CN102247855A - Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof - Google Patents

Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof Download PDF

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CN102247855A
CN102247855A CN2011102104571A CN201110210457A CN102247855A CN 102247855 A CN102247855 A CN 102247855A CN 2011102104571 A CN2011102104571 A CN 2011102104571A CN 201110210457 A CN201110210457 A CN 201110210457A CN 102247855 A CN102247855 A CN 102247855A
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sec
butyl alcohol
catalyst
mek
aqueous solution
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房德仁
任万忠
张慧敏
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Yantai University
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Abstract

The invention provides a catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation. In the catalyst, CuO, ZnO, ZrO2 and Al2O3 are used as main active components, and M2O is used as a catalyst modifying agent, wherein the content of each component in percentage by weight is as follows: 20 to 80 percent of Cu, 5 to 40 percent of ZnO, 21 to 40 percent of ZrO, 0.5 to 20 percent of Al2O3, and 0.5 to 8 percent of M2O. The preparation method of the catalyst comprises the following steps: mixing and dissolving soluble salt of copper, soluble salt of zinc, soluble salt of zirconium and soluble salt of aluminum in deionized water; adding an alkaline solution to perform co-precipitation; washing and drying a precipitate mixture after the precipitation is completed; adding the modifying agent or a modifying agent raw material and uniformly mixing; and roasting and tabletting to form the catalyst. According to the catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation, the conversion rate of the sec-butyl alcohol is greatly improved, and the selectivity of the methyl ethyl ketone is remarkably improved.

Description

A kind of sec-butyl alcohol dehydrogenizing prepares the MEK Catalysts and its preparation method
Technical field
The invention discloses a kind of sec-butyl alcohol dehydrogenizing and prepare the MEK Catalysts and its preparation method, belong to technical field of organic synthesis.
Background technology
MEK is a kind of crucial industrial chemicals and organic solvent, and purposes is very extensive.The main method of producing MEK at present is that sec-butyl alcohol dehydrogenizing prepares MEK, adopts CuO-ZnO-Al in this method 2O 3Catalyst.For example publication number is respectively in the Chinese invention patent of CN100360228C and CN1101262C and discloses CuO-ZnO-Al respectively 2O 3Sec-butyl alcohol dehydrogenizing prepares the MEK catalyst.In each method, all relate to the sec-butyl alcohol dehydrogenizing reaction, adopt CuO-ZnO-Al 2O 3The subject matter that catalyst exists is that catalytic activity is lower, and the selectivity of MEK is relatively poor.Therefore, develop high performance sec-butyl alcohol dehydrogenizing catalyst and just seem extremely important.
Summary of the invention
Prepare in order to solve sec-butyl alcohol dehydrogenizing in the above-mentioned prior art that MEK catalyst activity is lower, the problem of the MEK poor selectivity of preparation, the invention provides a kind of sec-butyl alcohol dehydrogenizing and prepare MEK catalyst and this Preparation of catalysts method, this catalyst has not only significantly improved the conversion ratio of sec-butyl alcohol, and has significantly improved the selectivity of MEK.
The present invention is by adopting CuO, ZnO, ZrO 2And Al 2O 3As main active component, use Na simultaneously 2O, K 2O, Li 2O, Cs 2O etc. carry out modification to catalyst to be handled, and it is good to obtain a kind of low temperature active, the sec-butyl alcohol dehydrogenizing catalyst that the MEK selectivity is high.
In order to achieve the above object, the technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of sec-butyl alcohol dehydrogenizing prepares the MEK catalyst, and it is with CuO, ZnO, ZrO 2And Al 2O 3Be main active component, with M 2O wherein, is a benchmark with the percentage by weight as catalyst modifier, and each constituent content is:
CuO?20～80％，ZnO?5～40％，ZrO 2?1～40％，Al 2O 3?0.5～20％，M 2O?0.5～8％。
Further, described M 2O is Na 2O, K 2O, Li 2O, Cs 2The mixture of one or more among the O.
Another object of the present invention is to provide a kind of above-mentioned sec-butyl alcohol dehydrogenizing to prepare MEK Preparation of catalysts method, may further comprise the steps:
Step a, the solubility salt of the solubility salt of the solubility salt of the solubility salt of copper, zinc, zirconium and aluminium is miscible in deionized water then, adds aqueous slkali and carries out co-precipitation, and precipitation finishes, and obtains precipitation mixture;
Step b, described precipitation mixture that step a is obtained through washing, drying after, add modifier or modifier raw material and mix, in roaster, carry out roasting then, last compression molding promptly gets described sec-butyl alcohol dehydrogenizing and prepares MEK catalyst finished product.
Further, the solubility salt of described copper is one or more the mixing in the acetate of chloride, copper of sulfate, the copper of nitrate, the copper of copper;
The solubility salt of described zinc is one or more the mixing in the acetate of chloride, zinc of sulfate, the zinc of nitrate, the zinc of zinc;
The solubility salt of described zirconium is one or more the mixing in the acetate of chloride, zirconium of sulfate, the zirconium of nitrate, the zirconium of zirconium;
The solubility salt of described aluminium is one or more the mixing in nitrate, sulfate, chloride, the acetate.
Further, described aqueous slkali is one or more the mixing in the aqueous solution of the aqueous solution, ammonium hydroxide of the aqueous solution, the potassium hydroxide of the aqueous solution, the NaOH of the aqueous solution, the carbonic hydroammonium of the aqueous solution, the ammonium carbonate of the aqueous solution, the saleratus of the aqueous solution, the potash of the aqueous solution, the sodium acid carbonate of sodium carbonate.
Further, described modifier is one or more the mixing in sodium oxide molybdena, potassium oxide, lithia, the cesium oxide.
Further, the described modifier raw material hydroxide that is sodium, the carbonate of sodium, the subcarbonate of sodium, the acetate of sodium, the nitrate of sodium, the oxalates of sodium, the hydroxide of potassium, the carbonate of potassium, the subcarbonate of potassium, the acetate of potassium, the nitrate of potassium, the oxalates of potassium, the hydroxide of lithium, the carbonate of lithium, the subcarbonate of lithium, the acetate of lithium, the nitrate of lithium, the oxalates of lithium, the oxalates of lithium, the hydroxide of caesium, the carbonate of caesium, the subcarbonate of caesium, the acetate of caesium, the nitrate of caesium, the mixing of one or more in the oxalates of caesium.
Further, the condition of co-precipitation is among the described step a: precipitation temperature is 30～95 ℃, and the pH value is 6.0～11.0.
Further, dry condition is among the described step b: baking temperature .80～150 ℃.
Further, the condition of roasting is among the described step b: sintering temperature is 250-600 ℃, and roasting time is 2～5 hours.
The invention has the beneficial effects as follows that a kind of sec-butyl alcohol dehydrogenizing of the present invention prepares the MEK catalyst, not only significantly improved the conversion ratio of sec-butyl alcohol, and significantly improved the selectivity of MEK.
The specific embodiment
Embodiment 1
Take by weighing Cu (NO respectively 3) 23H 2O 25g, Zn (NO 3) 26H 2O 15g, ZrOCl 28H 2O 10g, Al (NO 3) 39H 2O 1g is miscible in the 500mL deionized water, uses the Na of 1M under vigorous stirring 2CO 3The aqueous solution adjusts to 8.0 with the pH value, and the control reaction temperature continues to stir 60 minutes about 80 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and filter cake adds 1g K then 110 ℃ of dryings 2CO 3Mix, in roaster under air atmosphere 350 ℃ of roastings 5 hours, obtain a kind of catalyst A.
Embodiment 2
Take by weighing Cu (NO respectively 3) 23H 2O 60g, Zn (NO 3) 26H 2O 5g, ZrOCl 28H 2O 5g, Al (NO 3) 39H 2O 3g is miscible in the 500mL deionized water, uses 1M K under vigorous stirring 2CO 3The aqueous solution adjusts to 7.0 with the pH value, and the control reaction temperature continues to stir 90 minutes about 70 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and filter cake adds 1.5g Na then 110 ℃ of dryings 2CO 3Mix, in roaster under air atmosphere 400 ℃ of roastings 3 hours, obtain a kind of catalyst B.
Embodiment 3
Take by weighing Cu (NO respectively 3) 23H 2O 17g, Zn (NO 3) 26H 2O 30g, ZrOCl 28H 2O 26g, AlCl 35g is miscible in the 500mL deionized water, uses 1M (NH under vigorous stirring 4) 2CO 3The aqueous solution adjusts to 7.5 with the pH value, and the control reaction temperature continues to stir 70 minutes about 60 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and filter cake adds 2g Cs then 120 ℃ of dryings 2CO 3Mix, in roaster under air atmosphere 450 ℃ of roastings 2 hours, obtain a kind of catalyst C.
Embodiment 4
Take by weighing Cu (NO respectively 3) 23H 2O 55g, Zn (NO 3) 26H 2O 10g, Zr (NO 3) 45H 2O 15g, Al (NO 3) 39H 2O 10g is miscible in the 500mL deionized water, uses 1M Na under vigorous stirring 2CO 3The aqueous solution adjusts to 7.0 with the pH value, and the control reaction temperature continues to stir 70 minutes about 70 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and filter cake adds 1g Li then 100 ℃ of dryings 2CO 3Mix, in roaster under air atmosphere 350 ℃ of roastings 4 hours, obtain a kind of catalyst D.
Embodiment 5
Take by weighing Cu (NO respectively 3) 23H 2O 25g, Zn (NO 3) 26H 2O 20g, Zr (NO 3) 45H 2O 30g, Al (NO 3) 39H 2O 25g is miscible in the 500mL deionized water, uses 1M Na under vigorous stirring 2CO 3The aqueous solution adjusts to 7.5 with the pH value, and the control reaction temperature continues to stir 70 minutes about 75 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and filter cake adds 1g KOH then and mixes 100 ℃ of dryings, in roaster under air atmosphere 350 ℃ of roastings 4 hours, obtain a kind of catalyst E.
The comparative example 1
Take by weighing Cu (NO respectively 3) 23H 2O 35g, Zn (NO 3) 26H 2O 20g, Al (NO 3) 39H 2O 10g, miscible in the 500mL deionized water, under vigorous stirring, use 1M Na 2CO 3The aqueous solution adjusts to 7.5 with the pH value, and the control reaction temperature continues to stir 30 minutes about 65 ℃.Reaction finishes to be cooled to room temperature, material is drawn off and repeatedly washing, and through filtering, filter cake adds 1g K then 100 ℃ of dryings 2CO 3Mix, in roaster under air atmosphere 350 ℃ of roastings 4 hours, obtain a kind of catalyst F.
The catalyst sample that catalyst sample that embodiment 1 to 5 is obtained and comparative example 1 obtain is estimated its reactivity with the normal pressure evaluating apparatus.Evaluation method is: earlier catalyst sample is crushed to 40～60 orders, measures 5ml and pack in the reactor.Use H earlier 2Carry out temperature programmed reduction, be respectively 200 ℃ and 250 ℃ in reaction temperature then, the liquid air speed is 6h -1Condition under carry out activity rating.
The catalyst sample activity rating contrast table that catalyst sample that table 1 obtains for embodiment 1 to embodiment 5 and comparative example 1 obtain.
Table 1 sec-butyl alcohol dehydrogenizing catalyst activity evaluation test result
Figure BDA0000078635540000061
Figure BDA0000078635540000071
The reactivity that data declaration in the above table 1, sec-butyl alcohol dehydrogenizing of the present invention prepare the MEK catalyst obviously is better than prior art CuO-ZnO-Al 2O 3The selectivity that the reactivity of catalyst, sec-butyl alcohol dehydrogenizing of the present invention prepare product first and second alcohol that the MEK Preparation of Catalyst obtains also obviously is better than prior art CuO-ZnO-Al 2O 3The selectivity of the MEK of Preparation of Catalyst.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a sec-butyl alcohol dehydrogenizing prepares the MEK catalyst, it is characterized in that, it is with CuO, ZnO, ZrO 2And Al 2O 3Be main active component, with M 2O wherein, is a benchmark with the percentage by weight as catalyst modifier, and each constituent content is:
CuO?20~80%，ZnO?5~40%，ZrO 2?1~40%，Al 2O 3 0.5~20%，M 2O?0.5~8%。
2. a kind of sec-butyl alcohol dehydrogenizing according to claim 1 prepares the MEK catalyst, it is characterized in that: described M 2O is Na 2O, K 2O, Li 2O, Cs 2The mixture of one or more among the O.
3. a sec-butyl alcohol dehydrogenizing prepares MEK Preparation of catalysts method, it is characterized in that, may further comprise the steps:
Step a, the solubility salt of the solubility salt of the solubility salt of the solubility salt of copper, zinc, zirconium and aluminium is miscible in deionized water then, adds aqueous slkali and carries out co-precipitation, and precipitation finishes, and obtains precipitation mixture;
Step b, described precipitation mixture that step a is obtained through washing, drying after, add modifier or modifier raw material and mix, in roaster, carry out roasting then, last compression molding promptly gets described sec-butyl alcohol dehydrogenizing and prepares MEK catalyst finished product.
4. prepare MEK Preparation of catalysts method according to the described a kind of sec-butyl alcohol dehydrogenizing of claim 3, it is characterized in that:
The solubility salt of described copper is one or more the mixing in nitrate, sulfate, chloride, the acetate;
The solubility salt of described zinc is one or more the mixing in nitrate, sulfate, chloride, the acetate;
The solubility salt of described zirconium is one or more the mixing in nitrate, sulfate, chloride, the acetate;
The solubility salt of described aluminium is one or more the mixing in nitrate, sulfate, chloride, the acetate.
5. prepare MEK Preparation of catalysts method according to the described a kind of sec-butyl alcohol dehydrogenizing of claim 3, it is characterized in that:
Described aqueous slkali is one or more the mixing in the aqueous solution of the aqueous solution, ammonium hydroxide of the aqueous solution, the potassium hydroxide of the aqueous solution, the NaOH of the aqueous solution, the carbonic hydroammonium of the aqueous solution, the ammonium carbonate of the aqueous solution, the saleratus of the aqueous solution, the potash of the aqueous solution, the sodium acid carbonate of sodium carbonate.
6. prepare MEK Preparation of catalysts method according to the described a kind of sec-butyl alcohol dehydrogenizing of claim 3, it is characterized in that:
Described modifier is one or more the mixing in sodium oxide molybdena, potassium oxide, lithia, the cesium oxide.
7. a kind of sec-butyl alcohol dehydrogenizing according to claim 3 prepares MEK Preparation of catalysts method, it is characterized in that:
Described modifier raw material is the hydroxide of sodium, the carbonate of sodium, the subcarbonate of sodium, the acetate of sodium, the nitrate of sodium, the oxalates of sodium, the hydroxide of potassium, the carbonate of potassium, the subcarbonate of potassium, the acetate of potassium, the nitrate of potassium, the oxalates of potassium, the hydroxide of lithium, the carbonate of lithium, the subcarbonate of lithium, the acetate of lithium, the nitrate of lithium, the oxalates of lithium, the oxalates of lithium, the hydroxide of caesium, the carbonate of caesium, the subcarbonate of caesium, the acetate of caesium, the nitrate of caesium, the mixing of one or more in the oxalates of caesium.
8. a kind of sec-butyl alcohol dehydrogenizing according to claim 3 prepares MEK Preparation of catalysts method, it is characterized in that, the condition of co-precipitation is among the described step a: precipitation temperature is 30 ~ 95 ℃, and the pH value is 6.0 ~ 11.0.
9. a kind of sec-butyl alcohol dehydrogenizing according to claim 3 prepares MEK Preparation of catalysts method, it is characterized in that, condition dry among the described step b is: baking temperature is 80 ~ 150 ℃.
10. a kind of sec-butyl alcohol dehydrogenizing according to claim 3 prepares MEK Preparation of catalysts method, it is characterized in that, the condition of roasting is among the described step b: sintering temperature is 250-600 ℃, and roasting time is 2 ~ 5 hours.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN103739469A (en) * 2013-12-24 2014-04-23 山东滨州裕华化工厂有限公司 Process for preparing MEK (Methyl Ethyl Ketone) by utilizing C4 fraction in etherified liquefied petroleum gas
CN105056958A (en) * 2015-08-21 2015-11-18 宁波海越新材料有限公司 Catalyst for preparing methyl ethyl ketone through sec-butyl alcohol dehydrogenation and preparation method thereof
CN105709725A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for production of ethyl methyl ketone, and preparation method and application thereof
CN105903471A (en) * 2016-05-06 2016-08-31 北京石油化工学院 Catalyst for preparing MEK (Methyl Ethyl Ketone) by carrying out dehydrogenation on 2-butanol and preparation method and application thereof
CN107597125A (en) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 A kind of Catalysts of Dehydrogenation Secondary Butand of the potassium containing solid-state and preparation method thereof
CN111995504A (en) * 2020-05-31 2020-11-27 南京克米斯璀新能源科技有限公司 Method for preparing aldehyde by dehydrogenating alcohol
CN112892598A (en) * 2021-01-26 2021-06-04 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN115814781A (en) * 2022-12-13 2023-03-21 中国科学院山西煤炭化学研究所 Zirconium-based catalyst and preparation method and application thereof

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739469A (en) * 2013-12-24 2014-04-23 山东滨州裕华化工厂有限公司 Process for preparing MEK (Methyl Ethyl Ketone) by utilizing C4 fraction in etherified liquefied petroleum gas
CN105709725B (en) * 2014-12-04 2018-06-19 中国石油化工股份有限公司 A kind of catalyst for producing methyl ethyl ketone and its preparation method and application
CN105709725A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for production of ethyl methyl ketone, and preparation method and application thereof
CN105056958A (en) * 2015-08-21 2015-11-18 宁波海越新材料有限公司 Catalyst for preparing methyl ethyl ketone through sec-butyl alcohol dehydrogenation and preparation method thereof
CN105056958B (en) * 2015-08-21 2017-12-26 宁波海越新材料有限公司 A kind of preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst
CN105903471A (en) * 2016-05-06 2016-08-31 北京石油化工学院 Catalyst for preparing MEK (Methyl Ethyl Ketone) by carrying out dehydrogenation on 2-butanol and preparation method and application thereof
CN107597125A (en) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 A kind of Catalysts of Dehydrogenation Secondary Butand of the potassium containing solid-state and preparation method thereof
CN107597125B (en) * 2017-10-25 2020-08-28 山东齐鲁科力化工研究院有限公司 Sec-butyl alcohol dehydrogenation catalyst containing solid potassium and preparation method thereof
CN111995504A (en) * 2020-05-31 2020-11-27 南京克米斯璀新能源科技有限公司 Method for preparing aldehyde by dehydrogenating alcohol
CN112892598A (en) * 2021-01-26 2021-06-04 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN112892598B (en) * 2021-01-26 2022-05-24 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN115814781A (en) * 2022-12-13 2023-03-21 中国科学院山西煤炭化学研究所 Zirconium-based catalyst and preparation method and application thereof
CN115814781B (en) * 2022-12-13 2024-06-11 中国科学院山西煤炭化学研究所 Zirconium-based catalyst and preparation method and application thereof

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