CN101830787B - Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method - Google Patents
Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method Download PDFInfo
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- CN101830787B CN101830787B CN 201010145264 CN201010145264A CN101830787B CN 101830787 B CN101830787 B CN 101830787B CN 201010145264 CN201010145264 CN 201010145264 CN 201010145264 A CN201010145264 A CN 201010145264A CN 101830787 B CN101830787 B CN 101830787B
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- isobutyl ketone
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Abstract
The invention relates to a method for synthesizing methyl isobutyl ketone and diisobutyl ketone by an acetone gas-phase one-step method, which relates to a chemical solvent. A Pd/MgO-Al2O3-ZrO2 catalyst is used in the method, comprises the components of 1wt% of Pd, 55wt% of MgO, 10wt% of Al2O3 and 34wt% of ZrO2 and is prepared from a PdMgAlZr four-element houghite compound. under the condition that the reaction temperature is 150-200 DEG C,the liquid air speed is 4.8ml/gcat.h, and the hydrogen-ketone mol ratio is 1, in a fixed bed reactor, the acetone conversion rate is 30-73 percent, and the selectivity of the methyl isobutyl ketone and the diisobutyl ketone respectively reaches 50-60 percent and 23-30 percent. The catalyst has simple preparation process and is suitable for large-scale production. After the ZrO2 is added, the catalyst has proper acid-base property and higher activity. The catalyst can be simultaneously used for preparing the two products of the methyl isobutyl ketone and the diisobutyl ketone.
Description
Technical field
The present invention relates to a kind of Chemical Solvents, particularly relate to a kind of processing method by acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone.
Background technology
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of good medium-boiling solvent, stable chemical performance, can satisfy the particular requirement such as solid ingredient, evaporation rate, levelling property and coating intensity, outward appearance of high-grade paint, MIBK because of its have good solubility and with the fabulous mutual solubility of other solvents and suitable boiling point, be widely used as the solvent of producing high-grade paint, synthetic p-phenylenediamine rubber aging inhibitor is simultaneously also as solvent and the rare metal extraction agent of producing medicine, tackiness agent.Along with the fast development of automotive industry and high-grade paint, the demand of MIBK is constantly increased.
The working system of MIBK mainly is the acetone hydrogenation method.The reaction process of being produced MIBK by acetone hydrogenation is: condensation reaction occurs in acetone (AC) under the alkaline catalysts effect, generate diacetone alcohol (DAA), dehydration reaction occurs and generates mesityl oxide (MO) in DAA under an acidic catalyst effect, MO carries out hydrogenation reaction again and generates MIBK under the effect of hydrogenation catalyst.The MIBK that generates can generate diisobutyl ketone (DIBK) with the further condensation reaction of acetone again, and perhaps condensation reaction generation isophorone (IPO) occurs MIBK self.
In the acetone hydrogenation method, be divided into again acetone three-step approach and acetone through one-step method technique.Three-step approach is owing to the drawbacks such as technical process is long, number of devices is many, investment is large have restricted further developing of this technique.At present, MIBK produces the main single stage method that adopts.The acetone through one-step method technological process of production is shorter, main process be acetone and hydrogen under the asynchronous cooperation effect of dual-function catalyst, condensation, dehydration and hydrogenation reaction occur simultaneously generate MIBK.Acetone gas phase hydrogenation One-step production MIBK is the most practical operational path of present industrialization in the one-step technology.
Get in the MIBK technique in the acetone hydrogenation legal system, another primary product is diisobutyl ketone (DIBK).Diisobutyl ketone 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 coatings, can improve its moistureproof ability.Also can be used as the dispersion agent of making Organic aerosol and food is refining and the intermediate of some drugs, sterilant.The diisobutyl ketone product is domestic to there is no production, and dependence on import belongs to high value added product fully, and Development and Production DIBK can save a large amount of foreign exchanges, and output benefit is good.
Get in the MIBK technique in the acetone hydrogenation legal system, the catalyzer that extensively adopts is the Pd/ resin catalyst, but such catalyzer poor heat stability, the catalyst regeneration difficulty, operational condition requires harsh, and the active ingredient of catalyzer is precious metal.Catalyzer take transition metal Ni as catalytic active component is because cheap, very competitive.At present the Ni of report is catalyst based a Ni/Al
2O
3, Ni/MgO, Ni/CaO, Ni/MgAl hydrotalcite etc.For Ni/MgO-Al
2O
3-ZrO
2Catalyzer yet there are no report.
Summary of the invention
The object of the present invention is to provide the processing method of a kind of catalysis acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone, utilize this method can be by acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone under relatively mild reaction conditions.
The objective of the invention is to be achieved through the following technical solutions:
By the method for acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone, the method comprises uses Pd/MgO-Al
2O
3-ZrO
2Catalyzer consists of: Pd:1wt%, MgO:55wt%, Al
2O
3: 10wt%, ZrO
2: 34wt%; Its catalyzer makes by PdMgAlZr four-component hydrotalcite compound; 150～200 ℃ of temperature of reaction, liquid air speed 2.4～9.6ml/g
CatH, hydrogen ketone mol ratio is 0.5～2, gas-phase one-stage method synthesize methyl-isobutyl ketone and diisobutyl ketone in fixed-bed reactor.
Described method by acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone is with ZrO
2Add in the catalyzer, make Pd/MgO-Al take the PdMgAlZr four-component hydrotalcite compound that contains Zr as presoma
2O
3-ZrO
2Catalyzer.
Advantage of the present invention and effect are:
(1) adopt PdMgAlZr four-component hydrotalcite presoma that Zr is introduced in the catalyzer.(2) catalyst preparation process is simple, is suitable for scale operation.(3) on catalyzer of the present invention, the transformation efficiency of acetone reaches as high as 30～73%, and the selectivity of methyl iso-butyl ketone (MIBK) can reach 49～78%, and the selectivity of diisobutyl ketone can reach 13～30%.(4) add ZrO
2After, catalyzer has suitable acid-basicity, and activity is higher.(5) this catalyzer can prepare methyl iso-butyl ketone (MIBK) and two kinds of products of diisobutyl ketone simultaneously.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
It is that the method for catalyst precursor is introduced Zr in the catalyzer that the present invention adopts to contain the Zr houghite, regulates catalyst acid alkalescence to reach, and obtains active good catalysis acetone gas-phase one-step method synthesize methyl-isobutyl ketone and the catalyzer of diisobutyl ketone.The present invention adopts coprecipitation method take metal-nitrate solutions as starting soln, has prepared PdMgAlZr four-component hydrotalcite presoma in pH=9～10, obtains Pd/MgO-Al after the roasting
2O
3-ZrO
2Catalyzer consists of: Pd:1wt%, MgO:55wt%, Al
2O
3: 10wt%, ZrO
2: 34wt%, 150～200 ℃ of temperature of reaction, liquid air speed 2.4～9.6ml/g
CatH, hydrogen ketone mol ratio is under 0.5～2 the operational condition, gas-phase one-step synthesize methyl-isobutyl ketone and diisobutyl ketone in the fixed-bed reactor.
Embodiment 1
Use the distilled water that newly boils to prepare respectively the Pd (NO of 1.0mol/L
3)
2, Mg (NO
3)
2, Al (NO
3)
3And the Zr (NO of 0.5mol/L
3)
4Metal salt solution; Other prepares the NaOH solution of 1.0mol/L and the Na of 0.5mol/L
2CO
3Solution.Form Pd:1wt%, MgO:55wt%, Al according to catalyzer
2O
3: 10wt%, ZrO
2: 34wt%, Pd, Mg, four kinds of nitrate solutions of Al, Zr are made into mixing solutions, solution is designated as A.In beaker, add in advance Na
2CO
3Solution ［ CO
3 2-Molar weight=0.5(Al
3++ Zr
4+) molar weight, solution A and NaOH solution are titrated in the beaker simultaneously, the control rate of addition, and constantly stir, keep pH between 9～10.After dropwising, stirred in 60 ℃ of lower waters bath with thermostatic control aging 12 hours, washing, centrifugal until pH about 7, carries out suction filtration, is put into baking oven with filter cake, and drying is 12 hours under 80 ℃, obtains PdMgAlZr four-component hydrotalcite compound.The PdMgAlZr houghite precursor of preparation is placed retort furnace, at 500 ℃ of lower roasting 4h, obtain Pd/MgO-Al
2O
3-ZrO
2Oxide catalyst.Before the active testing 500 ℃ of lower hydrogen reducings 10 hours.
Get the above-mentioned catalyzer of 2g, the internal diameter of packing into is that the stainless steel fixed-bed reactor of 8mm are estimated, reaction is carried out under normal pressure, bed temperature is controlled at 150～200 ℃, acetone is squeezed into preheater (100 ℃) by micro pump, mix with hydrogen after the gasification, enter reactor and react, the liquid air speed control is built in 4.8ml/g
CatH, hydrogen ketone mol ratio is 1.Reaction product is collected by cold-trap, analyzes with gas-chromatography.Reaction result sees attached list 1.
Embodiment 2
Catalyzer is with embodiment 1,180 ℃ of temperature of reaction, and hydrogen ketone mol ratio is 1, reacts under the different liquid air speed, the results are shown in subordinate list 2.
Embodiment 3
Catalyzer is with embodiment 1,180 ℃ of temperature of reaction, and liquid air speed is 4.8ml/g
CatH reacts under the different hydro ketone mol ratio, the results are shown in subordinate list 3.
The catalytic performance of catalyzer under the subordinate list 1 differential responses temperature
The catalytic performance of catalyzer under the subordinate list 2 different liquid air speed
Subordinate list 3 different H
2The catalytic performance of catalyzer under the/acetone
Claims (2)
1. by the method for acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone, it is characterized in that the method comprises use Pd/MgO-Al
2O
3-ZrO
2Catalyzer consists of: Pd:1wt%, MgO:55wt%, Al
2O
3: 10wt%, ZrO
2: 34wt%; Its catalyzer makes by PdMgAlZr four-component hydrotalcite compound; 150～200 ℃ of temperature of reaction, liquid air speed 2.4～9.6ml/g
CatH, hydrogen ketone mol ratio is 0.5～2, gas-phase one-stage method synthesize methyl-isobutyl ketone and diisobutyl ketone in fixed-bed reactor.
2. the method by acetone gas-phase one-step method synthesize methyl-isobutyl ketone and diisobutyl ketone according to claim 1 is characterized in that ZrO
2Add in the catalyzer, make Pd/MgO-Al take the PdMgAlZr four-component hydrotalcite compound that contains Zr as presoma
2O
3-ZrO
2Catalyzer.
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| CN 201010145264 CN101830787B (en) | 2010-04-13 | 2010-04-13 | Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method |
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| CN 201010145264 CN101830787B (en) | 2010-04-13 | 2010-04-13 | Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method |
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| CN101830787B true CN101830787B (en) | 2013-04-03 |
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ID=42715030
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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 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698761A (en) * | 2012-01-17 | 2012-10-03 | 中国海洋石油总公司 | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application |
| CN104549252B (en) * | 2013-10-22 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of catalyst for synthesizing DIBK and preparation method thereof |
| CN105732305B (en) * | 2016-03-25 | 2018-05-25 | 中南大学 | A kind of preparation method of synthesizing methyl isobutyl ketone and methyl isobutyl alcohol |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666816A (en) * | 1968-10-12 | 1972-05-30 | Sumitomo Chemical Co | Method for production of methyl isobutyl ketone |
| CN1566059A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone |
| CN1566060A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774180B2 (en) * | 1987-12-08 | 1995-08-09 | 三菱化学株式会社 | Method for producing high-grade ketone |
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2010
- 2010-04-13 CN CN 201010145264 patent/CN101830787B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666816A (en) * | 1968-10-12 | 1972-05-30 | Sumitomo Chemical Co | Method for production of methyl isobutyl ketone |
| CN1566059A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for one-step synthesizing methyl isobutyl ketone by catalyzing acetone |
| CN1566060A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone |
Non-Patent Citations (1)
| Title |
|---|
| US 3666816 A, |
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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