JPH0975473A - Dechlorination method for aromatic chloride with formate using palladium and phase-transfer catalyst - Google Patents
Dechlorination method for aromatic chloride with formate using palladium and phase-transfer catalystInfo
- Publication number
- JPH0975473A JPH0975473A JP7260736A JP26073695A JPH0975473A JP H0975473 A JPH0975473 A JP H0975473A JP 7260736 A JP7260736 A JP 7260736A JP 26073695 A JP26073695 A JP 26073695A JP H0975473 A JPH0975473 A JP H0975473A
- Authority
- JP
- Japan
- Prior art keywords
- formate
- phase
- solution
- prescribed
- chloride
- 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.)
- Granted
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 title claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 18
- 238000006298 dechlorination reaction Methods 0.000 title abstract description 5
- 229910052763 palladium Inorganic materials 0.000 title description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- -1 for example Chemical compound 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims abstract description 3
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 claims abstract description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000003863 metallic catalyst Substances 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】 本発明は、世界的な環境汚染物
質とされているＰＣＢのような、難分解性芳香族塩化物
の簡便で危険性の少ない、経済的な、しかも穏和な条件
で行える脱塩素化法に関するものである。The present invention relates to a simple, low-risk, economical and mild condition for hardly decomposable aromatic chlorides such as PCB which is regarded as a global environmental pollutant. It relates to a practicable dechlorination method.
【０００２】[0002]
【従来の技術】ＰＣＢを含む芳香族塩化物の分解法につ
いては、燃焼法、湿式酸化、放射線分解法、紫外線分解
法、水素化分解法、微生物分解法等多くの方法が研究さ
れている。 しかし、反応効率、有害物の発生、経済的
な面から見て実用的な方法は確立されていない。その中
で、水素化分解法についてみると、ボンベに高圧充填さ
れた水素ガスを用い、金属触媒とアルカリの存在化で脱
塩素化する方法が研究されてきている。この方法は高圧
水素ガスを用いるので、その取り扱いが危険であるとと
もに、実験装置が複雑であり、操作に難しさがともな
う。2. Description of the Related Art As a method for decomposing aromatic chloride containing PCB, various methods such as combustion method, wet oxidation, radiation decomposition method, ultraviolet decomposition method, hydrogenolysis method and microbial decomposition method have been studied. However, practical methods have not been established from the viewpoints of reaction efficiency, generation of harmful substances, and economics. Among them, regarding the hydrocracking method, research has been conducted on a method of dechlorinating in the presence of a metal catalyst and an alkali using hydrogen gas filled in a cylinder under high pressure. Since this method uses high-pressure hydrogen gas, its handling is dangerous, and the experimental apparatus is complicated and its operation is difficult.
【０００３】[0003]
【発明が解決しようとする課題】 ＤＤＴやＰＣＢなど
の有機塩素化合物については、１９７０年早期からその
危険性が認識されて使用が禁止されたが、それまでに環
境中に放出されたこれらの物質は分解、消滅がきわめて
遅く海洋などでも検出されており、環境汚染物質として
問題になっている。未使用のものは工場などで未処理の
まま保存されているのが現状である。本発明はこのよう
な有害物質である有機塩素化合物を経済的に簡単な方法
で脱塩素化し、無害な物質にして環境汚染を防止するの
が目的である。SUMMARY OF THE INVENTION Organochlorine compounds such as DDT and PCB were banned from use in the early 1970's because of their danger, but these substances released into the environment until then. Is extremely slow to decompose and disappear, and has been detected in the ocean, etc., and is a problem as an environmental pollutant. Currently, unused ones are stored unprocessed in factories and the like. An object of the present invention is to dechlorinate an organic chlorine compound as a harmful substance by an economically simple method to make the substance harmless and prevent environmental pollution.
【０００４】[0004]
【課題を解決するための手段】 本発明者らは、パラジ
ウムとギ酸塩による有機化合物の水素移動水素化が比較
的穏和な条件下で還元が進み、その選択性が高いことか
ら種々の有機ハロゲン化合物の還元について研究を行っ
た。その結果、従来用いられているメタノ−ルやエタノ
−ル溶媒では、ＰＣＢなどのような化合物は溶解性が悪
く反応が進みにくい。界面活性剤を相間移動触媒として
用い、水と炭化水素系有機溶媒による２液層の溶液で還
元を行うと、ＰＣＢなどの芳香族塩素化合物は有機溶媒
層に均一に溶解し、一定温度以上では効率よく脱塩素化
されることを見い出し、詳細に検討を進めた結果、本発
明をなすに至った。MEANS TO SOLVE THE PROBLEMS The present inventors have proposed that reduction of hydrogen transfer hydrogenation of an organic compound by palladium and formate proceeds under relatively mild conditions and that the selectivity is high. A study was conducted on the reduction of compounds. As a result, compounds such as PCB are poorly soluble in the conventionally used methanol and ethanol solvents, and the reaction is difficult to proceed. When a surfactant is used as a phase transfer catalyst and reduction is performed with a two-liquid layer solution of water and a hydrocarbon-based organic solvent, aromatic chlorine compounds such as PCBs are uniformly dissolved in the organic solvent layer. As a result of finding out that dechlorination is performed efficiently and conducting detailed studies, the present invention has been accomplished.
【０００５】 本発明は、第二次世界大戦後の約２０年
間工業薬剤として多量に使用されたが、その残留性、難
分解性のため現在有害で環境汚染物質とされている有機
ハロゲン化合物を経済的に簡単な方法で脱ハロゲン化
し、無害な物質にする方法を提供するものである。[0005] The present invention has been used for a large amount as an industrial chemical for about 20 years after World War II. It is intended to provide a method for dehalogenating to a harmless substance by an economically simple method.
【０００６】 本発明方法において、還元基質を加える
前に、パラジウム触媒を含む水層に水素供与体であるギ
酸塩水溶液の１／３〜１／２量加えて攪拌し、パラジウ
ム触媒に水素を吸着させた後に還元基質を加えることが
注意点である。パラジウム触媒は空気と触れないように
処理すれば複数回使用することが可能である。反応液の
攪拌はマグネチックスタ−ラ−でも行えるが、２液層を
十分均一に混合させるためには超音波による攪拌のほう
が効率的であり、良い結果が得られる。In the method of the present invention, before adding a reducing substrate, 1/3 to 1/2 of an aqueous solution of formate as a hydrogen donor is added to an aqueous layer containing a palladium catalyst, and the mixture is stirred to adsorb hydrogen on the palladium catalyst. It is important to add the reducing substrate after the reaction. The palladium catalyst can be used more than once if it is treated so as not to come into contact with air. The reaction solution can be stirred with a magnetic stirrer, but in order to mix the two liquid layers sufficiently uniformly, ultrasonic stirring is more efficient and good results can be obtained.
【０００７】 還元後の処理で、反応混合液をろ過して
パラジウム触媒を分離し、有機溶媒および蒸留水で洗浄
するが、その際触媒の活性をできるだけ落とさないで再
利用するために、空気に直接触れないよう注意する必要
がある。少量の実験では、ろ過することなく有機溶媒層
を抜き取って水層から分離するが、どうしても少量の触
媒が含まれてくるので、ろ紙あるいはキムワイプなどを
つめたピペットなどをとうして除去する必要がある。有
機溶媒を留去するとほぼ純粋な脱ハロゲン化生成物が得
られ、他の試薬の合成に利用することが可能である。In the treatment after the reduction, the reaction mixture is filtered to separate the palladium catalyst, and the palladium catalyst is washed with an organic solvent and distilled water. At that time, the catalyst is reused without reducing the activity of the catalyst as much as possible. Be careful not to touch it directly. In a small amount of experiment, the organic solvent layer is extracted without filtration and separated from the aqueous layer.However, since a small amount of catalyst is included, it is necessary to remove it with a filter paper or a pipette filled with Kimwipe. is there. Evaporation of the organic solvent gives an almost pure dehalogenated product, which can be used for the synthesis of other reagents.
【０００８】 例えば、ＰＣＢの本実験法による還元で
はほぼ純粋なビフェニルが結晶として得られることが、
赤外線吸収スペクトルや液体クロマトグラフの測定結果
を標準試料のものと比較して確認できる。For example, reduction of PCB by the present experimental method yields almost pure biphenyl as crystals.
The measurement results of the infrared absorption spectrum and the liquid chromatograph can be confirmed by comparing with those of the standard sample.
【０００９】 ｐ−クロロニトロベンゼンなどのよう
に、一つの分子内に複数の官能基を有している場合、脱
塩素化とともに他の官能基も水素化され、この場合には
アニリンを生成する。反応条件および水素供与体を選ぶ
ことにより、ニトロ基のみを還元するなど選択還元も可
能である。When one molecule has a plurality of functional groups, such as p-chloronitrobenzene, the other functional groups are hydrogenated together with dechlorination, and in this case, aniline is generated. By selecting the reaction conditions and the hydrogen donor, selective reduction such as reduction of only the nitro group is possible.
【００１０】[0010]
【実施例】 １０％Ｐｄ−炭素触媒（２００ｍｇ）を蒸
留水（１０ｃｍ3）とともに５０ｃｍ3の冷却器、滴下ロ
−トおよびシリコン栓を連結した還元フラスコに入れ
る。容器内部が直接空気と接触しないように連結部の先
端にシリコン油を入れたトラップを取り付けておく。還
元フラスコにギ酸アンモニウムまたはギ酸カリウム（約
３００ｍｇ）を蒸留水（約１５ｃｍ3）に溶かした溶液
の中、約５〜６ｃｍ3を攪拌しながら加え、還元を行う
前に、パラジウム触媒に水素を吸着させる。ついで、塩
化フェニルトリメチルアンモニウム（相間移動触媒）
（約１０ｍｇ）とＰＣＢ（約５００ｍｇ）をシクロヘキ
サン（約１０ｃｍ3）に溶かした溶液を加える。還元フ
ラスコを一定温度（６５℃）に保った超音波洗浄器に入
れて反応液の温度を一定にした後、攪拌しながら残りの
ギ酸塩の水溶液を滴下して水素化を行う。一定時間毎に
シクロヘキサン層を注射器により抜き取り液体クロマト
グラフィ−および薄層クロマトグラフィ−により反応の
経時変化を調べる。約１時間で反応は終了する。反応溶
液を吸引ろ過してパラジウム触媒を除いた後、シクロヘ
キサン層を分離して無水硫酸ナトリウムで乾燥する。シ
クロヘキサンを留去するとビフェニルが結晶として得ら
れる。EXAMPLE A 10% Pd-carbon catalyst (200 mg) was placed in a reduction flask connected to a 50 cm 3 condenser, a dropping funnel and a silicon stopper together with distilled water (10 cm 3 ). Attach a trap containing silicone oil to the end of the connecting part so that the inside of the container does not come into direct contact with air. A solution of ammonium formate or potassium formate (about 300 mg) dissolved in distilled water (about 15 cm 3 ) is added to the reduction flask with stirring, and about 5 to 6 cm 3 is added with stirring to adsorb hydrogen on the palladium catalyst before reduction. Let it. Then, phenyltrimethylammonium chloride (phase transfer catalyst)
(About 10 mg) and a solution of PCB (about 500 mg) dissolved in cyclohexane (about 10 cm 3 ) are added. After the reduction flask is placed in an ultrasonic cleaner kept at a constant temperature (65 ° C.) to keep the temperature of the reaction solution constant, the remaining aqueous solution of formate is added dropwise with stirring to carry out hydrogenation. At regular intervals, the cyclohexane layer is withdrawn with a syringe, and the change over time in the reaction is examined by liquid chromatography and thin-layer chromatography. The reaction is completed in about one hour. After suction filtration of the reaction solution to remove the palladium catalyst, the cyclohexane layer is separated and dried over anhydrous sodium sulfate. After distilling off cyclohexane, biphenyl is obtained as crystals.
【００１１】[0011]
【発明の効果】 本発明者らは、上記したパラジウムと
相間移動触媒を用いた水素化法により、人工有機化合物
による環境汚染で問題になっているＰＣＢなど有機塩素
化合物を脱塩素化して無毒化できるので、環境汚染問題
の一つの具体的解決法に役立てることができる。EFFECTS OF THE INVENTION The present inventors detoxify an organic chlorine compound such as PCB, which is a problem in environmental pollution by artificial organic compounds, by dehydrogenation by the hydrogenation method using the above-mentioned palladium and a phase transfer catalyst. Therefore, it can be used for one concrete solution to the environmental pollution problem.
Claims (1)
００〜２００ｍｇの金属触媒Ｐｄ−Ｃ（５〜１０％）と
水素供与体であるギ酸塩（ギ酸カリウム、ギ酸アンモニ
ウム）５〜６ｇを炭化水素系溶媒に懸濁させて２液層反
応溶液とし、相間移動触媒のテトラ−ｎ−ブチルアンモ
ニウムブロマイドや塩化フェニルトリメチルアンモニウ
ム等の界面活性剤約１０ｍｇ共存させ、反応温度５０〜
６５℃で、攪拌しながら１〜３時間反応させ芳香族塩化
物を脱塩素化する方法。1. An amount of 1: 1 per 5 × 10 -3 mol of aromatic chloride
A 200-200 mg metal catalyst Pd-C (5-10%) and 5-6 g of a hydrogen donor formate (potassium formate, ammonium formate) are suspended in a hydrocarbon solvent to form a two-liquid layer reaction solution, Approximately 10 mg of a phase transfer catalyst such as tetra-n-butylammonium bromide or phenyltrimethylammonium chloride is allowed to coexist, and the reaction temperature is 50 to
A method of reacting at 65 ° C. for 1 to 3 hours with stirring to dechlorinate aromatic chlorides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7260736A JP2810978B2 (en) | 1995-09-12 | 1995-09-12 | Dechlorination of aromatic chlorides with formate using palladium and phase transfer catalyst. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7260736A JP2810978B2 (en) | 1995-09-12 | 1995-09-12 | Dechlorination of aromatic chlorides with formate using palladium and phase transfer catalyst. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0975473A true JPH0975473A (en) | 1997-03-25 |
| JP2810978B2 JP2810978B2 (en) | 1998-10-15 |
Family
ID=17352045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7260736A Expired - Lifetime JP2810978B2 (en) | 1995-09-12 | 1995-09-12 | Dechlorination of aromatic chlorides with formate using palladium and phase transfer catalyst. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2810978B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100462705B1 (en) * | 2002-04-09 | 2004-12-20 | 한국해양연구원 | Method of reducing a toxicity of PCB with Pd-Al2O3 and Ultrasonic |
| KR100462706B1 (en) * | 2002-07-15 | 2004-12-20 | 한국해양연구원 | METHOD FOR REDUCING A TOXICITY OF DIOXIN WITH Pd-Al2O3 AND ULTRASOUND |
| KR100749898B1 (en) * | 2004-10-25 | 2007-08-21 | 한국전력공사 | Method for removing polychlorinated biphenyls by catalyst |
| JP2011188949A (en) * | 2010-03-12 | 2011-09-29 | Nagoya Industrial Science Research Inst | Hydrodechlorination reaction device of aromatic chlorine compound |
| KR20180022636A (en) | 2015-06-30 | 2018-03-06 | 엠. 테크닉 가부시키가이샤 | Method for producing organic compounds |
-
1995
- 1995-09-12 JP JP7260736A patent/JP2810978B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100462705B1 (en) * | 2002-04-09 | 2004-12-20 | 한국해양연구원 | Method of reducing a toxicity of PCB with Pd-Al2O3 and Ultrasonic |
| KR100462706B1 (en) * | 2002-07-15 | 2004-12-20 | 한국해양연구원 | METHOD FOR REDUCING A TOXICITY OF DIOXIN WITH Pd-Al2O3 AND ULTRASOUND |
| KR100749898B1 (en) * | 2004-10-25 | 2007-08-21 | 한국전력공사 | Method for removing polychlorinated biphenyls by catalyst |
| JP2011188949A (en) * | 2010-03-12 | 2011-09-29 | Nagoya Industrial Science Research Inst | Hydrodechlorination reaction device of aromatic chlorine compound |
| KR20180022636A (en) | 2015-06-30 | 2018-03-06 | 엠. 테크닉 가부시키가이샤 | Method for producing organic compounds |
| US10287232B2 (en) | 2015-06-30 | 2019-05-14 | M. Technique Co., Ltd. | Method for producing an organic compound in a rotating forced thin-film microreactor |
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| Publication number | Publication date |
|---|---|
| JP2810978B2 (en) | 1998-10-15 |
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