JPH07171402A - Zeolite regeneration catalyst - Google Patents
Zeolite regeneration catalystInfo
- Publication number
- JPH07171402A JPH07171402A JP5324276A JP32427693A JPH07171402A JP H07171402 A JPH07171402 A JP H07171402A JP 5324276 A JP5324276 A JP 5324276A JP 32427693 A JP32427693 A JP 32427693A JP H07171402 A JPH07171402 A JP H07171402A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- hydration reaction
- olefin
- regenerated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000010457 zeolite Substances 0.000 title claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000011069 regeneration method Methods 0.000 title abstract description 18
- 230000008929 regeneration Effects 0.000 title abstract description 16
- 238000006703 hydration reaction Methods 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000000887 hydrating effect Effects 0.000 claims abstract 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 cyclic olefin Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【構成】 液相でのオレフィン水和反応に供したゼオラ
イト触媒を、該ゼオライトを８０ないし３５０℃で３０
分以上処理した後、分子状酸素を含有するガスと４００
℃以上で接触させてなるゼオライト再生触媒。また、該
ゼオライト再生触媒を用いて、オレフィンの水和反応を
行うことを特徴とするアルコールの製造方法。
【効果】 本発明の再生触媒は、従来の方法に比較し
て、簡便な処理にて、高い再生率で再生されており、し
かも、再生処理の繰り返しによる活性の劣化が小さいの
で、液相でのオレフィン水和反応を工業的に実施するう
えで好適に使用することができる。(57) [Summary] [Structure] The zeolite catalyst used for the olefin hydration reaction in the liquid phase is prepared by mixing the zeolite with the catalyst at 80 to 350 ° C. for 30 days.
After processing for more than 5 minutes, a gas containing molecular oxygen and 400
Zeolite regenerated catalyst that is contacted at above ℃. Also, a method for producing alcohol, which comprises hydrating an olefin using the zeolite regenerated catalyst. [Effect] Compared with the conventional method, the regenerated catalyst of the present invention is regenerated at a high regeneration rate by a simple treatment, and further, the activity deterioration due to repeated regeneration treatment is small. It can be preferably used for industrially carrying out the olefin hydration reaction.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ゼオライト再生触媒に
関する。詳しくは、液相でのオレフィンを水和反応し、
対応するアルコ−ルを製造する際に使用されるゼオライ
ト再生触媒に関する。FIELD OF THE INVENTION The present invention relates to a regenerated zeolite catalyst. Specifically, hydration reaction of olefin in liquid phase,
The present invention relates to a zeolite regenerated catalyst used in producing a corresponding alcohol.
【０００２】[0002]
【従来の技術】水和反応による工業的アルコールの製造
法としては、従来、鉱酸等を用いた均一系触媒による水
和反応が用いられてきたが、近年、これに代わるものと
して、固体酸触媒、特にゼオライトを触媒として使用す
る方法が提案されている（特開昭５７−７０８２８、特
開昭５８−１２４７２３、特開昭５８−１９４８２８
等）。この場合、ゼオライトを長時間にわたり、液相で
のオレ フィン水和反応の触媒として使用すると、原料
中の不純物の蓄積等により、反応活性は次第に低下する
ため、触媒の再生が必要となる。2. Description of the Related Art Conventionally, a hydration reaction using a homogeneous catalyst using a mineral acid has been used as an industrial alcohol production method by a hydration reaction. A method of using a catalyst, especially zeolite as a catalyst has been proposed (JP-A-57-70828, JP-A-58-124723, and JP-A-58-194828).
etc). In this case, if the zeolite is used as a catalyst for the olefin hydration reaction in the liquid phase for a long period of time, the reaction activity gradually decreases due to the accumulation of impurities in the raw material and the like, so that the catalyst must be regenerated.
【０００３】従来、このような触媒の再生方法として
は、通常、分子状酸素を含むガスによる高温での焼成処
理する方法（特公平３−２０１４、 特公平３−２０１
５)、液相中で酸、アルカリもしくは酸化剤と接触させ
る方法（特開平３−２２４６３２、 特開平３−２２４
６３３）などが知られている。Conventionally, as a method of regenerating such a catalyst, usually, a method of baking at a high temperature with a gas containing molecular oxygen (Japanese Patent Publication No. 3-2014, Japanese Patent Publication No. 3-201).
5), a method of bringing into contact with an acid, an alkali or an oxidizing agent in a liquid phase (JP-A-3-224632, JP-A-3-224)
633) and the like are known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
方法においては、触媒に蓄積した有機化合物の除去には
効果的であっても、水和反応活性の回復が充分ではな
く、また、処理操作が煩雑であるなどの問題もあり、液
相でのオレフィン水和反応に対する工業的触媒の再生法
として更なる改良が望まれる。However, in the above method, even though it is effective in removing the organic compound accumulated in the catalyst, the hydration reaction activity is not sufficiently recovered, and the treatment operation is Since there are problems such as complexity, further improvement is desired as an industrial catalyst regeneration method for olefin hydration reaction in the liquid phase.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の課
題を解決するために鋭意検討を重ねた結果、液相でのオ
レフィン水和反応に供したゼオライト触媒を再生するに
あたり、該ゼオライトをを特定条件下での気相加熱処理
により、従来の方法に比べ、著しく高い再生率で再生で
き、、再生の繰り返しによる触媒活性の低下がないこと
を見いだし、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted extensive studies in order to solve the above-mentioned problems, and as a result, in regenerating the zeolite catalyst used for the olefin hydration reaction in the liquid phase, the zeolite The present invention was completed by the gas-phase heat treatment under a specific condition, and was found to be reproducible at a remarkably high regeneration rate as compared with the conventional method, and there was no decrease in catalyst activity due to repeated regeneration. .
【０００６】すなわち、本発明は、液相でのオレフィン
水和反応に供したゼオライト触媒を、該ゼオライトを８
０ないし３５０℃で３０分以上処理した後、分子状酸素
を含有するガスと４００℃以上で接触させてなるゼオラ
イト再生触媒、および，そのゼオライト再生触媒を用い
て、オレフィンの水和反応を行うことを特徴とするアル
コールの製造方法に関するものである。That is, according to the present invention, the zeolite catalyst used for the olefin hydration reaction in the liquid phase is
A zeolite regenerated catalyst obtained by contacting with a gas containing molecular oxygen at 400 ° C. or higher after treatment at 0 to 350 ° C. for 30 minutes or more, and hydration reaction of olefins using the zeolite regenerated catalyst. And a method for producing alcohol.
【０００７】以下、本発明について詳細に説明する。本
発明において、再生対象となるゼオライト触媒は、触媒
として使用可能なゼオライトであれば特に限定されず、
例えば、モルデナイト、エリオナイト、フェリエライ
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、ガロシリケ
ート、フェロアルミノシリケート等の異元素含有ゼオラ
イト等の公知のゼオライトが例示できる。また、これら
のゼオライト触媒は、通常、プロトン交換型（Ｈ型）が
用いられるが、その一部がＭｇ、Ｃａ、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VIII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てもよい。あ
るいはＴｉ、Ｚｒ、Ｈｆ、Ｃｒ、Ｍｏ、Ｗ、Ｔｈなどを
含有していてもよい。The present invention will be described in detail below. In the present invention, the zeolite catalyst to be regenerated is not particularly limited as long as it can be used as a catalyst,
For example, known zeolites such as mordenite, erionite, ferrierite, crystalline aluminosilicates such as ZSM type zeolites announced by Mobil Co., and heteroelement-containing zeolites such as borosilicates, gallosilicates, and ferroaluminosilicates can be exemplified. Further, these zeolite catalysts are usually used in a proton exchange type (H type), but some of them are alkaline earth elements such as Mg, Ca and Sr, rare earth elements such as La and Ce, Fe and Co,
It may be exchanged with at least one cation species selected from Group VIII elements such as Ni, Ru, Pd and Pt. Alternatively, it may contain Ti, Zr, Hf, Cr, Mo, W, Th or the like.
【０００８】水和反応の原料となるオレフィンとして
は、好ましくは炭素数２〜１２の直鎖または分枝構造を
有するオレフィン、または、炭素数５〜１２の環状オレ
フィンであり、特に環状オレフィンの場合に有効であ
る。水和反応条件としては、触媒が水相またはオイル相
または両者の混合相からなる液相に存在している範囲で
あればよく、反応温度、反応圧力を特に規定するもので
はない。しかし、一般的にオレフィンの水和反応温度
は、水和反応の平衡面および副反応等の増大の意味から
低温が有利であるが、反応速度の面からは高温が有利な
ため、本発明では、通常５０〜２５０℃、特に環状オレ
フィンでは１００〜２００℃の反応温度で水和反応に用
いられた触媒が最適である。なお、ゼオライトの使用さ
れる形態はいかなるものでもよく、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。The olefin as a raw material for the hydration reaction is preferably an olefin having a straight chain or branched structure having 2 to 12 carbon atoms or a cyclic olefin having 5 to 12 carbon atoms, particularly in the case of a cyclic olefin. Is effective for. The hydration reaction conditions may be in the range in which the catalyst is present in the water phase, the oil phase or the liquid phase consisting of a mixed phase of both, and the reaction temperature and the reaction pressure are not particularly specified. However, in general, the olefin hydration reaction temperature is advantageous at low temperature in terms of equilibrium aspect of hydration reaction and increase of side reactions, but at the reaction rate, high temperature is advantageous. The catalyst used in the hydration reaction is most suitable at a reaction temperature of usually 50 to 250 ° C., particularly 100 to 200 ° C. for cyclic olefins. The zeolite may be used in any form, such as powder or granules. Further, alumina, silica, titania or the like can be used as a carrier or a binder.
【０００９】本発明は、以上のような液相でのオレフィ
ン水和反応に供したゼオライトの再生触媒に関するもの
である。本発明におけるゼオライトの再生手段は、基本
的にはゼオライトを分子状酸素を含有するガスと接触さ
せる気相加熱処理である。加熱装置としては、一般的な
管状炉、マッフル炉などの任意の形式のものでよく、ガ
ス流通法により固定床もしくは流動床形式でガスとの接
触操作が行なえるものが好ましい。分子状酸素を含むガ
ス中の酸素濃度は、通常０．０１〜９０モル％であり、
好ましくは１〜３０モル％である。分子状酸素以外のガ
ス成分としては、好ましくは窒素、ヘリウム、アルゴン
等が用いられ、ガス中の水分は予め除かれていることが
望ましい。また、ガス流量はゼオライトに対する重量時
間空間速度（ＷＨＳＶ）で表して０．２５〜１０ｈｒ-1
が用いられる。The present invention relates to a regenerated catalyst of zeolite which has been subjected to the olefin hydration reaction in the liquid phase as described above. The zeolite regenerating means in the present invention is basically a gas phase heat treatment in which the zeolite is brought into contact with a gas containing molecular oxygen. The heating device may be of any type such as a general tubular furnace or a muffle furnace, and is preferably a device capable of performing contact operation with gas in a fixed bed or fluidized bed form by a gas flow method. The oxygen concentration in the gas containing molecular oxygen is usually 0.01 to 90 mol%,
It is preferably 1 to 30 mol%. Nitrogen, helium, argon, etc. are preferably used as the gas component other than molecular oxygen, and it is desirable that the water content in the gas be removed in advance. Further, the gas flow rate is expressed as a weight hourly space velocity (WHSV) with respect to the zeolite and is 0.25 to 10 hr −1.
Is used.
【００１０】分子状酸素を含有するガスと接触させる工
程は、低温処理と高温処理に分けて行なう。低温処理と
しては、上記条件の分子状酸素を含むガスまたは酸素を
全く含まないガスの雰囲気下で、８０℃以上、好ましく
は９０℃以上で、かつ、３５０℃以下、好ましくは３０
０℃以下の処理温度で、３０分以上、好ましくは６０分
以上の時間で熱処理を行なう。処理温度は、処理時間中
一定でもよく、あるいは上記範囲内で変化してもよい。
処理温度が変化する場合は、１段以上の段階的変化でも
連続的変化でもよく、該温度範囲内での昇温制御による
処理も有効である。高温処理としては、上記範囲の分子
状酸素を含むガスと、４００℃以上、好ましくは４５０
℃以上、かつ、通常７００℃以下の処理温度で、１〜９
６時間、好ましくは２〜２０時間の処理時間接触させて
行なう。低温処理および高温処理は、通常、常圧下に行
なわれるが、もちろん減圧下もしくは加圧下に処理する
こともできる。The step of contacting with the gas containing molecular oxygen is carried out separately for low temperature treatment and high temperature treatment. As the low temperature treatment, in the atmosphere of a gas containing molecular oxygen or a gas containing no oxygen under the above conditions, the temperature is 80 ° C. or higher, preferably 90 ° C. or higher, and 350 ° C. or lower, preferably 30.
Heat treatment is performed at a processing temperature of 0 ° C. or lower for 30 minutes or longer, preferably 60 minutes or longer. The treatment temperature may be constant during the treatment time or may vary within the above range.
When the processing temperature changes, it may be a stepwise change of one or more steps or a continuous change, and the processing by the temperature rise control within the temperature range is also effective. As the high temperature treatment, a gas containing molecular oxygen in the above range and 400 ° C. or higher, preferably 450
1 to 9 at a treatment temperature of ℃ or higher and usually 700 ℃ or lower
It is carried out by contacting for 6 hours, preferably 2 to 20 hours. The low-temperature treatment and the high-temperature treatment are usually carried out under normal pressure, but it is of course possible to carry out the treatment under reduced pressure or under pressure.
【００１１】[0011]
【実施例】以下、実施例および比較例を示し、本発明を
具体的に述べる。 実施例１ （シクロヘキセンの連続流通水和反応）図１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
応を行なった。即ち、内容積２０００ｍｌの攪拌装置付
きステンレス製オ−トクレ−ブ反応器３に、水和触媒と
してＨ型ガロシリケ−ト（ＭＦＩ型、ＮＥケムキャット
製、シリカ／Ｇａ2Ｏ3比＝５０）を１００ｇと水２５０
ｇを仕込み系内を窒素ガス置換した。回転数５００ｒｐ
ｍで攪拌しつつ反応器３内温度を昇温し、反応温度１２
０℃とした後、供給管１よりシクロヘキセン（試薬：ア
ルドリッチ社製）を１２０ｇ／ｈｒの速度で供給した。
反応液は反応器内部に設置した内容積３０ｍｌの液液分
離器４内で油相と触媒スラリ−水相に分離された後オ−
バ−フロ−管５より油相のみが流出される。また、供給
管２からは水和反応で消費される水とオ−バ−フロ−管
５から油相への溶解度分として流出する水の合計量の水
を供給することにより反応器３内の水量を一定に保っ
た。原料シクロヘキセン供給開始５時間後における流出
オイル中のシクロヘキサノ−ル濃度は９．５重量％であ
った。また、５０時間経過後の流出オイル中のシクロヘ
キサノ−ル濃度は４．２重量％であった。EXAMPLES Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples. Example 1 (Continuous flow hydration reaction of cyclohexene) The hydration reaction of cyclohexene was carried out using a continuous flow reaction apparatus as shown in FIG. That is, 100 g of H-type gallosilicate (MFI type, manufactured by NE Chemcat, silica / Ga 2 O 3 ratio = 50) was used as a hydration catalyst in a stainless steel autoclave reactor 3 with an internal volume of 2000 ml equipped with a stirrer. And water 250
The inside of the charging system was replaced with nitrogen gas. Rotation speed 500 rp
The temperature inside the reactor 3 is raised with stirring at m
After the temperature was set to 0 ° C., cyclohexene (reagent: manufactured by Aldrich) was supplied from the supply pipe 1 at a rate of 120 g / hr.
The reaction liquid is separated into an oil phase and a catalyst slurry-water phase in a liquid-liquid separator 4 having an inner volume of 30 ml installed inside the reactor, and then the liquid phase
Only the oil phase is discharged from the flow-through pipe 5. Further, the total amount of water consumed in the hydration reaction and the water flowing out from the overflow pipe 5 as the solubility in the oil phase is supplied from the supply pipe 2 to supply water in the reactor 3. The amount of water was kept constant. The concentration of cyclohexanol in the spilled oil was 9.5% by weight 5 hours after starting the supply of the starting material cyclohexene. Further, the cyclohexanol concentration in the spilled oil after the lapse of 50 hours was 4.2% by weight.
【００１２】（触媒の再生）シクロヘキセンの連続流通
水和反応に使用した触媒を濾過、水洗、乾燥後、石英ガ
ラス管の中に充填し、４ｍｏｌ％の酸素と窒素からなる
混合ガスを１５０Ｎｌ／ｈの流量で常圧で流しつつ、２
００℃で２時間、続けて５００℃で５時間加熱した後、
冷却し、取り出した。 （連続流通水和反応と触媒再生の繰り返し）上記と全く
同じ反応条件、再生条件で連続流通水和反応と触媒再生
を同一の触媒を使用してさらに２回繰り返した。新触媒
および第１〜３回目再生後に行なった連続流通水和反応
５時間目における流出オイル中のシクロヘキサノ−ル濃
度を表−１に示す。また第１〜３回目再生後の触媒はす
べて純白であり、ＣＨＮ分析装置により分析しても炭素
成分の残存は認められなかった。(Regeneration of catalyst) The catalyst used for the continuous flow hydration reaction of cyclohexene was filtered, washed with water and dried, then filled in a quartz glass tube, and a mixed gas of 4 mol% oxygen and nitrogen was added at 150 Nl / h. While flowing at normal pressure with a flow rate of 2
After heating at 00 ° C for 2 hours and then at 500 ° C for 5 hours,
Cooled and removed. (Repeat of continuous flow hydration reaction and catalyst regeneration) Continuous flow hydration reaction and catalyst regeneration were repeated twice more using the same catalyst under the same reaction conditions and regeneration conditions as above. Table 1 shows the concentration of cyclohexanol in the effluent oil at the 5th hour of the continuous flow hydration reaction performed after the new catalyst and the 1st to 3rd regenerations. Further, the catalysts after the first to third regeneration were all pure white, and no carbon component remained even when analyzed by a CHN analyzer.
【００１３】比較例１ 実施例１の触媒の再生方法において、２００℃で２時間
の低温処理を行なわない以外は実施例１と全く同じ方法
と条件で連続流通水和反応と触媒再生の繰り返しを行な
った。新触媒および第１〜３回目再生後に行なった連続
流通水和反応５時間目における流出オイル中のシクロヘ
キサノ−ル濃度を表−１に示す。また第１〜３回目再生
後の触媒はすべて純白であり、ＣＨＮ分析装置により分
析しても炭素成分の残存は認められなかった。Comparative Example 1 In the catalyst regeneration method of Example 1, the continuous flow hydration reaction and catalyst regeneration were repeated under exactly the same conditions and conditions as in Example 1 except that the low temperature treatment was not performed at 200 ° C. for 2 hours. I did. Table 1 shows the concentration of cyclohexanol in the effluent oil at the 5th hour of the continuous flow hydration reaction performed after the new catalyst and the 1st to 3rd regenerations. Further, the catalysts after the first to third regeneration were all pure white, and no carbon component remained even when analyzed by a CHN analyzer.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】本発明の再生触媒は、従来の方法に比較
して、簡便な処理にて、高い再生率で再生されており、
しかも、再生処理の繰り返しによる活性の劣化が小さい
ので、液相でのオレフィン水和反応を工業的に実施する
うえで好適に使用することができる。EFFECTS OF THE INVENTION The regenerated catalyst of the present invention is regenerated at a high regeneration rate by a simple treatment as compared with the conventional method,
Moreover, since the deterioration of the activity due to the repeated regeneration treatment is small, it can be suitably used for industrially carrying out the olefin hydration reaction in the liquid phase.
【図１】 実施例および比較例で用いた連続流通反応装
置である。FIG. 1 is a continuous flow reactor used in Examples and Comparative Examples.
【符号の説明】 １，シクロヘキセン供給管、２，水供給管、３，オ−ト
クレ−ブ反応器 ４，液液分離器、５，オ−バ−フロ−管[Explanation of symbols] 1, cyclohexene supply pipe, 2, water supply pipe, 3, autoclave reactor 4, liquid-liquid separator, 5, overflow pipe
Claims (2)
オライト触媒を、該ゼオライトを８０ないし３５０℃で
３０分以上処理した後、分子状酸素を含有するガスと４
００℃以上で接触させてなるゼオライト再生触媒。1. A zeolite catalyst, which has been subjected to an olefin hydration reaction in a liquid phase, is treated with the gas containing molecular oxygen after treating the zeolite at 80 to 350 ° C. for 30 minutes or more.
A zeolite regenerated catalyst that is contacted at 00 ° C or higher.
て、オレフィンの水和反応を行うことを特徴とするアル
コールの製造方法。2. A method for producing alcohol, which comprises hydrating an olefin using the zeolite regenerated catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324276A JPH07171402A (en) | 1993-12-22 | 1993-12-22 | Zeolite regeneration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5324276A JPH07171402A (en) | 1993-12-22 | 1993-12-22 | Zeolite regeneration catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07171402A true JPH07171402A (en) | 1995-07-11 |
Family
ID=18164004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5324276A Pending JPH07171402A (en) | 1993-12-22 | 1993-12-22 | Zeolite regeneration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07171402A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432858B1 (en) | 1996-01-26 | 2002-08-13 | Mitsubishi Chemical Corporation | Process for the regeneration of hydration catalyst for cyclic olefins |
| WO2010035748A1 (en) | 2008-09-25 | 2010-04-01 | セントラル硝子株式会社 | Process for producing 1,3,3,3-tetrafluoropropene |
-
1993
- 1993-12-22 JP JP5324276A patent/JPH07171402A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432858B1 (en) | 1996-01-26 | 2002-08-13 | Mitsubishi Chemical Corporation | Process for the regeneration of hydration catalyst for cyclic olefins |
| WO2010035748A1 (en) | 2008-09-25 | 2010-04-01 | セントラル硝子株式会社 | Process for producing 1,3,3,3-tetrafluoropropene |
| US9051231B2 (en) | 2008-09-25 | 2015-06-09 | Central Glass Company, Limited | Process for producing 1,3,3,3-tetrafluoropropene |
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