JPH02290845A - Method for treating hydroperoxide mixture - Google Patents
Method for treating hydroperoxide mixtureInfo
- Publication number
- JPH02290845A JPH02290845A JP11164989A JP11164989A JPH02290845A JP H02290845 A JPH02290845 A JP H02290845A JP 11164989 A JP11164989 A JP 11164989A JP 11164989 A JP11164989 A JP 11164989A JP H02290845 A JPH02290845 A JP H02290845A
- Authority
- JP
- Japan
- Prior art keywords
- hydroperoxide
- aromatic
- decomposition
- mixture
- primary
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 5
- -1 hydroperoxymethyl group Chemical group 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 16
- 150000002432 hydroperoxides Chemical class 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 150000002978 peroxides Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229930007927 cymene Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- RMKJTYPFCFNTGQ-UHFFFAOYSA-N 1,3-dimethyl-5-propan-2-ylbenzene Chemical compound CC(C)C1=CC(C)=CC(C)=C1 RMKJTYPFCFNTGQ-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- AADQFNAACHHRLT-UHFFFAOYSA-N 3-Methyl-4-isopropyltoluene Natural products CC(C)C1=CC=C(C)C=C1C AADQFNAACHHRLT-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- GDEQPEBFOWYWSA-UHFFFAOYSA-N 1,2-dimethyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1C GDEQPEBFOWYWSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- ILNDSSCEZZFNGE-UHFFFAOYSA-N m-di-t-butylbenzene Natural products CC(C)(C)C1=CC=CC(C(C)(C)C)=C1 ILNDSSCEZZFNGE-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
- C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
- C07C409/08—Compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
- C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
- C07C409/08—Compounds containing six-membered aromatic rings
- C07C409/10—Cumene hydroperoxide
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は，芳香族一級ヒドロペルオキシドと芳香族三級
ヒドロペルオキシドを含有する油状ヒドロペルオキシド
混合物から、芳香族一級ヒドロペルオキシドを選択的に
分解して、芳香族一級ヒトロペルオキシドの含有率を減
少させる方法に関する．
〔従来の技術〕
アルキル芳香族化合物の液相酸化によって得られるヒド
ロペルオキシドを酸分解してフェノール類を製造する方
法は、フェノール、クレゾール，ヒトロキノン、レゾル
シンなどのｔＪａ方法として工業的に有用である。また
、このヒドロペルオキシドはベルオキシドや芳香族アル
コールの製造原料としても有用である。前記液相酸化に
おいて、アルキル芳香族化合物として２種以上の異なる
アルキル基を有するものを用いるときには、各アルキル
基がそれぞれヒドロペルオキシ化された２種以上のヒト
口ベルオキシト混合物として得られることが多い。この
ため、これらをそのまま前記のようなフェノール類など
の製造原料として用いるときには、希望しない化合物が
生成したり、あるいは反応に悪影響を及ぼすなどの不利
益を被ることがある。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a method for selectively decomposing an aromatic primary hydroperoxide from an oily hydroperoxide mixture containing an aromatic primary hydroperoxide and an aromatic tertiary hydroperoxide. This invention relates to a method for reducing the content of aromatic primary hydroperoxides. [Prior Art] A method for producing phenols by acid decomposition of hydroperoxides obtained by liquid phase oxidation of alkyl aromatic compounds is industrially useful as a tJa method for producing phenol, cresol, human quinone, resorcinol, etc. This hydroperoxide is also useful as a raw material for producing peroxides and aromatic alcohols. In the liquid phase oxidation, when an alkyl aromatic compound having two or more different alkyl groups is used, a mixture of two or more human peroxides in which each alkyl group is hydroperoxylated is often obtained. Therefore, when these materials are used as they are as raw materials for producing phenols, etc., they may suffer from disadvantages such as generation of undesired compounds or adverse effects on the reaction.
例えばシメンの液相酸化においては、メチル基の酸化さ
れた一級ヒドロベルオキシトと、イソプロピル基の酸化
された三級ヒドロベルオキシトが生成する。この両者を
含有する混合物から酸分解によってクレゾールを製造す
る場合には、一級ヒドロペルオキシドの酸分解によって
生じたホルムアルデヒドが生成したクレゾールと縮合し
て樹脂化し、クレゾールの収エタを低下させることが知
られている。このような欠点を解消するため、ヒドロペ
ルオキシド混合物中の一級ヒドロベルオキシトを選択的
に減少もしくは除去したり，あるいは反応に悪影響を及
ぼさない化合物に選択的に変換することが望まれている
。For example, in the liquid-phase oxidation of cymene, a primary hydroperoxide resulting from the oxidation of a methyl group and a tertiary hydroperoxide resulting from the oxidation of an isopropyl group are produced. When producing cresol from a mixture containing both of these by acid decomposition, it is known that formaldehyde generated by acid decomposition of primary hydroperoxide condenses with the generated cresol and becomes a resin, reducing the cresol yield. ing. In order to overcome these drawbacks, it is desired to selectively reduce or remove the primary hydroperoxide in the hydroperoxide mixture, or to selectively convert it into a compound that does not adversely affect the reaction.
このため、例えば芳香族一級ヒト口ベルオキシトと芳香
族三級ヒドロペルオキシドとの混合物を、ｐＨ１２〜１
４のアルカリ水溶液とＯ〜４０℃で接触させた後，油水
分着し、水層に抽出された芳香族一級ヒドロペルオキシ
ドを２０〜１００℃で分解する方法が特公昭６２−３４
７５５号に提案されている。しかし、この方法では芳香
族一級ヒドロペルオキシドの分解が充分でなく、かつ芳
香族三級ヒト口ベルオキシトの分解が充分に抑制されて
いるとはいえない。For this reason, for example, a mixture of an aromatic primary human peroxide and an aromatic tertiary hydroperoxide is prepared at a pH of 12 to 1.
Japanese Patent Publication No. 62-34 discloses a method in which the aromatic primary hydroperoxide is brought into contact with the alkaline aqueous solution of No. 4 at 0 to 40°C, followed by oil-water adsorption and extracted into the aqueous layer, and then decomposed at 20 to 100°C.
Proposed in No. 755. However, this method does not sufficiently decompose aromatic primary hydroperoxides, and it cannot be said that decomposition of aromatic tertiary human peroxides is sufficiently suppressed.
したがって、本発明の目的は上記のような問題点を解決
するため、芳香族一級ヒドロベルオキシトと芳香族三級
ヒドロペルオキシドとの混合物から，芳香族三級ヒドロ
ペルオキシドの分解を抑制し、かつ芳香族一級ヒドロベ
ルオキシトを選択的に分解して、芳香族一級ヒドロペル
オキシドの含有量を減少させた混合物が得られるヒドロ
ペルオキシド混合物の処理方法を提案することである。Therefore, an object of the present invention is to solve the above-mentioned problems by suppressing the decomposition of aromatic tertiary hydroperoxide from a mixture of aromatic primary hydroperoxide and aromatic tertiary hydroperoxide, and The object of the present invention is to propose a method for treating a hydroperoxide mixture in which a mixture with a reduced content of aromatic primary hydroperoxides is obtained by selectively decomposing aromatic primary hydroperoxides.
本発明は次のヒドロペルオキシド混合物の処理方法であ
る。The present invention is a method for treating a hydroperoxide mixture as follows.
（＋）（Ａ）芳香核に直結したヒドロペルオキシメチル
基を有する芳香族一級ヒドロベルオキシトと、（Ｂ）芳
香核に直結した２−ヒドロベルオキシ−２−プロピル基
を有する芳香族三級ヒ１〜［１ペルオキシ１一
とを含有する油状ヒドロペルオキシド混合物を、４５〜
６０℃の温度範囲で２〜３重址％の水酸化ナトリウム水
溶液と礫触させた後、４５〜６０℃の温度範囲で油水分
離し、水層に抽出された（Ａ）成分の少なくとも一部を
、７０〜９０℃の温度範囲で分解することを特徴とする
ヒドロベルオキシト混合物の処理方法。(+) (A) Aromatic primary hydroperoxyte having a hydroperoxymethyl group directly connected to an aromatic nucleus, and (B) Aromatic tertiary having a 2-hydroberoxy-2-propyl group directly connected to an aromatic nucleus. An oily hydroperoxide mixture containing 1 to 1 peroxy 1 to 45 to
After contacting with a 2-3% sodium hydroxide aqueous solution in a temperature range of 60°C, oil and water are separated in a temperature range of 45-60°C, and at least part of the component (A) extracted into the aqueous layer. 1. A method for treating a hydroperoxyte mixture, characterized in that it is decomposed at a temperature range of 70 to 90°C.
（２）油状ヒドロペルオキシド混合物が、芳香核に直結
したメチル基およびイソプロピル｝．（を有する芳香族
化合物の液相酸化生成物またはその，頽縮物である上記
（１）記載のヒドロペルオキシド混合物の処理方法。(2) The oily hydroperoxide mixture contains methyl groups and isopropyl directly bonded to the aromatic nucleus}. The method for treating a hydroperoxide mixture according to (1) above, which is a liquid-phase oxidation product of an aromatic compound or a condensation product thereof.
（３）分解を、（Ａ）成分の分解率が６０モル％以」二
、（［３）成分の分解率が３モル％以下となるように調
節する上記（１）または（２）記載のヒドロペルオキシ
ド混合物の処理方法。(3) Adjusting the decomposition so that the decomposition rate of the component (A) is 60 mol% or more; and ([3) the decomposition rate of the component is 3 mol% or less] as described in (1) or (2) above. Method for treating hydroperoxide mixtures.
（４）分解を、炭化水素類の共存下に行う−１二記（１
）ないし（３）の何れかに記載のヒドロペルオキシド混
合物の処理方法。(4) Decomposition is carried out in the coexistence of hydrocarbons-12 (1)
) to (3), the method for treating a hydroperoxide mixture according to any one of (3).
（処理混合物）
本発明において処理の対象となるヒト口ベルオキシド混
合物は、上記（Ａ）の芳香族一級ヒト口ベルオキシドと
（Ｂ）の芳香族三級ヒト口ベルオキシドとを含有する油
状ヒド口ベルオキシト混合物、あるいは芳香核に直結し
たメチル基およびイソブロビル基を有する芳香族化合物
の液相酸化生成物またはその濃縮物である。(Treatment mixture) The human peroxide mixture to be treated in the present invention is an oily hydroxide mixture containing the aromatic primary human peroxide of (A) and the aromatic tertiary human peroxide of (B). It is a liquid phase oxidation product of an aromatic compound having a methyl group and an isobrobyl group directly attached to an aromatic nucleus, or a concentrate thereof.
芳香核に直結したヒドロペルオキシメチル基を？する芳
香族一級ヒドロペルオキシド（Ａ）は、式Ａｒ−ＣＩ＋
■００１１ （Ａｒは置換または非置換の芳香族の基を
表す）で示される化合物で，具体的には，キシド（Ｂ）
は、式Ａｒ’−Ｃ（ＣＨ，）２００｝＋ （Ａｒ’は置
換または非置換の芳香族の基を表す）で示される化合物
で、具体的には、
などを例示することができる．
また，芳香核に直結した２−ヒドロベルオキシ−２−プ
ロピル基を有する芳香族三級ヒドロベルオなどを例示す
ることができる．
（＾）と（Ｂ）との混合割合は任意であるが、通常（Ａ
）５〜４０重量部、 とくにｌＯ〜３０重量部に対して
（ｎ）９５〜６０重量部、とくに９０〜７０重量部（両
者を合計して１００重量部）となる割合の混合物に適用
するのが好ましい。A hydroperoxymethyl group directly connected to an aromatic nucleus? The aromatic primary hydroperoxide (A) has the formula Ar-CI+
■Compounds represented by 0011 (Ar represents a substituted or unsubstituted aromatic group), specifically, oxide (B)
is a compound represented by the formula Ar'-C(CH,)200}+ (Ar' represents a substituted or unsubstituted aromatic group), and specific examples include the following. Further examples include aromatic tertiary hydroperocarbons having a 2-hydroberoxy-2-propyl group directly connected to an aromatic nucleus. The mixing ratio of (^) and (B) is arbitrary, but usually (A
) 5 to 40 parts by weight, especially (n) 95 to 60 parts by weight, especially 90 to 70 parts by weight (total of both is 100 parts by weight). is preferred.
上記混合物の典型的なものは、芳香核にメチル基および
イソプロピル基を有する芳香族化合物を、液相において
分子状酸素により酸化して得た反応生成物あるいはこれ
の濃縮物である。このような反応生成物として例えば，
■−シメン、ｐ−シメン、ｎｌ ， ｐ一混合シメン、
２，４−ジメチルイソプロピルベンゼン、３．５−ジメ
チルイソプロピルベンゼン、ｌ−メチル−７−イソプロ
ピルナフタリン等の酸化生成物やその濃縮物などを例示
することができる。A typical example of the above mixture is a reaction product obtained by oxidizing an aromatic compound having a methyl group and an isopropyl group in the aromatic nucleus with molecular oxygen in a liquid phase, or a concentrate thereof. Examples of such reaction products include:
■-cymene, p-cymene, nl, p-cymene,
Examples include oxidation products such as 2,4-dimethylisopropylbenzene, 3,5-dimethylisopropylbenzene, and l-methyl-7-isopropylnaphthalene, and their concentrates.
成分（Ａ）および（Ｂ）の混合物は、炭化水素、好まし
くは芳香族炭化水素、例えばベンゼン、トルエン，エチ
ルベンゼン、クメン，キシレン，シメン、ジイソプ口ピ
ルベンゼン、ジメチルイソブロピルベンゼンなどで希釈
されていることが望ましい。The mixture of components (A) and (B) is diluted with a hydrocarbon, preferably an aromatic hydrocarbon, such as benzene, toluene, ethylbenzene, cumene, xylene, cymene, diisopropylbenzene, dimethylisopropylbenzene, etc. is desirable.
その場合には、ヒドロペルオキシド濃度が１〜４０重量
％，とくに好ましくは５〜１５重量％に調整されている
ことが望ましい。In that case, it is desirable that the hydroperoxide concentration is adjusted to 1 to 40% by weight, particularly preferably 5 to 15% by weight.
前記のメチル基およびイソプロピル基を有する芳香族炭
化水素の酸化生成物あるいはその濃縮物は，通常原料の
芳香族炭化水素で希釈された状態にある．
酸化反応物は，非水状態で酸化されたものであってもよ
く、またアルカリ性水溶液の共存下で酸化されたもので
あってもよい。後者のものを使用する場合は，通常アル
カリ性水溶液を分離除去したものを用いるのが好ましい
。The above-mentioned oxidation products of aromatic hydrocarbons having methyl groups and isopropyl groups or their concentrates are usually diluted with the aromatic hydrocarbons as raw materials. The oxidation reactant may be oxidized in a non-aqueous state, or may be oxidized in the coexistence of an alkaline aqueous solution. When using the latter, it is usually preferable to use one in which the alkaline aqueous solution has been separated and removed.
（抽出工程）
本発明によれば、上述した成分（Ａ）および（Ｂ）を含
有する油状ヒドロペルオキシド混合物を２〜３重量％の
水酸化ナトリウム水溶液と接触させて、成分（Ａ）およ
び（Ｂ）のそれぞれ一部をアルカリ水溶液中に抽出する
。(Extraction step) According to the present invention, an oily hydroperoxide mixture containing the above-mentioned components (A) and (B) is brought into contact with a 2 to 3% by weight aqueous sodium hydroxide solution to extract the components (A) and (B). ) are extracted into an aqueous alkaline solution.
この場合、原料の油状ヒドロペルオキシド混合物中の（
Ａ）と（８）の割合（Ａ／Ｂ）よりも，アルカリ水溶液
中に抽出される（Ａ）と（Ｒ）の割合（Ａ／Ｂ）の方が
大であるため、抽出後の油層中の成分（Ａ）は減少され
た状態となる。In this case, (
Since the ratio (A/B) of (A) and (R) extracted into the alkaline aqueous solution is larger than the ratio (A/B) of A) and (8), Component (A) is in a reduced state.
水酸化す１−リウム水溶液との接触および油水分離は、
油層中の芳香族三級ヒドロペルオキシド（成分（８））
の分解をできるだけ抑制し，かつ水層中への芳香族一級
ヒドロペルオキシド（成分（Ａ））の抽出をできるだけ
選択的に行うために、４５〜６０℃，好ましくは４５〜
５０℃の温度範囲で行うことが必要である。Contact with 1-lium hydroxide aqueous solution and oil/water separation are as follows:
Aromatic tertiary hydroperoxide in oil layer (component (8))
45 to 60°C, preferably 45 to 60°C, in order to suppress the decomposition of
It is necessary to carry out the process in a temperature range of 50°C.
浦状ヒドロペルオキシド混合物に対する水酸化ナトリウ
ム水溶液の使用割合は、油状ヒドロペルオキシド混合物
１容量部に対して水酸化ナトリウム水溶液０．１〜５容
量部、とくに０．２〜１容量部の範囲とするのが好まし
い。両者の接触から分離までの時間は１分〜２時間程度
が好ましい。The ratio of the aqueous sodium hydroxide solution to the oily hydroperoxide mixture is 0.1 to 5 parts by volume, particularly 0.2 to 1 part by volume, of the aqueous sodium hydroxide solution per 1 part by volume of the oily hydroperoxide mixture. is preferred. The time from contact to separation of the two is preferably about 1 minute to 2 hours.
本発明では、抽出工程に使用する水酸化ナトリウム水溶
液の代りに水酸化カリウム水溶液を用いてもよく，また
これらの水溶液に炭酸ナトリウム、有機酸塩、とくに芳
香族有機酸塩例えばクミン酸ナトリウｌ１のような成分
が溶解されていてもよい。In the present invention, a potassium hydroxide aqueous solution may be used in place of the sodium hydroxide aqueous solution used in the extraction step, and sodium carbonate, an organic acid salt, especially an aromatic organic acid salt such as sodium cumate may be added to these aqueous solutions. Such components may be dissolved.
有機酸塩は，芳香族一級ヒドロベルオキシトをアルカリ
水溶液に多く抽出させる効果を有しているので、ｌ容解
されていることが望ましい。Since the organic acid salt has the effect of extracting a large amount of the aromatic primary hydroperoxyte into the aqueous alkali solution, it is desirable that the organic acid salt be dissolved in the alkaline aqueous solution.
油水分離後、芳香族一級ヒト口ベルオキシト濃度が相対
的に減じられた油層は，ａ縮するなどした後、フェノー
ル類などの製造原料に利用でき、例えば酸分解すること
により収率良くフェノール類を得ることができる。After oil and water separation, the oil layer with a relatively reduced concentration of aromatic primary peroxide can be used as a raw material for producing phenols, etc., after being subjected to a-condensation, etc. For example, phenols can be produced in high yield by acid decomposition. Obtainable.
一方、水層は下記分解工程において芳香族一級ヒドロペ
ルオキシドを選択的に分解する。On the other hand, in the aqueous layer, aromatic primary hydroperoxides are selectively decomposed in the decomposition step described below.
（分解工程）
上記の抽出操作により，水酸化ナトリウム水溶液相には
、芳香族一級ヒドロペルオキシド（成分（Ａ））が原料
の油状ヒドロベルオキシトにおける比率よりも高い割合
で、芳香族三級ヒト口ベルオキシド（成分（８））とと
もに存在している。(Decomposition process) Through the above extraction operation, the aromatic primary hydroperoxide (component (A)) is present in the sodium hydroxide aqueous solution phase in a higher proportion than in the raw material oily hydroperoxide. It is present together with peroxide (component (8)).
本発明によれば，この水酸化ナトリウム水溶液相を加熱
して芳香族一級ヒドロベルオキシトを選択的に分解して
アルデヒド（またはさらにアルコールとカルボン酸）に
変化させる。According to the present invention, the aqueous sodium hydroxide phase is heated to selectively decompose aromatic primary hydroperoxides and convert them into aldehydes (or further alcohols and carboxylic acids).
芳香族一級ヒドロペルオキシドの分解を選択的に行うた
めに、この分解温度は７０〜９０℃、好ましくは７０〜
８０℃で行う。分解時間は３〜６０分，好ましくは５〜
１５分で攪拌しながら行うのが好ましい。In order to selectively decompose aromatic primary hydroperoxides, the decomposition temperature is 70-90°C, preferably 70-90°C.
Perform at 80°C. Decomposition time is 3 to 60 minutes, preferably 5 to 60 minutes.
Preferably, this is carried out for 15 minutes with stirring.
分解に際しては，分解混合物から未分解の芳香族三級ヒ
ドロペルオキシドを抽出して回収するため、予じめ芳香
族炭化水素等の炭化水素類、特に好ましくは原料の油状
ヒドロペルオキシド混合物中に含有されている炭化水素
と同一の炭化水素類を存在させ、分解反応後に二層分離
により油層を回収することができる。また水層のみを分
解処理した後、炭化水素類を接触させて未分解の芳香族
三級ヒドロペルオキシドを抽出回収することもできる。During decomposition, in order to extract and recover undecomposed aromatic tertiary hydroperoxides from the decomposition mixture, hydrocarbons such as aromatic hydrocarbons, particularly preferably those contained in the raw material oily hydroperoxide mixture, are The oil layer can be recovered by two-layer separation after the decomposition reaction by allowing the same hydrocarbons to exist. Alternatively, after decomposing only the aqueous layer, undecomposed aromatic tertiary hydroperoxides can be extracted and recovered by contacting with hydrocarbons.
このようにして得られた芳香族三級ヒドロペルオキシド
を含む油層は、前記水酸化ナトリウム水溶液接触後に分
離された油層と混合され、例えばフェノール類の製造原
料として利用する６一方分解処理が行われた水層は分離
され、一過式で全量ブローも可能であるが，工業的には
その一部に新たな水酸化ナトリウム水溶液を添加するこ
とにより、芳香族一級ヒドロベルオキシト抽出用の水酸
化ナトリウム水溶液として再使用する方法が有利である
。The oil layer containing the aromatic tertiary hydroperoxide thus obtained was mixed with the oil layer separated after contact with the aqueous sodium hydroxide solution, and subjected to one-sided decomposition treatment for use as a raw material for producing, for example, phenols. The aqueous layer is separated and the entire amount can be blown in a one-pass method, but industrially, by adding fresh sodium hydroxide aqueous solution to a part of the aqueous layer, hydroxide for extraction of aromatic primary hydroperoxides is used. Advantageous is the method of reusing it as an aqueous sodium solution.
本発明においては、後述する実施例から明らかな通り、
芳香族一級ヒドロペルオキシドの分解率を６０モル％以
上、特に７０モル％以上に維持し、かつ芳香族三級ヒド
ロペルオキシドの分解率を３モル％以下、特に２モル％
以下に抑制することができる。In the present invention, as is clear from the examples described below,
The decomposition rate of aromatic primary hydroperoxides is maintained at 60 mol% or more, especially 70 mol% or more, and the decomposition rate of aromatic tertiary hydroperoxides is maintained at 3 mol% or less, especially 2 mol%.
It can be suppressed to below.
本発明によれば、芳香族三級ヒドロペルオキシドをあま
り損失させることなく芳香族一級ヒト口ベルオキシドを
選択的に分解し，その含有量を減少させた混合物を得る
ことができる。According to the present invention, it is possible to selectively decompose aromatic primary hydroperoxides without causing significant loss of aromatic tertiary hydroperoxides, and to obtain a mixture in which the content thereof is reduced.
このような混合物は、フェノール、クレゾール、ヒドロ
キノン、レゾルシン等のフェノール類の製造原料、ベル
オキシドや芳香族アルコールの製造原料などとして好適
に用いられる。Such a mixture is suitably used as a raw material for producing phenols such as phenol, cresol, hydroquinone, and resorcinol, and as a raw material for producing peroxides and aromatic alcohols.
次に実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to examples.
実施例１，
シメンをアルカリ水溶液安定剤の存在下で空気酸化した
後、油水分離して得たシメンヒド口ベルオキシド（以下
ＣｙＨＰという）を含有する油状ｄ？．金物（以下原料
混合物という）の処理を，第１図に示した装置を用いて
行った。Example 1: An oily d? ．． Metal objects (hereinafter referred to as raw material mixture) were processed using the apparatus shown in FIG.
この原料混合物の組成は以下の通りであった。The composition of this raw material mixture was as follows.
原料混合物；
ＣｙＨＩ）７ｌＡ度 １６重量％一級
ＣｙｌｌＰ／三級ＣｙＨＰ １４／８６（モル比）こ
の原料混合物１００容斌部（ＣｙＨＰとしてｌ４！１（
量部）と有機酸ナトリウム塩等を含有する２．７重量％
の水酸化ナトリウム水溶液４０容量部を管１からアルカ
リ抽出器Ｉに供給し，４５゜Ｃの抽出温度で１分間よく
接触させた。Raw material mixture; CyHI) 7lA degree 16% by weight Primary CyllP/tertiary CyHP 14/86 (molar ratio) 100 parts by volume of this raw material mixture (14!1 as CyHP)
2.7% by weight containing organic acid sodium salt, etc.
40 parts by volume of an aqueous sodium hydroxide solution was fed through tube 1 to alkaline extractor I and kept in good contact for 1 minute at an extraction temperature of 45°C.
得られた混合物を管２から静１ｉｆｆｉ槽ＩＩに移し、
油水分離した。Transfer the resulting mixture from tube 2 to static 1iffi tank II;
Oil and water were separated.
次いで水層を管３から抜き出し、管４から加えるシメン
４容量部とともに攪拌機を装備した分解槽１■に送り，
７０℃の温度で５分間分解を行った。Next, the aqueous layer is extracted from pipe 3 and sent to decomposition tank 1■ equipped with a stirrer together with 4 parts by volume of cymene added from pipe 4.
Decomposition was carried out at a temperature of 70°C for 5 minutes.
分解反応生成物を管５から静置槽ＩＶに送り、再び油水
分離する。水層を管６から抜き出し，その一部を再使用
するため管７を通じて管８に供給した。このとき水酸化
ナトリウムの濃度を２．７ｍ：）ｔ％に維持するため、
２５重斌％水酸化ナトリウム水溶液を管９から補給した
。前記管６から抜き出した水層の他の一部は，管１０か
ら系外に排出した。The decomposition reaction product is sent from pipe 5 to static tank IV, where oil and water are separated again. The aqueous layer was extracted from tube 6 and a portion thereof was fed through tube 7 to tube 8 for reuse. At this time, in order to maintain the concentration of sodium hydroxide at 2.7m:)t%,
A 25% sodium hydroxide aqueous solution was supplied through tube 9. The other part of the water layer extracted from the pipe 6 was discharged from the system through the pipe 10.
一方，静置槽■および静１ａ槽■の油層をそれぞれ管１
１および管ｌ２から抜き出し、これらを併せて一級Ｃｙ
ｌＩＰおよび三級Ｃ ｙ Ｈ Ｐの分解斌を求めた。そ
の結果一級ＣｙＨＰの７２モル％、 三級ＣｙｌｌＰの
１．１モル％が分解されていた。この場合、下記式で示
される一級ＣｙＨＰと三級ＣｙｌｌＰとの分解モル量の
比（以下一級／三級分解モル比という）はｌＯ．７であ
った。On the other hand, the oil layers in the static tank ■ and the static 1a tank ■ are
1 and pipe 12, and combine them to form first class Cy.
The decomposition values of lIP and tertiary C y H P were determined. As a result, 72 mol% of primary CyHP and 1.1 mol% of tertiary CyllP were decomposed. In this case, the ratio of decomposition molar amounts of primary CyHP and tertiary CyllP (hereinafter referred to as primary/tertiary decomposition molar ratio) expressed by the following formula is lO. It was 7.
一級／三級分解モル比
原料混合物中の一級Ｃ，ｙＨＰの量（モル）×（分解率
モル％）原料混合物中の三級Ｃｙｌｌｌ１の敏（モル）
×（分解率モル％）実施例２〜６
実施例１において、抽出温度と分Ｍｉｇ度をそれぞれ次
の組合せで行った以外は実施例１と同様に処理した。結
果を表１に示す。Primary/tertiary decomposition molar ratio Amount (mol) of primary C, yHP in the raw material mixture x (decomposition rate mol%) Density of tertiary Cyll1 in the raw material mixture (mol)
x (Decomposition rate mol %) Examples 2 to 6 The same procedure as in Example 1 was carried out except that the extraction temperature and minute Mig degree were set to the following combinations. The results are shown in Table 1.
実施例２：抽出温度 ５０℃、分解温度 ７０℃実施例
３：抽出温度 ５０℃、分解温度 ８０℃実施例４：抽
出温度 ５０℃、分解温度 ９０℃実施例５：抽出温度
５５℃，分解温度 ８０℃実施例６：抽出温度 ６０
℃、分解温度 ９０℃比較例１〜３
実施例ｌにおいて，抽出温度と分解温度をそれぞれ次の
組合せで行った以外は実施例１と同様に処理した。ただ
し比較例３のみ水酸化ナトリウム水溶液のｐｌｌを１３
．７とし，分解時間を１５分とした６結果を表１に示す
。Example 2: Extraction temperature 50°C, decomposition temperature 70°CExample 3: Extraction temperature 50°C, decomposition temperature 80°CExample 4: Extraction temperature 50°C, decomposition temperature 90°CExample 5: Extraction temperature 55°C, decomposition temperature 80°C Example 6: Extraction temperature 60
°C, decomposition temperature 90 °C Comparative Examples 1 to 3 The same procedure as in Example 1 was carried out except that in Example 1, the extraction temperature and decomposition temperature were set to the following combinations. However, only in Comparative Example 3, pll of sodium hydroxide aqueous solution was 13
．． 7 and the decomposition time was 15 minutes. The results are shown in Table 1.
比較例１：抽出温度 ７０℃、分解温度 ｌＯＯ℃比較
例２：抽出温度 ４０℃、分解温度 ６０℃比較例３：
抽出温度 ２０℃，分解温度 ６０℃表１から明らかな
ように，２〜３重量％の水酸化ナトリウム水溶液を用い
て、４５〜６０℃の温度で抽出工程を行い、この抽出工
程で分離された水層を７０〜９０℃の温度で分解処理を
行うことにより，芳香族三級ヒドロペルオキシドの分解
を抑制して芳香族一級ヒドロペルオキシドを選択的に分
解できることがわかる。Comparative example 1: Extraction temperature 70°C, decomposition temperature 1OO°C Comparative example 2: Extraction temperature 40°C, decomposition temperature 60°C Comparative example 3:
Extraction temperature: 20°C, decomposition temperature: 60°C As is clear from Table 1, the extraction step was carried out at a temperature of 45 to 60°C using a 2 to 3% by weight aqueous sodium hydroxide solution, and the separated It can be seen that by decomposing the aqueous layer at a temperature of 70 to 90°C, the decomposition of the aromatic tertiary hydroperoxide can be suppressed and the aromatic primary hydroperoxide can be selectively decomposed.
以上の通り、本発明によれば、芳香族一級ヒドロペルオ
キシドと芳香族三級ヒドロペルオキシドとの混合物を，
４５〜６０℃の温度範囲で２〜３重量％の水酸化ナトリ
ウム水溶液と接触させた後、４５〜６０℃の温度範囲で
油水分離し，水層に抽出された芳香族一級ヒドロペルオ
キシドを７０〜９０℃の温度で分解することにより、芳
香族一級ヒドロペルオキシドと芳香族三級ヒドロペルオ
キシドとの混合物から、芳香族三級ヒドロペルオキシド
の分解を抑制し，かつ芳香族一級ヒドロベルオキシトを
選択的に分解して、芳香族一級ヒト口ベルオキシドの含
有量を減少させた混合物が得られる。As described above, according to the present invention, a mixture of an aromatic primary hydroperoxide and an aromatic tertiary hydroperoxide,
After contacting with a 2-3% by weight aqueous sodium hydroxide solution at a temperature range of 45-60°C, oil and water are separated at a temperature range of 45-60°C, and the aromatic primary hydroperoxide extracted into the aqueous layer is heated to a temperature range of 70-60°C. By decomposing at a temperature of 90°C, the decomposition of the aromatic tertiary hydroperoxide is suppressed and the aromatic primary hydroperoxide is selectively removed from the mixture of the aromatic primary hydroperoxide and the aromatic tertiary hydroperoxide. A mixture with a reduced content of aromatic primary human peroxides is obtained.
このようにして得られた混合物は、フェノール類、ベル
オキシドおよび芳香族アルコールなどの製造原料として
好適に利用できる。The mixture thus obtained can be suitably used as a raw material for producing phenols, peroxides, aromatic alcohols, and the like.
第１図は本発明を実施するための装１斤の一例を示す系
統図である。
図中、Ｉはアルカリ抽出器、■は静置槽、ＩＩＩは分解
槽、■は静置槽、１〜１２は管を示す。
代理人 弁理士 柳 原 成FIG. 1 is a system diagram showing an example of one loaf of packaging for carrying out the present invention. In the figure, I is an alkali extractor, ■ is a standing tank, III is a decomposition tank, ■ is a standing tank, and 1 to 12 are tubes. Agent Patent Attorney Sei Yanagihara
Claims (4)
基を有する芳香族一級ヒドロペルオキシドと、（Ｂ）芳
香核に直結した２−ヒドロペルオキシ−２−プロピル基
を有する芳香族三級ヒドロペルオキシド とを含有する油状ヒドロペルオキシド混合物を、４５〜
６０℃の温度範囲で２〜３重量％の水酸化ナトリウム水
溶液と接触させた後、４５〜６０℃の温度範囲で油水分
離し、水層に抽出された（Ａ）成分の少なくとも一部を
、７０〜９０℃の温度範囲で分解することを特徴とする
ヒドロペルオキシド混合物の処理方法。(1) (A) An aromatic primary hydroperoxide having a hydroperoxymethyl group directly connected to an aromatic nucleus, and (B) an aromatic tertiary hydroperoxide having a 2-hydroperoxy-2-propyl group directly connected to an aromatic nucleus. an oily hydroperoxide mixture containing from 45 to
After contacting with a 2 to 3% by weight aqueous sodium hydroxide solution at a temperature range of 60°C, oil and water are separated at a temperature range of 45 to 60°C, and at least a part of the component (A) extracted into the aqueous layer is A method for treating a hydroperoxide mixture, characterized in that it decomposes in a temperature range of 70 to 90°C.
したメチル基およびイソプロピル基を有する芳香族化合
物の液相酸化生成物またはその濃縮物である請求項（１
）記載のヒドロペルオキシド混合物の処理方法。(2) Claim (1) wherein the oily hydroperoxide mixture is a liquid phase oxidation product of an aromatic compound having a methyl group and an isopropyl group directly connected to an aromatic nucleus or a concentrate thereof.
) Process for treating the hydroperoxide mixture described in ).
（Ｂ）成分の分解率が３モル％以下となるように調節す
る請求項（１）または（２）記載のヒドロペルオキシド
混合物の処理方法。(3) decomposition, the decomposition rate of component (A) is 60 mol% or more;
The method for treating a hydroperoxide mixture according to claim (1) or (2), wherein the decomposition rate of component (B) is adjusted to be 3 mol% or less.
ないし（３）の何れかに記載のヒドロペルオキシド混合
物の処理方法。(4) Claim (1) in which the decomposition is carried out in the coexistence of hydrocarbons.
The method for treating a hydroperoxide mixture according to any one of (3) to (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11164989A JP2682134B2 (en) | 1989-04-28 | 1989-04-28 | Method for treating hydroperoxide mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11164989A JP2682134B2 (en) | 1989-04-28 | 1989-04-28 | Method for treating hydroperoxide mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02290845A true JPH02290845A (en) | 1990-11-30 |
| JP2682134B2 JP2682134B2 (en) | 1997-11-26 |
Family
ID=14566676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11164989A Expired - Lifetime JP2682134B2 (en) | 1989-04-28 | 1989-04-28 | Method for treating hydroperoxide mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2682134B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5639922A (en) * | 1994-07-14 | 1997-06-17 | Sumitomo Chemical Company, Limited | Process for treatment of hydroperoxide mixture |
| EP1061047A1 (en) * | 1999-06-04 | 2000-12-20 | Phenolchemie GmbH & Co. KG | Process for the elimination of organic peroxides from process water |
-
1989
- 1989-04-28 JP JP11164989A patent/JP2682134B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5639922A (en) * | 1994-07-14 | 1997-06-17 | Sumitomo Chemical Company, Limited | Process for treatment of hydroperoxide mixture |
| EP1061047A1 (en) * | 1999-06-04 | 2000-12-20 | Phenolchemie GmbH & Co. KG | Process for the elimination of organic peroxides from process water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2682134B2 (en) | 1997-11-26 |
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