CN1264794C - Technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone - Google Patents
Technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone Download PDFInfo
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- CN1264794C CN1264794C CN 03145566 CN03145566A CN1264794C CN 1264794 C CN1264794 C CN 1264794C CN 03145566 CN03145566 CN 03145566 CN 03145566 A CN03145566 A CN 03145566A CN 1264794 C CN1264794 C CN 1264794C
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Abstract
The present invention discloses a technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone, wherein Pd-M/Al2O3 is used as a catalyst, the auxiliary agent M is one of Li, Na, K, Cs and La, whose weight percent is from 0.2 to 1.5%, and the content of Pd is 0.5 wt%. Under normal pressure and the following operating conditions that a reaction temperature is from 373 to 523K, an air speed is 1 to 2h<-1>, and the molar ratio of hydrogen to ketone is 0.5 to 2, and the one-step method for synthesizing methyl isobutyl ketone by catalyzing acetone is conducted in a fixed bed reactor.
Description
Technical field
The present invention relates to a kind of processing method of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK).
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.
By methylisobutanone synthesized from acetone, traditional method is a three-step approach, and the first step is carried out condensation by two molecule acetone under base catalysis, generates diacetone alcohol (DAA); Second step was that diacetone alcohol takes off a part water generation mesityl oxide under acid catalysis; The 3rd step be the mesityl oxide of gained in metal active in the heart shortening obtain purpose product MIBK.Three-step approach industrialization still is the main method of producing MIBK in the world for many years, and China Shanghai solvent factory promptly adopts this method to produce.Although product D AA, MO also are the important derived product of acetone in the middle of it, the technical process of this method is long, facility investment is big, complex operation, and the balance of the first step is not inclined to and forms the aldol condensation product, and other two steps product yield is low relatively.Therefore single stage method system MIBK is all adopted in development research in recent years, and key is the development and the exploitation of dual-function catalyst, and this catalyzer wants to make balance irreversible hydrogenation when generation MO direction moves of condensation of acetone step to generate MIBK.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 a kind of processing method of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK), utilize this method, can be by acetone one-step synthesis methyl iso-butyl ketone (MIBK) under relatively mild reaction conditions.
The catalyzer that the present invention adopts is Pd-M/Al
2O
3, wherein M represents a kind of among Li, Na, K, Cs, the La.Al
2O
3As the carrier of catalyzer, Pd is as the activity of such catalysts component, and M is as the auxiliary agent of catalyzer.
A kind of processing method of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK) is characterized in that this method use Pd-M/Al
2O
3Be catalyzer, auxiliary agent M represents a kind of among Li, Na, K, Cs, the La in the formula, and the content of M is 0.2～1.5wt%, and Pd content is 0.5wt%; In normal pressure, temperature of reaction is that 373～523K, air speed are 1～2h
-1, hydrogen ketone mol ratio is under 0.5～2 the operational condition, in fixed-bed reactor, catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK).
Catalyzer adopts immersion process for preparing, Al
2O
3Before using at 1023K roasting 3h.Used palladium salt is H
2PdCl
4, the salt that auxiliary agent adopted is nitrate or carbonate or muriate.Chlorine palladium aqueous acid is regulated pH value 2.6～3, and incipient impregnation floods the salts solution of corresponding additive again after the oven dry on carrier.Make catalyzer through super-dry, roasting and reduction then.
The outstanding feature of catalyzer of the present invention is: after (1) adopts catalyzer of the present invention, be that primary and secondary product is a spot of Virahol and valerone with methyl iso-butyl ketone (MIBK) in the reaction product.(2) adopt catalyzer of the present invention, acetone conversion is up to 40%, and the methyl iso-butyl ketone (MIBK) selectivity reaches as high as 97%.(3) Preparation of Catalyst is easy, and production technique is simple, can be mass-produced.(4) having added basic metal or rare earth metal in the catalyzer is auxiliary agent, has certain electronic effect of giving, and makes palladium be in the electron rich state; Changed the soda acid allotment of carrier simultaneously.(5) this catalyzer has promptly shown good catalytic performance for this reaction under normal pressure.
Embodiment
Embodiment 1
With γ-Al
2O
3Do carrier, at 1073K roasting 3h, the dipping pH value is 3 chlorine palladium acid solution before using, and floods lithium nitrate solution again behind the dry 3h of 373K, the dry 3h of 373K, and 623K roasting 3h makes Pd-Li/Al
2O
3Catalyzer.Pd content is 0.5wt%, and Li content is 1.0wt%.
Catalyzed reaction is to carry out in the 8mm stainless steel reactor at continuously feeding fixed bed internal diameter, gets this catalyzer of 2.1 grams, 30～50 orders, and aspect ratio is 4.Carry out under the temperature of reaction 423K, normal pressure, the liquid air speed is 2h
-1, hydrogen ketone mol ratio is 2.Acetone advances reactor before through the 373K preheating, and acetone and hydrogen are from top to bottom by beds, and product is by cold-trap cooling back collection.The analysis of product is by capillary gas chromatography, and chromatographic column is FFAP, and splitting ratio is 40/1.Reaction result sees Table 1.
Embodiment 2
Pd-Na/Al
2O
3The same Pd-Li/Al of Preparation of catalysts method
2O
3Catalyzer, used sodium salt are NaNO
3Pd content is 0.5wt%, and Na content is 1.0wt%.Catalyst levels is 2.1 grams, and reaction conditions is with embodiment 1, and reaction result sees Table 1
Embodiment 3
Pd-K/Al
2O
3The same Pd-Li/Al of Preparation of catalysts method
2O
3Catalyzer, used sylvite are KNO
3Pd content is 0.5wt%, and K content is 1.0wt%.Catalyst levels is 2.1 grams, and reaction conditions is with embodiment 1, and reaction result sees Table 1
Embodiment 4
Pd-Cs/Al
2O
3The same Pd-Li/Al of Preparation of catalysts method
2O
3Catalyzer, used cesium salt are Cs (CO
3)
2Pd content is 0.5%, and Cs content is 1%.Catalyst levels is 2.1 grams, and reaction conditions is with embodiment 1, and reaction result sees Table 1
Embodiment 5
Pd-La/Al
2O
3The same Pd-Li/Al of Preparation of catalysts method
2O
3Catalyzer, used lanthanum salt is La (NO
3)
36H
2O.Pd content is 0.5wt%, and La content is 1.0wt%.Catalyst levels is 2.1 grams, and reaction conditions is with embodiment 1, and reaction result sees Table 1
The catalytic performance of table 1 different catalysts
| Catalyzer | Acetone conversion (%) | MIBK yield (%) | MIBK selectivity (%) |
| Pd-Li/Al 2O 3 Pd-Na/Al 2O 3 Pd-K/Al 2O 3 Pd-Cs/Al 2O 3 Pd-La/Al 2O 3 | 39.55 37.80 26.40 33.84 22.29 | 35.10 32.68 24.04 32.62 18.55 | 88.76 86.46 91.05 96.39 83.24 |
Embodiment 6
Prepare the Pd-Cs/Al that Cs content is 0.2～1.5wt%
2O
3Catalyzer, Pd content are 0.5wt%.Urging catalyst levels is 2.1 grams, and reaction conditions is with embodiment 1, and reaction result sees Table 2.
The catalytic performance of the catalyzer that table 2 auxiliary agent content is different
| Catalyzer | Cs content (wt%) | Acetone conversion (%) | MIBK yield (%) | MIBK selectivity (%) |
| A B C D | 0.2 0.6 1.0 1.5 | 46.55 34.25 33.84 25.65 | 37.69 31.62 32.62 23.43 | 80.96 92.32 96.39 91.35 |
Embodiment 7
Getting the Cs content that makes among 2.1 grams, 30～50 order embodiment 5 is the 0.6wt% catalyzer, and placing internal diameter is the stainless steel reactor of 8mm, and aspect ratio is 4.Carry out under the temperature of reaction 398～523K, normal pressure, the liquid air speed is 2h
-1, hydrogen ketone mol ratio is 2.Acetone advances reactor before through the 373K preheating, and acetone and hydrogen are from top to bottom by beds, and product is by cold-trap cooling back collection.The analysis of product is by capillary gas chromatography, and chromatographic column is FFAP, and splitting ratio is 40/1.Reaction result sees Table 3.
Table 3 temperature of reaction is to the influence of catalyst performance
| Temperature of reaction (K) | Acetone conversion (%) | MIBK yield (%) | MIBK selectivity (%) |
| 398 423 448 473 498 523 | 25.26 34.25 40.21 48.49 45.73 38.46 | 24.95 31.62 35.98 39.20 37.30 32.52 | 98.77 92.32 89.48 80.84 81.57 84.56 |
Embodiment 8
Getting the Cs content that makes among 2.1 grams, 30～50 order embodiment 5 is the 0.6wt% catalyzer, and placing internal diameter is the stainless steel reactor of 8mm, and aspect ratio is 4.Carry out under the temperature of reaction 423K, normal pressure, the liquid air speed is 1～3h
-1, hydrogen ketone mol ratio is 2.Acetone advances reactor before through the 373K preheating, and acetone and hydrogen are from top to bottom by beds, and product is by cold-trap cooling back collection.The analysis of product is by capillary gas chromatography, and chromatographic column is FFAP, and splitting ratio is 40/1.Reaction result sees Table 4
Table 4 reaction velocity is to the influence of catalyst catalytic performance
| Reaction velocity (h-1) | Acetone conversion (%) | MIBK yield (%) | MIBK selectivity (%) |
| 1 1.6 2 3 | 36.27 35.22 34.24 20.85 | 33.98 32.83 31.52 16.69 | 93.68 93.21 92.32 80.04 |
Embodiment 9
Getting the Cs content that makes among 2.1 grams, 30～50 order embodiment 5 is the 0.6wt% catalyzer, and placing internal diameter is the stainless steel reactor of 8mm, and aspect ratio is 4.Carry out under the temperature of reaction 423K, normal pressure, the liquid air speed is 2h
-1, hydrogen ketone mol ratio is 0.5～2.5.Acetone advances reactor before through the 373K preheating, and acetone and hydrogen are from top to bottom by beds, and product is by cold-trap cooling back collection.The analysis of product is by capillary gas chromatography, and chromatographic column is FFAP, and splitting ratio is 40/1.Reaction result sees Table 5.
Table 5 hydrogen and acetone mol ratio are to the influence of catalyst catalytic performance
| Hydrogen ketone mol ratio | Acetone conversion (%) | MIBK yield (%) | MIBK selectivity (%) |
| 0.5 1 1.5 2 2.5 | 25.51 30.95 31.87 34.25 28.21 | 23.32 28.91 29.60 31.62 26.33 | 91.42 93.41 92.88 92.32 93.34 |
Claims (1)
1, a kind of processing method of catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK) is characterized in that this method use Pd-M/Al
2O
3Be catalyzer, auxiliary agent M represents a kind of among Li, Na, K, Cs, the La in the formula, and the content of M is 0.2～1.5wt%, and Pd content is 0.5wt%; In normal pressure, temperature of reaction is that 373～523K, air speed are 1～2h
-1, hydrogen ketone mol ratio is under 0.5～2 the operational condition, in fixed-bed reactor, catalysis acetone one-step synthesis methyl iso-butyl ketone (MIBK).
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|---|---|---|---|
| CN 03145566 CN1264794C (en) | 2003-07-03 | 2003-07-03 | Technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159263A (en) * | 2017-05-09 | 2017-09-15 | 北京化工大学 | Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone catalyst and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413837C (en) * | 2005-10-19 | 2008-08-27 | 中国石油化工股份有限公司 | Process for separating methylisobutanone synthesized from 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 |
| CN103420786B (en) * | 2012-05-14 | 2015-12-16 | 浙江新化化工股份有限公司 | The method of coproducing methyl isobutyl ketone and methyl isobutyl carbinol |
| CN103191728A (en) * | 2013-04-03 | 2013-07-10 | 中山职业技术学院 | Modified aluminum oxide catalyst, preparation method thereof and application of catalyst in synthesis of methyl isobutyl ketone (MIBK) |
| CN108097263B (en) * | 2017-12-25 | 2020-09-08 | 万华化学集团股份有限公司 | Method for preparing MIBK from industrial byproduct waste liquid acetone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159263A (en) * | 2017-05-09 | 2017-09-15 | 北京化工大学 | Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone catalyst and preparation method |
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