JPS641453B2 - - Google Patents
Info
- Publication number
- JPS641453B2 JPS641453B2 JP58209150A JP20915083A JPS641453B2 JP S641453 B2 JPS641453 B2 JP S641453B2 JP 58209150 A JP58209150 A JP 58209150A JP 20915083 A JP20915083 A JP 20915083A JP S641453 B2 JPS641453 B2 JP S641453B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- cycloolefin
- weak
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 39
- 150000001925 cycloalkenes Chemical class 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 15
- -1 ammonium ions Chemical class 0.000 claims description 13
- 238000006703 hydration reaction Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 8
- 238000010586 diagram Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical class CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 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 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-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
- 238000009826 distribution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、シクロアルカノールの水和反応によ
り、シクロアルカノールを製造する新規な方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing cycloalkanols by a hydration reaction of cycloalkanols.
更に詳しくは、シクロオレフインを水和し、シ
クロアルカノールを製造するに際し、一般式
M2O・Al2O3・XSiO2
(式中、Mはアルカリ金属イオン、アンモニウ
ムイオン及び水素イオンの少くとも1種を表わ
し、Xは10〜1000である)
に相当する組成を有し、かつX線回折図において
表−1〜表−3に示す回折角(2θ)及び相対強度
によつて特徴づけられる結晶性アルミノシリケー
トのアルカリ金属イオン及び/又はアンモニウム
イオンの一部または全部を水素イオンで置換した
ものを触媒として用いることを特徴とするシクロ
アルカノールの製造方法に関するものである。 More specifically, when hydrating a cycloolefin to produce a cycloalkanol , the general formula M 2 O.Al 2 O 3 . (X represents a species, X is 10 to 1000) and is characterized by the diffraction angle (2θ) and relative intensity shown in Tables 1 to 3 in an X-ray diffraction diagram. The present invention relates to a method for producing a cycloalkanol, which is characterized by using as a catalyst an aluminosilicate in which some or all of the alkali metal ions and/or ammonium ions have been replaced with hydrogen ions.
従来、シクロオレフインの水和反応により、シ
クロアルカノールを製造する方法としては、可溶
性酸触媒を使用する方法、固体触媒を使用する方
法が数多く提案されている。鉱酸、特に硫酸を使
用する方法は広く知られた公知の方法である。 Conventionally, as a method for producing cycloalkanol by the hydration reaction of cycloolefin, many methods using a soluble acid catalyst and methods using a solid catalyst have been proposed. The method of using mineral acids, especially sulfuric acid, is a widely known method.
また特公昭43−8104号公報、特公昭43−16123
号公報には芳香族スルホン酸を触媒とする方法、
特開昭53−9746号公報にはヘテロポリ酸を触媒と
する方法が記載されている。 Also, Special Publication No. 43-8104, Special Publication No. 43-16123
The publication describes a method using aromatic sulfonic acid as a catalyst,
JP-A-53-9746 describes a method using a heteropolyacid as a catalyst.
しかしながら、これら可溶性酸を触媒として使
用する場合には、反応生成物及び触媒の分離回収
に多大のエネルギーを消費するとともに、装置材
料の腐触を引き起こすという欠点がある。 However, when these soluble acids are used as catalysts, there are disadvantages in that a large amount of energy is consumed in separating and recovering reaction products and catalysts, and equipment materials are corroded.
これらの欠点を改善する方法として、固体触媒
を使用する方法が提案されている。例えば特公昭
38−15619号公報、特公昭44−26656号公報には、
イオン交換樹脂を使用する方法が記載されている
が、イオン交換樹脂は耐熱性が不充分であるこ
と、及び機械的崩壊による活性の低下に問題があ
り、長時間安定した触媒活性を維持することがで
きない。 As a method to improve these drawbacks, a method using a solid catalyst has been proposed. For example, Tokkosho
Publication No. 38-15619 and Special Publication No. 44-26656,
A method using ion exchange resins is described, but ion exchange resins have problems with insufficient heat resistance and a decrease in activity due to mechanical collapse, making it difficult to maintain stable catalytic activity for a long time. I can't.
また、特公昭47−45323号公報には、脱アルカ
リ処理したモルデナイト、クリノプチロライト、
もしくはホージヤサイト系ゼオライトを触媒とす
る方法が記載されている。ゼオライトは水に不溶
性であり、耐熱性及び機械的強度が優れており、
工業用触媒として期待されるが、未だ充分な触媒
活性を有しているとはいえない。特公昭47−
45323号公報には、シクロオレフインの水和反応
の例として、実施例−4にシクロヘキセンの例が
記載されているが、その例によれば、200〜210℃
の温度で15〜10時間もの長時間反応させているに
もかかわらず、反応に供した水のアルコールへの
転化率は0.05〜0.06%にすぎない。この記載よ
り、単位時間、単位触媒当りのシクロヘキサノー
ル生成量を計算すると0.0001〜0.0002(g/g−
触媒・時間)にすぎず、工業的に実施し得るに充
分な活性を有しているとは云えない。 In addition, Japanese Patent Publication No. 47-45323 describes dealkalized mordenite, clinoptilolite,
Alternatively, a method using a haujasite zeolite as a catalyst is described. Zeolite is insoluble in water, has excellent heat resistance and mechanical strength,
Although it is expected to be used as an industrial catalyst, it cannot be said that it has sufficient catalytic activity yet. Special Public Service 1977-
Publication No. 45323 describes an example of cyclohexene in Example 4 as an example of the hydration reaction of cycloolefin;
Despite the long reaction time of 15 to 10 hours at a temperature of , the conversion rate of the water used for the reaction to alcohol is only 0.05 to 0.06%. From this description, the amount of cyclohexanol produced per unit time and unit catalyst is calculated to be 0.0001 to 0.0002 (g/g-
It cannot be said that it has sufficient activity for industrial implementation.
これに対し、同じ実施例に記載されているプロ
ピレン、1−ブテンの反応例では反応時間が短い
にもかかわらず、それぞれのオレフインからのア
ルコールへの転化率は10〜20%、4〜7%(前記
と同様、水の転化率からの計算値)である。 In contrast, in the reaction examples of propylene and 1-butene described in the same example, although the reaction time was short, the conversion rates from olefin to alcohol were 10-20% and 4-7%, respectively. (Same as above, calculated value from the water conversion rate).
即ち、α−オレフイン(プロピレン、1−ブテ
ン等)に比べて内部オレフインのシクロヘキセン
の水和反応性は極めて低いことが予測される。 That is, it is predicted that the hydration reactivity of cyclohexene, which is an internal olefin, is extremely low compared to α-olefins (propylene, 1-butene, etc.).
本発明者らは、上記したこれらの種々の問題を
解決すべく鋭意研究検討を重ねた結果、表−1〜
表−3に示すX線回折図によつて特徴づけられる
結晶性アルミノシリケートのアルカリ金属イオン
及び/又はアンモニウムイオンの全部または一部
を水素イオンで置換したものをシクロオレフイン
の水和反応触媒として使用することにより、従来
のゼオライト系触媒に比し、極めて高い転化率か
つ高い選択率でシクロアルカノールを製造し得る
ことを見い出し、本発明を完成させるにいたつ
た。 As a result of intensive research and study to solve these various problems mentioned above, the present inventors have found Tables 1 to 1.
A crystalline aluminosilicate characterized by the X-ray diffraction diagram shown in Table 3, in which all or part of the alkali metal ions and/or ammonium ions have been replaced with hydrogen ions, is used as a cycloolefin hydration reaction catalyst. By doing so, we have discovered that cycloalkanols can be produced at extremely high conversion rates and high selectivity compared to conventional zeolite catalysts, and have completed the present invention.
すなわち、本発明は、シクロオレフインの水和
反応によりシクロアルカノールを製造するに際
し、触媒として、一般式
M2O・Al2O3・XSiO2
(式中、Mはアルカリ金属イオン、アンモニウ
ムイオン及び水素イオンの少くとも1種を表わ
し、Xは10〜1000である)
に相当する組成を有し、かつX線回折図において
表−1〜表−3の回折角(2θ)及び相対強度によ
り特徴づけられる結晶性アルミノシリケートのア
ルカリ金属イオン及び/又はアンモニウムイオン
の一部または全部を水素イオンで置換したものを
触媒として使用することを特徴とするシクロアル
カノールの製造方法に関するものである。 That is, the present invention uses the general formula M 2 O・Al 2 O 3・XSiO 2 (where M is an alkali metal ion, ammonium ion, and hydrogen (representing at least one type of ion, X is 10 to 1000), and characterized by the diffraction angle (2θ) and relative intensity shown in Tables 1 to 3 in an X-ray diffraction diagram. The present invention relates to a method for producing a cycloalkanol, characterized in that a crystalline aluminosilicate obtained by replacing some or all of the alkali metal ions and/or ammonium ions with hydrogen ions is used as a catalyst.
本発明の特徴は、前記特公昭47−45323号公報
の実施例の如く、通常のゼオライト系固体触媒
が、シクロオレフインの水和反応にほとんど活性
を示さないか、あるいは活性が非常に低いのに対
し、表−1〜表−6のX線回折図で特徴づけられ
る結晶性アルミノシリケートのアルカリ金属イオ
ン及び/又はアンモニウムイオンの一部または全
部を水素イオンで置換したものを触媒として使用
することにより、極めて高い転化率かつ高い選択
率で収率よくシクロアルカノールを製造し得るこ
とであり、このような事実は、これまで予想され
なかつた驚くべき知見である。 The feature of the present invention is that, as shown in the examples of Japanese Patent Publication No. 47-45323, ordinary zeolite-based solid catalysts exhibit little or very low activity in the hydration reaction of cycloolefins. In contrast, by using as a catalyst a crystalline aluminosilicate whose alkali metal ions and/or ammonium ions, which are characterized by the X-ray diffraction patterns shown in Tables 1 to 6, are partially or completely replaced with hydrogen ions. , it is possible to produce cycloalkanol in good yield with extremely high conversion rate and high selectivity, and this fact is a surprising finding that had not been expected until now.
シクロオレフインの水和反応においては、異性
化、重合等の副反応が生成するが、本発明のX線
回折図で特徴づけられる特定の結晶性アルミノシ
リケートを触媒とする場合には、これらの副反応
がほとんど生起しない。例えば、シクロヘキセン
の水和反応においては、メチルシクロペンテン
類、ビシクロヘキシルエーテル、ビシクロヘキシ
ルといつた副生物はほとんど生成せず、実質的に
収率よくシクロヘキサノールを製造することがで
き、本発明の大きな特徴の一つとなつている。 In the hydration reaction of cycloolefin, side reactions such as isomerization and polymerization occur, but when a specific crystalline aluminosilicate characterized by the X-ray diffraction pattern of the present invention is used as a catalyst, these side reactions occur. Almost no reaction occurs. For example, in the hydration reaction of cyclohexene, by-products such as methyl cyclopentenes, bicyclohexyl ether, and bicyclohexyl are hardly produced, and cyclohexanol can be produced with substantially high yield. This is one of its characteristics.
本発明のX線回折図によつて特徴づけられる特
定の結晶性アルミノシリケートが、高活性、高選
択性を示す理由は明らかではないが、特定の結晶
性に起因する酸強度、酸性度及びその分布がシク
ロオレフイン水和反応の高活性、高選択性に寄与
しているものと考えられる。 The reason why the specific crystalline aluminosilicate characterized by the X-ray diffraction diagram of the present invention exhibits high activity and high selectivity is not clear, but the acid strength, acidity and its It is thought that this distribution contributes to the high activity and selectivity of the cycloolefin hydration reaction.
本発明において、触媒として使用される結晶性
アルミノシリケートの製造方法は公知である。例
えば、シリカ供給物質、アルミナ供給物質、アル
カリ金属イオン供給物質、水及びカチオン性有機
チツ素化合物を含む反応混合物を100〜250℃の温
度に加熱して、結晶が生成するのに充分な時間反
応させることにより得られる。本発明では、この
ようにして得られた結晶性アルミノシリケートの
うち、表−1〜表−3に示すX線回折図の回折角
(2θ)及び相対強度によつて特徴づけられる特定
の結晶性を有するものが用いられる。このような
特定の結晶性を有するものとして、例えば、AZ
−1(特開昭59−128210号)、TPZ−3(特開昭58
−110419号)、Nu−10(特開昭57−200218号)が
挙げられる。 In the present invention, methods for producing crystalline aluminosilicate used as a catalyst are known. For example, a reaction mixture containing a silica feed material, an alumina feed material, an alkali metal ion feed material, water, and a cationic organic titanium compound is heated to a temperature of 100 to 250 °C and reacted for a sufficient time to form crystals. It can be obtained by In the present invention, among the crystalline aluminosilicate thus obtained, a specific crystalline aluminosilicate characterized by the diffraction angle (2θ) and relative intensity of the X-ray diffraction diagrams shown in Tables 1 to 3 is used. The one with the following is used. For example, AZ has such specific crystallinity.
-1 (Japanese Unexamined Patent Publication No. 128210/1982), TPZ-3 (Unexamined Japanese Patent Application No. 1983
-110419) and Nu-10 (Japanese Unexamined Patent Publication No. 57-200218).
なお、X線回折分析は理学電機工業者製ガイガ
ーフレツクスRAD型装置により、線源として
銅Kα線を用いて行なつた。 The X-ray diffraction analysis was carried out using a Geigerflex RAD model manufactured by Rigaku Denki Kogyo, using copper Kα rays as a radiation source.
表−1(AZ−1)
2 θ゜ 相対強度
7.8 弱
8.7 最強
8.9 最強
17.5 弱
17.7 弱
23.1 中〜強
23.6 中
表−2(TPZ−3)
2 θ゜ 相対強度
7.9 中〜強
8.9 中〜強
19.0 中
20.5 最強
22.1 強〜最強
23.2 中
23.9 弱〜中
25.9 弱〜強
26.7 弱〜強
27.2 中
表−3(Nu−10)
2 θ゜ 相対強度
8.1 中〜強
10.0 弱〜中
12.7 弱〜中
16.4 弱
19.4 弱
20.3 最強
24.1 〃
24.5 〃
25.6 中〜強
26.5 弱
26.9 弱
32.2 弱
35.4 中
36.8 弱
37.9 弱
48.4 弱
また、本発明においては、上記の結晶性アルミ
ノシリケートを触媒として使用するに先立つて、
アルカリ金属イオン及び/又はアンモニウムイオ
ンの一部または全部を水素イオンで置換する必要
がある。この置換の方法は、従来公知のいずれの
方法を用いてもよいが、一般的には、硫酸アンモ
ニウム、硝酸アンモニウム、塩化アンモニウム、
酢酸アンモニウム等の水溶性アンモニウム塩の水
溶液で処理した後、400〜650℃で1時間以上焼成
して得られる。この場合、水素イオンの置換率は
50モル%以上、好ましくは90モル%以上が適当で
ある。更に残りのカチオンが族、族、族又
は希土類等で置換されていても差支えない。Table-1 (AZ-1) 2 θ゜ Relative strength 7.8 Weak 8.7 Strongest 8.9 Strongest 17.5 Weak 17.7 Weak 23.1 Medium to strong 23.6 Medium Table-2 (TPZ-3) 2 θ゜ Relative strength 7.9 Medium to strong 8.9 Medium to strong 19.0 Medium 20.5 Strongest 22.1 Strong to Strong 23.2 Medium 23.9 Weak to Medium 25.9 Weak to Strong 26.7 Weak to Strong 27.2 Medium Table-3 (Nu-10) 2 θ゜ Relative Strength 8.1 Medium to Strong 10.0 Weak to Medium 12.7 Weak to Medium 16.4 Weak 19.4 Weak 20.3 Strongest 24.1 〃 24.5 〃 25.6 Medium to Strong 26.5 Weak 26.9 Weak 32.2 Weak 35.4 Medium 36.8 Weak 37.9 Weak 48.4 Weak Furthermore, in the present invention, prior to using the above-mentioned crystalline aluminosilicate as a catalyst,
It is necessary to replace some or all of the alkali metal ions and/or ammonium ions with hydrogen ions. Any conventionally known method may be used for this substitution, but generally ammonium sulfate, ammonium nitrate, ammonium chloride,
It is obtained by treating with an aqueous solution of a water-soluble ammonium salt such as ammonium acetate and then baking at 400 to 650°C for one hour or more. In this case, the hydrogen ion substitution rate is
A suitable amount is 50 mol% or more, preferably 90 mol% or more. Furthermore, the remaining cations may be substituted with group, group, group, rare earth element, or the like.
また、本発明において、触媒を使用するにあた
り、その形状は粉末状、顆粒状もしくはペレツト
状に成型したもの等どのような形状で使用しても
よく、更にアルミナ、シリカ、チタニア、ジルコ
ニア、活性白土等を担体もしくは成型結合剤とし
て使用することもできる。 Further, in the present invention, when using the catalyst, it may be used in any shape such as powder, granules, or pellets. etc. can also be used as carriers or molding binders.
本発明において使用されるシクロオレフインと
は、シクロペンテン、メチルシクロペンテン、シ
クロヘキセン、メチルシクロヘキセン、シクロオ
クテン、シクロドデセン等があり、これらのシク
ロオレフインは水和されて、相当するシクロアル
カノールを生成する。 The cycloolefins used in the present invention include cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cyclooctene, and cyclododecene, and these cycloolefins are hydrated to produce the corresponding cycloalkanol.
本発明の実施に際し、反応の温度はオレフイン
の水和反応の平衡の問題及び副反応の抑制の面か
ら低温が有利であるが、反応温度があまりに低く
すぎると反応速度が小さく経済的でない。本発明
では50〜300℃の範囲が好ましく、特に80〜180℃
の範囲が好ましく、更に好ましくは90〜160℃の
範囲が好ましい。 In carrying out the present invention, a low reaction temperature is advantageous from the viewpoint of equilibrium of the olefin hydration reaction and suppression of side reactions, but if the reaction temperature is too low, the reaction rate is low and it is not economical. In the present invention, the temperature is preferably in the range of 50 to 300°C, particularly 80 to 180°C.
The temperature range is preferably 90 to 160°C, and more preferably 90 to 160°C.
また反応の圧力は、減圧から加圧までの範囲で
適用可能で特に制限はないが、本発明の反応の特
性を考え、通常は反応の原料であるシクロオレフ
イン及び水の両方が液相を保ちうる圧力に保つこ
とが好ましい。 The reaction pressure can be applied in the range from reduced pressure to increased pressure and is not particularly limited, but considering the characteristics of the reaction of the present invention, usually both the cycloolefin and water, which are raw materials for the reaction, maintain a liquid phase. It is preferable to maintain the pressure at a certain level.
反応原料であるシクロオレフインと水のモル比
は広い範囲でとることができるが、シクロオレフ
インがあまりに過剰であると、シクロオレフイン
の転化率が低くなり、また水があまりに過剰であ
ると、シクロオレフインの転化率を高くできる
が、生成シクロアルカノールの分離精製の面で不
利となるばかりでなく、反応器の容積を大きくな
り経済的でない。従つて、本発明においては、水
とシクロオレフインとのモル比は0.5〜200の範囲
が好ましく、特に1〜50の範囲が好ましい。 The molar ratio of cycloolefin and water, which are the reaction raw materials, can be set within a wide range, but if the cycloolefin is in excess, the conversion rate of the cycloolefin will be low, and if the water is in excess, the cycloolefin will be reduced. Although this method can increase the conversion rate of cycloalkanol, it is not only disadvantageous in terms of separation and purification of the cycloalkanol produced, but also requires a large reactor volume, which is not economical. Therefore, in the present invention, the molar ratio of water to cycloolefin is preferably in the range of 0.5 to 200, particularly preferably in the range of 1 to 50.
また、シクロオレフインと触媒の重量比は、回
分式で行う場合0.01〜200の範囲、特に0.1〜20の
範囲が好ましく、反応時間はこれらシクロオレフ
インと水及び触媒比、さらには温度、圧力などに
よつて異なるが、一般には5〜600分、特に5〜
300分程度が好ましい。 In addition, the weight ratio of cycloolefin to catalyst is preferably in the range of 0.01 to 200, particularly 0.1 to 20 when carried out batchwise, and the reaction time depends on the ratio of cycloolefin to water and catalyst, temperature, pressure, etc. It varies depending on the situation, but generally 5 to 600 minutes, especially 5 to 600 minutes.
About 300 minutes is preferable.
また反応に際して、反応原料であるシクロオレ
フイン及び水の他にチツ素、アルゴン、水素、炭
酸ガス等の不活性気体及びないしは脂肪族飽和炭
化水素、芳香族炭化水素、ハロゲン化炭化水素、
アルコール類、エーテル類等の有機化合物が共存
していても差支えない。 In addition to the reaction raw materials cycloolefin and water, in the reaction, inert gases such as nitrogen, argon, hydrogen, and carbon dioxide, and aliphatic saturated hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons,
There is no problem even if organic compounds such as alcohols and ethers coexist.
以下に実施例及び比較例をあげて本発明を更に
詳細に説明する。 EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples below.
実施例 1
触媒調製
1.8−ジアミノ−4−アミノメチルオクタン10
g、硫酸アルミニウム〔Al2(SO4)3・18H2O〕0.5
g、水酸化ナトリウム0.5gを水15gにとかし、
更にシリカゾル(30%SiO2)20gを加えて均一
な溶液を得た。この溶液にかきまぜながら20%硫
酸を滴下してPH12に調整して均質なゲルを得た。
更にこのゲルをミキサーに入れ、1000rpm(刃先
端の線速度1m/sec)で10分間混合しゲル化を
促進した。このゲルをテフロン製試験管に仕込
み、ステンレス製耐圧容器中で170℃、48時間静
置して結晶化を行つた。Example 1 Catalyst Preparation 1.8-Diamino-4-aminomethyloctane 10
g, aluminum sulfate [Al 2 (SO 4 ) 3・18H 2 O] 0.5
g, dissolve 0.5 g of sodium hydroxide in 15 g of water,
Furthermore, 20 g of silica sol (30% SiO 2 ) was added to obtain a homogeneous solution. 20% sulfuric acid was added dropwise to this solution while stirring to adjust the pH to 12 to obtain a homogeneous gel.
Further, this gel was placed in a mixer and mixed for 10 minutes at 1000 rpm (linear velocity of the blade tip 1 m/sec) to promote gelation. This gel was placed in a Teflon test tube and allowed to stand at 170°C for 48 hours in a stainless steel pressure vessel to allow crystallization.
得られた生成物を過、洗浄したのち、120℃
で3時間乾燥し、さらに500℃で4時間焼成した。
このものはX線回折分析によりAZ−1と同定さ
れた。X線回折図の回折角(2θ)及び相対強度を
表−4に示す。 After filtering and washing the obtained product, it was heated to 120℃.
The mixture was dried at 500°C for 3 hours and then fired at 500°C for 4 hours.
This product was identified as AZ-1 by X-ray diffraction analysis. Table 4 shows the diffraction angle (2θ) and relative intensity of the X-ray diffraction diagram.
得られた結晶性アルミノシリケート200gを塩
化アンモニウムの2(モル/リツトル)水溶液2
リツトルで3回処理したのち、水洗、乾燥し更に
400℃で2時間焼成することにより触媒を調整し
た。ケイ光X線分析により求めたこの生成物の組
成は、H2O・Al2O3・100SiO2であつた。 200 g of the obtained crystalline aluminosilicate was mixed with 2 (mol/liter) aqueous solution of ammonium chloride.
After being treated with a little bottle three times, it is washed with water, dried, and then
The catalyst was prepared by calcining at 400°C for 2 hours. The composition of this product determined by fluorescent X - ray analysis was H2O.Al2O3.100SiO2 .
シクロヘキサノールの製造
調整した触媒1.5gにシクロヘキセン1.8g、水
4.05gを20ミリリツトルのガラス製アンプル管に
仕込み溶封した。これを130℃に加熱振とうしな
がら2時間反応させた。反応液を分離したのち、
触媒をジオキサンで洗浄し、洗浄液と反応液を合
してガスクロマトグラフイーで分析した。Production of cyclohexanol 1.5g of prepared catalyst, 1.8g of cyclohexene, water
4.05g was poured into a 20ml glass ampoule tube and sealed. This was heated to 130°C and reacted for 2 hours while shaking. After separating the reaction solution,
The catalyst was washed with dioxane, and the washing solution and reaction solution were combined and analyzed by gas chromatography.
シクロヘキセンの転化率は11.7%であり、シク
ロヘキサノールの選択率は98%であつた。また単
位時間・単位触媒当りのシクロヘキサノールの生
成量は0.084(g/g−触媒・時間)であつた。 The conversion rate of cyclohexene was 11.7%, and the selectivity of cyclohexanol was 98%. The amount of cyclohexanol produced per unit time/unit catalyst was 0.084 (g/g-catalyst/hour).
表−4
2 θ゜ 相対強度
7.8 16
8.7 94
8.9 100
17.5 12
17.7 22
23.1 38
23.6 30
実施例 2
反応温度を170℃、反応時間を1時間とした以
外は、実施例1と同じ条件で行なつた結果、シク
ロヘキセンの転化率は7.1%であり、シクロヘキ
サノールの選択率は95%であつた。またシクロヘ
キサノールの単位時間、単位触媒当りの生成量は
0.099(g/g−触媒・時間)であつた。Table 4 2 θ゜ Relative intensity 7.8 16 8.7 94 8.9 100 17.5 12 17.7 22 23.1 38 23.6 30 Example 2 The same conditions as Example 1 were used except that the reaction temperature was 170°C and the reaction time was 1 hour. As a result, the conversion rate of cyclohexene was 7.1%, and the selectivity of cyclohexanol was 95%. Also, the amount of cyclohexanol produced per unit time and per unit catalyst is
It was 0.099 (g/g-catalyst/time).
比較例 1
触媒として、実施例1の方法で水素置換された
天然モルデナイト(パームチツト)を用いた以外
は実施例2と同じ条件で行なつた結果、シクロヘ
キセンの転化率は0.11%であり、単位時間、単位
触媒当りのシクロヘキサノールの生成量は0.0016
(g/g−触媒・時間)であつた。Comparative Example 1 The same conditions as in Example 2 were used except that natural mordenite (palmchite) substituted with hydrogen by the method of Example 1 was used as a catalyst. As a result, the conversion rate of cyclohexene was 0.11%, and the conversion rate of cyclohexene was 0.11%, and the conversion rate of cyclohexene was 0.11%. , the amount of cyclohexanol produced per unit catalyst is 0.0016
(g/g-catalyst/time).
実施例 3
反応温度を110℃、反応時間を3時間とした以
外は、実施例1と同じ条件で行なつた結果、シク
ロヘキセンの転化率は12.3%、選択率は100%で
あつた。また単位時間・単位触媒当りのシクロヘ
キサノールの生成量は0.060(g/g−触媒・時
間)であつた。Example 3 The same conditions as in Example 1 were used except that the reaction temperature was 110° C. and the reaction time was 3 hours. As a result, the conversion rate of cyclohexene was 12.3% and the selectivity was 100%. The amount of cyclohexanol produced per unit time/unit catalyst was 0.060 (g/g-catalyst/hour).
実施例 4
特開昭57−200218号公報記載の方法により結晶
性アルミノシリケートを合成した。すなわち、水
ガラス(30%SiO2)77g、硫酸アルミニウム
〔Al2(SO4)3・18H2O〕3.3g、水200gを加え均一
な溶液を得た。この溶液にかきまぜながら98%硫
酸13.5gを加え、更にN,N,N′,N′−ヘキサ
メチル−1,6−ヘキサンジアンモニウム塩4.56
gを加え、均質なゲルを調製した。このゲルをス
テンレス製耐圧容器に仕込み、穏やかに撹拌しな
がら、160℃、1週間反応させて結晶化をはかつ
た。得られた生成物を過、洗浄したのち、120
℃で3時間乾燥し、更に500℃で4時間焼成した。
このものはX線回折よりTPZ−3と同定された。Example 4 Crystalline aluminosilicate was synthesized by the method described in JP-A-57-200218. That is, 77 g of water glass (30% SiO 2 ), 3.3 g of aluminum sulfate [Al 2 (SO 4 ) 3.18H 2 O], and 200 g of water were added to obtain a homogeneous solution. Add 13.5 g of 98% sulfuric acid to this solution while stirring, and add 4.56 g of N,N,N',N'-hexamethyl-1,6-hexanediammonium salt.
g was added to prepare a homogeneous gel. This gel was placed in a stainless steel pressure container and allowed to react at 160° C. for one week with gentle stirring to achieve crystallization. After filtering and washing the obtained product, 120
It was dried at 500°C for 3 hours and then fired at 500°C for 4 hours.
This product was identified as TPZ-3 by X-ray diffraction.
得られた結晶を実施例1の方法により水素置換
し触媒とした。ケイ光X線分析により求めたこの
触媒の組成は、H2O・Al2O3・80SiO2であつた。
この触媒1.5gを用いた以外は、実施例1と同じ
条件で行なつた結果、シクロヘキセンの転化率は
6.8%、選択率90%であつた。単位時間、単位触
媒当りのアルコール生成量は0.045(g/g−触
媒・時間)であつた。 The obtained crystals were subjected to hydrogen substitution according to the method of Example 1 to obtain a catalyst. The composition of this catalyst determined by fluorescent X-ray analysis was H 2 O.Al 2 O 3.80SiO 2 .
The conversion rate of cyclohexene was as follows.
The selection rate was 6.8%, and the selection rate was 90%. The amount of alcohol produced per unit time and unit catalyst was 0.045 (g/g-catalyst/hour).
実施例 5
特開昭57−200218号公報記載の方法により結晶
性アルミノシリケートを合成した。すなわち、水
ガラス(30%SiO2)142g中にテトラエチレンペ
ンタミン38gを分散させ、これに14%アルミン酸
ナトリウム水溶液12g、5.8%塩化ナトリウム水
溶液400gを混合撹拌し均質なゲルを得た。更に
このゲルをミキサーで30分間混合しゲル化を促進
させたのち、ステンレス製耐圧容器に入れ、穏や
かに撹拌しながら180℃の温度で3日間反応させ
た。Example 5 Crystalline aluminosilicate was synthesized by the method described in JP-A-57-200218. That is, 38 g of tetraethylenepentamine was dispersed in 142 g of water glass (30% SiO 2 ), and 12 g of a 14% aqueous sodium aluminate solution and 400 g of a 5.8% aqueous sodium chloride solution were mixed and stirred to obtain a homogeneous gel. This gel was further mixed with a mixer for 30 minutes to promote gelation, and then placed in a stainless steel pressure container and allowed to react at a temperature of 180° C. for 3 days with gentle stirring.
得られた生成物を過、水洗したのち、120℃
で3時間乾燥し、更に500℃で24時間焼成した。
このものはX線回折分析より、Nu−10と同定さ
れた。 After filtering and washing the obtained product with water, it was heated to 120°C.
It was dried for 3 hours and then fired at 500°C for 24 hours.
This product was identified as Nu-10 by X-ray diffraction analysis.
この結晶性アルミノシリケートを実施例1と同
じ方法で水素で置換し触媒を調製した。ケイ光X
線分析により求めたこの触媒の組成は、H2O・
Al2O3・50SiO2であつた。この触媒1.5gを用いた
以外は、実施例3と同じ条件で実験を行なつた結
果、シクロヘキセンの転化率9.7%、シクロヘキ
サノール選択率99%であつた。単位時間、単位触
媒当りのアルコール生成量は0.048(g/g−触
媒・時間)であつた。 This crystalline aluminosilicate was replaced with hydrogen in the same manner as in Example 1 to prepare a catalyst. Keikou X
The composition of this catalyst determined by line analysis is H 2 O.
It was Al 2 O 3 .50SiO 2 . An experiment was conducted under the same conditions as in Example 3, except that 1.5 g of this catalyst was used, and as a result, the conversion of cyclohexene was 9.7% and the selectivity of cyclohexanol was 99%. The amount of alcohol produced per unit time and unit catalyst was 0.048 (g/g-catalyst/hour).
Claims (1)
ノーを製造するに際し、一般式 M2O・Al2O3・XSiO2 (式中、Mはアルカリ金属イオン、アンモニウ
ムイオン及び水素イオンの少なくとも1種を表
し、Xは10〜1000である) に相当する組成を有し、かつX線回折図において
表−1〜表−3に示す回折角(2θ)及び相対強度
によつて特徴づけられる結晶性アルミノシリケー
トのアルカリ金属イオン及び/又はアンモニウム
イオンの一部または全部を水素イオンで置換した
ものを触媒として用いることを特徴とする新規な
シクロアルカノールの製造方法。[Claims] 1. When producing a cycloalkano by hydration of cycloolefin , the general formula M 2 O.Al 2 O 3 . (X is 10 to 1000), and characterized by the diffraction angle (2θ) and relative intensity shown in Tables 1 to 3 in the X-ray diffraction diagram. 1. A novel method for producing a cycloalkanol, which comprises using as a catalyst a crystalline aluminosilicate in which some or all of the alkali metal ions and/or ammonium ions have been replaced with hydrogen ions.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58209150A JPS60104030A (en) | 1983-11-09 | 1983-11-09 | Production of cycloalkanol |
JP58209148A JPS60104028A (en) | 1983-11-09 | 1983-11-09 | Production of cyclic alcohol |
GB08428219A GB2151224B (en) | 1983-11-09 | 1984-11-08 | Process for producing cyclic alcohols |
FR8417029A FR2554440B1 (en) | 1983-11-09 | 1984-11-08 | PROCESS FOR PRODUCING A CYCLIC ALCOHOL |
DE19843441072 DE3441072A1 (en) | 1983-11-09 | 1984-11-09 | METHOD FOR PRODUCING CYCLIC ALCOHOLS |
US06/669,976 US4588846A (en) | 1983-11-09 | 1984-11-09 | Process for producing cyclic alcohol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58209150A JPS60104030A (en) | 1983-11-09 | 1983-11-09 | Production of cycloalkanol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60104030A JPS60104030A (en) | 1985-06-08 |
JPS641453B2 true JPS641453B2 (en) | 1989-01-11 |
Family
ID=16568136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58209150A Granted JPS60104030A (en) | 1983-11-09 | 1983-11-09 | Production of cycloalkanol |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS60104030A (en) |
FR (1) | FR2554440B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4879422A (en) * | 1987-07-07 | 1989-11-07 | Sumitomo Chemical Company, Limited | Method for producing cycloalkanol |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4214107A (en) * | 1978-06-26 | 1980-07-22 | Mobil Oil Corporation | Hydration of olefins using zeolite catalysts |
JPS58194828A (en) * | 1982-05-10 | 1983-11-12 | Asahi Chem Ind Co Ltd | Preparation of cycloalkanol |
FR2534574B1 (en) * | 1982-10-13 | 1989-05-19 | Toyo Soda Mfg Co Ltd | PROCESS FOR THE PREPARATION OF ALCOHOLS BY HYDRATION OF OLEFINS |
-
1983
- 1983-11-09 JP JP58209150A patent/JPS60104030A/en active Granted
-
1984
- 1984-11-08 FR FR8417029A patent/FR2554440B1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2554440B1 (en) | 1987-06-26 |
FR2554440A1 (en) | 1985-05-10 |
JPS60104030A (en) | 1985-06-08 |
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