JPH0737412B2 - Method for producing methyl isobutyl ketone - Google Patents
Method for producing methyl isobutyl ketoneInfo
- Publication number
- JPH0737412B2 JPH0737412B2 JP61300697A JP30069786A JPH0737412B2 JP H0737412 B2 JPH0737412 B2 JP H0737412B2 JP 61300697 A JP61300697 A JP 61300697A JP 30069786 A JP30069786 A JP 30069786A JP H0737412 B2 JPH0737412 B2 JP H0737412B2
- Authority
- JP
- Japan
- Prior art keywords
- acetone
- reaction
- catalyst
- water
- methyl isobutyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 68
- 239000003054 catalyst Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229940044927 ceric oxide Drugs 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 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
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000003960 organic solvent 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
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010969 white metal Substances 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〕 本発明は有機溶剤として有用性の高いメチルイソブチル
ケトン（以下MIBKと略す）の改良製造法に関するもので
ある。TECHNICAL FIELD The present invention relates to an improved method for producing methyl isobutyl ketone (hereinafter abbreviated as MIBK), which is highly useful as an organic solvent.
MIBKは従来、アセトンと水素とを原料とし、ジアセトン
アルコール、およびメシチルオキシドを経由するいわゆ
る三段法により製造されている。しかしながらこの方法
は全工程が長く、しかも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、原料転化率を上げることがで
きず、能率が悪い。したがつてアセトンと水素から直接
一段階でMIBKを製造する方法に関しても従来より種々提
案されており、触媒として例えばパラジウム−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
−アルミナ等を用い液相で反応させる方法等が考えられ
ているが、触媒活性、触媒寿命などの点で問題が多かつ
た。さらには、触媒として白金属元素−ジルコニア、パ
ラジウム−チタニア、パラジウム−マグネシア−チタニ
ア等を用い、気相で反応させる試みもいくつか報告され
ているが、いずれも、MIBKの収率、触媒活性、触媒寿命
等の点から考えて実用的ではなかつた。MIBK has conventionally been produced by a so-called three-step method using acetone and hydrogen as raw materials and passing through diacetone alcohol and mesityl oxide. However, this method is long in all steps, and since the first diacetone alcohol production step is an equilibrium reaction, the raw material conversion cannot be increased and the efficiency is low. Therefore, various methods have been conventionally proposed for directly producing MIBK from acetone and hydrogen in one step.For example, palladium-ion exchange resin, palladium-zirconium phosphate, palladium-alumina or the like is used in a liquid phase as a catalyst. Although a reaction method and the like have been considered, there were many problems in terms of catalyst activity and catalyst life. Furthermore, using white metal element-zirconia, palladium-titania, palladium-magnesia-titania, etc. as a catalyst, some attempts to react in the gas phase have also been reported, both yields of MIBK, catalytic activity, It was not practical considering the catalyst life.
本発明者らはさきにセリウムの酸化物または水酸化物と
パラジウムとを必須成分とする触媒が、一段階でMIBKを
製造する触媒として活性が高く、有用であることを見出
した。しかしながら、その触媒系はきわめて高活性では
あるものの、MIBKの選択率は90％強にとどまるため、実
用的に使用し得る触媒としては、さらに選択率の高いこ
とが要求されていた。この選択率を低下させている主原
因は、アセトン三分子が縮合して生成するC9ケトン系の
化合物群の生成が多いことであると考えられる。The present inventors have previously found that a catalyst containing palladium and cerium oxide or hydroxide as essential components is highly active and useful as a catalyst for producing MIBK in one step. However, although the catalyst system is extremely highly active, the selectivity of MIBK remains at more than 90%, so that a catalyst that can be practically used is required to have higher selectivity. It is considered that the main reason for the decrease in the selectivity is the large amount of C 9 ketone-based compound groups formed by condensation of three acetone molecules.
本発明者らは従来技術のかかる問題点を解決すべく、セ
リウムの酸化物または水酸化物とパラジウムとを必須成
分とする触媒系で、アセトンと水素とから一段階で直接
MIBKを製造する際の選択性向上に努めてきた。その結
果、反応に用いるアセトンに、予め実質量の水素を含有
させることにより、上記問題点が解決できることを見出
し本発明に到達した。In order to solve the above-mentioned problems of the prior art, the present inventors have proposed a catalyst system containing palladium and cerium oxide or hydroxide as essential components.
We have endeavored to improve the selectivity when manufacturing MIBK. As a result, they have found that the above problems can be solved by previously adding a substantial amount of hydrogen to the acetone used in the reaction, and reached the present invention.
即ち本発明の目的はアセトンと水素とから一段で高収率
かつ高選択的にMIBKを製造する方法を提供することにあ
る。That is, an object of the present invention is to provide a method for producing MIBK with high yield and high selectivity from acetone and hydrogen in one step.
しかして、この目的は、アセトンと水素とを、セリウム
の酸化物または水酸化物とパラジウムとを必須成分とす
る触媒の存在下に反応させて一段でメチルイソブチルケ
トンを製造するに際し、該アセトン原料として、予め水
を実質的に含有させたアセトン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方法、によつて達成さ
れる。Therefore, this object is to react acetone and hydrogen in the presence of a catalyst containing cerium oxide or hydroxide and palladium as essential components to produce methyl isobutyl ketone in a single step. As a method for producing methyl isobutyl ketone, characterized by using acetone containing substantially water in advance.
以下に本発明方法につき更に詳細に説明する。Hereinafter, the method of the present invention will be described in more detail.
本発明方法を実施する際に用いられる触媒は、セリウム
の酸化物または水酸化物とパラジウムとを必須成分とす
るものである。The catalyst used for carrying out the method of the present invention contains cerium oxide or hydroxide and palladium as essential components.
触媒として用いられるセリウムの酸化物または水酸化物
は、公知の種々の方法で製造される。すなわち、可溶性
セリウム塩溶液に対するアルカリの作用、アルコキシド
の加水分解、不安定なセリウム化合物の熱分解、金属セ
リウムの酸化等である。The cerium oxide or hydroxide used as a catalyst is produced by various known methods. That is, the action of alkali on the soluble cerium salt solution, the hydrolysis of alkoxide, the thermal decomposition of unstable cerium compound, the oxidation of metallic cerium, and the like.
これらの製造方法のうち、水の存在する系で製造される
場合は生成するものは通常、かなり水を含んだ水酸化物
または酸化物であることが多い。これらのものは、その
ままあるいは乾燥して、本発明方法に使用することがで
きるが、更に適当な温度で焼成し加熱脱水したものも同
様に本発明に用いることができる。Of these production methods, when produced in a system in the presence of water, the product usually produces a hydroxide or oxide containing a large amount of water. These can be used in the method of the present invention as they are or after being dried, but those baked at a suitable temperature and heated and dehydrated can also be used in the present invention.
セリウムの酸化物または水酸化物の製造法によるアセト
ン縮合活性の違い、即ち、含水品を加熱脱水品とのアセ
トン縮合活性の大小の程度については一概には言えず、
含水状態で高活性のものも、また、脱水状態で高活性の
ものもある。しかしながら、本発明における触媒は含水
状態の有無にかかわらず公知の種々の触媒に比較し、よ
り高活性であり、MIBKをより良好に製造することができ
る。従つて、本発明の触媒を構成するセリウム酸化物と
しては含水酸化物を用いることもできる。The difference in the acetone condensation activity depending on the method for producing an oxide or hydroxide of cerium, that is, the degree of the acetone condensation activity between a water-containing product and a dehydrated product by heating cannot be generally stated
Some are highly active in the hydrated state and some are highly active in the dehydrated state. However, the catalyst of the present invention is more active than various known catalysts regardless of the presence or absence of water content, and MIBK can be produced better. Therefore, a hydrous oxide can also be used as the cerium oxide constituting the catalyst of the present invention.
なお用いるセリウムの原子価は３価であつても４価であ
つても良い。The valence of cerium used may be trivalent or tetravalent.
また、本発明方法にしたがつてアセトンからMIBKを製造
するには、水素化反応を触媒する成分が必要であり、特
にパラジウムの使用が好ましい。パラジウムの使用方法
としては、上記したセリウムの酸化物または水酸化物に
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、前記したセリウムの酸化物また
は水酸化物と混合して用いることもできる。Further, in order to produce MIBK from acetone according to the method of the present invention, a component that catalyzes a hydrogenation reaction is necessary, and the use of palladium is particularly preferable. As a method of using palladium, there is a method of supporting it on the above-mentioned cerium oxide or hydroxide, but by mixing a catalyst such as palladium-carbon or palladium-alumina with the above-mentioned cerium oxide or hydroxide. Can also be used.
パラジウムの使用量はセリウムの酸化物または水酸化物
に対し、0.001〜10重量％、好ましくは0.01〜５重量％
の範囲である。The amount of palladium used is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the oxide or hydroxide of cerium.
Is the range.
本発明方法の特徴は反応原料のアセトンとして予め水を
実質的に含有させた含水アセトンを用いることにある。
もちろん、工業的に得られるアセトンは通常0.3重量％
程度の水分を含有しているが、本発明方法の目的にはこ
の程度の含水量では不十分である。さらに、本反応は脱
水縮合反応であるので、反応が進行してゆくと系内に水
が蓄積してゆく。その量は例えばアセトンの転化率30％
とすれば計算上15モル％となるが、本発明方法は、ここ
に生成する水とは別に、あらかじめ一定量の水を触媒と
接触させる原料アセトンに混入させることが重要であ
る。A feature of the method of the present invention is that hydrous acetone containing substantially water in advance is used as the reaction raw material acetone.
Of course, industrially obtained acetone is usually 0.3% by weight.
Although it contains a certain amount of water, such a water content is not sufficient for the purpose of the method of the present invention. Furthermore, since this reaction is a dehydration condensation reaction, water accumulates in the system as the reaction proceeds. The amount is, for example, 30% conversion of acetone
However, in the method of the present invention, it is important to mix a predetermined amount of water with the raw material acetone to be brought into contact with the catalyst in advance, in addition to the water produced here.
水の含有量は原料アセトンに対し２〜100モル％、より
好ましくは５〜３モル％である。The content of water is 2 to 100 mol%, more preferably 5 to 3 mol% with respect to the starting acetone.
水の添加により特に、副生するC9ケトン類の生成が抑制
され、MIBKの選択率を向上させることができる。なお10
0モル％をこえると反応速度が遅くなる傾向がある。The addition of water suppresses the formation of by-produced C 9 ketones and improves the MIBK selectivity. 10
If it exceeds 0 mol%, the reaction rate tends to be slow.
アセトンからMIBKを製造する反応は液相で行なわれる。
反応温度はアセトンの臨界温度（235℃）以下がよい。
あまり低温では触媒活性が得られないので好ましくは30
〜200℃の範囲がよい。反応圧力はアセトンの自然発生
圧以上150kg/cm2以下、より好ましくは常圧ないし50kg/
cm2の範囲がよく、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。アセトン
の転化率は50％以下に抑えるのが好ましい。The reaction for producing MIBK from acetone is carried out in the liquid phase.
The reaction temperature is preferably below the critical temperature of acetone (235 ° C).
Since catalytic activity cannot be obtained at too low a temperature, it is preferably 30
A range of ~ 200 ° C is recommended. The reaction pressure is not less than the spontaneous pressure of acetone and not more than 150 kg / cm 2 , more preferably normal pressure to 50 kg /
The cm 2 range is good and is set under a hydrogen atmosphere. The catalyst may be used in the form of either a suspension bed or a fixed bed. The conversion of acetone is preferably suppressed to 50% or less.
次に実施例により本発明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つて
限定されるものではない。Next, the present invention will be described more specifically with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
実施例−１及び２ 市販の水酸化第二セリウム（和光純薬社製、粉末状）を
500℃で焼成し酸化第二セリウムとした。内容積約100ml
のステンレス製オートクレーブに上記酸化第二セリウム
と、予め400℃で水素還元した１％Pd/C（日本エンゲル
ハルド社製、粉末状）を所定量（第１表に記載）仕込
み、アセトン40mlと、アセトンに対し、それぞれ5.4モ
ル％（実施例１）、20.1モル％（実施例２）の水を加え
て140℃に昇温し、水素で全圧を10kg/cm2/Gにし、常に
全圧を10kg/cm2Gに保つために水素を連続的に供給しな
がら反応を行なつた。反応液は冷却後、触媒を分離し、
ガスクロマトグラフイーにより分析した。結果を第１表
に示す。Examples 1 and 2 Commercially available cerium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., powdered)
Firing at 500 ° C. gave cerium oxide. Internal volume approx. 100 ml
Into a stainless steel autoclave of the above, the above-mentioned cerium oxide and 1% Pd / C (manufactured by Nippon Engelhard Co., Ltd., powder form) which had been hydrogen-reduced at 400 ° C. in advance were charged in a predetermined amount (shown in Table 1), and 40 ml of acetone was added, 5.4 mol% (Example 1) and 20.1 mol% (Example 2) of water were added to acetone, respectively, and the temperature was raised to 140 ° C., and the total pressure was adjusted to 10 kg / cm 2 / G with hydrogen. The reaction was carried out while continuously supplying hydrogen in order to keep the temperature at 10 kg / cm 2 G. After cooling the reaction solution, the catalyst is separated,
It was analyzed by gas chromatography. The results are shown in Table 1.
比較例−１ 実施例−１で得た酸化第二セリウムと１％Pd/Cの混合触
媒を第１表に示す量で用い、アセトンに水を添加せずに
反応を行なつた以外は実施例１と同様とした。結果を第
１表に示す。Comparative Example-1 Performed except that the mixed catalyst of cerium oxide and 1% Pd / C obtained in Example-1 was used in the amounts shown in Table 1 and the reaction was carried out without adding water to acetone. Same as Example 1. The results are shown in Table 1.
実施例−３ 市販の水酸化第二セリウム（和光純薬社製、粉末状）を
300℃で焼成し酸化第二セリウムを得た。この酸化第二
セリウムと１％Pd/C（日本エンゲルハルド社製、粉末
状）とを触媒とし（添加量は第２表に示す）、オートク
レーブにアセトン40ml、水5.3モル％（対アセトン）を
加えた以外は実施例−１を同様にして反応を行なつた。
結果を第２表に示す。 Example-3 Commercially available ceric hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., powder)
Firing at 300 ° C. gave ceric oxide. This cerium oxide and 1% Pd / C (manufactured by Nippon Engelhard Co., Ltd., powder) were used as catalysts (addition amount is shown in Table 2), and 40 ml of acetone and 5.3 mol% of water (vs acetone) were added to the autoclave. The reaction was carried out in the same manner as in Example-1 except that the addition was made.
The results are shown in Table 2.
比較例−２ 水を添加せずに反応を行なつた以外は実施例−３と同様
にして反応を行なつた。結果を第２表に示す。Comparative Example-2 A reaction was carried out in the same manner as in Example-3 except that the reaction was carried out without adding water. The results are shown in Table 2.
実施例−４ 実施例−３で得た酸化第二セリウムと１％Pd/Cとを触媒
とし、オートクレーブにアセトン40ml、水5.6モル％
（対アセトン）を仕込み、110℃、10kg/cm2Gで反応を行
なつた以外は実施例−３と同様にして反応を行なつた。
結果を第２表に示す。Example-4 Using the ceric oxide obtained in Example-3 and 1% Pd / C as a catalyst, 40 ml of acetone and 5.6 mol% of water in an autoclave.
(To acetone) was charged, and the reaction was performed in the same manner as in Example-3 except that the reaction was performed at 110 ° C. and 10 kg / cm 2 G.
The results are shown in Table 2.
実施例−５ 実施例−３で得た水酸化第二セリウムと１％Pd/Cとを触
媒とし、オートクレーブにアセトン40ml、水19.5モル％
（対アセトン）を仕込み、170℃、20kg/cm2で反応を行
なつた以外は実施例−３と同様にして反応を行なつた。
結果を第２表に示す。Example-5 Using the ceric hydroxide obtained in Example-3 and 1% Pd / C as a catalyst, 40 ml of acetone and 19.5 mol% of water in an autoclave.
(To acetone) was charged, and the reaction was carried out in the same manner as in Example-3 except that the reaction was carried out at 170 ° C. and 20 kg / cm 2 .
The results are shown in Table 2.
実施例−６ 市販の水酸化セリウム（和光純薬社製、粉末状）をその
まま１％Pd/C（日本エンゲルハルド社製、粉末状）と混
合したものを触媒とし、オートクレーブ中、第３表に示
す量で添加し、アセトン40ml、水5.2モル％を仕込んだ
以外は実施例−１と同様に反応を行なつた。結果を第３
表に示す。 Example-6 Commercially available cerium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., powder form) was directly mixed with 1% Pd / C (manufactured by Nippon Engelhard Co., Ltd., powder form) as a catalyst, and in an autoclave, Table 3 The reaction was carried out in the same manner as in Example 1 except that 40 ml of acetone and 5.2 mol% of water were charged in the amount shown in. The result is the third
Shown in the table.
比較例−３ 触媒の添加量を第３表に示すように変え、水を加えずに
反応を行なつた以外は実施例−６と同様にして反応を行
なつた。結果を第３表に示す。Comparative Example-3 The reaction was performed in the same manner as in Example-6 except that the amount of the catalyst added was changed as shown in Table 3 and the reaction was performed without adding water. The results are shown in Table 3.
〔発明の効果〕 本発明の方法によれば、アセトンと水素とから一段階
で、高収率かつ高選択的に、MIBKを製造することができ
る。 [Effect of the Invention] According to the method of the present invention, MIBK can be produced from acetone and hydrogen in a single step with high yield and high selectivity.
Claims (2)
たは水酸化物とパラジウムとを必須成分とする触媒の存
在下に反応させて一段でメチルイソブチルケトンを製造
するに際し、該アセトン原料として、予め水を実質的に
含有させたアセトン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方法。1. Acetone and hydrogen are reacted in the presence of a catalyst containing cerium oxide or hydroxide and palladium as essential components to produce methyl isobutyl ketone in a single step. A method for producing methyl isobutyl ketone, which comprises using acetone substantially containing water in advance.
ブチルケトンの製造方法において、水の含有量がアセト
ンに対して２〜100モル％であることを特徴とする方
法。2. The method for producing methyl isobutyl ketone according to claim 1, wherein the content of water is 2 to 100 mol% with respect to acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300697A JPH0737412B2 (en) | 1986-12-17 | 1986-12-17 | Method for producing methyl isobutyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300697A JPH0737412B2 (en) | 1986-12-17 | 1986-12-17 | Method for producing methyl isobutyl ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63154638A JPS63154638A (en) | 1988-06-27 |
| JPH0737412B2 true JPH0737412B2 (en) | 1995-04-26 |
Family
ID=17887991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61300697A Expired - Lifetime JPH0737412B2 (en) | 1986-12-17 | 1986-12-17 | Method for producing methyl isobutyl ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737412B2 (en) |
-
1986
- 1986-12-17 JP JP61300697A patent/JPH0737412B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63154638A (en) | 1988-06-27 |
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