JPH0583230B2 - - Google Patents
Info
- Publication number
- JPH0583230B2 JPH0583230B2 JP62319324A JP31932487A JPH0583230B2 JP H0583230 B2 JPH0583230 B2 JP H0583230B2 JP 62319324 A JP62319324 A JP 62319324A JP 31932487 A JP31932487 A JP 31932487A JP H0583230 B2 JPH0583230 B2 JP H0583230B2
- Authority
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- Prior art keywords
- gas
- draft tube
- liquid
- vessel
- porous
- 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/232—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles
- B01F23/2323—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles by circulating the flow in guiding constructions or conduits
- B01F23/23231—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles by circulating the flow in guiding constructions or conduits being at least partially immersed in the liquid, e.g. in a closed circuit
- B01F23/232311—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles by circulating the flow in guiding constructions or conduits being at least partially immersed in the liquid, e.g. in a closed circuit the conduits being vertical draft pipes with a lower intake end and an upper exit end
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/30—Driving arrangements; Transmissions; Couplings; Brakes
- B01F35/32—Driving arrangements
- B01F35/32005—Type of drive
- B01F35/3203—Gas driven
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/18—Flow directing inserts
- C12M27/22—Perforated plates, discs or walls
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/06—Nozzles; Sprayers; Spargers; Diffusers
- C12M29/08—Air lift
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/30—Driving arrangements; Transmissions; Couplings; Brakes
- B01F35/32—Driving arrangements
- B01F35/32005—Type of drive
- B01F35/32015—Flow driven
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Sustainable Development (AREA)
- Biomedical Technology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Activated Sludge Processes (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、好気性発酵や排水処理における曝気
等の微生物反応プロセス並びに液相酸化に用いら
れる気泡塔型反応装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a bubble column reactor used in microbial reaction processes such as aerobic fermentation and aeration in wastewater treatment, and liquid phase oxidation.
気泡塔型反応装置は、その構造が簡単で機械的
駆動部を持たないので腐食性の液や高圧の反応に
適し、広範に使用されている。なかでも容器内に
上下端を開口させたドラフトチユーブを設け、該
ドラフトチユーブ下方の容器底部に設けたガス分
散器からガスをドラフトチユーブ内に連続的に吹
き込み、容器内の反応液をドラフトチユーブの内
外部の水圧差により循環させて気液接触を行う気
泡塔型反応装置は、比較的小さい動力で良好な液
混合を行えるので工業的な重要性が増加してい
る。
Bubble column reactors have a simple structure and do not have mechanical driving parts, so they are suitable for reactions with corrosive liquids and high pressure, and are widely used. In particular, a draft tube with open upper and lower ends is provided in the container, and gas is continuously blown into the draft tube from a gas distributor provided at the bottom of the container below the draft tube, and the reaction liquid in the container is transferred to the draft tube. Bubble column reactors, which perform gas-liquid contact by circulating water using a water pressure difference between the inside and outside, are gaining industrial importance because they can perform good liquid mixing with relatively little power.
ドラフトチユーブを備えた気泡塔型反応装置
は、上記のような利点を有するが、容器の大型化
に伴つて通気動力も大きくなり、またドラフトチ
ユーブを上昇する気泡の径がしだいに大きくな
り、かなりの量が上方へ放出されるので、気液混
合（即ち物質移動性）の面でさらに改善が望まれ
ている。
Bubble column reactors equipped with draft tubes have the above-mentioned advantages, but as the size of the container increases, the aeration power also increases, and the diameter of the bubbles rising through the draft tube gradually increases, resulting in considerable Since a large amount of gas is discharged upward, further improvement is desired in terms of gas-liquid mixing (i.e., mass transfer).
本発明は、上記の点に鑑み開発されたもので、
物質移動係数および気液界面積が大きく、容器全
体における液の混合が極めて速い気泡塔型反応装
置を得ることを目的としている。 The present invention was developed in view of the above points, and
The objective is to obtain a bubble column reactor that has a large mass transfer coefficient and a large gas-liquid interfacial area, and in which mixing of liquids throughout the container is extremely rapid.
上記目的を達成するために、本発明は、容器内
に上下端を開口させたドラフトチユーブを設け、
該ドラフトチユーブの下方から、ガスをドラフト
チユーブ内に連続的に吹き込み、容器内の反応液
をドラフトチユーブ内外部の水圧差により循環さ
せて気液接触を行う気泡塔型反応装置において、
前記ドラフトチユーブの少なくとも一部を多孔状
としたことを特徴とする。
In order to achieve the above object, the present invention provides a draft tube with open upper and lower ends in a container,
In a bubble column reactor that performs gas-liquid contact by continuously blowing gas into the draft tube from below the draft tube and circulating the reaction liquid in the container by a water pressure difference between the inside and outside of the draft tube,
At least a portion of the draft tube is porous.
上記の如く気泡塔型反応装置を構成することに
より、ドラフトチユーブ内を上昇するガスの一部
がドラフトチユーブの多孔部分を通過して環状部
へ流れ出し、この通過の際に気泡が微細化され、
さらに、多孔部分を出た微細な気泡が、ドラフト
チユーブの外周を下降する気液流れと向流接触し
て激しく混合するので、極めて短時間に気液混合
が行われる。
By configuring the bubble column reactor as described above, a part of the gas rising in the draft tube passes through the porous part of the draft tube and flows out to the annular part, and during this passage, the bubbles are made fine.
Furthermore, the fine air bubbles exiting the porous portion come into countercurrent contact with the gas-liquid flow descending around the outer periphery of the draft tube and mix vigorously, so that gas-liquid mixing is achieved in an extremely short time.
以下本発明を図面に基づいて説明する。 The present invention will be explained below based on the drawings.
第１図に示すように、本発明の気泡塔型反応装
置１は、円筒状の容器２内に、上下端を開口させ
た多孔状のドラフトチユーブ３を設けている。こ
のドラフトチユーブ３は、その径が容器２の径に
対してほぼ0.6程度であり、金網またはパンチン
グメタルを筒状に形成したものである。 As shown in FIG. 1, the bubble column reactor 1 of the present invention has a cylindrical container 2 provided with a porous draft tube 3 whose upper and lower ends are open. The draft tube 3 has a diameter approximately 0.6 times the diameter of the container 2, and is formed of wire mesh or punched metal into a cylindrical shape.
多孔状とする範囲は、ドラフトチユーブ３の全
長でなくてもよいが、部分的に多孔状にする場合
は、半分以上を多孔状とすることが望ましい。な
お、ドラフトチユーブ３下方の容器２底部にはブ
ロワに連通するガス分散器４が設けられ、容器２
の周壁には液供給口５、液取出口６、ガス抜孔７
がそれぞれ配設されている。 The range to be made porous does not have to cover the entire length of the draft tube 3, but if it is partially made porous, it is desirable that at least half of the draft tube 3 be made porous. A gas distributor 4 communicating with the blower is provided at the bottom of the container 2 below the draft tube 3.
A liquid supply port 5, a liquid outlet 6, and a gas vent hole 7 are provided on the peripheral wall of the
are arranged respectively.
本発明者等は、このように多孔状のドラフトチ
ユーブを備えた気泡塔型反応装置の流動特性に及
ぼす装置因子の影響について多くの実験を行なつ
たが、それによれば、ドラフトチユーブの形態と
して、多孔状部分の範囲を半分以上、また多孔部
の孔径を１〜５mm、開口率を30〜60％としたとき
に最も好ましい結果が得られた。 The present inventors conducted many experiments on the influence of device factors on the flow characteristics of a bubble column reactor equipped with a porous draft tube, and according to the experiments, it was found that the shape of the draft tube The most favorable results were obtained when the range of the porous portion was half or more, the pore diameter of the porous portion was 1 to 5 mm, and the aperture ratio was 30 to 60%.
以下に本発明の多孔状ドラフトチユーブについ
て行つた実験を図面を参照しながら説明する。 Experiments conducted on the porous draft tube of the present invention will be described below with reference to the drawings.
実験に使用した気泡塔型反応装置１は、第２図
に示す如きもので、内径164mm、高さ2500mmの透
明アクリル樹脂製の容器２内に、内径94mm、高さ
2000mmのドラフトチユーブ３を容器底面から50mm
浮かせて設置したものであり、容器２壁には液循
環流量測定用のトレーサ注入口８を設けた。
The bubble column reactor 1 used in the experiment is as shown in Figure 2, with a container 2 made of transparent acrylic resin having an inner diameter of 164 mm and a height of 2500 mm, and a container with an inner diameter of 94 mm and a height of 2,500 mm.
2000mm draft tube 3 50mm from the bottom of the container
It was installed floating, and a tracer injection port 8 for measuring the liquid circulation flow rate was provided on the wall of the container 2.
ドラフトチユーブ３の多孔部３ａには、金網を
用い、気体は空気、液体は水道水または亜硫酸ナ
トリウム水溶液を用いた。 A wire mesh was used for the porous portion 3a of the draft tube 3, air was used as the gas, and tap water or an aqueous sodium sulfite solution was used as the liquid.
実験は、ドラフトチユーブ３の全長に対する多
孔部３ａの割合η及び目開きｄの種々組合せにつ
いて、流動状態の観察及びガスホールドアツプε
の測定を行つた。亜硫酸ナトリウム水溶液の場合
には、出口ガスの酸素濃度を分析し、液相物質移
動容量係数KLａを算出した。なお、液温は27±
１℃とした。 The experiment was conducted by observing the flow state and adjusting the gas hold-up ε for various combinations of the ratio η of the porous portion 3a to the total length of the draft tube 3 and the opening d.
Measurements were made. In the case of a sodium sulfite aqueous solution, the oxygen concentration of the outlet gas was analyzed and the liquid phase mass transfer capacity coefficient K La was calculated. In addition, the liquid temperature is 27±
The temperature was set at 1°C.
第３図は、多孔部３ａの割合ηを0.5とし、通
気速度WG（容器断面積基準空塔速度）を変えた場
合の気液の流動状態を示す説明図である。 FIG. 3 is an explanatory diagram showing the flow state of gas and liquid when the ratio η of the porous portions 3a is 0.5 and the ventilation rate W G (superficial velocity based on the cross-sectional area of the container) is changed.
ガス分散器４からガスをドラフトチユーブ３内
に連続的に吹き込むと、ガスは細かい気泡となつ
てドラフトチユーブ３内を速い流速を保つて上昇
する。 When gas is continuously blown into the draft tube 3 from the gas distributor 4, the gas becomes fine bubbles and rises inside the draft tube 3 while maintaining a high flow rate.
このときドラフトチユーブ３の多孔部３ａから
上昇するガスの一部がドラフトチユーブ３の外周
の環状部へ流れ、多孔部３ａを通過する際に気泡
が微細化される。そして、多孔部３ａを出た微細
な気泡は、ドラフトチユーブ３の外周を下降する
気液流れと接触して激しく混合する。 At this time, a portion of the gas rising from the porous portion 3a of the draft tube 3 flows to the annular portion on the outer periphery of the draft tube 3, and bubbles are made fine when passing through the porous portion 3a. Then, the fine air bubbles exiting the porous portion 3a come into contact with the gas-liquid flow descending around the outer periphery of the draft tube 3, and mix vigorously.
通気速度WGの増加に伴い、ガスが環状部へ出
る頻度は高くなるが、上方からの気液の下降流量
が増大するため、気液が激しく混合するゾーンＺ
が短くなることが観察された。 As the ventilation speed W G increases, the frequency of gas exiting to the annular portion increases, but the descending flow rate of gas and liquid from above increases, resulting in a zone Z where gas and liquid mix intensely.
was observed to be shorter.
第４図は、液体が亜硫酸ナトリウム水溶液を用
い、多孔部３ａの目開きｄを３mmとして、多孔部
３ａの割合ηを変えた場合の通気速度WGに対す
るガスホールドアツプεと液相物質移動容量係数
KLａを示すものである。 Figure 4 shows gas hold up ε and liquid phase mass transfer capacity versus ventilation velocity W G when the liquid is a sodium sulfite aqueous solution, the opening d of the porous portions 3a is 3 mm, and the ratio η of the porous portions 3a is varied. coefficient
It shows K La .
ガスホールドアツプεは、η＝０の場合を含め
て明確な差異は認められない。また、ドラフトチ
ユーブ３上端で測定した循環液流量は、同一通気
速度WGにおいては、ηによらず一定であつた。
なお、水道水の場合も同様であつた。 No clear difference is observed in the gas hold up ε, including the case where η=0. Further, the circulating fluid flow rate measured at the upper end of the draft tube 3 was constant regardless of η at the same ventilation speed W G.
The same was true for tap water.
一方液相物質移動容量係数KLａは、ηが大き
いほど高くなつている。このKLａは、気液界面
積に比例するので、ηが大きくなるにつれて多孔
部３ａによる気泡の微細化効果がより大きく現
れ、平均気泡径が小さくなるものと思われる。 On the other hand, the liquid phase mass transfer capacity coefficient K La becomes higher as η becomes larger. Since K La is proportional to the gas-liquid interface area, it is thought that as η increases, the effect of making the bubbles smaller by the porous portions 3a becomes greater, and the average bubble diameter becomes smaller.
また同一WGにおいては、ηが大きくなるほど、
環状部にて気液が激しく混合するゾーンが長くな
ることが観察された。 Also, for the same W G , the larger η becomes,
It was observed that the zone where gas and liquid were intensively mixed became longer in the annular part.
第５図は、η＝0.5として、目開きｄを変えた
場合の通気速度WGに対するガスホールドアツプ
εと液相物質移動容量係数KLａを示すものであ
る。 FIG. 5 shows the gas hold-up ε and the liquid phase mass transfer capacity coefficient K L a with respect to the ventilation rate W G when the opening d is changed with η = 0.5.
ガスホールドアツプεは、いずれの目開きｄに
おいてもほとんど同じであるが、液相物質移動容
量係数KLａは、ｄ＝６mmでやや低く、この時に
は気泡径が大きいように観察された。このことに
より、目開きｄは比較的小径において気泡の微細
化効果が大きいと思われる。 Although the gas hold up ε was almost the same at any opening d, the liquid phase mass transfer capacity coefficient K La was slightly lower at d = 6 mm, and the bubble diameter was observed to be large at this time. From this, it seems that the effect of making the bubbles finer is greater when the opening d is relatively small.
第６図は、通気速度WGを変化させて混合時間
tnを測定したものである。混合時間tnは、トレー
サ注入口８から塩水を注水し、導電率計センサか
らの出力が増加して一定値になるまでの時間とし
た。多孔状ドラフトチユーブを設けたものはWG
が小さくても極めて短時間で混合することが解つ
た。 Figure 6 shows the mixing time by changing the aeration rate WG.
This is the measurement of t n . The mixing time t n was defined as the time required for the salt water to be injected from the tracer injection port 8 and for the output from the conductivity sensor to increase and reach a constant value. Those with a porous draft tube are W G
It was found that even if the amount is small, mixing takes place in an extremely short time.
以上のように本発明は、多孔状のドラフトチユ
ーブを用いたことにより、多孔部を通過する微細
な気泡を生成せしめるとともに、ドラフトチユー
ブ外周の下降気液流と向流接触を行わせしめるの
で、従来の無孔のドラフトチユーブを用いたもの
に比べ、物質移動係数および気液界面積が大きく
容器全体における液の混合が極めて速い反応装置
となり、とくに微生物の好気培養装置塔で、酸素
要求量の多い発酵に好適であるほか、通気動力の
軽減や装置の小型化も期待できる。
As described above, the present invention uses a porous draft tube to generate fine air bubbles that pass through the porous portion and to make countercurrent contact with the descending gas-liquid flow around the outer circumference of the draft tube. Compared to a non-porous draft tube, the mass transfer coefficient and gas-liquid interface area are large, and the mixing of the liquid throughout the container is extremely fast. In addition to being suitable for large-scale fermentation, it can also be expected to reduce ventilation power and downsize the equipment.
第１図は本発明の気泡塔型反応装置を示す概略
図、第２図は実験を行つた装置を示す概略図、第
３図はガス量の変化による装置内の気液の流動状
態を示す説明図、第４図は多孔部の割合を変化さ
せた場合のガスの通気速度に対するガスホールド
アツプ及び液相物質移動容量係数の変化を示す
図、第５図は目開きを変化させた場合のガスの通
気速度に対するガスホールドアツプ及び液相物質
移動容量係数の変化を示す図、第６図はドラフト
チユーブの形状を変化させた場合のガスの通気速
度と混合時間の関係を示す図である。
２……容器、３……ドラフトチユーブ、３ａ…
…多孔部、４……ガス分散器、５……液供給口、
６……液取出口、７……ガス抜孔、８……トレー
サ注入口、ｄ……目開き、KLａ……液相物質移
動容量係数、tn……混合時間、WG……通気速度、
ε……ガスホールドアツプ、η……多孔部の割
合。
Figure 1 is a schematic diagram showing the bubble column reactor of the present invention, Figure 2 is a schematic diagram showing the equipment in which the experiment was conducted, and Figure 3 is a diagram showing the flow state of gas and liquid in the equipment due to changes in gas amount. An explanatory diagram, Figure 4 is a diagram showing the change in gas hold up and liquid phase mass transfer capacity coefficient with respect to gas ventilation rate when the proportion of porous parts is changed, and Figure 5 is a diagram showing the change in gas hold up and liquid phase mass transfer capacity coefficient when the opening is changed. FIG. 6 is a diagram showing the change in gas hold-up and liquid phase mass transfer capacity coefficient with respect to the gas aeration rate, and FIG. 6 is a diagram showing the relationship between the gas aeration rate and the mixing time when the shape of the draft tube is changed. 2...Container, 3...Draft tube, 3a...
...Porous portion, 4...Gas disperser, 5...Liquid supply port,
6...Liquid outlet, 7...Gas vent hole, 8...Tracer inlet, d...Mesh opening, K L a...Liquid phase mass transfer capacity coefficient, tn ...Mixing time, W G ...Ventification speed,
ε...Gas hold up, η...Percentage of porous parts.
Claims (1)
ブを設け、該ドラフトチユーブの下方から、ガス
をドラフトチユーブ内に連続的に吹き込み、容器
内の反応液をドラフトチユーブ内外部の水圧差に
より循環させて気液接触を行う気泡塔型反応装置
において、前記ドラフトチユーブの少なくとも一
部を多孔状としたことを特徴とする気泡塔型反応
装置。1. A draft tube with open upper and lower ends is provided in the container, gas is continuously blown into the draft tube from below, and the reaction liquid in the container is circulated by the water pressure difference between the inside and outside of the draft tube. 1. A bubble column reactor that performs gas-liquid contact, characterized in that at least a portion of the draft tube is porous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62319324A JPH01160476A (en) | 1987-12-16 | 1987-12-16 | Bubble tower-type reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62319324A JPH01160476A (en) | 1987-12-16 | 1987-12-16 | Bubble tower-type reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01160476A JPH01160476A (en) | 1989-06-23 |
| JPH0583230B2 true JPH0583230B2 (en) | 1993-11-25 |
Family
ID=18108922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62319324A Granted JPH01160476A (en) | 1987-12-16 | 1987-12-16 | Bubble tower-type reactor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01160476A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2822075B2 (en) * | 1990-01-24 | 1998-11-05 | 川崎重工業株式会社 | Culture method and device |
| US5672507A (en) * | 1991-01-31 | 1997-09-30 | Boehringer Ingelheim Animal Health, Inc. | Apparatus for the surface culture of nucleated cells and cell culture dependent substances |
| FR2700714A1 (en) * | 1993-01-28 | 1994-07-29 | Atochem Elf Sa | New photochemical reactors and processes using them in particular halogenation process of alkylbenzenes. |
| KR100302458B1 (en) * | 1999-07-09 | 2001-09-22 | 박호군 | Method for supplying hydrofluoric acid in the synthesis of cfc or hcfc |
| US7399882B2 (en) * | 2004-09-02 | 2008-07-15 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7371894B2 (en) * | 2004-09-02 | 2008-05-13 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7572936B2 (en) * | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7910769B2 (en) * | 2004-09-02 | 2011-03-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| JP5274282B2 (en) * | 2009-01-30 | 2013-08-28 | 日本リファイン株式会社 | Gas-liquid reaction method and gas-liquid reaction apparatus using microbubbles |
-
1987
- 1987-12-16 JP JP62319324A patent/JPH01160476A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01160476A (en) | 1989-06-23 |
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