CN1080564A - The Catalysts and its preparation method of synthesize methyl-isobutyl ketone - Google Patents
The Catalysts and its preparation method of synthesize methyl-isobutyl ketone Download PDFInfo
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- CN1080564A CN1080564A CN 93105111 CN93105111A CN1080564A CN 1080564 A CN1080564 A CN 1080564A CN 93105111 CN93105111 CN 93105111 CN 93105111 A CN93105111 A CN 93105111A CN 1080564 A CN1080564 A CN 1080564A
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- palladium
- catalyzer
- ion exchange
- exchange resin
- hydrogen
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Abstract
A kind of Catalysts and its preparation method that is used for acetone and hydrogen synthesize methyl-isobutyl ketone, catalyzer is made up of a Hydrogen ion exchange resin and a year palladium activated alumina, palladium content on the activated alumina is 0.05-5.0% (w), and Hydrogen ion exchange resin is 0.1-2.0 with the weight ratio of carrying the palladium activated alumina.This catalyzer is not only active high, and selectivity is good, and has solved traditional year palladium resin catalyst loss of palladium in use, has satisfactory stability.
Description
The present invention relates to a kind of Catalysts and its preparation method by acetone and hydrogen synthesize methyl-isobutyl ketone.
Methyl iso-butyl ketone (MIBK) is a kind of important organic solvent, is used for paint, and cold coating, waxy oil dewaxing also are one of raw materials of producing by rubber antioxidant 4020, and it is of many uses.Shortcomings such as traditional production method is to adopt three step synthetic methods, as the described method of us3.666.816, because process is cumbersome, exists the separation of intermediate to purify, and productive rate is low are progressively replaced (us3.953.517) by one-step synthesis process.One-step technology is to be catalyzer with the Hydrogen ion exchange resin that carries palladium, though this technology improves greatly than three-steps process, but still has the loss of palladium, and poor catalyst stability and catalyzer expend high shortcoming.
The Ger.Pat.1238453 introduction mixes as catalyzer with the gac that carries palladium with Hydrogen ion exchange resin and is used for synthesize methyl-isobutyl ketone, but the transformation efficiency of acetone is low.
Make catalyzer with the activated alumina that carries palladium and also can be used for synthesize methyl-isobutyl ketone, the test situation of being introduced as the special public clear 63-119436 of Japanese Patent, but have the temperature of reaction height, problem such as transformation efficiency is low, and the selectivity of product methyl iso-butyl ketone (MIBK) is bad.
Purpose of the present invention is exactly in order to solve the shortcoming that above-mentioned catalyzer exists, to disclose a kind of loss that should overcome palladium, and is active at low temperatures high, the catalyzer that selectivity is good.
Catalyzer disclosed in this invention is a kind of Hydrogen ion exchange resin and carry a palladium 0.02-5.0%(w) the mixture of activated alumina, its weight ratio is 0.1-2.0.
Said year palladium aluminum oxide, relatively Shi Yi palladium content is 0.05-1.0%(w), 0.1-0.3%(w preferably).A Hydrogen ion exchange resin and a year palladium aluminum oxide, 0.2-2.0 is relatively good for its weight ratio, and the best is 0.4-0.8.
The Hydrogen ion exchange resin that is adopted is ion exchange resin for the strongly acidic styrene, and its preparation method is well-known, can be with reference to us4, and 269,943 methods of introducing.Pore-creating agent is being arranged, initiator obtains the polymerization bead by vinylbenzene and divinylbenzene in the aqueous phase suspension polymerization that contains dispersion agent under existing, purified then, halogenation, sulfonation and active group stabilization promptly get Hydrogen ion exchange resin, the performance index of the used Hydrogen ion exchange resin of the present invention are as follows: exchange capacity 4.46meq/g(does), wet density 0.75g/ml(is wet) percentage of water loss 61.86%.
Carry the palladium activated alumina catalyst and can adopt conventional dipping method, prepare certain density palladium salt brine solution on request, palladium salt can be Palladous nitrate or Palladous chloride, activated alumina put into contain palladium solution, soak for some time after-filtration, drying, roasting, promptly get and carry the palladium aluminium oxide catalyst, its palladium content 0.02-5.0%(w), the aluminum oxide performance that is adopted: specific surface 150-250m
2/ g, pore volume 0.3-0.7ml/g, mean pore size 50-150m
-10, specific surface is 180-190m preferably
2/ g, pore volume is preferably 0.5-0.6ml/g, and average pore diameter is 100-120m preferably
-10, its shape can be spherical or strip.
Hydrogen ion exchange resin is mixed the catalyzer that promptly can be used as synthesize methyl-isobutyl ketone with a year palladium aluminum oxide, both ratios are 0.2-2.0, the content that is lower than Virahol in 0.2 o'clock product increases, be higher than that mesityl oxide (MO) content increases in 2.0 o'clock products, Hydrogen ion exchange resin is 0.4-0.8 with the optimum proportion that contains the palladium aluminum oxide, and reaction process is described below:
When mixed catalyst uses, palladous oxide on the aluminum oxide will become palladium metal with hydrogen reducing, method of reducing can adopt conventional hydrogen reducing, normal temperature reduces or adds thermal reduction all can, but the thermal reduction temperature should not be above 120 ℃, but normal pressure during reduction also can pressurize, and the catalyzer after the reduction is not wanted ingress of air.
Reaction process can adopt intermittent type or continuous reaction, and reactor can also can be used overflow bed, the most handy trickle bed, easy handling with trickle bed.
Temperature of reaction 60-200 ℃, preferably be controlled at 100-200 ℃; Reaction pressure 3.0-10.0MPa is preferably 3.0-7.0MPa; Acetone feed volume space velocity 0.2-5.0h
-1, be preferably 0.5-2.0h
-1; The inlet amount of hydrogen can change in a big way, but hydrogen ketone is than not being lower than 0.5(mol).
When adopting continuous tubular reactor the filling of catalyzer can be earlier with two kinds of catalyst mix reactor of packing into after evenly, also can layering pack into and promptly contain palladium aluminum oxide and the acidic ion exchange resin reactor of alternately packing into respectively, make it in reactor, to be lamelliform, but the reactor of packing into after had better mixing.
Catalyzer of the present invention has not only overcome the palladium loss that resin catalyst exists, and the shortcoming of poor stability has also overcome the temperature of reaction height of palladium aluminium oxide catalyst existence in single year, the deficiency of poor selectivity simultaneously.Has good activity, selectivity and stability.And can reduce catalyst consumption and the energy consumption that methyl iso-butyl ketone (MIBK) is produced.
Embodiment 1
With 80g γ-Al
2O
3(water-intake rate 75%) immerses 160ml and contains in the palladium nitrate aqueous solution of palladium 0.12g, soaks 24 hours after-filtration, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 2 hours 480 ℃ of following roastings 4 hours, promptly get the activated alumina that carries palladium again, palladium content 0.15%(w), catalyzer called after HKC-1.
Embodiment 2
With 80 gram γ-Al
2O
3(water-intake rate 75%) immerses 160ml and contains in the palladium nitrate aqueous solution of palladium 0.4g, and other are with embodiment 1, and the palladium content that makes is 0.5%(w), catalyzer called after HKC-2.
Embodiment 3
With 80g γ-Al
2O
3(water-intake rate 75%) immerses 160ml and contains in the palladium nitrate aqueous solution of palladium 0.08g, and other palladium content that make with embodiment 1 are 0.1%, called after HKC-3.
Embodiment 4
The 50ml Hydrogen ion exchange resin (butt 20g) that drying is crossed and 37g embodiment 1～3 be described contain palladium aluminum oxide (being broken into the 8-20 order before the use) and mix after again with evenly pack into after the dilution white steel pipe type reactor of internal diameter 25mm of 100ml10-40 purpose quartz sand, raw material acetone, hydrogen enters from reactor top, product is through cooling and gas-liquid separation, vapor phase hydrogen emptying or recycle the liquid-phase product gas chromatographic analysis.At hydrogen and acetone than being 500(V) gained test-results such as table 1 under (molecular ratio is 0.84) condition.
Embodiment 5
Containing the palladium aluminum oxide adopts the HKC-1 catalyzer to be 500(V at hydrogen and acetone ratio) (molecular ratio 0.84), acetone feed air speed 1.0h
-1, reaction pressure be 6.0MPa other with embodiment 4, carried out long stability running its result such as table 2.
Table 2
| Continuous operation time h -1 | Temperature of reaction ℃ | Acetone conversion % | Product selectivity % MI BK |
| 100 300 600 800 1000 1010 1300 | 130 130 130 130 130 135 135 | 42.61 42.69 40.55 40.26 40.15 42.59 42.65 | 94.43 93.41 94.92 92.99 93.29 94.20 94.01 |
Embodiment 6
Hydrogen ion exchange resin 2ml(0.6g), HKC-1 catalyzer 4.8g is broken into the 16-20 order, and both mix, the two weight ratio is 0.125, pack in the white steel pipe reactor of internal diameter 19mm, reaction raw materials hydrogen is 500(V with the ratio of acetone), test-results such as table 3.
Table 3
| Temperature of reaction ℃ | Reaction pressure MPa | Air speed h -1 | Acetone conversion % | Product selectivity, % | |||
| MI?BK | IPA | MO | Other | ||||
| 120 140 | 6.0 6.0 | 1.0 1.0 | 31.82 48.30 | 63.85 66.15 | 31.92 26.85 | 0.82 1.17 | A small amount of |
Embodiment 7
Hydrogen ion exchange resin 8ml(2.4g), HKC-1 catalyzer 1.2g is broken into the 16-20 order, and the two ratio is 2.0, and other are with embodiment 6, and test-results is a table 4.
Table 4
| Temperature of reaction ℃ | Reaction pressure MPa | Air speed h -1 | Acetone conversion % | Product selectivity, % | |||
| MI?BK | IPA | MO | Other | ||||
| 120 140 | 6.0 6.0 | 1.0 1.0 | 16.83 23.12 | 59.71 65.77 | A small amount of | 31.59 13.26 | A small amount of |
Claims (3)
1, a kind of is the catalyzer of raw material synthesize methyl-isobutyl ketone with acetone and hydrogen, it is characterized in that be that the activated alumina of 0.02-5.0% (W) is formed by Hydrogen ion exchange resin with carrying the palladium amount, and both weight ratios are 0.1-2.0.
2, according to claim 1 year palladium aluminum oxide, reasonable palladium content is 0.05-1.0%(w), the best is 0.1-0.3%(w).
3, a Hydrogen ion exchange resin according to claim 1 and a year palladium aluminum oxide, its weight ratio 0.2～2.0 is relatively good, and the best is 0.4～0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105111 CN1080564A (en) | 1993-05-04 | 1993-05-04 | The Catalysts and its preparation method of synthesize methyl-isobutyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105111 CN1080564A (en) | 1993-05-04 | 1993-05-04 | The Catalysts and its preparation method of synthesize methyl-isobutyl ketone |
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| Publication Number | Publication Date |
|---|---|
| CN1080564A true CN1080564A (en) | 1994-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93105111 Pending CN1080564A (en) | 1993-05-04 | 1993-05-04 | The Catalysts and its preparation method of synthesize methyl-isobutyl ketone |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101269C (en) * | 1999-09-17 | 2003-02-12 | 中国石油化工集团公司 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
| CN1114585C (en) * | 1998-04-16 | 2003-07-16 | 中国石化金陵石油化工公司 | Bimetal resin type catalyst and its preparing process |
| 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) |
| CN114436794A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for synthesizing methyl isoamyl ketone |
| CN116041158A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one |
-
1993
- 1993-05-04 CN CN 93105111 patent/CN1080564A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114585C (en) * | 1998-04-16 | 2003-07-16 | 中国石化金陵石油化工公司 | Bimetal resin type catalyst and its preparing process |
| CN1101269C (en) * | 1999-09-17 | 2003-02-12 | 中国石油化工集团公司 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
| 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) |
| CN114436794A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for synthesizing methyl isoamyl ketone |
| CN116041158A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing methyl isobutyl ketone by liquid phase hydrogenation of 4-methyl-3-pentene-2-one |
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