JPS6170987A - Method of inclusive immobilization for aerobic bacterium - Google Patents
Method of inclusive immobilization for aerobic bacteriumInfo
- Publication number
- JPS6170987A JPS6170987A JP59190573A JP19057384A JPS6170987A JP S6170987 A JPS6170987 A JP S6170987A JP 59190573 A JP59190573 A JP 59190573A JP 19057384 A JP19057384 A JP 19057384A JP S6170987 A JPS6170987 A JP S6170987A
- Authority
- JP
- Japan
- Prior art keywords
- aerobic microorganisms
- high polymer
- substance
- aerobic bacterium
- polymer substance
- 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
- 238000000034 method Methods 0.000 title claims description 10
- 241000894006 Bacteria Species 0.000 title abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 244000005700 microbiome Species 0.000 claims description 18
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 3
- 230000003100 immobilizing effect Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052586 apatite Inorganic materials 0.000 abstract description 3
- 239000011324 bead Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 abstract description 3
- 230000001546 nitrifying effect Effects 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 4
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- UHKHUAHIAZQAED-UHFFFAOYSA-N phthalocyaninatoiron Chemical compound [Fe].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 UHKHUAHIAZQAED-UHFFFAOYSA-N 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、各種の産業で利用されている好気性微生換金
包括固定化する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for entrapping and immobilizing aerobic microorganisms, which is used in various industries.
今日、医薬品業界及びその他の多くの業界において、
（１）菌体端度七著るしく高めることが出来ること、
（２） 有価物１Ｘｔ−短時間に生産できること、（３
） 外界の壌゛境条件の変動に対して強いこと、（４
） 取り扱いが容易であり制御もしやすぐ、さらに連
続運転が苛能でめること −などの理由により
固定化微生物を利用した有価物質の生産に関する研究開
発が鋭意性なわれており、部分的にはすでに実用化の段
階にある。′しかしなから、これらの殆んどは酸素を全
く必要どしないか、或いは微好気的条件下でも生育し□
うる微生物を利用し友ものであり、例えば、現在各研究
機関で盛んに研究が行なわれているメタン発酵への適用
も嫌気条件下での反応である。 ゛
一方、好気性微生物への適用上意図した幾つかの研究事
例もあるが、そのいずれもが酸素のゲル内への拡散が強
い律速となるためにその有効性が疑問視されている。Today, in the pharmaceutical industry and many other industries, (1) it is possible to significantly increase the bacterial cell density, (2) it is possible to produce 1Xt of valuable materials in a short time, and (3)
) Must be resistant to fluctuations in the environmental conditions of the outside world, (4
) Research and development into the production of valuable substances using immobilized microorganisms is being carried out intensively for the following reasons: they are easy to handle, can be easily controlled, and can be operated continuously with extreme stress. It is already at the stage of practical application. 'However, most of these do not require any oxygen or can grow under microaerobic conditions.'
For example, methane fermentation, which is currently being actively researched at various research institutions, is a reaction under anaerobic conditions. On the other hand, there have been some research studies intended to apply it to aerobic microorganisms, but their effectiveness has been questioned because the diffusion of oxygen into the gel is a strong rate-limiting factor.
また、過酸化水素或いは過フッ化物（例えば過シッ化へ
キザンン全培地中に共存させ、グル内の酸ＪＡ濃度を高
めるなどの方法も報告されているが、長期間にわ几る微
生物活性の、維持及び培地調整の複雑さなど問題点が多
い。In addition, methods have been reported in which hydrogen peroxide or perfluoride (for example, persulfated hexane) is coexisting in the entire medium to increase the concentration of acid JA in the gel. However, there are many problems such as the complexity of maintenance and culture medium adjustment.
本発明は、好気性微生物を包括固定化するに当り、ゲル
内へ酸素を還元溶解する触媒物質全同時に包括固定する
ことにより微生物活性を高いレベルに維持しうる包括固
定化ゲルを提供することを目的とする。The present invention aims to provide an entrapping immobilization gel that can maintain microbial activity at a high level by simultaneously entrapping all catalyst substances that reduce and dissolve oxygen into the gel when entrapping aerobic microorganisms. purpose.
本発明は、好気性微生物を高分子物質で包括固定化する
に当り、空気中又は水中の酸素を水中に還元溶解する能
力を有するスルフォン化し穴金属７タロシアニンの溶液
を吸着性無機質粉末に含浸させ、不活性ガス雰囲気中に
おいて３００℃〜ａＯＯ℃の温度範囲で焼成し几後好気
性微生物と共に包括固定することを特徴とする好気性微
生物の包括固定化方法である。In entrapping and immobilizing aerobic microorganisms with a polymeric substance, the present invention involves impregnating an adsorbent inorganic powder with a solution of sulfonated hole metal 7 talocyanine, which has the ability to reduce and dissolve oxygen in the air or water. , is a method for comprehensive immobilization of aerobic microorganisms, which is characterized in that it is calcined at a temperature range of 300° C. to aOO° C. in an inert gas atmosphere, and is then immobilized together with aerobic microorganisms.
本発明は、前記の従来の包括固定化法の有するＲ素の拡
散阻害という致命的欠点ｔスルフォン化した金属フタロ
シアニンの浴液を無機性粉末に吸着させた触媒物質會好
気注微生物と共に包括固定化することにより解決したも
ので、好気性微生物の使用を着るしく改善し効率化する
ものである。The present invention has the fatal disadvantage of inhibiting the diffusion of R element in the conventional entrapment immobilization method.The present invention is capable of entrapping a bath solution of sulfonated metal phthalocyanine together with a catalytic substance adsorbed to an inorganic powder and an aerobic microorganism. The solution was to improve the efficiency of the use of aerobic microorganisms.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用するスルフォン１ヒ金属フタロシアニンの
金属成分としては、Ｐｅ、Ｏｕ、Ｎｉ などが用いら
れ、ま几該スルフォン化金属フタロシアニン會吸着させ
る吸着性無機質担体（粉末）としては、アルミナ、シリ
カゲル、炭素或いはアパタイト粉末等が用いられるが、
炭素あるいはアパタイト粉末が好ましい。The metal components of the sulfonated metal phthalocyanine used in the present invention include Pe, Ou, Ni, etc., and the adsorbent inorganic carrier (powder) for adsorbing the sulfonated metal phthalocyanine includes alumina, silica gel, Carbon or apatite powder is used, but
Carbon or apatite powder is preferred.
無機質担体に吸＊−ｇせるスルフォン化金属フタロシア
ニンの量は５重量−〜５０重量−位の範囲でよく、その
水浴液を無機質担体に含浸させｔ後乾燥しＮ累算囲気中
で３００℃〜８００℃に加熱することにより無機質担体
上にスルフォン化金属フタロシアニンを固定させる。こ
のように無機質担体上に固定することなく、あるいはス
ルフォン化金属ツタロシアエンをそのま＼用いる場合、
スルフォン化金属フタロシアニンはゲル外に浴出して行
くため、所期の効果が得られない。The amount of sulfonated metal phthalocyanine that can be absorbed into the inorganic carrier may range from 5 to 50% by weight, and the inorganic carrier is impregnated with the water bath solution, then dried at 300° C. The sulfonated metal phthalocyanine is fixed on the inorganic carrier by heating to 800°C. In this way, when using sulfonated metal tutalocyanene without fixing it on an inorganic carrier or as it is,
Since the sulfonated metal phthalocyanine leaks out of the gel, the desired effect cannot be obtained.
つぎに、本発明の好気性微生物の包括固定化方法につい
て詳しく説明する。Next, the method for comprehensive immobilization of aerobic microorganisms of the present invention will be explained in detail.
合成、又は天然の高分子物質或いは各種のプレポリマー
浴液に細菌のけん濁液を混合して包括固定ＩＬするに当
り、前記のようにして製造しｔ無機質担体上に担持され
たスルフォン化金属ツタロシアエン（以下触媒物質と略
記する）ｔ−ＩＳ２０ｖ／ｖ１％加え、膜状、ビーズ状
或いはキューブ状等任意の形に成形する。薄膜状に成形
し、ゲル内の触媒物質が有効にゲル外の酸素で運搬でき
るようにするのが好ましい。しかしながら、ビーズ状或
いはキューブ状に成形しても、触媒物質の濃度を高める
ことにエフ酸素の運搬は円滑に行なわれる。When a suspension of bacteria is mixed with a synthetic or natural polymeric substance or various prepolymer bath liquids for entrapping immobilization IL, the sulfonated metal produced as described above and supported on an inorganic carrier is used. Tutalocyanene (hereinafter abbreviated as catalyst substance) t-IS 20v/v1% is added and formed into any desired shape such as a film, bead, or cube. It is preferable to form the gel into a thin film so that the catalyst substance inside the gel can be effectively transported by oxygen outside the gel. However, even when formed into beads or cubes, transport of F-oxygen is carried out smoothly by increasing the concentration of the catalyst substance.
包括固定する際に用いる細菌の濃度に、遠心等で濃縮し
次もの、あるいは培養液そのもののいずれでもよいが、
濃縮した菌体を固定する方が、短期間に高い活性が得ら
れる。The concentration of bacteria used for comprehensive fixation can be either concentrated by centrifugation or the like, or the culture solution itself.
High activity can be obtained in a short period of time by fixing concentrated bacterial cells.
冥施例
ポリビニルアルコールを主鎖とする光硬、化性樹脂會用
い、偏性好気性菌である硝化細菌（菌体数１０７個／１
ＣＣ）ｔ−包括固定化した固定化物ｔ−１ｍ Ｘ ５
＋ｏ＋φの円板状に成形し几ゲル状物をみかけ充填率４
０％の割合で遮２図に示す流動床タイプの反応槽に充填
、し、２０℃でアンモニア合成磨水で通水しｔ場合の脱
アンモニアの連続実験結果を第１図に示す。Using a light hardening resin with polyvinyl alcohol as the main chain, nitrifying bacteria that are obligate aerobic bacteria (107 bacterial cells/1
CC) t-entrapping immobilized immobilized material t-1m x 5
Formed into a disk shape of +o+φ, a gel-like substance appears and the filling rate is 4.
Figure 1 shows the results of a continuous deammonification experiment in which the fluidized bed type reaction tank shown in Figure 2 was filled with a 0% blockage ratio and water was passed through with ammonia synthetic polishing water at 20°C.
なお、触媒物質としては、鉄フタロシアニン金２５重量
−の割合で骨炭粉末に吸着させ、！累算囲気中で７００
℃で焼成し友もの’（１″５％（”／／Ｖ）の割合で同
時に包括固定した。In addition, as a catalyst substance, iron phthalocyanine gold is adsorbed on bone char powder at a ratio of 25 parts by weight. 700 in total
It was fired at ℃ and simultaneously fixed at a rate of 1''5% (''//V).
また、比較の几めに硝フし細菌のみｔ包括固定化し几ゲ
ルについても同様に試験し几。For comparison, we also conducted the same test on a gel in which only the bacteria were immobilized using a nitrogen sieve.
第２図において、１は反応槽、２は原水導入管、５はブ
ロワ−１４に包括固定化物、５．６は隔壁を示す。In FIG. 2, 1 is a reaction tank, 2 is a raw water introduction pipe, 5 is a blower 14 containing the immobilized material, and 5.6 is a partition wall.
なお、この実施例において用い友アンモニア合成廃水の
組成は次のとおりであった−０（ＮＨ４）！８０４
１５ｍｔ／ｌ （Ｎとして）ＮａＨＯＯｓ
５００ ｍｆ／１ＫＨ１Ｐ０４
５０ ｍＷ ／ＬＣ＆０１Ｂ ” ２Ｈ１０４０
ＷＬｔ ／ＬＮａＯ２１８０ｍＷ ／Ｌ
Ｍｎ８０４ ・７ ＨｓＯ−５００ｍＷ／Ｌ第１図から
明らかなように、硝化細菌と触媒物質と共に包括固定化
させた本発明の包括固定化微生物を用いた場合、硝化ａ
菌のみを包括固定化したものに比し格段に優れている。The composition of the ammonia synthesis wastewater used in this example was as follows -0(NH4)! 804
15mt/l (as N) NaHOOs
500 mf/1KH1P04
50 mW /LC&01B” 2H1040
WLt /LNaO2 180mW /L Mn804 ・7 HsO-500mW/L As is clear from FIG.
It is much superior to those in which only bacteria are comprehensively immobilized.
以上説明しｆＩ−工うに、本発ｆ！Ａは微生物固定化法
の宿命的欠陥を抜本的に改善したものであり、微生物の
固定化法の適用範ｆｌｔ−拡大しうるものである。Having explained the above, the fI-work is now complete! A is a method that fundamentally improves the fatal flaws of the microorganism immobilization method, and can expand the scope of application of the microorganism immobilization method.
第１図は本発明による包括固定化物の効果金示す為の図
であり、ｇ２図は実施例において用いた反応槽の概略図
である。
１・・反応槽、２・・原水導入管、３・・プロワ−１４
・・包括固定化物FIG. 1 is a diagram showing the effect of entrapping immobilization according to the present invention, and FIG. g2 is a schematic diagram of a reaction tank used in Examples. 1. Reaction tank, 2. Raw water introduction pipe, 3. Prower 14
・Comprehensive immobilized product
Claims (1)
、空気中又は水中の酸素を水中に還元溶解する能力を有
するスルフォン化した金属フタロシアニンの溶液を吸着
性無機質粉末に含浸させ、不活性ガス雰囲気中において ３００℃〜８００℃の温度範囲で焼成した後好気性微生
物と共に包括固定することを特徴とする好気性微生物の
包括固定方法。[Claims] 1. In entrapping and immobilizing aerobic microorganisms with a polymeric substance, a solution of sulfonated metal phthalocyanine having the ability to reduce and dissolve oxygen in the air or water is used as an adsorbent inorganic powder. A method for comprehensive immobilization of aerobic microorganisms, which comprises impregnating the aerobic microorganisms with the aerobic microorganisms, calcining the mixture in an inert gas atmosphere at a temperature range of 300° C. to 800° C., and then entrapping the aerobic microorganisms together with the aerobic microorganisms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59190573A JPS6170987A (en) | 1984-09-13 | 1984-09-13 | Method of inclusive immobilization for aerobic bacterium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59190573A JPS6170987A (en) | 1984-09-13 | 1984-09-13 | Method of inclusive immobilization for aerobic bacterium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6170987A true JPS6170987A (en) | 1986-04-11 |
Family
ID=16260308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59190573A Pending JPS6170987A (en) | 1984-09-13 | 1984-09-13 | Method of inclusive immobilization for aerobic bacterium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6170987A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007268368A (en) * | 2006-03-30 | 2007-10-18 | Hitachi Plant Technologies Ltd | Entrapping immobilization carrier and wastewater treatment system using it |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5914278A (en) * | 1982-07-08 | 1984-01-25 | アンプ・インコ−ポレ−テツド | Method and device for centering electric connector |
-
1984
- 1984-09-13 JP JP59190573A patent/JPS6170987A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5914278A (en) * | 1982-07-08 | 1984-01-25 | アンプ・インコ−ポレ−テツド | Method and device for centering electric connector |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007268368A (en) * | 2006-03-30 | 2007-10-18 | Hitachi Plant Technologies Ltd | Entrapping immobilization carrier and wastewater treatment system using it |
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