JPH0418067A - Production of alkyl hydroperoxide - Google Patents
Production of alkyl hydroperoxideInfo
- Publication number
- JPH0418067A JPH0418067A JP12051690A JP12051690A JPH0418067A JP H0418067 A JPH0418067 A JP H0418067A JP 12051690 A JP12051690 A JP 12051690A JP 12051690 A JP12051690 A JP 12051690A JP H0418067 A JPH0418067 A JP H0418067A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- tertiary alkyl
- heating
- alkyl group
- concentration
- 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.)
- Pending
Links
- -1 alkyl hydroperoxide Chemical compound 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 150000007514 bases Chemical class 0.000 claims abstract description 20
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 16
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010543 cumene process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 150000007524 organic acids Chemical class 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 235000005985 organic acids Nutrition 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 4
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PBWHJRFXUPLZDS-UHFFFAOYSA-N (1-Ethylpropyl)benzene Chemical compound CCC(CC)C1=CC=CC=C1 PBWHJRFXUPLZDS-UHFFFAOYSA-N 0.000 description 1
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- 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
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- UUCHLIAGHZJJER-UHFFFAOYSA-N 1,2-diethylnaphthalene Chemical compound C1=CC=CC2=C(CC)C(CC)=CC=C21 UUCHLIAGHZJJER-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- VGVZNHQJMQJYJO-UHFFFAOYSA-N 1-methyl-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C)=C1C(C)C VGVZNHQJMQJYJO-UHFFFAOYSA-N 0.000 description 1
- KFRZGSPPBOQTEB-UHFFFAOYSA-N 1-methyl-4-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=C(C)C2=C1 KFRZGSPPBOQTEB-UHFFFAOYSA-N 0.000 description 1
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- UJCIERMQHAXPRF-UHFFFAOYSA-N 2-ethyl-1-methylnaphthalene Chemical compound C1=CC=CC2=C(C)C(CC)=CC=C21 UJCIERMQHAXPRF-UHFFFAOYSA-N 0.000 description 1
- 102100031272 Calcineurin B homologous protein 2 Human genes 0.000 description 1
- 241001510512 Chlamydia phage 2 Species 0.000 description 1
- 101000777239 Homo sapiens Calcineurin B homologous protein 2 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は第２級または第３級アルキル基含有化合物を酸
化して、第２級または第３級アルキルヒドロ過酸化物を
生成させ、次いで加熱濃縮を行うアルキルヒドロ過酸化
物の製造方法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention oxidizes a compound containing a secondary or tertiary alkyl group to produce a secondary or tertiary alkyl hydroperoxide, and then The present invention relates to a method for producing an alkyl hydroperoxide that involves heating and concentration.
第２級または第３級アルキルヒドロ過酸化物は、クメン
法などのフェノール類の製造方法における重要な中間体
であり、またそれ自体が各種重合開始剤、ポリマー架橋
剤等に使用される有用な化合物である。Secondary or tertiary alkyl hydroperoxides are important intermediates in phenol production methods such as the cumene process, and are themselves useful as various polymerization initiators, polymer crosslinking agents, etc. It is a compound.
従来、第２級または第３級アルキルヒドロ過酸化物は、
第２級アルキル基または第３級アルキル基含有化合物を
空気、酸素等で酸化した後、加熱により未反応原料を留
去し、過酸化物を濃縮して製造されている。ところが加
熱濃縮の際、過酸化物が一部熱分解されて、有機酸が生
成する。この有機酸は触媒として作用するため、過酸化
物が熱分解と同時に酸分裂反応を引き起こす。過酸化物
の酸分裂反応は、著しい発熱を伴ない、激しい場合には
暴走反応に至る。Traditionally, secondary or tertiary alkyl hydroperoxides are
It is produced by oxidizing a compound containing a secondary alkyl group or a tertiary alkyl group with air, oxygen, etc., then distilling off unreacted raw materials by heating, and concentrating the peroxide. However, during heating and concentration, some of the peroxide is thermally decomposed and an organic acid is produced. Since this organic acid acts as a catalyst, the peroxide causes an acid splitting reaction at the same time as thermal decomposition. The acid splitting reaction of peroxide is accompanied by significant heat generation and, in severe cases, can lead to a runaway reaction.
従来、このような有機酸による酸分裂反応を防止するた
めに、ナトリウム、カリウムの塩基性の化合物、アンモ
ニア、アミン等を反応液に添加し、中和しながら加熱濃
縮を行っている。Conventionally, in order to prevent such acid splitting reactions caused by organic acids, basic compounds such as sodium and potassium, ammonia, amines, etc. are added to the reaction solution, and the solution is heated and concentrated while being neutralized.
しかしながら、前述のような従来の製造方法では、ナト
リウム、カリウムの塩基性化合物が第２級または第３級
アルキル基含有化合物、あるいはそのヒドロ過酸化物に
ほとんど溶解しないため、固／液の中和反応となって、
効率が悪い。またナトリウム、カリウムの塩基性化合物
を水溶液として供給した場合、加熱濃縮時に未反応原料
とともに水分が留去され、濃縮系の器壁にナトリウム塩
やカリウム塩が析出固着するという問題点がある。However, in the conventional production method as described above, basic compounds such as sodium and potassium hardly dissolve in secondary or tertiary alkyl group-containing compounds or their hydroperoxides, so solid/liquid neutralization is required. As a reaction,
ineffective. Further, when basic compounds such as sodium and potassium are supplied as an aqueous solution, there is a problem that water is distilled off together with unreacted raw materials during heating and concentration, and sodium salts and potassium salts precipitate and stick to the walls of the concentration system.
また、アンモニアやアミン化合物を供給した場合、濃縮
時に未反応原料とともに留去され、酸化反応に循環する
未反応原料がアンモニア等により汚染されて、酸化反応
速度を低下させるという問題点がある。Furthermore, when ammonia or an amine compound is supplied, there is a problem that it is distilled off together with unreacted raw materials during concentration, and the unreacted raw materials that are recycled to the oxidation reaction are contaminated with ammonia and the like, reducing the oxidation reaction rate.
本発明の目的は、上記のような問題点を解決するため、
濃縮系に塩類が祈呂したり、あるいは留去する未反応原
料中に塩基が混入するのを防止して、生成する有機酸を
効率よく中和しながら、アルキルヒドロ過酸化物を効率
よく濃縮することができ、留去した未反応原料は酸化反
応の原料として循環使用することができるアルキルヒド
ロ過酸化物の製造方法を提案することである。The purpose of the present invention is to solve the above problems,
Efficiently concentrates alkyl hydroperoxides while efficiently neutralizing the organic acids produced by preventing salts from entering the concentration system or from mixing bases into the unreacted raw materials being distilled off. The object of the present invention is to propose a method for producing an alkylhydroperoxide in which the distilled unreacted raw material can be recycled as a raw material for an oxidation reaction.
本発明は、次のアルキルヒドロ過酸化物の製造方法であ
る。The present invention is the following method for producing an alkyl hydroperoxide.
（１）第２級または第３級アルキル基含有化合物を酸化
して、第２級または第３級アルキルヒドロ過酸化物を生
成させ、次いで反応液にルビジウムまたはセシウムの塩
基性化合物を添加して加熱濃縮することを特徴とするア
ルキルヒドロ過酸化物の製造方法。(1) A compound containing a secondary or tertiary alkyl group is oxidized to produce a secondary or tertiary alkyl hydroperoxide, and then a basic compound of rubidium or cesium is added to the reaction solution. A method for producing an alkyl hydroperoxide, which comprises heating and concentrating it.
（２）第２級または第３級アルキル基含有化合物は、第
２級または第３級アルキル基にアリール基が置換したア
ラルキル基含有化合物である上記（１）記載の方法。(2) The method according to (1) above, wherein the secondary or tertiary alkyl group-containing compound is an aralkyl group-containing compound in which a secondary or tertiary alkyl group is substituted with an aryl group.
（３）ルビジウムまたはセシウムの塩基性化合物が水酸
化物、炭酸塩または炭酸水素塩である上記（１）または
（２）記載の方法。(3) The method according to (1) or (2) above, wherein the basic compound of rubidium or cesium is a hydroxide, carbonate or bicarbonate.
（４）反応液および濃縮液のｐｉ（が３〜７．５を維持
するように、ルビジウムまたはセシウムの塩基性化合物
を添加して加熱濃縮するようにした上記（１）ないしく
３）のいずれかに記載の方法。(4) Any of the above (1) or 3), in which a basic compound of rubidium or cesium is added and concentrated by heating so that the pi of the reaction solution and the concentrated solution is maintained at 3 to 7.5. Method described in Crab.
本発明における第２級または第３級アルキル基含有化合
物（以下、単にアルキル基含有化合物と略記する）は、
分子中に第２級または第３級アルキル基を有する化合物
であり、クメン法等のフェノール類の製造などの場合に
は、第２級または第３級アルキル基にアリール基が置換
したアラルキル基を有する化合物が用いられる。このよ
うなアルキル基含有化合物としては、例えばエチルベン
ゼン、ジエチルベンゼン、トリエチルベンゼン。The secondary or tertiary alkyl group-containing compound (hereinafter simply abbreviated as alkyl group-containing compound) in the present invention is:
It is a compound that has a secondary or tertiary alkyl group in the molecule, and in the case of manufacturing phenols such as the cumene method, it is a compound that has an aralkyl group substituted with an aryl group on the secondary or tertiary alkyl group. A compound having the following properties is used. Examples of such alkyl group-containing compounds include ethylbenzene, diethylbenzene, and triethylbenzene.
エチルトルエン、ジエチルトルエン、クメン、ジイソプ
ロピルベンゼン、トリイソプロピルベンゼン、サイメン
、ジイソプロピルトルエン、エチルナフタレン、ジエチ
ルナフタレン、エチルメチルナフタレン、イソプロピル
ナフタレン、ジイソプロピルナフタレン、イソプロピル
メチルナフタレンなどがあげられる。Examples include ethyltoluene, diethyltoluene, cumene, diisopropylbenzene, triisopropylbenzene, cymene, diisopropyltoluene, ethylnaphthalene, diethylnaphthalene, ethylmethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, and isopropylmethylnaphthalene.
本発明では、これらのアルキル基含有化合物を酸化して
、第２級または第３級アルキルヒドロ過酸化物を生成さ
せる。アルキル基含有化合物の酸化は、空気、純酸素等
の酸素含有ガスにより酸化することにより行われる。酸
化の条件は、アルキル基含有化合物の種類によって種々
異なるが、代表例としてクメンをとりあげると、クメン
の酸化条件は温度８０〜１２０℃、圧力Ｏ〜１０ｋｇ／
ｆｆ１Ｇ、 時間１〜３時間であり、空気を酸化剤と
して用い１反応器の廃ガス中０□濃度を３〜１０容量％
とする。In the present invention, these alkyl group-containing compounds are oxidized to produce secondary or tertiary alkyl hydroperoxides. Oxidation of the alkyl group-containing compound is performed by oxidizing with an oxygen-containing gas such as air or pure oxygen. The oxidation conditions vary depending on the type of alkyl group-containing compound, but taking cumene as a typical example, the oxidation conditions for cumene are a temperature of 80 to 120°C and a pressure of O to 10 kg/kg.
ff1G, the time is 1 to 3 hours, and the concentration in the waste gas of one reactor is 3 to 10% by volume using air as the oxidizing agent.
shall be.
また安定剤としてＮａＯＨ，Ｎａ２Ｃｏ３等の塩基を用
いる。Further, a base such as NaOH or Na2Co3 is used as a stabilizer.
クメンの酸化によりクメンヒドロペルオキシドが得られ
る。Oxidation of cumene yields cumene hydroperoxide.
こうして酸化によりアルキルヒドロ過酸化物が生成した
反応液は、未反応原料であるアルキル基含有化合物を留
去するために加熱濃縮を行う。このとき一部の過酸化物
の熱分解により生成する有機酸を中和するために、ルビ
ジウムまたはセシウムの塩基性化合物を添加して加熱濃
縮を行う。The reaction solution in which the alkyl hydroperoxide is produced by oxidation is heated and concentrated in order to distill off the alkyl group-containing compound that is an unreacted raw material. At this time, in order to neutralize organic acids produced by thermal decomposition of some peroxides, a basic compound of rubidium or cesium is added and concentrated by heating.
ルビジウムまたはセシウムの塩基性化合物としては、水
酸化物、炭酸塩、炭酸水素塩などがあげられる。これら
は１種単独で、または２種以上の混合状態で使用するこ
とができる。これらのルビジウムまたはセシウムの塩基
性化合物は水溶性であり、水溶液として反応液に添加す
る。水溶液の濃度は任意であるが、−殻内には１〜１０
重量％、好ましくは３〜７重量％程度である。Basic compounds of rubidium or cesium include hydroxides, carbonates, hydrogen carbonates, and the like. These can be used alone or in a mixture of two or more. These basic compounds of rubidium or cesium are water-soluble and are added to the reaction solution as an aqueous solution. The concentration of the aqueous solution is arbitrary, but - within the shell is 1 to 10
It is about 3% to 7% by weight, preferably about 3% to 7% by weight.
これらの塩基性化合物を添加して加熱濃縮することによ
り、生成する有機酸は中和され、酸分裂反応は防止され
る。塩基性化合物の添加量は生成する有機酸の量によっ
て異なるが、反応液がアルカリ性になると、アルキルヒ
ドロ過酸化物のアルカリ分解が起こりやすいので、反応
液および濃縮液がｐＨ３〜７．５、好ましくはｐＨ４〜
７を維持するように添加するのが好ましい。By adding these basic compounds and heating and concentrating, the generated organic acids are neutralized and acid splitting reactions are prevented. The amount of the basic compound added varies depending on the amount of organic acid produced, but if the reaction solution becomes alkaline, alkaline decomposition of the alkylhydroperoxide is likely to occur, so the pH of the reaction solution and concentrated solution is preferably 3 to 7.5. is pH 4~
It is preferable to add so as to maintain 7.
加熱濃縮の条件は、原料であるアルキル基含有化合物の
種類、酸化の条件等によって異なるが、クメンの場合に
は加熱温度８０〜１３０℃、好ましくは１００−１２０
℃、圧力５−５０５−５Ｏ、好ましくは１０〜３０ｍｍ
Ｈｇ、時間１〜３０分、好ましくは１〜５分程度である
。この場合、未反応原料が留去され、かつ過酸化物が分
解あるいは留去されないように、加熱温度、圧力、時間
等を選択する。濃縮方法も制限はなく、バッチ式、連続
式など、任意の方法を採用することができる。Conditions for heating concentration vary depending on the type of alkyl group-containing compound used as a raw material, oxidation conditions, etc., but in the case of cumene, the heating temperature is 80 to 130°C, preferably 100 to 120°C.
°C, pressure 5-505-5O, preferably 10-30mm
Hg, time is about 1 to 30 minutes, preferably about 1 to 5 minutes. In this case, the heating temperature, pressure, time, etc. are selected so that unreacted raw materials are distilled off and peroxides are not decomposed or distilled off. There are no restrictions on the concentration method, and any method such as a batch method or a continuous method can be employed.
こうして加熱濃縮を行うことにより、生成する有機酸は
中和され、反応液中の未反応原料および低沸点の副生成
物などの低沸点物質は留去され、アルキルヒドロ過酸化
物が濃縮される。By heating and concentrating in this way, the generated organic acid is neutralized, low-boiling substances such as unreacted raw materials and low-boiling by-products in the reaction solution are distilled off, and alkyl hydroperoxides are concentrated. .
ルビジウムまたはセシウムの塩基性化合物はアルキル基
含有化合物およびアルキルヒドロ過酸化物に可溶である
ため、中和の効率は良好であり。Since the basic compound of rubidium or cesium is soluble in alkyl group-containing compounds and alkyl hydroperoxides, the neutralization efficiency is good.
また加熱濃縮中に未反応原料とともに水分が留去されで
も、これらの塩基性化合物は溶解状態を保ち、器壁等に
析出することはない。さらにこれらの塩基性化合物は、
アンモニアやアミンと異なり、揮発性でないため、未反
応原料とともに留去されることはない。このため留去し
た未反応原料を酸化反応系に循環して再使用しても、原
料を汚染することがない。Furthermore, even if water is distilled off along with unreacted raw materials during heating and concentration, these basic compounds remain dissolved and do not precipitate on the walls of the vessel. Furthermore, these basic compounds are
Unlike ammonia and amines, it is not volatile, so it will not be distilled off along with unreacted raw materials. Therefore, even if the distilled unreacted raw material is recycled to the oxidation reaction system and reused, the raw material will not be contaminated.
〔発明の効果〕
以上の通り、本発明では、第２級または第３級アルキル
基含有化合物を酸化して、アルキルヒドロ過酸化物を生
成させた反応液に、ルビジウムまたはセシウムの塩基性
化合物を添加して加熱濃縮するようにしたので、濃縮系
に塩類が析出したり、あるいは留去する未反応原料中に
塩基が混入するのを防止して、生成する有機酸を効率よ
く中和しながら、アルキルヒドロ過酸化物を効率よく濃
縮することができ、留去した未反応原料は酸化反応の原
料として循環使用することができる。[Effects of the Invention] As described above, in the present invention, a basic compound of rubidium or cesium is added to a reaction solution in which a secondary or tertiary alkyl group-containing compound is oxidized to produce an alkylhydroperoxide. By adding it and heating and concentrating, it is possible to prevent salts from precipitating in the concentration system or from mixing bases into unreacted raw materials to be distilled off, while efficiently neutralizing the organic acids produced. , the alkyl hydroperoxide can be efficiently concentrated, and the distilled off unreacted raw material can be recycled as a raw material for oxidation reaction.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１
クメンを空気酸化し、クメンヒドロペルオキシド（以下
、ＣＨＰと略記する）を生成させた。得られたＣＨＰ２
４０〜３５０ｇ／ｆｌの反応液を濾紙で濾過し、反応液
中のナトリウムを１ ｍｇＩＱ未満とした。Example 1 Cumene was air oxidized to produce cumene hydroperoxide (hereinafter abbreviated as CHP). Obtained CHP2
The reaction solution of 40 to 350 g/fl was filtered through a filter paper to reduce the sodium content in the reaction solution to less than 1 mgIQ.
この反応液に炭酸ルビジウムの５重量％水溶液を、油相
中のルビジウムが３０ｍｇ／Ｑとなるように添加し、十
分に撹拌した。その後１〜２０ｍｍＨｇの減圧下で９０
〜１２５°Ｃに加熱して、未反応原料であるクメンを留
去し、ＣＨＰ ８５０ｇ／Ｒの濃縮液を得た。加熱濃縮
中の濃縮液のｐＨは５〜６であり、留去したクメン中に
ルビジウムは検出されず、再使用可能であった。また濃
縮釜の器壁には、スケーリングは認められなかった。A 5% by weight aqueous solution of rubidium carbonate was added to this reaction solution so that the amount of rubidium in the oil phase was 30 mg/Q, and the mixture was thoroughly stirred. After that, under a reduced pressure of 1 to 20 mmHg,
The mixture was heated to ~125°C to distill off cumene, an unreacted raw material, to obtain a concentrated liquid with a CHP of 850 g/R. The pH of the concentrated solution during heating and concentration was 5 to 6, no rubidium was detected in the distilled cumene, and it was possible to reuse it. Moreover, no scaling was observed on the wall of the concentration pot.
比較例１
実施例１において、炭酸ルビジウムの代りに炭酸ナトリ
ウムを用いた以外は、同様にしてＣＨＰ８５０ｇ／Ｒの
濃縮液を得た。その結果、濃縮釜の器壁に炭酸ナトリウ
ムのスケーリングが認められた。Comparative Example 1 A concentrated solution of CHP 850 g/R was obtained in the same manner as in Example 1, except that sodium carbonate was used instead of rubidium carbonate. As a result, scaling of sodium carbonate was observed on the wall of the concentrator.
比較例２
実施例１において、炭酸ルビジウムの代りにアンモニア
を用いたが、留出するクメン中にアンモニアが多量に検
出された。Comparative Example 2 In Example 1, ammonia was used instead of rubidium carbonate, but a large amount of ammonia was detected in the distilled cumene.
実施例２〜４
実施例１において、炭酸ルビジウムの代りに炭酸セシウ
ム、水酸化ルビジウム、または炭酸水素ルビジウムを用
いた以外は、同様に行ったところ、同様の結果が得られ
た。Examples 2 to 4 The same procedure as in Example 1 was carried out except that cesium carbonate, rubidium hydroxide, or rubidium hydrogen carbonate was used instead of rubidium carbonate, and the same results were obtained.
実施例５
実施例１において、ＣＨＰの代りにエチルベンゼンヒド
ロペルオキシド（以下、ＥＨＰと略記する）を用い、７
００ｇ＃Ｉに濃縮した以外は同様に行った。その結果、
濃縮液のｐＨは５〜６であり、留出したエチルベンゼン
中にルビジウムは検出されず、また濃縮釜の器壁にはス
ケーリングは認められなかった。Example 5 In Example 1, ethylbenzene hydroperoxide (hereinafter abbreviated as EHP) was used instead of CHP, and 7
The same procedure was carried out except that the concentration was concentrated to 00 g #I. the result,
The pH of the concentrate was 5 to 6, no rubidium was detected in the distilled ethylbenzene, and no scaling was observed on the wall of the concentrator.
実施例６
実施例１において、ＣＨＰの代りにサイミルヒドロペル
オキシド（以下、ＣｙＨＰと略記する）を用い、８２０
ｇ／ｕに濃縮した以外は、同様に行った。Example 6 In Example 1, Cymil hydroperoxide (hereinafter abbreviated as CyHP) was used instead of CHP, and 820
The same procedure was performed except that the concentration was concentrated to g/u.
その結果、濃縮液のｐＨは４〜４．５であり、留出した
サイメン中にルビジウムは検出されず、また濃縮釜の器
壁にはスケーリングは認められなかった。As a result, the pH of the concentrate was 4 to 4.5, no rubidium was detected in the distilled Cymen, and no scaling was observed on the wall of the concentrator.
以上の実施例および比較例の条件ならびに結果をまとめ
て表１に示す。The conditions and results of the above Examples and Comparative Examples are summarized in Table 1.
Claims (4)
して、第２級または第３級アルキルヒドロ過酸化物を生
成させ、次いで反応液にルビジウムまたはセシウムの塩
基性化合物を添加して加熱濃縮することを特徴とするア
ルキルヒドロ過酸化物の製造方法。(1) A compound containing a secondary or tertiary alkyl group is oxidized to produce a secondary or tertiary alkyl hydroperoxide, and then a basic compound of rubidium or cesium is added to the reaction solution. A method for producing an alkyl hydroperoxide, which comprises heating and concentrating it.
２級または第３級アルキル基にアリール基が置換したア
ラルキル基含有化合物である請求項（１）記載の方法。(2) The method according to claim 1, wherein the secondary or tertiary alkyl group-containing compound is an aralkyl group-containing compound in which a secondary or tertiary alkyl group is substituted with an aryl group.
化物、炭酸塩または炭酸水素塩である請求項（１）また
は（２）記載の方法。(3) The method according to claim (1) or (2), wherein the basic compound of rubidium or cesium is a hydroxide, carbonate or bicarbonate.
るように、ルビジウムまたはセシウムの塩基性化合物を
添加して加熱濃縮するようにした請求項（１）ないし（
３）のいずれかに記載の方法。(4) Claims (1) to (4) wherein a basic compound of rubidium or cesium is added and concentrated by heating so that the pH of the reaction solution and the concentrated solution is maintained at 3 to 7.5.
The method described in any of 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12051690A JPH0418067A (en) | 1990-05-10 | 1990-05-10 | Production of alkyl hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12051690A JPH0418067A (en) | 1990-05-10 | 1990-05-10 | Production of alkyl hydroperoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0418067A true JPH0418067A (en) | 1992-01-22 |
Family
ID=14788166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12051690A Pending JPH0418067A (en) | 1990-05-10 | 1990-05-10 | Production of alkyl hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0418067A (en) |
-
1990
- 1990-05-10 JP JP12051690A patent/JPH0418067A/en active Pending
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