WO1997034713A1 - Method of dechlorinating organic chlorine compound - Google Patents

Method of dechlorinating organic chlorine compound Download PDF

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Publication number
WO1997034713A1
WO1997034713A1 PCT/JP1997/000923 JP9700923W WO9734713A1 WO 1997034713 A1 WO1997034713 A1 WO 1997034713A1 JP 9700923 W JP9700923 W JP 9700923W WO 9734713 A1 WO9734713 A1 WO 9734713A1
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Prior art keywords
reaction
polar solvent
dechlorination
recovered
tank
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Application number
PCT/JP1997/000923
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French (fr)
Japanese (ja)
Inventor
Fumio Tanimoto
Kiyohiko Tsukumo
Atsuhiko Nakamura
Tsuneo Yano
Mitoshi Higashiuchi
Toshinori Toma
Koichi Furuhashi
Original Assignee
Research Institute For Production Development
Mitsui & Co., Ltd.
Neos Co., Ltd.
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Application filed by Research Institute For Production Development, Mitsui & Co., Ltd., Neos Co., Ltd. filed Critical Research Institute For Production Development
Priority to AU19437/97A priority Critical patent/AU703494B2/en
Publication of WO1997034713A1 publication Critical patent/WO1997034713A1/en

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to a dechlorination method for safely treating organic chlorinated compounds such as polychlorinated biphenyls and dioxins, which are specific harmful substances.
  • PCB polychlorinated biphenyls
  • the inventors of the present application have conducted many more rigorous experiments, and as a result, have completed a more economical new process. That is, in the present invention, the organochlorine compound and excess alkali are stirred and mixed at 100 ° C. to 300 ° C. in a non-protonic polar solvent to thereby form a mixture in the reaction vessel.
  • organic chlorine compound refers to PCB, polychlorodibenzodioxin, polychlorodibenzofuran, or hardly decomposable organic chlorine such as 1,2,3 trichloro-14,1-nitro-biphenyl ether (CNP).
  • Alkali refers to at least one compound selected from the group consisting of caustic soda, caustic potassium, sodium lower alkoxide, potassium lower alkoxide, calcium hydroxide, and calcium oxide. A compound or a mixture of two or more. Caustic soda is particularly preferred in terms of economy.
  • the present inventors have found that a means for recovering an alkali with a lower alcohol is very effective for a dechlorination reaction. That is, not only the alcohol was sufficiently dissolved in the lower alcohol, but also the alcohol recovered in the lower alcohol increased to the newly added alcohol, which was found to have an effect of promoting the reaction. Was. The scholarly explanation of the reaction mechanism, etc. is currently being explored further and will be elucidated soon.
  • the excess alkali is recovered from the solids separated by filtration of the reaction solution with a lower alcohol or the like, and used for the next dechlorination reaction by a batch reaction. Part or most of it is recovered by distillation for the next batch reaction.
  • the concentration of the organochlorine compound participating in the reaction is relatively high and a solid is formed after cooling the reaction solution subjected to the dechlorination reaction, excess unreacted alkali is separated from the reaction product.
  • the generated solid is separated, and the alkali contained in the solid is dissolved in a lower alcohol, and separated and recovered.
  • the non-protonic polar solvent in the residual liquid from which the solid matter is separated is used as it is, or a part or most of the solvent is distilled and recovered, and reused in the dechlorination reaction.
  • the concentration of the organochlorine compound participating in the reaction is relatively low and the reaction solution that has undergone the dechlorination reaction is cooled, and the amount of solids produced is relatively small, unreacted alcohol
  • the reaction product is distilled without cooling to recover the non-protonic polar solvent, and the alcohol contained in the bottom is converted to lower alcohol. Dissolve, separate and collect.
  • the dechlorination reaction is carried out by dissolving and recovering with a lower alcohol.
  • the reactor is supplied with the recovered alkali that is reused in the reactor and the amount of alcohol that supplements the amount consumed in the dechlorination, and the temperature is raised together with the non-protonic polar solvent to start the reaction. It is preferable to distill most of the lower alcohol out of the system, recover it, and reuse it for the next recovery of the alcohol after the dechlorination reaction.
  • centrifugation, filtration under pressure, filtration under reduced pressure and the like are suitable for filtration of the reaction solution, which are selected in consideration of conditions such as the concentration of the raw material organic chlorine compound and the viscosity of the system.
  • Distillation and recovery of the solvent in the filtrate may be carried out in any form as long as it is an efficient method such as reduced pressure distillation and reduced pressure thin film distillation. If it is convenient for the distillation residue to become a dry solid, perform thorough distillation, crush the solid, filter it, and extract and wash the solid with low-grade alcohol to recover the alcohol.
  • the reaction product and the inorganic salt can be combined at room temperature with this nonprotonic polar solvent. Since it does not dissolve much, it can be separated by filtration without relatively complicated procedures, and only alkali is easily dissolved in lower alcohol, so that extraction and recovery can be performed advantageously.
  • one of the advantages of this process is that the alkali substance recovered with the lower alcohol is much more reactive than the first method used in this method.
  • the water content in the lower alcohol is suppressed to 10% or less, particularly preferably to only the attached water content.
  • a large amount of water was found to inhibit the dehalogenation reaction near the end point of the reaction because it dissolves the reaction product well as well as the corrosion of the equipment.
  • the role of trace water is still clear Although it has not been done, it is considered to play some effective role in the distribution of reaction products.
  • the lower alcohol used to separate and recover the alkali is at least one or two selected from the group consisting of alcohols having 1 to 4 carbon atoms and a water content of 10% or less. It is preferable to use a mixture composed of the above.
  • reaction solution a reaction solution containing a dechlorinated compound (hereinafter referred to as this reaction solution) .
  • the nonprotonic polar solvent is recovered and reused in the next dechlorination reaction. After the dechlorination reaction, it may be used for another purpose.
  • examples of the non-protonic polar solvent include sulfolane, dimethyl sulfoxide (hereinafter abbreviated as DMSO), 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), and dimethyl alcohol.
  • DMSO dimethyl sulfoxide
  • DMI 1,3-dimethyl-2-imidazolidinone
  • dimethyl alcohol Use is made of alkylene glycol, tetramethylurea, N-methylbi-lidone, etc., which contains 50% or more of one or more of the above-mentioned compounds. From the viewpoint of cost and the like, it is particularly preferable to use a solvent containing 50% or more of DMSO, DMI, or dimethylpolyalkylene glycol.
  • a suitable temperature is 100 ° C to 300 ° C, but if the processing temperature is lower than 100 ° C, it may take a very long time, and 300 ° C may be required. If it is higher than C, there is a risk of evaporation of non-protonic solvents and organochlorine compounds and unexpected gelation due to side reactions. Especially when no additive is used, it is 150. It is preferably carried out at C to 250 ° C.
  • the organochlorine compound to be supplied to the reaction tank, the recovered alkali to be reused, the newly supplied alkali, the non-protonic polar solvent to be newly supplied, and the recovered non-protonic polar solvent to be reused about
  • the dechlorination reaction proceeds by the reaction of the solvent dissolved in a non-protonic polar solvent such as DMI with PCB in the liquid phase. Therefore, in order to promote the reaction, the concentration of the alkali dissolved in the DMI must be kept high to promote the association and contact between the molecules and the PCB molecules in the presence of the DMI.
  • the alkali used for the reaction in, ⁇ is dissolved in the DMI consumed in the dechlorination reaction by suspending finely ground solid caustic soda or caustic soda in the DMI to facilitate dissolution in the DMI. It is necessary to make up for the energy that is generated. As a result of various studies on the method, a suspension was made in a mixing tank equipped with a stirrer that mixes DMI and finely ground alkali, and then stirred.
  • a circulation line that extracts the liquid containing PCB from the reaction tank, passes through a static mixer, and returns to the reaction tank Mixing the suspension at the inlet of the static mixer and passing through the static mixer promotes the dissolution of alkali into the DMI and makes operation easier.
  • the reaction tank is heated while or after the suspension is supplied in this way, and the dechlorination reaction proceeds with the reaction temperature kept constant. This is circulated through a stick mixer. By doing so, the dechlorination reaction can proceed and the intended purpose can be achieved.
  • FIG. 1 shows a representative sheet of a process to which the present invention is applied.
  • FIG. 1 A first figure.
  • FIG. 2 is a diagram showing a typical flow sheet of another process to which the present invention is applied.
  • Fig. 3 shows an example of the material balance in the case where there is no recovery of alkali and solvent in the flow test for the process to which the present invention is applied.
  • FIG. 4 is a diagram showing an example of a material balance in a case where an alkali and a solvent are recovered in a flow test on a process to which the present invention is applied.
  • Figure 5 shows that raw materials were supplied to the reaction tank in the process to which the present invention was applied.
  • . 5 is a diagram showing an example of a method of supplying.
  • FIG. 6 is a diagram showing a typical flow sheet of still another process to which the present invention is applied.
  • FIG. 7 is a diagram showing that harmless insulating oil is reused as fuel oil in a flow test of a process to which the present invention is applied.
  • FIG. 8 is a diagram showing the material balance when DMI and the recovered alkali are recycled 15 times and reused as fuel oil in the flow test of the process to which the present invention is applied.
  • Fig. 1, Fig. 2, Fig. 5, Fig. 6, and Fig. 7 show typical flow sheets of this process
  • Fig. 3 shows the case without alkali and solvent recovery
  • Fig. 4 shows the case with alkali and solvent recovery
  • Figure 8 shows the DMI and the material yield for the case of recycling recovered alkali.
  • FIG. 1 shows an example in which the present invention is implemented.
  • 9 is a relatively high-concentration insulating oil containing PCB, which contains about 7% of PCB.
  • 1 is a non-protonic polar solvent (eg DMI)
  • 2 is an alkali (Eg, caustic soda)
  • 14 indicates DMI recovered in the still after the reaction
  • 13 indicates lower alcohol (eg, ethanol) in which alkali is dissolved.
  • DMI non-protonic polar solvent
  • 2 is an alkali (Eg, caustic soda)
  • 14 indicates DMI recovered in the still after the reaction
  • 13 indicates lower alcohol (eg, ethanol) in which alkali is dissolved.
  • This liquid is cooled to room temperature by passing a low-temperature refrigerant through a jacket 5, and the slurry-like reaction liquid 20 containing the solid NaC 1 generated here is filtered by a filter (1) of 6.
  • the filtrate 10 is supplied to the still 8 to recover the solvent and reused in the next batch reaction.
  • the remaining tank 15 obtained in this way was analyzed for PCB.
  • the separated cake (1) of 11 is dissolved in the dissolving tank 19 to dissolve the unreacted alcohol contained in the cake in ethanol, and the filtrate 13 is filtered by the filter (2) 7.
  • the filtrate 13 that separates into the cake (2) in 12 is ethanol that dissolves the recovered alkali and is reused in the next reaction by batch operation.
  • two filters 6 and 7 are shown separately, but the same one can be used separately by batch operation without being divided into two.
  • 3, 14, 16, 17, 18, 18, 36, 37, and 38 are each agitator, recovered DMI, recovered ethanol, ethanol, replenishment ethanol, recovered DMI tank, and first condenser.
  • the second capacitor is one.
  • Fig. 3 shows an example of the mass balance of the first batch operation without the use of alkalis and solvents, in which a relatively high concentration of insulating oil containing PCB is decomposed.
  • 13 ⁇ 44 shows the case of decomposing insulating oil containing PCB at relatively high concentration.
  • An example of the material balance of the embodiment in the case of reusing the alkali and the solvent is shown.
  • the temperature and operating conditions of each part are almost the same as those shown in the first embodiment.
  • FIG. 2 shows another example in which the present invention is implemented.
  • FIG. 5 shows an example of a method for supplying a raw material to a reaction tank.
  • the numbers shown here are the same as in Figures 1 and 2.
  • These raw materials are mixed well in advance in a mixing tank 34 equipped with a stirrer 33, and then mixed into a reaction liquid circulation line 30 through a pipe 31 using a supply pump 32.
  • the mixed reaction circulating liquid is completely mixed by a static mixer 29 equipped with a heater 35, and then the reaction tank 4 with the stirrer 3 (stirred reaction tank) And further subjected to a stirring operation by the stirrer 3.
  • the static mixer 29 extracts a part of the liquid subjected to the stirring operation in the reaction tank 4 through the circulation pump 28, the mixing intensity in the static mixer 29 is limited to the mixing intensity in the stirring reaction tank. Naturally, it is necessary to select something stronger than the mixing strength.
  • Alkali is supplied as a solid, and is heavier than the specific gravity of the liquid.Therefore, a part of the alkali precipitates at the bottom of the agitation reactor, and in the case of a reactor that mainly uses centrifugal agitation, the suspension cannot be maintained. Contact with the reaction solution tends to be incomplete. As a method of improving this, it is possible to maintain and improve the state of suspension in the reaction solution by extracting the precipitated solid from the bottom and passing it through a stick mixer 29. This operation is continued even after the supply of raw materials.
  • reference numeral 35 denotes a heater that heats a part of the static mixer, compensating for the temperature drop due to heat loss in the circulation line and increasing the temperature as needed, thereby increasing the reaction speed. It can be held.
  • the raw material supply method is directly supplied to the reaction tank, and the raw material is supplied using a static mixer. As a result, the following effects were obtained.
  • Example 5 shows an example of processing a relatively low-concentration insulating oil containing PCB by the process flow shown in FIG.
  • a still is provided separately, and the solvent is recovered here. 5
  • DMI is used as a solvent
  • its boiling point is 225.5 ° C at normal pressure, whereas it is 250-470 ° C for insulating oil, so it can be easily separated by simple distillation.
  • the tank can be used as a still. In this way, the process can be simplified, equipment costs can be saved, and processing costs can be reduced. An example of this is shown in Figure 6.
  • the distillation may be performed under reduced pressure in consideration of the temperature of the heating source. For example, at an absolute pressure of 4 OmmHg, DMI can be distilled off from the reaction solution at 150 ° C.
  • PCBs can be removed from TFO (insulating oil) very economically by reusing the recovered DMI and alkali dissolved in alcohol, and it is harmless except for PCB.
  • the converted insulating oil can be reused as fuel oil.
  • Fig. 7 shows the process flow of this example, and Fig. 8 shows the material balance at that time.
  • Fig. 7, 39, 40, 41, 42, 43, 44, and 45 denote the adjustment tank, the cooling tank, the filtrate receiving tank, the distillate (DMI) receiving tank, the separator, and the high-pressure insulating oil (TFO).
  • Receiving tank. 46, 47, 48, 49, 50, 51, 52, 53 are alkali dissolution tanks, alcohol supply tanks, storage tanks containing alkali-containing alcohol solutions, alkali supply tanks, cake storage tanks, and raw materials (TFO containing PCBs) Tank, solvent (DMsI) supply tank, and new supply tank.
  • Reference numerals 54, 55, 56, and 57 denote a drive motor for stirring, a TFO washing tank, a TFO washing tank, and a TFO heavy oil mixing tank.
  • the recovered DMI was recycled 15 times
  • the alkali recovered in the metamorphic alcohol was recycled 15 times or more.
  • the PCB in the new TFO containing 80 ppm of PCB is dechlorinated using new DMI and new caustic soda.
  • the liquid after this is separated into a TFO phase and a DMI phase (solid-liquid phase containing caustic soda solid), and this DMI phase (containing caustic soda) is used again for the reaction.
  • the reaction is first separated and separated into a TFO and DMI phase.
  • a small amount of lower alcohol containing 10% or less of water
  • To further assist in phase separation perform a simple filtration once (pressurized or depressurized) and then separate phases.
  • the TF0 phase is washed with water, it is mixed with heavy oil and reused as fuel oil.
  • the DMI phase DMI and caustic soda are reused to decompose the PCB in the new TFO. Repeat this 15 times. A small amount of DMI and a small amount of caustic soda may be added as needed for the reaction.
  • the DMI phase containing caustic soda, reaction products and sodium chloride is usually first filtered through a centrifugal filter to separate the solid and liquid. Distill the liquid filtrate to recover DMI. This DMI is recycled to the next reaction.
  • solid phase cake
  • an amount of denatured ethyl alcohol that sufficiently dissolves caustic soda is added, and the remaining caustic soda after use in the dechlorination reaction is recovered.
  • most of the reaction product and the generated sodium chloride hardly dissolve in denatured ethyl alcohol, and therefore exist as a solid.
  • These mixtures are filtered through a centrifugal filter, Separate the solid and liquid. Most of the caustic soda transfers to the liquid filtrate and is recycled for the next reaction.
  • the recoveries of DMI and alkali were 99% and 91%, respectively.
  • the material balance of the process is almost the same as in Example 5, except that the solvent used is triethylene glycol dimethyl ether (boiling point 2 16 ° C) or tetraethylene glycol dimethyl ether (boiling point 275) instead of DMI.
  • the solvent used is triethylene glycol dimethyl ether (boiling point 2 16 ° C) or tetraethylene glycol dimethyl ether (boiling point 275) instead of DMI.
  • This is an example of a process in which the reaction was carried out 15 times by using caustic soda as the alkali.
  • the present invention can be applied to the treatment of hydrocarbon oils containing all concentrations of organochlorine compounds, for example, PCB-contaminated transformer oil or 100% PCB, with good results.
  • the hydrocarbon oil mentioned above will be regenerated and reused. Therefore, the method for dechlorinating an organic chlorinated compound according to the present invention relates to a process for dechlorinating and detoxifying an organic chlorinated compound in a very economical manner. As a result, it is possible to safely and economically contribute to the improvement of the environment.

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Abstract

In order to treat organic chlorine compounds, which are generally hard to decompose, by a method, which poses no problem in terms of processes and is excellent in safety and economy, excess alkali is used to make the treating complete when a PCB containing insulating oil (9) containing organic chlorine compounds such as PCB, and alkali such as caustic soda (2), are caused to react in an aprotic polar solvent such as 1,3-dimethyl-imidazolidinone (1) to undergo dechlorination. Further, excess alkali is made to be dissolved in a lower alcohol such as ethanol (17) and recovered, and the aprotic polar solvent is recovered, whereby a treating step is improved in safety, economy and serviceability, and the oil having been made harmless is reused for fuel oils and the like to make effective use of resources.

Description

明 細 書 有機塩素化合物の脱塩素化方法  Description Method for dechlorination of organochlorine compounds
, 技術分野 , Technical field
本発明は、 特定有害物質であるポリ塩化ビフエニール、 ダイォキ シン等の有機塩素化合物を安全に処理するための脱塩素化方法に関 するものである。 背景技術  The present invention relates to a dechlorination method for safely treating organic chlorinated compounds such as polychlorinated biphenyls and dioxins, which are specific harmful substances. Background art
ポリ塩化ビフエニール （以下、 P C Bと略す。 ） 等の有機塩素化 合物は現在、 厳重に保管されていることになつているが、 年月を絰 て、 その保管状態が必ずしも万全とはいえない様になりつつあり、 安全且つ経済的な処理法が望まれている。  Organic chlorinated compounds, such as polychlorinated biphenyls (hereinafter abbreviated as PCB), are currently being strictly stored, but their storage conditions are not always perfect over the years. Therefore, safe and economical treatment methods are desired.
従来、 高温分解法やアル力リ分解法等多くの試みがなされたが、 処理基準の問題や経済性の問題等の制約があり、 充分なプロセスは 確立されなかった。  Many attempts have been made in the past, such as the high-temperature decomposition method and the thermal decomposition method. However, due to problems such as problems with treatment standards and economics, a sufficient process has not been established.
本願発明者等は、 既にハロゲン化芳香族化合物のアル力リ分解方 法については、 多年の研究を行い、 注目すべき発明を完成している (特開平 6— 2 5 6 9 1号公報、 特開平 7— 8 5 7 2号公報、 特開 平 7— 3 1 3 6 2 0号公報を参照。 ） 。  The inventors of the present application have already conducted many years of research on a method for decomposing halogenated aromatic compounds, and have completed a remarkable invention (Japanese Patent Application Laid-Open No. 6-25691, See JP-A-7-85772 and JP-A-7-313620.)
これらの公報に開示されている本願発明者等の発明は、 誠に有効 かつ優れた方法であるといえるが、 よりよい結果を得るためには、 過剰のアル力リの使用が必要であることが知られている （特開平 7 - 3 1 3 6 2 0号公報を参照） 。  It can be said that the inventions of the present inventors disclosed in these publications are truly effective and excellent methods, but in order to obtain better results, it is necessary to use an excessive amount of force. It is known (see Japanese Patent Application Laid-Open No. Hei 7-31360).
従って、 実用性と絰済性を一層高めるには、 過剰のアルカリの回 収が極性溶剤の回収と共に重要な課題である。 又、 従来の方法では、 この反応によ り P C B濃度が高感度ガスク 口マ トグラフ質量分析法 （ G C— M S ) で分析検知限界以下になる までの反応時間が長くかかる問題があった。 この反応時間を短縮す ることも課題の一つである。 発明の開示 Therefore, the recovery of excess alkali is an important issue along with the recovery of polar solvents, in order to further improve practicality and affordability. In addition, in the conventional method, there was a problem that the reaction took a long time until the PCB concentration became lower than the detection limit in the high-sensitivity gas chromatography mass spectrometry (GC-MS) due to this reaction. Reducing the reaction time is also an issue. Disclosure of the invention
このような課題を解決するため、 本願発明者等は今般さらに厳密 な実験を数多く重ねた結果、 より一層経済的な新プロセスを完成す るに至った。 即ち、 本発明では、 有機塩素化合物と過剰のアルカリ とを、 非プロ トン性極性溶剤中で、 1 0 0 °Cないし 3 0 0 °Cにて攪 拌、 混合することによ り反応槽内で脱塩素化反応を行う工程におい て、 該脱塩素化反応後、 過剰の未反応アルカリは反応生成物より分 離回収して前記脱塩素化反応に再使用し、 非プロ トン性極性溶剤は そのままか、 或いは一部若しくは大部分を分離回収して前記脱塩素 化反応に再使用することにより、 前記工程の生成物をアルカリ塩酸 塩と原料有機塩素化合物の脱塩素化物に転化し、 且つ全て無害の一 般廃棄物とすることが可能なことを見出したのである。 従って、 排 出物のアル力リ塩酸塩と原料有機塩素化合物の脱塩素化合物とは、 それそれ分析に付されて有機塩素化合物等好ましからざる成分が充 分に取り除かれていることを分析により確認されるまで貯えられた 後、 再利用に供されるか、 あるいは一般廃棄物として処理される。 本発明において、 有機塩素化合物とは、 P C B、 ポリクロロジべ ンゾジォキシン、 ポリクロロジベンゾフラン、 或いは 1 , 2 , 3 ト リクロロ一 4， 一ニトロ一ビフエ二ルェ一テル （ C N P ) 等の難分 解性有機塩素化合物を指し、 アルカリ とは苛性ソーダ、 苛性カリ、 ナ ト リウム低級アルコキシド、 カリウム低級アルコキシ ド、 水酸化 カルシウム、 酸化カルシウムなる群から選ばれた少なく とも 1つの 化合物、 或いは 2つ以上の混合物を指す。 そして、 経済性から特に 好ましいのは、 苛性ソーダである。 In order to solve such a problem, the inventors of the present application have conducted many more rigorous experiments, and as a result, have completed a more economical new process. That is, in the present invention, the organochlorine compound and excess alkali are stirred and mixed at 100 ° C. to 300 ° C. in a non-protonic polar solvent to thereby form a mixture in the reaction vessel. After the dechlorination reaction, in the step of performing the dechlorination reaction, excess unreacted alkali is separated and recovered from the reaction product and reused in the dechlorination reaction, and the non-protonic polar solvent is The product of the above step is converted into an alkali hydrochloride and a dechlorinated product of a raw material organic chlorine compound as it is, or by separating and recovering part or most of the product and reusing it in the dechlorination reaction, and They found that it could be made harmless general waste. Therefore, it was confirmed by analysis that the waste hydrochloride and the dechlorinated compound of the raw organic chlorine compound were each subjected to analysis to remove undesired components such as organic chlorine compounds. After being stored, they are either reused or treated as municipal waste. In the present invention, the term "organic chlorine compound" refers to PCB, polychlorodibenzodioxin, polychlorodibenzofuran, or hardly decomposable organic chlorine such as 1,2,3 trichloro-14,1-nitro-biphenyl ether (CNP). Alkali refers to at least one compound selected from the group consisting of caustic soda, caustic potassium, sodium lower alkoxide, potassium lower alkoxide, calcium hydroxide, and calcium oxide. A compound or a mixture of two or more. Caustic soda is particularly preferred in terms of economy.
また、 本発明者等は、 低級アルコールによりアルカ リを回収する 手段が脱塩素化反応に非常に有効なことを見出した。 即ち、 アル力 リは低級アルコールに充分溶解するのみならず、 低級アルコールに て回収されたアル力リは、 新たに加えられたアル力リにも増して、 反応の促進効果のあることがわかった。 反応機構等、 その学理的説 明は、 目下さらに探求が行われており、 いずれ解明される。  In addition, the present inventors have found that a means for recovering an alkali with a lower alcohol is very effective for a dechlorination reaction. That is, not only the alcohol was sufficiently dissolved in the lower alcohol, but also the alcohol recovered in the lower alcohol increased to the newly added alcohol, which was found to have an effect of promoting the reaction. Was. The scholarly explanation of the reaction mechanism, etc. is currently being explored further and will be elucidated soon.
そこで、 本発明では、 過剰のアルカリは反応液を濾過して分離し た固形分より低級アルコール等にて回収して、 回分反応による次の 脱塩素化反応に用い、 濾液の溶剤はそのままか或いは一部、 若しく は大部分を蒸留回収して次の回分反応に供する。  Thus, in the present invention, the excess alkali is recovered from the solids separated by filtration of the reaction solution with a lower alcohol or the like, and used for the next dechlorination reaction by a batch reaction. Part or most of it is recovered by distillation for the next batch reaction.
たとえば、 反応にあずかる有機塩素化合物の濃度が比較的高く、 前記脱塩素化反応を行った反応液を冷却後、 固形物が生成する場合 には、 過剰の未反応アルカリを反応生成物よ り分離回収する際に、 前記反応液を冷却した後、 生成した固形分を分離し、 固形分中に含 まれるアルカリを低級アルコールに溶解、 分離回収する。  For example, if the concentration of the organochlorine compound participating in the reaction is relatively high and a solid is formed after cooling the reaction solution subjected to the dechlorination reaction, excess unreacted alkali is separated from the reaction product. At the time of recovery, after cooling the reaction solution, the generated solid is separated, and the alkali contained in the solid is dissolved in a lower alcohol, and separated and recovered.
本発明では、 固形物を分離した残液中の非プロ トン性極性溶剤は、 そのままか、 或いは一部若しくは大部分を蒸留回収して、 前記脱塩 素化反応に再使用することが好ましい。  In the present invention, it is preferable that the non-protonic polar solvent in the residual liquid from which the solid matter is separated is used as it is, or a part or most of the solvent is distilled and recovered, and reused in the dechlorination reaction.
これに対して、 反応にあずかる有機塩素化合物の濃度が比較的低 く、 前記脱塩素化反応を行った反応液を冷却後、 固形物の生成が比 較的少量の場合には、 未反応アル力リを反応生成物よ り分離回収す る際に、 反応生成物を冷却せずにそのまま蒸留して非プロ トン性極 性溶剤を回収し、 釜残中に含まれるアルカ リを低級アルコールに溶 解、 分離回収する。  On the other hand, if the concentration of the organochlorine compound participating in the reaction is relatively low and the reaction solution that has undergone the dechlorination reaction is cooled, and the amount of solids produced is relatively small, unreacted alcohol When separating and recovering the pressure from the reaction product, the reaction product is distilled without cooling to recover the non-protonic polar solvent, and the alcohol contained in the bottom is converted to lower alcohol. Dissolve, separate and collect.
本発明では、 低級アルコールで溶解回収されて前記脱塩素化反応 に再利用される回収アルカリ と、 脱塩素で消費された分を補うアル 力リ量とを含めて反応槽に供給し、 非プロ トン性極性溶剤と共に反 応開始のために昇温することにより、 該低級アルコールの大部分を 系外へ留出せしめ、 これを回収して次回の脱塩素化反応後のアル力 リ回収に再使用に供することが好ましい。 In the present invention, the dechlorination reaction is carried out by dissolving and recovering with a lower alcohol. The reactor is supplied with the recovered alkali that is reused in the reactor and the amount of alcohol that supplements the amount consumed in the dechlorination, and the temperature is raised together with the non-protonic polar solvent to start the reaction. It is preferable to distill most of the lower alcohol out of the system, recover it, and reuse it for the next recovery of the alcohol after the dechlorination reaction.
本発明において、 反応液の濾過には、 遠心分離、 加圧濾過、 吸引 減圧濾過等が適当であるが、 それは原料有機塩素化合物の濃度、 系 の粘度等の条件を考えて選ばれる。 濾液中の溶剤の蒸留回収は、 減 圧蒸留、 減圧薄膜蒸留等、 効率の良い方法であれば、 その実施の形 態を問わない。 蒸留残渣が乾いた固形状になるのが便利であれば、 徹底して蒸留を行い、 固形物を碎いて濾過し、 固形物は低級アルコ —ルで抽出洗浄してアル力リを回収すれば良く、 高粘度の流体であ れば、 数バッチを合わせ低級アルコールで希釈した後、 塩類を濾過 し、 濾液のアルカリを分析して、 次の回分反応の原料に用いる。 本発明において都合の良いことには、 非プロ トン性極性溶剤を適 当に選び、 アルカリを最も経済的に選択すれば、 反応生成物と無機 塩とは室温ではこの非プロ トン性極性溶剤にあま り溶解しないので、 比較的面倒な手順を経ずに濾過分別でき、 且つアルカリのみは低級 アルコールに溶解しやすいので、 抽出回収が有利に行える。  In the present invention, centrifugation, filtration under pressure, filtration under reduced pressure and the like are suitable for filtration of the reaction solution, which are selected in consideration of conditions such as the concentration of the raw material organic chlorine compound and the viscosity of the system. Distillation and recovery of the solvent in the filtrate may be carried out in any form as long as it is an efficient method such as reduced pressure distillation and reduced pressure thin film distillation. If it is convenient for the distillation residue to become a dry solid, perform thorough distillation, crush the solid, filter it, and extract and wash the solid with low-grade alcohol to recover the alcohol. If it is a good, high-viscosity fluid, combine several batches, dilute with lower alcohol, filter the salts, analyze the alkali in the filtrate, and use it for the next batch reaction. Advantageously, in the present invention, if the nonprotonic polar solvent is appropriately selected and the alkali is most economically selected, the reaction product and the inorganic salt can be combined at room temperature with this nonprotonic polar solvent. Since it does not dissolve much, it can be separated by filtration without relatively complicated procedures, and only alkali is easily dissolved in lower alcohol, so that extraction and recovery can be performed advantageously.
前述したごと く、 低級アルコールで回収されたアルカリ物質が、 本法では最初に使用するアル力リより尚一層反応活性があることも、 本プロセスの優れた点の一例である。  As mentioned above, one of the advantages of this process is that the alkali substance recovered with the lower alcohol is much more reactive than the first method used in this method.
本発明において、 さらに重要なことは、 低級アルコール中の水分 を 1 0 %以下、 特に好ましくは付着水分のみに抑制することである。 多量の水分は、 装置の腐蝕のみならず、 反応生成物をよく溶解する ので、 脱ハロゲン化反応を反応終点に近いところで阻害することを 見出された。 しかし、 極微量の水分の役割については未だ明らかに されていないが、 反応生成物の分布から見て、 何らかの有効な役割 を果たしていると考えられる。 In the present invention, it is more important that the water content in the lower alcohol is suppressed to 10% or less, particularly preferably to only the attached water content. A large amount of water was found to inhibit the dehalogenation reaction near the end point of the reaction because it dissolves the reaction product well as well as the corrosion of the equipment. However, the role of trace water is still clear Although it has not been done, it is considered to play some effective role in the distribution of reaction products.
そこで、 アルカリを分離、 回収するために使われる低級アルコー ルとしては、 水分 1 0 %以下の炭素数 1ないし 4のアルコール類か 5 らなる群から選ばれた、 少なく とも 1種、 或いは 2種以上からなる 混合物を用いることが好ましい。  Therefore, the lower alcohol used to separate and recover the alkali is at least one or two selected from the group consisting of alcohols having 1 to 4 carbon atoms and a water content of 10% or less. It is preferable to use a mixture composed of the above.
一方、 反応にあずかる有機塩素化合物の濃度が比較的低く、 前記 脱塩素化反応を行った反応液を冷却後、 固形物の生成が比較的少量 の場合には、 冷却した前記反応液を静置して非プロ トン性極性溶剤 On the other hand, if the concentration of the organochlorine compound participating in the reaction is relatively low, and the reaction solution that has undergone the dechlorination reaction is cooled, and the amount of solids produced is relatively small, the cooled reaction solution is allowed to stand. Non-protonic polar solvent
! 0 と脱塩素化合物を含む反応液 （以下、 本反応液という。 ） の 2相に 分離し、 非プロ ト ン性極性溶剤は回収して次の脱塩素化反応に再使 用し、 該脱塩素化反応後は別の用途に用いてもよい。 ! And a reaction solution containing a dechlorinated compound (hereinafter referred to as this reaction solution) .The nonprotonic polar solvent is recovered and reused in the next dechlorination reaction. After the dechlorination reaction, it may be used for another purpose.
この場合に、 非プロ トン性極性溶剤と前記本反応液の 2相に分離 する際には、 アル力リを回収する際に使用する低級アルコールを添 In this case, when separating into the two phases of the non-protonic polar solvent and the reaction solution, the lower alcohol used for recovering the alcohol is added.
I B 加し、 非プロ トン性極性溶剤と前記本反応液との分離を迅速化する ことが好ましい。 It is preferable to add IB to speed up the separation of the nonprotonic polar solvent from the reaction solution.
本発明において、 前記非プロ トン性極性溶剤としては、 スルフォ ラン、 ジメチルスルホキシ ド （以下、 D M S Oと略す） 、 1 , 3— ジメチルー 2 —イ ミダゾリジノン （以下、 D M I と略す） 、 ジメチ 0 ルポリアルキレングリコール、 テトラメチル尿素、 N—メチルビ口 リ ドン等であって、 これらの群から選ばれた 1種、 或いは 2種以上 の混合物を 5 0 %以上含むものを用いるが、 化学的安全性、 コス ト 等の点から、 D M S O、 D M I、 ジメチルポリアルキレングリコー ルのいずれかを 5 0 %以上含有する溶剤を用いるのが特に好ましい。 In the present invention, examples of the non-protonic polar solvent include sulfolane, dimethyl sulfoxide (hereinafter abbreviated as DMSO), 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), and dimethyl alcohol. Use is made of alkylene glycol, tetramethylurea, N-methylbi-lidone, etc., which contains 50% or more of one or more of the above-mentioned compounds. From the viewpoint of cost and the like, it is particularly preferable to use a solvent containing 50% or more of DMSO, DMI, or dimethylpolyalkylene glycol.
S これらの溶剤の含有率が 5 0 %以下になると、 塩素の完全な除去が 極めて困難となる。  S When the content of these solvents is less than 50%, it is extremely difficult to completely remove chlorine.
有機塩素化合物とアル力リとを非プロ トン性極性溶剤中で攪拌す る温度としては、 1 0 0 °Cないし 3 0 0 °Cが適当であるが、 処理温 度が 1 0 0 °C以下の場合は、 非常に長時間を要することがあり、 3 0 0 °C以上の場合は、 非プロ トン性溶剤や有機塩素化合物の蒸散、 副反応による予期せざるゲル化等の危険性がある。 特に添加物を使 5 用しない場合においては、 1 5 0。Cないし 2 5 0 °Cで行われるのが 好ましい。 Stir the organic chlorine compound and alcohol in a non-protonic polar solvent A suitable temperature is 100 ° C to 300 ° C, but if the processing temperature is lower than 100 ° C, it may take a very long time, and 300 ° C may be required. If it is higher than C, there is a risk of evaporation of non-protonic solvents and organochlorine compounds and unexpected gelation due to side reactions. Especially when no additive is used, it is 150. It is preferably carried out at C to 250 ° C.
本発明において、 反応槽に供給する有機塩素化合物、 再使用する 回収アルカリ、 新たに供給するアル力リ、 新たに供給する非プロ ト ン性極性溶剤、 及び再使用する回収非プロ トン性極性溶剤について In the present invention, the organochlorine compound to be supplied to the reaction tank, the recovered alkali to be reused, the newly supplied alkali, the non-protonic polar solvent to be newly supplied, and the recovered non-protonic polar solvent to be reused about
> 0 は、 予めそのうちの 2つ、 或いは 3つ以上を混合して反応槽に供給 することが好ましい。 It is preferable that two or three or more of them are mixed beforehand and supplied to the reaction tank.
この際に、 上記の各成分を予め混合する方法として、 攪拌機付き 混合槽とスタティ ックミキサーを単独、 若しくは組み合わせて使う ことが好ましい。 この場合には、 攪拌機付き混合槽に回収非プロ ト At this time, it is preferable to use a mixing tank with a stirrer and a static mixer alone or in combination as a method of mixing the above components in advance. In this case, the collected non-prototype
, 5 ン性極性溶剤及び新たに供給する非プロ トン性極性溶剤の一部を投 入した後、 アルカリ として微粉砕した固体苛性ソーダ又は苛性力リ 及び回収アル力リ とを混入してスラ リ一化した後、 反応槽にすでに 供給してある非ブロ トン性極性溶剤と有機塩素化合物の混合液の一 部を抜き出し、 それと混合して反応槽に供給することが好ましい。 go P C Bを過剰なアル力リの存在下 D M I等の溶媒中で反応させる には、 攪拌機付き反応槽で回分反応を行うことが好ましい。 この反 応は p p bオーダーまで P C B濃度を下げるため、 反応は P C B濃 度が極く希薄な状態下においても進行する必要がある。 又、 高濃度 P C Bを処理する場合も、 反応が進行していく過程で P C B濃度は, 5 down polar After the solvent and a part of newly supplied non pro ton polar solvents were projected input, slide Li one by mixing the finely divided solid caustic soda or caustic strength Li and recovering Al force Li as alkali After the conversion, it is preferable that a part of the mixed solution of the non-brotonic polar solvent and the organochlorine compound already supplied to the reaction tank is extracted, mixed therewith, and supplied to the reaction tank. In order to react go PCB in a solvent such as DMI in the presence of excess alcohol, it is preferable to perform a batch reaction in a reaction vessel equipped with a stirrer. Since this reaction lowers the PCB concentration to the order of ppb, the reaction needs to proceed even when the PCB concentration is extremely low. Also, when treating high-concentration PCBs, the PCB concentration will increase as the reaction proceeds.
2 5 希薄となる。 従って、 反応が進むためには当然希簿な P C B分子と アルカリ分子が接触しなけらばならず、 そのためには液を剪断、 会 合することにより液の混合度を上げる必要がある。 また、 スタティ ックミキサーが好ましいのは、 比較的小型で混合度を上げることが できることと、 混合に際してこのミキサー前後の圧力損失によるェ ネルギ一消費は攪拌機に比較して少なく、 従って非常に少ないエネ ルギ一で混合効果が得られることである。 2 5 becomes diluted. Therefore, in order for the reaction to proceed, the rare PCB molecules and alkali molecules must come into contact, and for that purpose, it is necessary to increase the mixing degree of the liquid by shearing and combining the liquid. Also, Mixers are preferred because they are relatively small and can increase the degree of mixing, and the energy consumption due to the pressure loss before and after the mixer during mixing is less than that of a stirrer, and therefore the mixing effect is very small. Is obtained.
5 また、 この反応は、 D M I等の非プロ トン性極性溶剤中に溶解し たアル力リと P C Bが液相で反応し、 脱塩素化反応が進行すると考 えられている。 そのため、 反応を促進するには、 D M I中に溶解し たアルカリ濃度を高く維持して、 D M I存在下でアル力リ分子と P C B分子が会合して接触することを促進しなければならない。 そこ 5 In this reaction, it is considered that the dechlorination reaction proceeds by the reaction of the solvent dissolved in a non-protonic polar solvent such as DMI with PCB in the liquid phase. Therefore, in order to promote the reaction, the concentration of the alkali dissolved in the DMI must be kept high to promote the association and contact between the molecules and the PCB molecules in the presence of the DMI. There
, ο で反応に使うアルカリは、 D M I中への溶解を容易にするために、 微粉砕した固体苛性ソーダ又は苛性力リを D M I 中に懸濁して、 脱 塩素化反応で消費される D M I 中に溶存するアル力リを補う必要が ある。 その方法について種々検討した結果、 D M I と微粉砕したァ ルカリを混合する攪拌機付き混合槽で懸濁液をつく り、 それを攪拌The alkali used for the reaction in, ο is dissolved in the DMI consumed in the dechlorination reaction by suspending finely ground solid caustic soda or caustic soda in the DMI to facilitate dissolution in the DMI. It is necessary to make up for the energy that is generated. As a result of various studies on the method, a suspension was made in a mixing tank equipped with a stirrer that mixes DMI and finely ground alkali, and then stirred.
1 5 機を備えた反応槽中の P C Bを含む液へ直接供給し混合する方法に 比べ、 P C Bを含む液を反応槽から抜き出してスタティ ック ミキサ —を通した後、 反応槽へ戻す循環ラインをつく り、 スタティ ック ミ キサ一の入口に前記懸濁液を混入してス夕ティ ックミキサ一を通す 方法のほうが、 D M I中へのアルカリの溶解が促進され、 操作が容 0 易になる。 このようにして懸濁液を供給しつつ、 又は供給した後反 応槽を昇温し、 反応温度を一定にして脱塩素化反応を進行させるが、 この過程においても、 常に反応液の一部をス夕ティ ックミキサ一を 通して循環させる、 このようにすることにより、 脱塩素化反応を進 行させ、 所期の目的を達成させることができる。Compared to the method of directly supplying and mixing the liquid containing PCB in a reaction tank equipped with 5 units, a circulation line that extracts the liquid containing PCB from the reaction tank, passes through a static mixer, and returns to the reaction tank Mixing the suspension at the inlet of the static mixer and passing through the static mixer promotes the dissolution of alkali into the DMI and makes operation easier. . The reaction tank is heated while or after the suspension is supplied in this way, and the dechlorination reaction proceeds with the reaction temperature kept constant. This is circulated through a stick mixer. By doing so, the dechlorination reaction can proceed and the intended purpose can be achieved.
5 以上の方法は、 あらゆる濃度の有機塩素化合物を含む炭化水素油、 例えば P C B汚染トランス油或いは 1 0 0 % P C Bの処理に適用し ても、 良い結果が得られ、 場合によっては、 前記炭化水素油が再生 され、 再利用が可能となる。 図面の簡単な説明 5 The above methods have been applied to the treatment of hydrocarbon oils containing all concentrations of organochlorine compounds, such as PCB-contaminated transformer oils or 100% PCBs. Oil regenerated It can be reused. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 本発明を適用したプロセスの代表的フ口一シートを示す FIG. 1 shows a representative sheet of a process to which the present invention is applied.
5 図である。 FIG.
図 2は、 本発明を適用した別のプロセスの代表的フローシ一トを 示す図である。  FIG. 2 is a diagram showing a typical flow sheet of another process to which the present invention is applied.
図 3は、 本発明を適用したプロセスに関するフロー試験において、 アルカリ、 溶剤回収がないケースについて物質収支の一例を示す図 Fig. 3 shows an example of the material balance in the case where there is no recovery of alkali and solvent in the flow test for the process to which the present invention is applied.
1 0 C'ある There is 1 0 C '
図 4は、 本発明を適用したプロセスに関するフロー試験において、 アルカリ、 溶剤回収があるケースについて物質収支の一例を示す図 である。  FIG. 4 is a diagram showing an example of a material balance in a case where an alkali and a solvent are recovered in a flow test on a process to which the present invention is applied.
図 5は、 本発明を適用したプロセスにおいて、 反応槽へ原料を供 Figure 5 shows that raw materials were supplied to the reaction tank in the process to which the present invention was applied.
. 5 給する方法の一例を示す図である。 . 5 is a diagram showing an example of a method of supplying.
図 6は、 本発明を適用したさらに別のプロセスの代表的フローシ 一トを示す図である。  FIG. 6 is a diagram showing a typical flow sheet of still another process to which the present invention is applied.
図 7は、 本発明を適用したプロセスのフロー試験において、 無害 ィ匕した絶縁油を燃料油に再利用することを示す図である。  FIG. 7 is a diagram showing that harmless insulating oil is reused as fuel oil in a flow test of a process to which the present invention is applied.
s o 図 8は、 本発明を適用したプロセスのフロー試験において、 D M I、 回収アルカリを 1 5回リサイクルし、 燃料油に再利用する際の マテリアルバランスを示す図である。 so FIG. 8 is a diagram showing the material balance when DMI and the recovered alkali are recycled 15 times and reused as fuel oil in the flow test of the process to which the present invention is applied.
(符合の説明）  (Description of sign)
図 1における符合  Sign in Figure 1
2 5 1 D M I 2 5 1 D M I
2 苛性ソーダ  2 Caustic soda
3 攪拌機 4 5U心榷3 Stirrer 4 5U heart 榷
5 ジャケッ ト 5 jackets
6 濾過器 （ 1 ) 6 Filter (1)
7 濾過器 （ 2 )7 Filter (2)
5 8 5 8
9 P CB含有絶縁油 9 P CB-containing insulating oil
1 0 濾液 （ 1 ) 1 0 Filtrate (1)
1 1 ケーキ （ 1 ) 1 1 Cake (1)
1 2 ケーキ （ 2 )1 2 Cake (2)
.o 1 3 濾液 （ 2 ) .o 1 3 Filtrate (2)
1 4 回収 D M I  1 4 Recovery D M I
1 5  1 5
1 6 回収エタノ一ル 1 6 Recovered ethanol
1 7 エタノール 1 7 Ethanol
• 5 1 8 補給エタノール • 5 1 8 Makeup ethanol
1 9 溶解槽 1 9 melting tank
2 0 反応液  20 Reaction liquid
3 6 回収 D M I貯槽 3 6 Collection D M I storage tank
3 7 コンデンサ一 o 3 8 コンデンサー 3 7 Capacitor 1 o 3 8 Capacitor
図 2における符合  Signs in Figure 2
2 1一 1 分液槽  2 1 1 1
2 1一 2 分液槽  2 1 1 2 Separation tank
2 2 エタノール/ Na< 5 2 U 水洗/中和槽  2 2 Ethanol / Na <52 U Wash / neutralization tank
2 4 油相  2 4 Oil phase
2 5 水相 2 6 水 2 5 water phase 2 6 water
2 7  2 7
上記以外の符合は図 1に示したものと共通である 図 5における符合 Symbols other than the above are the same as those shown in FIG. 1.
28 循環ポンプ  28 Circulation pump
29 スタティ ックミキサ一  29 Static Mixer
30 循環ライン 30 Circulation line
3 1 反応供給液の配管 3 1 Piping of reaction supply liquid
3 2 供給ポンプ 3 2 Feed pump
33 攪拌機 33 stirrer
34 混合槽 34 Mixing tank
35 加熱用ヒ一夕 35 Overnight heating
上記以外の符合は図 1 2に示したものと共通である 図 7における符合 Symbols other than the above are the same as those shown in FIG. 12.
39 調整槽  39 Conditioning tank
40 冷却槽  40 Cooling tank
4 1 濾液受槽 4 1 Filtrate receiving tank
42 留出液 （DM I ) 受槽 42 Distillate (DMI) receiving tank
43 分離器 43 separator
44 高圧絶縁油 （T F 0) 受槽  44 High pressure insulating oil (T F 0)
45 釜残液受槽 45 Remaining tank
46 アル力 リ溶解槽 46 AL force remelting tank
47 アルコール供給槽 47 Alcohol supply tank
48 アルカ リ含有アルコール溶液貯槽 48 Alkaline-containing alcohol solution storage tank
49 アル力 リ供給槽 49 Al power supply tank
50 ケーキ貯槽 50 cake storage tank
5 1 原料 （P CB含有 TFO) 供給槽 5 2 溶媒 （D M I ) 供給槽 5 1 Raw material (PCF containing TFO) supply tank 5 2 Solvent (DMI) supply tank
5 3 新アル力リ供給槽  5 3 New power supply tank
5 4 攪拌用駆動モーター  5 4 Stirring drive motor
5 5 T F 0水洗槽  5 5 T F 0 Rinse tank
5 5 6 T F 0水洗受槽  5 5 6 T F 0 Washing tank
5 7 T F 0重油混合槽  5 7 T F 0 Heavy oil mixing tank
上記以外の符合は図 1、 2に示したものと共通である。 発明を実施するための最良の形態  Reference numerals other than those described above are the same as those shown in FIGS. BEST MODE FOR CARRYING OUT THE INVENTION
, ο 本発明のプロセスの理解を深めるために、 次に本プロセスを図に よ り説明する。 又、 本プロセスの代表的フローシー トを図 1、 図 2 . 図 5、 図 6、 図 7に示し、 図 3にアルカリ、 溶剤回収がないケース について、 図 4にアルカリ、 溶剤回収があるケースについて、 図 8 に D M I、 回収アルカリをリサイクルするケースについての物質収 , ο In order to better understand the process of the present invention, the process will be described with reference to the drawings. Fig. 1, Fig. 2, Fig. 5, Fig. 6, and Fig. 7 show typical flow sheets of this process, Fig. 3 shows the case without alkali and solvent recovery, and Fig. 4 shows the case with alkali and solvent recovery. Figure 8 shows the DMI and the material yield for the case of recycling recovered alkali.
. 5 支の一例を示した。 なお、 物質収支を示す図 3および図 4では、 各 枠内のうち、 図面に向かって左側の枠内の数字は図 1 に示す各要素 の符合に対応し、 図面に向かって右側の枠内の数字は左側の枠内に 示す要素に対応するバランス値 （ g ) を示してある。 . An example of the five branches was given. In Figures 3 and 4 showing the material balance, the numbers in the boxes on the left side of the drawing correspond to the numbers of the elements shown in Figure 1 and in the boxes on the right side of the drawing. Indicates the balance value (g) corresponding to the element shown in the box on the left.
本プロセスの実施に当たっては、 原料或いは実施場所の条件に合 0 わせ、 フロ一の本質を変えない程度の変更を加えることは、 本発明 の精神を逸脱せざる限り、 図面により限定されないことは明白であ り、 本プロセスの優位性に何らの負の要因たり得ないことは、 自明 の理である。  In carrying out the present process, it is obvious that changes to the extent that does not change the essence of the flow according to the conditions of the raw materials or the place of execution are not limited by the drawings as long as they do not depart from the spirit of the present invention. It is self-evident that there is no negative factor in the superiority of this process.
実施例 1 Example 1
5 図 1は本発明を実施する場合の一例を示したものである。 9は比 較的高濃度の P C B含有絶縁油で、 約 7 %程度の P C Bを含有して いる。 1は非プロ トン性極性溶媒 （例えば D M I ) 、 2はアルカリ (例えば苛性ソーダ） 、 14は反応後蒸留器で回収された DM I、 1 3はアルカリを溶解した低級アルコール （例えばエタノール） を 示す。 これらをジャケッ ト 5付きの攪拌機付き反応槽 4に供給し、 ジャケッ ト 5に加熱した熱媒を通して約 2 1 0°Cに加熱し常圧で 1 〜 4時間反応させる。 反応後、 反応液 20中の P CBを分析し、 検 知限界以下になった時点で反応を終了させる。 この液をジャケッ ト 5に低温の冷媒を通して常温まで冷却し、 ここで生成した固体の N a C 1を含むスラ リー状の反応液 20を 6の濾過器 （ 1 ) で濾過す る。 濾液 1 0は蒸留器 8に供給して溶媒を回収し、 次の回分反応に 再使用する。 このようにして得られた釜残 1 5について、 P CBの 分析を行った。 5 FIG. 1 shows an example in which the present invention is implemented. 9 is a relatively high-concentration insulating oil containing PCB, which contains about 7% of PCB. 1 is a non-protonic polar solvent (eg DMI), 2 is an alkali (Eg, caustic soda), 14 indicates DMI recovered in the still after the reaction, and 13 indicates lower alcohol (eg, ethanol) in which alkali is dissolved. These are supplied to a reaction tank 4 with a stirrer equipped with a jacket 5, heated to about 210 ° C. through a heating medium heated in the jacket 5, and reacted at normal pressure for 1 to 4 hours. After the reaction, the PCB in the reaction solution 20 is analyzed. This liquid is cooled to room temperature by passing a low-temperature refrigerant through a jacket 5, and the slurry-like reaction liquid 20 containing the solid NaC 1 generated here is filtered by a filter (1) of 6. The filtrate 10 is supplied to the still 8 to recover the solvent and reused in the next batch reaction. The remaining tank 15 obtained in this way was analyzed for PCB.
その結果、 P C Bの含有量は検出限界の 0. 5 pp b ( G C -M S実績） 以下であった。 分離された 1 1のケーキ （ 1 ) は溶解槽 1 9で、 ケーキ中に含まれる未反応アル力リ分をェ夕ノール中に溶解 した後、 7の濾過器 （ 2 ) で濾液 1 3と 1 2のケーキ （ 2 ) に分離 する、 濾液 1 3は回収アルカリを溶存するエタノールで、 回分操作 により次の反応に再利用する。 ここでは濾過器 6と 7は 2つ別々に 示してあるが、 2つに分けずに回分操作によ り同一のものを使い分 けすることもできる。 なお、 3、 14、 1 6、 1 7、 1 8、 36、 37、 38は、 それそれ攪拌機、 回収 DM I、 回収エタノール、 ェ 夕ノール、 補給エタノール、 回収 DM I槽、 第 1のコンデンサ一、 第 2のコンデンサ一である。  As a result, the PCB content was below the detection limit of 0.5 ppb (GC-MS results). The separated cake (1) of 11 is dissolved in the dissolving tank 19 to dissolve the unreacted alcohol contained in the cake in ethanol, and the filtrate 13 is filtered by the filter (2) 7. The filtrate 13 that separates into the cake (2) in 12 is ethanol that dissolves the recovered alkali and is reused in the next reaction by batch operation. Here, two filters 6 and 7 are shown separately, but the same one can be used separately by batch operation without being divided into two. In addition, 3, 14, 16, 17, 18, 18, 36, 37, and 38 are each agitator, recovered DMI, recovered ethanol, ethanol, replenishment ethanol, recovered DMI tank, and first condenser. The second capacitor is one.
図 3は比較的高濃度の P CB含有絶縁油を分解するケースで、 ァ ルカリ、 溶剤を再使用しない、 最初の回分操作の物質収支の概略の 一例を示す。  Fig. 3 shows an example of the mass balance of the first batch operation without the use of alkalis and solvents, in which a relatively high concentration of insulating oil containing PCB is decomposed.
実施例 2  Example 2
1¾4は比較的高濃度の P C B含有絶縁油を分解するケースで、 ァ ルカリ、 溶剤を再使用する場合の実施例についての物質収支の一例 を示す。 各部の温度、 操作条件は実施例 1に示したものとほぼ同じ である。 1¾4 shows the case of decomposing insulating oil containing PCB at relatively high concentration. An example of the material balance of the embodiment in the case of reusing the alkali and the solvent is shown. The temperature and operating conditions of each part are almost the same as those shown in the first embodiment.
実施例 3  Example 3
5 図 2は本発明を実施する場合のもう一つの例を示したものである。 5 FIG. 2 shows another example in which the present invention is implemented.
9は比較的低濃度の P C B含有絶縁油で、 2 0 p p m程度の P C B を含有している。 ここでいう低濃度とは、 反応後冷却しても反応生 成物の析出が比較的少ない希薄な P C B濃度を指す。 それ以外の番 号は、 図 1で説明したものと同一のもの、 或いはほぼ同じ機能又は 9 is a relatively low-concentration insulating oil containing PCB, which contains about 20 ppm of PCB. The term “low concentration” as used herein refers to a dilute PCB concentration in which the reaction product is relatively little precipitated even after cooling after the reaction. Other numbers are the same as those described in FIG.
, 0 性質を有するものである。 攪拌反応槽での操作は実施例 1の場合と 同様であるが、 反応終了後、 反応液 2 0は脱塩素化反応の微粉碎苛 性ソ一ダ以外の固形物を含まないので、 そのまま蒸留器 8へ供給さ れ、 溶剤を回収し、 釜残 1 5は溶解槽 1 9で未反応アル力リをエタ ノ一ル中に溶解させる。 それを分液槽 2 1— 1で油相とアル力リを, 0 properties. The operation in the stirred reaction tank is the same as in Example 1, but after the reaction, the reaction solution 20 is distilled as it is because it does not contain solids other than the finely ground caustic soda in the dechlorination reaction. The solvent is supplied to the vessel 8, and the solvent is recovered. The remaining tank 15 dissolves unreacted alcohol in ethanol in the dissolution tank 19. Separate the oil phase and oil in the separation tank 2 1—1
, s 溶解したアルコール相 2 4に分け、 アルコール相 2 2は回分操作に より次の回分反応に再利用する。 油相は水洗/中和槽 2 3で水 2 6 で水洗後、 酸 2 7で中和し分液槽 2 1一 2で油相 2 と水相 2 5に 分離する。 ここで得られる '油相 2 4について P C Bを分析した結果 は、 P C Bは 0 . 5 p p b以下の検出限界以下まで除去されている 0 ことが分かつた。 , s Divide the dissolved alcohol phase 24 and reuse the alcohol phase 22 in the next batch reaction by batch operation. The oil phase is washed with water 26 in a water washing / neutralization tank 23, neutralized with an acid 27, and separated into an oil phase 2 and an aqueous phase 25 in a separation tank 21-12. The analysis of PCB for the oil phase 24 obtained here showed that PCB was removed to below the detection limit of 0.5 ppb or less.
実施例 4  Example 4
図 5は反応槽へ原料を供給する方法の一例を示したものである。 ここに示した番号は図 1、 2 と共通である。 これら原料は、 攪拌機 3 3付きの混合槽 3 4中で予めよく混合した後、 供給ポンプ 3 2を 5 使って配管 3 1を通して反応液循環ライン 3 0に混入する。 この混 入した反応循環液は加熱用ヒータ 3 5を備えるスタティ ックミキサ — 2 9で完全混合された後、 攪拌機 3付きの反応槽 4 (攪拌反応槽） に戻され、 更に攪拌機 3によ り攪拌操作を受ける。 FIG. 5 shows an example of a method for supplying a raw material to a reaction tank. The numbers shown here are the same as in Figures 1 and 2. These raw materials are mixed well in advance in a mixing tank 34 equipped with a stirrer 33, and then mixed into a reaction liquid circulation line 30 through a pipe 31 using a supply pump 32. The mixed reaction circulating liquid is completely mixed by a static mixer 29 equipped with a heater 35, and then the reaction tank 4 with the stirrer 3 (stirred reaction tank) And further subjected to a stirring operation by the stirrer 3.
このスタティ ック ミキサー 2 9は反応槽 4内で攪拌操作を受ける 液の一部を循環ポンプ 2 8を介して抜き出すため、 スタティ ック ミ キサー 2 9での混合強度は攪拌反応槽内での混合強度よりも更に強 力なものを選ぶ必要があるのは当然である。  Since the static mixer 29 extracts a part of the liquid subjected to the stirring operation in the reaction tank 4 through the circulation pump 28, the mixing intensity in the static mixer 29 is limited to the mixing intensity in the stirring reaction tank. Naturally, it is necessary to select something stronger than the mixing strength.
アルカ リは固体で供給され、 液の比重に比べて重いため、 攪拌反 応槽底部に一部が沈殿し、 遠心攪拌が主である反応器の場合には、 懸濁状態を維持できずに反応液との接触が不完全となる傾向がある。 これを改善する方法として、 沈殿した固形分を底部よ り抜き出しス 夕ティ ックミキサー 2 9を通すことにより、 反応液中への懸濁状態 を維持改善することが可能となる。 この操作は原料供給後も継続し て行う。  Alkali is supplied as a solid, and is heavier than the specific gravity of the liquid.Therefore, a part of the alkali precipitates at the bottom of the agitation reactor, and in the case of a reactor that mainly uses centrifugal agitation, the suspension cannot be maintained. Contact with the reaction solution tends to be incomplete. As a method of improving this, it is possible to maintain and improve the state of suspension in the reaction solution by extracting the precipitated solid from the bottom and passing it through a stick mixer 29. This operation is continued even after the supply of raw materials.
更に、 図 5で 3 5はスタティ ックミキサ一部を加熱するヒー夕で、 循環ライ ンでの熱損失による温度低下を補う と共に、 必要に応じて 昇温させ、 それにより反応速度を高める効果も合わせ持たせること ができるようになつている。  In addition, in Fig. 5, reference numeral 35 denotes a heater that heats a part of the static mixer, compensating for the temperature drop due to heat loss in the circulation line and increasing the temperature as needed, thereby increasing the reaction speed. It can be held.
このような方法により撹拌反応槽の反応温度 2 1 0 °C、 常圧で反 応を行う場合、 原料供給法について直接反応槽へ供給する方法と、 ス夕ティ ック ミキサーで供給する方法とを比較した結果、 以下の効 果が得られた。  When the reaction is carried out at a reaction temperature of 210 ° C and normal pressure in the stirred reaction tank by such a method, the raw material supply method is directly supplied to the reaction tank, and the raw material is supplied using a static mixer. As a result, the following effects were obtained.
( 1 ) 直接供給法に比べて、 混合槽を設ける方法では仕込操作が容 易になった。  (1) Compared with the direct supply method, the charging operation was easier with the method with a mixing tank.
( 2 ) 反応槽内でのアルカリ固形物の底部沈殿が防止され、 それに より懸濁状態が維持されることによって、 反応の促進効果が得られ た。  (2) The effect of accelerating the reaction was obtained by preventing the bottom precipitation of the alkali solids in the reaction tank and maintaining the suspended state.
( 3 ) その結果、 ス夕ティ ックミキサー使用の場合は、 直接法の所 要時間の約 8 0 %で所期の目的が達成された。 実施例 5 (3) As a result, in the case of using a stick mixer, the intended purpose was achieved in about 80% of the time required by the direct method. Example 5
実施例 5では図 2に示したプロセスフローにより比較的低濃度の P CB含有絶縁油についての処理例を示したものである。 ここでは 反応槽の他に蒸留器を別に設け、 ここで溶剤の回収を行っている。 5 溶剤として DM Iを用いた場合、 その沸点は常圧で 225. 5 °Cで あるのに対し、 絶縁油では 2 50〜 470 °Cであるため、 単蒸留で 容易に分離できるので、 反応槽を蒸留器としても使用可能である。 このようにするとプロセスは簡単にすることができ、 設備費も節約 できて処理コス トを低減することが可能となる。 この例を図 6に示 Example 5 shows an example of processing a relatively low-concentration insulating oil containing PCB by the process flow shown in FIG. Here, in addition to the reaction tank, a still is provided separately, and the solvent is recovered here. 5 When DMI is used as a solvent, its boiling point is 225.5 ° C at normal pressure, whereas it is 250-470 ° C for insulating oil, so it can be easily separated by simple distillation. The tank can be used as a still. In this way, the process can be simplified, equipment costs can be saved, and processing costs can be reduced. An example of this is shown in Figure 6.
] 0 した。 ] 0
尚、 蒸留は加熱源の温度を考慮して減圧で行っても良く、 例えば 絶対圧 4 OmmHgでは、 1 50°Cで DM Iを反応液より留出分離 することができる。  The distillation may be performed under reduced pressure in consideration of the temperature of the heating source. For example, at an absolute pressure of 4 OmmHg, DMI can be distilled off from the reaction solution at 150 ° C.
このプロセスでは、 回収された DM I及びアルコール中に溶解し is たアルカリを再使用することにより、 極めて経済的に TFO (絶縁 油） から P C Bを除去することができ、 更に P CBを除いて無害化 した絶縁油は、 燃料油として再利用できる。 この例のプロセスフロ 一を図 7、 その際のマテリアルバランスを図 8に示した。  In this process, PCBs can be removed from TFO (insulating oil) very economically by reusing the recovered DMI and alkali dissolved in alcohol, and it is harmless except for PCB. The converted insulating oil can be reused as fuel oil. Fig. 7 shows the process flow of this example, and Fig. 8 shows the material balance at that time.
図 7において、 39、 40、 4 1、 42、 43、 44、 45はそ 0 れそれ、 調整槽、 冷却槽、 濾液受槽、 留出液 （DM I ) 受槽、 分離 器、 高圧絶縁油 （TFO) 受槽、 釜残液受槽である。 46、 47、 48、 49、 50、 5 1、 52、 53はそれそれアルカリ溶解槽、 アルコール供給槽、 アルカリ含有アルコール溶液貯槽、 アルカリ供 給槽、 ケーキ貯槽、 原料 （P CB含有 T FO) 供給槽、 溶媒 （DM s I ) 供給槽、 新アル力リ供給槽である。 54、 55、 56、 57は それそれ、 攪拌用駆動モータ一、 T FO水洗槽、 T FO水洗受槽、 T FO重油混合槽である。 ここでは回収した DM Iを 1 5回リサイクルし、 変成ェチルアル コールで回収したアルカリは 1 5回以上リサイクルを行うことがで きた例である。 In Fig. 7, 39, 40, 41, 42, 43, 44, and 45 denote the adjustment tank, the cooling tank, the filtrate receiving tank, the distillate (DMI) receiving tank, the separator, and the high-pressure insulating oil (TFO). ) Receiving tank. 46, 47, 48, 49, 50, 51, 52, 53 are alkali dissolution tanks, alcohol supply tanks, storage tanks containing alkali-containing alcohol solutions, alkali supply tanks, cake storage tanks, and raw materials (TFO containing PCBs) Tank, solvent (DMsI) supply tank, and new supply tank. Reference numerals 54, 55, 56, and 57 denote a drive motor for stirring, a TFO washing tank, a TFO washing tank, and a TFO heavy oil mixing tank. In this example, the recovered DMI was recycled 15 times, and the alkali recovered in the metamorphic alcohol was recycled 15 times or more.
最初に、 新 DM I及び新苛性ソーダを使用して、 80 ppmの P CBを含有する新 TFO中の P CBを脱塩素化反応させる。 この後 の液は、 T FO相と DMI相 （苛性ソーダの固体を含んだ固液相） とに分相し、 この DM I相 （苛性ソーダを含む） を再び反応に使用 する。 80 p p mの P C Bを含有した T F 01 , 000 g · D M I 1， 000 g · 苛性ソーダ 60 gを加え、 反応槽に入れる。 200 °Cまで昇温し、 2時間強く攪拌する。 2時間後の系中の P C Bの残 存濃度は 0. 5 ppb (検出限界以下 =N. D. ) となる。  First, the PCB in the new TFO containing 80 ppm of PCB is dechlorinated using new DMI and new caustic soda. The liquid after this is separated into a TFO phase and a DMI phase (solid-liquid phase containing caustic soda solid), and this DMI phase (containing caustic soda) is used again for the reaction. Add TF 01,000 g containing 80 ppm of PCB · DMI 1,000 g · caustic soda 60 g, and put into the reactor. Heat to 200 ° C and stir vigorously for 2 hours. The residual concentration of PCB in the system after 2 hours is 0.5 ppb (lower than detection limit = ND).
反応液をまず分相させて、 T FO相と DM I相とに分離する。 こ のとき、 必要なら反応及び分相促進のため、 少量の低級アルコール ( 1 0%以下の水分含有） を加えても良い。 更に分相を助けるには 一度簡単な濾過を行い （加圧又は減圧） 、 その後分相をする。 TF 0相は水洗した後、 重油に混合して燃料油に再利用する。 DM I相 の DM Iと苛性ソーダは、 新しい T FO中の P CBを分解反応させ るために再使用する。 これを 1 5回繰り返す。 反応のために、 必要 に応じて少量の D M I及び少量の苛性ソーダを加えることもある。 苛性ソーダ、 反応生成物及び塩化ナト リウムを含んだ DM I相は、 通常はまず遠心濾過器で濾過し、 固液を分離する。 液相の濾液を蒸 留して DM Iを回収する。 この DM Iは、 次の反応にリサイ クルす る。 一方、 固相分 （ケーキ） は、 苛性ソーダを充分溶解する量の変 成エチルアルコールを加えて、 脱塩素化反応に使用した後の残存苛 性ソ一ダを回収する。 このとき、 反応生成物の大部分及び生成した 塩化ナ ト リウムは、 変成エチルアルコールにほとんど溶解しないの で、 固体として存在する。 これらの混合物を遠心濾過器で濾過して、 固液の分離を行う。 苛性ソーダは液相の濾液にほとんど移り、 次の 反応のためにリサイクルする。 D M I及びアルカリの回収率は、 そ れそれ 9 9 %及び 9 1 %であった。 The reaction is first separated and separated into a TFO and DMI phase. At this time, if necessary, a small amount of lower alcohol (containing 10% or less of water) may be added to promote the reaction and phase separation. To further assist in phase separation, perform a simple filtration once (pressurized or depressurized) and then separate phases. After the TF0 phase is washed with water, it is mixed with heavy oil and reused as fuel oil. The DMI phase DMI and caustic soda are reused to decompose the PCB in the new TFO. Repeat this 15 times. A small amount of DMI and a small amount of caustic soda may be added as needed for the reaction. The DMI phase containing caustic soda, reaction products and sodium chloride is usually first filtered through a centrifugal filter to separate the solid and liquid. Distill the liquid filtrate to recover DMI. This DMI is recycled to the next reaction. On the other hand, for the solid phase (cake), an amount of denatured ethyl alcohol that sufficiently dissolves caustic soda is added, and the remaining caustic soda after use in the dechlorination reaction is recovered. At this time, most of the reaction product and the generated sodium chloride hardly dissolve in denatured ethyl alcohol, and therefore exist as a solid. These mixtures are filtered through a centrifugal filter, Separate the solid and liquid. Most of the caustic soda transfers to the liquid filtrate and is recycled for the next reaction. The recoveries of DMI and alkali were 99% and 91%, respectively.
実施例 6  Example 6
プロセスのマテリアルバランスは、 実施例 5 とほぼ同じであるが、 溶剤として、 D M Iの代わりに ト リエチレングリコ一ルジメチルェ —テル （沸点 2 1 6 °C ) 或いはテ トラエチレングリコールジメチル エーテル （沸点 2 7 5 . 3 °C ) を使用し、 且つアルカリとして苛性 ソ一ダを使用して反応させ、 1 5回リサイクルしたプロセスに関す る実施例である。 溶剤と T F 0の分相において、 含水メタノール （ 1 0 %水分含有） を使用する。 産業上の利用可能性  The material balance of the process is almost the same as in Example 5, except that the solvent used is triethylene glycol dimethyl ether (boiling point 2 16 ° C) or tetraethylene glycol dimethyl ether (boiling point 275) instead of DMI. This is an example of a process in which the reaction was carried out 15 times by using caustic soda as the alkali. Use water-containing methanol (containing 10% water) in the phase separation between the solvent and TF0. Industrial applicability
本発明は、 以上説明したごとく、 あらゆる濃度の有機塩素化合物 を含む炭化水素油、 例えば P C B汚染トランス油或いは 1 0 0 % P C Bの処理に適用しても、 良い結果が得られ、 場合によっては、 前 記炭化水素油が再生され、 再利用が可能となる。 それ故、 本発明に 係る有機塩素化合物の脱塩素化方法は、 極めて経済的に有機塩素化 合物を脱塩素化及び無害化するプロセスに関するものであり、 従つ て、 本発明を実施することにより、 経済的に、 安全に環境の改善に 寄与することができる。  As explained above, the present invention can be applied to the treatment of hydrocarbon oils containing all concentrations of organochlorine compounds, for example, PCB-contaminated transformer oil or 100% PCB, with good results. The hydrocarbon oil mentioned above will be regenerated and reused. Therefore, the method for dechlorinating an organic chlorinated compound according to the present invention relates to a process for dechlorinating and detoxifying an organic chlorinated compound in a very economical manner. As a result, it is possible to safely and economically contribute to the improvement of the environment.

Claims

請 求 の 範 囲 The scope of the claims
1 . 有機塩素化合物と過剰のアル力リ とを、 非プロ ト ン性極性 溶剤中で、 1 0 0 °Cないし 3 0 0 °Cにて攪拌、 混合することによ り 反応槽内で脱塩素化反応を行う工程において、 該脱塩素化反応後、 過剰の未反応アル力リは反応生成物より分離回収して前記脱塩素化 反応に再使用し、 非プロ トン性極性溶剤はそのままか、 或いは一部 若しくは大部分を分離回収して前記脱塩素化反応に再使用すること により、 前記工程の生成物をアル力リ塩酸塩と原料有機塩素化合物 の脱塩素化物に転化することを特徴とする、 有機塩素化合物の脱塩 素化方法。 1. The organic chlorine compound and excess alcohol are removed in the reaction vessel by stirring and mixing at 100 ° C to 300 ° C in a non-protonic polar solvent. In the step of performing the chlorination reaction, after the dechlorination reaction, the excess unreacted alcohol is separated and recovered from the reaction product and reused in the dechlorination reaction, and the non-protonic polar solvent is left as it is. Alternatively, by separating and recovering a part or most of the product and reusing it in the dechlorination reaction, the product of the above process is converted into a dechlorinated product of an alkaline hydrochloride and a raw material organic chlorine compound. A method for dechlorination of an organic chlorine compound.
2 . 請求の範囲第 1項において、 反応にあずかる有機塩素化合 物の濃度が比較的高く、 前記脱塩素化反応を行った反応液を冷却後、 固形物が生成する場合には、 2. In claim 1, when the concentration of the organic chlorinated compound participating in the reaction is relatively high, and a solid is formed after cooling the reaction solution that has been subjected to the dechlorination reaction,
過剰の未反応アル力リを反応生成物より分離回収する際に、 前記 反応液を冷却した後、 生成した固形分を分離し、 固形分中に含まれ るアルカリを低級アルコールに溶解、 分離回収することを特徴とす る、 有機塩素化合物の脱塩素化方法。  When separating and recovering excess unreacted alcohol from the reaction product, the reaction solution is cooled, the generated solid is separated, and the alkali contained in the solid is dissolved in lower alcohol, separated and recovered. A method for dechlorinating an organic chlorine compound.
3 . 請求の範囲第 1項において、 反応にあずかる有機塩素化合 物の濃度が比較的低く、 前記脱塩素化反応を行った反応液を冷却後、 固形物の生成が比較的少量の場合には、 3. In claim 1, when the concentration of the organic chlorinated compound participating in the reaction is relatively low, and after the reaction solution that has been subjected to the dechlorination reaction is cooled, the amount of solid matter generated is relatively small, ,
未反応アル力リを反応生成物より分離回収する際に、 反応生成物 を冷却せずにそのまま蒸留して非プロ トン性極性溶剤を回収し、 釜 残中に含まれるアルカ リを低級アルコールに溶解、 分離回収するこ とを特徴とする、 有機塩素化合物の脱塩素化方法。 When separating and recovering unreacted alcohol from the reaction product, the reaction product is distilled without cooling to recover the nonprotonic polar solvent, and the alcohol contained in the bottom is converted to lower alcohol. A method for dechlorination of an organic chlorine compound, which comprises dissolving, separating and collecting.
4 . 請求の範囲第 1項において、 反応にあずかる有機塩素化合 物の濃度が比較的低く、 前記脱塩素化反応を行った反応液を冷却後、 固形物の生成が比較的少量の場合には、 4. In claim 1, when the concentration of the organic chlorinated compound participating in the reaction is relatively low, and after the reaction solution that has been subjected to the dechlorination reaction is cooled, the amount of solid matter generated is relatively small, ,
冷却した前記反応液を静置して非プロ トン性極性溶剤と脱塩素化 5 合物を含む本反応液の 2相に分離し、 非プロ ト ン性極性溶剤は回収 して次の脱塩素化反応に再使用し、 該脱塩素化反応後は別の用途に 用いることを特徴とする、 有機塩素化合物の脱塩素化方法。  The cooled reaction solution is allowed to stand and separated into two phases of the reaction solution containing a non-protonic polar solvent and a dechlorinated pentoxide, and the non-protonic polar solvent is recovered and subjected to the next dechlorination. A method for dechlorinating an organic chlorine compound, wherein the method is reused in a chlorination reaction and used for another purpose after the dechlorination reaction.
5 . 請求の範囲第 4項において、 非プロ ト ン性極性溶剤と前記 , ο 本反応液の 2相に分離する際に、 アルカリを回収する際に使用する 低級アルコールを添加し、 非プロ ト ン性極性溶剤と前記本反応液と の分離を迅速化することを特徴とする、 有機塩素化合物の脱塩素化 方法。 i s5. In claim 4, when separating into two phases of the non-protonic polar solvent and the above-mentioned reaction solution, the lower alcohol used for recovering the alkali is added, and the non-protonic polar solvent is added. A method for dechlorinating an organochlorine compound, comprising: speeding up the separation of a non-polar polar solvent from the reaction solution. i s
6 . 請求の範囲第 2項において、 固形物を分離した残液中の非 プロ トン性極性溶剤は、 そのままか、 或いは一部若しくは大部分を 蒸留回収して、 前記脱塩素化反応に再使用することを特徴とする、 有機塩素化合物の脱塩素化方法。 06. In Claim 2, the non-protonic polar solvent in the residual liquid from which the solids are separated is used as it is, or part or most of it is recovered by distillation and reused in the dechlorination reaction. A method for dechlorinating an organochlorine compound. 0
7 . 請求の範囲第 2項または第 3項において、 アルカリを分離. 回収するために使われる低級アルコールが、 水分 1 0 %以下の炭素 数 1ないし 4のアルコール類からなる群から選ばれた、 少なく とも 1種、 或いは 2種以上からなる混合物であることを特徴とする、 有 機塩素化合物の脱塩素化方法。7. In Claims 2 or 3, the alkali is separated. The lower alcohol used for recovery is selected from the group consisting of alcohols having 1 to 4 carbon atoms and a water content of 10% or less. A method for dechlorination of an organic chlorine compound, wherein the method is a mixture of at least one kind or two or more kinds.
5  Five
8 . 請求の範囲第 1項において、 前記非プロ トン性極性溶剤が、 スルフ ォラン、 ジメチルスルホキシ ド、 1， 3 —ジメチルー 2 —ィ ミダゾリジノ ン、 ジメチルポリアルキレングリコール、 テ トラメチ ル尿素、 N —メチルビロ リ ドンなる群から選ばれた少なく とも 1種、 或いは 2種以上の混合物を 5 0 %以上含むことを特徴とする、 有機 塩素化合物の脱塩素化方法。 8. The non-protonic polar solvent according to claim 1, wherein the non-protonic polar solvent is sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-di. An organic chlorine compound containing at least 50% of at least one kind or a mixture of two or more kinds selected from the group consisting of midazolidinone, dimethylpolyalkylene glycol, tetramethylurea, and N-methylvirolidone. Dechlorination method.
9 . 請求の範囲第 2項または第 3項において、 低級アルコール で溶解回収されて前記脱塩素化反応に再利用される回収アル力リ と、 脱塩素で消費された分を補うアル力リ量とを含めて反応槽に供給し、 非プロ トン性極性溶剤と共に反応開始のために昇温することによ り、 該低級アルコールの大部分を系外へ留出せしめ、 これを回収して次 回の脱塩素化反応後のアル力リ回収に再使用に供することを特徴と する、 有機塩素化合物の脱塩素化方法。 9. In Claims 2 or 3, the recovered energy that is dissolved and recovered with a lower alcohol and reused in the dechlorination reaction, and the amount of energy that supplements the amount consumed in the dechlorination. And the temperature was raised to start the reaction together with the non-protonic polar solvent, thereby distilling most of the lower alcohol out of the system. A method for dechlorinating an organochlorine compound, wherein the method is used for recovery after recovery of a number of dechlorination reactions.
1 0 . 請求の範囲第 1項において、 反応槽に供給する有機塩素化 合物、 再使用する回収アルカリ、 新たに供給するアルカリ、 新たに 供給する非プロ トン性極性溶剤、 及び再使用する回収非プロ トン性 極性溶剤を、 予め、 そのうちの 2つ、 或いは 3つ以上を混合して反 応槽に供給することを特徴とする、 有機塩素化合物の脱塩素化方法。 100. In Claim 1, the organic chlorinated compound to be supplied to the reaction tank, the recovered alkali to be reused, the newly supplied alkali, the newly supplied non-protonic polar solvent, and the recovered to be reused A method for dechlorinating an organochlorine compound, comprising supplying a nonprotonic polar solvent to a reaction tank by mixing two or three or more of them in advance.
1 1 . 請求の範囲第 1 0項において、 前記の予め混合する方法と して、 攪拌機付き混合槽とスタティ ックミキサーを単独、 若しくは 組み合わせて使うことを特徴とする、 有機塩素化合物の脱塩素化方 法。 11. The method for dechlorinating an organic chlorine compound according to claim 10, wherein the method of pre-mixing comprises using a mixing tank with a stirrer and a static mixer alone or in combination. Law.
1 2 . 請求の範囲第 1 1項において、 前記攪拌機付き混合槽を使 う方法として、 攪拌機付き混合槽に回収非プロ トン性極性溶剤及び 新たに供給する非プロ ト ン性極性溶剤の一部を投入した後、 アル力 リ として微粉砕した固体苛性ソーダ又は苛性力リ及び回収アル力 リ とを混入してスラリー化した後、 反応槽にすでに供給してある非プ 口 トン性極性溶剤と有機塩素化合物の混合液の一部を抜き出し、 そ れと混合して反応槽に供給することを特徴とする、 有機塩素化合物 の脱塩素化方法。 12. The method according to claim 11, wherein the method using the mixing tank with a stirrer includes: collecting a non-protonic polar solvent to the mixing tank with a stirrer and a part of a newly supplied non-protonic polar solvent. After the A mixture of the non-protonic polar solvent and the organochlorine compound already supplied to the reaction tank after mixing into a finely ground solid caustic soda or caustic A method for dechlorinating an organochlorine compound, comprising extracting a part, mixing the part, and supplying the mixture to a reaction tank.
PCT/JP1997/000923 1996-03-19 1997-03-19 Method of dechlorinating organic chlorine compound WO1997034713A1 (en)

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AU1943797A (en) 1997-10-10
AU703494B2 (en) 1999-03-25
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JP3197818B2 (en) 2001-08-13
JPH09253602A (en) 1997-09-30

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