JP4626360B2 - Treatment method for wastewater containing phenols - Google Patents

Treatment method for wastewater containing phenols Download PDF

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JP4626360B2
JP4626360B2 JP2005094039A JP2005094039A JP4626360B2 JP 4626360 B2 JP4626360 B2 JP 4626360B2 JP 2005094039 A JP2005094039 A JP 2005094039A JP 2005094039 A JP2005094039 A JP 2005094039A JP 4626360 B2 JP4626360 B2 JP 4626360B2
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phenols
wastewater
phenol
alkaline agent
waste water
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賢治 伊東
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Sumitomo Chemical Co Ltd
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Priority to EP06730727A priority patent/EP1873119A4/en
Priority to US11/909,304 priority patent/US8298378B2/en
Priority to KR1020077024751A priority patent/KR101311136B1/en
Priority to PCT/JP2006/306779 priority patent/WO2006104222A1/en
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Description

本発明は、フェノール類含有排水の処理方法に関する。さらに詳しくは、フェノール類を含有する排水中のフェノール類を容易に濃縮分離することができるという優れた特徴を有するフェノール類含有排水の処理方法に関するものである。   The present invention relates to a method for treating phenol-containing wastewater. More specifically, the present invention relates to a method for treating phenol-containing wastewater having an excellent characteristic that phenols in wastewater containing phenols can be easily concentrated and separated.

フェノール類等を製造するプロセスから排出されるプロセス排水中には、水に可溶なフェノール類が含有されており、そのまま放流することができない。そこで、一般的には蒸留分離を行った後、多量の水で薄めて、微生物による生物処理を実施するか、または燃焼焼却による処理等によりフェノール類が除去される。蒸留による分離は、水とフェノールが共沸物を作るため種々の工夫がなされている。その一つとして、共沸蒸留を利用した２塔方式による水-フェノールの精製分離方法が提案されている（特許文献１参照）。しかし、蒸留のエネルギーコストの削減、生物処理を行う場合の排水中のフェノール類の負荷の軽減等の問題について、一層の合理化が求められていた。   Process wastewater discharged from processes for producing phenols and the like contains phenols soluble in water and cannot be discharged as they are. Therefore, generally, after performing distillation separation, the phenols are removed by diluting with a large amount of water and performing biological treatment with microorganisms, or treatment by combustion incineration. Separation by distillation has been devised in various ways because water and phenol form an azeotrope. As one of them, a method for purifying and separating water-phenol by a two-column system using azeotropic distillation has been proposed (see Patent Document 1). However, further rationalization has been demanded for problems such as reduction of energy cost of distillation and reduction of the load of phenols in wastewater when biological treatment is performed.

特開平０９−２５３６２４号公報JP 09-253624 A

かかる従来技術の状況に鑑み、本発明はフェノール類を含有する排水中のフェノール類を容易に濃縮分離することができ、かつ、エネルギー的観点から有利に排水を処理することができるフェノール類含有排水の処理方法の提供を目的とする。   In view of the state of the prior art, the present invention can easily concentrate and separate phenols in wastewater containing phenols, and can efficiently treat wastewater from an energy viewpoint. The purpose is to provide a processing method.

すなわち、本発明は、下記の第１工程および第２工程を含むフェノール類含有排水の処理方法に係るものである。
第１工程：フェノール類を含有する排水にアルカリ剤を添加する工程
第２工程：第１工程においてアルカリ剤を添加した排水を蒸留して、フェノール類が濃縮された排液を分離する工程
前記第１工程において、アルカリ剤の添加をフェノール類含有排水のｐＨが１０〜１４になるように調整する場合、フェノール類含有排水が、触媒の存在下に有機過酸化物とプロピレンを反応させることによりプロピレンオキサイドを得る製造プロセスにおいて発生する排水であり、さらに、該有機過酸化物が、クメンハイドロパーオキサイドである場合は、本発明の有効な態様である。 That is, this invention relates to the processing method of the phenol containing waste water containing the following 1st process and 2nd process.
1st process: The process of adding an alkaline agent to the waste water containing phenols 2nd process: The process of distilling the waste water which added the alkaline agent in the 1st process, and isolate | separating the waste liquid which phenols concentrated The said 1st In one step, when adjusting the addition of the alkaline agent so that the pH of the phenol-containing wastewater is 10 to 14, the phenol-containing wastewater reacts with the organic peroxide and propylene in the presence of a catalyst. This is an effective aspect of the present invention when it is wastewater generated in the production process for obtaining oxide and the organic peroxide is cumene hydroperoxide.

本発明により、フェノール類を含有する排水にアルカリ剤を添加して蒸留することにより、排水中のフェノール類を容易に濃縮分離することができ、かつ、エネルギー的観点から有利に排水を処理することができるフェノール類含有排水の処理方法の提供が可能になった。   According to the present invention, by adding an alkaline agent to a wastewater containing phenols and distilling, the phenols in the wastewater can be easily concentrated and separated, and the wastewater is treated advantageously from an energy point of view. It is now possible to provide a method for treating wastewater containing phenols.

本発明において、フェノール類含有排水とは、フェノール、アルキル基を置換基にもつアルキルフェノール類、カテコール、レゾルシノール、ハイドロキノン等を含むプロセス排水であり、例えば、触媒の存在下に有機過酸化物とプロピレンを反応させることによりプロピレンオキサイドを得る製造プロセスにおいて発生する排水等であり、有機過酸化物がクメンハイドロパーオキサイドの場合は、クメンハイドロパーオキサイドの分解によりフェノールが生成しこれらがプロセス排水として排出される。   In the present invention, phenol-containing wastewater is process wastewater containing phenol, alkylphenols having an alkyl group as a substituent, catechol, resorcinol, hydroquinone, etc., for example, organic peroxide and propylene in the presence of a catalyst. Wastewater generated in the production process to obtain propylene oxide by reaction. When the organic peroxide is cumene hydroperoxide, phenol is generated by the decomposition of cumene hydroperoxide and these are discharged as process wastewater. .

以下、本発明の実施態様の一例を示す流れ図（図１）に基づいて、詳細に説明する。図１に示した例の流れ図は、主として加熱器１１、蒸留塔１２、冷却器１３、還流ドラム１４より構成されている。   Hereinafter, it demonstrates in detail based on the flowchart (FIG. 1) which shows an example of the embodiment of this invention. The flow chart of the example shown in FIG. 1 mainly includes a heater 11, a distillation column 12, a cooler 13, and a reflux drum 14.

第１工程は、フェノール類を含有する排水にアルカリ剤を添加する工程である。アルカリ剤としては、ＮaＯＨ、Ｎａ2ＣＯ3、Ｃａ（ＯＨ）2、Ｃａ2ＣＯ3、ＫＯＨや化学プロセスにおいて排出されるｐＨ１０以上のアルカリ性排水も利用することができる。これらのアルカリ剤のフェノール類含有排水への添加量は、混合後の排水のｐＨが１０〜１４になるように添加する。添加方法は、別に攪拌槽を設けて添加してもいいが配管中へ添加するラインミキシングでもよく、特に限定されない。 The first step is a step of adding an alkaline agent to wastewater containing phenols. As the alkaline agent, NaOH, Na 2 CO 3 , Ca (OH) 2 , Ca 2 CO 3 , KOH, or alkaline drainage having a pH of 10 or more discharged in a chemical process can be used. The amount of these alkaline agents added to the phenol-containing wastewater is added so that the pH of the wastewater after mixing is 10-14. The addition method may be performed by providing a separate stirring tank, but may be line mixing added to the pipe, and is not particularly limited.

アルカリ剤が多すぎると非経済的であり、少なすぎると本発明の効果が得られない。フェノール類を含有する排水がアルカリ剤と混合しｐＨが１０以上に調整されると、これらフェノール類は塩を形成して重質化し、水との比揮発度が低下し、塔頂から留出する排水中のフェノール類は抑制される。   If there are too many alkali agents, it is uneconomical, and if there are too few, the effect of this invention cannot be acquired. When the wastewater containing phenols is mixed with an alkaline agent and the pH is adjusted to 10 or more, these phenols form salts and become heavy, the relative volatility with water decreases, and distills from the top of the tower. Phenols in the drainage are suppressed.

第２工程は、ｐＨが１０以上に調整されたフェノール類含有排水を加熱器１１を介して蒸留塔１２へ供給し、蒸留してフェノール類が濃縮された排液を分離する工程である。フェノール類含有排水は、アルカリ剤と混合後加熱器１１で加温され、蒸留塔１２で蒸留される。加熱器１１の出口温度は１０〜１８０℃であり、加熱源としてはスチーム等何でも良いが、プラント内の排スチームやコンデンセートを使用することによりエネルギーが有効に使用される。蒸留塔１２の内部に充填物や棚段を設置すると分離効果は向上する。蒸留塔１２の運転条件は、１０ｔｏｒｒから１ＭＰａで温度は１０℃〜１８０℃、好ましくは、５０ｔｏｒｒ〜０．５ＭＰａで温度は３０〜１５０℃で操作される。   The second step is a step of supplying the phenol-containing wastewater whose pH is adjusted to 10 or more to the distillation tower 12 via the heater 11 and separating the drained liquid in which the phenols are concentrated by distillation. The phenol-containing wastewater is mixed with an alkaline agent, heated by a heater 11, and distilled by a distillation tower 12. The outlet temperature of the heater 11 is 10 to 180 ° C., and the heating source may be anything such as steam, but energy is effectively used by using exhaust steam or condensate in the plant. If a packing or a shelf is installed inside the distillation column 12, the separation effect is improved. The operation conditions of the distillation column 12 are 10 to 1 MPa, the temperature is 10 ° C. to 180 ° C., preferably 50 torr to 0.5 MPa, and the temperature is 30 to 150 ° C.

蒸留塔１２の塔底からは重質化したフェノール類濃縮排水４が排出され、蒸留塔１２の塔頂からは、フェノール類が除去された排水が留出する。フェノール類濃縮排水４は重質化したフェノール類が高濃度に濃縮されているので、排水量は少量になっている。したがって、燃焼焼却する場合も効率的、経済的に処理することが可能である。   From the bottom of the distillation column 12, the heavy phenols concentrated waste water 4 is discharged, and from the top of the distillation column 12, waste water from which phenols have been removed distills. The phenol concentration drainage 4 has a small amount of drainage because heavy phenols are concentrated at a high concentration. Therefore, it is possible to treat efficiently and economically when burning and incinerating.

一方、蒸留塔１２の塔頂から留出する、フェノール類が除去された排水は、冷却器１３で凝縮冷却後、還流ドラム１４に送られる。還流ドラム１４の液を一部蒸留塔１２へ還流液８として還流することにより、分離効果は向上する。還流ドラム１４に留出した排水は、生物処理において十分処理可能なレベルまで処理されている。   On the other hand, the wastewater from which phenols have been removed, distilled from the top of the distillation column 12, is condensed and cooled by the cooler 13, and then sent to the reflux drum 14. The separation effect is improved by partially refluxing the liquid in the reflux drum 14 to the distillation column 12 as the reflux liquid 8. The waste water distilled to the reflux drum 14 is treated to a level that can be sufficiently treated in biological treatment.

本排水が触媒の存在下、有機過酸化物とプロピレンを反応させることによりプロピレンオキサイドを得る製造プロセスにおいて発生する排水である場合は特に有用であり、有機過酸化物がクメンハイドロパーオキサイドの場合、クメンハイドロパーオキサイドの分解によりフェノールが生成し、これらフェノール類を含有する排水を処理する上で有用である。   This wastewater is particularly useful when it is a wastewater generated in the production process of obtaining propylene oxide by reacting an organic peroxide with propylene in the presence of a catalyst, and when the organic peroxide is cumene hydroperoxide, Phenol is produced by the decomposition of cumene hydroperoxide, which is useful in treating wastewater containing these phenols.

以下、本発明を実施例および比較例に基づいて具体的に説明するが、もとより本発明はこの実施例に限定されるものではない。
実施例および比較例
フェノール類含有排水へのアルカリ剤の添加量を調整することにより、ｐＨを実施例では１３、比較例では９とｐＨを変化させた排水をそれぞれ蒸留処理した。塔頂から留出される排水中のフェノールの割合を示す水に対する比揮発度は表１に示した通りであり、大部分は塔底から排出されるフェノール濃縮排水へ移行したことがわかる。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example from the first.
Examples and Comparative Examples By adjusting the amount of the alkaline agent added to the phenols-containing wastewater, the wastewater with pH changed to 13 in the example and 9 in the comparative example was distilled. The relative volatility with respect to water, which indicates the proportion of phenol in the waste water distilled from the top of the tower, is as shown in Table 1, and it can be seen that most of it has shifted to the concentrated phenol waste water discharged from the bottom of the tower.

Figure 0004626360
Figure 0004626360

上記の結果から次のことがわかる。本発明によるアルカリ剤添加によってｐＨを１０以上に調整を行って蒸留した実施例は、フェノール類の分離効果が良好である。一方、ｐＨが１０より低い比較例は十分な分離効果が得られない。   The following can be seen from the above results. The example which distilled by adjusting pH to 10 or more by addition of the alkaline agent by this invention has the favorable separation effect of phenols. On the other hand, the comparative example whose pH is lower than 10 cannot obtain a sufficient separation effect.

本発明の実施態様の一例を示す流れ図である。It is a flowchart which shows an example of the embodiment of this invention.

符号の説明Explanation of symbols

１…フェノール類含有排水、２…アルカリ剤、３…加熱媒体、４…フェノール類濃縮排水、５…塔頂留出ガス、６…塔頂留出冷却液、７…フェノール類除去排水、８…還流液、１１…加熱器、１２…蒸留塔、１３…冷却器、１４…還流ドラム
DESCRIPTION OF SYMBOLS 1 ... Phenol containing waste water, 2 ... Alkaline agent, 3 ... Heating medium, 4 ... Phenols concentration waste water, 5 ... Tower top distillate gas, 6 ... Tower top distillate cooling liquid, 7 ... Phenols removal waste water, 8 ... Reflux liquid, 11 ... heater, 12 ... distillation tower, 13 ... cooler, 14 ... reflux drum

Claims (3)

下記の第１工程および第２工程を含むフェノール類含有排水の処理方法。
第１工程：フェノール類を含有する排水にアルカリ剤を添加する工程であって、該アルカリ剤の添加量をフェノール類含有排水のｐＨが１０〜１４になるように調整する工程
第２工程：第１工程においてアルカリ剤を添加した排水を蒸留して、フェノール類が濃縮された排液を分離する工程 The processing method of the phenol containing waste water containing the following 1st process and 2nd process.
First step: a step of adding an alkaline agent to wastewater containing phenols, the step of adjusting the addition amount of the alkaline agent so that the pH of the phenols-containing wastewater is 10 to 14. Second step: second step: A step of distilling waste water to which an alkaline agent has been added in one step to separate a waste solution enriched with phenols. 前記フェノール類を含有する排水が、触媒の存在下に有機過酸化物とプロピレンを反応させることによりプロピレンオキサイドを得る製造プロセスにおいて発生する排水である請求項１記載のフェノール類含有排水の処理方法。 The method for treating wastewater containing phenols according to claim 1, wherein the wastewater containing phenols is wastewater generated in a production process for obtaining propylene oxide by reacting an organic peroxide and propylene in the presence of a catalyst. 有機過酸化物がクメンハイドロパーオキサイドである請求項２記載のフェノール含有排水の処理方法。 The method for treating phenol-containing wastewater according to claim 2 , wherein the organic peroxide is cumene hydroperoxide.
JP2005094039A 2005-03-29 2005-03-29 Treatment method for wastewater containing phenols Expired - Fee Related JP4626360B2 (en)

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Application Number Priority Date Filing Date Title
JP2005094039A JP4626360B2 (en) 2005-03-29 2005-03-29 Treatment method for wastewater containing phenols
EP06730727A EP1873119A4 (en) 2005-03-29 2006-03-24 Method for processing waste water containing oxygen-containing compound having phenolic hydroxyl group or carbonyl group
US11/909,304 US8298378B2 (en) 2005-03-29 2006-03-24 Method for treating waste water containing oxygen-containing compound having phenolic hydroxyl group of carbonyl group
KR1020077024751A KR101311136B1 (en) 2005-03-29 2006-03-24 Method for Processing Waste Water Containing Oxygen-Containing Compound Having Phenolic Hydroxyl Group or Carbonyl Group
PCT/JP2006/306779 WO2006104222A1 (en) 2005-03-29 2006-03-24 Method for processing waste water containing oxygen-containing compound having phenolic hydroxyl group or carbonyl group
CN2006800099557A CN101151217B (en) 2005-03-29 2006-03-24 Method for treating waste water containing oxygen-containing compound having phenol hydroxy group or carbonyl group

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WO2009138530A1 (en) * 2008-05-14 2009-11-19 Repsol Ypf, S.A. Revaluation of aqueous waste streams generated in the propylene oxide and styrene co-production process
JP6455318B2 (en) * 2015-05-28 2019-01-23 三菱ケミカル株式会社 Method for treating liquid and method for producing acrylonitrile or methacrylonitrile
JP7208375B2 (en) * 2019-12-19 2023-01-18 万華化学集団股▲フン▼有限公司 Method for treating production wastewater by preparing propylene oxide by co-oxidation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63143991A (en) * 1986-12-05 1988-06-16 Konica Corp Treatment of waste liquid from photographic process and apparatus thereof
JPH08502524A (en) * 1993-08-04 1996-03-19 アリステック ケミカル コーポレイション Recovery of low concentrations of phenol with sodium sulfate

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FR1602423A (en) * 1968-11-27 1970-11-23

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63143991A (en) * 1986-12-05 1988-06-16 Konica Corp Treatment of waste liquid from photographic process and apparatus thereof
JPH08502524A (en) * 1993-08-04 1996-03-19 アリステック ケミカル コーポレイション Recovery of low concentrations of phenol with sodium sulfate

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