JPS62258335A - Production of methyl isobutyl ketone - Google Patents
Production of methyl isobutyl ketoneInfo
- Publication number
- JPS62258335A JPS62258335A JP61101325A JP10132586A JPS62258335A JP S62258335 A JPS62258335 A JP S62258335A JP 61101325 A JP61101325 A JP 61101325A JP 10132586 A JP10132586 A JP 10132586A JP S62258335 A JPS62258335 A JP S62258335A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- oxide
- hydrogen
- alumina
- 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.)
- Granted
Links
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- -1 calcium oxide Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 38
- 238000000034 method Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 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
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はアセトンと水素とを原料とし、一段の反応でメ
チルイソブチルケトンを製造する方法しこ関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing methyl isobutyl ketone in a one-step reaction using acetone and hydrogen as raw materials.
メチルイソブチルケトン（以下ＭＩＢＫと称す）は有機
溶剤、塗料、安定剤等の原料として有用である。Methyl isobutyl ketone (hereinafter referred to as MIBK) is useful as a raw material for organic solvents, paints, stabilizers, and the like.
〈従来の技術〉 ＭＩＢＫは通常アセトンと水素を原料として。<Conventional technology> MIBK usually uses acetone and hydrogen as raw materials.
次のような三段法蚤こよって工業的（こ製造されている
。It is manufactured industrially using the following three-stage method.
この三段法の特徴は上式（こ示される縮合、脱水、およ
び水素添加の工程を順次行なうものである。まずアセト
／を水酸化バリウム等の団体塩基触媒を用いて１０〜２
０℃、常圧液相で反応させることによりジアセトンアル
コールヲ合ｐｌｔし１次に縮合して得られたジアセトン
アルコールを硫酸、リン酸等の酸触媒の存在下に液相で
１００〜１２０’ｃに加熱して脱水反応を行ないメンチ
ルオキシドを得る。続いて、このメンチルオキシドを分
離精製した後、ライ・−ニッケル触媒等の存在下に水素
添加を行なうことによりＭＩＢＫを製造するという方法
である。The feature of this three-step method is that the steps of condensation, dehydration, and hydrogenation shown in the above formula are carried out sequentially.
Diacetone alcohol is mixed by reacting it in a liquid phase at 0°C and normal pressure, and the diacetone alcohol obtained by first condensation is reacted in a liquid phase in the presence of an acid catalyst such as sulfuric acid or phosphoric acid to a concentration of 100 to 120 'C to perform a dehydration reaction and obtain menthyl oxide. Subsequently, this menthyl oxide is separated and purified, and then hydrogenated in the presence of a lye-nickel catalyst or the like to produce MIBK.
この方法は広く工業的に行なわれているが。This method is widely used industrially.
縮合、脱水、水素添加工程と三つの反応工程があり、ま
たそれぞれの工程でジアセトンアルコール Ｘルオキシ
ド等の中間体の分離精製が必要であり、操作が繁雑であ
る。さらにアセトンからジアセトンアルコールへの縮合
反応は平衡反応のため、その転化率は１５％程度と低い
という問題点がある。There are three reaction steps: condensation, dehydration, and hydrogenation, and each step requires separation and purification of intermediates such as diacetone alcohol X oxide, making the operation complicated. Furthermore, since the condensation reaction from acetone to diacetone alcohol is an equilibrium reaction, there is a problem that the conversion rate is as low as about 15%.
そのためにアセトンと水素から一工程でメチルイソブチ
ルケトンを製造する検討が行なわれている。この方法は
平衡的に有利であり、１回通過あたりの原料転化率を上
げることができ。To this end, studies are being conducted to produce methyl isobutyl ketone in one step from acetone and hydrogen. This process is equilibrium-friendly and can increase feed conversion per pass.
三段法に比して経済的に有利となる。このような−投法
によるＭＩＢＫの製造法として従来、酸型イオン交換樹
脂とパラジウム−炭素を触媒として使用する方法（ドイ
ツ特許第１２３８４５３号明細書）、リン酸ジルコニウ
ムにパラジウムを担持させた触媒を用いる方法（特公昭
４９−６９９４号公報）、Ｈ型ゼオライトにパラジウム
を担持させた触媒を用いる方法（特公昭４６−２６４３
号公報）等が報告されている。It is economically advantageous compared to the three-stage method. Conventional methods for producing MIBK by such a casting method include a method using an acid type ion exchange resin and palladium-carbon as a catalyst (German Patent No. 1238453), and a method using a catalyst in which palladium is supported on zirconium phosphate. (Japanese Patent Publication No. 49-6994), method using a catalyst in which palladium is supported on H-type zeolite (Japanese Patent Publication No. 46-2643)
Publication No.) etc. have been reported.
しかしながら、これらの従来の方法においては樹脂を用
いるために反応温度を上げることができず原料転化率が
低い、触媒の調製が煩雑である。あるいはＭ ＩＢＫ収
率が低いという欠点を有しており工業的に満足できる結
果が得られていなかりな。However, in these conventional methods, since a resin is used, the reaction temperature cannot be raised, the raw material conversion rate is low, and the preparation of the catalyst is complicated. Alternatively, MIBK has the disadvantage of a low yield, and industrially satisfactory results have not been obtained.
〈発明が解決しようとする問題点〉 本発明は、アセトンと水素とを原料として。<Problem that the invention seeks to solve> The present invention uses acetone and hydrogen as raw materials.
ＭＩＢＫを製造する方法において従来の方法の欠点、即
ち原料転化率が低く、ＭＩＢＫの収率が低いこと、触媒
調製が煩雑であること等の欠点を改善し、簡単な操作で
Ｍ ＩＢＫを高収率で得ることを目的とする。In the method for producing MIBK, the disadvantages of the conventional method, such as low raw material conversion rate, low yield of MIBK, and complicated catalyst preparation, have been improved, and MIBK can be produced in high yield with simple operations. The aim is to obtain at a high rate.
く問題点を解決するだめの手段〉
本発明は、アセトンと水素を反応させてメチルイソブチ
ルケトンを製造する方法において。Means for Solving the Problems The present invention relates to a method for producing methyl isobutyl ketone by reacting acetone and hydrogen.
アルミナと酸化カルシウム、酸化マ！゛イ・シウム。Alumina and calcium oxide, MA oxide!゛I-Shium.
酸化ストロンチウムのうちから選ばれた一種又は二種以
上の金属酸化物とから成る担体にパラジウムを担持した
触媒を用いることを特徴とするメチルイソブチルケトン
の製造法に関するものである。The present invention relates to a method for producing methyl isobutyl ketone, characterized by using a catalyst in which palladium is supported on a carrier comprising one or more metal oxides selected from strontium oxide.
以下１本発明を具体的に説明する。The present invention will be specifically explained below.
本発明方法に用いられる触媒はアルミナと酸化カルシウ
ム、酸化マグネシウム、酸化ストロンチウムのうちから
選ばれた一種又は二種以上の金属酸化物とから成る担体
にパラジウムを担持したものである。本発明方法に用い
られる担体は通常アルミナを酢酸カルシウム等の水溶液
をこ浸漬した後、焼成することにより製造される３゜ア
ルミナとしてはガンマ−アルミナが好ましく用いられる
。カルシウム、マグネシウム、ストロンチウムの水溶液
としてはこれらの金属の酢酸塩、硝酸塩、シーウ酸塩等
の水溶液が用いられ、好ましくはこれらの金属の酢酸塩
の水溶液が用いられる。焼成は通常３００〜６００℃の
温度で行なわれる。３００℃以下或いは６００℃以上の
焼成では低い活性しか得られない。The catalyst used in the method of the present invention has palladium supported on a carrier consisting of alumina and one or more metal oxides selected from calcium oxide, magnesium oxide, and strontium oxide. The carrier used in the method of the present invention is usually produced by dipping alumina in an aqueous solution of calcium acetate or the like, followed by firing.Gamma alumina is preferably used as the 3° alumina. As the aqueous solution of calcium, magnesium, and strontium, aqueous solutions of acetates, nitrates, and cealates of these metals are used, and preferably aqueous solutions of acetates of these metals are used. Firing is usually carried out at a temperature of 300 to 600°C. Calcination at temperatures below 300°C or above 600°C will only result in low activity.
パラジウムの担持量は通常０．０１〜５．ＯＮ１％であ
り、好ましくは０．０５〜１．０重量％である。The amount of palladium supported is usually 0.01 to 5. ON is 1%, preferably 0.05 to 1.0% by weight.
０．０１重量％以下では良好な活性が得られず、５．０
重量％以上では担持されたパラジウムが有効に用いられ
ない。If it is less than 0.01% by weight, good activity cannot be obtained;
If the amount exceeds % by weight, the supported palladium will not be used effectively.
本発明方法に用いられる触媒は通常アルミナを酢酸カル
シウム等の水溶液に浸漬、焼成した後パラジウムを担持
することにより製造されるが、場合によってはアルミナ
担体にパラジウムを担持した後にこれを酢酸カルシウム
等の水溶液に浸漬、焼成して製造することもできる。The catalyst used in the method of the present invention is usually produced by immersing alumina in an aqueous solution such as calcium acetate, calcining it, and then supporting palladium. It can also be manufactured by immersing it in an aqueous solution and firing it.
本発明方法の反応形態としては触媒を断熱あるいは等星
型反応器に充填し、そこにアセトンと水素とを通じるい
わゆる固定床流通反応を採用してもよいし、または触媒
をアセトン中に懸濁させ、そこに水素を吹き込んで反応
を行なわしめてもよい。固定床流通反応で反応を行なう
場合、気相で反応させてもよいし、液相で反応させても
よいが好ましくは液相でヌ応が行なわれる。懸濁法で反
応を行なう場合２反応を回分式または連続式のいずれの
方法で行なってもよい０
温度では反応速度が小さくなり、またこの温度より高温
ではアセトンの高縮合生成物が増罪する。As for the reaction form of the method of the present invention, a so-called fixed bed flow reaction may be adopted in which the catalyst is packed in an adiabatic or isogaster reactor and acetone and hydrogen are passed therein, or the catalyst may be suspended in acetone. The reaction may be carried out by blowing hydrogen into the reaction mixture. When the reaction is carried out in a fixed bed flow reaction, the reaction may be carried out in the gas phase or in the liquid phase, but preferably the reaction is carried out in the liquid phase. When the reaction is carried out using the suspension method, the two reactions may be carried out either batchwise or continuously.At temperatures above 0, the reaction rate decreases, and at temperatures higher than this temperature, high condensation products of acetone increase. .
反応圧力は通常大気圧〜５０気圧で反応が行なわれ１反
応温度にもよるが好ましくは１０〜３０気圧である。The reaction pressure is usually atmospheric pressure to 50 atm, and is preferably 10 to 30 atm, although it depends on the reaction temperature.
本発明方法は触媒の調製が容易であり、また触媒の活性
が高く２選択性も良好である。さらに触媒の安定性が高
く、その寿命が長いため長時間安定して高収率でＭＩＢ
Ｋを製造することができる。In the method of the present invention, the catalyst can be easily prepared, and the catalyst has high activity and good two-selectivity. Furthermore, the catalyst is highly stable and has a long lifespan, so MIB can be produced stably for a long time and in high yield.
K can be produced.
以下暑こ実施例によって本発明方法をさらに具体的に説
明するが１本発明の範囲はこれをこよって制限を受ける
ものではない。The method of the present invention will be explained in more detail below using examples, but the scope of the present invention is not limited thereby.
〈実施例〉
実施例１゜
アルミナペレット（住友アルミＷＫＨＤ −２４）ｌｏ
Ｏ−を１モル／リットルの酢酸力ルンウム水溶液５００
−に３時間浸漬した。その後このペレットを取り出し４
００℃で焼成した。<Example> Example 1゜Alumina pellet (Sumitomo Aluminum WKHD-24) lo
1 mol/liter of O- in aqueous acetic acid solution 500
- Soaked in water for 3 hours. Then take out this pellet 4
It was fired at 00°C.
この担体を塩化パラジウムの水溶液に浸漬し。This carrier is immersed in an aqueous solution of palladium chloride.
とドラジンで還元後３００℃で焼成した。パラジウムの
担持量はＯ，ｌ Ｍ量％であった。After reduction with dorazine and sintering at 300°C. The amount of palladium supported was 0,1M%.
この触媒１００−を内径２８謹の垂直に配置した反応管
内に充填し、温度１６０℃、圧力２０Ｋｐ／Ｊの条件下
アセトノを１５８９ ／ｈｒ （ＬＨ３Ｖ ＝ ２ ）
。This catalyst 100- was packed into a vertically arranged reaction tube with an inner diameter of 28 mm, and the acetonate was heated at 1589/hr (LH3V = 2) under conditions of a temperature of 160°C and a pressure of 20 Kp/J.
.
水素２５６Ｎ、／／”の供給速度で反応器に導入し反応
を行ない、第１表をこ示す結果を得た。反応結果は反応
液のガスクロマトグラフィー分析によって得た。Hydrogen was introduced into the reactor at a supply rate of 256N, //'' to carry out the reaction, and the results shown in Table 1 were obtained.The reaction results were obtained by gas chromatography analysis of the reaction solution.
第 １ 表
実施例２．〜４゜
実施例１．で用いた酢酸カルシウムのかわりに第２表に
記載した化合物を用いて触媒の調製を行ない、これらの
触媒を用いてＭＩＢＫの合成反応を行なった。なお酢酸
カルシウムのかわりに第２表に記載した化合物を用いる
以外の触媒調製条件及び反応条件についてはすべて実施
例１゜（こ記載したのと同じ条件で行なった。Table 1 Example 2. ~4゜Example 1. Catalysts were prepared using the compounds listed in Table 2 instead of the calcium acetate used in Example 1, and MIBK synthesis reactions were carried out using these catalysts. The catalyst preparation conditions and reaction conditions were all the same as those described in Example 1, except that the compounds listed in Table 2 were used in place of calcium acetate.
第 ２ 表
実施例５．〜７゜
実施例１．１こ記載した調製法【こ従って調製した触媒
を用いて第３表に示した反応条件で反応を行ない、第３
表に示す結果を得た。なお第３表（こ示した反応条件以
外はすべて実施例１．ニ記載したのと同じ条件で反応を
行なった。Table 2 Example 5. ~7゜Example 1.1 Preparation method described [Using the catalyst thus prepared, a reaction was carried out under the reaction conditions shown in Table 3.
The results shown in the table were obtained. Note that the reaction was carried out under the same conditions as described in Table 3 (Example 1.D except for the reaction conditions shown).
第３表 （注）第３表の値は反応開始１０時間後の値である。Table 3 (Note) The values in Table 3 are the values 10 hours after the start of the reaction.
実施例８゜
内容積２００艷の電磁攪拌機付オートクレーブ中にアセ
トン１００ｔｎｔと実施例１．に記載した方法で調製し
た触媒を粉砕し、粉末状にした触媒２ｆを加えた。オー
トクレーブを１６０℃に加熱し。Example 8 100 tons of acetone and Example 1 were placed in an autoclave with an internal volume of 200 mm and equipped with a magnetic stirrer. The catalyst prepared by the method described in 1 was pulverized and powdered catalyst 2f was added. Heat the autoclave to 160°C.
オートクレーブ内の圧力が２０Ｋｇ／ Ｃｊになるよう
に水素を加え攪拌しながら反応を行なりた。反応の進行
に伴りて消費される水素は連続的に補給し、全圧を常に
２０Ｖ４／ｉに保った。２時間反応を行なった後、オー
トクレーブを冷却し反応生成物を取り出し、水素ならび
に触媒を分離した後、ガスクロマトグラフィーにより分
析し下記の結果を得た。Hydrogen was added to the autoclave so that the pressure within the autoclave was 20 kg/Cj, and the reaction was carried out with stirring. Hydrogen consumed as the reaction progressed was continuously replenished, and the total pressure was always maintained at 20 V4/i. After carrying out the reaction for 2 hours, the autoclave was cooled, the reaction product was taken out, hydrogen and the catalyst were separated, and then analyzed by gas chromatography to obtain the following results.
アセトン転化率・・・・・・・・・４５゜７％ＭＩＢＫ
選択率・・・・・・・・・９３，１％ＩＰＡ選択率
・・・・・・・・・１．５％ＤＩ ＢＫ 選択率・・・
・・・・・・ ２６４％比較例１゜
アルミナペレット（住友アルミ製ＫＨＤ−２４）＋００
Ｔｎｌを塩化パラジウムの水溶液に浸漬し、ヒドラジ
ンで還元後３００°Ｃで焼成し、触媒を調製した。パラ
ジウムの担持量は０．１重量％であった。Acetone conversion rate...45°7% MIBK
Selection rate...93.1% IPA selection rate...1.5% DI BK selection rate...
...... 264% Comparative Example 1゜Alumina pellets (Sumitomo Aluminum KHD-24) +00
Tnl was immersed in an aqueous solution of palladium chloride, reduced with hydrazine, and then calcined at 300°C to prepare a catalyst. The amount of palladium supported was 0.1% by weight.
この触媒＋００ ｄを用いてＭＩＢＫの合成反応を行な
った。なお触媒以外の反応条件は実施例１゜に記載した
のと同じ条件で行なった。MIBK synthesis reaction was carried out using this catalyst +00 d. The reaction conditions other than the catalyst were the same as those described in Example 1.
反応開始１０時間後にサンプリングを行ない。Sampling was performed 10 hours after the start of the reaction.
反応液をガスクロマトグラフィーで分析し、下記の結果
を得た。The reaction solution was analyzed by gas chromatography, and the following results were obtained.
アセトン転化率・・・・・・Ｉ９．８％ ＩＰＡ選択率
・・・・・・９．６％ＭＩＢＫ選択率・・・・・・８６
，４％ ＤＩＢＫ選択率・・・・・・３．０％〈発明の
効果〉
以上の如く本発明によりアルミナと酸化カルシウム、酸
化マグネシウム、酸化ストロンチウムのうちから選ばれ
た１種又は二種以上の金属酸化物とから成る担体にパラ
ジウムを担持した触媒の存在下にアセトンと水素とを反
応させることにより一段の反応でメチルイソグチルケト
ンが収率よく得られるようになりた。Acetone conversion rate...I9.8% IPA selectivity...9.6% MIBK selectivity...86
, 4% DIBK selectivity...3.0% <Effect of the invention> As described above, according to the present invention, alumina and one or more selected from calcium oxide, magnesium oxide, and strontium oxide are combined. By reacting acetone with hydrogen in the presence of a catalyst in which palladium is supported on a carrier consisting of a metal oxide, methyl isobutyl ketone can now be obtained in good yield in a single reaction.
Claims (1)
製造する方法において、アルミナと酸化カルシウム、酸
化マグネシウム、酸化ストロンチウムのうちから選ばれ
た一種又は二種以上の金属酸化物とから成る担体にパラ
ジウムを担持した触媒を用いることを特徴とするメチル
イソブチルケトンの製造法。In a method for producing methyl isobutyl ketone by reacting acetone and hydrogen, palladium is supported on a carrier consisting of alumina and one or more metal oxides selected from calcium oxide, magnesium oxide, and strontium oxide. A method for producing methyl isobutyl ketone, characterized by using a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101325A JPH062702B2 (en) | 1986-04-30 | 1986-04-30 | Method for producing methyl isobutyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101325A JPH062702B2 (en) | 1986-04-30 | 1986-04-30 | Method for producing methyl isobutyl ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62258335A true JPS62258335A (en) | 1987-11-10 |
| JPH062702B2 JPH062702B2 (en) | 1994-01-12 |
Family
ID=14297667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61101325A Expired - Lifetime JPH062702B2 (en) | 1986-04-30 | 1986-04-30 | Method for producing methyl isobutyl ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062702B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5149881A (en) * | 1990-05-21 | 1992-09-22 | Mitsubishi Kasei Corporation | Method for producing methyl isobutyl ketone |
| US6706928B2 (en) | 2000-05-18 | 2004-03-16 | Johnson Matthey Plc | Aldol condensation reaction and catalyst therefor |
| CN102190568A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for synthesizing methyl isobutyl ketone |
| CN107185566A (en) * | 2017-06-15 | 2017-09-22 | 中南大学 | A kind of catalyst of acetone hydrogenation liquid phase method synthesizing methyl isobutyl ketone and application |
| CN116041158A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one |
-
1986
- 1986-04-30 JP JP61101325A patent/JPH062702B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5149881A (en) * | 1990-05-21 | 1992-09-22 | Mitsubishi Kasei Corporation | Method for producing methyl isobutyl ketone |
| US6706928B2 (en) | 2000-05-18 | 2004-03-16 | Johnson Matthey Plc | Aldol condensation reaction and catalyst therefor |
| CN102190568A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for synthesizing methyl isobutyl ketone |
| CN107185566A (en) * | 2017-06-15 | 2017-09-22 | 中南大学 | A kind of catalyst of acetone hydrogenation liquid phase method synthesizing methyl isobutyl ketone and application |
| CN107185566B (en) * | 2017-06-15 | 2020-01-07 | 中南大学 | Catalyst for synthesizing methyl isobutyl ketone by acetone hydrogenation liquid phase method and application |
| CN116041158A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH062702B2 (en) | 1994-01-12 |
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