JPH03287574A - Production of cumene hydroperoxide - Google Patents
Production of cumene hydroperoxideInfo
- Publication number
- JPH03287574A JPH03287574A JP2084840A JP8484090A JPH03287574A JP H03287574 A JPH03287574 A JP H03287574A JP 2084840 A JP2084840 A JP 2084840A JP 8484090 A JP8484090 A JP 8484090A JP H03287574 A JPH03287574 A JP H03287574A
- Authority
- JP
- Japan
- Prior art keywords
- cumene
- reaction
- weight
- oxidation
- liquid phase
- 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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000012530 fluid Substances 0.000 abstract 2
- 238000007086 side reaction Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 7
- 150000001447 alkali salts Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical class [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010543 cumene process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium and potassium Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、クメンを液相酸化してクメンハイドロパーオ
キサイド（以下ＣＨＰ と称する）を製造する方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing cumene hydroperoxide (hereinafter referred to as CHP) by liquid phase oxidation of cumene.
クメンを酸化してＣＨＰを台底する反応は、クメン法フ
ェノールプロセスの重要な工程であり、又ＣＯＰ も各
種反応の酸化剤として多く利用されていクメンの酸化は
、液相状態で酸素又は、酸素含有ガスの存在下に、好ま
しくは散気圧の加圧下で行われる０反応により生成する
物質はＣＨＰ以外では、ジメチルフェニルカルビノール
（以下Ｃ’ｎｏｌと称する）とアセトフェノン（以下Ａ
’ｎｏｎｅと称する）が大半を占めるが、ギ酸、酢酸等
の有機酸も一部副生ずる。 ＣＨＰは酸性領域では分解
し易い物質であり、有機酸の生成による反応液ｐｌ＋の
低下は、反応収率上好ましくないと言われていた。又、
アルカリ領域に於いてもＣＵＰは分解する。それ故、ク
メンの液相酸化反応は中性〜弱アルカリ性域に於いて行
われるのが一般的である。そこで、従来の方法に於いて
は、炭酸ナトリウム、炭酸カリウム等のアルカリ塩類を
添加する事により、反応液を中性〜弱アルカリ性域に保
った状態で反応が行われていた。The reaction of oxidizing cumene to the bottom of CHP is an important step in the cumene process phenol process, and COP is also often used as an oxidizing agent in various reactions. Other than CHP, the substances produced by the zero reaction carried out in the presence of a containing gas, preferably under diffused pressure, are dimethylphenylcarbinol (hereinafter referred to as C'nol) and acetophenone (hereinafter referred to as A).
'none) accounts for the majority, but some organic acids such as formic acid and acetic acid are also produced as by-products. CHP is a substance that easily decomposes in an acidic region, and it has been said that a decrease in the reaction solution pl+ due to the production of organic acids is unfavorable in terms of reaction yield. or,
CUP decomposes even in the alkaline region. Therefore, the liquid phase oxidation reaction of cumene is generally carried out in a neutral to slightly alkaline range. Therefore, in conventional methods, the reaction was carried out in a state where the reaction solution was kept in a neutral to slightly alkaline range by adding alkali salts such as sodium carbonate and potassium carbonate.
一方、アルカリ塩類の添加は、反応収率上有利でないと
も言われており、特公昭５４−９１８５にはアルカリ塩
類の添加を行わない方法が記載されている、又、特公昭
５５−８５０２にはｐＨ３〜６の範囲で反応を行う方法
が記載されているが、この方法もアルカリ塩類の添加を
行っていない。On the other hand, it is said that the addition of alkali salts is not advantageous in terms of reaction yield, and Japanese Patent Publication No. 54-9185 describes a method in which no alkali salts are added. A method is described in which the reaction is carried out in a pH range of 3 to 6, but this method also does not involve the addition of alkali salts.
本発明者らの検討によると、アルカリ塩類の添加を行わ
ない方法に於いては従来法に比べてＣＨＰの選択性は向
上するが、有機酸やフェノール等の両生が多く、これら
の物質が酸化反応を阻害するためか酸化速度が従来法に
比べて低い１１％に２０重量％以上のＣＵＰ壊皮下での
反応に於いてこの傾向が強い、この事は反応器の容積効
率が低下する事につながり、工業的に好ましくない。According to studies conducted by the present inventors, CHP selectivity is improved compared to conventional methods in a method that does not add alkali salts, but there are many amphibians such as organic acids and phenols, and these substances are oxidized. This tendency is strong in reactions under CUP necrosis of 11% to 20% by weight or more, where the oxidation rate is lower than in the conventional method, perhaps because it inhibits the reaction, and this results in a decrease in the volumetric efficiency of the reactor. connection, which is industrially undesirable.
本発明者らは上記問題点につき鋭意検討した結果、本発
明を完成するに至った。The present inventors have diligently studied the above-mentioned problems, and as a result, have completed the present invention.
即ち、本発明のクメンハイドロパーオキサイドの履造方
法はクメンを酸素又は酸素含有ガスの存在下に、液相酸
化してクメンハイドロパーオキサイドを製造する方法に
於いて、反応液の水素イオン濃度（ｐＨ）が３〜６の範
囲であり、かつアルカリ金属及び／又は、アルカリ土類
金属の存在下に反応を行う事を特徴とし、Ｃ’ｎｏｌや
Ａ’ｎｏｎｅ等の主要副生物及び有機酸やフェノールの
副生が少なく、かつ酸化速度の低下の少ないクメンの酸
化方法を提供するものである。That is, the method for producing cumene hydroperoxide of the present invention is a method for producing cumene hydroperoxide by oxidizing cumene in the liquid phase in the presence of oxygen or an oxygen-containing gas. pH) is in the range of 3 to 6, and the reaction is carried out in the presence of alkali metals and/or alkaline earth metals, and main by-products such as C'nol and A'none, as well as organic acids and The object of the present invention is to provide a method for oxidizing cumene that produces less phenol by-product and less decreases in oxidation rate.
ここで言うｐＨは、反応液と水をｌ：ｌ〜ｌ：２の割合
で混合し、十分振とうして後、オイル相から分離した水
相中のｐＨを意味するものであり、又、有機酸は遊離し
ている有機酸と上記金凰塩の合計量を示す。The pH here refers to the pH of the aqueous phase separated from the oil phase after mixing the reaction solution and water at a ratio of 1:1 to 1:2 and shaking thoroughly, and The organic acid indicates the total amount of free organic acid and the above-mentioned gold oxide salt.
本発明の方法によると、反応液のｐＨは３〜６、好まし
くは３．５〜５．５が良い、又、添加する金属は、ナト
リウム、カリウム等のアルカリ金属、及び／又はカルシ
ウム、マグネシウム等のアルカリ土類金属であり、一般
的にはこれら金属の炭酸塩や水酸化物等のアルカリ性物
質が用いられる。又、この場合は水溶液として添加され
るのが通常である。これら金属の添加量は通常はクメン
１トン当たりｌＯダラム当量以下、好ましくは０．１〜
６グラム当量が良い。According to the method of the present invention, the pH of the reaction solution is 3 to 6, preferably 3.5 to 5.5, and the metal added is an alkali metal such as sodium and potassium, and/or calcium, magnesium, etc. Alkaline earth metals, and alkaline substances such as carbonates and hydroxides of these metals are generally used. In this case, it is usually added as an aqueous solution. The amount of these metals added is usually less than 1 O Durham equivalent per ton of cumene, preferably 0.1 to
6 gram equivalent is good.
一般に水は、上記添加物を反応液中へ分散する目的で添
加されているが、水の蒸発による反応熱の除去にも利用
される。しかし、過刺水の添加はＣＨＰの選択率を低下
する事につながり、好ましくない０本発明の方法による
と、供給する水の量は、反応器中で蒸発した後の反応液
中の水の濃度が１．５重量％以下、好ましくは０．１〜
１．０重量％が良い、ここで言う水とは、クメン、ＣＯ
Ｐ等からなるオイル相中に溶解している水及び未溶解で
オイル相中に分散している水の合計量をさす０反応温度
は８０〜１３０℃、好ましくは９０〜１２０℃が良く、
これより低いと酸化速度が極めて遅くなり、逆に高くな
ると副生物の生成量が多くなる０反応圧力は一般的には
１０ｋｇ／−以下で行われる０反応液中のＣＩＩＰ １
１度は、次の段階で行われるＣＯＰの環線に要するエネ
ルギーを考えると、工業的には高い程好ましい、しかし
、高濃度ＣＨＰ下での反応はＣＨＰ選択率の低下につな
がり、一般的には４０重量％以下が好ましい、特にアル
カリ金属及び／又はアルカリ土類金属の添加を行わない
方法に於いては、同じｐＨ域においても酸化速度が低い
事に加えて２５・〜３０重量％ＣＵＰ濃度の所から酸化
速度の低下が見られる。しかし、本発明の方法では、２
５〜３５重量％のＣＨＰ濃度に於いても、酸化速度の低
下は殆ど見られず、かつ有機酸やフェノールの副生が少
ない。Generally, water is added for the purpose of dispersing the above-mentioned additives into the reaction solution, but it is also used to remove reaction heat by evaporating water. However, the addition of excessive water leads to a decrease in the selectivity of CHP, which is undesirable.According to the method of the present invention, the amount of water supplied is determined by controlling the amount of water in the reaction solution after evaporation in the reactor. Concentration is 1.5% by weight or less, preferably 0.1~
1.0% by weight is good; water here refers to cumene, CO
The reaction temperature is 80 to 130°C, preferably 90 to 120°C, which refers to the total amount of water dissolved in the oil phase consisting of P etc. and undissolved water dispersed in the oil phase.
If it is lower than this, the oxidation rate will be extremely slow, and if it is higher, the amount of by-products will increase.The reaction pressure is generally 10 kg/- or less.CIIP 1 in the reaction solution
Considering the energy required for the ring line of COP in the next step, higher degrees are preferable from an industrial perspective.However, reactions under high concentration of CHP lead to a decrease in CHP selectivity, and generally A CUP concentration of 40% by weight or less is preferable, especially in a method in which no alkali metal and/or alkaline earth metal is added. A decrease in the oxidation rate can be seen from some places. However, in the method of the present invention, 2
Even at a CHP concentration of 5 to 35% by weight, there is hardly any decrease in the oxidation rate, and little organic acid or phenol by-product is produced.
以下実施例により、本発明の方法を更に具体的に説明す
る。尚、説明の中で用いる酸化速度及び、酸化効率は、
次式で定義される。The method of the present invention will be explained in more detail with reference to Examples below. The oxidation rate and oxidation efficiency used in the explanation are as follows:
It is defined by the following formula.
反応器内液相の容積
生１ａＣＨＰ、Ｃ’ｎｏｌ、＾’ ｎｏｎｅのモル数の
和実施例１
内径３０１、液深２．７ｍのステンレス製反応器に、Ｃ
ＨＰを２重量％含有したクメンを毎時３６ｋｇ、 １重
量％の炭酸ナトリウム水溶液を毎時０．４ ｋｇの速度
で連続的に供給した。又、流出ガス中の酸素濃度が５モ
ル％になる様に空気を連続的に供給し１０５℃、７ｋｇ
／ｄゲージ圧力の下で反応を行った０反応液中のｐｌは
、４．８であり、水、ＣＨＰ、有機酸及びフェノールの
濃度はそれぞれ、０．３重量％、２５重量％、５０重量
ｐｐ−及び１重量ｐｐ■であった。又、この時の酸化速
度は、４１ｋｇ／ｒｒｒ−Ｈｒであり、酸化効率は９２
％であった。Volume of liquid phase in reactor 1a Sum of moles of CHP, C'nol, ^' none Example 1 In a stainless steel reactor with an inner diameter of 301 and a liquid depth of 2.7 m, C
Cumene containing 2% by weight of HP was continuously fed at a rate of 36 kg/hour, and a 1% by weight aqueous sodium carbonate solution was continuously fed at a rate of 0.4 kg/hour. In addition, air was continuously supplied so that the oxygen concentration in the outflow gas was 5 mol%, and the temperature was 7 kg at 105°C.
The pl in the reaction solution, which was reacted under /d gauge pressure, was 4.8, and the concentrations of water, CHP, organic acid, and phenol were 0.3% by weight, 25% by weight, and 50% by weight, respectively. pp- and 1 pp-by weight. Also, the oxidation rate at this time was 41 kg/rrr-Hr, and the oxidation efficiency was 92
%Met.
実施例２
クメンの供給速度を毎時３０ｋｇ、炭酸ナトリウム水溶
液の供給速度を、毎時０．３５ｋｇとした以外は、実施
例１と同じ方法で反応を行った。Example 2 The reaction was carried out in the same manner as in Example 1, except that the cumene feed rate was 30 kg/hour and the sodium carbonate aqueous solution feed rate was 0.35 kg/hour.
反応液中のｐＨは３．８であり、水、ＣＨＰ 、有機酸
及びフェノールの濃度はそれぞれ０．４重置％、２９重
量％、１２０重量ｐｐｍ 、 １２重量ｐｐ−であった
。又、この時の酸化速度は４０ｋｇ／ｎｆＢｒであり、
酸化効率は９０％であった。The pH in the reaction solution was 3.8, and the concentrations of water, CHP, organic acid, and phenol were 0.4% by weight, 29% by weight, 120 ppm by weight, and 12 ppm by weight, respectively. Also, the oxidation rate at this time was 40 kg/nfBr,
The oxidation efficiency was 90%.
比較例１
クメンの供給速度を毎時３３ｋｇとし、供給する炭酸ナ
トリウム水溶液の濃度及び供給速度を０．７重量％及び
毎時１．５ ｋｇとした以外は、実施例１と同じ方法で
反応を行った。Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that the feed rate of cumene was 33 kg/hour, and the concentration and feed rate of the aqueous sodium carbonate solution were 0.7% by weight and 1.5 kg/hour. .
反応液中のｐＨは、８．５であり、水、ＣＨＰ 、有機
酸及びフェノールの濃度はそれぞれ１．４重量％、２８
重量％、１１０重量ｐｐ−及び４重量ＰＰＭであった、
又、この時の酸化速度は４２ｋｇ／ｒｒｒ−Ｈｒ、酸化
効率は８７．５％であった。The pH in the reaction solution was 8.5, and the concentrations of water, CHP, organic acid, and phenol were 1.4% by weight and 28% by weight, respectively.
% by weight, 110 ppm by weight and 4 ppm by weight.
Further, the oxidation rate at this time was 42 kg/rrr-Hr, and the oxidation efficiency was 87.5%.
比較例２
クメンの供給速度を毎時２７ｋｇとし、炭酸ナトリウム
水溶液の供給を行わなかった以外は実施例１と同じ方法
で反応を行った０反応液のｐＨは３．２であり、ｃｕｐ
、有機酸及びフェノールの濃度はそれぞれ２８重量％
、５００重量ｐｐ−及び７０重量ｐｐｍであった。又、
この時の酸化速度は３４ｋｇ／ ｎｆ −Ｏｒ、酸化効
率は９０％であった。Comparative Example 2 The reaction was carried out in the same manner as in Example 1, except that the cumene supply rate was 27 kg/hour and the sodium carbonate aqueous solution was not supplied. The pH of the reaction solution was 3.2, and
, the concentration of organic acid and phenol was 28% by weight each.
, 500 ppm by weight and 70 ppm by weight. or,
The oxidation rate at this time was 34 kg/nf-Or, and the oxidation efficiency was 90%.
（発明の効果）
本発明の方法によると、副生ずる有機酸やフェノールに
よる酸化反応の阻害が抑制され、酸化速度の大きな低下
もなく、クメンハイドロパーオキサイドの選択率を向上
させる事が可能となる。又、有機酸の蓄積は、クメンハ
イドロパーオキサイドの酸分解の危険性を含んでいるが
、本方法によると反応液中の有機酸量は、従来の方法と
大差は見られない、これ故、安全性の面に於いても、ア
ルカリ塩類を添加しない方法に比べてはるかに改善され
る。(Effects of the Invention) According to the method of the present invention, inhibition of the oxidation reaction by by-produced organic acids and phenols is suppressed, and the oxidation rate does not decrease significantly, making it possible to improve the selectivity of cumene hydroperoxide. . Furthermore, accumulation of organic acids involves the risk of acid decomposition of cumene hydroperoxide, but according to this method, the amount of organic acids in the reaction solution is not much different from that of conventional methods. In terms of safety, this method is also much improved compared to methods that do not add alkali salts.
Claims (1)
てクメンハイドロパーオキサイドを製造する方法に於い
て、反応液の水素イオン濃度（ｐＨ）が３〜６の範囲で
あり、かつアルカリ金属及び／又は、アルカリ土類金属
の存在下に反応を行う事を特徴とするクメンハイドロパ
ーオキサイドの製造方法。In the method for producing cumene hydroperoxide by liquid phase oxidation of cumene in the presence of oxygen or an oxygen-containing gas, the hydrogen ion concentration (pH) of the reaction solution is in the range of 3 to 6, and the alkali metal and/or a method for producing cumene hydroperoxide, characterized in that the reaction is carried out in the presence of an alkaline earth metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2084840A JP3061394B2 (en) | 1990-04-02 | 1990-04-02 | Method for producing cumene hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2084840A JP3061394B2 (en) | 1990-04-02 | 1990-04-02 | Method for producing cumene hydroperoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03287574A true JPH03287574A (en) | 1991-12-18 |
| JP3061394B2 JP3061394B2 (en) | 2000-07-10 |
Family
ID=13841992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2084840A Expired - Lifetime JP3061394B2 (en) | 1990-04-02 | 1990-04-02 | Method for producing cumene hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3061394B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2708603A1 (en) * | 1993-08-06 | 1995-02-10 | Rhone Poulenc Chimie | Process for the preparation of cumene hydroperoxide. |
| US6043399A (en) * | 1994-08-08 | 2000-03-28 | Rhodia Chimie | Process for the preparation of cumene hydroperoxide |
| WO2004074241A1 (en) * | 2003-02-14 | 2004-09-02 | Shell Internationale Research Maatschappij B.V. | Process for producing alkylbenzene hydroperoxides |
| US7282613B2 (en) | 2003-02-14 | 2007-10-16 | Shell Oil Company | Process for producing phenol and methyl ethyl ketone |
| US7312365B2 (en) | 2003-02-14 | 2007-12-25 | Shell Oil Company | Process for low temperature cleavage of an oxidation mixture comprising hydroperoxides |
| JP2010528116A (en) * | 2007-06-27 | 2010-08-19 | エイチ アール ディー コーポレーション | High shear process for producing cumene hydroperoxide |
-
1990
- 1990-04-02 JP JP2084840A patent/JP3061394B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2708603A1 (en) * | 1993-08-06 | 1995-02-10 | Rhone Poulenc Chimie | Process for the preparation of cumene hydroperoxide. |
| WO1995004717A1 (en) * | 1993-08-06 | 1995-02-16 | Rhone-Poulenc Chimie | Process for the preparation of cumene hydroperoxide |
| EP0712392A1 (en) * | 1993-08-06 | 1996-05-22 | Rhone-Poulenc Chimie | Process for the preparation of cumene hydroperoxide |
| US6043399A (en) * | 1994-08-08 | 2000-03-28 | Rhodia Chimie | Process for the preparation of cumene hydroperoxide |
| WO2004074241A1 (en) * | 2003-02-14 | 2004-09-02 | Shell Internationale Research Maatschappij B.V. | Process for producing alkylbenzene hydroperoxides |
| JP2006517968A (en) * | 2003-02-14 | 2006-08-03 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Method for producing alkylbenzene hydroperoxide |
| US7141703B2 (en) | 2003-02-14 | 2006-11-28 | Shell Oil Company | Process for producing phenol and ketone using neutralizing base |
| US7282613B2 (en) | 2003-02-14 | 2007-10-16 | Shell Oil Company | Process for producing phenol and methyl ethyl ketone |
| US7312365B2 (en) | 2003-02-14 | 2007-12-25 | Shell Oil Company | Process for low temperature cleavage of an oxidation mixture comprising hydroperoxides |
| JP2010528116A (en) * | 2007-06-27 | 2010-08-19 | エイチ アール ディー コーポレーション | High shear process for producing cumene hydroperoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3061394B2 (en) | 2000-07-10 |
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