JPH04317730A - Composite filtration membrane - Google Patents
Composite filtration membraneInfo
- Publication number
- JPH04317730A JPH04317730A JP8693691A JP8693691A JPH04317730A JP H04317730 A JPH04317730 A JP H04317730A JP 8693691 A JP8693691 A JP 8693691A JP 8693691 A JP8693691 A JP 8693691A JP H04317730 A JPH04317730 A JP H04317730A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- filtration
- filtration membrane
- nonwoven fabric
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000001914 filtration Methods 0.000 title claims abstract description 185
- 239000012528 membrane Substances 0.000 title claims abstract description 185
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000012530 fluid Substances 0.000 claims abstract description 52
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 239000002759 woven fabric Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001471 micro-filtration Methods 0.000 claims description 12
- 239000012466 permeate Substances 0.000 claims description 12
- 238000011001 backwashing Methods 0.000 abstract description 41
- 239000000126 substance Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000010419 fine particle Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 244000005700 microbiome Species 0.000 abstract description 5
- 239000008223 sterile water Substances 0.000 abstract description 5
- 240000004808 Saccharomyces cerevisiae Species 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000011110 re-filtration Methods 0.000 abstract 1
- 230000004907 flux Effects 0.000 description 30
- 238000000034 method Methods 0.000 description 15
- 238000009295 crossflow filtration Methods 0.000 description 12
- 230000001580 bacterial effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000013076 target substance Substances 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012531 culture fluid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、精密濾過膜に関するも
のであり、特に大きい膜透過流束を維持するために懸濁
物質の捕捉性が高く逆洗洗浄性のよい複合膜に関するも
のである。本発明の複合濾過膜は、種々の高分子、微生
物、酵母、微粒子を含有あるいは懸濁する流体の分離、
精製、回収、濃縮などに適用され、特に濾過を必要とす
る微細な微粒子を含有する流体からその微粒子を分離す
る必要のあるあらゆる場合に適用することができ、例え
ば微粒子を含有する各種の懸濁液、発酵液あるいは培養
液などの他、顔料の懸濁液などから微粒子を分離する、
原子力発電の復水からクラッドを分離除去する場合にも
適用される。ところで近年バイオテクノロジーの急速な
発展にともない、培養、発酵、酵素反応等による生化学
物質の生産は、医薬品・食品・化学製品など多くの分野
で盛んに行われるようになってきた。これらの生産物質
は精製することによって付加価値が高まるが、この精製
操作に多くのコストがかけられるのが現状である。本発
明のデッドエンド型濾過方法はこれらの分野で特に有効
であり、例えば培養液中から反応阻害物質を連続的に除
去することにより高密度培養を行う、菌体外酵素生産菌
を用いた時に酵素を連続回収する、菌体内酵素生産菌を
破砕した溶液から酵素を回収する、バッチ式で得られた
培養液から生体触媒を除去する、など多岐にわたって適
用される。[Industrial Application Field] The present invention relates to a precision filtration membrane, and particularly to a composite membrane that has a high ability to trap suspended solids and has good backwashing ability in order to maintain a large membrane permeation flux. . The composite filtration membrane of the present invention can be used to separate fluids containing or suspending various polymers, microorganisms, yeast, and fine particles.
It can be applied in purification, recovery, concentration, etc., and in particular in any case where it is necessary to separate fine particles from a fluid containing fine particles that requires filtration, such as in various suspensions containing fine particles. Separating fine particles from liquids, fermentation liquids, culture liquids, pigment suspensions, etc.
It is also applied when separating and removing crud from condensate in nuclear power generation. However, with the rapid development of biotechnology in recent years, the production of biochemical substances through cultivation, fermentation, enzymatic reactions, etc. has become popular in many fields such as pharmaceuticals, foods, and chemical products. Although the added value of these produced substances increases by refining them, the current situation is that a lot of cost is incurred in this refining operation. The dead-end filtration method of the present invention is particularly effective in these fields, for example, when using exoenzyme-producing bacteria that perform high-density culture by continuously removing reaction inhibitors from the culture solution. It has a wide variety of applications, including continuous recovery of enzymes, recovery of enzymes from a solution obtained by crushing intracellular enzyme-producing bacteria, and removal of biocatalysts from culture solutions obtained in a batch process.
【0002】0002
【従来の技術】従来、膜を用いて懸濁物質を含有する原
流体から懸濁物質を分離する技術としては、例えば圧力
を駆動力とする逆浸透法、限外濾過法、精密濾過法、電
位差を駆動力とする電気透析法、濃度差を駆動力とする
拡散透析法等がある。これらの方法は、連続操作が可能
であり、分離操作中に温度やpHの条件を大きく変化さ
せることなく分離、精製あるいは濃縮ができ、粒子、分
子、イオン等の広範囲にわたって分離が可能であり、小
型プラント処理能力を大きく保つことができるので経済
的であり、分離操作に要するエネルギーが小さく、かつ
他の分離方法では難しい低濃度原流体の処理が可能であ
るなどの理由により広範囲に実施されている。そしてこ
れらの分離技術に用いられる膜としては、酢酸セルロー
ス、硝酸セルロース、再生セルロース、ポリスルホン、
ポリアクリロニトリル、ポリアミド、ポリイミド等の有
機高分子等を主体とした高分子膜や耐熱性、耐薬品性な
どの耐久性に優れている多孔質セラミック膜などがあり
、主としてコロイドの濾過を対象とする場合は限外濾過
膜が使用され、微細な粒子の濾過を対象とする精密濾過
ではそれに適した微孔を有する精密濾過膜が使用されて
いる。前述したようにバイオテクノロジーの進歩に伴い
、高純度化、高性能化、高精密化が要求されるようにな
り、従来から行われている遠心分離やけい藻土濾過に代
わって連続操作が可能で大量処理できる、濾過助剤や凝
集剤の添加が必要ない、分離の効率は菌体と懸濁液の比
重差に無関係であり培養液の物性や菌体の種類に関係な
く清澄な濾液が得られる、高濃度培養ができ生産効率が
向上する、完全密閉系が可能で菌の漏れがない、濃縮後
菌体の洗浄が可能である、スケールアップが容易で経済
性が高い等の理由で、精密濾過あるいは限外濾過技術の
応用分野が拡大しつつある。しかしながら、濾過膜の利
点が多いにもかかわらず精密濾過あるいは限外濾過膜を
用いて微粒子を分離する場合に、濃度分極の影響により
ケーク層が生じて透過流体の流れに抵抗が生じ、また濾
過膜の目詰まりによる抵抗が大きくなって膜透過流束が
急激にかつ著しく低下してしまうという問題があり、こ
れが精密濾過あるいは限外濾過の実用化を妨げる最大の
原因であった。またそれに用いられる膜は汚染されやす
く、その防止対策が必要である。BACKGROUND ART Conventionally, techniques for separating suspended solids from a raw fluid containing suspended solids using a membrane include, for example, reverse osmosis, ultrafiltration, microfiltration, which uses pressure as a driving force, There are electrodialysis methods that use a potential difference as a driving force, and diffusion dialysis methods that use a concentration difference as a driving force. These methods can be operated continuously, can separate, purify, or concentrate without significantly changing temperature or pH conditions during the separation operation, and can separate a wide range of particles, molecules, ions, etc. It is economical because it can maintain a large processing capacity in a small plant, requires little energy for separation operations, and can process low-concentration raw fluids that are difficult to use with other separation methods, so it has been widely implemented. There is. The membranes used in these separation techniques include cellulose acetate, cellulose nitrate, regenerated cellulose, polysulfone,
There are polymer membranes mainly made of organic polymers such as polyacrylonitrile, polyamide, polyimide, etc., and porous ceramic membranes with excellent durability such as heat resistance and chemical resistance, and are mainly used for colloid filtration. For microfiltration, ultrafiltration membranes are used, and microfiltration membranes with suitable pores are used for precision filtration, which targets the filtration of fine particles. As mentioned above, with the advancement of biotechnology, higher purity, higher performance, and higher precision are required, and continuous operation is now possible in place of the conventional centrifugation and diatomaceous earth filtration. There is no need to add filter aids or flocculants.The separation efficiency is independent of the difference in specific gravity between the bacterial cells and the suspension, and a clear filtrate is produced regardless of the physical properties of the culture solution or the type of bacterial cells. It is possible to obtain high concentration culture and improve production efficiency, it is possible to have a completely closed system and there is no leakage of bacteria, it is possible to wash the bacteria after concentration, it is easy to scale up and it is highly economical, etc. , the field of application of microfiltration or ultrafiltration technology is expanding. However, despite the many advantages of filtration membranes, when microparticles are separated using microfiltration or ultrafiltration membranes, a cake layer is generated due to the influence of concentration polarization, which creates resistance to the flow of the permeate fluid. There is a problem in that the resistance due to membrane clogging increases and the membrane permeation flux rapidly and significantly decreases, and this has been the biggest cause of hindering the practical application of precision filtration or ultrafiltration. Furthermore, the membrane used therein is easily contaminated, and measures to prevent this are required.
【0003】濾過方法としては、濾過されるべき全ての
流体が濾材(濾布や膜など)とケーク層を通過して流体
中に含まれている微粒子を分離するいわゆるデッドエン
ド型濾過方式がある。この従来のデッドエンド型濾過方
式では流体が通過して懸濁物質が濾過膜の内部に捕捉さ
れて分離される段階では高い透過流束が得られるが、濾
過膜の表面で捕捉される段階になるとケーク層が形成さ
れ、大量の原流体を処理する場合や形成されるケーク層
の比抵抗が極端に高い場合は大きな濾過抵抗となり、こ
のようなデッドエンド濾過を行うと膜透過流束が小さく
なる。このため、クロスフロー型濾過方式が考えられた
。このクロスフロー型濾過方式は、濾過膜の膜表面に平
行に濾過すべき原流体を流し、流体は濾過膜を通って反
対側へ透過し、この原流体と透過流体の流れが直交して
いるためにこのように称されている。このクロスフロー
型濾過方法は、濾過膜に平行な原流体の流れによって膜
面上に形成されたケーク層がはぎ取られるので従来のデ
ッドエンド型濾過方式に比べて膜透過流束が大きく、大
量の原流体を直接連続的に分離、精製、濃縮が可能であ
る。しかし懸濁物質の濾過比抵抗が極端に高い、すなわ
ち培養液、発酵液から菌体や高分子生成物を除くために
純水透過流束の大きいすなわち分画分子量の大きい限外
濾過膜や精密濾過膜を用いた場合は急激に膜透過流束が
低下して濾過開始初期の高い膜透過流束を保つことは困
難であり、結果としてデッドエンド型濾過方式と総透過
液量を比較すると効果は小さく経済的な透過流束を得る
には不十分であった。[0003] As a filtration method, there is a so-called dead-end filtration method in which all the fluid to be filtered passes through a filter medium (filter cloth, membrane, etc.) and a cake layer to separate fine particles contained in the fluid. . In this conventional dead-end filtration system, a high permeation flux is obtained when the fluid passes through and the suspended solids are trapped inside the filtration membrane and separated, but when the suspended solids are trapped on the surface of the filtration membrane, When a large amount of raw fluid is processed or when the specific resistance of the formed cake layer is extremely high, the filtration resistance becomes large, and when such dead-end filtration is performed, the membrane permeation flux is small. Become. For this reason, a cross-flow type filtration system was considered. In this cross-flow filtration system, the raw fluid to be filtered is passed parallel to the membrane surface of the filtration membrane, the fluid passes through the filtration membrane to the opposite side, and the flow of the raw fluid and the permeated fluid are perpendicular to each other. This is why it is called this way. In this cross-flow filtration method, the cake layer formed on the membrane surface is stripped off by the flow of the raw fluid parallel to the filtration membrane, so the membrane permeation flux is larger than in the conventional dead-end filtration method, and a large amount of It is possible to directly and continuously separate, purify, and concentrate raw fluids. However, in order to remove microbial cells and polymer products from culture fluids and fermentation fluids, which have extremely high filtration specific resistance for suspended solids, ultrafiltration membranes with high pure water permeation flux, or high molecular weight cutoff, and precision filters are used. When using a filtration membrane, the membrane permeation flux decreases rapidly and it is difficult to maintain a high membrane permeation flux at the beginning of filtration.As a result, when comparing the dead-end filtration method and the total permeate volume, was small and insufficient to obtain an economical permeation flux.
【0004】0004
【発明が解決しようとする課題】上述のように、クロス
フロー型濾過方式は原理的には高度な分離技術であるが
、最大の問題である膜透過流束は、従来のデッドエンド
型濾過方式に僅かに大きい程度で、精密濾過方法として
このクロスフロー方式を採用しても十分高い膜透過流束
が得られないという問題があった。また従来から行われ
ている懸濁物質と流体との分離の具体的な例を見ても、
例えば発酵液から菌体を分離する場合には、従来から行
われている遠心分離法、珪藻土濾過法などに代わってク
ロスフロー濾過方式を用いても膜面上に形成されたケー
ク層や目詰まりによって濾過時間の経過と共に膜透過流
束が低下するばかりでなく、原流体を循環する際の剪断
力によって菌体の活性が失われるという問題があった。[Problems to be Solved by the Invention] As mentioned above, the cross-flow filtration system is an advanced separation technology in principle, but the biggest problem, the membrane permeation flux, is lower than that of the conventional dead-end filtration system. However, even if this cross-flow method is adopted as a precision filtration method, a sufficiently high membrane permeation flux cannot be obtained. Also, looking at specific examples of conventional separation of suspended solids and fluids,
For example, when separating bacterial cells from a fermentation liquid, even if a cross-flow filtration method is used instead of the conventional centrifugation method or diatomaceous earth filtration method, a cake layer or clogging may occur on the membrane surface. Therefore, there is a problem that not only the membrane permeation flux decreases as the filtration time passes, but also the activity of the bacterial cells is lost due to the shear force when circulating the raw fluid.
【0005】透過流束を高める方法としては従来より濾
過膜への原流体の流入を断続的に停止したり、濾過膜の
透過流体側の弁を閉止することにより、濾過膜の膜面に
垂直にかかる圧力を断続的になくすあるいは減少させた
り、また濾過膜の透過液側から圧力を加え透過液側から
原流体側へ流体を流すことによって、濾過膜の原流体側
の膜面上に堆積しているケーク層や付着層を断続的に取
り除く「逆洗」と称する試みがなされているが、懸濁物
質の濾過比抵抗が小さい場合は逆洗により濾過膜に堆積
した懸濁物質は容易に脱着できるが、懸濁物質の濾過比
抵抗が高く濾過膜との付着力の強い高分子成分や菌体の
場合は、逆洗を行っても濾過膜から十分取り除くことが
できず膜透過流速が十分回復しないなどの問題点があっ
た。またこれら逆洗を行った際に濾過膜から脱着した懸
濁物質を濾過系内に残しておくと原流体中の懸濁物の濃
度が徐々に増加し、場合によっては原流体の粘度も上昇
するため膜透過流束は徐々に低下して逆洗を行っても透
過流束が十分回復しない等の問題があった。一方菌体の
活性を低下させない方法として、クロスフロー濾過の場
合は循環流速を低下させ剪断力を小さくすることが行わ
れているが、剪断力を小さくするとクロスフロー濾過方
式の効果が小さくなるため、実際に菌体活性を低下させ
ない方策をとると膜透過流束が低下する問題があった。
またポンプでの菌体の破砕を少なくするためダイヤフラ
ムポンプなどの剪断力の小さいポンプを用いるとポンプ
の脈動が大きくクロスフロー濾過方式の効果が小さくな
る等の問題もあった。Conventional methods for increasing permeation flux include intermittently stopping the flow of raw fluid into the filtration membrane, or closing the valve on the permeate side of the filtration membrane. By intermittently eliminating or reducing the pressure applied to the filtration membrane, or by applying pressure from the permeate side of the filtration membrane and flowing fluid from the permeate side to the raw fluid side, deposits can be removed on the membrane surface on the raw fluid side of the filtration membrane. Attempts have been made to intermittently remove the cake layer and adhering layer, but if the filtration specific resistance of suspended solids is small, backwashing can easily remove suspended solids that have accumulated on the filtration membrane. However, in the case of polymeric components and bacterial cells that have a high filtration specific resistance of suspended solids and strong adhesion to the filtration membrane, they cannot be sufficiently removed from the filtration membrane even if backwashing is performed, and the membrane permeation flow rate decreases. There were problems such as insufficient recovery. In addition, if the suspended solids desorbed from the filtration membrane during backwashing are left in the filtration system, the concentration of suspended solids in the raw fluid will gradually increase, and in some cases, the viscosity of the raw fluid will also increase. Therefore, there was a problem that the membrane permeation flux gradually decreased and the permeation flux did not recover sufficiently even if backwashing was performed. On the other hand, in the case of cross-flow filtration, the method of not reducing the activity of bacterial cells is to reduce the circulation flow rate and reduce the shearing force, but since reducing the shearing force reduces the effectiveness of the cross-flow filtration method. However, if measures were taken that did not actually reduce bacterial cell activity, there was a problem that the membrane permeation flux would decrease. Furthermore, when a pump with a small shearing force such as a diaphragm pump is used to reduce the crushing of bacterial cells by the pump, there is a problem that the pump pulsates so much that the effect of the cross-flow filtration system is reduced.
【0006】[0006]
【課題を解決するための手段】本発明は、上述した従来
技術にあった問題点を解決するために為されたものであ
って、実用性のある高い膜透過流束を持ち菌体などの活
性低下を減少させる新規な濾過膜を提供することを目的
とするものである。 すなわち本発明は、精密濾過膜
を用いて、懸濁物質を含む流体からなる原流体を供給し
濾過することにより流体と懸濁物質とを分離し濾過膜の
透過流体側の圧力を原流体側の圧力より大きくして周期
的に逆洗を行い、逆洗液と共に濾過膜から脱着した懸濁
物質を濾過系外へ排出するデッドエンド型濾過方式にお
いて、濾過膜が精密濾過膜と不織布、織布またはガラス
繊維との複合濾過膜であり、不織布、織布またはガラス
繊維の繊維太さが接する面の精密濾過膜表面孔径の0.
5倍以上5倍以下の太さであることにより達成される。
以下、本発明を詳細に説明する。本発明のデッドエ
ンド型濾過方法に用いる複合濾過膜は、種々の高分子、
微生物、酵母、微粒子を含有あるいは懸濁する流体の分
離、精製、回収、濃縮など、濾過を必要とする微細な微
粒子を含有する流体からその微粒子を分離する必要のあ
るあらゆる場合に適用することができるが、特に発酵液
、培養液からの酵素、微生物、細胞の分離、濃縮、回収
など懸濁物質の濾過比抵抗が極端に大きい場合に効果が
ある。[Means for Solving the Problems] The present invention has been made to solve the problems of the prior art described above, and has a practical high membrane permeation flux, and is capable of transporting bacterial cells, etc. The object of the present invention is to provide a novel filtration membrane that reduces the decrease in activity. That is, the present invention uses a precision filtration membrane to supply and filter a raw fluid consisting of a fluid containing suspended matter, thereby separating the fluid and suspended matter, and reducing the pressure on the permeate fluid side of the filtration membrane to the raw fluid side. In the dead-end filtration method, backwashing is performed periodically at a pressure greater than It is a composite filtration membrane with cloth or glass fiber, and the microfiltration membrane surface pore diameter on the surface where the fiber thickness of nonwoven fabric, woven fabric, or glass fiber comes into contact is 0.
This is achieved by having a thickness of 5 times or more and 5 times or less. The present invention will be explained in detail below. The composite filtration membrane used in the dead-end filtration method of the present invention can be made of various polymers,
It can be applied in any case where it is necessary to separate fine particles from a fluid containing microorganisms, yeast, or particles that require filtration, such as the separation, purification, recovery, and concentration of fluids containing or suspending microorganisms, yeast, and particles. However, it is particularly effective in cases where the filtration specific resistance of suspended substances is extremely high, such as when separating, concentrating, and recovering enzymes, microorganisms, and cells from fermentation liquids and culture liquids.
【0007】本発明の濾過方式で使用される濾過膜は懸
濁物質が阻止できる孔径を持つものが必要であり、精密
濾過膜では通常0.05〜10μmの孔径を有するもの
が使用される。これら精密濾過膜を0.5分から3分の
短い時間で濾過した場合の総濾過量は、濾過膜の構造に
著しく影響を受ける。濾過膜の種類として、その内部に
存在する微孔の孔径が実質的に変化せず、膜の両表面の
孔径が実質的に変わらない所謂等方性膜と、膜厚方向に
孔径が連続的または不連続的に変化し、膜の一方の表面
の孔径と他方の表面の孔径とが異なっている所謂異方性
膜と呼ばれる構造を有するものとに分類される。これら
のうち等方性膜は、特開昭58−98015号に記載さ
れているが、濾過にあたって膜全体が流体の流れに対し
て大きな抵抗を示し、小さな流速しか得られない(即ち
、単位面積当り、単位時間当り、単位差圧当り小さな流
量しか得られない)上、目詰まりがしやすく濾過寿命が
短い、耐ブロッキング性がない等の欠点があった。一方
異方性膜は特公昭55−6406、特開昭56−154
051号、特開昭63−139930に記載されている
如く緻密層と呼ばれている孔径の小さな層を膜の片方の
表面、または膜の内部に持ち、比較的大きな孔をあるい
は極端に大きなボイドを膜の内部からもう一方の表面に
かけて持ったものである。懸濁物質は等方性膜を用いる
かまたは異方性膜の孔径の小さい側に原流体を供給する
場合は濾過膜表面で捕捉され、一方異方性膜の孔径の大
きい側に原流体を供給する場合は懸濁物質は濾過膜の内
部で捕捉される。すなわち懸濁物質を濾過膜の表面で阻
止する場合は阻止された懸濁物質が非常に大きな濾過抵
抗となって透過流束が急激に低下し結果として総濾過量
は低くなるが、濾過膜が膜厚方向に孔径が連続的または
不連続的に変化し濾過膜の一方の表面の孔径と他方の表
面の孔径とが異なる構造を有するいわゆる異方性膜を表
面孔径の大きい側を原流体側に向けて使用することによ
り、濾過膜内部で懸濁物質が阻止できるため大きな総濾
過量を得ることが可能となる。ここで示す膜表面および
膜内部の平均孔径は、電子顕微鏡によって得られた写真
から算出した。The filtration membrane used in the filtration method of the present invention must have a pore size that can block suspended solids, and precision filtration membranes usually have a pore size of 0.05 to 10 μm. The total filtration amount when these microfiltration membranes are used for filtration in a short time of 0.5 to 3 minutes is significantly influenced by the structure of the filtration membrane. There are two types of filtration membranes: so-called isotropic membranes, in which the pore diameters of the micropores existing inside the membrane do not substantially change, and pore diameters on both surfaces of the membrane do not substantially change, and pore diameters that are continuous in the membrane thickness direction. Alternatively, it is classified as having a structure called an anisotropic membrane, in which the pore size on one surface of the membrane is different from the pore size on the other surface. Among these, isotropic membranes are described in JP-A No. 58-98015, but during filtration, the entire membrane exhibits a large resistance to the flow of fluid, and only a small flow rate can be obtained (i.e., (only a small flow rate can be obtained per unit time, per unit time, and per unit pressure difference), and it also has drawbacks such as easy clogging, short filtration life, and lack of blocking resistance. On the other hand, the anisotropic film is
As described in No. 051, JP-A No. 63-139930, the membrane has a layer with a small pore size called a dense layer on one surface of the membrane or inside the membrane, and has relatively large pores or extremely large voids. from the inside of the membrane to the other surface. Suspended solids are trapped on the filtration membrane surface when an isotropic membrane is used or when the raw fluid is supplied to the smaller pore side of the anisotropic membrane, whereas when the raw fluid is supplied to the larger pore side of the anisotropic membrane. When fed, suspended solids are trapped inside the filter membrane. In other words, when suspended solids are blocked on the surface of a filtration membrane, the blocked suspended solids create a very large filtration resistance and the permeation flux decreases rapidly, resulting in a lower total filtration rate. A so-called anisotropic membrane has a structure in which the pore diameter changes continuously or discontinuously in the membrane thickness direction, and the pore diameter on one surface of the filtration membrane is different from the pore diameter on the other surface.The side with the larger surface pore diameter is the raw fluid side. By using it for this purpose, suspended solids can be blocked inside the filtration membrane, making it possible to obtain a large total filtration amount. The average pore diameters on the membrane surface and inside the membrane shown here were calculated from photographs taken with an electron microscope.
【0008】本発明の複合濾過膜は、精密濾過膜と不織
布、織布またはガラス繊維を一体化した複合構造であり
、不織布等側を原液側にすることにより、さらに懸濁物
質の捕捉性および逆洗による洗浄性が高まる。特に、懸
濁物質の粒径分布が広い場合は大きい懸濁物質は不織布
内部に、小さい懸濁物質は多孔質濾過膜内部に捕捉され
るため効果は大きい。これら不織布、織布またはガラス
繊維はそれらを形成する繊維の太さ、空隙率、厚みによ
って懸濁物質の阻止性能が異なる。すなわち繊維の太さ
が細く、空隙率が低くなるほど細かい懸濁物質を阻止し
、また厚みが厚くなるほど多量の懸濁物質を阻止できる
。繊維の太さは不織布等が接する濾過膜の表面孔径と相
関がある。すなわち不織布等の実質的な孔径が不織布等
が接する濾過膜の表面孔径とほぼ同じか若干大きいこと
が好ましい。濾過膜と不織布の界面で孔径がほぼ連続的
となるための不織布等の繊維の太さは濾過膜表面孔径の
0.5倍以上5倍以下である。すなわち濾過膜表面の平
均孔径が2μmの場合、不織布等の繊維太さは1μm以
上5μm以下であることが好ましい。不織布等の空隙率
は極端に低くすると濾過抵抗が大きくなり、逆に高すぎ
ると懸濁物質を阻止しなくなるため、通常は50%以上
90%以下が好ましく、さらに60%以上75%以下が
好ましい。また不織布等の厚みが薄いと懸濁物質の捕捉
効果は得られず、濾過膜の厚みの1/2以上であること
が好ましい。不織布等の材質は特に限定されるものでは
ないが、一般的にポリエステル、ポリプロピレン、ポリ
アミド、ステンレスなどが用いられる。 また、周期
的に逆洗を行う場合は、逆洗時に濾過膜に対して大きな
負荷がかかり濾過膜強度が弱いときは濾過膜に亀裂が生
じるなどの問題がおこったが、濾過膜を不織布等と一体
化することにより濾過膜強度を極端に上昇させることが
可能となる。濾過膜と不織布等とを一体化する方法は、
点状または線状に接着剤で行うかヒートシールで溶融接
着を行ってもよいが、特公昭45−13931のごとく
濾過膜を製膜する際に製膜原液を直接不織布等にキャス
ティングして濾過膜が不織布等に一部侵入した状態で多
孔質構造を形成してもよい。The composite filtration membrane of the present invention has a composite structure in which a precision filtration membrane and a nonwoven fabric, woven fabric, or glass fiber are integrated, and by placing the nonwoven fabric side on the raw solution side, the ability to trap suspended substances and Improves cleaning performance through backwashing. In particular, when the particle size distribution of the suspended solids is wide, the effect is great because large suspended solids are trapped inside the nonwoven fabric and small suspended solids are trapped inside the porous filtration membrane. These nonwoven fabrics, woven fabrics, or glass fibers have different suspended solid blocking performance depending on the thickness, porosity, and thickness of the fibers forming them. That is, the thinner the fiber thickness and the lower the porosity, the more fine suspended solids can be blocked, and the thicker the thickness, the more suspended solids can be blocked. The thickness of the fibers has a correlation with the surface pore size of the filtration membrane with which the nonwoven fabric or the like comes into contact. That is, it is preferable that the substantial pore diameter of the nonwoven fabric or the like is approximately the same as or slightly larger than the surface pore diameter of the filtration membrane with which the nonwoven fabric or the like is in contact. The thickness of the fibers of the nonwoven fabric or the like is 0.5 times or more and 5 times or less the pore size on the surface of the filtration membrane so that the pore size becomes substantially continuous at the interface between the filtration membrane and the nonwoven fabric. That is, when the average pore diameter on the surface of the filtration membrane is 2 μm, the fiber thickness of the nonwoven fabric is preferably 1 μm or more and 5 μm or less. If the porosity of the nonwoven fabric is extremely low, the filtration resistance will increase, and if it is too high, it will not block suspended solids, so it is usually preferably 50% or more and 90% or less, and more preferably 60% or more and 75% or less. . Furthermore, if the thickness of the nonwoven fabric is too small, the effect of trapping suspended substances cannot be obtained, so it is preferable that the thickness is 1/2 or more of the thickness of the filtration membrane. Although the material of the nonwoven fabric is not particularly limited, polyester, polypropylene, polyamide, stainless steel, etc. are generally used. In addition, when backwashing is performed periodically, there are problems such as a large load on the filtration membrane during backwashing and cracks in the filtration membrane when the strength of the filtration membrane is weak. By integrating with the filtration membrane, it becomes possible to dramatically increase the strength of the filtration membrane. The method of integrating the filtration membrane and nonwoven fabric, etc. is as follows.
Melting bonding may be performed in dots or lines with an adhesive or by heat sealing, but when forming a filtration membrane as in Japanese Patent Publication No. 45-13931, it is also possible to directly cast the membrane-forming stock solution onto a nonwoven fabric etc. and filter it. A porous structure may be formed with the membrane partially penetrating a nonwoven fabric or the like.
【0009】本発明のデッドエンド濾過で行う逆洗はガ
スよりも液体で行う方が効果が大きく、系外からの異物
混入を避ける場合は逆洗液として透過液を用いることが
できる。また透過液を逆流させた分だけ透過量が減少す
ることを避ける場合は、濾過系外より洗浄液を供給して
必要に応じた逆洗液量で逆洗を行うことが好ましい。濾
過系外より供給する洗浄液は濾過膜の特性を低下させた
り原流体の特性を変化させなければ基本的には何でも良
いが、原流体が水溶液である場合には一般的には滅菌水
を用いることが好ましい。また、逆洗終了後逆洗液を濾
過系内に残したくない場合はガスによる脱水を行うこと
が好ましい。 逆洗は膜透過流束が極端に低くなって
から行うと逆洗後の膜透過流束の回復性は悪くなる。こ
れは懸濁物質が濾過膜の内部に深く侵入したり堆積した
懸濁物質が圧密化したり、また長時間濾過を行うと懸濁
物質が濾過膜に強く結合するため、逆洗時に堆積した懸
濁物質を完全に取り除くことができなくなるためである
。
このため定圧濾過を行う場合は濾過初期の透過流速の1
/100に達する前に逆洗を行うことが好ましく、さら
に高い透過流速を得るためには1/10に達する前に逆
洗を行うことが好ましい。また、定速濾過を行う場合は
濾過膜間差圧が極端委高くなってから逆洗を行うと逆洗
後の濾過膜間差圧の回復性すなわち濾過膜の洗浄性が悪
くなるため、濾過初期の濾過膜間差圧の100倍に達す
る前に逆洗を行うことが好ましく、さらに好ましくは1
0倍に達する前に逆洗を行う。従って濾過開始から逆洗
に至るまでの時間は短く、懸濁物質の比抵抗が大きい場
合は濾過を0.5分以上3分以内行った後に逆洗を行う
ことが好ましい。また、逆洗液は高い透過流速で多量に
濾過膜内を通過させる方が洗浄性は高くなるが、逆洗液
の透過流束を高めて長時間逆洗を行うことは逆洗液量が
膨大となるばかりでなく、濾過時間に対する逆洗時間の
比率が高まり事実上平均透過流束は低くなるため、十分
透過流束が回復できる範囲で透過流速は1×10−4m
3 /m2 /sec以上であり、時間は1秒以上30
秒以内であることが好ましい。Backwashing performed in the dead-end filtration of the present invention is more effective when carried out with a liquid than with a gas, and a permeated liquid can be used as the backwashing liquid if foreign matter contamination from outside the system is to be avoided. In addition, in order to avoid a decrease in the permeation amount by the amount of backflow of the permeate, it is preferable to supply a cleaning liquid from outside the filtration system and perform backwashing with an amount of backwash liquid as required. Basically, any cleaning liquid supplied from outside the filtration system may be used as long as it does not degrade the properties of the filtration membrane or change the properties of the raw fluid, but if the raw fluid is an aqueous solution, sterile water is generally used. It is preferable. Further, if it is desired not to leave the backwash liquid in the filtration system after the backwash is completed, it is preferable to perform dehydration using gas. If backwashing is performed after the membrane permeation flux becomes extremely low, the recovery of the membrane permeation flux after backwashing will deteriorate. This is due to suspended solids penetrating deeply into the filtration membrane, the accumulated suspended solids becoming compacted, or the suspended solids strongly bonding to the filtration membrane when filtration is performed for a long time. This is because the turbid substances cannot be completely removed. Therefore, when performing constant pressure filtration, 1 of the permeation flow rate at the initial stage of filtration
It is preferable to perform backwashing before reaching 1/100, and in order to obtain an even higher permeation flow rate, it is preferable to perform backwashing before reaching 1/10. In addition, when performing constant-speed filtration, if backwashing is performed after the pressure difference between the filtration membranes becomes extremely high, the recovery of the pressure difference between the filtration membranes after backwashing, that is, the cleaning performance of the filtration membranes, will deteriorate. It is preferable to carry out backwashing before the pressure difference between the filtration membranes reaches 100 times the initial pressure difference between the membranes, more preferably 1
Perform backwashing before reaching 0 times. Therefore, the time from the start of filtration to backwashing is short, and if the specific resistance of the suspended solids is large, it is preferable to perform backwashing after filtration is performed for 0.5 minutes or more and up to 3 minutes. In addition, cleaning performance will be higher if a large amount of backwash liquid is passed through the filtration membrane at a high permeation flow rate, but if the permeation flux of backwash liquid is increased and backwash is performed for a long time, Not only will the amount be enormous, but the ratio of backwashing time to filtration time will increase, effectively lowering the average permeation flux, so the permeation flow rate should be 1 x 10-4 m as long as the permeation flux can be recovered sufficiently.
3/m2/sec or more, and the time is 1 second or more 30
Preferably within seconds.
【0010】次に本発明のデッドエンド型濾過方式を図
面に基づいて説明する。図1は従来のデッドエンド型濾
過を行った際に濾過膜に堆積する懸濁物の様子を示して
おり、経時とともに堆積する懸濁物質量は増加し、最終
的には透過流束はゼロに近づく。 図2はクロスフロ
ー濾過を行った際に濾過膜に堆積する懸濁物質の様子を
示しており、濾過開始初期においては懸濁物質が徐々に
増加するが原流体の剪断力によって堆積する懸濁物質量
は一定値をとり透過流束も最終的には一定値に近づく。
図3は本発明のデッドエンド型濾過方式のフローを示し
ている。濾過を一定時間行った後透過流体側から原流体
側に滅菌水を流して濾過膜から脱着した懸濁物質と共に
排出する。その後ガスにより濾過系内に残留している滅
菌水を排出し、再び濾過を行う。このサイクルを繰り返
すことによって原流体の懸濁物質濃度も上昇せずに高い
透過流束を維持することが可能となる。図4は異方性膜
の孔径の小さい側を原液側にして懸濁物質を濾過膜表面
で阻止した場合の濾過膜断面を示しており、図5は異方
性の孔径の小さい側を原液側にした場合の濾過膜断面を
示している。 図6は本発明の複合膜を示している。
本発明の複合膜構造では不織布等の内部と濾過膜内部で
懸濁物質が阻止されるため、著しく大きな濾過抵抗とは
ならず結果として高い濾過量が得られる。Next, the dead-end filtration system of the present invention will be explained based on the drawings. Figure 1 shows the state of suspended matter that accumulates on the filtration membrane when performing conventional dead-end filtration.The amount of suspended matter that accumulates increases over time, and the permeation flux eventually reaches zero. approach. Figure 2 shows the state of suspended solids deposited on the filtration membrane when cross-flow filtration is performed.At the beginning of filtration, the suspended solids gradually increase, but the suspended solids accumulate due to the shear force of the raw fluid. The amount of substance takes a constant value, and the permeation flux eventually approaches a constant value. FIG. 3 shows the flow of the dead-end filtration method of the present invention. After filtration is performed for a certain period of time, sterilized water is passed from the permeate side to the raw fluid side and discharged together with the suspended solids desorbed from the filtration membrane. Thereafter, the sterilized water remaining in the filtration system is discharged using gas, and filtration is performed again. By repeating this cycle, it becomes possible to maintain a high permeation flux without increasing the concentration of suspended solids in the raw fluid. Figure 4 shows a cross section of the filtration membrane when the side with the smaller pore size of the anisotropic membrane is placed on the stock solution side and suspended matter is blocked on the filtration membrane surface, and Figure 5 shows the side with the smaller anisotropic pore size on the stock solution side. This shows a cross section of the filtration membrane when it is turned to the side. Figure 6 shows a composite membrane of the invention. In the composite membrane structure of the present invention, suspended solids are blocked inside the nonwoven fabric and the filtration membrane, so that there is no significant filtration resistance, resulting in a high filtration rate.
【0011】[0011]
【実施例】以下に具体例をあげて本発明をさらに詳しく
説明するが、発明の主旨を越えない限り本発明は実施例
に限定されるものではない。
実施例1
市販のビールにタンニン酸20ppmを溶かして、タン
パク質を凝集させたものを懸濁液として用いて、本発明
の逆洗を周期的に行うデッドエンド型濾過を行った。異
方性膜はポリスルホン(アモコ社製 P3500)1
5部、ポリビニルピロリドン15部、水3部を、N−メ
チルピロリドン70部に溶解した製膜原液を、繊維太さ
約4μm、空隙率70%、厚み150μmのポリプロピ
レン製の不織布に液膜厚さ180μmでキャスティング
コーターを通して流延し、その液膜表面に25℃相対湿
度45%に調節した空気を2m/secで5秒間当て、
その後直ちに水を満たした凝固液槽へ浸漬して作成した
。
得られた濾過膜は平均孔径1.5μmの内部緻密層を持
つ異方性の精密濾過膜であり、不織布と接する側の平均
孔径が5μmとなり、不織布側を原液側として周期的逆
洗を行う濾過を行った。使用した濾過器は有効膜面積1
00cm2 で、実験条件は圧力差0.5×105 P
a、液温度2℃であり、濾過時間60秒、逆洗流束5×
10−3m3 /m2/sec、逆洗時間4秒で行い逆
洗液には滅菌水を用いた。図7に本発明の複合膜を用い
た場合と不織布を使用せずに上記方法で作成した異方性
膜を孔径の大きい方を原液側にした場合と孔径の小さい
側を原液側にした場合の、総濾過量の経時変化を示した
。本発明の複合膜を用いた逆洗を周期的に行うデッドエ
ンド型濾過では高い濾過量を示した。[Examples] The present invention will be explained in more detail with reference to specific examples below, but the present invention is not limited to the examples unless it goes beyond the gist of the invention. Example 1 Dead-end filtration in which backwashing of the present invention is periodically performed was performed using a suspension of protein aggregates obtained by dissolving 20 ppm of tannic acid in commercially available beer. The anisotropic membrane is polysulfone (P3500 manufactured by Amoco) 1
A film-forming stock solution prepared by dissolving 5 parts of polyvinylpyrrolidone, 15 parts of polyvinylpyrrolidone, and 3 parts of water in 70 parts of N-methylpyrrolidone was applied to a polypropylene nonwoven fabric with a fiber thickness of approximately 4 μm, a porosity of 70%, and a thickness of 150 μm. It was cast at 180 μm through a casting coater, and air adjusted to 25° C. and 45% relative humidity was applied to the surface of the liquid film at 2 m/sec for 5 seconds.
Thereafter, it was immediately immersed in a coagulation bath filled with water. The obtained filtration membrane is an anisotropic precision filtration membrane having an internal dense layer with an average pore diameter of 1.5 μm, and the average pore diameter on the side in contact with the nonwoven fabric is 5 μm, and periodic backwashing is performed with the nonwoven fabric side as the stock solution side. Filtered. The filter used has an effective membrane area of 1
00cm2, and the experimental conditions were a pressure difference of 0.5×105P.
a, liquid temperature 2°C, filtration time 60 seconds, backwash flux 5x
Backwashing was carried out at a rate of 10-3 m3/m2/sec and a time of 4 seconds, and sterilized water was used as the backwashing liquid. Figure 7 shows a case where the composite membrane of the present invention is used, an anisotropic membrane prepared by the above method without using a nonwoven fabric, with the side with larger pores on the undiluted solution side, and cases where the side with smaller pores is on the undiluted solution side. The graph shows the change in total filtration amount over time. Dead-end filtration using the composite membrane of the present invention with periodic backwashing showed a high filtration rate.
【0012】実施例2
実施例1の懸濁液を濾過原液として用い、実施例1の方
法で各種の不織布に緻密層平均孔径1.5μmの異方性
の精密濾過膜を形成させた複合膜を用いて逆洗を周期的
に行うデッドエンド型濾過を行った。不織布は繊維太さ
がそれぞれ2μm、4μm、20μm、30μmであり
、空隙率は約70%、厚みは150μmである。使用し
た濾過器は有効膜面積100cm2 で、実験条件は圧
力差0.5×105 Pa、液温度2℃であり、濾過時
間60秒、逆洗流束5×10−3m3 /m2 /se
c、逆洗時間4秒で行い逆洗液には滅菌水を用いた。図
8に上記複合膜を不織布側を原液側として用いた場合の
濾過運転5時間後の総濾過量の結果を示した。この結果
、不織布繊維の太さは不織布が接する部分の濾過膜平均
孔径5μmの0.5倍〜5倍、すなわち2.5μmから
25μmの時高い濾過量が得られた。Example 2 A composite membrane in which an anisotropic microfiltration membrane with a dense layer average pore diameter of 1.5 μm was formed on various nonwoven fabrics by the method of Example 1 using the suspension of Example 1 as the filtration stock solution. Dead-end filtration with periodic backwashing was carried out. The fiber thickness of the nonwoven fabric is 2 μm, 4 μm, 20 μm, and 30 μm, respectively, the porosity is about 70%, and the thickness is 150 μm. The filter used had an effective membrane area of 100 cm2, the experimental conditions were a pressure difference of 0.5 x 105 Pa, a liquid temperature of 2°C, a filtration time of 60 seconds, and a backwash flux of 5 x 10-3 m3/m2/se.
c. Backwashing was carried out for 4 seconds, and sterile water was used as the backwashing liquid. FIG. 8 shows the results of the total filtration amount after 5 hours of filtration operation when the above composite membrane was used with the nonwoven fabric side as the stock solution side. As a result, a high filtration rate was obtained when the thickness of the nonwoven fabric fibers was 0.5 to 5 times the average pore diameter of the filtration membrane of 5 μm in contact with the nonwoven fabric, that is, 2.5 μm to 25 μm.
【0013】実施例3
実施例1の懸濁液を濾過原液として用い、実施例1の方
法で厚みの違う不織布に緻密層平均孔径1.5μm、厚
み180μmの異方性の精密濾過膜を形成させた複合膜
を用いて逆洗を周期的に行うデッドエンド型濾過を行っ
た。不織布は厚みがそれぞれ80μm、120μm、2
00μm、300μmで、繊維太さが4μm、空隙率約
70%である。使用した濾過器は有効膜面積100cm
2 で、実験条件は圧力差0.5×105 Pa、液温
度2℃であり、濾過時間60秒、逆洗流束5×10−3
m3 /m2 /sec、逆洗時間4秒で行い逆洗液に
は滅菌水を用いた。図9にそれぞれの複合膜を用いた場
合の濾過運転5時間後の総濾過量を示した。この結果、
不織布厚さは濾過膜の厚さ180μmの1/2以上、す
なわち90μm以上で高い濾過量が得られた。Example 3 Using the suspension of Example 1 as a filtration stock solution, anisotropic precision filtration membranes with a dense layer average pore diameter of 1.5 μm and a thickness of 180 μm were formed on nonwoven fabrics of different thicknesses by the method of Example 1. Dead-end filtration with periodic backwashing was carried out using the composite membrane. The thickness of the nonwoven fabric is 80 μm, 120 μm, and 2
00 μm and 300 μm, the fiber thickness is 4 μm, and the porosity is about 70%. The filter used has an effective membrane area of 100 cm.
2, the experimental conditions were a pressure difference of 0.5 x 105 Pa, a liquid temperature of 2°C, a filtration time of 60 seconds, and a backwash flux of 5 x 10-3.
The backwashing was performed at a rate of m3/m2/sec and a time of 4 seconds, and sterilized water was used as the backwashing liquid. FIG. 9 shows the total filtration amount after 5 hours of filtration operation when each composite membrane was used. As a result,
A high filtration rate was obtained when the thickness of the nonwoven fabric was 1/2 or more of the thickness of the filtration membrane, 180 μm, that is, 90 μm or more.
【0014】[0014]
【発明の効果】本発明によれば、複合膜を用いた逆洗を
周期的に行うデッドエンド型濾過方式において高い膜透
過流束が得られ、それによって種々の懸濁物質を含有す
る液体から各懸濁成分の分離、回収、精製、濃縮などが
きわめて効率的しかも経済的に行われる。そしてさらに
プロセスの連続化及び装置の小型化が可能であり、膜の
選択性を利用して目的物のみを連続的に選択的に分離す
ることができ、酵母や菌体などのバイオリアクターへの
応用ができ、従来技術に比べて運転管理が容易であるな
ど諸々の効果が奏せられる。Effects of the Invention According to the present invention, a high membrane permeation flux can be obtained in a dead-end filtration system in which backwashing is performed periodically using a composite membrane. Separation, recovery, purification, concentration, etc. of each suspended component are performed extremely efficiently and economically. Furthermore, it is possible to make the process continuous and downsize the equipment, and by utilizing the selectivity of the membrane, it is possible to continuously and selectively separate only the target substance, and it is possible to separate only the target substance continuously and selectively, and it is possible to use the membrane to selectively separate only the target substance. It can be applied and has various effects such as easier operation management than conventional technology.
【図1】従来のデッドエンド型濾過における懸濁物質の
堆積状態を示している。FIG. 1 shows the state of accumulation of suspended solids in conventional dead-end filtration.
【図2】従来のクロスフロー濾過における懸濁物質の堆
積状態を示している。FIG. 2 shows the state of accumulation of suspended solids in conventional cross-flow filtration.
【図3】本発明の逆洗を周期的に行うデッドエンド型濾
過方式のフローを示している。FIG. 3 shows a flowchart of a dead-end filtration system in which backwashing is performed periodically according to the present invention.
【図4】異方性膜を孔径の小さい側から懸濁物質を濾過
膜表面に阻止した場合の膜断面状態を示している。FIG. 4 shows a cross-sectional state of the anisotropic membrane when suspended substances are blocked on the surface of the filtration membrane from the side with the smaller pore size.
【図5】異方性膜を孔径の大きい側から懸濁物質を阻止
した時の膜断面状態を示している。FIG. 5 shows a cross-sectional state of the anisotropic membrane when suspended substances are blocked from the side with larger pores.
【図6】本発明の複合膜の不織布側から懸濁物質を阻止
した場合の膜断面状態を示している。FIG. 6 shows a cross-sectional state of the composite membrane of the present invention when suspended substances are blocked from the nonwoven fabric side.
【図7】タンパク凝集ビールを用いて本発明の複合膜で
逆洗を周期的に行うデッドエンド型濾過を行った際の総
濾過量を示している。FIG. 7 shows the total filtration amount when protein-agglomerated beer was used for dead-end filtration with periodic backwashing using the composite membrane of the present invention.
【図8】タンパク凝集ビールを用いて不織布繊維の太さ
の違う複合膜で逆洗を周期的に行うデッドエンド型濾過
を行った際の総濾過量を示している。FIG. 8 shows the total filtration amount when protein-agglomerated beer was used in dead-end filtration in which backwashing was performed periodically using composite membranes with different thicknesses of nonwoven fibers.
【図9】タンパク凝集ビールを用いて不織布厚みの違う
複合膜で逆洗を周期的に行うデッドエンド型濾過を行っ
た際の総濾過量を示している。FIG. 9 shows the total filtration amount when protein-agglomerated beer was used in dead-end filtration in which backwashing was performed periodically using composite membranes with different thicknesses of nonwoven fabrics.
1 デッドエンド濾過の原流体の流れ2 デッドエ
ンド濾過の透過液の流れ3 デッドエンド濾過の懸濁
物質の移動方向4 濾過膜上に堆積している懸濁物質
5 濾過膜
6 クロスフロー濾過の原流体の流れ7 クロスフ
ロー濾過の透過液の流れ8 クロスフロー濾過の懸濁
物質の移動方向9 濾過膜上に堆積している懸濁物質
10 濾過膜
11 原流体入口
12 透過液出口
13 逆洗液入口
14 排液出口
15 濾過器
16 濾過膜
17 ガス入口
18 圧力計
19 ポンプ
20 滅菌フィルター
21 電磁弁
22 濾過膜断面
23 懸濁物質
24 濾過膜断面
25 懸濁物質
26 濾過膜断面
27 不織布断面
28 懸濁物質
29 本発明の複合濾過膜1 Flow of raw fluid in dead-end filtration 2 Flow of permeate in dead-end filtration 3 Movement direction of suspended solids in dead-end filtration 4 Suspended solids deposited on the filtration membrane 5 Filter membrane 6 Raw material in cross-flow filtration Fluid flow 7 Flow of permeate in cross-flow filtration 8 Movement direction of suspended solids in cross-flow filtration 9 Suspended solids deposited on the filtration membrane 10 Filtration membrane 11 Raw fluid inlet 12 Permeate outlet 13 Backwash liquid Inlet 14 Drainage outlet 15 Filter 16 Filtration membrane 17 Gas inlet 18 Pressure gauge 19 Pump 20 Sterilization filter 21 Solenoid valve 22 Filtration membrane cross section 23 Suspended solids 24 Filtration membrane cross section 25 Suspended solids 26 Filtration membrane cross section 27 Nonwoven fabric cross section 28 Suspension Turbid substance 29 Composite filtration membrane of the present invention
Claims (6)
流体からなる原流体を供給し濾過することにより流体と
懸濁物質とを分離する濾過方式において、濾過膜が精密
濾過膜と不織布、織布またはガラス繊維との積層複合膜
であり、不織布、織布またはガラス繊維の繊維太さが接
する面の濾過膜表面孔径の0.5倍以上5倍以下の太さ
のであることを特徴とする複合濾過膜。Claim 1: A filtration method in which a raw fluid consisting of a fluid containing suspended matter is supplied and filtered using a precision filtration membrane to separate the fluid from the suspended matter, wherein the filtration membrane is a combination of the precision filtration membrane and a nonwoven fabric. , a laminated composite membrane with woven fabric or glass fiber, characterized in that the fiber thickness of the nonwoven fabric, woven fabric, or glass fiber is 0.5 times or more and 5 times or less the pore diameter of the surface of the filtration membrane on the contacting surface. Composite filtration membrane.
を原流体側の圧力より大きくして周期的に逆洗を行い、
逆洗液と共に濾過膜から脱着した懸濁物質を濾過系外へ
排出するデッドエンド型濾過方式に使用することを特徴
とする請求項1項記載の複合濾過膜。2. The filtration membrane is periodically backwashed by making the pressure on the permeate side of the filtration membrane higher than the pressure on the raw fluid side,
2. The composite filtration membrane according to claim 1, wherein the composite filtration membrane is used in a dead-end filtration system in which suspended solids desorbed from the filtration membrane are discharged from the filtration system together with the backwash liquid.
みが精密濾過膜の厚みの1/2以上であることを特徴と
する請求項1項記載の複合濾過膜。3. The composite filtration membrane according to claim 1, wherein the thickness of the nonwoven fabric, woven fabric, or glass fiber is 1/2 or more of the thickness of the microfiltration membrane.
たはガラス繊維に含浸していることを特徴とする請求項
1項記載の複合濾過膜。4. The composite filtration membrane according to claim 1, wherein a part of the microfiltration membrane is impregnated with nonwoven fabric, woven fabric, or glass fiber.
的または不連続的に変化し、精密濾過膜の一方の表面孔
径と他方の表面孔径とが異なる異方性構造を有し、表面
孔径の大きい側に不織布、織布またはガラス繊維が存在
することを特徴とする請求項1項記載の複合濾過膜。5. The microfiltration membrane has an anisotropic structure in which the pore diameter changes continuously or discontinuously in the membrane thickness direction, and the pore diameter on one surface of the microfiltration membrane is different from the pore diameter on the other surface, 2. The composite filtration membrane according to claim 1, wherein a nonwoven fabric, woven fabric, or glass fiber is present on the side with larger surface pores.
ラス繊維の側を原流体側に向けることを特徴とする請求
項1項に記載の複合濾過膜。6. The composite filtration membrane according to claim 1, wherein the nonwoven fabric, woven fabric, or glass fiber side of the composite filtration membrane faces the raw fluid side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8693691A JPH04317730A (en) | 1991-04-18 | 1991-04-18 | Composite filtration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8693691A JPH04317730A (en) | 1991-04-18 | 1991-04-18 | Composite filtration membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04317730A true JPH04317730A (en) | 1992-11-09 |
Family
ID=13900757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8693691A Pending JPH04317730A (en) | 1991-04-18 | 1991-04-18 | Composite filtration membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04317730A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06226057A (en) * | 1993-02-05 | 1994-08-16 | Daicel Chem Ind Ltd | Hollow fiber membrane type element and hollow fiber membrane module |
| US5703359A (en) * | 1996-07-29 | 1997-12-30 | Leybold Inficon, Inc. | Composite membrane and support assembly |
| JP2000070685A (en) * | 1998-08-27 | 2000-03-07 | Daicel Chem Ind Ltd | Cleaning method for solid-liquid separation membrane |
-
1991
- 1991-04-18 JP JP8693691A patent/JPH04317730A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06226057A (en) * | 1993-02-05 | 1994-08-16 | Daicel Chem Ind Ltd | Hollow fiber membrane type element and hollow fiber membrane module |
| US5703359A (en) * | 1996-07-29 | 1997-12-30 | Leybold Inficon, Inc. | Composite membrane and support assembly |
| JP2000070685A (en) * | 1998-08-27 | 2000-03-07 | Daicel Chem Ind Ltd | Cleaning method for solid-liquid separation membrane |
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