CN101537352B - Preparation method of mesoporous aluminum oxide material loading platinum catalyst - Google Patents
Preparation method of mesoporous aluminum oxide material loading platinum catalyst Download PDFInfo
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Abstract
The invention discloses a mesoporous aluminum oxide material loading platinum catalyst as well as a preparation method and an application thereof. The invention is characterized in that the catalyst is a mesoporous aluminum oxide material loading platinum catalyst assembled by using mesoporous silicon oxide (SBA-15) as the substrate threshold; in the preparation method of the catalyst, Al(NO3)3.9H2O is taken as the aluminum source, introduced by solid phase grinding into the porous channel of the mesoporous silicon oxide for which surface active agent is not deprived yet, and is calcinated to obtain a mesoporous aluminum oxide composite material; and platinic chloride is taken as an active component precursor and the mesoporous aluminum oxide is used as a carrier, the active component precursor and the carrier are soaked and dried before being reduced in aqueous solution of sodium formate to obtain the catalyst. The catalyst can be used in multi-phase asymmetrical hydrogenation reaction of alpha-Keto ester after the surface of the catalyst is modified by cinchonidine. Compared with the prior art, the invention has the advantages of simple method, good material water thermal stability and high aluminum oxide dispersion degree, the catalysis performance of the catalyst is good, the optical selectivity of the product R-(+)- ethyl lactate can be over 93%ee.
Description
Technical field
The present invention relates to chemical catalysis material and synthesis technical field, specifically a kind of mesoporous aluminum oxide material loading platinum catalyst and preparation method and application.
Background technology
Activated alumina is owing to known by masses in the extensive use of adsorbing domain and catalytic field.It not only can come dry gas and liquid as adsorbent; Also often be widely used as the catalyst or the catalyst carrier of oil and chemical engineering industry.In recent years, the platinum catalyst of gama-alumina load (Pt/ γ-Al
2O
3) or palladium catalyst (Pd/ γ-Al
2O
3) asymmetric catalytic hydrogenation of chiral carbonyl compounds or latent chirality carbon-carbon double bond substrate that is used for diving behind the chirality molecular modification, synthetic fine chemicals (as chiral drug, agricultural chemicals, spices and food additives etc.) with high added value be one of successful example of heterogeneous asymmetric catalysis field only a few research (Accounts of Chemical Research 37 (2004) 909; Advanced Synthesis﹠amp; Catalysis345 (2003) 45; Current Organic Chemistry 10 (2006) 1533).The platinum catalyst of alumina load (Pt/ γ-Al
2O
3) asymmetric hydrogenation of the chiral carbonyl compounds (comprising 2-ketoacid ester and derivative thereof) that after cinchona alkaloid (cinchona alkaloid) chirality is modified, can be used for diving, show very high catalytic activity and optical selective, had industrial applications to produce the example of chiral drug precursor at present.
Heterogeneous asymmetry catalysis not only has advantages such as chirality increment, high optical selective, economy makes it become the most rising research field in the chiral drug industrial preparation, and realize the separation and the processing of chiral catalyst easily, and be easy to carry out continuous reaction, have better industrial application prospect, therefore also more and more cause the extensive concern and the attention (Chemical﹠amp of academia and industrial quarters in recent years; EngineeringNews 79 (2001) 79; 81 (2003) 45).Yet, because numerous influence factors has caused the system that research is successful in the heterogeneous asymmetric catalysis field also few in the heterogeneous asymmetry catalysis system.Platinum catalyst system (Pt/ γ-Al that cinchona alkaloid chirality mentioned above is modified
2O
3-cinchona alkaloid) be exactly to study one of more successful example in the heterogeneous asymmetric catalysis field.For this research system, both at home and abroad the colleague has carried out finding after a large amount of research the asymmetric hydrogenation of chiral carbonyl compounds in acetic acid solvent of diving on the alumina load platinum catalyst that cinchonidine (one of cinchona alkaloid) chirality modifies, can obtain advantages of high catalytic activity and optical selective (for some substrate, optical selective can reach more than the 97%ee).The Li Can academician's of the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences research group is exactly the forerunner of this research field, and they have also obtained good result (Catalysis Reviews-Science and Engineering 46 (2004) 419).But because aluminium oxide can produce surperficial peptization (peptization) phenomenon when the medium-term and long-term use of acid medium, this has just caused the alumina load platinum catalyst system (Pt/ γ-Al of excellent performance
2O
3) nano particle of active component platinum makes it can not haptoreaction substrate and chirality dressing agent molecule gradually by the alumina-coated of peptizationization when reusing in acetic acid solvent, thereby make catalytic performance along with reusable number of times reduces significantly.
In addition, along with the growing interest of in recent years ordered mesoporous material being studied, the many researchers that comprise Li Can academician think the duct limit threshold effect that utilizes ordered mesoporous material, can provide the more space influence factor for the formation of reaction system middle transition attitude, should help improving the optical selective of product.There are many examples also to prove this point (Catalysis Reviews-Science and Engineering 46 (2004) 419).Li Can academician's research group also once attempted using directly synthetic meso-porous alumina as carrier loaded platinum catalyst, yet did not realize satisfactory results.This is because the meso-porous alumina hydrothermal stability that the direct synthetic method of using for reference silica-based or other ordered mesoporous material is synthesized is poor, and the platinum catalyst of alumina load (Pt/ γ-Al
2O
3) in preparation process, adopt the aqueous solution of platinum salt precursor to come the oxide impregnation alumina supporter mostly.And; in view of present people are progressively giving increasing attention for Green Chemistry and green chemical industry; people's environmental protection consciousness is more and more stronger; therefore water also more and more causes people's attention as solvent a kind of green, eco-friendly or reaction medium; people expect to have more chemical reaction process to carry out in water, and the hydrothermal stability that improves mesoporous aluminum oxide material is very necessary.
In sum, we can find, improve the acid resistance of alumina material, the hydrothermal stability of raising mesoporous aluminum oxide material, alumina load platinum catalyst system and catalyzing (Pt/ γ-Al that the cinchona alkaloid chirality is modified
2O
3-cinchona alkaloid) performance is further perfect, thereby this individual system can be more widely used in heterogeneous asymmetric catalytic hydrogenation field, has become new challenging research topic and the task of pendulum in face of us.
Mesoporous material is a kind of aperture (novel porous material between 2～50nm) between micropore and macropore.It has the excellent specific property that other porous material does not have: specific area is big; Pore passage structure with high-sequential, mesoporous aperture homogeneous is adjustable; Mesoporous shape is various, and the composition and the character of hole wall are adjustable; Inner surface is easy to modify; Skeleton structure is stable, and other component is easy to mix; Can obtain the mesoporous material of high thermal stability and hydrothermal stability by the optimization of synthesis condition.Ordered mesoporous material just obtains the great attention of international physics, chemistry and material circle from being born, become one of focus of interdisciplinary research rapidly, and potential using value is arranged at numerous areas such as chemical, biological medicine, environmental science, separation science and functional materials.Recently, the method of Nanjing University Zhu Jianhua professor's research group by solid-phase grinding with oxide (cupric oxide, magnesia etc.) high degree of dispersion in duct without the pure silicon mesoporous material SBA-15 of removed template method, successfully prepare the metal oxide oxidation catalyst material of high degree of dispersion, also realized the functionalization (Advanced Materials 17 (2005) 323) of pure silicon mesoporous material SBA-15.
Therefore, can utilize silica-based ordered mesoporous material (as SBA-15 etc.) to be substrate, prepare novel meso-porous alumina composite (Al by method with precursor solid-phase grinding, liquid impregnation or the vapour deposition of aluminium salt
2O
3@SBA-15), and as carrier-supported precious metal platinum active component (Pt/Al
2O
3@SBA-15), be used for heterogeneous asymmetric hydrogenation after its surface being modified and then by chiral molecules.
Summary of the invention
A kind of mesoporous aluminum oxide material loading platinum catalyst and preparation method and the application that provide at the deficiencies in the prior art is provided, it adopts silica is the meso-porous alumina composite load platinum of substrate limit threshold assembling, aluminium oxide decentralization height, good hydrothermal stability, the heterogeneous asymmetric hydrogenation that is used for the 2-ketoacid ester after by chiral molecules the platinum surface being modified, its catalytic performance is good, conversion ratio is about 100%, and the optical selective of product R-(+)-ethyl lactate can reach more than the 93%ee.
The concrete technical scheme that realizes the object of the invention is: a kind of mesoporous aluminum oxide material loading platinum catalyst, characteristics are that this catalyst is that the meso-porous alumina composite that substrate limit threshold is assembled is a carrier with mesopore silicon oxide (SBA-15), chloroplatinic acid is the active component precursor, its metal platinum is 0.03～0.18 at the decentralization of carrier surface, loading is 2.4～4.0wt.% (percentage by weight), the platinum particles average grain diameter is 6.3～40.0nm, and the expression of mesoporous aluminum oxide material loading platinum catalyst is Pt/xAS;
Wherein: AS represents the composite (Al of aluminium oxide and silica
2O
3@SBA-15);
X represents the alumina weight degree of AS, and when x equaled 0, expression was Pt/SBA-15; When x equaled 100, expression was Pt/Al
2O
3
A kind of preparation method of above-mentioned mesoporous aluminum oxide material loading platinum catalyst, characteristics are that this method is with Al (NO
3)
39H
2O is the aluminium source, be introduced into by solid-phase grinding and do not remove surfactant P123 (its molecular formula is EO20PO70EO20, mean molecule quantity is 5800) the duct of mesopore silicon oxide (SBA-15) in, after roasting, obtain mesoporous oxidation clad aluminum material, and be that active component precursor, meso-porous alumina composite are carrier with the chloroplatinic acid, reduction makes mesoporous aluminum oxide material loading platinum catalyst in the aqueous solution at sodium formate after dipping, the drying, and concrete preparation may further comprise the steps:
A, with Al (NO
3)
39H
2O with without the mesopore silicon oxide that removes surfactant (SBA-15), adopt solid-phase grinding to mix its Al (NO
3)
39H
2O and silica (SBA-15) weight ratio was respectively 0.7137: 1; 1.3480: 1; 2.1776: 1 and 3.3088: 1, mix the back and obtained alumina content in 5～6 hours at 500 ℃ of roasting temperatures and be respectively 15%, 25%, 35% and 45% meso-porous alumina composite;
B, be 15%, 25%, 35% and 45% meso-porous alumina composite and the silica (SBA-15), the Al that have removed surfactant P123 (its molecular formula is EO20PO70EO20, and mean molecule quantity is 5800) with the above-mentioned alumina content that obtains
2O
3Be carrier, drip platinum acid chloride solution respectively in carrier, the weight ratio of metal platinum and carrier is 1: 24～40.6, stirs solvent evaporated after 4 hours, and drying got the mesoporous aluminum oxide material loading platinum catalyst precursor in 12 hours in 120 ℃ of baking ovens then;
C, with above-mentioned catalyst precarsor 350～500 ℃ of roasting temperatures 2 hours or without roasting;
D, be that 0.06～0.1mol/L, temperature are that 95 ℃ aqueous sodium formate solution refluxed 2 hours in concentration with above-mentioned roasting or without the catalyst precarsor of roasting, catalyst after obtaining reducing, the mol ratio of sodium formate in its aqueous sodium formate solution and catalyst precarsor platinum content is 10: 1;
D, the catalyst after the above-mentioned reduction is spent deionised water after filtering, and with 100 ℃ of dryings 10～15 hours mesoporous aluminum oxide material loading platinum catalyst.
Described platinum acid chloride solution is the ethanol solution of chloroplatinic acid, pure water solution or the absolute ethyl alcohol of chloroplatinic acid and the mixed solution of pure water of chloroplatinic acid, and chloroplatinic acid and absolute ethyl alcohol are preparation in 1: 25 by weight in the ethanol solution of its chloroplatinic acid; Chloroplatinic acid and pure water are preparation in 1: 31.6 by weight in the pure water solution of chloroplatinic acid; Chloroplatinic acid, absolute ethyl alcohol, pure water are preparation in 1: 12.5: 15.8 by weight in the absolute ethyl alcohol of chloroplatinic acid and the mixed solution of pure water.
A kind of application of above-mentioned mesoporous aluminum oxide material loading platinum catalyst, characteristics are the heterogeneous asymmetric hydrogenations that are used for the 2-ketoacid ester after by cinchonidine its surface being modified, and specifically may further comprise the steps:
A, with preliminary treatment in the hydrogen of mesoporous aluminum oxide material loading platinum catalyst under 400 ℃ of temperature 2 hours.
B, above-mentioned pretreated catalyst and cinchonidine, acetate, ethyl pyruvate are fed the pure hydrogen that pressure is 4.0 MPas in reactor, under electromagnetic agitation, carry out asymmetric catalytic hydrogenation reaction 5～30 minutes, reaction temperature is a room temperature, and its catalyst, cinchonidine, acetate, ethyl pyruvate weight ratio are 10: 1: 2100: 208.
After finishing, c, hydrogenation, and its product is analyzed with gas-chromatography with after its product and the catalyst separation.
It is simple that the present invention compared with prior art has method, easy to operate advantage, and material water Heat stability is good, aluminium oxide decentralization height, the heterogeneous asymmetric hydrogenation that is used for the 2-ketoacid ester after its load platinum catalyst is modified its surface by chiral molecules, its catalytic performance is good, conversion ratio 100%, and the optical selective of product R-(+)-ethyl lactate can reach more than the 93%ee.
Description of drawings
Fig. 1 is the little angle x-ray diffraction pattern (XRD) of carrier among the present invention
Fig. 2～Fig. 7 is the little angle x-ray diffraction pattern (XRD) of catalyst of the present invention
Fig. 8～Figure 12 is the N of catalyst of the present invention
2The adsorption-desorption curve
Figure 13～Figure 15 is transmission electron microscope (TEM) photo of catalyst of the present invention
Figure 16 is the big angle x-ray diffraction pattern (XRD) of catalyst of the present invention
The specific embodiment
The present invention is described in further detail by following specific embodiment.
A, preparation alumina content are 15%, 25%, 35% and 45% meso-porous alumina composite
(1) takes by weighing 1g respectively without silica that removes surfactant P123 (SBA-15) and 0.7137gAl (NO
3)
39H
2O; 1g is without silica that removes surfactant P123 (SBA-15) and 1.3480gAl (NO
3)
39H
2O; 1g is without silica that removes surfactant P123 (SBA-15) and 2.1776gAl (NO
3)
39H
2O; 1g is without silica that removes surfactant P123 (SBA-15) and 3.3088gAl (NO
3)
39H
2O is standby.
(2) above-mentioned four parts of different proportion raw material were fully ground 1 hour in agate mortar respectively, powder after will grinding then is placed in Muffle furnace or the tube furnace air atmosphere through 500 ℃ of roastings 6 hours, making alumina weight percentage respectively is the alumina material of 15%, 25%, 35% and 45% mesopore silicon oxide limit threshold assembling, and its numbering is respectively 15AS; 25AS; 35AS; 45AS.
B, preparation catalyst
(1) takes by weighing the alumina material 15AS that above-mentioned alumina weight percentage is the assembling of 15%, 25%, 35% and 45% mesopore silicon oxide limit threshold respectively; 25AS; 35AS; Each 1 gram of 45AS and 1 gram have removed silica (SBA-15), the 1 gram Al of surfactant P123 (its molecular formula is EO20PO70EO20, and mean molecule quantity is 5800)
2O
3For carrier standby.
(2) in above-mentioned six kinds of different carriers, drip the ethanol solution of 2.76mL chloroplatinic acid respectively, and then adding 10mL anhydrous ethanol solvent, dipping is after 4 hours under electromagnetic agitation, the solvent that evaporate to dryness is unnecessary, put into baking oven with 120 ℃ of oven dry 12 hours, the catalyst precarsor that to make six kinds of metal platinum loadings respectively be 4.0% (percentage by weight), the ethanol solution of chloroplatinic acid is pressed: (molecular formula is H to 1 gram, six hydration chloroplatinic acids
2PtCl
66H
2O, molecular weight are 517.92, and wherein the content of Pt is 37%) be dissolved in 25 milliliters absolute ethyl alcohol, being mixed with concentration is the chloroplatinic acid ethanol solution of 14.8g Pt/L.
(3) with six kinds of catalyst precarsors of above-mentioned preparation respectively in Muffle furnace in 500 ℃ of roastings 2 hours.
(4) six kinds of catalyst precarsors after the above-mentioned roasting were refluxed 2 hours in the sodium formate solution of 20mL respectively, reflux temperature is 95 ℃, sodium formate concentrations is 0.1mol/L, backflow after finishing is filtered catalyst precarsor, and with the washing of a large amount of deionized water, dried 12 hours with 100 ℃ in baking oven then, reduction makes six kinds of mesoporous aluminum oxide material loading platinum catalysts.
These six kinds carrier loaded platinum series catalyst, it is numbered: 4.0wt.%Pt/xAS-E-500, the metal platinum that records with the CO chemisorbed sees Table 1 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier xAS is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 2; The N of catalyst
2Adsorption-desorption is seen Fig. 8; The transmission electron microscope of catalyst is seen Figure 13; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 1. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 4.0wt.％Pt/15AS-E-500? | 4.0? | |
500? | 25.4? | 4.45? |
| 4.0wt.％Pt/25AS-E-500? | 4.0? | |
500? | 40.8? | 2.77? |
| 4.0wt.％Pt/35AS-E-500? | 4.0? | |
500? | 29.3? | 3.87? |
| 4.0wt.％Pt/45AS-E-500? | 4.0? | |
500? | 21.9? | 5.16? |
The meso-porous alumina composite of a, preparation 15%, 25% and 35%
(1) takes by weighing 1g respectively without silica that removes surfactant P123 (SBA-15) and 0.7137gAl (NO
3)
39H
2O; 1g is without silica that removes surfactant P123 (SBA-15) and 1.3480gAl (NO
3)
39H
2O; 1g is without silica that removes surfactant P123 (SBA-15) and 2.1776gAl (NO
3)
39H
2O is standby.
(2) above-mentioned three parts of different proportion raw material were fully ground 1 hour in agate mortar respectively, powder after will grinding then is placed in Muffle furnace or the tube furnace air atmosphere through 500 ℃ of roastings 6 hours, making alumina weight percentage is the alumina material of 15%, 25% and 35% mesopore silicon oxide limit threshold assembling, and its numbering is respectively: 15AS; 25AS; 35AS.
B, preparation catalyst
(1) takes by weighing the alumina material 15AS that above-mentioned alumina weight percentage is the assembling of 15%, 25% and 35% mesopore silicon oxide limit threshold respectively; 25AS; Each 1 gram of 35AS and 1 gram have removed silica (SBA-15), the 1 gram Al of surfactant
2O
3For carrier standby.
(2) in above-mentioned five kinds of different carriers, drip the ethanol solution of 2.76mL chloroplatinic acid respectively, and then adding 10mL anhydrous ethanol solvent, dipping is after 4 hours under electromagnetic agitation, the solvent that evaporate to dryness is unnecessary, put into baking oven with 120 ℃ of oven dry 12 hours, the catalyst precarsor that to make six kinds of metal platinum loadings respectively be 4.0% (percentage by weight), the ethanol solution of chloroplatinic acid is pressed: (molecular formula is H to 1 gram, six hydration chloroplatinic acids
2PtCl
66H
2O, molecular weight are 517.92, and wherein the content of Pt is 37%) be dissolved in 25 milliliters absolute ethyl alcohol, being mixed with concentration is the chloroplatinic acid ethanol solution of 14.8g Pt/L.
(3) with five kinds of catalyst precarsors of above-mentioned preparation respectively in Muffle furnace in 350 ℃ of roastings 2 hours.
(4) five kinds of catalyst precarsors after the above-mentioned roasting were refluxed 2 hours in the sodium formate solution of 20mL respectively, reflux temperature is 95 ℃, sodium formate concentrations is 0.1mol/L, backflow after finishing is filtered catalyst precarsor, and with the washing of a large amount of deionized water, dried 14 hours with 100 ℃ in baking oven then, reduction makes five kinds of mesoporous aluminum oxide material loading platinum catalysts.
These five kinds carrier loaded platinum series catalyst, it is numbered: 4.0wt.%Pt/xAS-E-350, the metal platinum that records with the CO chemisorbed sees Table 2 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 3; The N of catalyst
2Adsorption-desorption is seen Fig. 9; The transmission electron microscope of catalyst is seen Figure 14; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 2. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 4.0wt.％Pt/15AS-E-350? | 4.0? | |
350? | 45.1? | 2.51? |
| 4.0wt.％Pt/25AS-E-350? | 4.0? | |
350? | 11.0? | 10.3? |
| 4.0wt.％Pt/35AS-E-350? | 4.0? | |
350? | 28.9? | 3.92? |
The meso-porous alumina composite of a, preparation 15%, 25% and 35%
With a step among the embodiment 2.
B, preparation catalyst
(1) with the b step (1) among the embodiment 2.
(2) with the b step (2) among the embodiment 2.
(3) above-mentioned five kinds of catalyst precarsors were refluxed 2 hours in the sodium formate solution of 20mL respectively, reflux temperature is 95 ℃, sodium formate concentrations is 0.1mol/L, backflow after finishing is filtered catalyst precarsor, and with the washing of a large amount of deionized water, dried 11 hours with 100 ℃ in baking oven then, reduction makes five kinds of mesoporous aluminum oxide material loading platinum catalysts.
These five kinds carrier loaded platinum series catalyst, it is numbered: 4.0wt.%Pt/xAS-E, the metal platinum that records with the CO chemisorbed sees Table 3 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 4; The N of catalyst
2Adsorption-desorption is seen Figure 10; The transmission electron microscope of catalyst is seen Figure 15; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 3. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 4.0wt.％Pt/15AS-E? | 4.0? | Ethanol | --? | 19.4? | 5.84? |
| 4.0wt.％Pt/25AS-E? | 4.0? | Ethanol | --? | 15.9? | 7.1? |
| 4.0wt.％Pt/35AS-E? | 4.0? | Ethanol | --? | 15.7? | 7.2? |
The meso-porous alumina composite of a, preparation 15%, 25% and 35%
With a step among the embodiment 2.
B, preparation catalyst
(1) with the b step (1) among the embodiment 2.
(2) in above-mentioned five kinds of different carriers, drip the pure water solution of 2.76mL chloroplatinic acid respectively, and then adding 10mL pure water solvent, dipping is after 4 hours under electromagnetic agitation, the solvent that evaporate to dryness is unnecessary, put into baking oven with 120 ℃ of oven dry 12 hours, the catalyst precarsor that to make five kinds of metal platinum loadings respectively be 4.0% (percentage by weight), the pure water solution of chloroplatinic acid is pressed: (molecular formula is H2PtCl66H2O to 1 gram, six hydration chloroplatinic acids, molecular weight is 517.92, wherein the content of Pt is 37%) be dissolved in 25 milliliters pure water, being mixed with concentration is the chloroplatinic acid pure water solution of 14.8g Pt/L.
(3) with the b step (3) among the embodiment 3.
These five kinds carrier loaded platinum series catalyst, it is numbered: 4.0wt.%Pt/xAS-W, the metal platinum that records with the CO chemisorbed sees Table 4 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 5; The N of catalyst
2Adsorption-desorption is seen Figure 11; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 4. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 4.0wt.％Pt/15AS-W? | 4.0? | Water | --? | 19.9? | 5.7? |
| 4.0wt.％Pt/25AS-W? | 4.0? | Water | --? | 14.5? | 7.8? |
| 4.0wt.％Pt/35AS-W? | 4.0? | Water | --? | 20.9? | 5.4? |
The meso-porous alumina composite of a, preparation 15%, 25% and 35%
With a step among the embodiment 2.
B, preparation catalyst
(1) with the b step (1) among the embodiment 2.
(2) in above-mentioned five kinds of different carriers, drip the absolute ethyl alcohol of 2.76mL chloroplatinic acid and the mixed solution of pure water respectively, and then the mixed solvent of adding 10mL absolute ethyl alcohol and pure water, dipping is after 4 hours under electromagnetic agitation, the solvent that evaporate to dryness is unnecessary, put into baking oven with 120 ℃ of oven dry 12 hours, the catalyst precarsor that to make five kinds of metal platinum loadings respectively be 4.0% (percentage by weight), the absolute ethyl alcohol of chloroplatinic acid and the mixed solution of pure water are pressed: (molecular formula is H to 1 gram, six hydration chloroplatinic acids
2PtCl
66H
2O, molecular weight is 517.92, wherein the content of Pt is 37%) be dissolved in the mixed solvent that 25 milliliters absolute ethyl alcohol and pure water are formed, wherein the volume ratio of absolute ethyl alcohol and pure water is 1: 1, is mixed with concentration and is the absolute ethyl alcohol of chloroplatinic acid of 14.8g Pt/L and the mixed solution of pure water.
(3) with the b step (4) among the embodiment 2.
These five kinds of mesoporous aluminum oxide material loading platinum series catalyst, it is numbered: 4.0wt.%Pt/xAS-W+E, the metal platinum that records with the CO chemisorbed sees Table 5 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 6; The N of catalyst
2Adsorption-desorption is seen Figure 12; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 5. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 4.0wt.％Pt/15AS-W+E? | 4.0? | Ethanol, water | --? | 6.65? | 17.0? |
| 4.0wt.％Pt/25AS-W+E? | 4.0? | Ethanol, water | --? | 6.30? | 17.9? |
| 4.0wt.％Pt/35AS-W+E? | 4.0? | Ethanol, water | --? | 7.49? | 15.1? |
The meso-porous alumina composite of a, preparation 15%, 25% and 35%
With a step among the embodiment 2.
B, preparation catalyst
(1) takes by weighing the alumina composite material 15AS that above-mentioned alumina weight percentage is the assembling of 15%, 25% and 35% mesopore silicon oxide limit threshold respectively; 25AS; Each 1 gram of 35AS is standby for carrier.
(2) in above-mentioned three kinds of different carriers, drip the pure water solution of 1.62mL chloroplatinic acid respectively, and then adding 10mL pure water solvent, dipping is after 4 hours under electromagnetic agitation, the solvent that evaporate to dryness is unnecessary, put into baking oven with 120 ℃ of oven dry 12 hours, the catalyst precarsor that to make five kinds of metal platinum loadings respectively be 2.4% (percentage by weight), the pure water solution of chloroplatinic acid is pressed: (molecular formula is H2PtCl66H2O to 1 gram, six hydration chloroplatinic acids, molecular weight is 517.92, wherein the content of Pt is 37%) be dissolved in 25 milliliters pure water, being mixed with concentration is the chloroplatinic acid pure water solution of 14.8g Pt/L.
(3) above-mentioned three kinds of catalyst precarsors were refluxed 2 hours in the sodium formate solution of 20mL respectively, reflux temperature is 95 ℃, sodium formate concentrations is 0.06mol/L, backflow after finishing is filtered catalyst precarsor, and with the washing of a large amount of deionized water, dried 15 hours with 100 ℃ in baking oven then, reduction makes three kinds of meso-porous alumina composite load platinum catalysts.
These three kinds of meso-porous alumina composite load platinum series catalyst, it is numbered: 2.4wt.%Pt/xAS-W, the metal platinum that records with the CO chemisorbed sees Table 6 at the decentralization on carrier xAS surface and the mean size of platinum particles; The little angle X-ray diffraction of carrier is seen Fig. 1; The little angle X-ray diffraction of catalyst is seen Fig. 7; The big angle X-ray diffraction of catalyst is seen Figure 16.
Table 6. metal platinum is at the decentralization on xAS surface and the mean size of platinum particles
| Catalyst | Platinum loading (wt.%) | The solvent of platinum acid chloride solution | Sintering temperature | Platinum particles size (nm) | Decentralization (%) |
| 2.4wt.％Pt/15AS-W? | 2.4? | Water | --? | 19.8? | 5.7? |
| 2.4wt.％Pt/25AS-W? | 2.4? | Water | --? | 16.3? | 6.9? |
| 2.4wt.％Pt/35AS-W? | 2.4? | Water | --? | 8.3? | ? |
Embodiment 7
The heterogeneous asymmetric hydrogenation that is used for the 2-ketoacid ester after each serial mesoporous aluminum oxide material loading platinum catalyst: 4.0wt.%Pt/xAS-E-500,4.0wt.%Pt/xAS-E-350,4.0wt.%Pt/xAS-W+E, 4.0wt.%Pt/xAS-W, 4.0wt.%Pt/xAS-E, the 2.4wt.%Pt/xAS-W that the various embodiments described above are obtained modifies its surface by cinchonidine.
With the specific embodiment of 4.0wt.%Pt/xAS-E-500 mesoporous aluminum oxide material loading platinum catalyst in the reaction of ethyl pyruvate asymmetric catalytic hydrogenation application of the present invention is described in further detail below, its concrete steps are as follows:
A, took by weighing in the 0.100 gram hydrogen of 4.0wt.%Pt/xAS-E-500 mesoporous aluminum oxide material loading platinum catalyst under 400 ℃ of temperature preliminary treatment 2 hours.
B, above-mentioned pretreated catalyst moved in 20 milliliters of analytically pure acetic acid solvents that contain 10 milligrams of chiral molecules cinchonidines rapidly mix, put into 100 milliliters autoclave then, the ethyl pyruvate that adds 2 milliliter 98%, it is that 4.0 MPas, purity are 99.99% hydrogen that the autoclave sealing is fed pressure, and under electromagnetic agitation, carry out asymmetric catalytic hydrogenation and react, reaction temperature is a room temperature, and the reaction time is 30 minutes.
After after c, hydrogenation finish its product being isolated catalyst, with gas-chromatography product is analyzed, it the results are shown in Table 7.
The performance of table 7. different catalysts in the ethyl pyruvate asymmetric oxidation reaction
| Catalyst | Reaction time (minute) | Conversion ratio (%) | Optical selective (%) |
| 4.0wt.％Pt/SBA-15-E-500? | 30? | 1.7? | 85.6? |
| 4.0wt.％Pt/15AS-E-500? | 30? | 29.3? | 75.9? |
| 4.0wt.％Pt/25AS-E-500? | 30? | 22.4? | 82.8? |
| 4.0wt.％Pt/35AS-E-500? | 30? | 26.2? | 77.8? |
| 4.0wt.％Pt/45AS-E-500? | 30? | 39.4? | 44.9? |
| 4.0wt.％Pt/Al 2O 3-E-500? | 30? | 100? | 83.7? |
| 4.0wt.％Pt/SBA-15-E-350? | 30? | 3.3? | 45.2? |
| 4.0wt.％Pt/15AS-E-350? | 30? | 38.6? | 81.1? |
| 4.0wt.％Pt/25AS-E-350? | 30? | 36.0? | 80.9? |
| 4.0wt.％Pt/35AS-E-350? | 30? | 19.8? | 73.6? |
| 4.0wt.％Pt/Al 2O 3-E-350? | 30? | 99.8? | 89.2? |
| 4.0wt.％Pt/SBA-15-W+E? | 30? | 0.8? | 85.6? |
| 4.0wt.％Pt/15AS-W+E? | 30? | 99.3? | 88.8? |
| 4.0wt.％Pt/25AS-W+E? | 30? | 99.8? | 92.1? |
| 4.0wt.％Pt/35AS-W+E? | 30? | 99.3? | 91.4? |
| 4.0wt.％Pt/Al 2O 3-W+E? | 30? | 87.5? | 90.6? |
| 4.0wt.％Pt/SBA-15-W? | 30? | 0.2? | 37.8? |
| 4.0wt.％Pt/15AS-W? | 30? | 9.5? | 71.8? |
| 4.0wt.％Pt/25AS-W? | 30? | 22.4? | 75.8? |
| 4.0wt.％Pt/35AS-W? | 30? | 96.1? | 93.4? |
| 4.0wt.％Pt/Al 2O 3-W? | 30? | 99.7? | 92.3? |
| 4.0wt.％Pt/SBA-15-E? | 30? | 48.3? | 82.2? |
| 4.0wt.％Pt/15AS-E? | 30? | 99.7? | 91.7? |
| 4.0wt.％Pt/25AS-E? | 30? | 99.7? | 92.5? |
| 4.0wt.％Pt/35AS-E? | 30? | 99.8? | 93.1? |
| 4.0wt.％Pt/Al 2O 3-E? | 30? | 99.7? | 92.8? |
| 2.4wt.％Pt/15AS-W? | 30? | 1? | 62.1? |
| 2.4wt.％Pt/25AS-W? | 30? | 4.8? | 56.7? |
| 2.4wt.％Pt/35AS-W? | 30? | 33.3? | 81.4? |
Embodiment 8
A, took by weighing in the 0.100 gram hydrogen of 4.0wt.%Pt/xAS-E mesoporous aluminum oxide material loading platinum catalyst under 400 ℃ of temperature preliminary treatment 2 hours.
B, above-mentioned pretreated catalyst moved into rapidly put into 100 milliliters autoclave after mixing in 20 milliliters of analytically pure acetic acid solvents that contain 10 milligrams of chiral molecules cinchonidines, the ethyl pyruvate that adds 2 milliliter 98%, it is that 4.0 MPas, purity are 99.99% hydrogen that the autoclave sealing is fed pressure, and under electromagnetic agitation, carry out asymmetric catalytic hydrogenation and react, reaction temperature is a room temperature, and the reaction time is 5 minutes.
After after c, hydrogenation finish its product being isolated catalyst, with gas-chromatography product is analyzed, it the results are shown in Table 8.
The performance of table 8. different catalysts in the ethyl pyruvate asymmetric hydrogenation
| Catalyst | Reaction time (minute) | Conversion ratio (%) | Optical selective (%) |
| 4.0wt.％Pt/15AS-E? | 5? | 28.8? | 91.1? |
| 4.0wt.％Pt/25AS-E? | 5? | 34.6? | 92.5? |
| 4.0wt.％Pt/35AS-E? | 5? | 66.6? | 93.1? |
| 4.0wt.％Pt/Al 2O 3-E? | 5? | 32.3? | 89.5? |
More than each embodiment just the present invention will be further described, be not in order to restriction patent of the present invention, allly implement for the present invention's equivalence, all should be contained within the claim scope of patent of the present invention.
Claims (2)
1. the preparation method of a mesoporous aluminum oxide material loading platinum catalyst, this catalyst is that the meso-porous alumina composite that substrate limit threshold is assembled is a carrier with mesopore silicon oxide SBA-15, chloroplatinic acid is the active component precursor, its metal platinum is 0.03～0.18 at the decentralization of carrier surface, loading is 2.4～4.0wt.% (percentage by weight), the platinum particles average grain diameter is 6.3～40.0nm, and the expression of mesoporous aluminum oxide material loading platinum catalyst is Pt/xAS;
Wherein: AS represents the composite of aluminium oxide and mesopore silicon oxide SBA-15;
X represents the alumina weight degree of AS, it is characterized in that this method is with Al (NO
3)
39H
2O is the aluminium source, be introduced into by solid-phase grinding in the duct of the mesopore silicon oxide SBA-15 that does not remove surfactant P123, the P123 molecular formula is EO20PO70EO20, mean molecule quantity is 5800, after roasting, obtain the meso-porous alumina composite, and be that active component precursor, meso-porous alumina composite are carrier with the chloroplatinic acid, reduction makes mesoporous aluminum oxide material loading platinum catalyst in dipping, the aqueous solution of dry back at sodium formate, specifically prepares may further comprise the steps:
A, with Al (NO
3)
39H
2O with without the mesopore silicon oxide SBA-15 that removes surfactant, adopt solid-phase grinding to mix its Al (NO
3)
39H
2O and mesopore silicon oxide SBA-15 weight ratio were respectively 0.7137: 1; 1.3480: 1; 2.1776: 1 and 3.3088: 1, mix the back and obtained alumina content in 5～6 hours at 500 ℃ of roasting temperatures and be respectively 15%, 25%, 35% and 45% meso-porous alumina composite;
B, be that 15%, 25%, 35% and 45% meso-porous alumina composite is a carrier with the above-mentioned alumina content that obtains, in carrier, drip platinum acid chloride solution respectively, the weight ratio of metal platinum and carrier is 1: 24～40.6, stir solvent evaporated after 4 hours, drying got the mesoporous aluminum oxide material loading platinum catalyst precursor in 12 hours in 120 ℃ of baking ovens then;
C, with above-mentioned catalyst precarsor 350～500 ℃ of roasting temperatures 2 hours or without roasting;
D, be that 0.06～0.1mol/L, temperature are that 95 ℃ aqueous sodium formate solution refluxed 2 hours in concentration with above-mentioned roasting or without the catalyst precarsor of roasting, catalyst after obtaining reducing, the mol ratio of sodium formate in its aqueous sodium formate solution and catalyst precarsor platinum content is 10: 1;
E, the catalyst after the above-mentioned reduction is spent deionised water after filtering, and with 100 ℃ of dryings 10～15 hours mesoporous aluminum oxide material loading platinum catalyst.
2. according to the preparation method of the described mesoporous aluminum oxide material loading platinum catalyst of claim 1, it is characterized in that described platinum acid chloride solution is the ethanol solution of chloroplatinic acid, pure water solution or the absolute ethyl alcohol of chloroplatinic acid and the mixed solution of pure water of chloroplatinic acid, chloroplatinic acid and absolute ethyl alcohol are preparation in 1: 25 by weight in the ethanol solution of its chloroplatinic acid; Chloroplatinic acid and pure water are preparation in 1: 31.6 by weight in the pure water solution of chloroplatinic acid; Chloroplatinic acid, absolute ethyl alcohol, pure water are preparation in 1: 12.5: 15.8 by weight in the absolute ethyl alcohol of chloroplatinic acid and the mixed solution of pure water.
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| CN102633581A (en) * | 2012-04-01 | 2012-08-15 | 华东师范大学 | Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation |
| CN111330563B (en) * | 2020-03-25 | 2022-12-06 | 杭州楚环科技股份有限公司 | Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof |
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