JPH0380783B2 - - Google Patents
Info
- Publication number
- JPH0380783B2 JPH0380783B2 JP61299918A JP29991886A JPH0380783B2 JP H0380783 B2 JPH0380783 B2 JP H0380783B2 JP 61299918 A JP61299918 A JP 61299918A JP 29991886 A JP29991886 A JP 29991886A JP H0380783 B2 JPH0380783 B2 JP H0380783B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- cyclohexene
- hydration
- zeolite
- reaction
- 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 - Lifetime
Links
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000006703 hydration reaction Methods 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010457 zeolite Substances 0.000 claims description 18
- 150000001451 organic peroxides Chemical class 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- -1 cyclic olefin Chemical class 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000036571 hydration Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 230000000694 effects Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 210000003918 fraction a Anatomy 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229940057054 1,3-dimethylurea Drugs 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical class CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- MUGCFKANMVCDNO-UHFFFAOYSA-N cyclohexene;hydrogen peroxide Chemical compound OO.C1CCC=CC1 MUGCFKANMVCDNO-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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)
Description
〔産業上の利用分野〕
本発明は環状オレフインの水和により環状アル
コールを製造する新規な方法に関するものであ
る。さらに詳しくは、有機過酸化物が実質的に存
在しない反応系で触媒としてゼオライトを用い接
触水和を行なうことを特徴とする環状アルコール
の製造方法に関するものである。
〔従来の技術〕
従来、オレフインの水和反応によるアルコール
の好ましい製造方法としては、結晶性アルミノシ
リケート等のゼオライトを使用する方法（例え
ば、特公昭47−45323号、特公昭53−15485号、特
開昭57−70828号、特開昭58−124723号、特開昭
58−194828号等の各公報）が知られている。
〔発明が解決しようとする問題点〕
固体触媒としてゼオライトを用いる方法は、製
品アルコールの分離、回収が容易であり、又反応
器の材質も特に制約されないという利点がある。
しかし、ゼオライトを触媒とする方法は、種々検
討した結果、その触媒活性が経時的に低下すると
いう問題があることが分つた。
したがつて、環状オレフインの水和反応を行な
う場合には、活性の低下した触媒を再生あるいは
新たに補充あるいは交換する必要があり、そのた
め多大の費用が必要となり、工業的に行なう場合
に問題がある。
〔問題点を解決するための手段〕
本発明者らは、上記のゼオライトを触媒として
使用するときの問題点を解決すべく鋭意検討を重
ねた結果、有機過酸化物が実質的に存在しない反
応系で接触水和を行なうことにより、触媒活性の
経時的な低下が著しく抑制されることを見出し、
本発明を完成するに至つた。
すなわち本発明は、触媒としてゼオライトを用
い環状オレフインの接触水和により環状アルコー
ルを製造するに際し、有機過酸化物が実質的に存
在しない反応系で接触水和を行なうことを特徴と
する環状アルコールの製造方法である。
従来の方法と比較して本発明において触媒活性
の経時的な低下が著しく抑制される理由は明確で
はないが、およそ次のように考えられる。
本発明者の検討結果、通常、環状オレフインに
は有機過酸化物が含まれていることが判明した。
環状オレフイン、例えばシクロヘキセンは商業的
にはクロルシクロヘキサンの脱ハロゲン化水素に
より生産されている。このような製造方法によつ
て製造されたシクロヘキセン中には有機過酸化物
が含まれている。
また、本発明者の検討結果によるとシクロヘキ
セン中に含まれる有機過酸化物は、その貯蔵中に
も増加することが判つた。通常、シクロヘキセン
中には20ミリグラム当量／Kg〜100ミリグラム当
量／Kgが、場合によつてはそれ以上の有機過酸化
物が含有している。
水和反応触媒の経時的活性低下に影響を及ぼす
重要な因子がこのような有機過酸化物であること
はこれまで知られておらず、本発明者らによつて
初めて見い出されたものである。すなわち従来の
水和反応では、製品アルコールの収率に影響を及
ぼさない程度の有機過酸化物の存在は、それ以上
の除去を不要のものとして見過していた。しかし
そのような微量の有機過酸化物であつても、ゼオ
ライトを触媒として用い、水和反応を長時間行な
う場合には、触媒活性の顕著な低下が観測され
た。
結晶性アルミノシリケート等のゼオライトを触
媒として水和反応を行なう場合、触媒の経時的な
活性低下の理由は、原料に不純物として存在して
いる有機過酸化物に基づくゼオライトの活性点で
の反応により生成する極性の高い高分子状の副反
応生成物が、触媒のその活性点上に非可逆的に吸
着し、結果として触媒活性点を被覆して活性を低
下させるものと考えられる。一方、均一系触媒を
用いた水和反応では、上記の高分子状の副反応生
成物は、たとえ生成しても、触媒活性には影響せ
ずしかも濾過や吸着等の操作により触媒との分離
を容易に行なうことができ、本質的問題とならな
い。
したがつて、この効果は、固体触媒であるゼオ
ライトを触媒として用いる本発明における特有の
ものである。
本発明の製造方法、すなわち有機過酸化物が実
質的に存在しない反応系で環状オレフインの接触
水和を行なうときは、上記のような現象は本質的
に起こらないため、触媒の活性は長時間接続する
ことができる。
本発明の方法では、水和触媒として結晶性アル
ミノシリケート等のゼオライトが使用される。好
ましいゼオライトの例としてはモルデナイト、エ
リオナイト、フエリエライト、モービル社発表の
ZSM系ゼオライト等の結晶性アルミノシリケー
トおよびボロシリケート等の異元素含有ゼオライ
トが用いられる。
また、ゼオライトの交換可能なカチオン種は通
常プロトン交換型が用いられるが、Mg，Oa，Sr
等のアルカリ土類元素、La，Ce等の希土類元素、
Fe，Co，Ni，Ru，Pd，Pt等の族元素から選
ばれた少なくとも一種のカチオン種で交換されて
いることも有効である。あるいは、Ti，Zr，Hf，
Cr，Mo，Ｗ等を含有させることも有効である。
また、本発明の方法に用いるゼオライト触媒の
形態は如何なるものでもよく、例えば粉末状、顆
粒状等のものが使用できる。また、担体あるいは
バインダーとしてアルミナ、シリカ、チタニア等
を使用することもできる。
本発明で使用される環状オレフインは、好まし
くはシクロペンテン、メチルシクロペンテン類、
シクロヘキセン、メチルシクロヘキセン類、シク
ロオクテン、シクロドデセン等である。
本発明において有機過酸化物とは、分子内に酸
素−酸素−重結合を有する有機化合物を示し、例
えば下記の一般式に示す化合物である。
(1) ハイドロパーオキサイド
ROOH Ｒ＝アルキル、シクロアルキ
ル
(2) パーオキサイド
R1OOR2 R1，R2＝アルキル、シクロ
アルキル
(3) 過酸
[Industrial Field of Application] The present invention relates to a novel method for producing cyclic alcohols by hydration of cyclic olefins. More specifically, the present invention relates to a method for producing a cyclic alcohol characterized by carrying out catalytic hydration using zeolite as a catalyst in a reaction system substantially free of organic peroxides. [Prior Art] Conventionally, a preferred method for producing alcohol by hydration reaction of olefin is a method using zeolite such as crystalline aluminosilicate (for example, Japanese Patent Publication No. 47-45323, Japanese Patent Publication No. 53-15485, Japanese Patent Publication No. 53-15485, JP-A-57-70828, JP-A-58-124723, JP-A-Sho
58-194828, etc.) are known. [Problems to be Solved by the Invention] The method of using zeolite as a solid catalyst has the advantage that product alcohol can be easily separated and recovered, and there are no particular restrictions on the material of the reactor.
However, as a result of various studies, it has been found that the method using zeolite as a catalyst has a problem in that the catalytic activity decreases over time. Therefore, when carrying out the hydration reaction of cyclic olefins, it is necessary to regenerate, replenish, or replace the catalyst whose activity has decreased, which requires a large amount of cost and is problematic when carried out industrially. be. [Means for Solving the Problems] As a result of intensive studies to solve the problems when using the above-mentioned zeolite as a catalyst, the present inventors have developed a reaction method in which organic peroxides are not substantially present. We discovered that by performing catalytic hydration in the system, the decline in catalyst activity over time was significantly suppressed.
The present invention has now been completed. That is, the present invention provides a method for producing a cyclic alcohol by catalytic hydration of a cyclic olefin using zeolite as a catalyst, which is characterized in that the catalytic hydration is carried out in a reaction system substantially free of organic peroxides. This is the manufacturing method. The reason why the decline in catalyst activity over time is significantly suppressed in the present invention compared to conventional methods is not clear, but it is thought to be approximately as follows. As a result of studies conducted by the present inventors, it has been found that cyclic olefins usually contain organic peroxides.
Cyclic olefins, such as cyclohexene, are commercially produced by dehydrohalogenation of chlorocyclohexane. Cyclohexene produced by such a production method contains an organic peroxide. Further, according to the study results of the present inventors, it was found that the organic peroxide contained in cyclohexene increases even during its storage. Usually, cyclohexene contains between 20 milligram equivalents/Kg and 100 milligram equivalents/Kg, and sometimes more, of organic peroxide. It has not been previously known that such organic peroxides are an important factor that affects the decline in activity of hydration reaction catalysts over time, and this was discovered for the first time by the present inventors. . That is, in conventional hydration reactions, the presence of organic peroxides to the extent that they do not affect the yield of product alcohol is overlooked as unnecessary to remove. However, even with such a trace amount of organic peroxide, when zeolite was used as a catalyst and the hydration reaction was carried out for a long time, a significant decrease in catalytic activity was observed. When a hydration reaction is carried out using zeolite such as crystalline aluminosilicate as a catalyst, the reason why the activity of the catalyst decreases over time is due to the reaction at the active sites of the zeolite based on the organic peroxide present as an impurity in the raw material. It is thought that the generated highly polar polymeric side reaction products irreversibly adsorb onto the active sites of the catalyst, thereby coating the catalyst active sites and reducing the activity. On the other hand, in the hydration reaction using a homogeneous catalyst, even if the above-mentioned polymeric side reaction products are generated, they do not affect the catalytic activity and can be separated from the catalyst by operations such as filtration or adsorption. can be easily done and poses no essential problem. Therefore, this effect is unique to the present invention, which uses zeolite, which is a solid catalyst, as a catalyst. In the production method of the present invention, that is, when catalytic hydration of a cyclic olefin is carried out in a reaction system substantially free of organic peroxides, the above-mentioned phenomenon essentially does not occur, so the activity of the catalyst is maintained for a long time. Can be connected. In the method of the invention, zeolites such as crystalline aluminosilicates are used as hydration catalysts. Examples of preferred zeolites include mordenite, erionite, ferrierite, and those published by Mobil.
Crystalline aluminosilicates such as ZSM-based zeolites and zeolites containing different elements such as borosilicate are used. In addition, the proton exchange type is usually used as the exchangeable cation species of zeolite, but Mg, Oa, Sr
alkaline earth elements such as, rare earth elements such as La, Ce, etc.
It is also effective to exchange with at least one cation species selected from group elements such as Fe, Co, Ni, Ru, Pd, and Pt. Or Ti, Zr, Hf,
It is also effective to include Cr, Mo, W, etc. Further, the zeolite catalyst used in the method of the present invention may be in any form, for example, powder, granules, etc. can be used. Furthermore, alumina, silica, titania, etc. can also be used as a carrier or binder. The cyclic olefin used in the present invention is preferably cyclopentene, methylcyclopentenes,
These include cyclohexene, methylcyclohexene, cyclooctene, and cyclododecene. In the present invention, the organic peroxide refers to an organic compound having an oxygen-oxygen-polymer bond in the molecule, and is, for example, a compound represented by the following general formula. (1) Hydroperoxide ROOH R = alkyl, cycloalkyl (2) Peroxide R 1 OOR 2 R 1 , R 2 = alkyl, cycloalkyl (3) Peracid
【式】 Ｒ＝アルキル、シクロアルキ ル (4) 過酸エステル[Formula] R = alkyl, cycloalkyl le (4) Peracid ester
以下に実施例および比較例を示し、本発明を具
体的に述べる。
参考例
（触媒の調製）
ケイ酸ソーダ（水ガラス３号）1450ｇを水700
ｇに溶解し（Ａ液）、また、硫酸アルミニウム104
ｇと濃硫酸35ｇを水400ｇに溶解し（Ｂ液）、さら
に、１，３−ジメチル尿素170ｇを水800ｇに溶解
した（Ｃ液）。Ａ液をホモジナイザーを用いて撹
拌しながら、Ｂ，Ｃ液と混合した。得られたゲル
状の水性混合物を内容積５の撹拌機付きステン
レス製オートクレーブへ仕込み、撹拌周速
1.5m／secで撹拌しながら、20時間160℃に加熱
した。生成した結晶性アルミノシリケートを遠心
分離機で分離し、水洗後、120℃で４時間乾燥し
た。次いで、空気気流下に550℃で５時間焼成し
た。さらに、塩化アンモニウム2M水溶液でカチ
オン交換を３回繰りかえした。水洗、濾過、乾燥
後、400℃で２時間焼成し、プロトン交換型結晶
性アルミノシリケートした。
（触媒１）
実施例 １
シクロヘキセン（和光、特級品）を真空脱気
後、窒素下で硫酸鉄（）0.5mol／水溶液で
３回洗浄し、さらに精密分留装置で十分に酸素を
除去し常圧蒸留を行ない沸点82〜83℃の留分(A)を
得た。未処理シクロヘキセンと処理シクロヘキセ
ン（留分Ａ）をそれぞれ分析し、含有される有機
過酸化物を定量した。結果を第１表に示す。
図面に示すような連続流通反応装置を用いて、
シクロヘキセンの水和反応を行なつた。
内容積500mlの撹拌装置付ステンレス製オート
クレーブ反応器３に、参考例で調製した触媒１を
40ｇと水120ｇを仕込み、系内を窒素ガス置換し
た。回転数500rpmで撹拌しつつ反応器を昇温し、
反応温度135℃とした後、供給管１よりシクロヘ
キセン（留分Ａ）を250ｇ／hrの速度で、また、
液面の高さが一定となるように供給管２より水
を、それぞれ供給する。反応器から溢流した反応
混合物は、溢流管４より液液分離器５へ導入され
る。分離された反応混合物中のオイル相は、排出
管６より系外へ抜き出され、触媒−水相は復帰管
７により反応器へ回収される。原料シクロヘキセ
ン供給開始３時間後における排出オイル中のシク
ロヘキサノール濃度は9.2重量％であつた。また、
250時間経過後の排出オイル中のシクロヘキサノ
ール濃度は8.5重量％であつた。
Examples and comparative examples are shown below to specifically describe the present invention. Reference example (preparation of catalyst) Add 1450g of sodium silicate (water glass No. 3) to 700g of water.
(solution A), and also aluminum sulfate 104
g and 35 g of concentrated sulfuric acid were dissolved in 400 g of water (solution B), and further, 170 g of 1,3-dimethylurea was dissolved in 800 g of water (solution C). Solution A was mixed with solutions B and C while being stirred using a homogenizer. The resulting gel-like aqueous mixture was charged into a stainless steel autoclave with an internal volume of 5 and equipped with a stirrer, and the stirring peripheral speed was increased.
The mixture was heated to 160° C. for 20 hours while stirring at 1.5 m/sec. The produced crystalline aluminosilicate was separated using a centrifuge, washed with water, and then dried at 120°C for 4 hours. Then, it was fired at 550° C. for 5 hours under a stream of air. Furthermore, cation exchange was repeated three times with a 2M ammonium chloride aqueous solution. After washing with water, filtering, and drying, it was calcined at 400°C for 2 hours to form a proton exchange type crystalline aluminosilicate. (Catalyst 1) Example 1 After vacuum degassing of cyclohexene (Wako, special grade), it was washed three times with 0.5 mol of iron sulfate ()/aqueous solution under nitrogen, and oxygen was thoroughly removed using a precision fractionator, and the mixture was heated under normal conditions. Pressure distillation was performed to obtain a fraction (A) with a boiling point of 82-83°C. Untreated cyclohexene and treated cyclohexene (Fraction A) were each analyzed to determine the amount of organic peroxide contained therein. The results are shown in Table 1. Using a continuous flow reactor as shown in the drawing,
The hydration reaction of cyclohexene was carried out. Catalyst 1 prepared in the reference example was placed in a stainless steel autoclave reactor 3 with an internal volume of 500 ml and equipped with a stirring device.
40g and 120g of water were charged, and the inside of the system was replaced with nitrogen gas. Raise the temperature of the reactor while stirring at a rotation speed of 500 rpm,
After the reaction temperature was set to 135°C, cyclohexene (fraction A) was added from supply pipe 1 at a rate of 250 g/hr, and
Water is supplied from the supply pipes 2 so that the height of the liquid level is constant. The reaction mixture overflowing from the reactor is introduced into the liquid-liquid separator 5 through the overflow pipe 4. The oil phase in the separated reaction mixture is taken out of the system through a discharge pipe 6, and the catalyst-water phase is recovered into the reactor through a return pipe 7. The concentration of cyclohexanol in the discharged oil 3 hours after the start of supply of the raw material cyclohexene was 9.2% by weight. Also,
The concentration of cyclohexanol in the discharged oil after 250 hours was 8.5% by weight.
【表】
比較例 １
原料として前記の試薬シクロヘキセンを使用し
た他は実施例１と同一の反応条件で水和反応を行
なつた。原料シクロヘキセン供給開始３時間後に
おける排出オイル中のシクロヘキサノール濃度は
8.6重量％であつた。また96時間後の排出オイル
中のシクロヘキサノール濃度は1.1重量％であつ
た。
実施例 ２〜４
実施例１に使用したシクロヘキセンに別途調製
したシクロヘキセンハイドロパーオキシドを加え
第２表に示す有機過酸化物含有量のシクロヘキセ
ンを作り、原料として用いた他は実施例１と同一
の反応条件で水和反応を行つた。原料シクロヘキ
セン供給開始200時間経過後の排出オイル中のシ
クロヘキサノール濃度を第２表に示す。[Table] Comparative Example 1 A hydration reaction was carried out under the same reaction conditions as in Example 1, except that the above-mentioned reagent cyclohexene was used as a raw material. The concentration of cyclohexanol in the discharged oil 3 hours after starting the supply of raw material cyclohexene is
It was 8.6% by weight. The concentration of cyclohexanol in the discharged oil after 96 hours was 1.1% by weight. Examples 2 to 4 Cyclohexene hydroperoxide prepared separately was added to the cyclohexene used in Example 1 to produce cyclohexene having the organic peroxide content shown in Table 2. The hydration reaction was carried out under reaction conditions. Table 2 shows the concentration of cyclohexanol in the discharged oil 200 hours after the start of supply of the raw material cyclohexene.
本発明によれば、環状オレフインの接触水和に
より環状アルコールを製造するに際し、有機過酸
化物が実質的に存在しない反応系で触媒としてゼ
オライトを用い接触水和を行なうことにより、従
来の方法と比較して触媒活性の経時的な低下が著
しく抑制され、活性が長時間持続する。
According to the present invention, when producing a cyclic alcohol by catalytic hydration of a cyclic olefin, the catalytic hydration is carried out using zeolite as a catalyst in a reaction system substantially free of organic peroxides, which is different from the conventional method. In comparison, the decline in catalyst activity over time is significantly suppressed, and the activity lasts for a long time.
図面は実施例および比較例で用いた連続流通反
応装置である。図中、１はシクロヘキセン供給
管、２は水供給管、３はオートクレーブ反応器、
４は溢流管、５は液液分離器、６は排出管、７は
復帰管を示す。
The drawing shows a continuous flow reactor used in Examples and Comparative Examples. In the figure, 1 is a cyclohexene supply pipe, 2 is a water supply pipe, 3 is an autoclave reactor,
4 is an overflow pipe, 5 is a liquid-liquid separator, 6 is a discharge pipe, and 7 is a return pipe.
Claims (1)
の接触水和により環状アルコールを製造するに際
し、有機過酸化物が実質的に存在しない反応系で
接触水和を行なうことを特徴とする環状アルコー
ルの製造方法。 ２ 環状オレフインがシクロヘキセンである特許
請求の範囲第１項記載の方法。[Claims] 1. A cyclic alcohol characterized in that when a cyclic alcohol is produced by catalytic hydration of a cyclic olefin using zeolite as a catalyst, the catalytic hydration is carried out in a reaction system substantially free of organic peroxides. Method of producing alcohol. 2. The method according to claim 1, wherein the cyclic olefin is cyclohexene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61299918A JPS63154636A (en) | 1986-12-18 | 1986-12-18 | Production of cyclic alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61299918A JPS63154636A (en) | 1986-12-18 | 1986-12-18 | Production of cyclic alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63154636A JPS63154636A (en) | 1988-06-27 |
| JPH0380783B2 true JPH0380783B2 (en) | 1991-12-26 |
Family
ID=17878499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61299918A Granted JPS63154636A (en) | 1986-12-18 | 1986-12-18 | Production of cyclic alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63154636A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0785188A1 (en) | 1995-07-20 | 1997-07-23 | Mitsubishi Chemical Corporation | Process for the preparation of epsilon-caprolactam |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047106C (en) * | 1993-12-11 | 1999-12-08 | 中国科学院大连化学物理研究所 | Zeolite catalyst for producing p-methyl-ethyl benzene with ethylene and toluene |
| JP2713127B2 (en) * | 1993-12-22 | 1998-02-16 | 三菱化学株式会社 | Method for producing cyclohexanol |
| CN101448765A (en) * | 2006-05-19 | 2009-06-03 | 国际壳牌研究有限公司 | Process for the alkylation of a cycloalkene |
-
1986
- 1986-12-18 JP JP61299918A patent/JPS63154636A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0785188A1 (en) | 1995-07-20 | 1997-07-23 | Mitsubishi Chemical Corporation | Process for the preparation of epsilon-caprolactam |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63154636A (en) | 1988-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1147510A (en) | Process for production of epoxides from olefins | |
| KR20030043979A (en) | Crystalline mww-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst | |
| JP2002508779A (en) | Method for epoxidation of propylene | |
| JPH0380783B2 (en) | ||
| US5906954A (en) | Removal of titanium atoms from titanium silicate molecular sieves | |
| CN110694679B (en) | EMT/FAU core-shell molecular sieve catalyst, and preparation method and application thereof | |
| JP2577941B2 (en) | Method for producing alcohol using ZSM-5 | |
| JP2501210B2 (en) | Method for producing cyclic alcohol | |
| CN104557450B (en) | A kind of method of oxidizing ethyle alkyl | |
| JPH032014B2 (en) | ||
| CN101455981B (en) | Improved titanium-containing catalyst regeneration method | |
| CN105523910A (en) | Oxidation method for cyclohexane | |
| JP3969078B2 (en) | Method for producing pentasil-type zeolite and method for producing ε-caprolactam | |
| JP2852950B2 (en) | Regeneration method of olefin hydration catalyst | |
| JPH0930999A (en) | Hydration of olefin | |
| JPH11511176A (en) | Method for producing 1,4-butenediol | |
| JP3158162B2 (en) | Method for producing olefin hydration catalyst | |
| JP3489869B2 (en) | Method for producing methylamines | |
| CN109721516B (en) | Thioether oxidation method | |
| JP3042367B2 (en) | Purification method of metadiisopropylbenzene | |
| JP2903326B2 (en) | Regeneration method of olefin hydration catalyst | |
| CN101575266A (en) | Method for refining phenol by acid-treated aluminium cross-linked montmorillonite catalyst | |
| JPH032015B2 (en) | ||
| JPH0985098A (en) | Regeneration of hydrated catalyst | |
| JPS60248635A (en) | Production of alcohol by catalytic hydration of olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |