CN101716500A - Hydrotalcite-like compound-based magnesium-zirconium-aluminum composite oxide catalyst and use thereof - Google Patents
Hydrotalcite-like compound-based magnesium-zirconium-aluminum composite oxide catalyst and use thereof Download PDFInfo
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Abstract
The invention discloses a hydrotalcite-like compound-based magnesium-zirconium-aluminum composite oxide catalyst and use thereof. The catalyst is prepared by roasting magnesium-zirconium-aluminum hydrotalcite (Mg/Zr/Al-LDH). The composition of the magnesium-zirconium-aluminum composite oxide catalyst (Mg/Zr/Al-LDO) is represented by (MgO)x(Zro2)y(Al2O3)0.5, wherein x is between 0 and 20 and y is between 0 and 1. The catalyst can be used in the reaction for preparing corresponding alcohol compounds by reducing ketones (particularly cyclohexanone or acetophenone) by hydrogenation and has the advantages of mild reaction conditions, low reaction energy consumption, high catalytic activity and selectivity, simple post-reaction processing, simple preparation process and low cost.
Description
(1) technical field
The present invention relates to a kind of houghite based magnesium-zirconium-aluminum composite oxide thing Mg/Zr/Al-LDO catalyst and application, mainly is to prepare application in the corresponding alcohol compound (as cyclohexanol, alpha-phenyl ethyl alcohol etc.) at the ketone hydrogenating reduction.
(2) background technology
Alcohol compound such as cyclohexanol, secondary octanol, alpha-phenyl ethyl alcohol, α, beta unsaturated alcohol etc. all are important chemical material, are widely used in washing agent, surfactant, synthetic perfume, medicine and fine-chemical intermediate etc.One of effective way of synthetic above-mentioned alcohol is by corresponding ketone hydrogenating reduction; But ketone is the more stable compound of a class, generally, is difficult to hydrogenation and generates alcohol, must reduce its activation energy in the presence of catalyst, just can react.So prepare the focus that a kind of catalyst efficiently becomes research, also have extensive market prospects.
The method that for example hydrogenation of acetophenone is reduced to alpha-phenyl ethyl alcohol is known in the art technology.Known these class methods are usually with tetrahydro lithium, sodium borohydride or aluminium isopropoxide reduction preparation alpha-phenyl ethyl alcohol, no doubt can obtain the unsaturated alcohol of high yield, but product separates difficulty with reducing agent, solvent etc., the post processing trouble of product, the refuse that produces is also a lot, causes environmental pollution easily.If adopt the method for heterogeneous catalytic hydrogenation then can realize that product effectively separates, and solvent only needs simple distillation or decompression distillation can realize and reactants separate, can greatly reduce reaction cost.In known catalyst, be usually included under the HTHP, acetophenone is contacted with hydrogen, thereby hydrogenation of acetophenone is reduced to corresponding alpha-phenyl ethyl alcohol, described catalyst contains one or more metals of the IA family, IIB family, VI family and the VIII family that are selected from the periodic table system, defines as the 72nd edition 1-11 page or leaf of CRC Handbook of Chemistry and Physics in 1991.For example: 1. describe a kind of catalyst that contains at least a alkali carbonate and at least a alkaline earth metal compound among the .EP-A-0714877 based on copper.This catalyst is used hydrogen reducing before use, activity of such catalysts is restricted at low temperatures, and therefore possible productive rate also is restricted, and at high temperature activity of such catalysts can improve, but also can make the alpha-phenyl ethyl alcohol of generation be dehydrated into styrene, therefore reduce the selectivity of reaction.2. .CN 1557545A (04.12.29) has described a kind of amorphous alloy catalyst of nickeliferous and boron, but this Preparation of catalysts more complicated, and the pressure of reaction is also higher.
Also have in the report of this external ketone hydrogenating reduction: the first kind, copper-based catalysts, 1. .CN90108584 (91.10.09) has described a kind of to be raw material with coconut oil and palm oil, to carry out its preparation process of catalyst that medium pressure hydrogenation prepares alcohols.Its catalyst is Cu-Cr-Zn ternary oxide or composite oxides, adopts the coprecipitation preparation, adopts hydrogen as reducing agent, and required pressure (8MP) and temperature (230-300 ℃) are higher.2. .WO95/198844 (95.7.27) (CN94190945) has described a kind of cupric hydrogenization catalyst preparation method, comprise gaseous mixture with hydrogen and inert gas, the moulding parent of liquid phase two-stage reduction copper-containing hydrogenation reaction catalyst in solvent streams, in the continuous fixed bed reaction or continuous system, can make alcohol compound through the ketone hydrogenation with this catalyst.3. to have described a kind of be raw material with secondary octanone to .CN1279127A (01.01.10), carry out the secondary octanol of hydrogenation preparing, its catalyst is the Cu-Mg-Zn-Al composite oxides, adopts the coprecipitation preparation, adopt hydrogen as reducing agent, required pressure (1-4MP) and temperature (150-300 ℃) are higher.This class catalyst all must reduce active component before reaction, and when reaction, and required temperature and pressure is all higher.Second class, the precious metal element catalyst, 1.. the Pt-Sn/MCM-41 Preparation of catalysts method of document Microporous and Mesoporous Materials 44-45 (2001) 477-482 report, and, show higher activity and selectivity to the application of beta-unsaturated ketone/aldehyde compound hydrogenation.2. .US Pat.4,459,419 (July10,1984) have been described a kind of preparation method who loads on the ruthenium catalyst (containing ruthenium 1-2%) on the molecular sieve and to the application of organic ketone or aldehyde compound hydrogenation, have wherein been exemplified the effect of furfuryl alcohol liquid-phase hydrogenatin system tetrahydrofurfuryl alcohol.Though this class catalyst is better to the activity and the selectivity of required pure hydrogenation reaction, adopt hydrogen as reducing agent, the pressure of reaction is higher relatively, and owing to used precious metal element, the Preparation of catalysts cost is too high.3. .USPat.4,182,721 (Jan.8,1980) described a kind of molybdenum modification skeletal nickel catalyst (nickeliferous about 3-5%) the preparation method and to the application of organic ketone or aldehyde compound hydrogenation, wherein exemplify the effect of preparing furancarbinol from liquid-phase furol hydrogenation and tetrahydrofurfuryl alcohol.Though the method condition of this catalyst relaxes, the selectivity of product is low, and product separates and purification difficult.
The reducing agent that above-mentioned catalyst adopts when reaction all is a hydrogen, the pressure and temperature that reacts required is higher, to having relatively high expectations of reaction unit, and when reactant has other unsaturated bond, there is the competition reduction in reaction, easily other unsaturated bond is carried out hydrogenation, the selectivity that causes reacting reduces.The more class hydrogen transfer reaction of research recently also is to be used for reaction such as MPV (Meerwein-Ponndorf-Verley) reaction that aldehyde/ketone prepares correspondent alcohol, it is (to be reflected under the normal pressure under temperate condition, temperature is carried out under 75～100 ℃) with alcohol hydrogen source, carbonyl (C=O) is carried out the reaction of high-selective and hydrogenating reduction, when existing carbonyl (C=O) in the reactant has other unsaturated bond as (C=C) etc. again, only carbonyl (C=O) is carried out hydrogenating reduction and do not influence other unsaturated bond, the preparation of especially suitable unsaturated alcohol (as α, beta unsaturated alcohol, medicine intermediates such as alpha-phenyl ethyl alcohol).In the report, the homogeneous catalyst in the MPV reaction mostly is the metal alkoxide compound greatly, as Al (OR) at present
3, Zr (OR)
4Deng, catalytic efficiency is higher, but is difficult to reuse, separation difficulty, and the reaction back produces a large amount of pollutants.Heterogeneous catalyst can better overcome the above problems, more the having of research at present: metal oxides such as MgO, CaO, people such as Zhu Y.Z have studied zeolite molecular sieves such as Ti β, Zr β, Sn β, application in the MPV reaction such as the mesopore molecular sieve of grafting metal alkoxide, wherein contain Zr catalyst activity height, but Zr β zeolite is subjected to its limited aperture, reaction that can not effectively catalysis large scale molecule.The mesopore molecular sieve of grafting active high, the aperture is big, but needs vacuum or water-less environment during preparation, and preparation and regenerative process need a large amount of organic solvents.Mg-Al composite oxide (Mg/Al-LDO) has higher activity and selectivity in the MPV reaction, and prepare fairly simple, but the higher and suitable sintering temperature scope of sintering temperature of preparation Mg/Al-LDO is narrower, be generally 450～550 ℃, and regenerability is relatively poor, and the time of reacting required is longer.If can prepare a kind of catalyst, its characteristics comprise: all relative higher, the post-reaction treatment of required reaction condition gentleness, activity of such catalysts and selectivity is simple, preparation process is simple relatively, cost is cheap relatively, and this class catalyst will have market prospects very much.
The present application people discloses a kind of carrier zirconium oxide (ZrO in CN200910097548.1
2-Mg/Al-LDO) catalyst, the Al-Mg composite metal oxide Mg/Al-LDO that obtains with magnalium hydrotalcite Mg/Al-LDH roasting is a carrier, to be carried on the Zirconium oxide ZrO of carrier surface
2Be major catalyst, this catalyst is used for the reaction that the ketone hydrogenating reduction prepares alcohol compound, have advantages of high catalytic activity.But it double roasting can occur in preparation process, can increase the energy consumption of Preparation of Catalyst like this, and at load ZrO
2ZrO appears in the process sometimes
2Crystal grain disperses uneven phenomenon.At above-mentioned defective, the invention provides a kind of houghite based magnesium-zirconium-aluminum composite oxide thing (Mg/Zr/Al-LDO) Preparation of catalysts and application, it is simpler in preparation process, energy consumption is lower, and wherein Mg, Zr, three kinds of cationic distributing very evenly of Al, catalytic activity also increases.
(3) summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of houghite based magnesium-zirconium-aluminum composite oxide thing (Mg/Zr/Al-LDO) catalyst, this catalyst is applied to the reaction that the ketone hydrogenating reduction prepares alcohol compound, has that reaction condition gentleness, energy consumption of reaction are low, all relative higher, post-reaction treatment simple, preparation process is simple relatively, cost is cheap relatively a advantage with selectivity of activity of such catalysts.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is to be made through roasting by magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH; The composition of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is expressed as follows: (MgO)
x(ZrO
2)
y(Al
2O
3)
0.5, wherein x is 0～20, y is 0～1, wherein x, y all are not 0.Preferred x is 0.5～10; Preferred y is 0.06～1.
Magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH of the present invention is that a kind of interlayer is an anion, laminate is the Mg that is built bridge by hydroxyl, the laminated structure nano material that Zr and Al form, its preparation method adopts the preparation method of conventional hydrotalcite, preparation method commonly used is a coprecipitation, with the solubility magnesium salts, zirconates, aluminium salt, alkali and carbonate etc. are raw material, magnesium salts wherein, zirconates and aluminium salt can be nitrate, hydrochloride or sulfate etc., alkali can adopt NaOH, potassium hydroxide, ammoniacal liquor etc., carbonate can adopt sodium carbonate, potash etc. also can adopt urea to replace alkali and carbonate.Coprecipitation can adopt single (magnesium-zirconium-aluminum salt solution) method or two (magnesium-zirconium-aluminum salt solution and alkali-carbonate solution), under the condition of 0～80 ℃ of temperature (preferred 5～60 ℃), pH value 8.5～12.5 (preferred 9～11), obtain the co-precipitation slurries, obtain magnesium zirconium aluminum hydrotalcite through crystallization, washing, drying.Among the present invention, the molar ratio Zr/Al of the molar ratio Mg/Al of magnesium and aluminium and zirconium and aluminium can be with reference to the amount of the mol ratio Zr/Al of the mol ratio Mg/Al of magnesium among the magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO of needs preparation and aluminium and zirconium and aluminium in the preparation magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH process.
But magnesium zirconium aluminum hydrotalcite is through the high-temperature roasting dehydroxylation, veneer structure is destroyed, change magnesium zirconium aluminum composite metal oxide Mg/Zr/Al-LDO into, those skilled in the art can implement above-mentioned by the transformation of hydrotalcite Mg/Zr/Al-LDH to magnesium zirconium aluminum composite metal oxide Mg/Zr/Al-LDO according to prior art.The present invention recommends to carry out as follows: with magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH in air in 250～1000 ℃ of roasting 5～12h, obtain magnesium zirconium aluminum composite metal oxide Mg/Zr/Al-LDO.Preferred sintering temperature is 250～900 ℃; Further preferred sintering temperature is 300～900 ℃; Further preferred 300～700 ℃ again; Further preferred 300～500 ℃.Roasting time is little to the activity of such catalysts influence that makes, and it all can at 5～12h.
Second technical problem that the present invention will solve is that described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is applied in the reaction that the ketone hydrogenating reduction prepares the correspondent alcohol compounds.Described application is specific as follows: ketone, pure A and magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO are mixed, be heated to 60～120 ℃ of reducing carbonyls under stirring, fully obtain corresponding alcohol compound after the reaction; Described pure A is isopropyl alcohol or isobutanol, preferred isopropyl alcohol.The adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is counted 0.3～1.1g/3mmol with the molal quantity of ketone.
In the above-mentioned application technology scheme, reaction temperature is preferably 70～100 ℃;
In above-mentioned application technology scheme, usually after the reaction regular hour, take out response sample with the gas chromatographic analysis content that wherein cyclohexanol, cyclohexanone or alpha-phenyl ethyl alcohol, acetophenone and other may products.Reaction time is generally at 4～24h.
Above-mentioned application technology scheme is particularly useful for the hydrogenating reduction of cyclohexanone and acetophenone, when described ketone is cyclohexanone, the adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is preferably 0.3～0.5g/3mmol in the molal quantity of cyclohexanone, more preferably 0.4～0.5g/3mmol; When described ketone was acetophenone, the adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO was preferably 0.5～0.7g/2mmol in the molal quantity of acetophenone, more preferably 0.6～0.7g/2mmol.
It is 1: 3～30 that the present invention recommends the molar ratio of described ketone and pure A, preferred 1: 5～20.
Among the present invention, mixing speed is generally 30～180rpm, preferred 60～120rpm.
Beneficial effect of the present invention is mainly reflected in following several respects:
(1) the required reaction condition of catalyst provided by the invention relaxes: reaction temperature just can well be reacted at 75～100 ℃; Need not to react under the condition of high pressure, generally under normal pressure, just can react effectively.This can reduce energy consumption of reaction effectively.
(2) catalyst provided by the invention is a heterogeneous catalyst, this catalyst need not to use hydrogen reducing before reaction, just can directly use after the roasting, post catalyst reaction is comparatively easy with separating of reactant and product, and this selection of catalysts is very high: during to the beta-unsaturated ketone hydrogenating reduction, only carbonyl is carried out hydrogenating reduction, and do not influence other unsaturated bonds.
(3) catalyst provided by the invention used reducing agent when reaction is an isopropyl alcohol, it is simultaneously also as the solvent of ketone when reacting, rather than the used in the past reducing agent of picture is a hydrogen, also need to add another kind of organic solvent, hydrogen is dissolved in the organic solvent could react.So just make the post processing of ketone hydrogenation reduction easier.
(4) catalyst provided by the invention (Mg/Zr/Al-LDO) and disclosed carrier zirconium oxide (ZrO before
2-Mg/Al-LDO) catalyst is compared, and its preparation process is simpler, and energy consumption is lower, and wherein Mg, Zr, three kinds of cationic distributing very evenly of Al, and catalytic activity increases.Especially at the catalyst of low-temperature bake, its activity is significantly improved, and the speed of catalytic reaction also is significantly improved.
(4) description of drawings
Fig. 1 is different sintering temperature catalyst (Mg
2/ Zr
0.06/ Al
1-LDO) X-ray diffraction spectrogram.
(5) specific embodiment
With specific embodiment technical scheme of the present invention is further described below, but protection scope of the present invention is not limited thereto:
Embodiment 1: houghite based magnesium-zirconium-aluminum composite oxide thing (Mg/Zr/Al-LDO) Preparation of catalysts
The preparation of presoma magnesium zirconium aluminium houghite (Mg/Zr/Al-LDH): adopt coprecipitation, add 38.46g Mg (NO respectively
3)
26H
2O, 1.94g Zr (NO
3)
45H
2O and 28.13gAl (NO
3)
39H
2O in the deionized water of 100g, abundant stirring and dissolving.The Na that in a 500mL there-necked flask, adds 250mL
2CO
3Solution drops to magnesium zirconium aluminium mixed solution wherein, regulates the pH value 10.0 with NaOH solution simultaneously.After dropwising, white opacity liquid is put in the crystallizing kettle washing and filtering behind the crystallization 18h, with the white solid thing 100 ℃ down oven dry obtain magnesium zirconium aluminum hydrotalcite Mg
2/ Zr
0.06/ Al
1-LDH.
With above-mentioned magnesium zirconium aluminium houghite (Mg
2/ Zr
0.06/ Al
1-LDH) in air, obtain houghite based magnesium-zirconium-aluminum composite oxide thing (Mg behind 500 ℃ of following roasting 8h
2/ Zr
0.06/ Al
1-LDO-500) catalyst.
Embodiment 2: the Mg/Zr/Al-LDO Preparation of catalysts of different sintering temperatures
Method according to embodiment 1 makes catalyst precursor magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH, by changing the sintering temperature of catalyst precursor, make the Mg/Zr/Al-LDO catalyst of different sintering temperatures (250 ℃, 300 ℃, 400 ℃, 700 ℃, 900 ℃), roasting time is 8h.The gained catalyst is designated as: Mg
2/ Zr
0.06/ Al
1-LDO-300, Mg
2/ Zr
0.06/ Al
1-LDO-400, Mg
2/ Zr
0.06/ Al
1-LDO-700, Mg
2/ Zr
0.06/ Al
1-LDO-900.
Embodiment 3: carrier zirconium oxide (ZrO
2-Mg/Al-LDO) Preparation of catalysts
The preparation of carrier Mg-Al composite oxide (Mg/Al-LDO): adopt coprecipitation, add 38.46g Mg (NO respectively
3)
26H
2O and 28.13g Al (NO
3)
39H
2O in the deionized water of 100g, abundant stirring and dissolving.The Na that in a 500mL there-necked flask, adds 250mL
2CO
3Solution drops to the magnalium mixed solution wherein, regulates the pH value 10.0 with NaOH solution simultaneously.After dropwising, white opacity liquid is put in the crystallizing kettle washing and filtering behind the crystallization 12h, with the white solid thing 100 ℃ down oven dry to obtain the Mg/Al mol ratio be 2: 1 magnalium hydrotalcite (Mg
2/ Al
1-LDH).With the above-mentioned magnalium hydrotalcite (Mg that makes
2/ Al
1-LDH), in air, obtain Al-Mg composite metal oxide (Mg behind 500 ℃ of following roasting 8h
2/ Al
1-LDO).
And then with 1.47g Zr (NO
3)
45H
2O is dissolved in the 100g deionized water, adds 8g Mg again
2/ Al
1-LDO obtains the catalyst precursor Zr (NO of zirconium nitrate in the load at 100 ℃ of following dephlegmates
3)
4-Mg
2/ Al
1-LDO; At last it is dried down at 100 ℃, grind the back and obtain loaded catalyst behind 500 ℃ of roasting temperature 8h in air, the load capacity of gained loaded catalyst is 5%, is designated as 5%-ZrO
2-Mg
2/ Al
1-LDO-500.
Embodiment 4: the carrier zirconium oxide (ZrO of different sintering temperatures
2-Mg/Al-LDO) Preparation of catalysts
The catalyst precursor Zr (NO of zirconium nitrate in the load that makes according to the method for embodiment 3
3)
4-Mg
2/ Al
1-LDO by changing the sintering temperature of catalyst precursor, makes the 5%-ZrO of different sintering temperatures (250 ℃, 300 ℃, 400 ℃, 500 ℃, 700 ℃, 900 ℃)
2-Mg
2/ Al
1-LDO catalyst, roasting time 8h.The gained catalyst is designated as: 5%-ZrO
2-Mg
2/ Al
1-LDO-250,5%-ZrO
2-Mg
2/ Al
1-LDO-300,5%-ZrO
2-Mg
2/ Al
1-LDO-400,5%-ZrO
2-Mg
2/ Al
1-LDO-500,5%-ZrO
2-Mg
2/ Al
1-LDO-700,5%-ZrO
2-Mg
2/ Al
1-LDO-900.
Embodiment 5: the Mg/Zr/Al-LDO Preparation of catalysts of different Mg/Al ratio
According to the method for embodiment 1, keep Zr (NO
3)
45H
2O and Al (NO
3)
39H
2The consumption of O is constant, by changing Mg (NO
3)
26H
2The amount that O added, other conditions are with embodiment 1, and make the magnesium zirconium aluminum hydrotalcite (Mg/Zr/Al-LDH) of different Mg/Al content: the Mg/Al mol ratio among the Mg/Zr/Al-LDH was respectively 0.5: 1,1: 1,3: 1,4: 1,10: 1.Carry out roasting according to the method for embodiment 1 respectively then and obtain 5 kinds of magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO, the gained catalyst is designated as: Mg
0.5/ Zr
0.06/ Al
1-LDO, Mg
1/ Zr
0.06/ Al
1-LDO, Mg
3/ Zr
0.06/ Al
1-LDO, Mg
4/ Zr
0.06/ Al
1-LDO, Mg
10/ Zr
0.06/ Al
1-LDO.
Embodiment 6-1: the Mg/Zr/Al-LDO Preparation of catalysts of different zirconium content
According to the method for embodiment 1, keep Mg (NO
3)
26H
2O and Al (NO
3)
39H
2The consumption of O is constant, by changing the Zr (NO that is added
3)
45H
2The O amount, other conditions make different zirconium content magnesium zirconium aluminum hydrotalcites (Mg/Zr/Al-LDH) with embodiment 1: the Mg/Zr/Al mol ratio among the Mg/Zr/Al-LDH is respectively: 2: 0.06: 1,2: 0.1: 1,2: 0.2: 1,2: 0.5: 1,2: 0.7: 1.Under 300 ℃, carry out roasting then respectively and obtain 4 kinds of magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO, roasting time 8h.The gained catalyst is designated as: Mg
2/ Zr
0.06/ Al
1-LDO-300, Mg
2/ Zr
0.1/ Al
1-LDO-300, Mg
2/ Zr
0.2/ Al
1-LDO-300, Mg
2/ Zr
0.5/ Al
1-LDO-300, Mg
2/ Zr
0.7/ Al
1-LDO-300.
Embodiment 6-2
Sintering temperature changes 500 ℃ into, and other are operated with embodiment 6-1, and the gained catalyst is designated as: Mg
2/ Zr
0.1/ Al
1-LDO-500, Mg
2/ Zr
0.2/ Al
1-LDO-500, Mg
2/ Zr
0.5/ Al
1-LDO-500, Mg
2/ Zr
0.7/ Al
1-LDO-500.
Embodiment 7:
Use the catalyst (Mg of embodiment 1 preparation
2/ Zr
0.06/ Al
1-LDO-500), in the 50mL single necked round bottom flask, add 0.5g catalyst, 3mmol cyclohexanone, 60mmol isopropyl alcohol, on connect a condenser pipe, the other end of condenser pipe need not sealing, heats in 82 ℃ of oil baths, uses magnetic agitation simultaneously, behind the reaction 10h, take out response sample, with the gas chromatographic analysis content of cyclohexanol, cyclohexanone wherein, the result is as shown in table 1.
Embodiment 8:
According to the processing method of embodiment 7, it is cyclohexanol that the catalyst that adopts embodiment 2 to prepare carries out hydrogenating reduction to cyclohexanone, and other conditions are with embodiment 7, and the result is as shown in table 1:
The reaction result of table 1. embodiment 8
Embodiment 9:
According to the processing method of embodiment 7, it is cyclohexanol that the catalyst that adopts embodiment 4 to prepare carries out hydrogenating reduction to cyclohexanone, and other conditions are with embodiment 7, and the result is as shown in table 2:
The reaction result of table 2. embodiment 9
Embodiment 10:
According to the processing method of embodiment 7, adopt the catalyst (Mg of embodiment 1 and 3 preparations
2/ Zr
0.06/ Al
1-LDO-500,5%-ZrO
2-Mg
2/ Al
1-LDO-500) cyclohexanone to be carried out hydrogenating reduction be cyclohexanol, gets the reactant analysis at regular intervals, and other conditions are with embodiment 7, and the result is as shown in table 3:
The reaction result of table 3. embodiment 10
Embodiment 11:
According to the processing method of embodiment 7, it is cyclohexanol that the catalyst that adopts embodiment 1 and embodiment 5 to prepare carries out hydrogenating reduction to cyclohexanone, and other conditions are with embodiment 7, and the result is as shown in table 4:
The reaction result of table 4. embodiment 11
Embodiment 12:
According to the processing method of embodiment 7, it is cyclohexanol that the catalyst that adopts embodiment 6-1 to prepare carries out hydrogenating reduction to cyclohexanone, and other conditions are with embodiment 7, and the result is as shown in table 5:
The reaction result of table 5. embodiment 12
Embodiment 13:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6-2 preparation
2/ Zr
0.5/ Al
1-LDO-500), add the amount of catalyst by changing, add 0.1g, 0.3g, 0.5g catalyst respectively, other conditions are with embodiment 7, and it is cyclohexanol that cyclohexanone is carried out hydrogenating reduction, and the result is as shown in table 6:
The reaction result of table 6. embodiment 13
Embodiment 14:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 1 preparation
2/ Zr
0.06/ Al
1-LDO-500), in flask, add the 0.7g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 91.98%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 15:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6-2 preparation
2/ Zr
0.2/ Al
1-LDO-500), in flask, add the 0.7g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 94.45%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 16:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6-2 preparation
2/ Zr
0.2/ Al
1-LDO-500), in flask, add the 0.5g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 64.45%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 17:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6-2 preparation
2/ Zr
0.5/ Al
1-LDO-500), in flask, add the 0.7g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 95.06%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 18:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6 preparations
2/ Zr
0.5/ Al
1-LDO-500), in flask, add the 0.5g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 70.33%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 19:
According to the processing method of embodiment 7, use the catalyst (Mg of embodiment 6-2 preparation
2/ Zr
0.7/ Al
1-LDO-500), in flask, add the 0.7g catalyst, the 2mmol acetophenone, the 40mmol isopropyl alcohol behind the reaction 24h, takes out the response sample analysis.The conversion ratio of acetophenone is 86.58%, and the selectivity of alpha-phenyl ethyl alcohol is 100%.
Embodiment 20:
According to the processing method of embodiment 7, adopt the catalyst (Mg of embodiment 1 and 3 preparations
2/ Zr
0.06/ Al
1-LDO-500,5%-ZrO
2-Mg
2/ Al
1-LDO-500) cyclohexanone to be carried out hydrogenating reduction be cyclohexanol, after reaction is finished, with the washed with isopropyl alcohol oven dry, once more cyclohexanone carried out the reaction that hydrogenating reduction is a cyclohexanol at 350 ℃ of following roasting 5h then.The conversion ratio of cyclohexanone and the selectivity of cyclohexanol such as result are as shown in table 7:
The reaction result of table 7. embodiment 20
Claims (10)
1. a magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is to be made through roasting by magnesium zirconium aluminum hydrotalcite Mg/Zr/Al-LDH; The composition of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is expressed as follows: (MgO)
x(ZrO
2)
y(Al
2O
3)
0.5, wherein x is 0～20, y is 0～1.
2. magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO as claimed in claim 1 is characterized in that the condition of described roasting is: 250～1000 ℃ of roastings 5～12 hours.
3. magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO as claimed in claim 2 is characterized in that sintering temperature is 250～900 ℃.
4. as the described magnesium-zirconium-aluminum composite oxide thing of one of claim 1～3 catalyst Mg/Zr/Al-LDO, it is characterized in that described x is 0.5～10.
5. as the described magnesium-zirconium-aluminum composite oxide thing of one of claim 1～3 catalyst Mg/Zr/Al-LDO, it is characterized in that described y is 0.06～1.
6. magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO as claimed in claim 1 prepares application in the correspondent alcohol compounds at the ketone hydrogenating reduction, it is characterized in that described application is specific as follows: ketone, pure A and magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO are mixed, be heated to 60～150 ℃ of reducing carbonyls under stirring, fully obtain corresponding alcohol compound after the reaction; Described pure A is isopropyl alcohol or isobutanol; Described ketone is cyclohexanone or acetophenone; The adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is counted 0.3～1.1g/3mmol with the molal quantity of ketone.
7. application as claimed in claim 6, the molar ratio that it is characterized in that described ketone and pure A is 1: 5～20.
8. as claim 6 or 7 described application, it is characterized in that being heated to 70～100 ℃ of reducing carbonyls.
9. as claim 6 or 7 described application, it is characterized in that described ketone is cyclohexanone, the adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is counted 0.3～0.5g/3mmol with the molal quantity of cyclohexanone.
10. as claim 6 or 7 described application, it is characterized in that described ketone is acetophenone, the adding quality of described magnesium-zirconium-aluminum composite oxide thing catalyst Mg/Zr/Al-LDO is counted 0.5～0.7g/2mmol with the molal quantity of acetophenone.
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Cited By (5)
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| CN103691416A (en) * | 2013-12-31 | 2014-04-02 | 张锦碧 | Catalyst for synthesizing isophorone |
| CN103920480A (en) * | 2014-04-19 | 2014-07-16 | 江苏怡达化学股份有限公司 | Magnesium-aluminum-zirconium solid catalyst for embedded synthesis of alkoxy alcohol ether ester in one step |
| CN109678655A (en) * | 2019-01-23 | 2019-04-26 | 江南大学 | Nickel-ferric spinel catalyst is preparing the application in benzyl alcohol |
| CN112221480A (en) * | 2020-09-01 | 2021-01-15 | 河北工业大学 | Catalyst for preparing styrene by dehydrating phenethyl alcohol and preparation and application methods thereof |
| CN112808273A (en) * | 2021-02-04 | 2021-05-18 | 福州大学 | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed |
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2009
- 2009-12-03 CN CN200910154745A patent/CN101716500A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691416A (en) * | 2013-12-31 | 2014-04-02 | 张锦碧 | Catalyst for synthesizing isophorone |
| CN103920480A (en) * | 2014-04-19 | 2014-07-16 | 江苏怡达化学股份有限公司 | Magnesium-aluminum-zirconium solid catalyst for embedded synthesis of alkoxy alcohol ether ester in one step |
| CN103920480B (en) * | 2014-04-19 | 2015-12-30 | 江苏怡达化学股份有限公司 | An a kind of step embeds the magnesium-aluminum-zirconium solid catalyst of synthesis alkoxyl alcohol ether-ether |
| CN109678655A (en) * | 2019-01-23 | 2019-04-26 | 江南大学 | Nickel-ferric spinel catalyst is preparing the application in benzyl alcohol |
| CN109678655B (en) * | 2019-01-23 | 2020-05-08 | 江南大学 | Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol |
| CN112221480A (en) * | 2020-09-01 | 2021-01-15 | 河北工业大学 | Catalyst for preparing styrene by dehydrating phenethyl alcohol and preparation and application methods thereof |
| CN112221480B (en) * | 2020-09-01 | 2021-09-14 | 河北工业大学 | Catalyst for preparing styrene by dehydrating phenethyl alcohol and preparation and application methods thereof |
| CN112808273A (en) * | 2021-02-04 | 2021-05-18 | 福州大学 | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed |
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