CN102633581A - Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation - Google Patents
Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation Download PDFInfo
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Abstract
The invention discloses application of nano titanium oxide mesoporous composite loaded platinum catalyst to hydrogenation of unsaturated compounds such as aromatic aldehyde, ketone and olefin. The nano titanium oxide mesoporous composite loaded platinum catalyst has the advantages of high hydrothermal stability, high reusability and high titanium oxide dispersity, catalytic activity is excellent, reaction conversion rate is as high as 100%, and selectivity of corresponding product alcohol can be higher than 99%.
Description
Technical field
The present invention relates to chemical catalysis material Application Areas, being specifically related to is the application of a kind of nano-titanium oxide mesoporous composite material load platinum catalyst in catalytic hydrogenation.
Background technology
From discovery titanium oxide (TiO such as Fujishima in 1972
2) since the phenomenon of photochemical catalyzing, the research of conductor photocatalysis material has received payes attention to widely that (Nature 238 (1972) 37; Chem. Rev. 95 (1995) 69), while TiO
2It also is a kind of common support of the catalyst.But TiO
2As carrier have specific surface area little, be prone to run off and be difficult to shortcoming such as recyclings, so seek suitable carrier with load TiO
2Research more and more cause people's attention.Along with the growing interest of in recent years ordered mesoporous material being studied; The investigator thinks can provide the growth of nanoparticle in more space influence factor and the restriction duct for the formation of reaction system middle transition attitude by the duct limit threshold effect that utilizes ordered mesoporous material.In addition; In view of present People more and more is paid attention to Green Chemistry and green chemical industry; Environmental protection consciousness is more and more stronger, and water has also attracted people's sight gradually as reaction medium a kind of green, eco-friendly, and people expect to have more chemical reaction process in water, to carry out; Therefore, the hydrothermal stability of raising titania meterial and reusability thereof are very necessary.
Ordered mesoporous material is a kind of aperture novel porous material of (between 2-50 nm) between micropore and macropore.It has the excellent specific property that other porous material does not have: specific surface 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.Wherein SBA-15 ordered mesoporous silica dioxide material has preferably hydrothermal stability, has stable skeleton structure simultaneously, internal surface is easy to advantages such as modification, other component that is easy to mix; Can obtain the mesoporous material of high thermal stability and hydrothermal stability through 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 the potential using value is arranged at numerous areas such as chemical, biological medicine, environmental science, separation science and functional materialss.
Reduction reaction occupies an important position in organic synthesis, and the catalytic reduction of various greasy hydrogenation and aromatic series and verivate thereof all has a large amount of bibliographical informations.Oil prodution industry is the important component part of national economy, and is related to national economy, and the value and significance of research is very great, and the reduzate of most aromatic series and verivate thereof all is of great value fine chemical product or pharmaceutical intermediate.Because heterogeneous hydrogenation has overcome shortcomings such as reactant and catalyst separating are difficult in the homogeneous hydrogenation reaction system, purifying products is loaded down with trivial details, so heterogeneous catalyst is widely used in this type catalyzed reaction, on industrial production, also obtains application more and more widely.Although the hydrogenation catalyst of many excellent performances is successfully developed and is widely applied in the industrial production; But can under the reaction conditions of gentleness, carry out in order to make hydrogenation reactions such as aromatic ring on the industrial production, ester group, carboxyl and alkene; Thereby reduce energy consumption, economize on resources; Reduce production costs, people also are devoted to the activity and the higher catalyzer of selectivity of development of new always.
The advantage of platinum catalyst is that its catalytic performance is excellent; It is gentle to have excellent low temperature hydrogenation performance and reaction conditions; Can unsaturated aldehyde, ketone selective hydrogenation be obtained unsaturated alcohol, this is because the further hydrogenation of carbon-carbon double bond can be avoided for the strong absorption of carbonyl in the platinum catalyst surface.
Up to now, the report of nano-titanium oxide material loading platinum catalyst catalytic hydrogenation research is actually rare.The present invention overcomes defective and the problem that prior art exists; The application of a kind of nano-titanium oxide mesoporous composite material load platinum catalyst in the hydrogenation of aromatic aldehyde, ketone, olefinically unsaturated compounds is provided, utilizes silica-based ordered mesoporous material (like SBA-15) to be the nano oxidized titanium composite material (TiO of substrate with the sol-gel method preparation
2SBA-15), and as carrier-supported precious metal platinum active ingredient (Pt/TiO
2SBA-15) make nano-titanium oxide mesoporous composite material load platinum catalyst, and with the hydrogenation of this catalyst applications in aromatic aldehyde, ketone, olefinically unsaturated compounds.
Summary of the invention
Goal of the invention of the present invention provides the application of a kind of nano-titanium oxide mesoporous composite material load platinum catalyst in catalytic hydrogenation.
Among the present invention, nano-titanium oxide mesoporous composite material load platinum catalyst is applied to the catalytic hydrogenation of aromatic aldehyde, ketone and alkene organic cpds, can obtain high reactivity and highly selective.
Among the present invention, said nano-titanium oxide mesoporous composite material load platinum catalyst is to comprise carrier and load on the platinum on this carrier; This carrier is to be the nano-titanium oxide mesoporous composite material of substrate limit threshold assembling with the ordered meso-porous silicon oxide.
Among the present invention, the surperficial dispersity of metal platinum on this carrier is 0.05-0.61.Loading is 5.0 % weight percents.The median size of metal platinum particle is 1.8-21nm.
Wherein, the expression of said nano-titanium oxide mesoporous composite material load platinum catalyst is: Pt/xTS-W/E-T; Wherein: TS representes said carrier, promptly is the nano-titanium oxide mesoporous composite material (TiO of substrate limit threshold assembling with the ordered meso-porous silicon oxide
2SBA-15); X representes the weight percentage of titanium oxide among the TS; W/E representes the different dispersion of Platinic chloride precursor, and W represents the aqueous solution, and E represents ethanolic soln; T representes the different maturing temperatures of said carrier TS.
During the present invention uses; Said nano-titanium oxide mesoporous composite material load platinum catalyst prepares through following method: be the titanium source with the butyl(tetra)titanate; Be introduced into through sol-gel method in the duct of said ordered meso-porous silicon oxide material (SBA-15); After roasting, obtain the nano-titanium oxide mesoporous composite material, with this as carrier; Then, in this carrier, add Platinic chloride, obtain catalyst precursor through immersion process for preparing as the active ingredient precursor; Then, dry back with above-mentioned catalyst precursor reduction, obtains said catalyst nano medium pore of titania matrix material load platinum catalyst after filtration, washing, drying in the aqueous solution of sodium formiate.Concrete steps comprise:
(a) under the 298K; A certain amount of ordered meso-porous silicon oxide material SBA-15 powder is joined supersound process 2 h in the Virahol (weight ratio of SBA-15 and Virahol is 1:15); Aqueous isopropanol (tetrabutyl titanate and Virahol volume ratio are 1:10) with tetrabutyl titanate is added drop-wise in the mixed system of above-mentioned SBA-15/ Virahol then; Slowly add suitable quantity of water (volume ratio of tetrabutyl titanate and water is 1:20) after fully mixing 1 h; Obtain white suspension liquid after continuing to stir 2 h; Through filtering and with a large amount of water and washing with alcohol, dried overnight under 353 K again is after 623-773 K roasting 2 h obtain final nano-titanium oxide mesoporous composite material.Different according to required titanium oxide content in the matrix material, tetrabutyl titanate and silicon oxide (SBA-15) weight ratio is respectively 0.2288:1; 0.4830:1; 0.7673:1 and 1.0869:1, obtain weight content at last and be respectively 5%, 10%, 15% and 20% nano-titanium oxide mesoporous composite material;
(b) be carrier with the above-mentioned nano-titanium oxide mesoporous composite material that obtains; In carrier, drip the aqueous solution of Platinic chloride or the ethanolic soln of Platinic chloride; The weight ratio of metal platinum and carrier is 1: 19; Stir solvent evaporated after 4-6 hour, in baking oven, obtained nano-titanium oxide mesoporous composite material load platinum catalyst precursor then under the 393K in dry 12 hours;
(c) above-mentioned catalyst precursor was refluxed 2 hours in the aqueous sodium formate solution of 368 K, the catalyzer after obtaining reducing, wherein the mol ratio of platinum content is 10:1 in sodium formiate and the catalyst precursor;
(d) catalyzer after the above-mentioned reduction is used a large amount of deionized water wash after filtering, obtain the platinum catalyst of nano-titanium oxide mesoporous composite material load through drying under 373 K after 12 hours.
The present invention uses said catalyzer in catalytic hydrogenation, in the hydrogen atmosphere under 673 K temperature nano-titanium oxide mesoporous composite material load platinum catalyst is carried out pre-treatment earlier.
During the present invention uses, before the pre-treatment of catalyzer is meant and uses under comparatively high temps, in the hydrogen atmosphere with the Impurity removal of catalyst surface absorption to obtain the catalyst surface of cleaning.
During the present invention used, said catalytic hydrogenation was meant the catalytic hydrogenation of aromatic aldehyde, ketone and alkene organic cpds, comprises phenyl aldehyde and verivate thereof, pimelinketone, vinylbenzene or tetrahydrobenzene etc.
Among the present invention, the catalytic hydrogenation of aromatic aldehyde, ketone and alkene unsaturated organic compound is under pressure is the pure hydrogen of 4.0 MPas, to carry out, and reaction solvent is water or ethanol, and temperature of reaction is room temperature or 333K.
During the present invention uses; Pretreated catalyzer and solvent (water or ethanol), reaction substrate (aromatic aldehyde, ketone or alkene) are placed in the reaction kettle; Feeding pressure is the pure hydrogen of 4.0 MPas; Under room temperature or 333K, induction stirring is carried out catalytic hydrogenation, after reaction for some time reaction is stopped.After finishing, hydrogenation, its reaction product is analyzed with gc with after its product and the catalyst separating.
Compared with prior art; During the present invention uses, the catalyzer that is adopted be with the ordered meso-porous silicon oxide material be the nano-titanium oxide mesoporous composite material of substrate limit threshold assembling as carrier, and come loaded metal platinum with this carrier; The titanium oxide dispersity is high, good hydrothermal stability.This catalyst stability is high, and in use the catalyst activity component is difficult for running off, and can be repeatedly used; Significantly be superior to platinum catalyst conventional titania oxide supported in the prior art.Catalyst Pt/xTS-E-T with the preparation of Platinic chloride ethanolic soln dipping possesses regular meso-hole structure, less Pt particle diameter, and higher dispersity.Specific surface area that this catalyzer is bigger and pore volume help the diffusion of reaction substrate and intermediate product, and its catalytic performance is good.Be used for aromatic aldehyde, ketone and olefin hydrogenation reaction, transformation efficiency is about 100%, and the selectivity of product alcohol can reach more than 99%.The catalytic performance of this catalyzer in water solvent obviously is superior to the catalytic performance in organic solvent such as the ethanol, thereby further reduces energy consumption, economize on resources, and reduces production costs, and reduces discharging of waste liquid, helps protecting environment.
Description of drawings
Fig. 1 is the little angle x-ray diffraction pattern of application carrier nano-titanium oxide mesoporous composite material of the present invention.
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of application carrier nano-titanium oxide mesoporous composite material of the present invention.
Fig. 3 is the big angle x-ray diffraction pattern of application carrier nano-titanium oxide mesoporous composite material of the present invention.
Fig. 4 is the little angle x-ray diffraction pattern of the nano-titanium oxide mesoporous composite material load platinum catalyst of the present invention's application.
Fig. 5 is the big angle x-ray diffraction pattern of the nano-titanium oxide mesoporous composite material load platinum catalyst of the present invention's application.
Fig. 6 is the N of the nano-titanium oxide mesoporous composite material load platinum catalyst of the present invention's application
2Adsorption-desorption curve and graph of pore diameter distribution.
Fig. 7 is the N of the nano-titanium oxide mesoporous composite material load platinum catalyst of the present invention's application
2Adsorption-desorption curve and graph of pore diameter distribution.
Fig. 8 is the transmission electron microscope picture of the nano-titanium oxide mesoporous composite material load platinum catalyst of the present invention's application.Fig. 8 (A), Fig. 8 (B) are respectively the nano-titanium oxide mesoporous composite material load platinum catalyst Pt/5TS-E-773 of the present invention's application and the transmission electron microscope picture of Pt/10TS-E-773.
The nano-titanium oxide mesoporous composite material load platinum catalyst that Fig. 9 uses for the present invention recycle figure.
Figure 10 is nano-titanium oxide mesoporous composite material load platinum catalyst catalysis benzaldehyde derivative hydrogenation reaction result of the present invention.
Embodiment
In conjunction with following specific embodiment and accompanying drawing, the present invention is done further detailed description, protection content of the present invention is not limited to following examples.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.The process of embodiment of the present invention, condition, reagent, experimental technique etc. except that the following content of mentioning specially, are the universal knowledege and the common practise of this area, and the present invention does not have special limiting content.
A, preparation carrier promptly prepare titanium oxide content and are 5%, 10%, 15% and 20% nano oxidized titanium composite material
(1) under the 298K, take by weighing each 1 g of four parts of ordered mesoporous silicon material SBA-15 and put into four 100ml beakers that are labeled as 1#, 2#, 3#, 4# respectively, add the 15g Virahol respectively, for use behind supersound process 2 h then..
(2) respectively to 1,2,3, splash into the aqueous isopropanol (tetrabutyl titanate and Virahol volume ratio are 1:10) of tetrabutyl titanate in the 4# beaker; Wherein, Tetrabutyl titanate and SBA-15 weight ratios are followed successively by 0.2288:1,0.4830:1,0.7673:1,1.0869:1 by the beaker numbering from 1# to 4#, after mixing 1 h, slowly add suitable quantity of water (volume ratio of tetrabutyl titanate and water is 1:20); Continue to stir and obtain white suspension liquid after 2 h make the tetrabutyl titanate complete hydrolysis; With the white solid filtration and with a large amount of water and alcohol flushing, dried overnight under 353K is behind 773K roasting 2 h then; Obtain the nano oxidized titanium composite material that titanium oxide content is respectively the assembling of 5%, 10%, 15% and 20% mesopore silicon oxide limit threshold, be labeled as 5TS-773,10TS-773,15TS-773 and 20TS-773 respectively.
B, preparation catalyst precursor
(1) takes by weighing each 1g of 5TS-773,10TS-773,15TS-773 and 20TS-773 and 1g SBA-15 and 1g TiO respectively
2Carrier is subsequent use.
(2) in above-mentioned six kinds of carriers, dripping platiniferous concentration respectively is ethanolic soln 6.4 ml of the Platinic chloride of 7.4mg/ml; The loading of control metal platinum is 5.0 wt.% (weight percents; The weight ratio of platinum and carrier is 1:19); Stir solvent evaporated after 6 hours, drying obtained nano-titanium oxide mesoporous composite material load platinum catalyst precursor after 12 hours under the 393K in baking oven.
C, make catalyzer
(1) above-mentioned catalyst precursor was refluxed 2 hours in the aqueous sodium formate solution of 368K, the catalyzer after obtaining reducing, wherein, the mol ratio of platinum content is 10:1 in sodium formiate and the catalyst precursor;
(2) catalyzer after the above-mentioned reduction is used a large amount of deionized water wash after filtering, after under the 373K dry 12 hours, obtain nano-titanium oxide mesoporous composite material load platinum catalyst.
Above-mentioned serial five kinds of catalyzer are numbered Pt/xTS-E-773, record metal platinum with the CO chemisorption and see the following form 1 at the dispersity on carrier xTS-773 surface and the mean size of platinum particles; Little angle and the big angle X-ray diffraction of carrier xTS-773 are seen Fig. 1 and Fig. 3; The ultraviolet-visible absorption spectroscopy of carrier xTS-773 is seen Fig. 2; The little angle and the big angle X-ray diffraction of catalyzer are seen Fig. 4 and Fig. 5; The N of catalyzer
2Adsorption-desorption is seen Fig. 6, and the transmission electron microscope of catalyzer is seen Fig. 8 (A), Fig. 8 (B).
Experimental result shows that nano-titanium oxide mesoporous composite material xTS-773 has still kept the orderly symmetric meso-hole structure of two-dimentional p6mm, and is as shown in Figure 1.As shown in Figures 2 and 3; Titanium oxide content is lower than at 20% o'clock; Titanium oxide becomes the metamict of high dispersing in the SBA-15 duct, when titanium oxide content reaches 20%, the crystalline phase diffraction peak of titanium oxide occurred; Explain that titanium oxide content has surpassed the dispersion threshold on surface, SBA-15 duct, gathering has taken place in nano oxidized titanium particle.Fig. 4 and Fig. 6 experimental result are explained the order mesoporous structure that has still kept carrier xTS-773 behind the nano oxidized titanium composite material supported platinum nano particle.The platinum particles size reduces along with the increase of titanium oxide content gradually in Fig. 5, Fig. 8 (A), Fig. 8 (B) and the table 1 explanation catalyzer, and dispersity improves.
Table 1, metal platinum are at the dispersity on carrier xTS-773 surface and the mean size of platinum particles
| Catalyzer | The dispersion medium of Platinic chloride | Platinum particles size (nm) | Dispersity (%) |
| Pt/5TS-E-773 | Ethanol | 21.0 | 5.16 |
| Pt/10TS-E-773 | Ethanol | 13.0 | 8.65 |
| Pt/15TS-E-773 | Ethanol | 7 | 16.06 |
| Pt/20TS-E-773 | Ethanol | 1.8 | 61.3 |
| Pt/TiO 2-E-773 | Ethanol | 2.3 | 48.1 |
Other experimental procedures and condition are with embodiment 1, and just used solution is the aqueous solution of Platinic chloride in preparation catalyzer step b (2), makes catalyzer and is numbered Pt/xTS-W-773.Little angle and the big angle X-ray diffraction of carrier xTS-773 are seen Fig. 1 and Fig. 3; The ultraviolet-visible absorption spectroscopy of carrier xTS-773 is seen Fig. 2; The little angle and the big angle X-ray diffraction of catalyzer are seen Fig. 4 and Fig. 5; The N of catalyzer
2Adsorption-desorption is seen Fig. 6.Like Fig. 4 and shown in Figure 6, experimental result explanation platinum catalyst has still kept the order mesoporous structure of carrier xTS-773.Fig. 5 explains that the platinum particles size reduces along with the increase of titanium oxide content gradually in the catalyzer, and dispersity improves; By H
2PtCl
6The Pt particle of catalyst Pt/xTS-W-773 of aqueous solution preparation less than by H
2PtCl
6The platinum particles of catalyst Pt/xTS-E-773 of ethanolic soln preparation, this is because in the duct of SBA-15, introduce TiO
2After, TiO
2SBA-15 mesoporous compound titanium oxide material has had amphiphilic; Be the relative hydrophobicity of SBA-15 and the wetting ability of titanium oxide; Because the relative wetting ability of titanium oxide; Therefore it is more abundant that chloroplatinic acid aqueous solution contacts with titanium oxide, and the platinum particles by the catalyzer of the aqueous solution preparation of Platinic chloride is relatively littler.
Other experimental procedures and condition are with embodiment 1; Prepared the carrier titanium oxide content and be 10% nano oxidized titanium composite material; Just used maturing temperature is 623K in the nano oxidized titanium composite material step a of preparation (2), makes catalyzer and is numbered Pt/10TS-E-T.Little angle and the big angle X-ray diffraction of carrier xTS-T are seen Fig. 1 and Fig. 3; The ultraviolet-visible absorption spectroscopy of carrier xTS-T is seen Fig. 2; The little angle and the big angle X-ray diffraction of catalyzer are seen Fig. 4 and Fig. 5; The N of catalyzer
2Adsorption-desorption is seen Fig. 6 and Fig. 7.Prepare that used maturing temperature can also be 673K among the nano oxidized titanium composite material step a (2).
Fig. 1 experimental result explanation nano-titanium oxide mesoporous composite material xTS-T has still kept the orderly symmetric meso-hole structure of two-dimentional p6mm.Fig. 2 shows that with Fig. 3 titanium oxide becomes the metamict of high dispersing in the SBA-15 duct, and Fig. 4, Fig. 6 and Fig. 7 experimental result explanation platinum catalyst have still kept the order mesoporous structure of carrier xTS-T.
The nano-titanium oxide mesoporous composite material load platinum catalyst Pt/xTS-E-773, Pt/xTS-W-773, the Pt/10TS-E-T that respectively above-mentioned each embodiment 1-3 are obtained are applied to the phenyl aldehyde catalytic hydrogenation.
Pt/xTS-E-773 nano-titanium oxide mesoporous composite material load platinum catalyst is applied in the phenyl aldehyde catalytic hydrogenation, and concrete steps are following:
A, took by weighing in the hydrogen atmosphere of 0.1g 5.0 wt.% Pt/xTS-E-773 catalyzer under the 673K temperature pre-treatment 2 hours;
B, above-mentioned pretreated catalyzer and 20 ml water solvents, phenyl aldehyde (21 mmol) are fed pressure in reaction kettle be the pure hydrogen of 4.0 MPas, and at room temperature induction stirring is carried out catalytic hydrogenation and recording reacting time.
In this step, also can adopt 20 ml alcohol solvents; Also can react in induction stirring under the 333K.
With product and catalyst separating, with gc product is analyzed after c, hydrogenation finish, its result sees the following form 2.
The nano-TiO of high dispersing is introduced in table 2 explanation in the duct of SBA-15
2, catalytic activity significantly improves after the platinum active ingredient.Just obtain transformation efficiency 22% on the Pt/SBA-15-E-773 catalyzer in hydrogenation 1 h of phenyl aldehyde; And the hydrogenation of phenyl aldehyde only need react 0.75 h transformation efficiency just up to 93.9% on the Pt/15TS-E-773 catalyzer; The interior hydrogenation transformation efficiency to phenyl aldehyde of 1 h is reduced to 62.5% on the Pt/20TS-E-773 catalyzer.Show loaded platinum catalyst to the catalytic performance of phenyl aldehyde hydrogenation along with TiO in the carrier
2The increase of content and improve the TiO that in the SBA-15 mesopore orbit, introduces
2Content has surpassed the dispersion threshold on mesoporous surface, causes TiO
2Nanoparticle is bigger, and specific surface area is smaller, can't embody the advantage of mesoporous SBA-15 material, influenced it and done the raising of carrier loaded platinum metal catalyst catalytic performance, so transformation efficiency reduces.In addition; The Pt/xTS-W-773 catalyzer that table 2 result also shows chloroplatinic acid aqueous solution preparation is lower than the Pt/xTS-E-773 catalyzer of Platinic chloride ethanolic soln preparation to the catalytic activity of phenyl aldehyde hydrogenation; This possibly be because the platinum particles of the platinum catalyst of chloroplatinic acid aqueous solution preparation is smaller; The reactivity on surface is bigger, and in reaction process, reaction heat is not easy to derive; So often between metallics be prone to fuse, process such as sintering and react and inactivation, so the transformation efficiency reduction with carrier.
Table 2, the performance of different catalysts in the phenyl aldehyde catalytic hydrogenation
| Catalyzer | Reaction times (h) | Solvent | Transformation efficiency (%) | Selectivity (%) |
| Pt/5TS-E-773 | 2 | H 2O | 94.3 | 100 |
| Pt/5TS-E-773 | 1 | H 2O | 73 | 100 |
| Pt/10TS-E-773 | 1 | H 2O | 92.6 | 100 |
| Pt/15TS-E-773 | 0.75 | H 2O | 93.9 | 100 |
| Pt/15TS-E-773 | 1 | H 2O | 100 | 100 |
| Pt/15TS- |
1 | EtOH | 64.3 | 100 |
| Pt/20TS-E-773 | 1 | H 2O | 62.5 | 100 |
| Pt/5TS-W-773 | 1 | H 2O | 41.1 | 100 |
| Pt/10TS-W-773 | 1 | H 2O | 71.8 | 100 |
| Pt/15TS-W-773 | 1 | H 2O | 90.7 | 100 |
| Pt/10TS-E-673 | 1 | H 2O | 97.4 | 100 |
| Pt/10TS-E-623 | 1 | H 2O | 34.8 | 100 |
| Pt/TiO 2-E-773 | 1 | H 2O | 98.3 | 100 |
| Pt/TiO
2- |
1 | EtOH | 76.1 | 100 |
| Pt/TiO 2-W-773 | 1 | H 2O | 75.4 | 100 |
| Pt/TiO 2-W-773 | 1 | EtOH | 42.6 | 100 |
| Pt/SBA-15-E-773 | 1 | H 2O | 22.0 | 100 |
With Pt/15TS-E-773 is the repeated use situation of example explanation nano-titanium oxide mesoporous composite material load platinum catalyst as catalyzer.Other experimental procedures and condition be with embodiment 4, and just finish the centrifugal catalyzer that makes in back and from reaction system, separate, with alcohol solvent washing catalyst 5 times, repetition embodiment 4, its result sees Fig. 9.Experimental result explanation catalyst Pt/15TS-E-773 has good repeat performance in water solvent, this is because the nano-titanium oxide mesoporous composite material has hydrothermal stability preferably, and in the SBA-15 mesopore orbit, introduces the nano-TiO of high dispersing
2Particle can produce stronger interaction with platinum particles, thereby makes nano platinum particle in use neither run off, also not assemble, and can stable existence, so catalyzer can recycle repeatedly.
Embodiment 6
Other experimental procedures and condition are with embodiment 4, and just catalyzer is Pt/15TS-E-773, and substrate is each verivate of phenyl aldehyde, and its result sees Figure 10.The experimental result explanation is except NSC 43794 and 4-chloro-benzaldehyde, and the Pt/15TS-E-773 catalyzer all is superior to Pt/TiO to the catalytic performance of other aromatic aldehydes
2-E-773 catalyzer, aubepine, p-Fluorobenzenecarboxaldehyde at the last transformation efficiency of catalyst Pt/15TS-E-773 apparently higher than Pt/TiO
2The result of-E-773 catalyzer, and the transformation efficiency of 4-chloro-benzaldehyde on two catalyzer is suitable.
Embodiment 7
Other experimental procedures and condition are with embodiment 4, and just catalyzer is Pt/15TS-E-773, and substrate is a pimelinketone, and solvent is 20ml (water and ethanol volume ratio are 9:1), and temperature of reaction is 333k, and its result sees the following form 3.
Experimental result explanation Pt/15TS-E-773 catalyzer has catalytic performance preferably to the pimelinketone hydrogenation, and the selectivity of corresponding product hexalin is up to more than 99%, and the catalytic performance of Pt/15TS-E-773 catalyzer significantly is superior to Pt/TiO
2-E-773 catalyzer.
Embodiment 8
Other experimental procedures and condition are with embodiment 4, and just catalyzer is Pt/15TS-E-773, and substrate is tetrahydrobenzene or vinylbenzene, and solvent is 20 ml (water and ethanol volume ratio are 9:1), and temperature of reaction is 333 K, and its result sees table 3.
Experimental result explanation Pt/15TS-E-773 catalyzer has catalytic performance preferably to tetrahydrobenzene and cinnamic hydrogenation, and corresponding product selectivity is up to more than 99%, and the catalytic performance of Pt/15TS-E-773 catalyzer significantly is superior to Pt/TiO
2-E-773 catalyzer.
Table 3, the Pt/15TS-E-773 catalyzer performance in the catalytic hydrogenation in other unsaturated compounds
More than just the present invention being further described, is not in order to the restriction this patent, all for the present invention's equivalence enforcement, all should be contained within the claim scope of this patent.
Claims (8)
1. the application of a nano-titanium oxide mesoporous composite material load platinum catalyst in catalytic hydrogenation.
2. application as claimed in claim 1 is characterized in that, said nano-titanium oxide mesoporous composite material load platinum catalyst comprises carrier and loads on the platinum on the said carrier; Said carrier is to be the nano-titanium oxide mesoporous composite material of substrate limit threshold assembling with the ordered meso-porous silicon oxide.
3. application as claimed in claim 2 is characterized in that, said platinum is 0.05-0.61 at the dispersity of said carrier surface; Loading is 5.0% weight percent.
4. application as claimed in claim 2 is characterized in that, the median size of said platinum is 1.8-21nm.
5. application as claimed in claim 2; It is characterized in that; The preparation method of said nano-titanium oxide mesoporous composite material load platinum catalyst is: be the titanium source with the butyl(tetra)titanate, be introduced into through sol-gel method in the duct of said ordered meso-porous silicon oxide, after roasting, obtain said carrier; Then, in said carrier, add Platinic chloride, prepare catalyst precursor; Then, with above-mentioned catalyst precursor reduction, after filtration, washing, drying, obtain said catalyzer.
6. application as claimed in claim 1 is characterized in that, pre-treatment in the hydrogen atmosphere of said nano-titanium oxide mesoporous composite material load platinum catalyst under 673 K temperature.
7. application as claimed in claim 1 is characterized in that, said catalytic hydrogenation is under pressure is the pure hydrogen of 4.0 MPas, to carry out, and reaction solvent is water or ethanol, and temperature of reaction is room temperature or 333K.
8. application as claimed in claim 1 is characterized in that, said catalytic hydrogenation is meant the catalytic hydrogenation of aromatic aldehyde, ketone, alkene unsaturated organic compound.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999116A (en) * | 2017-12-14 | 2018-05-08 | 湘潭大学 | For being catalyzed the catalyst of chloro virtue nitro compound selection hydrogenation |
| CN108031485A (en) * | 2017-12-14 | 2018-05-15 | 湘潭大学 | A kind of method that parachloronitrobenzene selective hydrogenation prepares parachloroanilinum |
| CN108607596A (en) * | 2018-05-11 | 2018-10-02 | 东华大学 | A kind of Composite Pt/TiO with visible photocatalysis water hydrogen manufacturing performance2-xNxCatalyst and its preparation and application |
| CN108947775A (en) * | 2018-08-07 | 2018-12-07 | 斯爱玲 | A method of catalysis dibenzofuran open loop prepares o-phenyl phenol |
| WO2019114767A1 (en) * | 2017-12-14 | 2019-06-20 | 湘潭大学 | Catalyst and preparation method thereof for catalytic selective hydrogenation of chloroaromatic nitro compounds |
| CN110614124A (en) * | 2018-12-20 | 2019-12-27 | 南京工程学院 | Nano-gold catalyst with multi-stage structure and preparation method thereof |
| WO2023090303A1 (en) * | 2021-11-16 | 2023-05-25 | 株式会社フルヤ金属 | Catalyst carrier, catalyst, and methods respectively for producing those products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007281A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Novel preparation method of amorphous alloy catalyst |
| CN101076400A (en) * | 2004-12-09 | 2007-11-21 | 瓦克化学有限公司 | Platinum catalysts that are supported on nanoscale titanium dioxide, use thereof in hydrosilylation, hydrosilylation method using said catalysts and compositions comprising said catalysts |
| US20070282138A1 (en) * | 2006-05-31 | 2007-12-06 | Richards Ryan M | Supported polyoxometalates and process for their preparation |
| CN101537352A (en) * | 2009-04-22 | 2009-09-23 | 华东师范大学 | Mesoporous aluminum oxide material loading platinum catalyst as well as preparation method and application |
| KR20090099837A (en) * | 2008-03-18 | 2009-09-23 | 한국화학연구원 | Catalysts for hydrocracking of heavy crude oil and hydrocracking method using the same |
-
2012
- 2012-04-01 CN CN2012100951578A patent/CN102633581A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076400A (en) * | 2004-12-09 | 2007-11-21 | 瓦克化学有限公司 | Platinum catalysts that are supported on nanoscale titanium dioxide, use thereof in hydrosilylation, hydrosilylation method using said catalysts and compositions comprising said catalysts |
| US20070282138A1 (en) * | 2006-05-31 | 2007-12-06 | Richards Ryan M | Supported polyoxometalates and process for their preparation |
| CN101007281A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Novel preparation method of amorphous alloy catalyst |
| KR20090099837A (en) * | 2008-03-18 | 2009-09-23 | 한국화학연구원 | Catalysts for hydrocracking of heavy crude oil and hydrocracking method using the same |
| CN101537352A (en) * | 2009-04-22 | 2009-09-23 | 华东师范大学 | Mesoporous aluminum oxide material loading platinum catalyst as well as preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| MI-YOUNG KIM ET AL: "Preparation of Highly Dispersive and Stable Platinum Catalysts Supported on Siliceous SBA-15 Mesoporous Material: Roles of Titania Layer Incorporation and Hydrogen Peroxide Treatment", 《CATAL LETT》 * |
| 沈亚丽等: "手性修饰的介孔树脂材料负载铂催化剂上丙酮酸乙酯的不对称氢化反应", 《高等学校化学学报》 * |
| 郑雯丽等: "高度分散TiO2@SBA-15负载铂催化剂上苯甲醛的氢化反应", 《第十三届全国青年催化学术会议论文集》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999116A (en) * | 2017-12-14 | 2018-05-08 | 湘潭大学 | For being catalyzed the catalyst of chloro virtue nitro compound selection hydrogenation |
| CN108031485A (en) * | 2017-12-14 | 2018-05-15 | 湘潭大学 | A kind of method that parachloronitrobenzene selective hydrogenation prepares parachloroanilinum |
| WO2019114767A1 (en) * | 2017-12-14 | 2019-06-20 | 湘潭大学 | Catalyst and preparation method thereof for catalytic selective hydrogenation of chloroaromatic nitro compounds |
| CN107999116B (en) * | 2017-12-14 | 2020-11-03 | 湘潭大学 | Catalyst for catalyzing selective hydrogenation of chloro-aromatic nitro compound |
| US11040336B2 (en) | 2017-12-14 | 2021-06-22 | Xiangtan University | Catalyst of platinum/zirconium dioxide/SBA-15 and method for preparing p-chloroaniline using the same |
| CN108607596A (en) * | 2018-05-11 | 2018-10-02 | 东华大学 | A kind of Composite Pt/TiO with visible photocatalysis water hydrogen manufacturing performance2-xNxCatalyst and its preparation and application |
| CN108947775A (en) * | 2018-08-07 | 2018-12-07 | 斯爱玲 | A method of catalysis dibenzofuran open loop prepares o-phenyl phenol |
| CN110614124A (en) * | 2018-12-20 | 2019-12-27 | 南京工程学院 | Nano-gold catalyst with multi-stage structure and preparation method thereof |
| WO2023090303A1 (en) * | 2021-11-16 | 2023-05-25 | 株式会社フルヤ金属 | Catalyst carrier, catalyst, and methods respectively for producing those products |
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Application publication date: 20120815 |