CN1872412A - Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method - Google Patents
Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method Download PDFInfo
- Publication number
- CN1872412A CN1872412A CN 200510073113 CN200510073113A CN1872412A CN 1872412 A CN1872412 A CN 1872412A CN 200510073113 CN200510073113 CN 200510073113 CN 200510073113 A CN200510073113 A CN 200510073113A CN 1872412 A CN1872412 A CN 1872412A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ketone
- fabricated
- alkali metal
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for preparing ketone by dehydrogenating alcohol is prepared from Cu as active component, Zn, Cr, or K as active assistant and alumina as carrier through co-depositing, coating alkali metal by immersing or spraying, drying, and calcining. It has high activity and selectivity.
Description
Technical field
The present invention relates to a kind of ketone catalyst fabricated by dehydrogenating alcohol and preparation method thereof, relating to a kind of more specifically is the sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone Catalysts and its preparation method of main active constituent with copper.
Background technology
Most ketone catalyst fabricated by dehydrogenating alcohol with copper as main active component, and add zinc, chromium, magnesium, calcium isoreactivity auxiliary component to form more stable metal mixed crystal with copper, improve the decentralization of copper, reduce the content of copper, by active constituent and coagent component being loaded on the decentralization that further improves the copper crystallite on the carrier such as aluminium oxide.Prior art is a lot of about the technology report of copper-zinc, chromium, magnesium-aluminium oxide catalyst system, as Chinese patent CN1160152C, and CN1150990C and CN1056067A etc.But these catalyst are mainly at the development of cyclohexanol gas phase or dehydrogenation in liquid phase preparing cyclohexanone, and have the catalytic activity instability, and the low and preparation process of selectivity is than problems such as complexity.
Chinese patent CN1289638A " a kind of preparation method of Cu-contained catalyst " has introduced a kind of preparation method of cupric system ketone catalyst fabricated by dehydrogenating alcohol, it comes down to the expansion on traditional copper series catalysts production technology basis, promptly after coprecipitation is produced the moulding of preparation Cu-series catalyst, continuing after dipping alkali metal soln, the drying once more, roasting generates alkali metal oxide to decompose alkali metal salt.Though the catalyst by this method system has shown main reaction activity preferably and service life, because the little water absorption rate of base catalyst pore volume after its moulding, roasting is low, alkali metal amount that can load is limited, and the selectivity of main reaction is not very high.And its preparation process must be through double roasting, complex technical process, and preparation cost is higher.
Summary of the invention
In order to overcome the defective of existing ketone catalyst fabricated by dehydrogenating alcohol, the invention provides that a kind of preparation technology is simple, cost is lower and active height and stable, the ketone good ketone catalyst fabricated by dehydrogenating alcohol of MEK selectivity especially.
In the fabricated by dehydrogenating alcohol reactive ketone, under the prerequisite of the conversion ratio that keeps certain alcohol, the content of alkali metal load and uniformity are very big to the selectivity influence of ketone on the catalyst.
As everyone knows, the pore volume of the catalyst behind the compression molding and water absorption rate are all less, and water absorption rate is the highest only to be reached about 20%, and load capacity was low excessively when the alkali metal impregnation concentration was low; When impregnation concentration was higher, the distribution of the alkali metal of load in catalyst was not too even, and alkali metal concentrates on catalyst surface and duct inlet mostly, influenced the catalytic performance of catalyst.
Ketone catalyst fabricated by dehydrogenating alcohol of the present invention adopts and flood/spray alkali-metal method preparation in the co-precipitation filter cake.Because the water absorption rate of dried filter cake is big, can reach 100%-150%, therefore, can regulate alkali-metal adsorbance on the catalyst easily, and alkali metal is evenly distributed in catalyst, the catalytic performance of catalyst is uniform and stable.
Ketone catalyst fabricated by dehydrogenating alcohol of the present invention is main active component with copper, is carrier with the aluminium oxide, also can add zinc, chromium, manganese, potassium etc. and help active component, and its preparation method adopts traditional coprecipitation.
Concrete, ketone catalyst fabricated by dehydrogenating alcohol of the present invention, it is main active component with copper, is carrier with the aluminium oxide, prepares by the method that may further comprise the steps:
1) with copper ions solution and the precipitating reagent neutralization that contains aluminium hydroxide and/or aluminium oxide, through co-precipitation, the aging precipitation mixture that obtains; Or with copper ions solution and precipitating reagent neutralization, add aluminium hydroxide and/or aluminium oxide after the co-precipitation, the aging precipitation mixture that obtains;
2) step 1) gained sediment mixture after filtration, after the washing, drying, flood/spray alkali metal soln obtains base catalyst;
3) step 2) after gained base catalyst drying, the roasting, compression molding obtains the catalyst finished product.
Zinc, chromium, manganese etc. help active component can prevent the copper grain growth, prolong the regeneration period and the service life of catalyst.The catalytic activity height of one pack system copper catalyst and bi-component Cu-Zn catalyst, and the three component Cu-Zn-Cr catalyst activities of interpolation Cr reduce, but help the adding of active component that selection of catalysts is had certain influence simultaneously.The said copper ions solution of the present invention can contain zinc ion and/or chromium ion, also can be to contain aluminum ions hybrid ionic solution simultaneously.There is not strict requirement for concentration, generally at 5%～40 (weight) %.
Precipitating reagent of the present invention can be that alkaline precipitating agent also can be the organic acid precipitating reagent, wherein alkaline precipitating agent can be a solution at least a in alkali-metal carbonate, bicarbonate or the hydroxide, as sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus and potassium hydroxide; The organic acid precipitating reagent can be at least a in ethanedioic acid, malonic acid, the succinic acid etc.
Alkali metal soln of the present invention contains potassium ion and/or sodium ion.Potassium ion and/or sodium ion can be introduced by the carbonate or the nitrate of potassium and sodium, as sodium carbonate, sodium nitrate, potash, potassium nitrate etc.Increase with alkali metal promoter, the selectivity of MEK increases, but catalytic activity reduces during too high levels (greater than 5%).Alkali metal soln of the present invention is preferably and contains potassium solution.
Ketone catalyst fabricated by dehydrogenating alcohol of the present invention can be used for various fabricated by dehydrogenating alcohol reactive ketones, is preferred for the reaction of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone.
Preparation method of the present invention can be specified as: under temperature 60-75 ℃ condition, drip copper ions solution in the alcaliotropism precipitant solution and carry out co-precipitation, the control pH value is not less than 7, dripped 0.5-2.5 hour, after finishing, neutralization precipitation adds aluminium hydroxide/alumina powder, got precipitation mixture in aging 0.5-2 hour, filter, with 4～6 numbers of pure water washing, 110～120 ℃ dry 4-8 hour, soak the alkali metal soln that sprays 0.2-0.4M etc. weight, decomposed 4～6 hours 350-400 ℃ of following roasting suitably dry back, and interpolation 1%-2% graphite mixes the back compression molding.Or: under temperature 60-75 ℃ condition, add aluminium hydroxide/alumina powder or its solution in the alcaliotropism precipitant solution, drip copper ion solution then and carry out co-precipitation, 0.5-2.5 hour dropping time, the control pH value is not less than 7, aging 4～6 numbers of filtration washing after 0.5-2 hour, 110～120 ℃ dry 4-8 hour, soak the alkali metal soln that sprays 0.2-0.4M etc. weight, decomposed 4～6 hours 350-400 ℃ of following roasting suitably dry back, and interpolation 1%-2% graphite mixes the back compression molding.
In the present invention, flood/when spraying alkali metal soln, should make dried co-precipitation filter cake wetting as far as possible, so that alkali metal fully contacts with coprecipitate, thereby the concentration of alkali metal soln is preferably 0.2-0.4M, do not have specific (special) requirements for flooding/spray temperature, gets final product under the room temperature.
In the present invention, catalyst mainly is made up of cupric oxide, aluminium oxide, alkali metal oxide after moulding is decomposed in roasting, contains or oxygen-free zinc and/or chromium oxide.Wherein, be benchmark with the catalyst total amount, the weight content of each component is: cupric oxide 20%-80%, aluminium oxide 10%-80%, zinc oxide be or/and chromium oxide 0%-60%, alkali metal oxide 0.5%-5%; The weight content of preferred each component is cupric oxide 20%-50%, and aluminium oxide 10%-20%, zinc oxide be or/and chromium oxide 20%-50%, alkali metal oxide 1%-3%.
The present invention also provides the preparation method of the simple ketone catalyst fabricated by dehydrogenating alcohol of a kind of technology.
Ketone catalyst fabricated by dehydrogenating alcohol preparation method involved in the present invention may further comprise the steps:
1) copper ions solution and the precipitating reagent neutralization that contains aluminium hydroxide and/or aluminium oxide are through co-precipitation, the aging precipitation mixture that obtains; Or with copper ions solution and precipitating reagent neutralization, add aluminium hydroxide and/or aluminium oxide after the co-precipitation, the aging precipitation mixture that obtains;
2) step 1) gained sediment mixture after filtration, after the washing, drying, flood/spray alkali metal soln obtains base catalyst;
3) step 2) after gained base catalyst drying, the roasting, compression molding obtains the catalyst finished product.
Catalyst of the present invention should reduce before using, and reduction is carried out in the hydrogen atmosphere in reactor usually, and medium is pure hydrogen gas or nitrogen hydrogen mixeding gas, is preferably pure hydrogen.Reduction temperature is 230-270 ℃.
The fabricated by dehydrogenating alcohol reactive ketone carries out usually at atmospheric or low pressure, and reaction temperature is 200-300 ℃, is preferably 230-270 ℃, and pure liquid phase feeding air speed is 1-8h
-1, be preferably 2-4h
-1When catalyst of the present invention was used for the reaction of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone, the conversion ratio of sec-butyl alcohol was 80%-90%, and the selectivity of MEK is 96%-99%.
Catalysts and its preparation method of the present invention has following advantage:
1, Preparation of catalysts technology is simple, easy operating.Alkali metal floods/sprays in the sediment filter cake with the form of solion, decomposes with slaines such as copper again, and bakes to burn the article decomposes can make finished catalyst, and the catalyst cost is low.
2, the equipment of Preparation of Catalyst is saved, and floods/spray alkali metal by the inventive method, need not increase the dipping that flows device/the spray equipment of taking back on traditional copper Catalyst Production device in addition.
3, because alkali metal combines with the catalyst precursor thing is full and uniform, and catalytic activity was stable when catalyst was used for the fabricated by dehydrogenating alcohol reactive ketone, the accessory substance growing amount is few, the catalyst selectivity height.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but invention itself is not limited by embodiment.
Embodiment 1
I. Preparation of Catalyst
Take by weighing and analyze pure copper nitrate 261.4g, zinc nitrate 314.4g is dissolved in and makes the slaine mixed liquor in the 1500g deionized water, sodium carbonate 238g is dissolved in the 2100g deionized water makes precipitating reagent, other takes by weighing technical grade one water-aluminum hydroxide powder 53.8g and is dissolved in the 66g deionized water as bonding agent, potash 2.2g and makes alkali metal soln.
Above-mentioned alkaline precipitating agent is added in 5 liters of there-necked flasks, be heated to 70 ℃ in electric food warmer, stirring state drips above-mentioned slaine mixed liquor down, keeps 70 ± 5 ℃ of neutralization reaction temperature, and control drips flow, dropwises about 1 hour.Regulate the pH value of neutralization reaction terminal point in addition with 10% sodium carbonate liquor, making pH value is between the 7.0-7.5.The co-precipitation neutralization finishes, and adds aluminium hydrate powder by charge door, stirs, and wears out 1 hour under 70 ℃ of conditions.
Sediment after aging filters and with washing 5 times under the deionized water room temperature, about 5 liters of water consumption, 120 ℃ of dryings 8 hours.Take by weighing dried filter cake 66 grams, roll to powder and add above-mentioned alkali metal soln, be stirred to fully evenly wetting getting final product of filter cake.Decomposed 4 hours 350 ℃ of roastings suitably dry back, sneaks into 1 gram graphite then, and compressing tablet becomes the cylinder of Ф 5 * 3-4, the catalyst A that gets product 50g.The catalyst A percentage by weight consists of cupric oxide 41%, zinc oxide 41%, aluminium oxide 13%, potassium oxide 3%, and surplus is a graphite.
II. dehydrogenation reaction
The catalyst A 30ml of above-mentioned preparation is used for the sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone, and reactor inside diameter is 20mm.Earlier catalyst is reduced reducing gases air speed 100h with pure hydrogen gas under temperature 230-270 ℃
-110 hours recovery times, sec-butyl alcohol enters reactor with pump with the flow of 120ml/h per hour afterwards, carries out dehydrogenation under 200 ℃ of beds inlet temperatures, 250 ℃ of conditions of outlet, the conversion ratio of sec-butyl alcohol is 83.3% o'clock, and the selectivity that generates MEK is 97.3%.
Embodiment 2
Take by weighing and analyze pure copper nitrate 182.3g, zinc nitrate 73.1g and be dissolved in and make the slaine mixed liquor in the 700g deionized water, sodium carbonate 111.4g is dissolved in the 1000g deionized water makes precipitating reagent, other claims 38.5g technical grade one water-aluminum hydroxide powder to be dissolved in the 66g deionized water as bonding agent, potash 2.2g to make alkali metal soln.
Preparation process gets finished catalyst B50g with embodiment 1.The catalyst B percentage by weight consists of cupric oxide 56%, zinc oxide 19%, aluminium oxide 19%, potassium oxide 3%, and surplus is a graphite.
Dehydrogenation reaction is carried out according to the same procedure of embodiment 1, and reaction result is: the conversion ratio of sec-butyl alcohol is 80.5% o'clock, and the selectivity that generates MEK is 96.2%.
Embodiment 3
Take by weighing and analyze pure copper nitrate 182.3g, zinc nitrate 36.5 grams, chromic nitrate 26.3 grams and be dissolved in the 700 gram deionized waters and make the slaine mixed liquor, sodium carbonate 97.7 grams are dissolved in the 900 gram deionized waters makes precipitating reagent, and other takes by weighing, and about water-aluminum hydroxide powder of 48.1 gram industry is made bonding agent, potash 2.2 grams are dissolved in the 66 gram deionized waters and make alkali metal soln.
Preparation process gets finished catalyst C 50 grams with embodiment 1.Catalyst C percentage by weight consists of cupric oxide 56%, zinc oxide 9.5%, and chromium oxide 5%, aluminium oxide 23.5%, potassium oxide 3%, all the other are graphite.
Dehydrogenation reaction is carried out according to the same procedure of embodiment 1, and reaction result is: the conversion ratio of sec-butyl alcohol is 81.2% o'clock, and the selectivity that generates MEK is 96.4%.
Comparative Examples 1
By the set of dispense identical with embodiment 1 when preparation condition prepare catalyst D, unique difference is that catalyst D did not soak the spray alkali metal soln before roasting is decomposed.Catalyst D percentage by weight consists of cupric oxide 42%, zinc oxide 42%, and aluminium oxide 13%, all the other are graphite etc.
Dehydrogenation reaction is carried out according to the same procedure of embodiment 1, and reaction result is: the conversion ratio of sec-butyl alcohol is 83.5% o'clock, and the selectivity that generates MEK is 91.9%.
Comparative Examples 2
Preparation method according to catalyst A among the embodiment among the Chinese patent CN1289638A obtains comparative catalyst E.Concrete steps are as follows:
Get 338g copper nitrate, 254g zinc nitrate and 220g aluminum nitrate and be dissolved in 3 liters of deion aqueous solutions, be made into the slaine mixed solution.Again 498g sodium carbonate is dissolved in 3 liters of deionized waters as precipitating reagent.
Above two kinds of solution are heated to 85 ℃ in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 85 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 15 minutes, adding between 85 ℃ of bath temperatures and the suspension pH value 7.0～8.0, regulate pH value to 9.5 with small amounts of sodium hydroxide solution again.Sediment is after aging half an hour, filters and with after the deionized water washes clean, is dried to little wetting, add the 25g graphite powder, mix the back compression molding, as base catalyst E 305g, percentage by weight consists of cupric oxide 46%, zinc oxide 35.5%, aluminium oxide 18.5% after 380 ℃ of roastings.
2 liters of the potassium nitrate solutions of preparation 1.5mol/L are standby.
Get the above-mentioned base catalyst E150g that makes, put into a flask, flask is furnished with the water condensation return channel, the potassium nitrate solution 300ml that adds 1.5mol/L, added hot reflux 3 hours, obtain final catalyst E after back drying, 360 ℃ of roastings, percentage by weight consists of cupric oxide 45.4%, zinc oxide 35.1%, aluminium oxide 18.3%, potassium oxide 1.2%.
Dehydrogenation reaction is carried out according to the same procedure of embodiment 1.Catalyst E reaction result under identical dehydrogenation reaction conditions is: the conversion ratio of sec-butyl alcohol is 83.4% o'clock, and the selectivity that generates MEK is 95.1%.
Compare as can be known with the experimental result of embodiment 1 catalyst A, under same reaction conditions, when the sec-butyl alcohol conversion ratio was basic identical, the MEK selectivity of catalyst A of the present invention was better than the catalyst E that uses preparation method of the prior art to obtain.
With the catalyst A and the catalyst E that uses prior art for preparing to obtain of embodiments of the invention 1 preparation, the content with X-gamma ray spectrometer detection alkali metal potassium the results are shown in Table 1.Use instrument to be Vantage ESI numeral X-X-ray microanalysis X instrument (U.S. Thermo NORAN company), the operating condition of this instrument is as follows:
Accelerating potential 15KV, operating distance 10mm, electron beam spot size 3
Multiplication factor 1200 is received 13.7 minutes spectrum time.
Testing result shows: adopt the catalyst E of prior art for preparing, owing to soak the potassium metallic solution again after the moulding, the potassium Metal Distribution is inhomogeneous; The potassium Metal Distribution is even in the catalyst A particle of employing the present invention preparation.
Potassium content distributes in table 1 catalyst granules
| Catalyst | A | E | ||
| Particle-1 | Particle-2 | Particle-1 | Particle-2 | |
| Mean value, % | 1.98 | 2.04 | 1.72 | 1.02 |
| Marginal value, % | 2.00 | 1.91 | 2.52 | 1.71 |
| The middle part value, % | 1.88 | 2.22 | 1.07 | 0.41 |
Claims (9)
1, a kind of ketone catalyst fabricated by dehydrogenating alcohol, it is main active component with copper, is carrier with the aluminium oxide, prepares by the method that may further comprise the steps:
1) with copper ions solution and the precipitating reagent neutralization that contains aluminium hydroxide and/or aluminium oxide, through co-precipitation, the aging precipitation mixture that obtains; Or with copper ions solution and precipitating reagent neutralization, add aluminium hydroxide and/or aluminium oxide after the co-precipitation, the aging precipitation mixture that obtains;
2) step 1) gained precipitation mixture after filtration, after the washing, drying, flood/spray alkali metal soln obtains base catalyst;
3) step 2) after gained base catalyst drying, the roasting, compression molding obtains the catalyst finished product.
2, ketone catalyst fabricated by dehydrogenating alcohol according to claim 1 is characterized in that described alcohol is sec-butyl alcohol, and described ketone is MEK.
3, ketone catalyst fabricated by dehydrogenating alcohol according to claim 1 and 2 is characterized in that the described precipitating reagent of step 1) is alkaline precipitating agent or organic acid precipitating reagent.
4, ketone catalyst fabricated by dehydrogenating alcohol according to claim 3 is characterized in that described alkaline precipitating agent is a solution at least a in alkali-metal carbonate, bicarbonate and the hydroxide; The organic acid precipitating reagent is at least a in ethanedioic acid, malonic acid and the succinic acid.
5, ketone catalyst fabricated by dehydrogenating alcohol according to claim 1 and 2 is characterized in that containing zinc ion and/or chromium ion in the described copper ions solution of step 1).
6, ketone catalyst fabricated by dehydrogenating alcohol according to claim 1 and 2 is characterized in that step 2) described alkali metal soln contains potassium ion and/or sodium ion.
7, ketone catalyst fabricated by dehydrogenating alcohol according to claim 6 is characterized in that described alkali metal soln contains the carbonate and/or the nitrate of potassium and/or sodium.
8, ketone catalyst fabricated by dehydrogenating alcohol according to claim 1 and 2 is characterized in that the concentration of described alkali metal soln is 0.2-0.4M, floods/sprays at room temperature and carry out.
9, the preparation method of the described ketone catalyst fabricated by dehydrogenating alcohol of one of claim 1-8, it may further comprise the steps:
1) copper ions solution and the precipitating reagent neutralization that contains aluminium hydroxide and/or aluminium oxide are through co-precipitation, the aging precipitation mixture that obtains; Or with copper ions solution and precipitating reagent neutralization, add aluminium hydroxide and/or aluminium oxide after the co-precipitation, the aging precipitation mixture that obtains;
2) step 1) gained sediment mixture after filtration, after the washing, drying, flood/spray alkali metal soln obtains base catalyst;
3) step 2) after gained base catalyst drying, the roasting, compression molding obtains the catalyst finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100731135A CN100360228C (en) | 2005-05-31 | 2005-05-31 | Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100731135A CN100360228C (en) | 2005-05-31 | 2005-05-31 | Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872412A true CN1872412A (en) | 2006-12-06 |
| CN100360228C CN100360228C (en) | 2008-01-09 |
Family
ID=37483110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100731135A Active CN100360228C (en) | 2005-05-31 | 2005-05-31 | Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100360228C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247855A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN102247866A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN104399474A (en) * | 2014-11-20 | 2015-03-11 | 西安近代化学研究所 | Catalyst for synthesizing methoxy acetone through alcohol dehydrogenization, preparation method and application of catalyst |
| 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 |
| CN105709752A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Sec-butyl alcohol dehydrogenation catalyst and its preparation method and use |
| 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 |
| CN111036230A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method thereof |
| CN111318282A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Copper-based catalyst, preparation method thereof and application thereof in preparation of hydroxyketone compound |
| CN111320531A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Preparation method of hydroxyketone compound |
| CN114192156A (en) * | 2021-12-09 | 2022-03-18 | 沈阳化工大学 | Preparation method of sec-butyl alcohol dehydrogenation methyl ethyl ketone catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8001878A (en) * | 1980-03-29 | 1981-11-02 | Stamicarbon | PROCESS FOR THE PREPARATION OF ALDEHYDES. |
| DE19626587A1 (en) * | 1996-07-02 | 1998-01-08 | Basf Ag | Cyclohexanol dehydrogenation catalyst |
| DE19722567A1 (en) * | 1997-05-28 | 1998-12-03 | Basf Ag | Process for the continuous industrial production of unsaturated aliphatic aldehydes in a tube bundle reactor |
| CN1101262C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
-
2005
- 2005-05-31 CN CNB2005100731135A patent/CN100360228C/en active Active
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102408305B (en) * | 2010-09-21 | 2014-04-02 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102247866A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof |
| CN102247855B (en) * | 2011-07-26 | 2013-03-13 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN102247855A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN104399474A (en) * | 2014-11-20 | 2015-03-11 | 西安近代化学研究所 | Catalyst for synthesizing methoxy acetone through alcohol dehydrogenization, preparation method and application of catalyst |
| CN105709752B (en) * | 2014-12-04 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of Catalysts of Dehydrogenation Secondary Butand 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 |
| CN105709752A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Sec-butyl alcohol dehydrogenation catalyst and its preparation method and use |
| 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 |
| 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 |
| 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 |
| CN111036230A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method thereof |
| CN111318282A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Copper-based catalyst, preparation method thereof and application thereof in preparation of hydroxyketone compound |
| CN111320531A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Preparation method of hydroxyketone compound |
| CN111320531B (en) * | 2018-12-13 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of hydroxyketone compound |
| CN111318282B (en) * | 2018-12-13 | 2023-11-07 | 中国石油化工股份有限公司 | Copper-based catalyst, preparation method thereof and application thereof in preparation of hydroxyketone compound |
| CN114192156A (en) * | 2021-12-09 | 2022-03-18 | 沈阳化工大学 | Preparation method of sec-butyl alcohol dehydrogenation methyl ethyl ketone catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100360228C (en) | 2008-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1872412A (en) | Ketone catalyst fabricated by dehydrogenating alcohol, and preparation method | |
| KR20210052938A (en) | Ruthenium-based ammonia decomposition catalyst and preparation method thereof | |
| CN1101262C (en) | Process for preparing Cu-contained catalyst | |
| CN113058595A (en) | Ru-based ammonia decomposition hydrogen production catalyst and preparation method thereof | |
| CN102407122B (en) | Preparation method of octylene aldehyde gas phase hydrogenation catalyst for octanol production | |
| Saito et al. | Synergistic effect of MgO and CeO 2 as a support for ruthenium catalysts in ammonia synthesis | |
| CN1772378A (en) | Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its prepn | |
| EP2709755A1 (en) | Method for preparing a supported ruthenium catalyst | |
| CN101081362A (en) | Carrier containing magnalium complexes and method for preparing the same | |
| CN1562472A (en) | Copper base catalyst in use for preparing hydrogen by reforming vapor of methanol and preparation method | |
| CN1586718A (en) | Nano carbon material modified copper base catalyst and its preparing method | |
| CN102247856A (en) | Eggshell nickel-based bifunctional hydrogenation catalyst and preparation method and application thereof | |
| CN1418725A (en) | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube | |
| CN110204444B (en) | Synthesis method of dimethyl carbonate | |
| US10668460B2 (en) | Composite catalyst, method for manufacturing composite catalyst and application thereof | |
| CN1954910A (en) | Preparation method of ruthenium-base ammonia synthetic catalyst | |
| CN1569329A (en) | Novel catalyst for methanol cracking reaction to produce CO and H2 | |
| CN113429291B (en) | Heterogeneous catalyst CaO/Al2O3@XaSiObApplication in process of synthesizing dimethyl carbonate | |
| CN112517020B (en) | Preparation method and application of nano Cu-Ce alloy catalyst | |
| CN115245827A (en) | Method for preparing nitrous oxide decomposition catalyst by coprecipitation-impregnation | |
| CN115245828A (en) | Nitrous oxide decomposition catalyst | |
| CN1754825A (en) | A kind of hydrogen through reforming oxidized methyl alcohol catalyzer and method for making and application | |
| CN116408057A (en) | Vapor phase aldehyde hydrogenation catalyst, and preparation method and application thereof | |
| CN113083307B (en) | Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof | |
| CN115888754B (en) | Preparation method of catalyst for preparing hydrogen by reforming methanol with low copper content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |