CN1125018C - Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst - Google Patents
Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst Download PDFInfo
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- CN1125018C CN1125018C CN00108059A CN00108059A CN1125018C CN 1125018 C CN1125018 C CN 1125018C CN 00108059 A CN00108059 A CN 00108059A CN 00108059 A CN00108059 A CN 00108059A CN 1125018 C CN1125018 C CN 1125018C
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Abstract
The present invention relates to a reaction process for jointly producing methyl isobutyl ketone and diisobutyl ketone, which is characterized in that a normal-pressure one-step vapor phase process is adopted for synthesis, a mixture of isopropyl alcohol or isopropyl alcohol and propanone is adopted as a raw material, and a composite catalyst is added. The composite catalyst is characterized in that ZnO is adopted as a main body, is loaded with CuO and is mixed with macroporous Al2O3, and the catalyst comprises 20 to 80% of ZnO, 20 to 60% of CuO and 10 to 50% of Al2O3. The present invention has the advantage that methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK) are jointly produced and synthesized in one step, and the present invention has the characteristics of high activity, good selectivity, etc. The conversion rate of isopropyl alcohol can reach more than 90%, and the selectivity of methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK) can respectively reach 30%.
Description
The present invention relates to be used for the reaction process and the employed catalyzer of coproducing methyl isobutyl ketone and diisobutyl ketone.
Methyl iso-butyl ketone (MIBK) and diisobutyl ketone have good solubility property, it is important senior organic solvent, can be used as the solvent of the senior paint of automobile specified, and in cellulose-type coating such as printing ink, paint, Resins, epoxy, tackiness agent, nitrated silk floss, ethyl cellulose and resin type coating etc. are produced, use.Methyl iso-butyl ketone (MIBK) also can be used for producing multiple derived product, and extracting aspects such as precious metal, medicine, agricultural chemicals in oil dewaxing, tape production, metal ore dressing all has application extremely widely.Nineteen sixty-eight, methyl iso-butyl ketone (MIBK) realized suitability for industrialized production, at present, about 20～250,000 tons/year of worldwide production, the main place of production is the U.S., Japan and West Europe.There is the Yi Siman chemical company in the manufacturer of the U.S., exxon chemical company and union carbide corporation, and overall throughput is 9.75 ten thousand tons/year; There are Mitsui Petrochemical Ind., Ltd., Mitsubishi Chemical Ind and consonance oiling company in the manufacturer of Japan, and overall throughput is about 2.7 ten thousand tons/year; There are Rheinpreussen and Veba Chemie company in the important manufacturer of Germany, and overall throughput is about 3.9 ten thousand tons/year.The production method of methyl iso-butyl ketone (MIBK) can be divided into liquid phase method and vapor phase process by response behaviour; Can be divided into by raw material: isopropanol method, acetone-isopropanol method, acetone method, 4-propyl group amylene method.Can be divided into three-step approach, two step method and single stage method again by processing step.Up to now, the methyl iso-butyl ketone (MIBK) production method that has researched and developed out in the laboratory mainly contains acetone three-step approach and single stage method, CO-acetone method, isopropanol method, acetone-isopropanol method and 4-propyl group amylene method etc., wherein based on acetone three-step approach and single stage method, all the other each production technique are eliminated just gradually.(1) acetone three-step approach: the main production before this genealogy of law the seventies accounts for Gross World Product more than 70%.At alkaline catalysts such as Ba (OH)
2Or Ca (OH)
2Effect under, condensation of acetone changes into diacetone alcohol, then under an acidic catalyst effect, the diacetone alcohol dehydration generates mesityl oxide, repeated hydrogenation generates methyl iso-butyl ketone (MIBK).The whole process of production handiness is big, can produce diacetone alcohol, mesityl oxide and three kinds of products of methyl iso-butyl ketone (MIBK) according to the market requirement, but long flow path, investment is big, production cost is high and the easy poison deactivation of hydrogenation catalyst.(2) acetone single stage method: single stage method research in the world started from the sixties, and a company by Germany realizes suitability for industrialized production in nineteen sixty-eight the earliest, and also there was the report that adopts single stage method production methyl iso-butyl ketone (MIBK) in Japan in 1977.Along with nearest twenty or thirty year the developing rapidly of catalyzer, acetone single stage method production methyl iso-butyl ketone (MIBK) becomes possibility in industrial popularizing.The employed Mg-Si-Pd of original research etc. contains the mixed catalyst of palladium and employed afterwards TiO
2-SnO
2-Ni catalyzer all exists the too much shortcoming of byproduct of reaction.Until the eighties, the catalyst system that external exploitation again makes new advances is as CeO
2-Pd/C, Nb
2O
5-PdCl
2, Ti-Sn-Fe-Al-Ce-Nb etc. the anhydrous metal oxide compound, the too much problem of by product is solved effectively.Therefore the production equipment invested to build later on of the eighties adopts this method more, and the output of single stage method has accounted for 20% of Gross World Product at present.Its concrete steps be liquid acetone through preheating, under catalyst action, at fixed-bed reactor condensation, dehydration and a hydrogenation, promptly above-mentioned three the reaction one the step finishes.Characteristics such as this method flow process is short, investment is little, transformation efficiency is high, production cost is low.From the technical standpoint analysis, the exploitation of acetone three-steps process early, and is also ripe, still occupies an leading position industrial at present.The performance that focuses on continually developing and improving the selection hydrogenation catalyst of three-step approach research from now on, and strengthen its anti-poisoning capability, increase the service life.The direction of single stage method then is further research and exploitation high-performance, bifunctional catalyzer, and in the hope of reaching under the processing condition of non-harshness with high selectivity and transformation efficiency one-step synthesis methyl iso-butyl ketone (MIBK), thereby shortened process improves product yield.The current main direction of studying of this method is relevant reaction process technology and the high performance catalyst thereof of developing high reactivity, highly selective, high stability, high mechanical strength, being convenient to the technical scale manufacturing.
The objective of the invention is to develop a kind of reaction process and catalyzer thereof that is used for coproducing methyl isobutyl ketone and diisobutyl ketone, this technology adopts the normal pressure one-step vapor phase process synthetic, operational condition mitigation, product yield height, catalyst stability is good, intensity is high, technology is simple, is easy to industry's enlarging production.
Technical scheme of the present invention: a kind of reaction process that is used for coproducing methyl isobutyl ketone and diisobutyl ketone, it is characterized in that its employing normal pressure one-step vapor phase process is synthetic, its raw material adopts Virahol or Virahol and acetone mixture, add composite catalyst, temperature of reaction is 200-350 ℃, and the raw material liq volume space velocity is 0.05-5.0h
-1, reactor adopts continuous fixed bed reactor.
Composite catalyst in a kind of above-mentioned reaction process is characterized in that it is that employing ZnO is a main body, and loaded copper oxide is also sneaked into a kind of macroporous aluminium oxide, and its proportioning is ZnO:33.3-53.3%, CuO:26.7-40%, Al
2O
3: 20-33.3%, add releasing agent, will be through the mix powder granulation of above-mentioned processing, compression molding on sheet-punching machine, natural air drying was dried 5-20 hour down at 80-150 ℃, and 300-500 ℃ of following roasting, activation obtained composite catalyst in 5-10 hour.
Technique effect of the present invention and superiority: 1, a step coproduction synthesize methyl-isobutyl ketone and a diisobutyl ketone.Have characteristics such as activity is high, selectivity is good, the Virahol transformation efficiency can reach more than 90%, and methyl iso-butyl ketone (MIBK) and diisobutyl ketone selectivity can reach 30% respectively; 2, employed catalyst life is long, intensity is high, and this kind catalyzer is easy to accomplish the repeatability preparation on the preparation method, be convenient to industrial-scale production.
Further specify present technique below in conjunction with embodiment.
Embodiment 1:
Preparation of Catalyst: 1) measuring 251 milliliters of the copper nitrate solutions of 1 mol, is that 1: 1 proportioning adds ZnO powder 20 grams by CuO and ZnO weight ratio;
2) at normal temperatures, mix 24 hours; In rotatory evaporator, evaporate drying;
3) press mixture and Al
2O
3Weight ratio is that 4: 1 proportioning adds Al
2O
3Powder stirs evenly jointly;
4) add a small amount of releasing agent, use the sheet-punching machine punching;
5) at room temperature air-dry more than 24 hours;
6) in baking oven, dried 8 hours down in 120 ℃;
7) in retort furnace, in 400 ℃ of following roastings, activation 5 hours and put to room temperature,
The proportioning of above-mentioned catalyzer is ZnO:40%, CuO:40%, Al
2O
3: 20%;
Reaction process:
Take by weighing 10 milliliters of above-mentioned catalyzer in fixed bed continuous reactor, in 220-300 ℃ of reduction 3 hours, temperature of reaction: 220 ℃, raw material was a Virahol, isopropanol liquid air speed 1.0h under hydrogen stream
-1Reaction product adopts gas chromatographic analysis after condenser is collected, calculate transformation efficiency and the methyl iso-butyl ketone (MIBK) and the diisobutyl ketone selectivity of Virahol.Reaction result sees Table 1.
Embodiment 2:
Is that 1: 1.5 proportioning adds ZnO powder 20 grams with 167 milliliters of the copper nitrate solutions of 1 mol by CuO and ZnO weight ratio, and the proportioning of above-mentioned catalyzer is at Al
2O
3: under 20% the prerequisite, ZnO:48%, CuO:32%.
Embodiment 3:
Is that 1: 2 proportioning adds ZnO powder 20 grams with 125 milliliters of the copper nitrate solutions of 1 mol by CuO and ZnO weight ratio, and the proportioning of above-mentioned catalyzer is at Al
2O
3: under 20% the prerequisite, ZnO:53.3%, CuO:26.7%.The results are shown in Table 1.
Embodiment 4:
With example 1, be mixture and Al
2O
3Weight ratio is that 2: 1 proportioning adds Al
2O
3Powder stirs evenly jointly.The proportioning of above-mentioned catalyzer is at ZnO:33.3%, under the prerequisite of CuO:33.3%, and Al
2O
3: 33.3%.The results are shown in Table 1.
Embodiment 5:
With example 1; Be Al
2O
3Be extraordinary macroporous type, pore volume is more than the 0.7ml/g, and other is with example 1; The results are shown in Table 1.Wherein: methyl iso-butyl ketone (MIBK) is MIBK, and diisobutyl ketone is DIBK
Several main catalyst activity evaluation results of table 1
Embodiment 6:
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Virahol transformation efficiency (mol%) | 99 | 92 | 80 | 90 | 99 |
| MIBK yield (mol%) | 30 | 25 | 20 | 25 | 35 |
| DIBK yield (mol%) | 20 | 15 | 8 | 15 | 25 |
Reaction process is investigated
Catalyzer is with example 1, and temperature of reaction is 250 ℃, and the Virahol transformation efficiency is 99%; The methyl iso-butyl ketone (MIBK) yield is 35%, and the diisobutyl ketone yield is 30%.
Embodiment 7:
Reaction process is investigated
Catalyzer is with example 1, isopropanol liquid air speed 2.0h
-1, the Virahol transformation efficiency is 90%; The methyl iso-butyl ketone (MIBK) yield is 20%, and the diisobutyl ketone yield is 10%.
Embodiment 8:
Reaction process is investigated
Catalyzer is with example 1, and unspent hydrogen reduces before the reaction, and other condition is with example 1, and the Virahol transformation efficiency is 99%; The methyl iso-butyl ketone (MIBK) yield is 28%, and the diisobutyl ketone yield is 18%.
Embodiment 9:
Reaction raw materials is Virahol and acetone mixture, and weight ratio is 1: 1, and catalyzer is with example 1, and other condition is with example 1, and the Virahol transformation efficiency is 99%; The methyl iso-butyl ketone (MIBK) yield is 32%, and the diisobutyl ketone yield is 18%.
Above-mentioned catalyzer has good stability.With the catalyzer in the example 1 is example, with liquid air speed 1.0h
-1, 220 ℃ of temperature of reaction are initial, and the Virahol transformation efficiency is more than 90%, and methyl iso-butyl ketone (MIBK) and diisobutyl ketone selectivity are reacted and were not seen active obviously decline in 1000 hours all greater than 20%.
This catalyzer raw material is easy to get, and is easily manufactured, and the physical strength height can very well adapt to industrial needs.
Claims (10)
1, a kind of reaction process that is used for coproducing methyl isobutyl ketone and diisobutyl ketone, it is characterized in that its employing normal pressure one-step vapor phase process is synthetic, its raw material adopts Virahol or Virahol and acetone mixture, add composite catalyst, it is main body that this composite catalyst adopts ZnO, and loaded copper oxide is also sneaked into a kind of macroporous aluminium oxide, and its proportioning is ZnO:33.3-53.3%, CuO:26.7-40%, Al
2O
3: 20-33.3%, above-mentioned temperature of reaction is 200-350 ℃, the raw material liq volume space velocity is 0.05-5.0h
-1, reactor adopts continuous fixed bed reactor.
2, a kind of composite catalyst is characterized in that it is that employing ZnO is a main body, and loaded copper oxide is also sneaked into a kind of macroporous aluminium oxide, and its proportioning is ZnO:33.3-53.3%, CuO:26.7-40%, Al
2O
3: 20-33.3%, add releasing agent, will be through the mix powder granulation of above-mentioned processing, compression molding on sheet-punching machine, natural air drying was dried 5-20 hour down at 80-150 ℃, and 300-500 ℃ of following roasting, activation obtained composite catalyst in 5-10 hour.
3, by the said composite catalyst of claim 2, it is characterized in that catalyzer is to be finished by following process: 1) measuring 251 milliliters of the copper nitrate solutions of 1 mol, is that 1: 1 proportioning adds ZnO powder 20 grams by CuO and ZnO weight ratio; 2) at normal temperatures, mix 24 hours; In rotatory evaporator, evaporate drying; 3) press mixture and Al
2O
3Weight ratio is that 4: 1 proportioning adds Al
2O
3Powder stirs evenly jointly; 4) add a small amount of releasing agent, use the sheet-punching machine punching; 5) at room temperature air-dry more than 24 hours; 6) in baking oven, dried 8 hours down in 120 ℃; 7) in retort furnace, in 400 ℃ of following roastings, activation 5 hours and put to room temperature, the proportioning of above-mentioned catalyzer was ZnO:40%, CuO:40%, Al
2O
3: 20%.
4, by the said composite catalyst of claim 2, it is characterized in that catalyzer is to be finished by following process: 1) measuring 167 milliliters of the copper nitrate solutions of 1 mol, is that 1: 1.5 proportioning adds ZnO powder 20 grams by CuO and ZnO weight ratio; 2) at normal temperatures, mix 24 hours; In rotatory evaporator, evaporate drying; 3) press mixture and Al
2O
3Weight ratio is that 4: 1 proportioning adds Al
2O
3Powder stirs evenly jointly; 4) add a small amount of releasing agent, use the sheet-punching machine punching; 5) at room temperature air-dry more than 24 hours; 6) in baking oven, dried 8 hours down in 120 ℃; 7) in retort furnace, in 400 ℃ of following roastings, activation 5 hours and put to room temperature, the proportioning of above-mentioned catalyzer was ZnO:48%, CuO:32%, Al
2O
3: 20%.
5, by the said composite catalyst of claim 2, it is characterized in that catalyzer is to be finished by following process: 1) measuring 125 milliliters of the copper nitrate solutions of 1 mol, is that 1: 2 proportioning adds ZnO powder 20 grams by CuO and ZnO weight ratio; 2) at normal temperatures, mix 24 hours; In rotatory evaporator, evaporate drying; 3) press mixture and Al
2O
3Weight ratio is that 4: 1 proportioning adds Al
2O
3Powder stirs evenly jointly; 4) add a small amount of releasing agent, use the sheet-punching machine punching; 5) at room temperature air-dry more than 24 hours; 6) in baking oven, dried 8 hours down in 120 ℃; 7) in retort furnace, in 400 ℃ of following roastings, activation 5 hours and put to room temperature, the proportioning of above-mentioned catalyzer was ZnO:53.3%, CuO:26.7%, Al
2O
3: 20%.
6, by the said composite catalyst of claim 2, it is characterized in that catalyzer is to be finished by following process: 1) measuring 251 milliliters of the copper nitrate solutions of 1 mol, is that 1: 1 proportioning adds ZnO powder 20 grams by CuO and ZnO weight ratio; 2) at normal temperatures, mix 24 hours; In rotatory evaporator, evaporate drying; 3) press mixture and Al
2O
3Weight ratio is that 2: 1 proportioning adds Al
2O
3Powder stirs evenly jointly; 4) add a small amount of releasing agent, use the sheet-punching machine punching; 5) at room temperature air-dry more than 24 hours; 6) in baking oven, dried 8 hours down in 120 ℃; 7) in retort furnace, in 400 ℃ of following roastings, activation 5 hours and put to room temperature, the proportioning of above-mentioned catalyzer was ZnO:33.3%, CuO:33.3%, Al
2O
3: 33.3%.
7, by the said composite catalyst of claim 2, it is characterized in that Al
2O
3Be extraordinary macroporous type, pore volume is more than the 0.7ml/g.
8, by the said a kind of reaction process that is used for coproducing methyl isobutyl ketone and diisobutyl ketone of claim 1, it is characterized in that temperature of reaction is 250 ℃, the Virahol transformation efficiency is 99%; The methyl iso-butyl ketone (MIBK) yield is 35%, and the diisobutyl ketone yield is 30%.
9, by the said a kind of reaction process that is used for coproducing methyl isobutyl ketone and diisobutyl ketone of claim 1, it is characterized in that reaction raw materials is a Virahol, the isopropanol liquid air speed is 2.0h
-1, the Virahol transformation efficiency is 90%; The methyl iso-butyl ketone (MIBK) yield is 20%, and the diisobutyl ketone yield is 10%.
10, by the said a kind of reaction process that is used for coproducing methyl isobutyl ketone and diisobutyl ketone of claim 1, it is characterized in that reaction raw materials is Virahol and acetone mixture, weight ratio is 1: 1, the Virahol transformation efficiency is 99%; The methyl iso-butyl ketone (MIBK) yield is 32%, and the diisobutyl ketone yield is 18%.
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|---|---|---|---|
| CN00108059A CN1125018C (en) | 2000-06-09 | 2000-06-09 | Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00108059A CN1125018C (en) | 2000-06-09 | 2000-06-09 | Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst |
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|---|---|
| CN1273231A CN1273231A (en) | 2000-11-15 |
| CN1125018C true CN1125018C (en) | 2003-10-22 |
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| CN00108059A Expired - Fee Related CN1125018C (en) | 2000-06-09 | 2000-06-09 | Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1931615A1 (en) * | 2005-09-27 | 2008-06-18 | Union Carbide Chemicals & Plastics Technology LLC | Method to make methyl isobutyl ketone and diisobutyl ketone |
| EP2517788B1 (en) * | 2011-04-27 | 2017-11-22 | King Abdulaziz City for Science & Technology (KACST) | Synthesizing and utilizing novel ruthenium nanoparticle-activated charcoal-nano-zinc oxide composite catalyst |
| CN102516027B (en) * | 2011-11-14 | 2014-12-17 | 中国海洋石油总公司 | Method for preparing catalyst for coproducing alcohol and ketone according to acetone hydrogenation method |
| CN103420792A (en) * | 2012-05-14 | 2013-12-04 | 浙江新化化工股份有限公司 | Combined production method of isopropanol and methyl isobutyl ketone |
| CN104588041B (en) * | 2013-11-01 | 2017-02-22 | 中国石油化工股份有限公司大连石油化工研究院 | Palladium/alumina catalyst and preparation method thereof |
| CN103755537B (en) * | 2014-01-14 | 2015-11-04 | 浙江新化化工股份有限公司 | The co-production of a kind of hexone and diisobutyl ketone |
| CN109718786B (en) * | 2017-10-30 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof |
| EP3735401B1 (en) * | 2018-01-04 | 2023-04-26 | GEVO, Inc. | Upgrading fusel oil mixtures over heterogeneous catalysts to higher value renewable chemicals |
| CN111001432A (en) * | 2018-10-08 | 2020-04-14 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof |
| CN115260013B (en) * | 2022-07-20 | 2023-10-20 | 润泰化学（泰兴）有限公司 | Method for one-step synthesis of methyl isobutyl ketone by catalyzing isopropanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704480A (en) * | 1986-08-04 | 1987-11-03 | Allied Corporation | Process for the production of ketones and carbinols |
-
2000
- 2000-06-09 CN CN00108059A patent/CN1125018C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704480A (en) * | 1986-08-04 | 1987-11-03 | Allied Corporation | Process for the production of ketones and carbinols |
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