CN103212407B - Unsupported mesoporous palladium heterogeneous chiral hydrogenation catalyst and preparation method thereof - Google Patents
Unsupported mesoporous palladium heterogeneous chiral hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103212407B CN103212407B CN201310135240.8A CN201310135240A CN103212407B CN 103212407 B CN103212407 B CN 103212407B CN 201310135240 A CN201310135240 A CN 201310135240A CN 103212407 B CN103212407 B CN 103212407B
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to an unsupported mesoporous palladium heterogeneous chiral hydrogenation catalyst and a preparation method thereof. The catalyst has a neat two-dimensional hexagonal, three-dimensional cubical simple-helical or three-dimensional cubical double-helical mesoporous structure, the specific surface area is 30-80 m<2>.g<-1>, and the pore volume is 0.20-0.50 cm<3>g<-1>. The catalyst is prepared by taking a mesoporous silica molecular sieve as a hard template and adopting an ultrasonic double-solvent method. Through controlling the topological structure of the mesoporous silica hard template, the temperature of hydro-thermal treatment and the type of reductants, the mesoporous structure, pore size and crystal plane structure of a mesoporous palladium catalyst can be controlled. The unsupported mesoporous palladium heterogeneous chiral hydrogenation catalyst and preparation method thereof disclosed by the invention have the characteristics that the catalyst is large in specific surface area, and adjustable in mesoporous structure, pore size and crystal plane structure; and the catalyst has high hydrogenation activity and enantio-selectivity in the reaction of preparing chiral alpha-phenylethyl alcohol from acetophenone and derivatives thereof through heterogeneous chiral hydrogenation.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the mesoporous palladium Chitosan of non-loading type Catalysts and its preparation method.
Background technology
The development of chipal compounds and exploitation have huge economic and social benefit.According to statistics, agricultural chemicals more than more than 50% medicine and 15% has chirality in the world at present.Taking chiral drug as example, the chiral drug sales volume of individual isomer in 2005 has broken through 1,720 hundred million dollars, becomes new high-tech industry very important in global economy.Taking chiral drug as example, medical practices prove in a large number, and physiologically active and the pharmacological action of racemic two enantiomters are not quite similar, and sometimes even completely contradict, and the chiral drug of therefore developing and develop individual isomer is the focus of international research always.As the important channel that obtains individual isomer chipal compounds, Heterogeneous asymmetric catalysis hydrogenation has caused the extensive concern of countries in the world.
Chirality alpha-phenyl ethyl alcohol is very important organic synthesis and medicinal intermediates.Compared with other synthetic methods, acetophenone multi-phase chiral catalytic hydrogenation generates the tool Atom economy of chirality alpha-phenyl ethyl alcohol, meets the demand for development of world today's Green Chemistry; And intrinsic easily separated, the easy-operating advantage of heterogeneous catalyst makes it reusable, have more economic worth and prospects for commercial application, thereby people are very active to its research.But, because acetophenone is two unsaturated functional group compounds, in molecule, not only contain phenyl ring but also have C=O, may there is hydrogenation reaction in phenyl ring and C=O in hydrogenation process, therefore want highly selective to obtain alpha-phenyl ethyl alcohol not a duck soup, corresponding, difficulty is higher high antimer optionally to obtain the chirality alpha-phenyl ethyl alcohol of single configuration.T r k, Perosa and Hess etc. have studied the Pt/Al of acetophenone at Cinchonidine modifier
2o
3hydrogenation on catalyst, finds that its enantio-selectivity is generally less than 20% (Torok B., Bal á zsik K., Szollosi G., Felfoldi K., Bart ó k M., Chirality, 1999,11,470; Perosa A., Tundo P., Selva M., J. Mol. Catal. A:Chem., 2002,180,169; Hess R., Mallat T., Baiker A., J. Catal., 2003,218,453.).Tungler etc. have studied the hydrogenation of acetophenone on the Pd/C catalyst of L-PROLINE modification, realize 22% optical selective, (R) yield of-1-benzyl carbinol is 78% (Tungler A., Tarnai T., M á th é T., Petr ó J., J. Mol. Catal., 1991,67,277.).Vetere etc. have studied the hydrogenation of acetophenone on the Pt catalyst of chirality organotin modification, also only obtained 20% enantio-selectivity (Vetere V., Faraoni M.B., Santori G.F., Podesta J., Casella M.L., Ferretti O.A., J. Catal. 2004,226,457.).Recently, the researchs such as Cheng, Marzialetti and Yang find that support type Ru and Ir catalyst that chirality is modified show the enantio-selectivity that is better than Pt and Pd in the chiral hydrogenation of aromatic ketone, but the loss of Ru and Ir is a severe problem (Cheng H.Y., Hao J.M., Wang H.J., Xi C.Y., Meng X.C., Cai S.X., Zhao F.Y., J. Mol. Chem. A:Chem., 2007,278,6; Marzialetti T., Oportus M., Ruiz D., Fierro J. L. G., Reyes P., Catal. Today, 2008,133-135,711; Yang C. F., Jiang H. Y., Feng J., Fu H. Y., Li R. X., Chen H., Li X. J., J. Mol. Catal. A:Chem., 2009,300,98.).In sum, at present also quite limited about the research of aromatic ketone Chitosan, the stability of chiral catalyst and reaction enantio-selectivity still need further to be improved.
Summary of the invention
The object of the present invention is to provide that a kind of catalytic efficiency is high, the C=O new catalyst for acetophenone and derivative chiral hydrogenation thereof that selectively good, enantio-selectivity is higher and preparation method thereof.
New catalyst provided by the invention is the mesoporous palladium Chitosan of a kind of non-loading type catalyst, and it has following feature: (1) has regular bidimensional six sides, three-dimensional cubic single-screw or the double-helical meso-hole structure of three-dimensional cubic; (2) wherein the mesoporous palladium catalyst of bidimensional hexagonal structure has single pore size distribution, and aperture is 2 ~ 4 nm; The mesoporous palladium catalyst of three-dimensional cubic single coil configuration has single pore size distribution, and aperture is 10 ~ 15 nm; The double-stranded mesoporous palladium catalyst of three-dimensional cubic has diplopore and distributes, and macropore diameter is 10 ~ 15 nm, and small aperture is 2 ~ 4 nm; (3) specific surface is 30 ~ 80 m
2g
-1, pore volume 0.20 ~ 0.50 cm
3g
-1.
The mesoporous palladium Chitosan of non-loading type provided by the invention catalyst, adopts ultrasonic Double solvent method to make using mesoporous silica molecular sieve as hard template; By controlling topological structure, the hydrothermal treatment consists temperature of mesoporous silica molecular sieve, the kind of reducing agent, can regulate and control meso-hole structure, pore size and the crystal plane structure of mesoporous palladium catalyst.
The preparation method of mesoporous palladium chiral hydrogenation catalyst of the present invention, concrete steps are:
At different topology structure and hydrothermal treatment consists temperature, (for example 35 DEG C-130 DEG C) synthetic mesoporous silica molecular sieve (as SBA-15 and KIT-6 etc.) is as hard template, with H
2pdCl
4or PdCl
2solution, as palladium (Pd) presoma, adopts ultrasonic Double solvent method Pd presoma to be introduced in the duct of mesoporous silica molecular sieve hard template;
Again with KBH
4, hydrazine hydrate or H
2as reducing agent reduction Pd presoma, obtain the mesopore molecular sieve of supported palladium;
Finally remove mesopore molecular sieve with HF solution, obtain the mesoporous palladium catalyst of black.
In above-mentioned preparation method, the consumption of palladium presoma is the 35-65 % of hard template quality; Adopt KBH
4or reduction temperature is 0 DEG C-40 DEG C when hydrazine hydrate reduction Pd presoma, preferably 10 DEG C-30 DEG C, adopt H
2during as reducing agent, reduction temperature is 250 DEG C-450 DEG C, preferably 300 DEG C-400 DEG C.The mol ratio of Pd presoma and reducing agent is 1: 4-250, preferably 1: 10-100.
The chiral hydrogenation performance test of mesoporous palladium of the present invention (Pd) catalyst, comprises using proline as chiral modifier, carries out hydrogenation of acetophenone in three-necked bottle under normal pressure in methanol solvate.Wherein hydrogen flow rate is 40-100 ml min
-1, reaction temperature is 0 ~ 35 DEG C, stir speed (S.S.) is greater than 1000 revs/min.
Mesoporous palladium catalyst of the present invention shows good activity in the reaction of acetophenone Chitosan, has 100% the selective and higher enantio-selectivity of C=O.
Brief description of the drawings
Fig. 1 is taking SBA-15 mesoporous silica molecular sieve as hard template, with PdCl
2for presoma, with KBH
4the transmission electron microscope picture of the mesoporous Pd catalyst of two-dimentional hexagonal structure (being designated as Pd-hex) making for reducing agent.(a) [100] direction (b) [110] direction
.
Fig. 2 is that KIT-6 mesoporous silica molecular sieve taking 35 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with KBH
4the mesoporous Pd catalyst of three-dimensional cubic single coil configuration making for reducing agent (is designated as Pd-35-KBH
4) (a) high resolution scanning and (b) transmission electron microscope picture.
Fig. 3 is that KIT-6 mesoporous silica molecular sieve taking 35 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with KBH
4the mesoporous Pd catalyst of three-dimensional cubic single coil configuration making for reducing agent (is designated as Pd-35-KBH
4) nitrogen adsorption-desorption thermoisopleth and graph of pore diameter distribution (illustration).
Fig. 4 is that KIT-6 mesoporous silica molecular sieve taking 100 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with KBH
4the mesoporous Pd catalyst of three-dimensional cubic double-spiral structure making for reducing agent (is designated as Pd-100-KBH
4) (a) high resolution scanning and (b) transmission electron microscope picture.
Fig. 5 is that KIT-6 mesoporous silica molecular sieve taking 100 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with H
2the mesoporous Pd catalyst obtaining for reducing agent (is designated as Pd-100-H
2) X-ray diffracting spectrum.
Fig. 6 is that KIT-6 mesoporous silica molecular sieve taking 130 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with KBH
4the mesoporous Pd catalyst of three-dimensional cubic double-spiral structure making for reducing agent (is designated as Pd-130-KBH
4) (a) high resolution scanning and (b) transmission electron microscope picture.
Fig. 7 is that KIT-6 mesoporous silica molecular sieve taking 130 DEG C of Hydrothermal Synthesiss is as hard template, with H
2pdCl
4for presoma, with KBH
4the double-stranded mesoporous Pd catalyst of three-dimensional cubic making for reducing agent (is designated as Pd-130-KBH
4) upper benzyl carbinol yield and enantio-selectivity curve over time.
Detailed description of the invention
Further describe the present invention below by specific embodiment.
embodiment 1: get 1 g SBA-15 mesoporous silica molecular sieve, under ultrasonic assisting, vigorous stirring 2 hours, is scattered in 40 ml n-hexanes.Under agitation then, by the PdCl of 2 ml 0.56M
2the aqueous solution dropwise adds, and the n-hexane that rear removal is unnecessary will flood Pd
2+sBA-15 120 DEG C of oven dry.With the KBH of 0.3 M
4aqueous solution reduction (BH
4 -/ Pd=10), treat to react complete without Bubble formation.HF acid treatment 30 min remove after silica, and the catalyst obtaining is first washed till to neutrality with distilled water, then wash replacing water 3 times with ethanol, and catalyst is finally kept in ethanol.The characterization result of gained catalyst P d-hex corresponding diagram 1.
embodiment 2: get the KIT-6 mesoporous silica molecular sieve that 35 DEG C of Hydrothermal Synthesiss of 1 g obtain, be scattered in 40 ml n-hexanes, assist lower vigorous stirring 30 minutes ultrasonic.Then, under vigorous stirring, dropwise drip the H of a certain amount of 0.56M
2pdCl
4the aqueous solution, the n-hexane that rear removal is unnecessary, will flood Pd
2+kIT-6 120 DEG C of oven dry.Then repeat above-mentioned steps, repeatedly dipping, makes the load capacity of Pd reach 25wt.%.With the KBH of 0.3 M
4aqueous solution reduction (BH
4 -/ Pd=20), treat to react complete without Bubble formation.HF acid treatment 30 min remove after silica, and the catalyst obtaining is first washed till to neutrality with distilled water, then wash replacing water 3 times with ethanol, and catalyst is finally kept in ethanol.Gained catalyst P d-35-KBH
4the characterization result of corresponding diagram 2 and Fig. 3.
embodiment 3: get the KIT-6 mesoporous silica molecular sieve that 100 DEG C of Hydrothermal Synthesiss of 1 g obtain, be scattered in 40 ml n-hexanes, assist lower vigorous stirring 30 minutes ultrasonic.Then, under vigorous stirring, dropwise drip the H of a certain amount of 0.56M
2pdCl
4the aqueous solution, the n-hexane that rear removal is unnecessary, will flood Pd
2+kIT-6 120 DEG C of oven dry.Then repeat above-mentioned steps, repeatedly dipping, makes the load capacity of Pd reach 50wt.%.With the KBH of 0.3 M
4aqueous solution reduction (BH
4 -/ Pd=20), treat to react complete without Bubble formation.HF acid treatment 30 min remove after silica, and the catalyst obtaining is first washed till to neutrality with distilled water, then wash replacing water 3 times with ethanol, and catalyst is finally kept in ethanol.Gained catalyst P d-100-KBH
4the characterization result of corresponding diagram 4.
embodiment 4: get the KIT-6 mesoporous silica molecular sieve that 100 DEG C of Hydrothermal Synthesiss of 1 g obtain, be scattered in 40 ml n-hexanes, assist lower vigorous stirring 30 minutes ultrasonic.Then, under vigorous stirring, dropwise drip the H of a certain amount of 0.56M
2pdCl
4the aqueous solution, the n-hexane that rear removal is unnecessary, will flood Pd
2+kIT-6 120 DEG C of oven dry.Then repeat above-mentioned steps, repeatedly dipping, makes the load capacity of Pd reach 50wt.%.At 300 DEG C, adopt H
2reduction, the sample obtaining is removed after silica with HF acid treatment 30 min, and the catalyst obtaining is first washed till to neutrality with distilled water, then washes replacing water 3 times with ethanol, is finally kept in ethanol.Gained catalyst P d-100-H
2the characterization result of corresponding diagram 5.
embodiment 5: get the KIT-6 mesoporous silica molecular sieve that 130 DEG C of Hydrothermal Synthesiss of 1 g obtain, be scattered in 40 ml n-hexanes, assist lower vigorous stirring 30 minutes ultrasonic.Then, under vigorous stirring, dropwise drip the H of a certain amount of 0.56M
2pdCl
4the aqueous solution, the n-hexane that rear removal is unnecessary, will flood Pd
2+kIT-6 120 DEG C of oven dry.Then repeat above-mentioned steps, repeatedly dipping, makes the load capacity of Pd reach 50wt.%.With the KBH of 0.3 M
4aqueous solution reduction (BH
4 -/ Pd=20), treat to react complete without Bubble formation.HF acid treatment 30 min remove after silica, and the catalyst obtaining is first washed till to neutrality with distilled water, then wash replacing water 3 times with ethanol, and catalyst is finally kept in ethanol.Gained catalyst P d-130-KBH
4the characterization result of corresponding diagram 6.
embodiment 6:by 0.4g L-PROLINE; 17 ml methyl alcohol join and in 100 ml three-necked bottles, make it to dissolve the methanol solution that obtains proline; then above-mentioned solution is transferred in ice-water bath, added the acetophenone of 0.02 ml, under nitrogen protection, add the mesoporous Pd-130-KBH of 0.050 g
4catalyst, then passes into normal pressure H
2, close nitrogen, mixing speed is transferred to 1000 rpm and eliminates diffusion effect.In course of reaction, carry out intermittent sampling, determine composition and the content of product through gas chromatographic analysis.Mesoporous Pd-130-KBH
4the chiral catalysis performance corresponding diagram 7 of catalyst.
Claims (3)
1. a preparation method for the mesoporous palladium Chitosan of non-loading type catalyst, this catalyst has regular bidimensional six sides, three-dimensional cubic single-screw or three-dimensional cubic double helix meso-hole structure; The mesoporous palladium catalyst of described bidimensional hexagonal structure has single pore size distribution, and aperture is 2 ~ 4 nm; The mesoporous palladium catalyst of three-dimensional cubic single coil configuration has single pore size distribution, and aperture is 10 ~ 15 nm; The double-stranded mesoporous palladium catalyst of three-dimensional cubic has diplopore and distributes, and macropore diameter is 10 ~ 15 nm, and small aperture is 2 ~ 4 nm; The specific surface of described catalyst is 30 ~ 80 m
2.g
-1, pore volume is 0.20 ~ 0.50 cm
3g
-1;
It is characterized in that concrete steps are: using mesoporous silica molecular sieve synthetic at different topology structure and hydrothermal treatment consists temperature as hard template, with H
2pdCl
4or PdCl
2solution, as palladium presoma, adopts ultrasonic Double solvent method palladium presoma to be introduced in the duct of mesoporous silica molecular sieve hard template; Again with KBH
4, hydrazine hydrate or H
2as reducing agent reduction palladium presoma, obtain the mesopore molecular sieve of supported palladium; Finally remove mesopore molecular sieve with HF solution, obtain the mesoporous palladium catalyst of black.
2. preparation method according to claim 1, the consumption that it is characterized in that palladium presoma is the 35-65 % of hard template quality.
3. preparation method according to claim 1, is characterized in that adopting KBH
4or when hydrazine hydrate reduction Pd presoma, reduction temperature is 0 DEG C-40 DEG C, adopt H
2during as reducing agent, reduction temperature is 250 DEG C-450 DEG C; The mol ratio of Pd presoma and reducing agent is=1: 4-250.
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| CN101862682A (en) * | 2010-04-29 | 2010-10-20 | 上海师范大学 | In-situ reduction preparation method for ordered mesoporous heterogeneous palladium catalyst |
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| CN101862682A (en) * | 2010-04-29 | 2010-10-20 | 上海师范大学 | In-situ reduction preparation method for ordered mesoporous heterogeneous palladium catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Ordered Mesoporous Materials from Metal Nanoparticle–Block Copolymer Self-Assembly;Scott C.Warren等;《SCIENCE》;20080627;第320卷;1748-1752 * |
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Granted publication date: 20141203 Termination date: 20170418 |