CN117983060A - Membrane filtration method using pharmaceutical active carbon - Google Patents
Membrane filtration method using pharmaceutical active carbon Download PDFInfo
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- CN117983060A CN117983060A CN202311433758.XA CN202311433758A CN117983060A CN 117983060 A CN117983060 A CN 117983060A CN 202311433758 A CN202311433758 A CN 202311433758A CN 117983060 A CN117983060 A CN 117983060A
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- 238000005374 membrane filtration Methods 0.000 title claims abstract description 35
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
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- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 239000008363 phosphate buffer Substances 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Disclosed is a membrane filtration method which can efficiently, economically and continuously produce a high-quality filtrate. A method for adding powdered activated carbon to a liquid to be purified containing an object to be removed, and separating the object to be removed from the powdered activated carbon by membrane filtration of the liquid to be purified. The powdered activated carbon contains a medicinal activated carbon having a particle size of 0.5 μm or more. The pore diameter of the membrane is 0.45 μm or less.
Description
[ Field of technology ]
The present disclosure relates to a membrane filtration process using pharmaceutical activated carbon.
[ Background Art ]
Conventionally, in a method for purifying an intermediate product of a product such as a chemical product, a food product, a beverage, a pharmaceutical product, or a cosmetic product, as a treatment method for removing a substance affecting discoloration, odor and flavor components, taste, preservability, or the like of the product, when the intermediate product is a liquid (hereinafter, referred to as a "liquid intermediate product"), activated carbon is generally added to the liquid intermediate product. However, since activated carbon is generally fine in structure and light in specific gravity, separation after treatment is often difficult when activated carbon is added to a liquid intermediate product. Examples of such a separation method of activated carbon include a natural sedimentation method, a diatomaceous earth filtration method, and a membrane filtration method. As the membrane filtration method, a membrane filtration method using a ceramic membrane and an Ultrafiltration (UF) membrane based on a cross-flow filtration method, a Microfiltration (MF) membrane based on an external pressure full filtration method, and the like are generally used.
However, natural sedimentation separation requires a long time, and sedimentation is often incomplete. Therefore, it is difficult to efficiently produce a high-quality separation liquid.
When the diatomite filtration method uses only a filter cloth as a filter medium, clogging of the filter cloth by activated carbon is serious, and it is difficult to put it to practical use. Therefore, a precoating operation is generally performed to form a cake of filter aid such as diatomaceous earth or perlite on a filter cloth, and the activated carbon is removed by pressing a mixed solution of a liquid intermediate product (for example, sugar solution) and the activated carbon. However, at the beginning of the pressing operation, since the activated carbon leaks from the cake layer on the surface of the filter cloth and is mixed into the filtrate, the filtrate needs to be recycled (circulated) until the activated carbon is not leaked. Further, the long-term filtration increases the thickness of the cake layer on the surface of the filter cloth, increases the filtration resistance, and must increase the pressing pressure of the liquid intermediate product. Therefore, it is necessary to stop the filtration at an appropriate time, peel off the cake layer on the filter cloth surface of the filter, and clean the filter cloth. Thus, the diatomaceous earth filtration method requires a complicated operation of one cycle of precoating operation, filtrate recycling operation, filtration (press-in) operation, and cake layer peeling operation. In addition, when a precoating operation, a filtrate recycling operation, and a cake layer peeling operation are performed in one filter, clear filtrate cannot be obtained, and the production must be interrupted, so that the purification step cannot be continuously performed. Therefore, if two or more filters are provided, and the cake peeling operation, the precoating operation, and the filtrate recycling operation are performed by one filter during the filtration operation by the other filter, the production as a whole in the purification step is not stopped, and a clear filtrate can be continuously obtained. However, it is uneconomical to provide two or more expensive filters, and on the other hand, there is little waste caused by the interruption of the production of one filter.
In the ceramic membrane filtration method of the cross-flow filtration system, as described in patent document 1, when a liquid intermediate product supplied to the ceramic membrane filtration apparatus contains hard SS (suspended substances) such as activated carbon, if a pretreatment apparatus is not used, abrasion marks are found near the raw liquid inlet of the ceramic membrane at a stage of 10000 hours, and separation performance is lowered. In addition, ceramic membrane filtration devices are generally more expensive and uneconomical than organic membrane (UF and MF membrane) filtration devices.
As described in patent document 2, the external pressure type full filtration method requires a treatment for increasing the particle size of the sediment to aggregate the sediment components, and if this treatment is not performed, clogging is caused in the pore portion of the membrane. Therefore, in addition to activated carbon, a sediment precipitating agent must be used, and depending on the kind of liquid intermediate product, for example, in the case of sake, the kind and amount of sediment precipitating agent such as zeolite and gelatin need to be selected. Further, if the throughput of the liquid intermediate product increases, the cake production increases, and clogging may cause difficulty in regeneration of the membrane, so that the washing with the chemical liquid must be repeated.
Patent document 3 describes a membrane filtration method using a UF membrane, in which activated carbon is added to sake and sediment components and activated carbon in sake are removed simultaneously under specific conditions. According to this method, the activated carbon and the sediment can be removed at the same time without adding the sediment precipitating agent, and clogging hardly occurs, and the concentration filtration can be performed at a high concentration degree, so that the production can be economically and efficiently stabilized.
[ Prior Art literature ]
[ Patent literature ]
Japanese patent application laid-open No. 2017-131823 (patent document 1)
Japanese patent application laid-open No. 57-206378
Japanese patent application laid-open No. 9-313162
[ Invention ]
[ Problem to be solved by the invention ]
However, the conventional membrane filtration method using activated carbon has room for improvement in producing a high-quality filtrate efficiently, economically and continuously. It is an object of the present disclosure to provide a membrane filtration method capable of efficiently, economically and continuously producing a high quality filtrate.
[ Means for solving the problems ]
Examples of embodiments of the present disclosure are set forth below.
[1] A method for adding powdered activated carbon to a liquid to be purified containing an object to be removed, and membrane-filtering the liquid to be purified to separate the object to be removed from the powdered activated carbon,
The powdered activated carbon contains a pharmaceutical activated carbon having a particle size of 0.5 μm or more,
And the pore diameter of the membrane is 0.45 μm or less.
[2] The method according to item 1, wherein the liquid to be purified is an intermediate product of a product selected from the group consisting of chemicals, foods, beverages, pharmaceuticals, and cosmetics.
[3] The method according to item 1 or 2, wherein the powdered activated carbon contains the drug activated carbon as a main component.
[4] The method according to any one of items 1 to 3, wherein the membrane filtration is internal pressure cross-flow filtration based on hollow fiber membranes.
[5] The method according to item 4, wherein the material of the hollow fiber membrane is a thermoplastic resin.
[6] The method according to item 4 or 5, wherein the hollow fiber membrane has an inner diameter of 1.0mm or more and 14.5mm or less.
[7] The method according to any one of items 4 to 6, wherein the hollow fiber membrane has a pore diameter of 0.05 μm or more and 0.30 μm or less.
[8] The method according to any one of items 1 to 7, wherein the structure of the membrane for the membrane filtration is a homogeneous structure.
[9] The method according to any one of items 1 to 8, wherein the membrane used for the above membrane filtration is an MF membrane.
[10] The method according to any one of items 1 to 9, wherein the concentration of the powdered activated carbon contained in the purification target liquid concentrated after membrane filtration is 15% by weight or less.
[ Effect of the invention ]
According to the present disclosure, a membrane filtration method capable of efficiently, economically and continuously producing a high quality filtrate can be provided.
[ Description of the drawings ]
Fig. 1 is a schematic diagram showing a concentration (recovery) circuit for discharging a filtrate (4) out of a system for evaluation of a membrane filtration method.
Fig. 2 is a schematic diagram showing a circuit for returning the filtrate (4) to the raw liquid tank (not concentrated) for evaluation by the membrane filtration method.
[ Detailed description ] of the invention
Membrane filtration method
The membrane filtration method of the present disclosure is a method for adding powdered activated carbon to a liquid to be purified containing an object to be removed, and separating the object to be removed from the powdered activated carbon by membrane filtration of the liquid to be purified. The powdered activated carbon contains a medicinal activated carbon having a particle size of 0.5 μm or more. And the pore diameter of the membrane is 0.45 μm or less. The membrane filtration method of the present disclosure can provide a membrane filtration method capable of producing a high-quality filtrate efficiently, economically and continuously by having the above-described configuration. The reason for this is not clear at the date of application of the present application, but the present inventors have examined the following. That is, generally, pharmaceutical activated carbon tends to contain more plate-like particles, whereas water vapor activated carbon tends to contain more needle-like particles. The planar particles have a large projected area when viewed from a direction perpendicular to the plane thereof, and have a relatively large aspect ratio when viewed from a direction parallel to the plane thereof. The needle-shaped particles have a small projected area when viewed in the longitudinal direction and a small aspect ratio. Therefore, even if the particle diameters are the same, it is considered that the number of plate-like pores is smaller than that of needle-like pores. In the present disclosure, it is considered that by using the drug activated carbon having a particle diameter of 0.5 μm or more and combining with the filtration membrane having a pore diameter of 0.45 μm or less, clogging of the membrane pores by the activated carbon can be effectively prevented. Thus, the membrane filtration process of the present disclosure is capable of producing high quality filtrate efficiently, economically and continuously.
Purified liquid
The purification target liquid is preferably a liquid intermediate product of a product selected from the group consisting of chemicals, foods, beverages, pharmaceuticals, and cosmetics. The term "liquid intermediate" refers to an intermediate product which is used for the production of finished products such as chemicals, foods, beverages, medicines, cosmetics, etc., and which is processed several times to obtain a finished product, and which is liquid at room temperature (25 ℃). If the liquid intermediate product as the purification target liquid is a liquid, the final product thereof does not necessarily have to be a liquid. The purification target liquid contains the removal target. The removal target is a substance that affects discoloration, odor and flavor components, taste, preservability, and the like of the finished product, and means a substance adsorbed by the activated carbon of the drug. It should be noted that the membrane filtration method of the present disclosure does not need to completely remove the removal object, as long as the desired removal rate can be achieved according to the purpose.
Powdered activated carbon
The powdered activated carbon contains pharmaceutical activated carbon having a particle size of 0.5 μm or more. The active carbon is made of carbon material, and substances which can be heated and carbonized can be used as raw materials. Here, "powdered activated carbon" generally means powdered activated carbon produced by carbonization and activation using wood (wood chips) as a raw material. While "granular activated carbon" generally means crushed, cylindrical or beaded activated carbon produced by carbonization and activation starting from coal (bituminous coal) or coconut (coconut shell), in the present disclosure, "powdered activated carbon" and "granular activated carbon" are distinguished. The step of forming a large number of micropores in the carbon material is referred to as activation. "pharmaceutical activated carbon" generally means a porous carbon material activated by chemicals. Typically, the activated carbon for pharmaceuticals is activated by immersing chemicals in substances such as wood (wood chips) or the like as raw materials for the activated carbon, followed by heating, and simultaneously carbonizing and activating. Examples of chemicals used for activating the activated carbon include zinc chloride, phosphoric acid, potassium hydroxide, and sodium hydroxide, and zinc chloride is preferable. By "gas activated carbon" is meant generally a porous carbon material activated by a gas such as water vapor or carbon dioxide. Among the gas activated carbon, the porous carbon material activated by water vapor is called "water vapor activated carbon".
From the viewpoint of efficiently, economically and continuously producing a high-quality filtrate, the powdered activated carbon preferably contains a pharmaceutical activated carbon having a particle size of 0.5 μm or more as a main component. In the present disclosure, "main component" means a component constituting at most wt% of each component contained in the subject composition. The amount of the activated carbon is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 80% by weight or more, particularly preferably 90% by weight or more, and may be 100% by weight, based on the total weight of the activated carbon powder, from the viewpoint of efficiently, economically and continuously producing a high-quality filtrate.
The powdered activated carbon may also contain activated carbon of a type other than pharmaceutical activated carbon, such as water vapor activated carbon. However, from the viewpoint of efficiently, economically and continuously producing a high-quality filtrate, the powdered activated carbon is preferably a vapor-free activated carbon. It is noted that the filtration method of the present disclosure may further use granular activated carbon based on specific powdered activated carbon, but preferably does not use granular activated carbon.
The particle size of the activated carbon for pharmaceutical use is 0.5 μm or more, preferably 0.5 μm or more and 0.5mm or less, from the viewpoint of producing a high-quality filtrate efficiently, economically and continuously. The lower limit of the particle diameter is 0.5 μm or more, preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. When the particle diameter of the medicine active carbon is 0.5 μm or more, the membrane can be effectively prevented from being blocked by the medicine active carbon, and the flux is obviously reduced. The upper limit of the particle diameter of the pharmaceutical active carbon that can be combined with any of these lower limits is preferably 0.50mm or less, more preferably 0.45mm or less, still more preferably 0.40mm or less, still more preferably 0.35mm or less, and particularly preferably 0.30mm or less. When the particle diameter of the drug activated carbon is 0.50mm or less, the possibility that the drug activated carbon is settled and the hollow fiber membrane inlet is blocked can be reduced. The particle size of the drug active carbon is particularly preferably 3 μm or more and 0.30mm or less.
From the viewpoint of efficiently, economically and continuously producing a high-quality filtrate, the particle diameter of the powdered activated carbon is 0.5 μm or more, preferably 0.5 μm or more and 0.5mm or less. The lower limit of the particle diameter is 0.5 μm or more, preferably 1 μm or more, more preferably 3 μm or more. When the particle diameter of the powdery activated carbon is 0.5 μm or more, the membrane can be effectively prevented from being blocked by the powdery activated carbon, which results in a significant decrease in flux. The upper limit of the particle diameter of the powdered activated carbon, which can be arbitrarily combined with these lower limits, is preferably 0.50mm or less, more preferably 0.45mm or less, still more preferably 0.40mm or less. When the particle diameter of the powdery activated carbon is 0.50mm or less, the possibility that the powdery activated carbon is settled and the inlet of the hollow fiber membrane is blocked can be reduced. The particle size of the powdered activated carbon is particularly preferably 3 μm or more and 0.40mm or less.
Powdered activated carbon is generally purified and pulverized into powder after carbonization and activation. The shape of the powdered activated carbon is varied depending on the nature of the raw material, the production conditions, and the like, and is generally a flat or needle-shaped powder. Pharmaceutical activated carbon generally tends to contain more plate-like particles, while water vapor activated carbon tends to contain more needle-like particles.
Filtering membrane
The pore diameter of the filtration membrane is 0.45 μm or less. The shape of the filtration membrane is not particularly limited, and examples thereof include a flat membrane shape, a hollow fiber shape, and the like. The filtration membrane is preferably a hollow fiber membrane from the viewpoint of efficiently, economically and continuously producing a high-quality filtrate.
The material of the filtration membrane may be an inorganic material such as ceramic, a resin material such as thermoplastic resin or thermosetting resin, and the like, and preferably a thermoplastic resin. The filtration membrane is more preferably a thermoplastic resin hollow fiber membrane from the viewpoint of efficiently, economically and continuously producing a high-quality filtrate. Examples of the thermoplastic resin include polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene (PE), polystyrene (PS), polysulfone, polyethersulfone (PEs), and Polyacrylonitrile (PAN).
When the filtration membrane is a hollow fiber membrane, the lower limit of the inner diameter is preferably 1.0mm or more. The upper limit of the inner diameter is 14.5mm or less.
The pore diameter of the filtration membrane is preferably 0.05 μm or more and 0.45 μm or less. The upper limit of the pore diameter of the filtration membrane may be 0.45 μm or less, preferably 0.40 μm or less, more preferably 0.35 μm or less, and still more preferably 0.30 μm or less. When the pore diameter of the filtration membrane is 0.45 μm or less, the membrane can be effectively prevented from being clogged with activated carbon, which results in a significant decrease in flux, and the recovery from washing after use is excellent. The lower limit of the pore diameter which can be arbitrarily combined with these upper limits is preferably 0.05 μm or more. When the pore diameter of the filtration membrane is 0.05 μm or more, a sufficiently high flux can be ensured, and filtration can be performed more efficiently. The pore diameter of the filtration membrane is particularly preferably 0.05 μm or more and 0.30 μm or less.
The structure of the pores of the filter membrane is preferably a homogeneous structure. In the present disclosure, the "homogeneous structure" means a structure in which the pore diameter distribution is homogeneous in a direction from the 1 st side (stock solution side) to the 2 nd side (filtrate side) in a section in the film thickness direction, and the "heterogeneous structure" (or "inclined structure") means a structure in which the pore diameter distribution is intermittently or continuously changed in a direction from the 1 st side (stock solution side) to the 2 nd side (filtrate side) in a section in the film thickness direction. Hereinafter, the filtration membrane having a homogeneous pore structure will be referred to as a "mesh filter", and the filtration membrane having a heterogeneous (inclined) structure will be referred to as a "depth filter". The pore structure inside the mesh filter membrane is substantially uniform in size from 1 to 2 sides. Therefore, the particles to be filtered hardly enter the membrane, and can be trapped mainly on the membrane surface. The depth filter preferably changes the pore diameter distribution such that the average pore diameter decreases from the 1 st-order side to the 2 nd-order side in the structure inside the membrane. Thus, the particles to be filtered can be captured on the surface and inside the membrane. The mesh filter is less likely to cause particles to be filtered to enter the membrane than the deep layer filter, and is excellent in cleaning recovery after use.
Examples of the classification of filtration membranes based on the filtration model include microfiltration membranes (MF membranes), ultrafiltration membranes (UF membranes), and reverse osmosis membranes (RO membranes). The filtration membrane is preferably an MF membrane from the viewpoint of efficiently, economically and continuously producing a high-quality filtrate.
Filtering method
The filtration method is not particularly limited as long as the powdered activated carbon is added to the liquid to be purified containing the object to be removed, whereby the component to be removed is adsorbed on the powdered activated carbon, and then at least a part of the object to be removed is separated from the powdered activated carbon by membrane filtration. Examples of the type of the membrane include a method using a hollow fiber membrane and a method using a flat membrane; the filtration method includes a full-scale filtration method, a cross-flow filtration method, and the like. In the case of using hollow fiber membranes, the method is further classified into an internal pressure method and an external pressure method. Among them, as the filtration method, it is preferable to remove the removal target component and activated carbon in the liquid intermediate product at the same time by internal pressure cross-flow filtration by a hollow fiber membrane. As a filtration method using a hollow fiber membrane, external pressure cross-flow filtration may also be used. However, the internal pressure cross-flow filtration is more preferable, and the reason is not limited to theory, but the activated carbon does not cause clogging between fiber bundles, and the variation in linear velocity in the membrane module is suppressed, and the linear velocity on the hollow fiber membrane surface is faster than that in the external pressure cross-flow filtration even with the same amount of the passing liquid, so that the passing liquid becomes high.
Linear velocity
The linear velocity in the cross-flow filtration is preferably 0.3 m/sec or more and 3.0 m/sec or less. In the present disclosure, "linear velocity" refers to a value obtained by dividing the flow rate (m 3/sec) in the hollow fiber-like membrane by the membrane cross-sectional area (m 2) thereof. The lower limit value of the linear velocity is more preferably 0.5 m/sec or more, still more preferably 0.6 m/sec or more, and particularly preferably 0.7 m/sec or more. The upper limit of the linear velocity that can be arbitrarily combined with these lower limits is preferably 3.0 m/sec or less, more preferably 2.5 m/sec or less, and still more preferably 2.0 m/sec. At a linear velocity of 3.0 m/sec or less, the pump may be small, and the possibility of causing a decrease in the film capacity (abrasion generated on the ceramic) decreases.
In general, when the liquid intermediate product containing no activated carbon is subjected to internal pressure cross-flow filtration using a hollow fiber membrane, the liquid intermediate product may be used at a low linear velocity, for example, a linear velocity of less than 0.7 m/sec, because activated carbon is not added. However, when a suspension of a liquid intermediate product containing powdered activated carbon is passed through a hollow fiber membrane, the linear velocity is increased to, for example, 0.7 m/s or more, whereby the blocking of the activated carbon in the hollow portion of the hollow fiber membrane and the precipitation of the activated carbon in the tank when the cross-flow filtration is performed using a stock tank can be effectively suppressed, and stable high-concentration filtration can be realized.
Transmembrane pressure difference
The lower limit of the transmembrane pressure difference may be arbitrarily set according to the obtained filtration rate, and may be, for example, 0.01MPa or more. The upper limit of the transmembrane pressure difference is preferably 0.3MPa or less, more preferably 0.2MPa or less, and still more preferably 0.1MPa or less. When the transmembrane pressure difference is 0.3MPa or less, membrane rupture can be prevented to stably use the membrane for a long period of time.
Concentration degree
The concentration of the drug activated carbon contained in the concentrated purification target liquid (hereinafter referred to as "concentrated liquid" in the present disclosure) obtained by filtering the purification target liquid is preferably 15% by weight or less. As the concentration of activated carbon increases, the viscosity increases and the fluidity of the liquid intermediate product becomes poor. For example, in the case of performing internal pressure cross-flow filtration, since a part of the activated carbon is settled and/or the concentration is likely to be uneven, the concentration of the drug activated carbon in the concentrated solution is more preferably 12% by weight or less. When the concentration is low, the filtration can be stably performed.
Back flushing and other conditions
As a method of performing filtration more stably, back flushing with a pump or a gas return filtrate is effective at regular intervals. The gas is not limited as long as it does not affect the product, and examples thereof include inert gases such as air and nitrogen. In the case of cross-flow filtration of liquid medicine activated carbon, even if back washing is not performed, the flux is easily stabilized, and thus back washing may not be performed. However, when the concentration of activated carbon increases, the back flushing is preferably performed because the back flushing can effectively prevent the blocking in the hollow portion. When the concentration level increases, the blocking is caused by the blocking by the portion serving as a fuse, and thus the blocking is not caused on the surface or inside of the membrane, which contributes to the stable operation of the cross-flow filtration. For stable filtration, a filter treatment as pretreatment may be performed to separate coarse matters.
[ Example ]
Method for measurement and evaluation
Particle size of active carbon
A laser diffraction/scattering type particle size distribution measuring apparatus (HORIBA Co., PARTICA LA-950) was used, and a slurry in which activated carbon was mixed in pure water to a concentration of 1 wt% was used as a sample. The measurement method was to add the slurry of the present concentration to the dispersion medium in the apparatus until the laser transmittance reached about 85% (about 10mL maximum), and to measure the particle size (μm).
Hollow fiber inner diameter
The hollow fiber membrane was cut into thin sheets in a cross section orthogonal to the longitudinal direction using a razor, and the inner diameter was measured by a magnifying glass. For one sample, the average value was measured at intervals of 30mm in the longitudinal direction on 60 cut surfaces, and the average value was taken as the inner diameter (mm) of the hollow fiber membrane.
Membrane pore size
Four or more kinds of polystyrene latex particles having different particle diameters were used and dispersed in 0.5 wt% aqueous sodium dodecyl sulfate so that the particle concentration was 0.01 wt%, respectively, to prepare a latex particle dispersion. The latex particle dispersions were filtered through a porous membrane, and the transmittance was determined from the concentration ratio before and after filtration. The transmittance thus obtained was plotted, and the size of particles having a transmittance of 90% was calculated and used as the pore diameter (blocking pore diameter, μm) of the membrane. However, the particle size of the polystyrene latex particles is selected so that the particles of the four types contain a particle size having a transmittance of 50% or more at the lowest point and a particle size having a transmittance of 90% or more.
Molecular weight cut-off
Four or more proteins having different molecular weights were dissolved in 0.1M Phosphate Buffer (PBS) buffer aqueous solution to give protein concentrations of 0.01 wt%, respectively, to prepare protein solutions. The protein solutions were filtered by ultrafiltration membranes, and the transmittance was determined from the concentration ratio before and after filtration. The transmittance thus obtained was plotted against the molecular weight, and the molecular weight having a transmittance of 90% was used as the molecular weight cut-off of the membrane.
Concentration (recovery rate)
(1) Concentration (concentration ratio)
The concentration degree is a value obtained by dividing the feed liquid volume by the concentrate volume. For example, the concentration degree at a feed liquid volume of 1000mL and a concentrate volume of 200mL is calculated as 1000 mL/200 mL=5 times.
(2) Recovery rate
The recovery rate is a value obtained by dividing the filtrate volume (=feed volume—concentrate volume) by the feed volume multiplied by 100, with the rejection rate of valuable substances on the membrane being set to 0% (the essential components are not rejected when the stock solution is filtered from 1 time to 2 times). For example, the recovery rate at a feed volume of 1000mL and a filtrate volume of 800mL was calculated as 800 mL/1000 mL=80%.
Post-use Water Flux (Flux) retention
(1) Measuring and calculating method
The membrane module was mounted on a tester, and pure water was added to the stock solution container. Pure water at 25℃was circulated and filtered under a pressure of 0.02MPa to 0.03MPa in terms of transmembrane pressure difference, and the amount of pure water passing through the outer surface side of the membrane was measured for 1 minute. The value of the pure water flux was calculated according to the following formula.
Pure water flux (mL/min, 0.1MPa, 25 ℃) = pure water volume (mL/min) ×transmembrane pressure difference (MPa)/(0.1 (MPa))
(2) Flux of water before use
The water flux before use means the pure water flux before the first filtration evaluation. The retention rate was 100% because it was not used.
(3) Post-use water flux
The water flux after use means the pure water flux measured at the end of water washing by performing water washing of the membrane module after filtration of the evaluation liquid.
(4) Flux of water after washing with liquid medicine
The flux after the chemical liquid washing means the flux of pure water measured after the evaluation liquid is filtered and then the membrane module is washed with the chemical liquid (a mixed liquid of NaClO and NaOH), and then the chemical liquid component is further washed with water.
(5) Water flux retention after use
Retention% = (3)/(2) ×100
(6) Water flux retention rate after cleaning with liquid medicine
Retention% = (4)/(2) ×100
(7) Evaluation
The evaluation was performed according to the following criteria.
A: 50% or more and 100% or less
B: more than or equal to 10 percent and less than 50 percent
C: more than or equal to 0 percent and less than 10 percent
Examples of Membrane filtration methods
1. Concentration (recovery) test based on activated carbon
(1) Starch saccharification liquid
As the purification target liquid, a "starch saccharification liquid before diatomaceous earth filtration after saccharification step" (hereinafter "liquid b") obtained by an enzyme treatment starch solution liquefaction step and saccharification step, and a "glucose liquid after diatomaceous earth filtration" (hereinafter "liquid a") obtained by diatomaceous earth filtration were used. Liquid a contains no solid component, while liquid b contains a large amount of solid component, and has high turbidity.
[ Table 1]
Table 1 liquid (starch saccharification liquid)
| Brix (Brix) | Viscosity (60 ℃ C.) | Turbidity degree | |
| Liquid a | 33.40％ | 1.53m·Pas | 5.71 |
| Liquid b | 32.50％ | 1.43m·Pas | 2932 |
The purified liquid (liquid a or liquid b) was prepared as a stock solution to be filtered, with or without adding Activated Carbon (AC) of the type and amount shown in tables 2 and 3. In the table, the activated carbon indicated by "medicine" and "steam" is as follows.
"Medicine": fuji film and light pure medicine Co., ltd., activated carbon 037-02115. Is powdered activated carbon activated with a drug (zinc chloride) and having a particle size of 5 μm to 270 μm and an average particle size of 44 μm.
"Water vapor": fuji film and light pure medicine Co., ltd., activated carbon 035-18101. Is powdered activated carbon activated by water vapor and having a particle size of 3.5 μm to 400 μm and an average particle size of 58. Mu.m.
The porous hollow fiber membrane was placed in a housing of a membrane module having an effective length of 20cm to have a membrane area of 0.0088m 2, to prepare a membrane module. As schematically shown in fig. 1, a concentration (recovery) circuit for discharging the filtrate (4) from the system was produced. The stock solution (2) prepared as above was sent to the membrane module (1) at a linear velocity of 2.0 m/sec using the circulation pump (3), and separated into a filtrate (4) and a filtered concentrate (5). The filtrate (4) was recovered in a tank outside the system. The time to obtain 800mL of filtrate (4) was measured and the average filtration Flux (Flux) was derived.
[ Table 2]
TABLE 2 results of saccharification of starch solution (solution a) after diatomite filtration
| Example 1 | Comparative example 1 | Reference example 1 | Example 2 | |
| Film type | MF | MF | MF | UF |
| Activated carbon species | Medicine | Water vapor | Is not added with | Medicine |
| AC addition amount | 4g | 4g | - | 4g |
| Membrane structure | Screen mesh | Screen mesh | Screen mesh | Double-layer |
| Film material | PVDF | PvDF | PVDF | PS |
| Inner diameter of fiber | 1.4mm | 1.4mm | 1.4mm | 1.4mm |
| Pore diameter | 0.3μm | 0.3μm | 0.3μm | 10,000* |
| Linear velocity (Lv) | 2m/s | 2m/s | 2m/s | 2m/s |
| Transmembrane pressure difference (TMP) | 0.05MPa | 0.05MPa | 0.05MPa | 0.05MPa |
| Filtration temperature | 60℃ | 60℃ | 60℃ | 60℃ |
| Backwash method | Without any means for | Without any means for | Without any means for | Without any means for |
| Stock solution volume mL | 1000 | 1000 | 1000 | 1000 |
| Filter fluid volume mL | 800 | 800 | 800 | 800 |
| Concentration (Hui mu rate) | 5 Times (80%) | 5 Times (80%) | 5 Times (80%) | 5 Times (80%) |
| Filtration time | 11.6 Minutes | 15.4 Minutes | 11.8 Minutes | 59.1 Minutes |
| Average Flux (Flux) | 469.2LMH | 354.4LMH | 461.3LMH | 52.3LMH |
| Post-use Water Flux (Flux) retention | B(21％) | C(9％) | B(20％) | B(18％) |
* Molecular weight cut-off
From the results of table 2, the average Flux (Flux) was higher in the case of using a microfiltration membrane (MF membrane) (example 1) than in the case of using an ultrafiltration membrane (UF membrane) (example 2). In addition, the MF membrane and the UF membrane were both good in terms of the water Flux (Flux) retention after use, but the MF membrane was high. The average Flux (Flux) and the post-use water Flux (Flux) retention rates were approximately the same in the case of containing drug activated carbon (example 1) and in the case of not containing activated carbon (reference example 1). This indicates that the drug activated carbon is not prone to clogging as is the case without activated carbon. In the case of containing steam activated carbon (comparative example 1), the average Flux (Flux) was much lower than that of the case of containing drug activated carbon (example 1), and the retention rate of the water Flux (Flux) after use was also low. It is therefore known that pharmaceutical active carbon can give better results, especially in combination with MF membranes.
[ Table 3]
TABLE 3 results of the saccharification of starch solution (solution b) before the filtration of diatomaceous earth after the saccharification step
| Example 3 | Comparative example 2 | Reference example 2 | |
| Film type | MF | MF | MF |
| Activated carbon species | Medicine | Water vapor | Is not added with |
| AC addition amount | 4g | 4g | - |
| Membrane structure | Screen mesh | Screen mesh | Screen mesh |
| Film material | PVDF | PVDF | PVDF |
| Inner diameter of fiber | 1.4mm | 1.4mm | 1.4mm |
| Pore diameter | 0.3μm | 0.3μm | 0.3μm |
| Linear velocity (Lv) | 2m/s | 2m/s | 2m/s |
| Transmembrane pressure difference (TMP) | 0.05MPa | 0.05MPa | 0.05MPa |
| Filtration temperature | 60℃ | 60℃ | 60℃ |
| Backwash method | Without any means for | Without any means for | Without any means for |
| Stock solution volume mL | 1000 | 1000 | 1000 |
| Filter fluid volume mL | 800 | 800 | 800 |
| Concentration (recovery rate) | 5 Times (80%) | 5 Times (80%) | 5 Times (80%) |
| Filtration time | 22.6 Minutes | 31.8 Minutes | 22.2 Minutes |
| Average Flux (Flux) | 241.9LMH | 177.2LMH | 245.4LMH |
| Post-use Water Flux (Flux) retention | B(18％) | C(6％) | B(19％) |
According to the results of Table 3, the average Flux (Flux) was about the same in the case of containing the drug active carbon (example 3) and in the case of not containing the active carbon (reference example 2). In the case of activated carbon containing water vapor (comparative example 2), the average Flux (Flux) was much lower than in the case of activated carbon containing no drug (example 3). Therefore, it is known that the combination of the drug activated carbon and the MF membrane can exert a good effect even when the stock solution contains a large amount of solid components.
(2) Soy sauce
As the purification target liquid, raw soy sauce (raw soy sauce) (liquid c) was used in which various flavors were fermented and ripened, and then subjected to press filtration, and then allowed to stand in a clarifier tank to remove sediment.
[ Table 4]
Table 4 liquid (Soy sauce)
| Brix (Brix) | Viscosity (25 ℃ C.) | Turbidity degree | |
| Liquid c | 37.40％ | 3.0mPa·s | 12.3 |
The purified liquid (liquid c) was prepared as a stock solution to be filtered, with or without adding Activated Carbon (AC) of the type and amount shown in table 5. The "medicine" or "steam" activated carbon used was activated carbon manufactured by Fuji film and Wako pure chemical industries, ltd.
The porous hollow fiber membrane was placed in a housing of a membrane module having an effective length of 20cm to have a membrane area of 0.0088m 2, to prepare a membrane module. In the concentration (recovery) circuit schematically shown in fig. 1, the stock solution (2) prepared as above was sent to the membrane module (1) at a linear velocity of 1.0 m/sec using the circulation pump (3), and separated into a filtrate (4) and a filtered concentrate (5). The filtrate (4) was recovered in a tank outside the system. The time to obtain 900mL of filtrate (4) was measured and the average filtration Flux (Flux) was derived.
[ Table 5]
TABLE 5 results of Soy sauce (c liquid)
| Example 4 | Comparative example 3 | Reference example 3 | Example 5 | |
| Film type | MF | MF | MF | UF |
| Activated carbon species | Medicine | Water vapor | Is not added with | Medicine |
| AC addition amount | 4g | 4g | - | 4g |
| Membrane structure | Screen mesh | Screen mesh | Screen mesh | Double-layer |
| Film material | PVDF | PVDF | PVDF | PAN |
| Inner diameter of fiber | 1.4mm | 1.4mm | 1.4mm | 1.4mm |
| Pore diameter | 0.3μm | 0.3μm | 0.3μm | 13,000* |
| Linear velocity (Lv) | 1m/s | 1m/s | 1m/s | 1m/s |
| Transmembrane pressure difference (TMP) | 0.15MPa | 0.15MPa | 0.15MPa | 0.15MPa |
| Filtration temperature | 40℃ | 40℃ | 40℃ | 40℃ |
| Reverse discharge washing | Without any means for | Without any means for | Without any means for | Without any means for |
| Stock solution volume mL | 1000 | 1000 | 1000 | 1000 |
| Filter fluid volume mL | 900 | 900 | 900 | 900 |
| Concentration (recovery rate) | 10 Times (90%) | 10 Times (90%) | 10 Times (90%) | 10 Times (90%) |
| Filtration time | 210 Minutes | 273 Min | 208 Minutes | 405 Min |
| Average Flux (Flux) | 29.2LMH | 22.5LMH | 29.5LMH | 15.2LMH |
| Post-use Water Flux (Flux) retention | B(20％) | C(8％) | B(19％) | A(68％) |
* Molecular weight cut-off
From the results of table 5, the average Flux (Flux) was higher in the case of using a microfiltration membrane (MF membrane) (example 4) than in the case of using an ultrafiltration membrane (UF membrane) (example 5). In addition, the MF membrane and the UF membrane were both good in terms of the water Flux (Flux) retention after use, but the MF membrane was high. The average Flux (Flux) and the post-use water Flux (Flux) retention were approximately the same in the case of containing drug activated carbon (example 4) and in the case of not containing activated carbon (reference example 4). This indicates that the drug activated carbon is not prone to clogging as is the case without activated carbon. In the case of containing steam activated carbon (comparative example 3), the average Flux (Flux) was much lower than that of the case of containing drug activated carbon (example 4), and the retention rate of the water Flux (Flux) after use was also low. It is therefore known that pharmaceutical active carbon can give better results, especially in combination with MF membranes.
2. Activated carbon-based run test
As the purification target liquid, a glucose solution (solution d) obtained by an enzyme treatment, a liquefaction step of a starch solution, a saccharification step, and a filtration through celite was used.
[ Table 6]
Table 6 liquid (starch saccharification liquid)
| Brix (Brix) | Viscosity (60 ℃ C.) | Turbidity degree | |
| D liquid | 32.80％ | 1.48m·Pas | 5.22 |
The purified liquid (d liquid) was added with Activated Carbon (AC) of the types and amounts shown in tables 7 to 11 to prepare a stock solution to be filtered.
The porous hollow fiber membrane was placed in a housing of a membrane module having an effective length of 20cm so that the membrane area was 0.12m 2, to prepare a membrane module. As schematically shown in fig. 2, a circuit for returning the filtrate (4) to the raw liquid tank (not concentrated) was produced. The stock solution (2) is sent to the membrane component (1) by using the circulating pump (3) and is separated into filtrate (4) and filtered concentrated solution (5). The filtrate (4) is returned to the stock solution tank. Backwash was performed at a rate of 10 seconds every 5 minutes from the start of filtration. The back flushing is performed by stopping the circulation pump (3) and introducing the filtrate into the hollow fibers at a pressure of 0.02MPa by a pump (not shown) for back flushing. Based on the Flux (Flux) at the start of evaluation (100%), the Flux (Flux) immediately after back flushing at 15 minutes for the filtration time and immediately before back flushing at 20 minutes for the filtration time was measured.
(1) Medicine active carbon (Zinc chloride)
Using the above-mentioned drug activated carbon as Activated Carbon (AC), liquid feeding was performed at a linear velocity of 0.7 m/sec or 0.5 m/sec.
[ Table 7]
[ Table 8]
(2) Gas activated carbon (steam activated carbon)
The liquid feed was carried out at a linear velocity of 0.7 m/sec using the above-mentioned gas activated carbon as Activated Carbon (AC).
[ Table 9]
(3) Mixed (medicine and gas activated) active carbon
The drug activated carbon and the gas activated carbon were mixed in various weight ratios (gas activated carbon: drug activated carbon=s: c) shown in table 10 to prepare a mixed activated carbon. The mixed activated carbon of the type and amount shown in Table 10 was used as Activated Carbon (AC), and the liquid feed was performed at a linear velocity of 0.7 m/sec.
[ Table 10 ]
3. Confirmation of concentration limits
As the purification target liquid, a glucose solution (e solution) obtained by an enzyme treatment, a liquefaction step of a starch solution, a saccharification step, and a filtration through celite was used.
[ Table 11 ]
Table 11 liquid (starch saccharification liquid)
| Brix (Brix) | Viscosity (60 ℃ C.) | Turbidity degree | |
| E liquid | 33.80％ | 1.55m·Pas | 4.88 |
The purified liquid (e liquid) was added with Activated Carbon (AC) of the type and amount shown in table 12 to prepare a stock solution to be filtered. The above-mentioned pharmaceutical active carbon was used as the Active Carbon (AC).
The porous hollow fiber membrane was placed in a housing of a membrane module having an effective length of 20cm so that the membrane area was 0.12m 2, to prepare a membrane module. In the concentration (recovery) circuit schematically shown in fig. 1, the stock solution (2) prepared as above was sent to the membrane module (1) at a linear velocity of 2.0 m/sec using the circulation pump (3), and separated into a filtrate (4) and a filtered concentrate (5). Backwash was performed at a rate of 10 seconds every 5 minutes from the start of filtration. The back flushing is performed by stopping the circulation pump (3) and introducing the filtrate into the hollow fibers at a pressure of 0.02MPa by a pump (not shown) for back flushing. The filtration was terminated when the concentration degree (recovery rate) and the concentration of the activated carbon after concentration reached the values shown in Table 12, and the filtration time (minutes) was recorded. At the end of filtration, the circulation end surface of the membrane module was gently rinsed with water, and the presence or absence of clogging of the membrane was visually confirmed. The water Flux (Flux) retention at the time of washing after the drug washing was measured by the above method based on the Flux (Flux) at the time of evaluation initiation (100%).
[ Table 12 ]
TABLE 12 Water Flux (Flux) retention based on different degrees of concentration (recovery)
| Example 23 | Example 24 | Example 25 | Example 26 | |
| Film type | MF | MF | MF | MF |
| Activated carbon species | Medicine | Medicine | Medicine | Medicine |
| AC addition amount | 500g | 500g | 500g | 500g |
| Membrane structure | Screen mesh | Screen mesh | Screen mesh | Screen mesh |
| Film material | PVDF | PVDF | PVDF | PVDF |
| Inner diameter of fiber | 14mm | 1.4mm | 14mm | 08mm |
| Pore diameter | 03μm | 0.3μm | 03μm | 03μm |
| Linear velocity (Lv) | 20m/s | 2.0m/s | 20m/s | 20m/s |
| Filtration flux (valve adjustment) | About 150LMH | About 150LMH | About 150LMH | About 153LMH |
| Filtration flux (actual) | 152LMH | 152LMH | 152LMH | 151LMH |
| Filtration temperature | 60℃ | 60℃ | 60℃ | 60℃ |
| Backwash method | Has the following components | Has the following components | Has the following components | Has the following components |
| Stock solution amount | 10L | 10L | 10L | 10L |
| Liquid amount of filtrate | 5.8L | 67L | 75L | 1.6L |
| Concentration (Hui mu rate) | 24 Times (58%) | 3 Times (67%) | 4 Times (75%) | 12 Times (16%) |
| Concentration of activated carbon after concentration | 12％ | 15％ | 20％ | 6％ |
| Filtration time | 19 Minutes | 22 Minutes | 247 Minutes | 53 Minutes |
| Without occlusion at the end | Without any means for | Without any means for | Has the following components | Has the following components |
| Water Flux (Flux) retention% | 99 | 95 | 80 | 70 |
* Cleaning with NaClO+NaOH mixed solution
[ PREPARATION ] A method for producing a polypeptide
1. Membrane module
2. Stock solution
3. Circulation pump
4. Filter liquid
5. Concentrated solution
10. Membrane filtration circuit
Claims (10)
1. A method for adding powdered activated carbon to a liquid to be purified containing an object to be removed, and membrane-filtering the liquid to be purified to separate the object to be removed from the powdered activated carbon,
The powdered activated carbon comprises pharmaceutical activated carbon having a particle size of 0.5 μm or more,
And the pore diameter of the membrane is 0.45 μm or less.
2. The method of claim 1, wherein the purification subject liquid is a liquid intermediate product of a product selected from the group consisting of chemicals, foods, beverages, pharmaceuticals, and cosmetics.
3. The method according to claim 1 or 2, wherein the powdered activated carbon contains the pharmaceutical activated carbon as a main ingredient.
4. The method according to claim 1 or 2, wherein the membrane filtration is internal pressure cross-flow filtration based on hollow fiber membranes.
5. The method of claim 4, wherein the material of the hollow fiber membrane is a thermoplastic resin.
6. The method of claim 5, wherein the hollow fiber membrane has an inner diameter of 1.0mm and above and 14.5mm and below.
7. The method according to claim 5, wherein the hollow fiber membrane has a pore diameter of 0.05 μm and more and 0.30 μm and less.
8. The method according to claim 1 or 2, wherein the structure of the membrane for the membrane filtration is a homogeneous structure.
9. The method according to claim 1 or 2, wherein the membrane used for the membrane filtration is an MF membrane.
10. The method according to claim 1 or 2, wherein the concentration of the powdered activated carbon contained in the purification target liquid concentrated after membrane filtration is 15% by weight or less.
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