CN1566060A

CN1566060A - Technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone

Info

Publication number: CN1566060A
Application number: CN 03145567
Authority: CN
Inventors: 徐贤伦; 刘晓红; 刘淑文; 汤爱华
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2003-07-03
Filing date: 2003-07-03
Publication date: 2005-01-19
Anticipated expiration: 2023-07-03
Also published as: CN1218921C

Abstract

The invention discloses a technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone, wherein Pd/ZrO2 is used as catalyst, and the Pd content is 0.5 wt%. In the fixed-bed reactor, the acetone conversion rate is as high as 62%.

Description

The processing method of methylisobutanone synthesized from acetone and valerone

Technical field

The present invention relates to the processing method of a kind of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK) and valerone.

Background technology

Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of important organic solvent, has good solubility property, can most paint of dissolving use resins, also can be used as the solvent of producing tsiklomitsin, penicillin, in oil refining, as the oil dewaxing agent, can save cold, reduce solvent consumption, improve the device working ability, reduce production costs, improve yield, also can be used for producing Refined Paraffin Wax and microcrystalline wax.

Valerone (DIBK) has the boiling point height, and velocity of evaporation is fast, can be used as that nitro sprays paint, the solvent of ethenoid resin paint and other synthetic resin coating, can improve its moistureproof ability.Also can be used as and make organic aerocolloidal dispersion agent and food is refining and the intermediate of some drugs, sterilant.

It is reported that what present method by acetone single stage method synthesize methyl-isobutyl ketone extensively adopted is palladium-resin type catalyzer (US3,953,517), but such catalyzer poor heat stability, the catalyst regeneration difficulty, the control of operational condition requires harsh.Problems such as the activated alumina that carries palladium that the special public clear 63-119436 of Japanese Patent is introduced is done catalyzer synthesize methyl-isobutyl ketone method, has the temperature of reaction height, and transformation efficiency is low, and the selectivity of methyl iso-butyl ketone (MIBK) is bad.And how traditional method by methylisobutanone synthesized from acetone under high pressure carries out.

Summary of the invention

The object of the present invention is to provide the processing method of a kind of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK) and valerone, utilize this method, can be by acetone one-step synthesis methyl iso-butyl ketone (MIBK) and valerone under relatively mild reaction conditions.

The present invention searches out a kind of Pd/ZrO ₂Catalyzer, be exactly with zirconium white as carrier, precious metal palladium is as the catalyzer of active ingredient, can reach catalysis acetone and hydrogen once going on foot synthetic purpose product methyl iso-butyl ketone (MIBK) and valerone.

The processing method of a kind of methylisobutanone synthesized from acetone and valerone is characterized in that this method use Pd/ZrO ₂Be catalyzer, catalyst P d content is 0.5wt%, is 2h in normal pressure, temperature of reaction 423K, liquid air speed ^-1, hydrogen ketone mol ratio is under 2 the operational condition, in fixed-bed reactor, one-step synthesis methyl iso-butyl ketone (MIBK) and valerone.

The support of the catalyst zirconium white adopts the coprecipitation method preparation, with ZrOCl ₂8H ₂O is mixed with the solution of 0.2～0.5mol/l, the dilution of precipitation agent ammoniacal liquor is the solution of 0.2～0.5mol/l, at room temperature stir, precipitation agent is added drop-wise in the zirconium salt solution, or zirconium salt solution is added drop-wise in the precipitation agent, the pH value 9.0～10 of final blending liquid, pass through ageing then, throw out washs through suction filtration, and dry and roasting makes support of the catalyst.At last, after the carrier moulding, active ingredient Pd is supported on the Zirconia carrier with pickling process.

The outstanding feature of catalyzer of the present invention is: (1) adopts catalyzer of the present invention, and reaction product is mainly methyl iso-butyl ketone (MIBK) and valerone.(2) on catalyzer of the present invention, acetone conversion reaches as high as 62%, and methyl iso-butyl ketone (MIBK) and valerone selectivity are up to 100%.(3) Catalyst Production technology is simple, can be mass-produced.(4) catalyzer has suitable acid-basicity, and is active higher.(5) this catalyzer can be prepared methyl iso-butyl ketone (MIBK) and these two kinds of broad-spectrum products of valerone simultaneously.

Embodiment

Embodiment 1:

Take by weighing 26.15gZrOCl ₂8H ₂O is dissolved in the deionized water, is mixed with the aqueous solution of 0.20mol/l.Other gets 44.63ml ammoniacal liquor (28%), dilutes the aqueous solution for 0.2mol/l.With ZrOCl ₂8H ₂The aqueous solution of O is added drop-wise in the precipitation agent ammonia soln, and the pH value of maintenance solution is about 10.After dropwising, ageing 24 hours in mother liquor makes Zr (OH) under the normal temperature ₄The water-sol.With Zr (OH) ₄The water-sol with the deionized water thorough washing to there not being Cl ^-1Exist, filter, filter cake is dry 10h in the 383K air atmosphere, roasting 3h in the 823K air then, and the zirconium white particle diameter is 18.09nm.With the product compression molding that obtains, be ground into 30～50 purpose particles.

By Pd content is 0.5wt%, gets the H of 0.0094g/ml ₂PdCl ₄Solution, regulating pH value is 3, the above-mentioned carrier of incipient impregnation, drying, roasting, logical hydrogen reduction 3h under the 573K then.Can make required catalyzer.

Get the above-mentioned catalyzer of 3g, the internal diameter of packing into is that the stainless steel reactor of 8mm is estimated, and the outer wall of reactor is provided with controllable heating system, be reflected under the normal pressure and carry out, bed temperature is controlled at 423K, and acetone advances reactor before through the 373K preheating, and the liquid air speed is 2h ^-1, hydrogen ketone ratio is 2 (mol ratios).Product is collected by cold-trap, analyzes with gas chromatograph, and chromatographic column is the FFAP capillary column, and splitting ratio is 40/1.The results are shown in subordinate list.

Embodiment 2

The preparation of the zirconium white water-sol is with embodiment 1.After dropwising, reaction solution is hot digestion backflow 3h under 373K, again with the deionized water thorough washing to there not being Cl ^-1Exist.Filter, filter cake is dry 10h in the 383K air atmosphere, roasting 3h in the 823K air then, and the zirconium white particle diameter is 14.00nm.The products therefrom compression molding is ground into 30～50 purpose particles.

Get the above-mentioned catalyzer of 3g and pack in the reactor, reaction conditions the results are shown in subordinate list with embodiment 1.

Embodiment 3

Zr (OH) ₄The preparation of the water-sol is with embodiment 1.With Zr (OH) ₄The water-sol joins in the NaOH solution, and pH value is remained on about 11, hot digestion backflow 3h under 373K.Use again the deionized water thorough washing to ionic conductivity less than 15 μ Ω ^-1, in 373K air drying 10h, roasting 3h in the 823K air, zirconium white particle diameter are 12.16nm.With the product compression molding that obtains, be ground into 30～50 purpose particles.

Embodiment 4

Take by weighing 39.23g ZrOCl ₂8H ₂O is dissolved in the deionized water, is mixed with the aqueous solution of 0.20mol/l.Other gets the ammoniacal liquor (28%) of 66.95ml, dilutes the aqueous solution for 0.2mol/l.Ammonia soln is added drop-wise to ZrOCl ₂8H ₂In the aqueous solution of O, after dripping, keeping the reaction solution pH value is 10, and ageing 24h makes Zr (OH) at normal temperatures ₄The water-sol.With Zr (OH) ₄The water-sol with the deionized water thorough washing to there not being Cl ^-1Exist, filter, filter cake is dry 10h in the 383K air atmosphere, roasting 3h in the 823K air then, and the zirconium white particle diameter is 28.79nm.With the product compression molding that obtains, be ground into 30～50 purpose particles.

The catalytic performance of subordinate list different catalysts

Acetone conversion Virahol selectivity MIBK selective d IBK selectivity

Embodiment zirconium white crystal grain

Size (nm) is (%) (%) (%) (%)

1 18.09 61.39 18.74 35.72 45.54

2 14.00 65.13 7.79 30.78 61.43

3 12.16 52.74 9.10 60.64 30.23

4 28.79 45.43 / 63.70 36.30

Claims

1. A process for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone, characterized in that the method uses Pd/ _ZrO as a catalyst, and the catalyst Pd content is 0.5wt%, at normal pressure, reaction temperature 423K, Methyl isobutyl ketone and diisobutyl ketone were synthesized in a fixed-bed reactor under the operating conditions of liquid space velocity of 2h ^-1 and hydroketone molar ratio of 2.