JPH0784449B2 - Propylene oxide production method - Google Patents
Propylene oxide production methodInfo
- Publication number
- JPH0784449B2 JPH0784449B2 JP15430087A JP15430087A JPH0784449B2 JP H0784449 B2 JPH0784449 B2 JP H0784449B2 JP 15430087 A JP15430087 A JP 15430087A JP 15430087 A JP15430087 A JP 15430087A JP H0784449 B2 JPH0784449 B2 JP H0784449B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene oxide
- acid
- hydrogen peroxide
- propylene
- water
- 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 - Fee Related
Links
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitrogen gas Natural products 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はプロピレンオキサイドの製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing propylene oxide.
従来より提案されている、プロピレンと過酸化水素とか
らプロピレンオキサイドを製造する方法として、 （１） 酸触媒、過酸化水素、プロピオン酸を10〜70℃
で反応させ過プロピオン酸を製造し、得られた反応混合
物からベンゼン、二塩化プロパン等で過プロピオン酸を
抽出した後、40〜100℃の温度及び２〜30kg/cm2の圧力
で過剰のプロピレンと反応させ、プロピレンオキサイド
を製造する方法（例えば特公昭59-38231号、特公昭59-3
8232号、特公昭59-38951号、特開昭51-101906号、特開
昭53-59611号など）、 （２） 水とヘテロ共沸物を形成しうる不活性有機溶媒
の存在下、過酸化水素とカルボン酸を反応させ、反応混
合物中に存在する水を共沸蒸留により除去して過カルボ
ン酸を得た後、（１）と同様にしてプロピレンオキサイ
ドを製造する方法（例えば、特開昭56-18973号）、 （３） エポキシ化触媒として酸化ホウ素、ホウ素のオ
キシ酸、又は、ホウ素のオキシ酸エステルを使用し、過
酸化水素とプロピレンを０〜120℃でエポキシ化する方
法であって、その際過酸化水素と共に導入した水、及び
反応により生成した水を反応媒体から連続的に除去する
方法（例えば、特公昭58-50990号）、 （４） 砒素触媒の存在下においてプロピレンと過酸化
水素とを混和し、25〜200℃の温度で反応させ、プロピ
レンオキサイドを製造する方法、又は（３）と同様に共
沸脱水により連続的に水を除去する方法（例えば、特公
昭53-44442号、特開昭53-95901号）などが知られてい
る。Conventionally proposed methods for producing propylene oxide from propylene and hydrogen peroxide include (1) acid catalyst, hydrogen peroxide, and propionic acid at 10 to 70 ° C.
To produce perpropionic acid, and after extracting the perpropionic acid from the obtained reaction mixture with benzene, dichloropropane, etc., excess propylene was added at a temperature of 40 to 100 ° C and a pressure of 2 to 30 kg / cm 2. And a method for producing propylene oxide (for example, JP-B-59-38231 and JP-B-59-3).
8232, JP-B-59-38951, JP-A-51-101906, JP-A-53-59611, etc.) (2) In the presence of an inert organic solvent capable of forming a heteroazeotrope with water, A method in which hydrogen oxide and a carboxylic acid are reacted, water present in the reaction mixture is removed by azeotropic distillation to obtain a percarboxylic acid, and then propylene oxide is produced in the same manner as in (1) (for example, Japanese Patent Application Laid-Open Publication No. H09-242242). No. 56-18973), (3) A method of epoxidizing hydrogen peroxide and propylene at 0 to 120 ° C. using boron oxide, an oxyacid of boron, or an oxyacid ester of boron as an epoxidation catalyst. At that time, water introduced together with hydrogen peroxide and water produced by the reaction are continuously removed from the reaction medium (for example, Japanese Patent Publication No. 58-50990), (4) With propylene in the presence of an arsenic catalyst. Mix with hydrogen peroxide and react at a temperature of 25 to 200 ° C And a method of continuously removing water by azeotropic dehydration in the same manner as (3) (for example, JP-B-53-44442 and JP-A-53-95901). ing.
しかしながら上記（１）の方法では反応液中から高収率
で過プロピオン酸を抽出するためには大量の溶剤と多く
の抽出段数を必要とする。またエポキシ化反応液よりプ
ロピレンオキサイドの分離精製、溶媒の回収、循環に多
大のエネルギーと装置を必要とする。また実用上過カル
ボン酸は20〜30％以上の濃度で使用されるため、次式に
示される非常に爆発の危険性の高いジアシルパーオキサ
イドの副生濃縮の可能性があり、安全上問題である。However, the above method (1) requires a large amount of solvent and a large number of extraction stages in order to extract perpropionic acid from the reaction solution in high yield. Also, a large amount of energy and equipment are required for separation and purification of propylene oxide from the epoxidation reaction solution, recovery of the solvent, and circulation. In addition, since percarboxylic acid is used at a concentration of 20 to 30% or more for practical purposes, there is a possibility of diacyl peroxide by-product concentration shown in the following formula, which has a very high risk of explosion, and is a safety concern. is there.
RCOOOH＋RCOOH→RCOO−OOCR＋H2O 上記（２）の方法では反応混合物中の水を有機溶媒との
共沸により除去するため、過酸化水とに基づく過プロピ
オン酸の収率という点では優れているが、上記（１）と
同様プロピレンオキサイドの精製、溶媒の回収、ジアシ
ルパーオキサイドの副生等の問題が残る。RCOOOH + RCOOH → RCOO-OOCR + H 2 O In the above method (2), water in the reaction mixture is removed by azeotropic distillation with an organic solvent, so that it is excellent in terms of yield of perpropionic acid based on water with peroxide. As in the case of (1) above, problems such as propylene oxide purification, solvent recovery, and diacyl peroxide by-product remain.
上記（３）、（４）の方法では触媒に強酸を使用しない
ため、生成したエポキシドの開環などの副反応は
（１）、（２）の方法に比べて低く抑えられるという利
点を有するが、過酸化水素自身のエポキシ化力が過カル
ボン酸に比べて極めて弱いため上記（１）、（２）の方
法と同条件では過酸化水素の転化率は低く、一方反応温
度、圧力等を上げると過酸化水素の転化率は向上する
が、プロピレンオキサイドの開環によりプロピレンオキ
サイドの選択率は逆に低下してしまう。また経済性、安
全性の問題から触媒の回収が必要であり、プロセスが煩
雑になる、等の問題がある。Since the methods (3) and (4) do not use a strong acid as a catalyst, side reactions such as ring-opening of the produced epoxide have an advantage that they can be suppressed lower than those of the methods (1) and (2). Since the epoxidizing power of hydrogen peroxide itself is extremely weaker than that of percarboxylic acid, the conversion ratio of hydrogen peroxide is low under the same conditions as the above methods (1) and (2), while increasing the reaction temperature, pressure, etc. Although the conversion rate of hydrogen peroxide and hydrogen peroxide is improved, the selectivity of propylene oxide is decreased due to the ring opening of propylene oxide. Further, there is a problem that the catalyst is required to be recovered from the viewpoint of economical efficiency and safety, and the process becomes complicated.
本発明の目的は、過カルボン酸の濃縮の起こらない、安
全性の高いプロピレンオキサイドの直接製造法を提供す
ることにある。An object of the present invention is to provide a highly safe direct production method of propylene oxide which does not cause concentration of percarboxylic acid.
本発明者らは、上記問題を解決するため種々検討した結
果、遂に本発明を完成するに至った。As a result of various studies to solve the above problems, the present inventors finally completed the present invention.
すなわち本発明は、プロピレンと過酸化水素とからプロ
ピレンオキサイドを製造するに際し、 溶媒として水とヘテロ共沸物を形成するとともに過
酸化水素およびプロピレンオキサイドとは不活性な溶媒
を使用し、 かつ有機モノカルボン酸の存在下に、 系内に導入された水及び反応により生成した水を該
溶媒及び生成したプロピレンオキサイドと共に反応系外
に取り出しながら 反応することを特徴とするプロピレンオキサイドの製造
方法である。That is, the present invention, when producing propylene oxide from propylene and hydrogen peroxide, forms a heteroazeotrope with water as a solvent, uses a solvent that is inactive with hydrogen peroxide and propylene oxide, and A method for producing propylene oxide, which comprises reacting water introduced into the system and water produced by the reaction together with the solvent and the produced propylene oxide out of the reaction system in the presence of a carboxylic acid.
本発明に使用する有機モノカルボン酸としては、酢酸、
プロピオン酸、酪酸、イソ酪、安息香酸等の炭素数２〜
８個の有機モノカルボン酸が適当である。As the organic monocarboxylic acid used in the present invention, acetic acid,
2 to 2 carbon atoms such as propionic acid, butyric acid, isobutyric acid and benzoic acid
Eight organic monocarboxylic acids are suitable.
反応温度は、使用する有機モノカルボン酸によって異な
るが、40〜120℃、好ましくは、50〜90℃である。40℃
未満ではプロピレンのエポキシ化速度が遅く、プロピレ
ンオキサイドの生成が不充分であり、120℃を越えると
過酸化水素が反応に関与せずに分解したり、生成したプ
ロピレンオキサイドが開環してプロピレングリコール等
になる副反応が促進され、プロピレンオキサイド選択率
が低下するので好ましくない。反応圧力は特に制約され
ないが、常圧ないし若干加圧が好ましい。The reaction temperature varies depending on the organic monocarboxylic acid used, but is 40 to 120 ° C, preferably 50 to 90 ° C. 40 ° C
If the temperature is less than 1, the epoxidation rate of propylene is slow and the production of propylene oxide is insufficient. Etc. are promoted and the propylene oxide selectivity is lowered, which is not preferable. The reaction pressure is not particularly limited, but normal pressure or slightly increased pressure is preferable.
溶媒としては水とヘテロ共沸物を形成し、水と容易に二
層分離し得る溶剤が使用される。かかる溶剤としては例
えば、1,2−ジクロルエタン、1,2−ジクロルプロパン等
の塩素系溶剤、シクロヘキサン、ベンゼン、トルエン等
の炭化水素系溶剤を挙げることが出来る。As the solvent, a solvent that forms a heteroazeotrope with water and can be easily separated into two layers with water is used. Examples of such a solvent include chlorine-based solvents such as 1,2-dichloroethane and 1,2-dichloropropane, and hydrocarbon-based solvents such as cyclohexane, benzene and toluene.
過酸化水素と共に導入した水及び反応により生成した水
の除去は、上記した水とヘテロ共沸物を形成する溶媒と
の共沸蒸留による方法、プロピレン及び必要に応じて窒
素ガス等の不活性ガスによる随伴脱水法が用いられる。The water introduced together with hydrogen peroxide and the water generated by the reaction are removed by a method by azeotropic distillation of the above-mentioned water and a solvent forming a heteroazeotrope, propylene and an inert gas such as nitrogen gas as necessary. The associated dehydration method is used.
本発明で用いる過酸化水素及び有機モノカルボン酸は市
販のものが支障なく使用できる。特に過酸化水素は30〜
60重量％水溶液が市販品として入手でき好ましい。有機
モノカルボン酸の使用量は特に限定されないが、過酸化
水素を効率良く反応させるためには、有機モノカルボン
酸を過酸化水素の２〜10モル倍使用することが望まし
い。また、過酸化水素を有効に反応させるためには、同
様にプロピレンを過酸化水素の1.5〜10モル倍使用する
ことが望ましい。また経済上から未反応過酸化水素、プ
ロピレンは循環使用することが好ましい。As the hydrogen peroxide and the organic monocarboxylic acid used in the present invention, commercially available products can be used without any trouble. Especially hydrogen peroxide is 30 ~
A 60% by weight aqueous solution is commercially available and preferred. Although the amount of the organic monocarboxylic acid used is not particularly limited, it is desirable to use the organic monocarboxylic acid in an amount of 2 to 10 mol times that of hydrogen peroxide in order to efficiently react hydrogen peroxide. Further, in order to effectively react hydrogen peroxide, it is desirable to use propylene in an amount of 1.5 to 10 mol times that of hydrogen peroxide. From the economical viewpoint, it is preferable to circulate unreacted hydrogen peroxide and propylene.
原料は一括、分割又は連続のいずれの方法でも供給する
ことができる。The raw materials can be supplied by any method of batch, division or continuous.
生成したプロピレンオキサイドは水、溶媒、未反応プロ
ピレン、又は必要に応じて窒素ガス等の不活性ガスと共
に反応器上部より反応系外に取り出され、通常の方法で
分離、精製される。The produced propylene oxide is taken out of the reaction system from the upper part of the reactor together with water, a solvent, unreacted propylene, or an inert gas such as nitrogen gas, if necessary, and separated and purified by a usual method.
以下実施例により本発明をさらに詳細に説明する。但
し、本発明は以下の実施例に限定されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.
実施例−１ 常圧下、塔頂部に40℃の温水を循環した分縮コンデンサ
を付けた、80段オルダーショウ蒸留塔付パイレックスガ
ラス製500ml反応器の塔頂より20段目に、プロピオン酸3
29.7g/hr（4.45mol/hr）、1,2−ジクロルエタン765.0g/
hr（7.73mol/hr）を70℃に加熱して装入し、塔頂より30
段目に60重量％過酸化水素43.1g/hr（0.76mol/hr）を70
℃に加熱して装入した。Example-1 Under normal pressure, with a partial condenser condensing hot water of 40 ° C at the top of the column, 20th stage from the top of a Pyrex glass 500 ml reactor with an 80-stage Oldershaw distillation column, propionic acid 3
29.7g / hr (4.45mol / hr), 1,2-dichloroethane 765.0g /
Heat hr (7.73mol / hr) to 70 ℃ and load it.
60% by weight hydrogen peroxide 43.1g / hr (0.76mol / hr) 70
It was heated to ℃ and charged.
一方反応器ボトムよりプロピレンをガス状で159.6g/hr
（3.80mol/hr）、窒素ガスを120l/hr装入し、反応器ボ
トムをオイルバスにより70℃に加熱した。On the other hand, 159.6 g / hr of propylene in gaseous form from the bottom of the reactor
(3.80 mol / hr), nitrogen gas was charged at 120 l / hr, and the reactor bottom was heated to 70 ° C. by an oil bath.
プロピレンオキサイド、未反応プロピレン、窒素、1,2
−ジクロルエタンを含むガス相は分縮コンデンサを経て
反応系外へ、また未反応過酸化水素、プロピオン酸等を
含む液相は反応器ボトムより連続的に抜き出された。Propylene oxide, unreacted propylene, nitrogen, 1,2
-The gas phase containing dichloroethane was extracted from the reaction system through the partial condensation condenser, and the liquid phase containing unreacted hydrogen peroxide, propionic acid, etc. was continuously extracted from the bottom of the reactor.
反応を開始してから10時間後に分縮コンデンサ出のガス
組成をガスクロマトグラフィーにより測定したところ、
未反応プロピレンは145.0g/hr（3.45mol/hr）、プロピ
レンオキサイドは19.7g/hr（0.340mol/hr）であり、プ
ロピレンオキサイド選択率は97.1％であった。反応条件
及び結果を表−１に示す。After 10 hours from the start of the reaction, the gas composition of the partial condenser was measured by gas chromatography,
Unreacted propylene was 145.0 g / hr (3.45 mol / hr), propylene oxide was 19.7 g / hr (0.340 mol / hr), and the propylene oxide selectivity was 97.1%. The reaction conditions and results are shown in Table 1.
実施例−２ 1,2−ジクロルエタンの代わりに、1,2−ジクロルプロパ
ン765.0g/hr（6.77mol/hr）を使用する以外は実施例−
１と同様の方法で実施した。反応条件及び結果を表−１
に示す。Example-2 Example-2, except that 1,2-dichloropropane 765.0 g / hr (6.77 mol / hr) was used in place of 1,2-dichloroethane-
It carried out by the method similar to 1. Table 1 shows the reaction conditions and results.
Shown in.
実施例−３ 1,2−ジクロルエタンの代わりに、1,2−ジクロルプロパ
ン765.0g/hr（6.77mol/hr）、プロピオン酸の代わりに
酢酸402.3g/hr（6.70mol/hr）を使用する以外は実施例
−１と同様の方法で実施した。反応条件及び結果を表−
１に示す。Example-3 Instead of 1,2-dichloroethane, 765.0 g / hr (6.77 mol / hr) of 1,2-dichloropropane and 402.3 g / hr (6.70 mol / hr) of acetic acid instead of propionic acid are used. Except for the above, the same procedure as in Example 1 was carried out. Table of reaction conditions and results
Shown in 1.
実施例−４ 1,2−ジクロルエタンの代わりに、1,2−ジクロルプロパ
ン765.0g/hr（6.77mol/hr）、プロピオン酸の代わりに
酪酸636.2g/hr（7.22mol/hr）を使用する以外は実施例
−１と同様の方法で実施した。反応条件及び結果を表−
１に示す。Example 4 1,2-dichloropropane 765.0 g / hr (6.77 mol / hr) is used in place of 1,2-dichloroethane, and butyric acid 636.2 g / hr (7.22 mol / hr) is used in place of propionic acid. Except for the above, the same procedure as in Example 1 was carried out. Table of reaction conditions and results
Shown in 1.
実施例−５ 1,2−ジクロルエタンの代わりに、ベンゼン764.7g/hr
（9.79mol/hr）を使用する以外は、実施例−１と同様の
方法で実施した。反応条件及び結果を表−１に示す。Example-5 Instead of 1,2-dichloroethane, 764.7 g / hr of benzene
It carried out by the method similar to Example-1 except using (9.79 mol / hr). The reaction conditions and results are shown in Table 1.
〔発明の効果〕 本発明は実施例において明らかなように、過酸化水素と
プロピレンとから直接プロピレンオキサイドを製造で
き、過カルボン酸の濃縮が回避され安全性が大幅に向上
するとともに、装置の小型化が可能になるため経済性に
優れ、その産業上の利用価値は大きい。 [Effects of the Invention] As is apparent from the examples, the present invention can directly produce propylene oxide from hydrogen peroxide and propylene, avoids the concentration of percarboxylic acid, greatly improves safety, and reduces the size of the apparatus. Because it is possible to commercialize it, it is highly economical and has great industrial utility value.
Claims (2)
オキサイドを製造するに際し、 溶媒として水とヘテロ共沸物を形成するとともに過
酸化水素およびプロピレンオキサイドとは不活性な溶媒
を使用し、 かつ有機モノカルボン酸の存在下に、 系内に導入された水及び反応により生成した水を該
溶媒及び生成したプロピレンオキサイドと共に反応系外
に取り出しながら 反応することを特徴とするプロピレンオキサイドの製造
方法。1. When producing propylene oxide from propylene and hydrogen peroxide, a solvent that forms a heteroazeotrope with water and is inert to hydrogen peroxide and propylene oxide is used, and A method for producing propylene oxide, which comprises reacting in the presence of a carboxylic acid while taking out water introduced into the system and water produced by the reaction together with the solvent and the produced propylene oxide from the reaction system.
酸、酪酸またはイソ酪酸である特許請求の範囲第１項記
載の方法。2. The method according to claim 1, wherein the organic monocarboxylic acid is acetic acid, propionic acid, butyric acid or isobutyric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15430087A JPH0784449B2 (en) | 1987-06-23 | 1987-06-23 | Propylene oxide production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15430087A JPH0784449B2 (en) | 1987-06-23 | 1987-06-23 | Propylene oxide production method |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPS6480A JPS6480A (en) | 1989-01-05 |
| JPH0180A JPH0180A (en) | 1989-01-05 |
| JPH0784449B2 true JPH0784449B2 (en) | 1995-09-13 |
Family
ID=15581117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15430087A Expired - Fee Related JPH0784449B2 (en) | 1987-06-23 | 1987-06-23 | Propylene oxide production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784449B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4652895A (en) * | 1982-08-09 | 1987-03-24 | Harris Corporation | Zener structures with connections to buried layer |
-
1987
- 1987-06-23 JP JP15430087A patent/JPH0784449B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6480A (en) | 1989-01-05 |
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