adsorption filtration membranes with graft polymer chains having weakly electrolytic ion exchange groups formed on the pore surface” as constituent members, on the other hand, adsorption progressed and leakage of adsorbed substances began. Since FLUX decreases locally, it is possible to suppress the amount of leakage of the adsorbed substance, and on the other hand, the adsorbed substance is preferentially supplied to the local area where adsorption has just started. Finally, the module as a whole can maintain a high utilization of the adsorption capacity of the adsorption filtration membrane.

Further, the “adsorption ability” will be described here.
The terms representing the adsorption capacity include “static adsorption capacity” (or “equilibrium adsorption capacity”) and “dynamic adsorption capacity”, which are widely used in the industry. In the present invention, unless otherwise specified, the adsorption capacity refers to the dynamic adsorption capacity, and the unit is expressed in mg / ml.
The static adsorption capacity refers to an adsorption capacity when an adsorbed substance is adsorbed to an adsorbent to a saturated state.
On the other hand, the dynamic adsorption capacity is the adsorption up to the time when the adsorbed substance is discharged at the reference concentration from the outlet when the fluid containing the adsorbed substance is introduced and discharged from the fixed adsorbent. This refers to the numerical value converted per unit amount. This reference concentration is called a breakthrough point. Generally, the breakthrough point is selected from the range of 5% to 20% of the adsorbed substance concentration at the time of discharge with respect to the adsorbed substance concentration at the time of introduction. % Concentration was defined as the breakthrough point.

Next, the explanation about “adsorption capacity” will be supplemented.
The amount of the substance to be adsorbed by the adsorbent is referred to as “adsorption amount”, and a numerical value obtained by converting the adsorption amount into a value per unit amount of the adsorbent is referred to as “adsorption capacity”.
The adsorbed amount may be a unit suitable for expressing its characteristics such as weight, volume and number of moles, but is defined by weight in the present invention. As the unit amount of the adsorbent, a unit suitable for expressing its characteristics such as a unit weight, a unit volume, and a unit filling volume can be used.
The unit membrane volume is calculated differently depending on the shape of the flat membrane and the shape of the hollow fiber. In the present invention, the unit membrane volume in the case of a flat membrane simply adopts a value obtained by multiplying the effective membrane area and the membrane thickness. In the present invention, the unit membrane volume in the case of the shape of the hollow fiber membrane adopts an annular cross-sectional volume, and the annular cross-sectional volume means the outer diameter of the hollow fiber membrane Do, the inner diameter Di, and contributes to adsorption filtration. When the effective film length to be expressed is represented by L, it indicates a value that can be defined by L × {(Do / 2) 2− (Di / 2) 2} × π.
Therefore, the adsorption capacity is defined as a value obtained by dividing the adsorption weight by the unit membrane volume, and in the present invention, the unit is expressed in mg / ml.

  That is, the above-mentioned effective utilization of the adsorption capacity of the adsorption membrane module is a measure of how much the adsorption capacity inherent in the adsorption filtration membrane is exerted when it is made into a module shape. It is defined as the ratio of the adsorption capacity of the adsorption filtration membrane when measured in the module shape to the adsorption capacity when measured with. In the present invention, the standard dimension is, for example, a membrane length of 7 cm in the case of a hollow fiber membrane, and a basic dimension of a diameter of 2.5 cm in the case of a flat membrane.

  There is no restriction on the composition and the fine structure of such an adsorption filtration membrane, as long as FLUX is lowered by adsorption of ionic chemical species. As specifically described, as an example of such an adsorption filtration membrane, an adsorption filtration membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed on the pore surface is suitably used. be able to.

The structure of the graft polymer chain is not limited as long as FLUX decreases with the adsorption of ionic species as described above. However, the structure of the graft polymer chain is a polymer chain with a non-crosslinked structure rather than a polymer chain with a cross-linked structure. Some are more preferable because they can be easily stretched, so that the decrease in FLUX accompanying adsorption becomes larger.
Therefore, when the graft polymer chain is formed by a polymerization method, a production method using no crosslinking agent is preferred.

  The form of such an adsorption filtration membrane is not particularly limited as long as the solution can be passed therethrough, and examples thereof include a flat membrane, a nonwoven fabric, a hollow fiber membrane, a monolith, and a capillary. Among these forms, the adsorption filtration membrane is preferably a hollow fiber membrane from the viewpoints of ease of production, scale-up property, packing property upon module molding, and the like. The hollow fiber membrane is a cylindrical or fibrous porous membrane having a hollow portion, and the inner layer and the outer layer of the hollow fiber are continuous by pores that are through holes, and the inner layer to the outer layer or the outer layer by the pores. Means a porous body having a property of allowing liquid to permeate into the inner layer. As the hollow fiber membrane material, a material generally used for a hollow fiber membrane can be used. However, when an adsorption function is imparted by post-processing by chemical processing or physical processing on the hollow fiber membrane, it is necessary to select a material that does not change or decompose due to the processing conditions, and inevitably processing. In some cases, possible materials are limited. Furthermore, when a physical load such as a temperature load, a chemical load, a use pressure, or a vibration is generated depending on the use application, it is necessary to select a material suitable for each use. A method for producing a hollow fiber porous membrane using a polyolefin polymer is known to those skilled in the art, and examples thereof include a method disclosed in JP-A-3-42025.

The effective membrane length of the hollow fiber membrane is preferably 5 cm or more and less than 10 cm because it is suitable for use at the laboratory level, and is preferably 10 cm or more and less than 20 cm because the accuracy of confirmation in scale-up from the laboratory level to small, medium, and large scales is high. ~ Suitable for use in medium-scale purification sites, preferably 20 cm or more and less than 50 cm. Suitable for use in large-scale purification sites, and excellent handling, preferably 50 cm or more and 100 cm or less. Large-scale purification sites And more than 100 cm and less than 250 cm are preferable.
Here, the effective membrane length of the hollow fiber membrane is the average length per one hollow fiber membrane installed in the module, and is the length of the portion that contributes to filtration, and does not indicate the total length of the module. Absent.

Regarding the ratio between the outer diameter and the inner diameter of the hollow fiber membrane, it is preferable to appropriately consider the balance between the strength of the hollow fiber membrane material and the filtration water transmission rate. For example, the outer diameter / inner diameter ratio of the hollow fiber membrane is preferably selected between 1.3 and 10.0.
When the ratio of the outer diameter / inner diameter of the hollow fiber membrane is small, the hollow fiber membrane may not endure the load of filtration pressure and may be ruptured or crushed. On the other hand, when the ratio of the outer diameter / inner diameter of the hollow fiber membrane is too large, the filtration water transmission rate may be reduced.
From the above, the outer diameter / inner diameter ratio of the hollow fiber membrane is preferably 1.3 to 10.0, more preferably 1.3 to 3.0, and still more preferably 1.5 to 2.0.

  On the other hand, the inner diameter of the hollow fiber membrane may greatly affect the pressure loss in the pipe of the fluid flowing through the hollow portion. It is necessary to reduce the in-pipe pressure loss as much as possible. The pressure loss becomes a factor that causes a local filtration permeation rate distribution in the longitudinal direction of the hollow fiber membrane 2, and as a result, induces a difference in the timing of adsorption breakthrough in the longitudinal direction of the hollow fiber membrane 2. Because. That is, on the one hand, there is a local part immediately after the start of adsorption, while on the other hand, there is a state where there is a local part that has already been adsorbed, and the effective utilization of the adsorption capacity of the adsorption filtration membrane is significantly reduced. However, as a result of intensive studies, the inventors have been able to maintain an effective utilization of the adsorption capacity of the adsorption filtration membrane by using an adsorption filtration membrane having a feature that FLUX decreases as the adsorption proceeds. The relationship between the optimum inner diameter of the hollow fiber membrane and the effective membrane length of the module was found.

Practically, it is preferable to select the hollow fiber membrane so that the effective utilization of the adsorption capacity when the hollow fiber membrane 2 has a modular structure is in the range of 0.60 or more. More preferably, it is the range of 0.80 or more, More preferably, it is the range of 0.90 or more. Especially preferably, it is the range of 0.95 or more and 1.00 or less.
Below, the relationship between the effective membrane length of the adsorption filtration membrane, the hollow fiber inner diameter, and the effective utilization of the adsorption capacity is described.

  When the effective membrane length of an adsorption filtration membrane comprising an adsorption filtration membrane having a feature that FLUX decreases with the progress of adsorption is 10 cm or more and 20 cm or less, the inner diameter dimension of the adsorption filtration membrane may be 0.28 mm or more. Preferably, 0.43 mm or more is more preferable. When the effective length of the adsorption filtration membrane was 20 cm and the inner diameter was 0.28 mm, the effective utilization of the adsorption capacity could be 0.63. Moreover, when the effective membrane length of the adsorption filtration membrane was 20 cm and the inner diameter dimension was 0.43 mm, the effective utilization of the adsorption capacity could be 0.90. Furthermore, when the effective membrane length of the adsorption filtration membrane was 20 cm and the inner diameter dimension was 2.20 mm, the effective utilization of the adsorption capacity could be 1.00.

  When the effective membrane length of an adsorption filtration membrane comprising an adsorption filtration membrane having a characteristic that FLUX decreases with the progress of adsorption is more than 20 cm and within 50 cm, the inner diameter of the adsorption filtration membrane is 0.43 mm or more. Is preferable, and more preferably 0.60 mm or more. More preferably, it is 0.76 mm or more. When the effective length of the adsorption filtration membrane was 50 cm and the inner diameter dimension was 0.43 mm, the effective utilization of the adsorption capacity could be 0.64. Moreover, when the effective membrane length of the adsorption filtration membrane was 50 cm and the inner diameter dimension was 0.60 mm, the effective utilization of the adsorption capacity could be 0.83. Furthermore, when the effective membrane length of the adsorption filtration membrane was 50 cm and the inner diameter dimension was 0.76 mm, the effective utilization of the adsorption capacity could be 0.94. Furthermore, when the effective length of the adsorption filtration membrane was 50 cm and the inner diameter dimension was 2.2 mm, an effective utilization of the adsorption capacity of 0.98 was achieved.

  When the effective membrane length of the adsorption filtration membrane comprising the adsorption filtration membrane having the characteristic that FLUX decreases with the progress of adsorption is more than 50 cm and within 100 cm, the inner diameter dimension of the adsorption filtration membrane is 0.60 mm or more. Is more preferable, and 0.76 mm or more is more preferable. 1.02 mm or more is more preferable. When the effective length of the adsorption filtration membrane was 100 cm and the inner diameter was 0.60 mm, the effective utilization of the adsorption capacity could be 0.68. Moreover, when the effective membrane length of the adsorption filtration membrane was 100 cm and the inner diameter dimension was 0.76 mm, the utilization of the adsorption capacity could be 0.80. Furthermore, when the effective length of the adsorption filtration membrane was 100 cm and the inner diameter was 1.02 mm, the effective utilization of the adsorption capacity could be 0.919. Furthermore, when the effective membrane length of the adsorption filtration membrane was 100 cm and the inner diameter dimension was 2.2 mm, an effective utilization rate of adsorption capacity of 0.98 was achieved.

  When the effective membrane length of an adsorption filtration membrane comprising an adsorption filtration membrane having a characteristic that FLUX decreases with the progress of adsorption is more than 100 cm and within 150 cm, the inner diameter of the adsorption filtration membrane is 0.76 mm or more. Is more preferable, and 1.02 mm or more is more preferable. More preferably, it is 1.22 mm or more. When the effective length of the adsorption filtration membrane was 150 cm and the inner diameter dimension was 0.76 mm, the effective utilization of the adsorption capacity could be 0.63. Further, when the effective length of the adsorption filtration membrane was 150 cm and the inner diameter dimension was 1.02 mm, the effective utilization of the adsorption capacity could be 0.85. Furthermore, when the effective membrane length of the adsorption filtration membrane was 150 cm and the inner diameter dimension was 1.22 mm, the effective utilization of the adsorption capacity could be 0.92. Furthermore, when the effective membrane length of the adsorption filtration membrane was 150 cm and the inner diameter dimension was 2.2 mm, an effective utilization rate of adsorption capacity of 0.98 was achieved.

  When the effective membrane length of the adsorption filtration membrane comprising the adsorption filtration membrane having the characteristic that FLUX decreases with the progress of adsorption is more than 150 cm and within 200 cm, the inner diameter of the hollow fiber filtration membrane is 0.86 mm or more. It is more preferable that it is 1.22 mm or more. When the effective length of the adsorption filtration membrane was 200 cm and the inner diameter was 0.86 mm, the effective utilization of the adsorption capacity could be 0.63. When the effective membrane length of the adsorption filtration membrane was 200 cm and the inner diameter dimension was 1.22 mm, the effective utilization of the adsorption capacity could be 0.86. Furthermore, when the effective length of the adsorption filtration membrane was 200 cm and the inner diameter dimension was 2.2 mm, an effective utilization of the adsorption capacity of 0.98 was achieved.

Hereinafter, specific examples and comparative examples of the present invention will be described.
The present invention is not limited to the following examples.

[Production Example 1] Production of hollow fiber porous membrane as base material 27.2 parts by mass of finely divided silicic acid (Aerosil R972 grade), 54.3 parts by mass of dibutyl phthalate (DBP), polyethylene resin powder (Asahi Kasei Sun Fine SH- (800 grade) 18.5 parts by mass were premixed and then extruded into a hollow fiber in a twin screw extruder.
Next, dibutyl phthalate (DBP) and finely divided silicic acid were extracted by immersing in methylene chloride and subsequently in an aqueous NaOH solution, respectively, and then washed with water and dried to obtain a hollow fiber porous membrane made of polyethylene.

[Production Example 2] Production of Hollow Fiber Porous Membrane Having Adsorption Function The polyethylene hollow fiber porous membrane produced in [Production Example 1] was placed in a sealed container, and the air in the sealed container was replaced with nitrogen.
Thereafter, while cooling with dry ice from the outside of the sealed container, irradiation with 200 gGy of γ rays was performed to generate radicals, thereby obtaining a polyethylene hollow fiber porous membrane having radicals.
The polyethylene hollow fiber porous membrane having radicals obtained as described above was put in a reaction vessel, and the pressure in the reaction vessel was reduced to 200 Pa or less to remove oxygen in the reaction vessel.
On the other hand, a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) adjusted to 40 ° C. and 97 parts by volume of methanol was bubbled with nitrogen to remove oxygen from the reaction solution.
The reaction liquid from which the oxygen was removed was poured into a reaction vessel from which the polyethylene hollow fiber porous membrane had been removed. Then, according to the time described in the examples and comparative examples described later, the sealed stationary state was maintained, and a graft polymerization reaction was performed on the polyethylene hollow fiber porous membrane at a reaction temperature of 40 ° C.
Then, it washed thoroughly with methanol and dried to obtain a GMA graft hollow fiber membrane.
Then, by the method described in the Example and comparative example which are mentioned later, it was converted into the functional group which has an adsorption function by making a reagent act on the epoxy group of the GMA graft chain of a GMA graft hollow fiber membrane. Thereby, a GMA graft hollow fiber membrane having a functional group was obtained.

[Production Example 3] Definition of Graft Rate The graft rate in the GMA graft hollow fiber membrane having a functional group produced in the above [Production Example 2] is represented by the following formula (1).

W0: Weight of base film [g]
W1: Weight of GMA graft hollow fiber membrane after graft polymerization [g]

[Production Example 4] Definition of Functional Group Substitution Rate The functional group conversion rate in the GMA grafted hollow fiber membrane having the functional group produced in [Production Example 2] is represented by the following formula (2).

W2: Weight of GMA-grafted hollow fiber membrane having a functional group [g]
M1: Molecular weight of GMA (142.15)
M2: Molecular weight of functional group having adsorption function

[Evaluation Method Example 1] Measuring Device for Hollow Fiber Membrane Having Adsorption Function The GMA grafted hollow fiber membrane having a functional group produced in [Production Example 2] has the functional group so that the effective membrane length is 7 cm. Both ends of the GMA graft hollow fiber membrane were connected to a pipe, one end of the GMA graft hollow fiber membrane was connected to a tube pump via a pressure gauge, and a cock was connected to the other end to provide a hollow fiber membrane measuring device.

[Evaluation Method Example 2] Measurement of Adsorption Capacity of Hollow Fiber Filtration Membrane Having Adsorption Function For an adsorption filtration membrane having an effective membrane length of 7 cm attached to the measurement apparatus of [Evaluation Method Example 1], an index as an adsorbed substance The adsorption ability using protein was measured.
The use of a purified protein commercial product as an adsorbed substance is generally used when displaying the performance of a biotechnology purification apparatus. As the model substance, it is preferable to use the most suitable protein for showing the performance of the purification apparatus, but generally used proteins include BSA (bovine serum albumin) and lysozyme. As these index proteins, BSA used A7906-100G manufactured by SIGMA, and lysozyme used L6876-10G manufactured by SIGMA, and the adsorption capacity was defined as follows.
Supplied after the Tris-HCl buffer is supplied to the hollow part of the hollow fiber membrane and the residual air in the hollow part is eliminated with respect to the adsorption filtration membrane having an effective membrane length of 7 cm attached to the measuring apparatus of [Evaluation Method Example 1]. The cock on the opposite side was closed. Subsequently, the Tris-HCl buffer was filtered by the internal pressure method until the filtration pressure was stabilized at a predetermined flow rate setting. An indicator protein is dissolved in Tris-HCl buffer to prepare a concentration of 1 g / L, and supplied to an adsorption filtration membrane having an effective membrane length of 7 cm with the filtration pressure stabilized at 20 ° C. Filtration continued at the flow rate. The trend of protein leakage to the filtrate side was followed by absorbance at a wavelength of 280 nm, and the filtrate amount [ml] at the time when the ratio of the absorbance of the filtrate to the absorbance of the indicator protein aqueous solution reached 10% was confirmed. By converting the amount of this filtrate into the protein weight from the relationship of 1 g / L, the protein adsorption amount [mg] at the time when the absorbance ratio reached 10% was derived.
The protein adsorption amount [mg] was divided by the annular membrane volume [ml] of the hollow fiber membrane used for filtration to obtain the protein adsorption amount [mg / ml] per unit membrane volume.
The protein adsorption amount per unit membrane volume when the absorbance ratio reached 10% was defined as “membrane-specific dynamic adsorption capacity”.
In the field of biotechnology purification, etc., “dynamic adsorption capacity” is a commonly used term.

[Evaluation Method Example 3] Apparatus for Measuring Adsorption Capacity of Hollow Fiber Membrane Module The adsorption capacity of the hollow fiber membrane module was measured using a high performance liquid chromatography (HPLC) system.
As HPLC, AKTAexplorer100 of GE Healthcare Bioscience Co., Ltd. or medium pressure chromatograph BP-5000S-L of YMC Co., Ltd. was used.

[Evaluation Method Example 4] Measurement of Adsorption Capacity of Hollow Fiber Filtration Membrane Module Having Adsorption Function The HPLC and hollow fiber filtration membrane module described in [Evaluation Method Example 3] above, and the supply pipe of HPLC as the hollow fiber membrane inner surface of the module The HPLC discharge piping was connected to the outer surface side of the hollow fiber membrane of the module. Thereafter, Tris-HCl buffer was supplied so that there was no residual air on the inner surface side and the outer surface side of the hollow fiber membrane, and an internal pressure filtration operation was performed for setup.
An indicator protein aqueous solution (BSA or lysozyme) prepared to a concentration of 1 g / L in Tris-HCl buffer is supplied to the hollow fiber filtration membrane module at 20 ° C., and the internal pressure type is supplied at a predetermined constant flow rate. Filtration continued. The supply flow rate was set to a flow rate proportional to the effective membrane length in order to match the filtration water permeability load per unit membrane area between the measurement in [Evaluation Method Example 2] and the main measurement.
The trend of protein leakage to the filtrate side was followed by absorbance at a wavelength of 280 nm, and the filtrate amount [ml] at the time when the ratio of the absorbance of the filtrate to the absorbance of the indicator protein aqueous solution reached 10% was confirmed. By converting the filtrate amount [ml] into the protein weight [mg] from the relationship of 1 g / L, the protein adsorption amount [mg] when the absorbance ratio reached 10% was derived.
The protein adsorption amount [mg / ml] per unit membrane volume is obtained by dividing the protein adsorption amount [mg] by the total annular membrane volume [ml] of all the hollow fiber membranes constituting the measured hollow fiber filtration membrane module. Converted into
The protein adsorption amount per unit membrane volume when the absorbance ratio was 10% was defined as “dynamic adsorption capacity in module form”.

[Example 1]
A hollow fiber type adsorption filtration membrane having a diethylamino group as a weakly electrolytic ion exchange group in the graft polymer chain will be described. In a filtration membrane having weakly electrolytic ion exchange groups, this is an example showing that the filtration pressure increases (FLUX decreases) with adsorption.

A polyethylene hollow fiber porous membrane having an inner diameter of 2.0 mm and an outer diameter of 3.1 mm was obtained according to the method of [Production Example 1].
A polyethylene hollow fiber porous membrane 4 from which a reaction solution comprising 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of isopropyl alcohol was used, and the other conditions were the same as in [Production Example 2] above, except that oxygen was removed. By injecting 96 parts by mass of the reaction liquid from which oxygen was removed with respect to parts by mass and maintaining a reaction time of 15 minutes, a GMA graft hollow fiber membrane was obtained with a graft rate of 53%.
Thereafter, a reaction solution consisting of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 23 hours. Thus, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 93%, a diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 2.20 mm and an outer diameter of 3.54 mm. A yarn membrane was obtained.

The BSA solution was fed to the inner surface side at a feeding rate of 2.0 mL / min to the GMA grafted hollow fiber membrane having the diethylamino group (weakly electrolytic ion exchange group) by the method of [Evaluation Method Example 2]. The liquid is filtered to the outer surface side, and the ratio of the absorbance of the filtrate to the absorbance of the BSA aqueous solution to be supplied becomes 10%, and the filtration operation is continued until it exceeds 90%, and the filtrate weight, absorbance, and filtration pressure are continued. And monitored.
It took 20.5 mL to reach an absorbance ratio of 10%. From this, the dynamic adsorption capacity of this membrane was calculated to be 48.5 mg / mL in terms of the amount of BSA adsorption. Moreover, the relationship between the filtrate amount, the absorbance and the filtration pressure until the absorbance ratio of the filtrate exceeds 90% is as shown in FIG. 7, but the GMA graft hollow having the present diethylamino group (weakly electrolytic ion exchange group) It is clear that the yarn membrane has a characteristic that the filtration pressure increases with the progress of adsorption, that is, FLUX decreases.

[Example 2]
As in Example 1, a hollow fiber type adsorption filtration membrane having a diethylamino group as a weakly electrolytic ion exchange group in the graft polymer chain will be described. It is an example which shows that filtration pressure rises with adsorption similarly to Example 1 (FLUX falls).

A polyethylene hollow fiber porous membrane having an inner diameter of 2.0 mm and an outer diameter of 3.1 mm was obtained according to the method of [Production Example 1].
A reaction liquid consisting of 10 parts by volume of glycidyl methacrylate (GMA) and 90 parts by volume of methanol was used, and the other conditions were the same as in [Production Example 2] above. 96 mass parts of the reaction solution from which oxygen was removed was injected to maintain a reaction time of 11 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 158%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. Thus, a GMA graft hollow having a diethylamino group (M2 = 73.14) at a functional group conversion of 82%, a diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 2.37 mm and an outer diameter of 3.96 mm. A yarn membrane was obtained.

The BSA solution was fed to the inner surface side at a feeding rate of 2.0 mL / min to the GMA grafted hollow fiber membrane having the diethylamino group (weakly electrolytic ion exchange group) by the method of [Evaluation Method Example 2]. The liquid is filtered to the outer surface side, and the ratio of the absorbance of the filtrate to the absorbance of the BSA aqueous solution to be supplied becomes 10%, and the filtration operation is continued until it exceeds 90%, and the filtrate weight, absorbance, and filtration pressure are continued. And monitored.
It took 55.3 mL to reach an absorbance ratio of 10%. From this, the dynamic adsorption capacity of this membrane was calculated as 99.6 mg / mL in terms of the amount of BSA adsorbed. Further, the relationship between the filtrate amount, the absorbance, and the filtration pressure until the absorbance ratio exceeds 90% is as shown in FIG. 8, but the GMA graft hollow fiber membrane having the present diethylamino group (weakly electrolytic ion exchange group) is It is clear that the membrane has a characteristic that the filtration pressure increases as the adsorption proceeds, that is, FLUX decreases.

[Comparative Example 1]
A hollow fiber type adsorption filtration membrane having a trimethylammonium group as a strong electrolytic anion exchange group in a graft polymer chain will be described. In a filtration membrane having a strong electrolytic anion exchange group, it is an example showing that there is no increase due to filtration pressure with adsorption (FLUX does not decrease).

A polyethylene hollow fiber porous membrane having an inner diameter of 2.0 mm and an outer diameter of 3.1 mm was obtained according to the method of [Production Example 1].
Using a reaction solution consisting of 1 part by volume of glycidyl methacrylate (GMA) and 99 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction liquid from which oxygen had been removed was injected into the part, and the reaction time was maintained for 12 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 12%.
Thereafter, a 0.5 M trimethylammonium chloride aqueous solution adjusted to pH 12 with NaOH was used as a reaction solution, and allowed to act on the GMA graft hollow fiber membrane at 60 ° C. for 30 minutes, whereby trimethylammonium · Cl group (M2 = 95.57). A GMA graft hollow fiber membrane having a trimethylammonium group (strongly electrolytic ion exchange group) having a functional group conversion of 99%, an inner diameter of 2.00 mm, and an outer diameter of 3.18 mm.

By the method of [Evaluation Method Example 2], the BSA solution was applied to the inner surface side at a liquid feed rate of 2.0 mL / min onto the GMA graft hollow fiber membrane having the trimethylammonium group (strongly electrolytic ion exchange group). The liquid was fed and filtered to the outer surface side, and the ratio of the absorbance of the filtrate to the absorbance of the BSA aqueous solution to be supplied reached 10%, and the filtration operation was continued until it exceeded 90%, and the filtrate weight, absorbance, and filtration were continued. The pressure was monitored.
It took 9.6 mL until the absorbance ratio reached 10%. From this, the dynamic adsorption capacity of this membrane was calculated to be 29.0 mg / mL in terms of the amount of BSA adsorbed. Further, the relationship between the filtrate amount, the absorbance and the filtration pressure until the absorbance ratio exceeds 90% is as shown in FIG. 9, but the GMA grafted hollow fiber membrane having the present trimethylammonium group (strongly electrolytic ion exchange group). It is clear that the membrane does not show an increase in filtration pressure with the progress of adsorption, that is, does not show a decrease in FLUX.

[Comparative Example 2]
A hollow fiber type adsorption filtration membrane having a sulfonic acid group in the graft polymer chain as a strong electrolytic cation exchange group will be described. In a filtration membrane having a strong electrolytic cation exchange group, this is an example showing that the filtration pressure does not increase (FLUX does not decrease) with adsorption.

A polyethylene hollow fiber porous membrane having an inner diameter of 2.0 mm and an outer diameter of 3.1 mm was obtained according to the method of [Production Example 1].
A polyethylene hollow fiber porous membrane 4 from which a reaction liquid consisting of 2 parts by volume of glycidyl methacrylate (GMA) and 98 parts by volume of methanol was used, and oxygen was removed by the same method as in [Production Example 2] above. By injecting 96 parts by weight of the reaction liquid from which oxygen was removed with respect to parts by weight and maintaining a reaction time of 12 minutes, a GMA graft hollow fiber membrane was obtained with a graft rate of 23%.
Thereafter, a mixed solution of 10 parts by weight of sodium sulfite, 15 parts by weight of isopropyl alcohol, and 75 parts by weight of pure water was used as a reaction solution and allowed to act on the GMA graft hollow fiber membrane at 80 ° C. for 10 minutes, thereby sulfonic acid / Na group (M2 = 103.05), an adsorption film having a functional group conversion of 3.9% was obtained. Thereafter, in order to diolate the epoxy groups in the remaining GMA graft chains, 0.5 M sulfuric acid aqueous solution was allowed to act as a reaction solution at 80 ° C. for 3 hours, and finally the inner diameter was 2.18 mm and the outer diameter was 3.54 mm. A GMA graft hollow fiber membrane having a sulfonic acid group (strongly electrolytic ion exchange group) was obtained.

By the method of [Evaluation Method Example 2], the BSA solution was applied to the inner surface side at a liquid feed rate of 2.0 mL / min onto the GMA grafted hollow fiber membrane having the sulfonic acid group (strongly electrolytic ion exchange group). The liquid was fed and filtered to the outer surface side, and the ratio of the absorbance of the filtrate to the absorbance of the BSA aqueous solution to be supplied reached 10%, and the filtration operation was continued until it exceeded 90%, and the filtrate weight, absorbance, and filtration were continued. The pressure was monitored.
It took 8.9 mL to reach an absorbance ratio of 10%. From this, the dynamic adsorption capacity of this membrane was calculated as 25.2 mg / mL in terms of the amount of BSA adsorbed. Further, the relationship between the filtrate amount, the absorbance and the filtration pressure until the absorbance ratio exceeds 90% is as shown in FIG. 10, but the GMA grafted hollow fiber membrane having the present sulfonic acid group (strongly electrolytic ion exchange group). It is clear that the membrane does not show an increase in filtration pressure with the progress of adsorption, that is, does not show a decrease in FLUX.

[Example 3]
A polyethylene hollow fiber porous membrane having an inner diameter of 1.1 mm and an outer diameter of 1.7 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction liquid from which oxygen had been removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 55%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. Thus, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 92%, an diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 1.22 mm and an outer diameter of 1.95 mm. A yarn membrane was obtained.

[Example 4]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.8 mm and an outer diameter of 1.3 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 10 parts by volume of glycidyl methacrylate (GMA) and 90 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed from the hollow fiber porous polyethylene film 4 weight 96 parts by weight of the reaction liquid from which oxygen was removed was injected into the part, and the reaction time of 11 minutes was maintained, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 160%. Thereafter, a reaction solution comprising 50 parts by volume of diethylamine and 50 parts by volume of pure water is allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours, thereby converting the diethylamino group (M2 = 73.14) to a functional group conversion rate of 94. %, A GMA graft hollow fiber membrane having a diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 1.02 mm and an outer diameter of 1.63 mm was obtained.

[Example 5]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.8 mm and an outer diameter of 1.3 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction solution from which oxygen had been removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained with a graft rate of 49%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. Thus, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 95%, an diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 0.86 mm and an outer diameter of 1.38 mm. A yarn membrane was obtained.

[Example 6]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.7 mm and an outer diameter of 1.1 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction solution from which oxygen had been removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 55%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. As a result, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 90%, an diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 0.76 mm and an outer diameter of 1.22 mm. A yarn membrane was obtained.

[Example 7]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.54 mm and an outer diameter of 0.85 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction liquid from which oxygen was removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 54%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. Thus, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 92%, an inner diameter of 0.60 mm, and an outer diameter of 0.96 mm (diethylamino group (weakly electrolytic ion exchange group)) A yarn membrane was obtained.

[Example 8]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.37 mm and an outer diameter of 0.62 mm was obtained from the above [Production Example 1]. Except for using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, in the same manner as in [Production Example 2], 4 parts by weight of the polyethylene hollow fiber porous membrane from which oxygen was removed By injecting 96 parts by weight of the reaction liquid from which oxygen was removed and maintaining the reaction time for 15 minutes, a GMA film was obtained with a graft ratio of 50%. Thereafter, a reaction solution comprising 50 parts by volume of diethylamine and 50 parts by volume of pure water is allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours, thereby converting the diethylamino group (M2 = 73.14) to a functional group conversion rate of 94. %, And a GMA graft hollow fiber membrane having a diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 0.43 mm and an outer diameter of 0.69 mm was obtained.

[Example 9]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.25 mm and an outer diameter of 0.40 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction solution from which oxygen had been removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained with a graft rate of 49%.
Thereafter, a reaction solution composed of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 2.3 hours. As a result, a GMA graft hollow having a diethylamino group (M2 = 73.14) having a functional group conversion of 93%, a diethylamino group (weakly electrolytic ion exchange group) having an inner diameter of 0.28 mm and an outer diameter of 0.45 mm. A yarn membrane was obtained.

[Example 10]
The adsorption filtration membranes of Examples 1 and 3 to 9 were attached to the apparatus of [Evaluation Method Example 1], and the dynamic adsorption capacity of each membrane was measured. At this time, the number of hollow fibers attached to the apparatus of [Evaluation Method Example 1] was 1 for the membrane of Example 1, 3 for the membrane of Example 3, 5 for the membrane of Example 4, and Example 5 7 films, 10 films of Example 6, 15 films of Example 7, 25 films of Example 8, and 60 films of Example 9.
Using these hollow fiber membranes in accordance with the method of [Evaluation Method Example 2], as an adsorbed substance, an aqueous solution (1 g / L) of BSA as an indicator protein was used, and the supply flow rate was set to 2.0 ml / min. The dynamic adsorption capacity was determined. Table 1 shows the structures of these adsorption filtration membranes and the results of adsorption capacity evaluation.

[Example 11]
An adsorption filtration membrane module was prepared using the adsorption filtration membranes of Examples 1 and 3-9. At this time, the film of Example 1 is 1, the film of Example 3 is 3, the film of Example 4 is 5, the film of Example 5 is 7, the film of Example 6 is Ten pieces were prepared by inserting 15 pieces in the film of Example 7, 25 pieces in the film of Example 8, and 60 pieces in the film of Example 9 into an outer cylinder having an inner diameter of 1 cm. Regarding the effective membrane length of the adsorption membrane module, the membrane of Example 1 was processed so that the effective membrane length was 20 cm, 50 cm, 100 cm, 150 cm, and 200 cm. The film of Example 3 was processed to 150 cm and 200 cm. The film of Example 4 was processed to be 100 cm and 150 cm. The film of Example 5 was processed to 200 m. The film of Example 6 was processed to be 50 cm, 100 cm, and 150 cm. The film of Example 7 was processed to be 50 cm and 100 cm. The film of Example 8 was processed to 20 cm and 50 cm. The film of Example 9 was processed to 20 cm.
These adsorption filtration membrane modules were evaluated for adsorption capacity according to [Evaluation Method Example 4]. As an adsorbed substance, an aqueous solution (1 g / L) of BSA which is an indicator protein was used. Table 2 shows the results of the adsorption capacity evaluation of the adsorption membrane module. In any of the adsorption filtration membrane modules, the retention rate of the dynamic adsorption capacity, that is, the effective utilization rate of the adsorption capacity compared with the case of the membrane effective length of 7 cm in Example 10, was a result exceeding 0.6.

[Comparative Example 3]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.54 mm and an outer diameter of 0.85 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction liquid from which oxygen was removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 54%.
Thereafter, a 0.5 M trimethylammonium chloride aqueous solution adjusted to pH 12 with NaOH was used as a reaction solution, and allowed to act on the GMA graft hollow fiber membrane at 60 ° C. for 30 minutes, whereby trimethylammonium · Cl group (M2 = 95.57). A GMA graft hollow fiber membrane having a trimethylammonium group (strongly electrolytic ion exchange group) having a functional group conversion of 98%, an inner diameter of 0.62 mm, and an outer diameter of 0.99 mm.

[Comparative Example 4]
A polyethylene hollow fiber porous membrane having an inner diameter of 0.54 mm and an outer diameter of 0.85 mm was obtained according to the method of [Production Example 1]. Using a reaction solution consisting of 3 parts by volume of glycidyl methacrylate (GMA) and 97 parts by volume of methanol, the other conditions were the same as in [Production Example 2], except that oxygen was removed and the hollow fiber porous membrane made of polyethylene 4 wt. 96 parts by weight of the reaction liquid from which oxygen was removed was injected into the part, and the reaction time was maintained for 15 minutes, whereby a GMA graft hollow fiber membrane was obtained at a graft rate of 54%.
Thereafter, a mixed solution of 10 parts by weight of sodium sulfite, 15 parts by weight of isopropyl alcohol, and 75 parts by weight of pure water was used as a reaction solution and allowed to act on the GMA graft hollow fiber membrane at 80 ° C. for 10 minutes, thereby sulfonic acid / Na group (M2 = 103.05), an adsorption film having a functional group conversion of 4.2% was obtained. Thereafter, in order to diolify the epoxy groups in the remaining GMA graft chains, 0.5 M sulfuric acid aqueous solution was allowed to act as a reaction solution at 80 ° C. for 3 hours, and finally the inner diameter was 0.61 mm and the outer diameter was 0.98 mm. A GMA graft hollow fiber membrane having a sulfonic acid group (strongly electrolytic ion exchange group) was obtained.

[Comparative Example 5]
The adsorption filtration membranes of Comparative Examples 3 and 4 were attached to the apparatus of [Evaluation Method Example 1], and the dynamic adsorption capacity of each membrane was measured. At this time, the number of hollow fibers attached to the apparatus of [Evaluation Method Example 1] was 15 in both cases.
These hollow fiber membranes were subjected to the method of [Evaluation Method Example 2]. As an adsorbed substance, an aqueous solution of BSA (1 g / L) was used for the membrane of Comparative Example 3, and lysozyme was used for the membrane of Comparative Example 4. A dynamic adsorption capacity was determined using an aqueous solution (1 g / L) and a supply flow rate of 2.0 ml / min. Table 2 shows the structures of these adsorption filtration membranes and the results of adsorption capacity evaluation.

[Comparative Example 6]
An adsorption filtration membrane module was prepared using the adsorption filtration membranes of Comparative Examples 3 and 4. At this time, 15 films of Comparative Examples 3 and 4 were both inserted into an outer cylinder having an inner diameter of 1 cm and an effective length of 100 cm.
These adsorption filtration membrane modules were evaluated for adsorption capacity according to [Evaluation Method Example 4]. As the substance to be adsorbed, an aqueous BSA solution (1 g / L) is used in the case of the adsorption filtration membrane module of Example 3, and an aqueous lysozyme solution (1 g / L) is used in the case of the adsorption filtration membrane module of Example 4. used. Table 2 shows the results of the adsorption capacity evaluation of the adsorption filtration membrane module. In any of the adsorption filtration membrane modules, the retention rate of the dynamic adsorption capacity, that is, the effective utilization rate of the adsorption capacity, compared with the adsorption membrane module having a membrane effective length of 7 cm in Comparative Example 5, was less than 0.6.

[Example 12]
A polyethylene hollow fiber porous membrane having an inner diameter of 1.9 mm and an outer diameter of 3.2 mm was obtained according to the method of [Production Example 1].
In the same manner as in [Production Example 2], 92 parts by mass of the reaction solution from which oxygen was removed was injected into 8 parts by mass of 970 polyethylene hollow fiber porous membranes having a length of 1.3 m from which oxygen was removed, By maintaining the reaction time of 18 hours, a GMA graft hollow fiber membrane was obtained with a graft rate of 56.0%.
Thereafter, a reaction solution consisting of 50 parts by volume of diethylamine and 50 parts by volume of pure water was allowed to act on the GMA graft hollow fiber membrane at 30 ° C. for 20 hours to convert the diethylamino group (M2 = 73.14) to a functional group conversion of 96%. Thus, a GMA graft hollow fiber membrane having a diethylamino group (weakly electrolytic ion exchange group) having an average inner diameter of 2.44 mm and an average outer diameter of 3.62 mm was obtained.

The BSA solution was fed to the inner surface side at a feeding rate of 2.0 mL / min to the GMA grafted hollow fiber membrane having the diethylamino group (weakly electrolytic ion exchange group) by the method of [Evaluation Method Example 2]. The liquid was filtered and filtered to the outer surface side, and the filtration operation was continued until the ratio of the absorbance of the filtrate to the absorbance of the BSA aqueous solution supplied exceeded 10%, and the filtrate weight, absorbance, and filtration pressure were monitored.
It took 22.6 mL to reach an absorbance ratio of 10%. From this, the dynamic adsorption capacity of this membrane was calculated to be 57.5 mg / mL in terms of BSA adsorption.

Using an outer cylinder with an inner diameter of 13 cm and an effective length of 94 cm, a large weak electrolytic anion exchange type comprising a bundle of 920 GMA grafted hollow fiber membranes having the diethylamino group (weak electrolytic ion exchange group). A hollow fiber membrane module was produced.
In this example, the large weak-electrolyte anion exchange type hollow fiber membrane module was configured such that both ends of a bundle of hollow fiber membranes were fixed with a sealing resin, and openings were exposed at both ends. Polysulfone was used for the material of the outer cylinder. An epoxy adhesive was used as the sealing resin.
According to the method of [Evaluation Method Example 4], adsorption capacity was evaluated using BP-5000SL as an HPLC system. However, the supply flow rate was 4.5 L / min. As an adsorbed substance, an aqueous solution (1 g / L) of BSA which is an indicator protein was used. It took 270 L for the absorbance of the filtrate of the hollow fiber membrane module to reach 10% of the absorbance of the BSA aqueous solution.
As a result, the dynamic adsorption capacity of the GMA grafted hollow fiber membrane having a diethylamino group (weakly electrolytic ion exchange group) in Example 12 was calculated to be 55.6 mg / mL in terms of the amount of BSA adsorbed.

  In the large weak electrolytic anion exchange type hollow fiber membrane module comprising the GMA grafted hollow fiber membrane having a diethylamino group (weak electrolytic ion exchange group) in Example 12 as described above, the effective utilization of the adsorption capacity is 0. .99 was confirmed.

  The hollow fiber membrane module of the present invention is an apparatus for separating and purifying a target substance from a liquid phase by an adsorption method in the fields of biotechnology, genetic engineering, pharmaceutical industry, chemical industry, beverage industry, food industry, environmental protection and resource recycling. There is industrial applicability.

DESCRIPTION OF SYMBOLS 1 Outer cylinder 2 Hollow fiber membrane 3 Sealing resin fixed to the outer cylinder 4 Sealing resin not fixed to the outer cylinder 5 Adhesive end face 6 in which the hollow part is opened 6 Adhesive end face 7 in which the hollow part is closed Exist in the sealing resin Slit 8 Liquid tank 9 Pipe connecting member 10 Fixing jig 11 Indirect member 12 Hollow fiber membrane module

Claims (10)

  An adsorption filtration membrane module comprising an adsorption filtration membrane in which a graft polymer chain having a weak electrolytic ion exchange group is formed on the pore surface of the porous membrane, and the effective membrane length of the adsorption filtration membrane is 10 cm or more   The adsorptive filtration according to claim 1, wherein the weakly electrolytic ion exchange group is at least one selected from the group consisting of a tertiary amino group, a secondary amino group, a primary amino group, a carboxylic acid group, and a phosphoric acid group. Membrane module   The adsorption filtration membrane module according to claim 1 or 2, wherein the weakly electrolytic ion exchange group is a diethylamino group.   The adsorption filtration membrane module according to any one of claims 1 to 3, wherein the graft polymer chain has a non-crosslinked structure.   The adsorption filtration membrane module according to any one of claims 1 to 4, wherein an effective membrane length of the adsorption filtration membrane is 10 cm or more and 20 cm or less, and an inner diameter of the hollow fiber is 0.28 mm or more.   The adsorption filtration membrane module according to any one of claims 1 to 4, wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 20 cm and within 50 cm, and an inner diameter of the hollow fiber is 0.43 mm or more.   The adsorption filtration membrane module according to any one of claims 1 to 4, wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 50 cm and within 100 cm, and an inner diameter of the hollow fiber is 0.60 mm or more.   The adsorption filtration membrane module according to any one of claims 1 to 4, wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 100 cm and within 150 cm, and an inner diameter of the hollow fiber is 0.76 mm or more.   The adsorption filtration membrane module according to any one of claims 1 to 4, wherein an effective membrane length of the adsorption filtration membrane is in a range exceeding 150 cm and within 200 cm, and an inner diameter of the hollow fiber is 0.86 mm or more.   The adsorption filtration membrane module according to any one of claims 1 to 9, wherein the adsorption filtration membrane is a hollow fiber membrane.

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