JPS599531B2 - Method for producing phenols - Google Patents

Method for producing phenols

Info

Publication number
JPS599531B2
JPS599531B2 JP54091817A JP9181779A JPS599531B2 JP S599531 B2 JPS599531 B2 JP S599531B2 JP 54091817 A JP54091817 A JP 54091817A JP 9181779 A JP9181779 A JP 9181779A JP S599531 B2 JPS599531 B2 JP S599531B2
Authority
JP
Japan
Prior art keywords
hpo
reaction
phenol
methyl
cumene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP54091817A
Other languages
Japanese (ja)
Other versions
JPS5616430A (en
Inventor
義生 河合
紘一 木田
秀雄 五十嵐
司 土岐
義治 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP54091817A priority Critical patent/JPS599531B2/en
Publication of JPS5616430A publication Critical patent/JPS5616430A/en
Publication of JPS599531B2 publication Critical patent/JPS599531B2/en
Expired legal-status Critical Current

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Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

【発明の詳細な説明】 本発明はフェノール類、特に異性体を含まない: 置換
フェノール類を高収率に得る方法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for obtaining phenols, particularly isomer-free substituted phenols, in high yields.

フェノールの製造には、一般にクメン法と言われる方法
が用いられており、先ずクメンを酸化して第三級ヒドロ
ペルオキシドの1種であるクメンヒドロペルオキシド(
以下C−HPOと略記する)0 を高収率で得、次いで
反応液を70〜80wt%のC−HPO濃度に濃縮しC
−HPO濃縮物とした後、酸で分解してフェノールとア
セトンとを対クメン選択率85〜90mol%で得てい
る。一方クレゾール等の置換フェノール類の製造法゛5
としても、クメン法に対応するシメン法が知られてお
り、置換基とイソプロビル基とを有する芳香族化合物に
ついてクメン法と同様の反応を行なつて対応する置換フ
ェノール類を得ている。しかしこのシメン法の場合置換
基を有する芳香族化合物■0 をプロピレンでアルキル
化してイソプロピル基を導入する際に、置換異性体が不
可避的に生成し、それが最終製品の置換フェノール類に
異性体を混在させる結果となる。これに対し、メチル置
換芳香族化合物の1個の■5 メチル基を酸化して対応
する第一級ヒドロペルオキシド(以下1−■℃ と記す
)を合成し、次いでこれを分解して対応するフェノール
類を得る方法、例えばp−キシレンからp−メチルベン
ジルヒドロペルオキシド(以下pc−HPOと記す)を
フ0 合成し、次いでこれよりp−クレゾールを得る方
法が、米国特許第2683751号公報、ジャーナル
オブ アメリカン ケミカル ソサイテイー 第77巻
第4035頁等に記載されている。
A method called the cumene method is generally used to produce phenol, in which cumene is first oxidized to produce cumene hydroperoxide (a type of tertiary hydroperoxide).
(hereinafter abbreviated as C-HPO) was obtained in high yield, and then the reaction solution was concentrated to a C-HPO concentration of 70 to 80 wt%.
-HPO concentrate is decomposed with acid to obtain phenol and acetone with a selectivity to cumene of 85 to 90 mol%. On the other hand, a method for producing substituted phenols such as cresol ゛5
However, the cymene method, which corresponds to the cumene method, is known, and the corresponding substituted phenols are obtained by performing a reaction similar to the cumene method on an aromatic compound having a substituent and an isoprobyl group. However, in the case of the cymene method, when an aromatic compound with a substituent (0) is alkylated with propylene to introduce an isopropyl group, substituted isomers are inevitably generated, and these are converted into substituted phenols in the final product. This results in a mixture of In contrast, one 5-methyl group of a methyl-substituted aromatic compound is oxidized to synthesize the corresponding primary hydroperoxide (hereinafter referred to as 1-■℃), which is then decomposed to produce the corresponding phenol. For example, a method for synthesizing p-methylbenzyl hydroperoxide (hereinafter referred to as pc-HPO) from p-xylene and then obtaining p-cresol from this is described in U.S. Patent No. 2,683,751, Journal
of the American Chemical Society, Vol. 77, p. 4035, etc.

この方法によれば、置換フェノール、例えばp’35−
ギシレンからp−クレゾール、m−キシレンからm−ク
レゾール、メシチレンから3・ 5−キシレノールを製
造する場合に、異性体を含まない高純度のものが得られ
る等の利点があり、シメン法に比し工業的価値は高い。
しかし乍ら、この方法は酸化工程では1−HPOを高収
率で得ることが難しく、また分解工程では分解生成物の
一つであるホルムアルデヒドとフェノールとの副反応生
成物が多いため、生成するフェノール類の収率は低く、
工業的な製造方法とはなつていない。
According to this method, substituted phenols, such as p'35-
When producing p-cresol from ghylene, m-cresol from m-xylene, and 3,5-xylenol from mesitylene, it has the advantage of being able to obtain highly pure products that do not contain isomers, and is superior to the cymene method. It has high industrial value.
However, with this method, it is difficult to obtain 1-HPO in high yield in the oxidation process, and in the decomposition process, there are many side reaction products between formaldehyde, which is one of the decomposition products, and phenol. The yield of phenols is low;
It has not become an industrial manufacturing method.

本発明者らはこれらの問題を解決する方法として、酸化
工程については、脂肪族第三級ヒドロペルオキシドを反
応助剤として共存させて1−HPOを高収率に得る方法
(特願昭53−121643)を、分解工程については
、有機溶媒と三弗化硼素との共存(特願昭52−480
20)、特定割合のアルコールと三弗化硼素との共存(
特願昭5364105)、特定割合の脂肪族アルコール
及びケトンと弗化水素との共存(特願昭5312541
4)によりフェノール類を高収率に得る方法を見出した
As a method for solving these problems, the present inventors have developed a method for obtaining 1-HPO in high yield by allowing an aliphatic tertiary hydroperoxide to coexist as a reaction aid in the oxidation step (Japanese Patent Application No. 121643), and for the decomposition process, the coexistence of an organic solvent and boron trifluoride (Japanese Patent Application No. 52-480
20), coexistence of a specific proportion of alcohol and boron trifluoride (
Patent Application No. 5364105), coexistence of specific proportions of aliphatic alcohols and ketones with hydrogen fluoride (Japanese Patent Application No. 5312541)
We have discovered a method for obtaining phenols in high yield using 4).

しかし酸化工程についての上記発明の場合、高濃度で用
いる脂肪族第三級ヒドロペルオキシドが高価であり、そ
して多量の過剰分は循環使用する必要がある等の問題が
残つていた。本発明者らは、これらの点に鑑み鋭意研究
の結果、上記クメン法におけるC−HPO濃縮物を反応
助剤として共存させてメチルベンゼン類の酸化反応をさ
せることにより、1−HPOの収率を高めることが出来
、しかもこの酸化反応液から1HP0とC−HPOとを
分離することなく酸分解して各々に対応するフェノール
類(本発明の原料メチル置換芳香族に由来するフェノー
ル類は、トルエンに由来するフェノールを含め、以下の
記載ではフェノール類と記し、C−HPOに由来するフ
ェノールと区別する。
However, in the case of the above-mentioned invention regarding the oxidation step, there remain problems such as the aliphatic tertiary hydroperoxide used at a high concentration is expensive and a large amount of excess must be recycled. In view of these points, the present inventors have conducted intensive research and found that the yield of 1-HPO can be increased by causing the oxidation reaction of methylbenzenes in the above-mentioned cumene method by allowing the C-HPO concentrate to coexist as a reaction aid. In addition, 1HP0 and C-HPO can be acid-decomposed without separating them from this oxidation reaction solution to produce their corresponding phenols (phenols derived from methyl-substituted aromatics as raw materials of the present invention are treated with toluene). In the following description, including the phenol derived from C-HPO, it will be referred to as phenol to distinguish it from the phenol derived from C-HPO.

)とフェノールとを得ることを見出し本発明に到達した
。即ち本発明は、クメンの酸化反応生成液を濃縮して得
られるC−HPO濃縮物の共存下にメチル置換芳香族化
合物を分子状酸素含有ガスにより液相酸化し、該メチル
置換芳香族化合物のメチル基の1つを酸化して対応する
1−HPOを生成せし・め、得られた反応生成物を濃縮
してC−HPOと1−HPOとを含有する濃縮液となし
、次いで該濃縮液を酸性触媒存在下での分解反応に供し
て、C−HPO及び1−HPOをフェノールおよびフェ
ノール類にそれぞれ転化せしめる方法である。
) and phenol, and arrived at the present invention. That is, the present invention oxidizes a methyl-substituted aromatic compound in the liquid phase with a molecular oxygen-containing gas in the coexistence of a C-HPO concentrate obtained by concentrating the cumene oxidation reaction product solution, and One of the methyl groups is oxidized to form the corresponding 1-HPO, and the resulting reaction product is concentrated to a concentrated solution containing C-HPO and 1-HPO; In this method, a liquid is subjected to a decomposition reaction in the presence of an acidic catalyst to convert C-HPO and 1-HPO into phenol and phenols, respectively.

本発明において原料となるメチル置換芳香族化合物とは
、芳香環に置換した1つ以上のメチル基を有する芳香族
化合物及び1つ以上のメチル基の他に酸化反応に関与し
ないt−ブチル基やハロゲン等を有しエチル基、イソプ
ロピル基は有しない芳香族化合物であり、例えばトルエ
ン、o−、m、又はp−キシレン、1・2・3−、1・
2・4一又は1・3・5−トリメチルベンゼン、ジユレ
ン、d−メチルナフタリン、β−メチルナフタリン、o
−m一又はp−t−ブチルトルエン、ジメチルーt−ブ
チルベンゼン、o−、m一又はp−クロルトルエン、o
−、m−、p−ニトロトルエン等である。酸化反応は分
子状酸素含有ガスにより大気圧以上の加圧で行なうこと
が望ましく、圧力が高いほど反応は促進されるが、3〜
20k9/C7ilGの範囲の圧力が適当である。
The methyl-substituted aromatic compound used as a raw material in the present invention refers to an aromatic compound having one or more methyl groups substituted on an aromatic ring, and a t-butyl group that does not participate in the oxidation reaction in addition to one or more methyl groups. It is an aromatic compound that has halogen etc. but does not have ethyl group or isopropyl group, such as toluene, o-, m-, or p-xylene, 1, 2, 3-, 1,
2.4- or 1.3.5-trimethylbenzene, diurene, d-methylnaphthalene, β-methylnaphthalene, o
- m- or p-t-butyltoluene, dimethyl-t-butylbenzene, o-, m- or p-chlorotoluene, o-
-, m-, p-nitrotoluene, etc. The oxidation reaction is preferably carried out using a molecular oxygen-containing gas at a pressure higher than atmospheric pressure, and the higher the pressure, the faster the reaction.
Pressures in the range 20k9/C7ilG are suitable.

反応温度は低いほど1−HPOへの選択率は向上するも
のの反応速度が低下し、一方反応温度が高いとC−HP
Oll−HPOの分解が増加するので、90−140℃
の温度範囲が工業的には適当である。
The lower the reaction temperature, the higher the selectivity to 1-HPO but the lower the reaction rate, while the higher the reaction temperature, the higher the selectivity to 1-HPO.
90-140℃ as the decomposition of Oll-HPO increases.
The temperature range is industrially appropriate.

酸化反応の反応助剤であると共に最終的にはフェノール
の原料となるC−HPO濃縮物は、通常のクメン法に於
ける酸化反応生成物の濃縮物であり、一般には70〜8
0wt%程度のC−HPO含量のものであるが、その添
加量は、反応液中の純C−HPO濃度が10〜70wt
%、好ましくは10〜40wt%となる量が適当である
C-HPO concentrate, which is a reaction aid for the oxidation reaction and is ultimately a raw material for phenol, is a concentrate of the oxidation reaction product in the ordinary cumene process, and generally has a concentration of 70 to 8
Although the C-HPO content is approximately 0 wt%, the amount added is such that the pure C-HPO concentration in the reaction solution is 10 to 70 wt%.
%, preferably 10 to 40 wt%.

反応時間は0.5〜10時間、好ましくは1〜6時間が
適当である。
The appropriate reaction time is 0.5 to 10 hours, preferably 1 to 6 hours.

原料の反応率を高くすると1−HPOへの選択率が低下
するので選択率の点では反応率はできるだけ低く抑える
のが望ましいが、反応器容積当りの得量が低下すること
となるので、反応率は5〜20%にするのが好ましい。
If the reaction rate of the raw materials is increased, the selectivity to 1-HPO will decrease, so from the point of view of selectivity it is desirable to keep the reaction rate as low as possible, but since this will reduce the yield per reactor volume, Preferably, the ratio is between 5 and 20%.

C−HPO濃縮物、反応原料以外に溶媒を用いても良い
が特に必要はない。
A solvent may be used in addition to the C-HPO concentrate and the reaction raw materials, but it is not particularly necessary.

反応形式は、回分、半回分、連続のいずれの形式でも良
いが、連続の場合は多段槽式反応器にするのが望ましい
The reaction format may be batch, semi-batch, or continuous, but in the case of continuous reaction, it is preferable to use a multi-stage tank reactor.

反応器の材質は1−HPOの生成に影響しない不活性の
もの、例えばテフロン、ガラス、アルミニウム、チタン
などが好ましい。
The material of the reactor is preferably an inert material that does not affect the production of 1-HPO, such as Teflon, glass, aluminum, titanium, etc.

反応は発熱反応であるので外部より冷却するか、内部の
液の蒸発で除熱を行なう。
Since the reaction is exothermic, heat is removed by cooling from the outside or by evaporating the internal liquid.

分子状酸素含有ガスとしては純酸素または酸素と不活性
ガスとの混合物が使用でき、空気が好適である。
As the molecular oxygen-containing gas, pure oxygen or a mixture of oxygen and an inert gas can be used, with air being preferred.

分子状酸素含有ガスの流量は反応系からの排出ガス中に
酸素が実質的に無いか又は少量残る程度に調節するのが
適当である。酸化反応後の反応生成液は、原料液組成、
反応率に応じて4〜10wt%の1−HPOllO〜7
0wt%のC−HPOおよび未反応の原料、副生成物な
どを含んでいるが、これを減圧下に蒸留し原料のメチル
置換芳香族化合物の大部分を留去する。
It is appropriate to adjust the flow rate of the molecular oxygen-containing gas to such an extent that substantially no oxygen or only a small amount of oxygen remains in the exhaust gas from the reaction system. The reaction product liquid after the oxidation reaction has a raw material liquid composition,
4-10 wt% 1-HPOllO-7 depending on reaction rate
Although it contains 0 wt % of C-HPO, unreacted raw materials, by-products, etc., this is distilled under reduced pressure to remove most of the methyl-substituted aromatic compounds as raw materials.

この結果、蒸留前の液の30〜70wt%程度にまで濃
縮されるが、濃縮温度を低く抑えることにより1−HP
OおよびC−HPOの損失は殆んど無い〜 かくして得られた濃縮液は次いで分解反応に供し、1−
HPOを対応するフェノール類に、CHPOをフェノー
ルにそれぞれ転化せしめる。
As a result, the liquid is concentrated to about 30 to 70 wt% of the liquid before distillation, but by keeping the concentration temperature low, 1-HP
There is almost no loss of O and C-HPO ~ The concentrate obtained in this way is then subjected to a decomposition reaction, and 1-
HPO is converted to the corresponding phenols and CHPO is converted to phenol.

分解反応は、この種反応に用いられる公知方法、従来方
法を広く適用して実施することができ、各種の有機溶媒
中、弗化水素、弗化硼素、硫酸、塩酸などの鉱酸、イオ
ン交換型固体酸触媒などの存在下に行なうが、特に前記
した、有機溶媒と三弗化硼素との組合せ(特願昭52−
48020)アルコールと三弗化硼素とを1〜20:1
のモル比で使用する組合せ(特願昭53−64105)
、脂肪族アルコール1〜30重量部と脂肪族ケトン99
〜70重量部とからなる溶媒100重量部と弗化水素0
.2〜15重量部とを使用する組合せ(特願昭53−1
25414)等が好適である。分解反応後の生成液は、
触媒を分離した後蒸留によつて溶媒等の軽沸成分を除き
、次いで精留によつてフェノールおよびフェノール類を
分離して製品とする。なおトルエンを原料とする場合は
フェノールのみが製品である。本発明はクメン法フェノ
ール製造プロセスと組合せる態様、即ち本発明の工程に
クメン法フェノール製造プロセスの前段である、クメン
を酸化してC−HPOを製造工程を結合する態様で実施
すれば最も工業的効果が著しい。
The decomposition reaction can be carried out by widely applying known and conventional methods used for this type of reaction, and can be carried out using various organic solvents, mineral acids such as hydrogen fluoride, boron fluoride, sulfuric acid, and hydrochloric acid, and ion exchange. It is carried out in the presence of a type solid acid catalyst, etc., and in particular, the above-mentioned combination of an organic solvent and boron trifluoride (Japanese Patent Application No. 1973-
48020) Alcohol and boron trifluoride in a ratio of 1 to 20:1
Combination used at molar ratio of
, 1 to 30 parts by weight of aliphatic alcohol and 99 parts by weight of aliphatic ketone
100 parts by weight of a solvent consisting of ~70 parts by weight and 0 parts by weight of hydrogen fluoride
.. Combination using 2 to 15 parts by weight (Patent Application 1987-1)
25414) etc. are suitable. The product liquid after the decomposition reaction is
After separating the catalyst, light boiling components such as solvents are removed by distillation, and then phenol and phenols are separated by rectification to produce a product. Note that when toluene is used as a raw material, only phenol is the product. The present invention can be realized in an embodiment in which it is combined with the cumene process for producing phenol, that is, in an embodiment in which the process of the present invention is combined with the process for producing C-HPO by oxidizing cumene, which is the first stage of the cumene process for producing phenol. The effect is significant.

本発明による効果は次の如くである。The effects of the present invention are as follows.

(1)C−HPO濃縮物の共存によりメチル置換芳香族
化合物の酸化反応における1−HPOの収率が向上し、
副生成物も減少する。
(1) The coexistence of C-HPO concentrate improves the yield of 1-HPO in the oxidation reaction of methyl-substituted aromatic compounds,
By-products are also reduced.

従つて最終フェノール類の収率が向上する。(2)C−
HPO濃縮物は、クメン法フェノール製造工場が近接す
るか又は工程として組合わさつていれば、安価に入手で
き、又本発明の酸化工程での損失は失なく、大部分はフ
ェノールに転化され、更に一部分解して出来るクミルア
ルコールはクメン法フェノール製造装置でクメンに再生
することができるから、実際上のC−HPOのコストは
少ない。
Therefore, the yield of final phenols is improved. (2) C-
HPO concentrate can be obtained at low cost if a cumene process phenol manufacturing plant is nearby or combined as a process, and most of the HPO concentrate is converted to phenol without loss in the oxidation process of the present invention. Furthermore, the cumyl alcohol produced by partial decomposition can be regenerated into cumene in a cumene process phenol production apparatus, so the actual cost of C-HPO is low.

(3) トルエン以外のメチル置換芳香族化合物を原料
とする場合に得られる置換フェノールとCHPOより得
られるフェノールとの分離は蒸留により容易に実施でき
る。
(3) Separation of the substituted phenol obtained when a methyl-substituted aromatic compound other than toluene is used as a raw material and the phenol obtained from CHPO can be easily carried out by distillation.

実施例1 p−キシレン2007、C−HPO濃縮液1007(C
−HPO73.2wt%、クミルアルコール9.7wt
%、アセトフェノン1.5wt%、クメン13.8wt
%)を内容積500CCのチタン製反応器に仕込み反応
温度120゜Cで空気を吹込んで10kg/DGの圧力
にて4時間酸化反応を行なつた。
Example 1 p-xylene 2007, C-HPO concentrate 1007 (C
-HPO73.2wt%, cumyl alcohol 9.7wt
%, acetophenone 1.5wt%, cumene 13.8wt%
%) was charged into a titanium reactor having an internal volume of 500 cc, and an oxidation reaction was carried out at a reaction temperature of 120°C, air was blown in, and a pressure of 10 kg/DG for 4 hours.

反応生成液の組成分析よりC−HPO74]7、Px−
HPOl9.57、p−ギシレン179.47、クメン
8.9y1アセトフェノン2.47、クミルアルコール
16.07、その他2.17であつた。p−キシレンの
反応率は10.3%、?HPOへの選択率は72.7m
01%であつた。C一HPOが増加したのはクメンから
の生成によるものである。次にこの酸化反応生成液を真
空度10mT1LHgの減圧下、底部温度50℃まで加
熱してpキシレン、クメンなどの軽沸分を除き、C−H
PO含量60Wt%、μmHPO含量15.6wt%の
濃縮液123.57を取得した。濃縮工程でのPx−H
POの回収率は99%であつた。次に内容積が250m
1のポリエチレン製反応器にアセトン100yと上記濃
縮液307とを採取し氷冷した。これに弗化水素の30
wt%メタノール溶液207を添加した。この混合物を
50℃に30分間加熱してヒドロペルオキシドの分解反
応を行なつた。反応終了後反応液の分析を行なつた結果
、C−HPOおよびPx−HPOは完全に反応しており
、それらからのフェノールおよびp−クレゾールの収率
は、それぞれ98m01%および96m01%であつた
。またp−クレゾールの原料p−キシレンからの通算選
択率は69m01%であつた。
From the composition analysis of the reaction product liquid, C-HPO74]7, Px-
HPOl was 9.57, p-gysylene 179.47, cumene 8.9yl acetophenone 2.47, cumyl alcohol 16.07, and others 2.17. The reaction rate of p-xylene is 10.3%, ? Selectivity to HPO is 72.7m
It was 0.1%. The increase in C-HPO is due to production from cumene. Next, this oxidation reaction product liquid was heated to a bottom temperature of 50°C under a reduced pressure of 10mT1LHg to remove light boiling components such as p-xylene and cumene, and C-H
123.57 of a concentrated liquid having a PO content of 60 wt% and a μmHPO content of 15.6 wt% was obtained. Px-H in the concentration process
The recovery rate of PO was 99%. Next, the internal volume is 250m
Acetone 100y and the above concentrated liquid 307 were collected in a polyethylene reactor No. 1 and cooled on ice. Add to this 30% of hydrogen fluoride.
A wt% methanol solution 207 was added. This mixture was heated to 50° C. for 30 minutes to perform a hydroperoxide decomposition reaction. After the reaction was completed, analysis of the reaction solution revealed that C-HPO and Px-HPO had completely reacted, and the yields of phenol and p-cresol from them were 98m01% and 96m01%, respectively. . The total selectivity of p-cresol from the raw material p-xylene was 69m01%.

実施例2〜6 原料、反応条件等を種々変えて反応を行なつた。Examples 2-6 The reaction was carried out by variously changing the raw materials, reaction conditions, etc.

その結果は第1表の如くであつた。なお表中C−HPO
濃縮液および弗化水素−メ※くタノール溶液は実施例1
と同じ組成のものを意味する。
The results were as shown in Table 1. In addition, C-HPO in the table
Concentrated liquid and hydrogen fluoride-metanol solution are as in Example 1.
means the same composition as.

Claims (1)

【特許請求の範囲】[Claims] 1 反応生成液に対し10〜70重量%の割合となるよ
うに添加されたクメンヒドロペルオキシドの共存下に、
酸化反応に関与する置換基としてメチル基のみが芳香核
に置換しているメチル置換芳香族化合物を分子状酸素含
有ガスにより液相酸化し、該メチル置換芳香族化合物の
メチル基の1つを酸化して対応する第一級ヒドロペルオ
キシドを生成せしめ、得られた反応生成液を濃縮してク
メンヒドロペルオキシドと該第一級ヒドロペルオキシド
とを含有する濃縮液となし、次いで該濃縮液を酸性触媒
存在下での分解反応に供して、クメンヒドロペルオキシ
ド及び該第一級ヒドロペルオキシドをフェノール及び対
応するフェノール類にそれぞれ転化せしめることを特徴
とするフェノール類の製造法。
1 In the coexistence of cumene hydroperoxide added to the reaction product liquid in a proportion of 10 to 70% by weight,
A methyl-substituted aromatic compound in which only a methyl group is substituted on the aromatic nucleus as a substituent participating in the oxidation reaction is oxidized in a liquid phase using a molecular oxygen-containing gas, and one of the methyl groups of the methyl-substituted aromatic compound is oxidized. to produce the corresponding primary hydroperoxide, and the resulting reaction product liquid is concentrated to obtain a concentrated liquid containing cumene hydroperoxide and the primary hydroperoxide, and then the concentrated liquid is treated in the presence of an acidic catalyst. A method for producing phenols, which comprises converting cumene hydroperoxide and the primary hydroperoxide into phenol and corresponding phenols, respectively, by subjecting them to the decomposition reaction described below.
JP54091817A 1979-07-19 1979-07-19 Method for producing phenols Expired JPS599531B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP54091817A JPS599531B2 (en) 1979-07-19 1979-07-19 Method for producing phenols

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP54091817A JPS599531B2 (en) 1979-07-19 1979-07-19 Method for producing phenols

Publications (2)

Publication Number Publication Date
JPS5616430A JPS5616430A (en) 1981-02-17
JPS599531B2 true JPS599531B2 (en) 1984-03-03

Family

ID=14037179

Family Applications (1)

Application Number Title Priority Date Filing Date
JP54091817A Expired JPS599531B2 (en) 1979-07-19 1979-07-19 Method for producing phenols

Country Status (1)

Country Link
JP (1) JPS599531B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6473609A (en) * 1987-09-14 1989-03-17 Nec Corp Laminated ceramic capacitor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683751A (en) * 1950-10-31 1954-07-13 Hercules Powder Co Ltd Phenol production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683751A (en) * 1950-10-31 1954-07-13 Hercules Powder Co Ltd Phenol production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6473609A (en) * 1987-09-14 1989-03-17 Nec Corp Laminated ceramic capacitor

Also Published As

Publication number Publication date
JPS5616430A (en) 1981-02-17

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