JPH0774180B2 - Method for producing high-grade ketone - Google Patents
Method for producing high-grade ketoneInfo
- Publication number
- JPH0774180B2 JPH0774180B2 JP62310626A JP31062687A JPH0774180B2 JP H0774180 B2 JPH0774180 B2 JP H0774180B2 JP 62310626 A JP62310626 A JP 62310626A JP 31062687 A JP31062687 A JP 31062687A JP H0774180 B2 JPH0774180 B2 JP H0774180B2
- Authority
- JP
- Japan
- Prior art keywords
- ketone
- zirconium oxide
- catalyst
- producing
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000002576 ketones Chemical class 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 21
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- AKRJXOYALOGLHQ-UHFFFAOYSA-N 2-methylheptan-4-one Chemical compound CCCC(=O)CC(C)C AKRJXOYALOGLHQ-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CAPHFMAKLBLGBE-UHFFFAOYSA-N palladium zirconium Chemical compound [Zr].[Pd] CAPHFMAKLBLGBE-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical group [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は高級ケトンの製造方法に関する。詳しくは本発
明は塗料、樹脂、溶剤或いは各種有機合成の原料又は中
間体として有用性の高い飽和高級ケトンの製造方法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a higher ketone. More specifically, the present invention relates to a method for producing a saturated higher ketone, which is highly useful as a coating material, a resin, a solvent, a raw material or an intermediate for various organic syntheses.
低級ケトンを原料としてその２分子の縮合によって得ら
れる炭素骨格を有する飽和高級ケトンを製造する方法が
種々提案されている。例えば代表的な飽和高級ケトンで
あるメチルイソブチルケトン（以下、MIBKという）の製
造法について述べると、アセトンと水素とを原料とし、
ジアセトンアルコール、メシチルオキシドを経由するい
わゆる三段法が用いられている。しかしこの方法は工程
も長く、最初のジアセトンアルコール製造工程が平衡反
応のため原料転化率が低い。従って、アセトン等の低級
ケトンと水素とから直接一工程で飽和高級ケトンを製造
する方法について種々検討がなされ、触媒として次のよ
うな提案がなされている。Various methods have been proposed for producing a saturated higher ketone having a carbon skeleton, which is obtained by condensing two molecules of a lower ketone as a raw material. For example, the production method of methyl isobutyl ketone (hereinafter referred to as MIBK), which is a typical saturated higher ketone, is described by using acetone and hydrogen as raw materials,
A so-called three-step method via diacetone alcohol and mesityl oxide is used. However, this method has a long process and the raw material conversion rate is low because the first diacetone alcohol production process is an equilibrium reaction. Therefore, various studies have been made on a method for directly producing a saturated higher ketone from a lower ketone such as acetone and hydrogen in one step, and the following proposals have been made as catalysts.
パラジウム−イオン交換樹脂、パラジウム−リン酸
ジルコニウム、パラジウム−アルミナ等を液相で用いる
方法。A method of using palladium-ion exchange resin, palladium-zirconium phosphate, palladium-alumina or the like in a liquid phase.
パラジウム−IV B属金属酸化物を用いる方法（時公
昭52−15574）。Method using palladium-IV group B metal oxide (Tokiko Sho 52-15574).
しかしながら上記の触媒は触媒活性、触媒寿命、安定
性等の点で問題があった。また上記の触媒は反応温度
150ないし400℃で使用されているが、気相での実施例の
結果は目的とする飽和高級ケトンへの選択率が低く、満
足すべき結果は得られていない。さらに触媒活性も高く
ないので、目的とする飽和高級ケトンへの選択率が高く
なると思われる液相での使用は事実上不可能であること
が推察される。However, the above-mentioned catalysts have problems in catalytic activity, catalyst life, stability and the like. In addition, the above catalyst has a reaction temperature
Although it is used at 150 to 400 ° C., the results of the examples in the gas phase are low in the selectivity to the desired saturated higher ketone, and satisfactory results have not been obtained. Furthermore, since the catalytic activity is not high, it is surmised that it is practically impossible to use it in the liquid phase where the selectivity to the desired saturated higher ketone will be high.
本発明者らはかかる従来技術の問題点を解決すべく、低
級ケトンと水素とから一工程で飽和高級ケトンを製造し
得る高活性かつ高選択性を示す触媒の開発に鋭意努めた
結果、特定の物性を有するジルコニウム酸化物とパラジ
ウムとを必須成分とする触媒を用いることにより上記の
問題点が解決できることを見出して本発明に到達した。In order to solve the problems of the prior art, the inventors of the present invention have made diligent efforts to develop a catalyst showing high activity and high selectivity capable of producing a saturated higher ketone from a lower ketone and hydrogen in one step, The present invention has been achieved by finding that the above problems can be solved by using a catalyst containing zirconium oxide and palladium having the above physical properties as essential components.
即ち本発明の要旨は、低級ケトンと水素とを触媒の存在
下に液相で反応させて一段で飽和高級ケトンを製造する
に際し、ハメット指示薬法により測定される表面酸−塩
基強度が実質的に中性であるジルコニウム酸化物とパラ
ジウムとを必須成分とする触媒を使用することを特徴と
する高級ケトンの製造方法、に存する。That is, the gist of the present invention is that when a lower ketone and hydrogen are reacted in the liquid phase in the presence of a catalyst to produce a saturated higher ketone in one step, the surface acid-base strength measured by the Hammett indicator method is substantially A method for producing a higher ketone, which comprises using a catalyst containing neutral zirconium oxide and palladium as essential components.
以下、本発明方法につき詳細に説明する。Hereinafter, the method of the present invention will be described in detail.
本発明方法の出発原料である低級ケトンとしては、α位
に水素原子を有する種々のケトンが用いられ、好ましく
は炭素数が３〜８個の脂肪族ジアルキルケトンが用いら
れる。具体的にはアセトン、メチルエチルケトン、メチ
ルイソブチルケトン、エチルプロピルケトン、ジイソプ
ロピルケトン、プロピルイソブチルケトン等が挙げられ
る。As the lower ketone which is the starting material for the method of the present invention, various ketones having a hydrogen atom at the α-position are used, and preferably aliphatic dialkyl ketone having 3 to 8 carbon atoms. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl propyl ketone, diisopropyl ketone and propyl isobutyl ketone.
本発明方法においては、触媒として特定の表面酸−塩基
強度を有するジルコニウム酸化物とパラジウムとからな
る二成分系を用いることが重要である。用いるジルコニ
ウム酸化物は、より具体的には、ハメット指示薬法（J.
Amer.Chem.Soc.,78,5490（1956））により測定される表
面酸−塩基強度が実質的に中性、好ましくは酸強度
（H0）＋3.3以上かつ塩基強度（H_）＋7.2以下、さらに
好ましくは酸強度（H0）＋6.8以上かつ塩基強度（H_）
＋7.2以下の測定値を有するジルコニウム酸化物であ
る。なおジルコニウム酸化物として含水状態のものを用
いることもできる。In the method of the present invention, it is important to use, as a catalyst, a binary system composed of zirconium oxide having a specific surface acid-base strength and palladium. The zirconium oxide used is more specifically the Hammett indicator method (J.
Amer.Chem.Soc., 78, 5490 (1956)), the surface acid-base strength is substantially neutral, preferably acid strength (H 0 ) +3.3 or more and base strength (H_) +7. 2 or less, more preferably acid strength (H 0 ) +6.8 or more and base strength (H_)
It is a zirconium oxide having a measured value of +7.2 or less. The zirconium oxide may be in the hydrous state.
ジルコニウム酸化物の調製法として一般的には沈殿法、
熱分解法、酸化法等が挙げられる。例えば塩化物、オキ
シ塩化物、硫酸塩等の可溶性塩の水溶液にアルカリを作
用させて沈殿させ、必要に応じ適当な温度で焼成、脱水
して酸化物を得る方法がある。しかしながらこのような
方法で得られた沈殿には原料の金属塩に由来するCl~、S
O4 2~等の陰イオンが含まれている場合が多く、本発明者
らの検討によれば、これらの不純物の有無が、得られる
ジルコニウム酸化物の表面酸−塩基強度、時に酸強度、
に大きく影響し、低級ケトンから飽和高級ケトンを製造
する触媒の活性、選択性に対して決定的な影響を及ぼす
ことが判明した。従って本発明においては、ジルコニウ
ム酸化物の調製法として沈殿法を用いる場合、得られた
沈殿を十分に水洗し、必要により酸又はアルカリによる
処理を行なうことにより不純物を除いて、表面酸−塩基
強度が実質的に中性となるようにしなければならない。
また他の調製法を用いる場合にも例えば極めて高純度の
原料を使用するなどして、得られる酸化ジルコニウムの
表面酸−塩基強度が実質的に中性となるようにしなけれ
ばならない。Generally, a precipitation method as a method for preparing zirconium oxide,
Pyrolysis method, oxidation method and the like can be mentioned. For example, there is a method in which an alkali is allowed to act on an aqueous solution of a soluble salt such as chloride, oxychloride, or sulfate to cause precipitation, which is then baked and dehydrated at an appropriate temperature to obtain an oxide. However, the precipitate obtained by such a method contains Cl ~, S derived from the metal salt of the raw material,
In many cases, an anion such as O 4 2 or the like is contained, and according to the study by the present inventors, the presence or absence of these impurities is the surface acid-base strength of the obtained zirconium oxide, and sometimes the acid strength,
It was found that the activity of the catalyst for producing a saturated higher ketone from a lower ketone and the selectivity are decisively influenced. Therefore, in the present invention, when the precipitation method is used as the method for preparing the zirconium oxide, the obtained precipitate is sufficiently washed with water and, if necessary, treated with an acid or an alkali to remove impurities to obtain a surface acid-base strength. Must be substantially neutral.
Also, when other preparation methods are used, the surface acid-base strength of the resulting zirconium oxide must be made substantially neutral, for example, by using an extremely high-purity raw material.
また、本発明に従って低級ケトンから飽和高級ケトンを
製造するには水素化能のある触媒成分が必要である。一
般に白金族元素が用いられるが、特にパラジウムが有効
であり、本発明ではこれを使用する。パラジウムの使用
形態としては上記のジルコニウム酸化物に担持する方法
があるが、パラジウム−炭素、パラジウム−アルミナ等
の触媒をジルコニウム酸化物と混合して用いることもで
きる。パラジウムの使用量はジルコニウム酸化物に対し
て通常0.001〜10重量％、好ましくは0.01〜５重量％の
範囲である。Further, a catalyst component having a hydrogenation ability is required for producing a saturated higher ketone from a lower ketone according to the present invention. Generally, a platinum group element is used, but palladium is particularly effective and is used in the present invention. As a form of using palladium, there is a method of supporting it on the zirconium oxide, but a catalyst such as palladium-carbon or palladium-alumina may be mixed with the zirconium oxide and used. The amount of palladium used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the zirconium oxide.
本発明方法の反応は液相で行なわれる。反応は低級ケト
ンの臨界温度（アセトンの場合235℃）以下で進行する
が、高温、通常150℃以上では特にカルボニル基の水素
化によるアルコール体への選択率が高くなり、目的とす
る飽和高級ケトンの収率が若干低下する傾向が見られ
る。またあまり低温では触媒活性が得られないので、反
応温度は好ましくは30〜150℃の範囲がよい。反応圧力
は低級ケトンの自然発生圧力以上、通常150kg/cm2以
下、好ましくは１〜50kg/cm2の間がよく、水素雰囲気下
で設定される。触媒は懸濁床、固定床いずれの形態で用
いてもよい。低級ケトンの転化率は50％以下に抑えるの
が好ましい。The reaction of the method of the present invention is carried out in the liquid phase. The reaction proceeds below the critical temperature of the lower ketone (235 ° C in the case of acetone), but at high temperatures, usually above 150 ° C, the selectivity for alcohols due to hydrogenation of the carbonyl group becomes high, and the desired saturated higher ketone There is a tendency that the yield of is slightly reduced. Further, since the catalytic activity cannot be obtained at a too low temperature, the reaction temperature is preferably in the range of 30 to 150 ° C. The reaction pressure is autogenous pressure or more lower ketones, usually 150 kg / cm 2 or less, preferably better between 1 to 50 kg / cm 2, is set in a hydrogen atmosphere. The catalyst may be used in the form of either a suspension bed or a fixed bed. It is preferable to control the conversion of the lower ketone to 50% or less.
次に実施例により本発明の実施態様をさらに具体的に説
明するが、本発明はその要旨を越えない限り、以下の実
施例によって限定されるものではない。Next, the embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
参考例１（ジルコニウム酸化物の調製） 三種の市販の水酸化ジルコニルをそれぞれ400℃で３時
間焼成してジルコニウム酸化物とし、ハメット指示薬法
により表面酸−塩基強度を測定した。即ち、Benesiの方
（J.Amer.Chem.So.,78,5490（1956））に従い、予め400
℃で３時間焼成して得たジルコニウム酸化物0.3gを脱水
処理したベンゼン10mlに浸漬し、ここに指示薬数滴を摘
下し、色調変化により酸−塩基強度を測定した。各指示
薬のpKa価により酸−塩基強度を示した測定結果を第１
表に示す。Reference Example 1 (Preparation of Zirconium Oxide) Three types of commercially available zirconyl hydroxide were each baked at 400 ° C. for 3 hours to give a zirconium oxide, and the surface acid-base strength was measured by the Hammett indicator method. That is, according to Benesi (J. Amer. Chem. So., 78, 5490 (1956)), 400
0.3 g of zirconium oxide obtained by firing at 3 ° C. for 3 hours was immersed in 10 ml of dehydrated benzene, and a few drops of the indicator were removed, and the acid-base strength was measured by the change in color tone. The first is the measurement result showing the acid-base strength according to the pKa value of each indicator.
Shown in the table.
実施例１及び比較例１〜２ 参考例１で得られた三種のジルコニウム酸化物1.8gと２
％Pd/C（日本エンゲルハルド社製）0.3gとを混合して触
媒とし、反応に用いた。 Example 1 and Comparative Examples 1 and 2 1.8 g of the three types of zirconium oxides obtained in Reference Example 1 and 2
% Pd / C (manufactured by Nippon Engelhard Co., Ltd.) (0.3 g) was mixed to form a catalyst, which was used for the reaction.
内容積約100mlのSUS316製 オートクレーブに上記混合
触媒とアセトン40mlとを仕込み、140℃に加熱し、水素
圧で全圧を10kg/cm2（ゲージ圧）として反応を行なっ
た。反応中は水素を連続的に供給して常に全圧を一定に
保った。反応液は冷却後、触媒を分離し、ガスクロマト
グラフィーにより分析した。結果を第２表に示す。The above-mentioned mixed catalyst and 40 ml of acetone were charged in an autoclave made of SUS316 having an internal volume of about 100 ml, and the mixture was heated to 140 ° C. and reacted at a hydrogen pressure of 10 kg / cm 2 (gauge pressure). During the reaction, hydrogen was continuously supplied to keep the total pressure constant. After cooling the reaction solution, the catalyst was separated and analyzed by gas chromatography. The results are shown in Table 2.
実施例２〜３ 実施例１で用いたジルコニウム酸化物Ａの原料の水酸化
ジルコニウムを予め1Nのアンモニア水で処理し、〔Pd
（NH3）４〕Cl2−H2Oを用いるイオン交換法により0.1重
量％相当のパラジウムを担持させた。これを300℃で４
時間水素還元して触媒とし、反応に用いた。実施例１と
同様にアセトン40mlと担持触媒とをオートクレーブに仕
込み、140℃、10kg/cm2G及び170℃、18kg/cm2Gの条件で
反応を行なった。結果を第３表に示す。 Examples 2 to 3 Zirconium hydroxide as a raw material of zirconium oxide A used in Example 1 was previously treated with 1N ammonia water, and [Pd
0.1% by weight of palladium was supported by the ion exchange method using (NH 3 ) 4 ] Cl 2 —H 2 O. This at 300 ℃ 4
It was reduced with hydrogen for a period of time to obtain a catalyst, which was used in the reaction. As in Example 1, 40 ml of acetone and the supported catalyst were charged into an autoclave, and the reaction was carried out under the conditions of 140 ° C., 10 kg / cm 2 G and 170 ° C., 18 kg / cm 2 G. The results are shown in Table 3.
実施例４ 実施例１で用いたジルコニウム酸化物A0.5g及び２％Pd/
C0.02gとメチルエチルケトン20mlとをオートクレーブに
仕込み、実施例１と同様に140℃、水素圧で全圧10kg/cm
2Gで反応を行なった。反応時間５時間後の結果はメチル
エチルケトン転化率22.8％、５−メチル−ヘプタン−３
−オン（エチルアミルケトン）選択率95.4％、２−ブタ
ノール選択率2.8％であった。 Example 4 0.5 g of zirconium oxide A used in Example 1 and 2% Pd /
The autoclave was charged with 0.02 g of C and 20 ml of methyl ethyl ketone, and the total pressure was 10 kg / cm at 140 ° C. and hydrogen pressure as in Example 1.
The reaction was performed at 2 G. After the reaction time of 5 hours, the conversion was 22.8% for methyl ethyl ketone, and 5-methyl-heptane-3.
The -one (ethyl amyl ketone) selectivity was 95.4% and the 2-butanol selectivity was 2.8%.
本発明方法に従って高活性かつ高選択性の触媒を使用す
ることにより、低級ケトンと水素とから経済的に有利に
飽和高級ケトンを製造することができる。By using a highly active and highly selective catalyst according to the method of the present invention, a saturated higher ketone can be economically produced from a lower ketone and hydrogen.
Claims (3)
で反応させて一段で飽和高級ケトンを製造するに際し、
ハメット指示薬法により測定される表面酸−塩基強度が
実質的に中性であるジルコニウム酸化物とパラジウムと
を必須成分とする触媒を使用することを特徴とする高級
ケトンの製造方法。1. When a lower ketone and hydrogen are reacted in the liquid phase in the presence of a catalyst to produce a saturated higher ketone in one step,
A method for producing a higher ketone, which comprises using a catalyst containing, as essential components, zirconium oxide whose surface acid-base strength measured by the Hammett indicator method is substantially neutral, and palladium.
の製造方法において、ジルコニウム酸化物の表面酸−塩
基強度が酸強度（H0）＋3.3以上、かつ塩基強度（H_）
＋7.2以下であることを特徴とする方法。2. The method for producing a higher ketone according to claim 1, wherein the surface acid-base strength of the zirconium oxide is acid strength (H 0 ) +3.3 or more and the base strength (H_).
A method characterized by being +7.2 or less.
高級ケトンの製造方法において、反応を30〜150℃の温
度で行なうことを特徴とする方法。3. The method for producing a higher ketone according to claim 1 or 2, wherein the reaction is carried out at a temperature of 30 to 150 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62310626A JPH0774180B2 (en) | 1987-12-08 | 1987-12-08 | Method for producing high-grade ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62310626A JPH0774180B2 (en) | 1987-12-08 | 1987-12-08 | Method for producing high-grade ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01151533A JPH01151533A (en) | 1989-06-14 |
| JPH0774180B2 true JPH0774180B2 (en) | 1995-08-09 |
Family
ID=18007523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62310626A Expired - Fee Related JPH0774180B2 (en) | 1987-12-08 | 1987-12-08 | Method for producing high-grade ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774180B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712606B (en) | 2009-11-24 | 2012-07-25 | 沈阳化工学院 | Process for producing methylisobutylketone and diisobutyl ketone by using acetone |
| CN101830787B (en) * | 2010-04-13 | 2013-04-03 | 沈阳化工学院 | Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method |
| JP7842634B2 (en) * | 2022-05-13 | 2026-04-08 | 株式会社日本触媒 | Acetone hydrogenation catalyst and method for producing isopropanol |
-
1987
- 1987-12-08 JP JP62310626A patent/JPH0774180B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01151533A (en) | 1989-06-14 |
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