JPH0534955B2 - - Google Patents
Info
- Publication number
- JPH0534955B2 JPH0534955B2 JP7663086A JP7663086A JPH0534955B2 JP H0534955 B2 JPH0534955 B2 JP H0534955B2 JP 7663086 A JP7663086 A JP 7663086A JP 7663086 A JP7663086 A JP 7663086A JP H0534955 B2 JPH0534955 B2 JP H0534955B2
- Authority
- JP
- Japan
- Prior art keywords
- acetobacterium
- acetic acid
- mutant strain
- carbon dioxide
- strain
- 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.)
- Expired - Lifetime
Links
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 241000093709 Acetobacterium sp. Species 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 7
- 238000012258 culturing Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 238000012136 culture method Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 241001468161 Acetobacterium Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZEMWIYASLJTEHQ-UHFFFAOYSA-J aluminum;sodium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZEMWIYASLJTEHQ-UHFFFAOYSA-J 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
（産業上の利用分野）
この発明は、アセトバクテリウム・エスピーNo.
446（Acetobacterium sp No.446）の新規な変異
株アセトバクテリウム・エスピーMA−１を用い
て二酸化炭素と水素から酢酸を製造する方法に関
するものである。酢酸は食品用あるいは工業用原
料の分野で用いられている。
（従来技術）
水素と二酸化炭素とを資化して、酢酸を蓄積す
る微生物として、アセトバクテリウム・エスピー
No.446（微工研菌寄第7017号 FERM Ｐ−7017）
がある。この菌が生育するのは中性のPH領域であ
り、PH5.8の液体培地中では、22日間培養しても
ほとんど生育しない。中性領域で培養すると生成
物である酢酸が液体培地のPHを低下させ、生育を
停止するので、酸を水酸化ナトリウムのような塩
基で中和しないと発酵を継続できない。この中和
により発酵を継続させた場合、酢酸を酢酸塩とし
て取り出し、次いで遊離酸に再生するという複雑
な工程が必要である。
（発明が解決しようとする問題点）
本発明の目的は、アセトバクテリウム・エスピ
ーNo.446がほとんど生育できないPH5.8以下の液体
培地で生育するアセトバクテリウム・エスピーNo.
446の変異株を得て、二酸化炭素と水素を基質と
する酢酸の新規な製造方法である。本発明者ら
は、アセトバクテリウム・エスピーNo.446をPH5.8
の酸性培地に馴化させることによつて、PH5.8以
下でも生育する菌体を得ることに成功し、本発明
に到達した。
（問題点を解決するための手段）
本発明は、二酸化炭素と水素を基質として5.8
のPHで少なくとも0.50day-1の比増殖速度で生育
できるアセトバクテリウム・エスピーNo.446の新
規な変異株アセトバクテリウム・エスピーMA−
１を培養し、生成蓄積された酢酸を回収すること
を特徴とする酢酸の製造方法である。
本発明で用いられる微生物は、親株がほとんど
生育できない5.8のPHで、少なくとも約0.50day-1
の比増殖速度で生育することができるという点
で、アセトバクテリウム・エスピーNo.446の変異
株と考えられる。次にアセトバクテリウム・エス
ピーNo.446の変異株アセトバクテリウム・エスピ
ーMA−１の創製法を示す。
（創製法）
本変異株は下記の方法で分離することができ
る。すなわち第１表に示す。液体培地を滅菌後、
初発PH7.3の液体培地をアセトバクテリウム・エ
スピーNo.446の前培養液とする。次に、同じ組成
でPHのみを若干低く調整した培地に上記前培養液
を接種し、気相を水素・二酸化炭素を含む除菌ガ
スで置換後培養する。菌の生育がみられた場合、
更にPHのみをより低く調整した培地に継代し、同
様に培養を続ける。このように、順次低いPHの培
地で培養し、最終的に初発PH5.8で培養し、本変
異株を得ることができる。本菌の培養後のPHは
5.1であつた。
(Industrial Application Field) This invention is directed to Acetobacterium sp.
The present invention relates to a method for producing acetic acid from carbon dioxide and hydrogen using a novel mutant strain of Acetobacterium sp No. 446, Acetobacterium sp. MA-1. Acetic acid is used in the fields of food and industrial raw materials. (Prior art) Acetobacterium sp. is a microorganism that assimilates hydrogen and carbon dioxide and accumulates acetic acid.
No.446 (FERM P-7017)
There is. This bacterium grows in a neutral pH range, and in a liquid medium with a pH of 5.8, it hardly grows even after 22 days of culture. When cultured in a neutral region, the product acetic acid lowers the pH of the liquid medium and stops growth, so fermentation cannot continue unless the acid is neutralized with a base such as sodium hydroxide. If fermentation is allowed to continue through this neutralization, a complicated process is required in which acetic acid is extracted as acetate and then regenerated into free acid. (Problems to be Solved by the Invention) The purpose of the present invention is to treat Acetobacterium sp. No. 446, which grows in a liquid medium with a pH of 5.8 or lower, where Acetobacterium sp. No. 446 can hardly grow.
This is a novel method for producing acetic acid using carbon dioxide and hydrogen as substrates by obtaining 446 mutant strains. The present inventors have developed Acetobacterium sp. No. 446 at pH 5.8.
By acclimating the microorganisms to an acidic medium, we succeeded in obtaining microbial cells that can grow even at pH 5.8 or lower, leading to the present invention. (Means for solving the problems) The present invention uses carbon dioxide and hydrogen as substrates to
A novel mutant strain of Acetobacterium sp. No. 446, Acetobacterium sp. MA-, which can grow at a specific growth rate of at least 0.50 day -1 at a pH of
This is a method for producing acetic acid, which is characterized by culturing A. 1 and collecting the produced and accumulated acetic acid. The microorganism used in the present invention has a pH of 5.8, at which the parent strain can hardly grow, and has a pH of at least about 0.50 day -1.
It is considered to be a mutant strain of Acetobacterium sp. No. 446 in that it can grow at a specific growth rate of . Next, a method for creating Acetobacterium sp. MA-1, a mutant strain of Acetobacterium sp. No. 446, will be described. (Creation method) This mutant strain can be isolated by the following method. That is, as shown in Table 1. After sterilizing the liquid medium,
Use the liquid medium with an initial pH of 7.3 as the preculture solution for Acetobacterium sp. No. 446. Next, the above preculture solution is inoculated into a medium with the same composition but with only the pH adjusted slightly lower, and the culture is performed after replacing the gas phase with a sterilizing gas containing hydrogen and carbon dioxide. If bacterial growth is observed,
Furthermore, only the PH is subcultured into a medium adjusted to be lower, and culture is continued in the same manner. In this way, the present mutant strain can be obtained by culturing in successively lower pH media and finally culturing at an initial pH of 5.8. The pH after culturing this bacterium is
It was 5.1.
【表】【table】
【表】【table】
【表】【table】
【表】
さらにこの菌株は、工業技術院微生物工業技術
研究所に「微工研菌寄第8676号（FERMP−
8676）として寄託した」
（培養方法）
培養方法は原則的には、一般の微生物の場合と
同様であるが、酸素の混入を防ぐことが必要であ
り、実験室的には、ゴム栓等で密栓した培養器中
で、静置あるいは振盪する方法が用いられる。や
や大きい規模では、通常用いられる醗酵槽がその
まま利用でき、装置内の酸素は、窒素などの不活
性気体あるいは原料気体などで置換することによ
り嫌気的な雰囲気をつくることが可能である。醗
酵槽の形式は特に問わないが、普通に使用される
撹拌混合槽のほか、一段あるいは多段の気泡塔型
やドラフトチユーブ型の醗酵槽も利用できる。
培養に用いる炭素源は、通常、二酸化炭素ガス
として供給するが、培地中に溶解二酸化炭素ある
いは炭酸塩、炭酸水素塩として加えることもでき
る。窒素源は塩化アンモニウムのごときアンモニ
ウム塩や硝酸ソーダのような硝酸塩のごとく、通
常の醗酵に用いうる各種の窒素化合物を用いるこ
とができる。
その他必要に応じ、リン酸二水素カリ、硫酸マ
グネシウム、硫酸マンガン、塩化ナトリウム、硫
酸鉄、塩化コバルト、塩化カルシウム、硫酸亜
鉛、硫酸銅、明ばん、モリブデン酸ソーダ、硼酸
などの無機化合物、あるいはビオチンや酵母エキ
スなどのビタミン類を添加することは、通常行な
われる通りである。
（発明の効果）
変異株と親株をPHの相異する培地で培養して、
８日目の生育状況で変異株と親株の生育のPH領域
を比較すると、第１図に示すとおりであり、変異
株は親株に比べて生育PH領域が0.7〜0.8酸側に移
動していることがわかる。PH6.3以下での酸性側
では変異株の方が親株よりも生育が優れている。
特に、PH5.8における生育は親株よりも変異株の
方がきわめて良い。PH5.8で培養した時、変異株
は親株に比べて比増殖速度が20倍以上になつてい
る。PH5.8の培養液の最終PHは5.1であつた。以上
のことから、本変異株を利用することにより、酢
酸を酢酸塩として取り出して、次に遊離酸に再生
する必要がなくなる。
（実施例）
第１表に示す液体培地を試験管に５ml分注後、
滅菌してPHを5.8に調整した。そして取得した変
異株アセトバクテリウム・エスピーMA−１の前
培養液を200μ接種し、気相を水素（67％）、二
酸化炭素（33％）を含む除菌ガスに置換した後、
30℃で静置培養した。この時の比増殖速度は
0.53day-1であり、14日間培養後の酢酸蓄積は0.2
ｇ／であつた。そして、培養液の最終PHは5.1
であつた。
（比較例）
親株を初発PH5.8の液体培地で30℃、14日間静
置培養を行なつた。この時酢酸酸生成は認められ
なかつた。また、最終PHは5.8であつた。[Table] Furthermore, this strain was submitted to the Institute of Microbial Technology, Agency of Industrial Science and Technology as “FERMP-
8676) (Culture method) The culture method is basically the same as that for general microorganisms, but it is necessary to prevent oxygen from entering, and in the laboratory, it is A method of standing or shaking in a tightly closed culture vessel is used. On a slightly larger scale, a commonly used fermenter can be used as is, and an anaerobic atmosphere can be created by replacing the oxygen in the device with an inert gas such as nitrogen or a raw material gas. The type of fermentation tank is not particularly limited, but in addition to commonly used stirring and mixing tanks, single- or multi-stage bubble column or draft tube fermentation tanks can also be used. The carbon source used for culture is usually supplied as carbon dioxide gas, but it can also be added to the medium as dissolved carbon dioxide, carbonate, or bicarbonate. As the nitrogen source, various nitrogen compounds that can be used in normal fermentation can be used, such as ammonium salts such as ammonium chloride and nitrates such as sodium nitrate. Other inorganic compounds such as potassium dihydrogen phosphate, magnesium sulfate, manganese sulfate, sodium chloride, iron sulfate, cobalt chloride, calcium chloride, zinc sulfate, copper sulfate, alum, sodium molybdate, boric acid, or biotin. It is common practice to add vitamins such as yeast extract and yeast extract. (Effect of the invention) By culturing the mutant strain and the parent strain in media with different pH,
Comparing the growth PH range of the mutant strain and the parent strain on the 8th day, as shown in Figure 1, the growth PH range of the mutant strain has shifted to the 0.7 to 0.8 acid side compared to the parent strain. I understand that. On the acidic side at pH 6.3 or below, the mutant strain grows better than the parent strain.
In particular, the growth of the mutant strain at pH 5.8 is significantly better than that of the parent strain. When cultured at pH 5.8, the specific growth rate of the mutant strain was more than 20 times that of the parent strain. The final pH of the culture solution with pH 5.8 was 5.1. From the above, by using this mutant strain, there is no need to extract acetic acid as acetate and then regenerate it into free acid. (Example) After dispensing 5 ml of the liquid medium shown in Table 1 into test tubes,
It was sterilized and the pH was adjusted to 5.8. After inoculating 200μ of the preculture solution of the obtained mutant strain Acetobacterium sp. MA-1 and replacing the gas phase with a sterilizing gas containing hydrogen (67%) and carbon dioxide (33%),
It was statically cultured at 30°C. The specific growth rate at this time is
0.53day -1 , and the acetic acid accumulation after 14 days of culture is 0.2
It was g/. And the final pH of the culture solution is 5.1
It was hot. (Comparative Example) The parent strain was statically cultured at 30°C for 14 days in a liquid medium with an initial pH of 5.8. At this time, no acetic acid production was observed. Moreover, the final pH was 5.8.
第１図はアセトバクテリウム・エスピーNo.446
株と変異株アセトバクテリウム・エスピーMA−
１の培養８日目における生育状況を示すグラフで
ある。第２図はPH5.8の培地における変異株アセ
トバクテリウム・エスピーMA−１の増殖の経時
変化を示すグラフである。
Figure 1 is Acetobacterium sp. No.446
Strains and mutants Acetobacterium sp. MA-
1 is a graph showing the growth status on the 8th day of culturing No. 1. FIG. 2 is a graph showing changes over time in the growth of the mutant strain Acetobacterium sp. MA-1 in a pH 5.8 medium.
Claims (1)
少なくとも0.50day-1の比増殖速度で生育できる
アセトバクテリウム・エスピーNo.446の新規な変
異株を培養し、生成蓄積された酢酸を回収するこ
とを特徴とする酢酸の製造方法。1. Cultivate a new mutant strain of Acetobacterium sp. No. 446 that can grow at a specific growth rate of at least 0.50 day -1 at a pH of 5.8 using carbon dioxide and hydrogen as substrates, and collect the acetic acid produced and accumulated. A method for producing acetic acid, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7663086A JPS62236490A (en) | 1986-04-04 | 1986-04-04 | Production of acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7663086A JPS62236490A (en) | 1986-04-04 | 1986-04-04 | Production of acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62236490A JPS62236490A (en) | 1987-10-16 |
| JPH0534955B2 true JPH0534955B2 (en) | 1993-05-25 |
Family
ID=13610688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7663086A Granted JPS62236490A (en) | 1986-04-04 | 1986-04-04 | Production of acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62236490A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5229904B2 (en) * | 2009-05-27 | 2013-07-03 | 独立行政法人産業技術総合研究所 | Method for producing lactic acid and / or acetic acid by halophilic bacteria |
-
1986
- 1986-04-04 JP JP7663086A patent/JPS62236490A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62236490A (en) | 1987-10-16 |
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