CN103801338B - Catalyst for preparing methyl isobutyl ketone and preparation method - Google Patents
Catalyst for preparing methyl isobutyl ketone and preparation method Download PDFInfo
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- CN103801338B CN103801338B CN201210440218.XA CN201210440218A CN103801338B CN 103801338 B CN103801338 B CN 103801338B CN 201210440218 A CN201210440218 A CN 201210440218A CN 103801338 B CN103801338 B CN 103801338B
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Abstract
The invention discloses a catalyst for preparing methyl isobutyl ketone, which adopts nickel as an active component, adopts manganese sulfate and/or chromium sulfate, preferably manganese sulfate, as auxiliary agents, and adopts alumina as a carrier. The catalyst comprises, on a basis that the total weight is 100% of, 5 wt%-15 wt%, preferably 5 wt%-10 wt%, of nickel elements, 1 wt%-3.5 wt%, preferably 1.5 wt%-2.5 wt%, of auxiliary agents, and the balance of alumina carriers. The catalyst has a specific surface area of 90-130 m2/g, and a pore volume of 0.7-1.2 ml/g. The preparation method of the catalyst comprises the following steps: (1) dipping the alumina carrier in a nickel-containing soluble salt solution, performing drying and roasting to obtain a nickel-containing alumina carrier; (2) preparing a sulfate solution, spraying the nickel-containing alumina carrier obtained in step (1) with the sulfate solution, and then drying to obtain the product. The catalyst of the invention is used in reaction for synthesizing methyl isobutyl ketone by an acetone one-step method; when compared with catalysts of the same kind, the catalyst of the invention improves the acetone conversion rate and the methyl isobutyl ketone selectivity.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of Catalysts and its preparation method for Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone.
Background technology
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of excellent organic solvent, has excellent dissolubility, stable chemical performance.Being mainly used in paint, cold coating, is also one of raw material of synthetic rubber age resistor.Also be used as to produce medicine, adhesive and rare metal extractant simultaneously.Along with the fast development of auto industry and high-grade paint, the demand of methyl iso-butyl ketone (MIBK) is constantly increased.
The conventional method of acetone synthesizing methyl isobutyl ketone is three-step approach, there is the problems such as environmental pollution, flow process is numerous and diverse, production cost is high.
At present, be state-of-the-art technical method by the method for acetone one-step synthesis methyl iso-butyl ketone (MIBK).The main process of acetone through one-step method is: acetone and hydrogen, under the asynchronous cooperation effect of bifunctional catalyst, condensation, dehydration and hydrogenation reaction occur, and generate methyl iso-butyl ketone (MIBK).Catalyst for this technology is mainly divided into following two classes: the first kind is the palladium-resin catalyst be widely used, such catalyst poor heat stability, and catalyst regeneration difficulty, operating condition control overflow is harsh.Equations of The Second Kind is organic catalyst, and this kind of catalytic benefits is that active component not easily runs off, not etching apparatus.This kind of catalyst can be divided into again noble metal type and base metal type.Noble metal type is mainly with Pd/Al
2o
3be main with Pd/ molecular sieve catalyst.Non-precious metal catalyst take nickel as the in the majority of active component.Be wherein the catalyst of active component with nickel, due to cheap and have good application prospect and competitiveness.The Raney nickel of current report has: Ni/Al
2o
3, Ni/MgO, Ni/CaO, Ni/MgAl hydrotalcite etc.Catalyst is by infusion process, coprecipitation or prepare NiMgAl hydrotalcite as precursor by coprecipitation, and roasting obtains.
CN101875012A and CN101712606A describes a kind of for Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone, take nickel as the catalyst of active component.The method uses Ni/MgO-Al
2o
3-ZrO
2catalyst.Catalyst consist of Ni:4wt% and 6wt%, MgO:53wt% and 60 wt%, Al
2o
3: 43wt% and 21wt%.Catalyst is obtained by reconstruct NiMgAl houghite compound.Synthetic reaction is carried out in fixed bed reactors.Catalyst is when obtaining acetone maximum conversion 70.56%, and the selective of methyl iso-butyl ketone (MIBK) only has 39.9%, and when methyl iso-butyl ketone (MIBK) reaches most high selectivity 69.47%, acetone conversion is 49.46%.Activity, selective the awaiting of this catalyst are improved.
Summary of the invention
For prior art Problems existing, the invention provides a kind of catalyst for the preparation of methyl iso-butyl ketone (MIBK) and preparation method.Catalyst of the present invention is used for, in the reaction of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone, comparing similar catalyst, improves the selective of acetone conversion and methylisobutylketone.
For the preparation of a catalyst for methyl iso-butyl ketone (MIBK), nickel is active component, and manganese sulfate and/or chromium sulfate are auxiliary agent, and be preferably manganese sulfate, aluminium oxide is carrier.Catalyst is in gross weight 100%, and wherein nickel element is 5wt% ~ 15wt%, preferred 5wt% ~ 10wt%, and auxiliary agent is 1wt% ~ 3.5wt%, preferred 1.5wt% ~ 2.5wt%, and surplus is alumina support.Wherein alumina support is the α-Al of 5 ~ 20wt%
2o
3with the γ-Al of 80 ~ 95wt%
2o
3the mixed carrier of composition.The specific area of catalyst is at 90 ~ 130m
2between/g, pore volume is between 0.7 ~ 1.2ml/g.
The preparation method of a kind of catalyst for the preparation of methyl iso-butyl ketone (MIBK) of the present invention, comprises following content:
(1) nickeliferous soluble salt solutions is used, oxide impregnation alumina supporter, after filtration, dry, roasting, obtained nickeliferous alumina support;
(2) prepare sulfate liquor, the alumina carrier containing Ni that step (1) obtains is sprayed, then dry, obtained product.
Nickeliferous soluble-salt described in the inventive method step (1) is one or more in nitrate, acetate and sulfate, preferred nickel nitrate.
Drying condition in the inventive method step (1) is: drying 4 ~ 8 hours at 90 ~ 120 DEG C.Roasting condition is: roasting 4 ~ 8 hours at 350 ~ 450 DEG C.
In the inventive method step (2), sulfate is manganese sulfate and/or chromium sulfate.
Drying condition in the inventive method step (2) is: at 110 ~ 140 DEG C 6 ~ 8 hours.
Alumina support of the present invention can be prepared into suitable particle shape according to the needs used, as made bar shaped, spherical or cylindrical etc.Active component content can be determined according to response situation, generally changes the content of active component by reconciling impregnation concentration.
Catalyst of the present invention needs before use at 350 ~ 450 DEG C of temperature, and reduce 4 ~ 6 hours under hydrogen existence condition, during reduction, hydrogen gas space velocity is 100 ~ 150h
-1, adopt reduction in device, the catalyst after reduction completely cuts off air and preserves.Catalyst of the present invention is applicable to successive reaction or intermittent reaction.
Catalyst of the present invention can be applied to the reaction of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone.Catalyst application of the present invention is in the reaction of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone, and good process conditions are: reaction temperature 180 ~ 230 DEG C, reaction pressure 2 ~ 4MPa, and acetone feed air speed is 2.5 ~ 3.5h
-1(V), H
2/ acetone (V/V) 400 ~ 800.
In catalyst of the present invention, institute's adding assistant is manganese sulfate and/or chromium sulfate, and this auxiliary agent is also finally exist with the form of sulfate, effectively can stop polymerisation and occur, and reduces the generation of acetone trimerization product DIBK, improves the selective of catalyst.Catalyst of the present invention adopts α-Al
2o
3with γ-Al
2o
3the mixed carrier of composition, reduces the acidity of catalyst, reduces the polymerizable functional of catalyst, reduces the generation of acetone trimerization product DIBK, improves the selective of catalyst.When the conversion ratio of acetone is 49.87%, the selective of methyl iso-butyl ketone (MIBK) is 73.53%, and the yield of methyl iso-butyl ketone (MIBK) is 36.67%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.Carrier used in embodiment is the α-Al containing 15wt% if no special instructions
2o
3with the γ-Al of 85wt%
2o
3mixed oxidization alumina supporter, specific area is 120m
2/ g, pore volume is 1.2mL/g.
Embodiment 1
By 60 grams of Ni (NO
3) 7H
2o joins in 200mL distilled water and is made into the aqueous solution, with this solution impregnation 60 grams of alumina supports, floods 4 hours.Pour out raffinate, 100 DEG C of dryings 6 hours after being dried by the carrier flooding nickel, then in atmosphere in 380 DEG C of roastings 6 hours, make nickeliferous carrier Z-1.
By 0.45 gram of MnSO
44H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays on 20 grams of nickeliferous carrier Z-1, and in 110 DEG C of dryings 8 hours, obtained catalyst C-1.This catalyst is nickeliferous is 5wt%, MnSO
4be 1.5 wt%.
Comparative example 1
By 60 grams of Ni (NO
3) 7H
2o joins in 200mL distilled water and is made into the aqueous solution, with this solution impregnation 60 grams of γ-Al
2o
3carrier, floods 4 hours.Pour out raffinate, 100 DEG C of dryings 6 hours after being dried by the carrier flooding nickel, then in atmosphere in 380 DEG C of roastings 6 hours, make nickeliferous carrier A-1.
By 0.42 gram of Mn (NO
3)
24H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays in 20 grams of nickeliferous carrier A-1, and in 110 DEG C of dryings 8 hours, obtained catalyst B-1.This catalyst is nickeliferous is 5wt%, Mn (NO
3)
2for 1.5wt%.
Comparative example 2
The preparation of nickeliferous carrier is with comparative example 1.
By 0.45 gram of MnSO
44H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays in 20 grams of nickeliferous carrier A-1, and in 110 DEG C of dryings 8 hours, obtained catalyst B-2.This catalyst is nickeliferous is 5wt%, MnSO
4be 1.5 wt%.
Embodiment 2
By 100 grams of Ni (NO
3) 7H
2o joins in 200mL distilled water and is made into the aqueous solution, with this solution impregnation 60 grams of carriers, floods 6 hours.Pour out raffinate, 110 DEG C of dryings 8 hours after being dried by the carrier flooding nickel, then in atmosphere in 400 DEG C of roastings 8 hours, make nickeliferous carrier Z-2.
By 0.6 gram of MnSO
44H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays on 20 grams of nickeliferous carrier Z-2, and in 120 DEG C of dryings 8 hours, obtained catalyst C-2.This catalyst is nickeliferous is 7wt%, MnSO
4for 2wt%.
Embodiment 3
By 70 grams of Ni (NO
3) 7H
2o joins in 100mL distilled water and is made into the aqueous solution, with this solution impregnation 30 grams of alumina supports, floods 6 hours.Pour out raffinate, 100 DEG C of dryings 6 hours after being dried by the carrier flooding nickel, then in atmosphere in 420 DEG C of roastings 6 hours, make nickeliferous carrier Z-3.
By 0.6 gram of MnSO
44H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays on 20 grams of nickeliferous carrier Z-3, and in 130 DEG C of dryings 8 hours, obtained catalyst B-3.This catalyst is nickeliferous is 10wt%, MnSO
4be 2 wt%.
Embodiment 4
The preparation of nickeliferous carrier is with embodiment 2.
By 0.51 gram of Cr
2(SO
4)
36H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays on 20 grams of nickeliferous carrier Z-2, and in 110 DEG C of dryings 8 hours, obtained catalyst C-4.This catalyst is nickeliferous is 7wt%, Cr
2(SO
4)
3for 2wt%.
Embodiment 5
By 100 grams of Ni (NO
3) 7H
2o joins in 100mL distilled water and is made into the aqueous solution, with this solution impregnation 30 grams of alumina supports, floods 6 hours.Pour out raffinate, 120 DEG C of dryings 6 hours after being dried by the carrier flooding nickel, then in atmosphere in 430 DEG C of roastings 8 hours, make nickeliferous carrier Z-5.
By 0.75 gram of MnSO
44H
2o is dissolved in 15mL distilled water and is made into the aqueous solution, then sprays on 20 grams of nickeliferous carrier Z-4, and in 110 DEG C of dryings 8 hours, obtained catalyst C-5.This catalyst is nickeliferous is 14wt%, MnSO
4be 2.5 wt%.
Embodiment 6
Catalyst C-1 is loaded reactor, adopts reducing process reduction in device.Reducing condition is: reduce 6 hours under 400 DEG C of hydrogen existence conditions, during reduction, hydrogen gas space velocity is 120h
-1.
Raw material acetone, hydrogen enter from reactor bottom, product through cooling and gas-liquid separation, vapor phase hydrogen emptying or recycle, liquid-phase reaction product gas chromatographic analysis.Reaction temperature is 190 DEG C, and pressure is 2.5MPa, and acetone feed air speed is 2.5h
-1, H
2/ acetone (V/V) is 500.
Embodiment 7
With method evaluate catalysts C-2, C-3, C-4, C-5, B-1 and B-2 respectively of embodiment 6.Relatively the performance of different catalysts, the results are shown in Table 1.
Table 1 catalyst performance evaluation.
| Catalyst | Acetone conversion, % | Methylisobutylketone is selective, % | Methylisobutylketone yield, % |
| C-1 | 49.87 | 73.53 | 36.67 |
| C-2 | 56.43 | 70.77 | 39.94 |
| C-3 | 62.52 | 69.69 | 43.57 |
| C-4 | 56.06 | 68.04 | 38.14 |
| C-5 | 72.67 | 60.73 | 44.13 |
| B-1 | 49.18 | 61.95 | 30.47 |
| B-2 | 49.30 | 70.75 | 34.88 |
As can be seen from the table, the activity of the catalyst obtained by the present invention, yield that is selective and methyl iso-butyl ketone (MIBK) compared with prior art have raising by a relatively large margin.
Claims (11)
1. for the preparation of a catalyst for methyl iso-butyl ketone (MIBK), it is characterized in that: nickel is active component, manganese sulfate and/or chromium sulfate are auxiliary agent, aluminium oxide is carrier, and catalyst is in gross weight 100%, and wherein nickel element is 5wt% ~ 15wt%, auxiliary agent is 1wt% ~ 3.5wt%, and surplus is alumina support.
2. catalyst according to claim 1, is characterized in that: catalyst is in gross weight 100%, and nickel element is 5wt% ~ 10wt%, and auxiliary agent is 1.5wt% ~ 2.5wt%, and surplus is alumina support.
3. catalyst according to claim 1, is characterized in that: the specific area of catalyst is at 90 ~ 130m
2between/g, pore volume is between 0.7 ~ 1.2ml/g.
4. catalyst according to claim 1, is characterized in that: alumina support is the α-Al of 5 ~ 20wt%
2o
3with the γ-Al of 80 ~ 95wt%
2o
3the mixed carrier of composition.
5. a preparation method for catalyst according to claim 1, is characterized in that comprising following content:
(1) nickeliferous soluble salt solutions is used, oxide impregnation alumina supporter, drying, roasting, obtained nickeliferous alumina support;
(2) prepare sulfate liquor, the alumina carrier containing Ni that step (1) obtains is sprayed, then dry, obtained product.
6. preparation method according to claim 5, is characterized in that: the nickeliferous soluble-salt described in step (1) is one or more in nitrate, acetate and sulfate.
7. preparation method according to claim 5, is characterized in that: the drying condition in step (1) is: drying 4 ~ 8 hours at 90 ~ 120 DEG C, roasting condition is: roasting 4 ~ 8 hours at 350 ~ 450 DEG C.
8. preparation method according to claim 5, is characterized in that: in step (2), sulfate is manganese sulfate and/or chromium sulfate.
9. preparation method according to claim 5, is characterized in that: the drying condition in step (2) is: at 110 ~ 140 DEG C 6 ~ 8 hours.
10. the application of catalyst according to claim 1 in the reaction of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone.
11. application according to claim 10, it is characterized in that process conditions are: reaction temperature 180 ~ 230 DEG C, reaction pressure 2 ~ 4MPa, acetone feed volume space velocity is 2.5 ~ 3.5h
-1, H
2/ acetone volume ratio is 400 ~ 800.
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| CN107930638B (en) * | 2016-10-13 | 2020-02-18 | 中国石油化工股份有限公司 | Copper-based catalyst for synthesizing methyl isobutyl ketone by acetone one-step method |
| CN116041158B (en) * | 2021-10-28 | 2024-08-09 | 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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| CN1081937A (en) * | 1992-08-13 | 1994-02-16 | 中国石油化工总公司抚顺石油化工研究院 | The catalyzer and the method for making of Virahol synthesize methyl-isobutyl ketone/diisobutyl ketone |
| CN1289754A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for synthesizing methyl isobutanone from acetone |
| CN101712606A (en) * | 2009-11-24 | 2010-05-26 | 沈阳化工学院 | Process for producing methylisobutylketone and diisobutyl ketone by using acetone |
| CN101875012A (en) * | 2010-04-13 | 2010-11-03 | 沈阳化工学院 | Method for preparing Ni/MgO-Al2O3 catalyst for coproduction of methylisobutylketone and diisobutylketone |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5554201B2 (en) * | 2009-11-25 | 2014-07-23 | ローム アンド ハース カンパニー | Metal alloy catalyst composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081937A (en) * | 1992-08-13 | 1994-02-16 | 中国石油化工总公司抚顺石油化工研究院 | The catalyzer and the method for making of Virahol synthesize methyl-isobutyl ketone/diisobutyl ketone |
| CN1289754A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for synthesizing methyl isobutanone from acetone |
| CN101712606A (en) * | 2009-11-24 | 2010-05-26 | 沈阳化工学院 | Process for producing methylisobutylketone and diisobutyl ketone by using acetone |
| CN101875012A (en) * | 2010-04-13 | 2010-11-03 | 沈阳化工学院 | Method for preparing Ni/MgO-Al2O3 catalyst for coproduction of methylisobutylketone and diisobutylketone |
| 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 |
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