CN104607232A - Preparation method for Pd/S-C catalyst and application of Pd/S-C catalyst to catalyzing of 1,5-cyclooctadiene hydrogenation - Google Patents
Preparation method for Pd/S-C catalyst and application of Pd/S-C catalyst to catalyzing of 1,5-cyclooctadiene hydrogenation Download PDFInfo
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Abstract
The invention discloses a preparation method for a Pd/S-C catalyst and application of the Pd/S-C catalyst to catalyzing of 1,5-cyclooctadiene hydrogenation. A Pd-loaded catalyst with different grain sizes is obtained by taking a carbonitride-meso-porous silicon composite compound as a carrier and controlling a thermal treatment temperature. At a certain temperature and under certain pressure, selectivity of generating cyclooctene or cyclooctane can be controlled though the Pd/S-C catalyst prepared at different thermal treatment temperatures or different catalytic reaction temperatures, and a conversion rate for the 1,5-cyclooctadiene is kept to be larger than 99%; under normal pressure and temperature, the conversion rate of the Pd/S-C loaded by a carrier treated at 300 DEG C to 1,5-cyclooctadiene hydrogenation reaction is as high as 95%, and the selectivity is kept to be larger than 99%; even at 0 DEG C, the conversion rate of generating cyclooctene through 1,5-cyclooctadiene hydrogenation is 60%, and the selectivity is larger than 98%.
Description
Technical field
The invention belongs to the Synthesis and applications technical field of new material, be specifically related to a kind of Pd/S-C catalyst preparation method and in catalysis 1, application in 5-cyclo-octadiene hydrogenation reaction, especially prepares the application in cyclo-octene in the selective hydrogenation of catalysis 1,5-cyclo-octadiene.
Background technology
Due to the needs such as sustainable development and environmental protection, the production standard in chemical process is changed to the selective of product gradually by the conversion ratio of original reactant, namely will improve the atom utilization of reactant.This will ask used catalyst in course of reaction not only will have higher activity, also will have selective preferably simultaneously.How to improve catalyst conversion ratio and selective because of but great study a question (Angew.Chem.Int.Ed.2008,47 a, 9212-9228) at present urgently to be resolved hurrily in Chemical Manufacture.The solution of this problem can be carried out from the design aspect of catalyst.The size such as controlling catalyst aperture can prevent large molecule access hole internal active sites, makes Small molecular can enter and react; Control the size of particle, shape, nano particle contact surface catalyst then can be made to have different activity and selectivities to substrate, thus obtain different products (J.Am.Chem.Soc.2011,133,2362-2365).
Hydrogenation reaction is the important organic reaction of a class, is also an important route of synthesis fine-chemical intermediate.Along with recent years is to the enhancing of environmental consciousness, this technology receives much concern.Cyclo-octene is a kind of important intermediate in industrial production, therefore, cyclo-octene prepared by 1,5-cyclo-octadiene selec-tive hydrogenation obtain and pay close attention to widely with green route.In addition, 1,5-cyclo-octadiene has two identical C=C double bonds, thus also will be to evaluate a catalyst for hydrogenation optionally model reaction.Really, catalyst (as: Pd/C, Pd/Al of bibliographical information
2o
3) 1,5-cyclo-octadiene deep hydrogenation can be made to generate cyclooctane, reduce selective (AICHE J.2008,54,258-268) to cyclo-octene.Therefore, find there is high activity, high selectivity and reusable selective hydrocatalyst are a current problem having challenge and an attraction.
In the application, inventor with carbonitride-porous silicon compound (S-C) for carrier, palladium nano-particles is active component, by carrying out the process of different temperatures to carrier, obtains the palladium nanocatalyst (Pd/S-C) with different-grain diameter.Result shows, and this catalyst generates in cyclo-octene reaction at 1,5-cyclo-octadiene selec-tive hydrogenation and shows good activity and selectivity.Disclosed with United States Patent (USP) 5525211 is carrier with magnesium aluminate spinel, compared with the molybdenum cobalt catalyst that is active component, in the present invention, the preparation method of Pd/S-C catalyst is simple and have higher activity and stability.In addition, this catalyst separation is easy, regenerability is good, thus by be a class potential be used for the industrial applications catalyst that 1,5-cyclo-octadiene selec-tive hydrogenation generates cyclo-octene.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of with carbonitride-porous silicon (S-C) be carrier the preparation method of Pt-supported catalyst (i.e. Pd/S-C) and application in catalysis 1,5-cyclo-octadiene selective hydrogenation thereof.By changing the heat treatment temperature of carrier, the structure of carrier and chemical property can be controlled thus the granular size of control load palladium catalyst, finally controlling the activity and selectivity of catalyst to reaction according to the size of nano particle.
Technical scheme of the present invention is:
A kind of preparation of Pd/S-C catalyst and the application in the reaction of catalysis 1,5-cyclo-octadiene hydrogenation generation cyclo-octene thereof, concrete steps are as follows:
1, the preparation method of Pd/S-C catalyst, its step is as follows:
(1) cyanamid dimerization is dissolved in the mixed solvent be made up of distilled water and absolute ethyl alcohol, is heated to 80 DEG C, after dissolving, add the SBA-15 with the quality such as cyanamid dimerization again, keep 80 DEG C and stirring to volatilize completely to the solvent of system;
Described mixed solvent is that distilled water and absolute ethyl alcohol mix according to the volume ratio of 1:4;
Described cyanamid dimerization and mixed solvent solid-to-liquid ratio are 3g:(40-50) mL;
The inventive method does not have particular/special requirement to SBA-15, and the application SBA-15 used is conventionally prepared for inventor laboratory, and concrete preparation method is shown in detailed description of the invention;
(2) product drying that step (1) obtains is spent the night, then from room temperature to 300-500 DEG C in nitrogen atmosphere, heat preservation hot process 4h, then cools, takes out, obtain catalyst carrier;
The speed of described intensification is 2 DEG C/min;
(3) catalyst carrier is joined the PdCl of 0.001M by solid-to-liquid ratio 0.5g:50mL
2in solution, ultrasonic 5 minutes, then dipping absorption 4h, suction filtration, washing, vacuum drying, the sample obtained was again in H
2from room temperature to 300 DEG C heat preservation hot process 3h (heating rate is 1 DEG C/min) under atmosphere, hydrogen flow rate is 50mL/min.
2, the application of cyclo-octene is prepared in the selective hydrogenation of catalyst 1,5-cyclo-octadiene:
(1) under uniform temperature and pressure condition: experimental provision is autoclave and the heat-collecting magnetic stirring device of 50mL.In reactor, add 50mg catalyst, 0.25mL1,5-cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane, Hydrogen Vapor Pressure is 2MPa, and 80 DEG C are reacted 90 minutes, and sample is analyzed with gas chromatograph after carrying out centrifugation, filtration.
(2) under normal temperature and pressure: experimental provision is 50mL three-neck flask.Left neck connects a hydrogen balloon, and middle neck connects a rubber tube and is used for release hydrogen, and right neck connects a sampler.In three-neck flask, add 50mg catalyst, 0.25mL1,5-cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane, sealed reactor, pass into hydrogen deaeration, sample after certain hour, sample, after being separated, filtering, uses gas chromatographic analysis.
Compared with prior art, advantage of the present invention and beneficial effect as follows:
(1) catalyst preparing is simple, without the need to special material and condition, and can be recycled.
(2) conversion ratio of raw material is high, target product selective good.Prior art is low to 1,5-cyclo-octadiene list hydrogenation selectivity, and needs to carry out under uniform temperature and pressure condition.The present invention is under normal temperature and pressure conditions, and reported first Pd/S-C catalyst 1,5-cyclo-octadiene generates cyclo-octene, and the conversion ratio of raw material is high, and the selective height of target product.
(3) reaction time is short, efficiency is high.Under condition of the present invention, the reaction time that catalysis 1,5-cyclo-octadiene generates cyclo-octene is 90min.Compared with other catalyst, there is the advantage that the reaction time is short, reaction efficiency is high.
(4) catalytic reaction condition gentle, be easy to operation, can reach under normal temperature and pressure conditions higher than the conversion ratio of 93% and 99% selective.Due to the high activity of Pd/S-C_300, even under the condition of 0 DEG C, also can to reaction and display go out higher than 60% activity and 98% cyclo-octene selective.
(5) whole catalytic process is environmentally friendly, and atom utilization is high.Raw material 1, the 5-cyclo-octadiene consumed can generate single cyclo-octene substantially completely, and flow process is simple, is suitable for industrial applications.
Accompanying drawing explanation
Fig. 1 is nitrogen physisorption-desorption isothermal curve and the graph of pore diameter distribution of SBA-15 and S-C_T (T=300,400,500) carrier prepared by embodiment 1.
Fig. 2 is the big angle XRD spectra of Pd/S-C_T (T=300,400,500) catalyst prepared by embodiment 1.
Fig. 3 is the XPS spectrum figure of Pd/S-C_T (T=300,400,500) catalyst prepared by embodiment 1.
Fig. 4 is the transmission electron microscope picture of Pd/S-C_T (T=300,400,500) catalyst prepared by embodiment 1 and corresponding Pd grain diameter.
Fig. 5 A is that Pd/S-C_T in embodiment 2 (T=300,400,500) catalyst is at H
2pressure is 2MPa, to the activity and selectivity (t=90min) of cyclo-octadiene catalytic hydrogenation reaction when 80 DEG C; Fig. 5 B be in embodiment 3 Pd/S-C_300 catalyst at H
2pressure is 2MPa, and temperature is the activity and selectivity (t=90min) to cyclo-octadiene catalytic hydrogenation reaction under 50,60,80 DEG C of conditions.
In Fig. 5 A and B, blank post represents the selective of cyclo-octene, and column with slant lines represents the selective of cyclooctane.
Fig. 6 is Pd/S-C_T in embodiment 4 (T=300,400,500) catalyst generates cyclo-octene reaction at normal temperatures and pressures activity variation diagram in time to cyclo-octadiene catalytic hydrogenation.
Fig. 7 be in embodiment 5 Pd/S-C_300 catalyst 0 DEG C, cyclo-octadiene catalytic hydrogenation is generated under condition of normal pressure to the activity variation diagram in time of cyclo-octene reaction.
Fig. 8 is the stability test figure that in embodiment 6, Pd/S-C_300 catalyst generates cyclo-octene reaction at normal temperatures and pressures to cyclo-octadiene catalytic hydrogenation.
Detailed description of the invention
Applicant is by being described in detail the preparation method of catalyst of the present invention and application in conjunction with specific embodiments below, further understands so that those skilled in the art have the present invention.But following examples should not be interpreted as the restriction to claims of the present invention request protection domain by any way.
Embodiment 1: a kind of preparation method of Pd/S-C catalyst, step is as follows:
(1) 3g cyanamid dimerization is dissolved in the mixed solvent be made up of 10mL distilled water and 40mL absolute ethyl alcohol, is incubated after being heated to 80 DEG C, after cyanamid dimerization dissolves completely, adds 3g SBA-15, continue be incubated and stir until solvent volatilizees completely.
The preparation method of the SBA-15 related in the present embodiment is as follows:
Get 5g P123 to be dissolved in the mixed solvent be made up of 75g distilled water and 150g HCl (concentration 2M).After at 35 DEG C, vigorous stirring is dissolved completely to P123, after slowly dripping 10.5g tetraethyl orthosilicate, continue to stir 24h at 35 DEG C.Then 100 DEG C of crystallization 24h in crystallization tank, cooling, washing, suction filtration, obtain white powder.And then cool after 550 DEG C of calcining 6h in 100 DEG C of dry 24h, Muffle furnace, to obtain final product.
(2) product drying that step (1) obtains is spent the night, in nitrogen atmosphere, be incubated 4h with the ramp of 2 DEG C/min to T DEG C (T=300-500) from room temperature again to heat-treat, then cool, take out, gained identified as samples is designated as S-C_T, for subsequent use as catalyst carrier, T corresponds to aforementioned heat treated actual temp numerical value (unit be DEG C), the present embodiment is parallel has established three different temperatures: 300 DEG C, 400 DEG C, 500 DEG C, then T is respectively 300,400,500, obtains carrier S-C_300, S-C_400, S-C_500 respectively.
(3) the S-C_T carrier that 0.5g step (2) obtains is joined respectively the PdCl of 50mL 0.001mol/L
2in solution, ultrasonic 5 minutes, then dipping absorption 4h, suction filtration, washing, vacuum drying, the sample obtained was again in H
2from room temperature to 300 DEG C insulation 3h heat treatment (heating rate is 1 DEG C/min) under atmosphere, hydrogen flow rate is 50mL/min.Gained catalyst is labeled as Pd/S-C_T (T=300,400,500), and the load capacity of Pd is 1%.
The instrumental characterizing of product:
(1) nitrogen physisorption-desorption isothermal curve of carrier S-C_T is shown in accompanying drawing 1A.All samples (comprising the homemade SBA-15 of embodiment 1) all has typical IV type adsorption-desorption isothermal curve, and is that 0.6-0.75 scope has H1 type hysteresis loop at relative pressure, and the meso-hole structure with SBA-15 is described.Accompanying drawing 1B is shown in by the pore-size distribution of carrier S-C_T, defines multi-stage porous in known sample, and also increases along with the aperture of the rising multi-stage porous of temperature thereupon.
(2) accompanying drawing 2 is the big angle XRD spectra of catalyst.By contrast standard PDF card, find sample in 2 θ=40.1 °, 46.4 ° corresponding with the crystallographic plane diffraction peak of Metal Palladium (111), (200) and (220) respectively with the diffraction maximum of 67.9 °, there is Pd nano particle in interpret sample.And along with the reduction of vehicle treated temperature, the diffraction peak intensity of Pd particle reduces and half-peak breadth increases, the palladium nano-particles particle diameter reduction formed is described.
(3) accompanying drawing 3 is the XPS spectrum figure of catalyst.Result shows that the existence form of palladium is mainly the Pd of metallic state
0, have and exist with the form of PdO on a small quantity.
(4) transmission electron microscope picture of Pd/S-C_T catalyst is shown in accompanying drawing 4.Pd particle is highly dispersed at the surface of SBA-15 and its particle diameter changes along with the difference of vehicle treated temperature, particle size order is Pd/S-C_300<Pd/S-C_400<Pd/S-C_5 00, illustrate that carrier has good dispersibility to Pd particle, and the particle diameter of its treatment temperature to Pd particle has a great impact.In addition, in figure, still can see the pore passage structure of SBA-15 rule, illustrate that the structure of SBA-15 is not destroyed in catalyst preparation process.
It is below the Application Example of embodiment 1 prepared catalyst.
Embodiment 2:
Pd/S-C_T catalyst 1,5-cyclo-octadiene selective hydrogenation under uniform temperature and pressure condition:
Experimental provision is autoclave and the heat-collecting magnetic stirring device of 50mL.In reactor, add 50mg catalyst, 0.25mL 1,5-cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane, Hydrogen Vapor Pressure is 2MPa, and 80 DEG C are reacted 90 minutes, and sample is analyzed with gas chromatograph after carrying out centrifugation, filtration.
Accompanying drawing 5A compares Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 catalyst under these conditions to the activity and selectivity of reaction.To reaction, all there is higher activity after can finding out the carrier loaded Pd catalyst that treatment of different temperature is crossed, selective then closely related with the size of Pd particle: selective very high to cyclooctane of small particle diameter Pd catalyst (that is: Pd/S-C_300), Large stone Pd catalyst (that is: Pd/S-C_500) is selective very high to cyclo-octene, and the precondition of this result is HTHP.That is can by changing selective to 1,5-cyclo-octadiene hydrogenation reaction of the treatment temperature control Pd catalyst of carrier under high-temperature and high-pressure conditions.Due to the high activity of Pd/S-C_300 catalyst, it will make reaction depth hydrogenation generate cyclooctane under this condition.For this reason, in subsequent reactions we with it for catalyst, by reduce reaction condition, by reaction controlling in the cyclo-octene stage.Can high yield be obtained, can the energy be saved again.
Embodiment 3:
Take Pd/S-C_300 as catalyst, reaction temperature is 50,60 and 80 DEG C, and other conditions are with embodiment 2.Experimental result as shown in fig. 5b.Visible temperature is very large on optionally affecting, and when dropping to 50 DEG C from 80, catalyst P d/S-C_300 becomes 8% to the selective of cyclooctane from 94%, and rises to 90% to the selective of cyclo-octene by 4%.Illustrate that temperature is to 1, the selective of 5 cyclo-octadiene hydrogenation has larger impact.Low temperature can suppress the deep hydrogenation reacted, and is conducive to the generation of cyclo-octene.
Embodiment 4:
Pd/S-C_T catalyst 1,5-cyclo-octadiene selective hydrogenation under normal temperature and pressure:
Experimental provision is that the left neck of 50mL three-neck flask connects a hydrogen balloon, and middle neck connects a rubber tube release hydrogen, and right neck connects a sampler.Experimentation is as follows: in three-neck flask, add 50mg catalyst, 0.25mL 1,5-cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane, sealed reactor, pass into hydrogen deaeration, normal-temperature reaction certain hour, sample carries out centrifugation, filters and gas chromatographic analysis.Accompanying drawing 6 compares Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 catalyst under these conditions to the activity variation diagram in time of reaction.
Under result is presented at normal temperature and pressure conditions, Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 catalyst has selective more than 98% to cyclo-octene, and Pd/S-C_300 shows higher activity at normal temperatures and pressures.
Embodiment 5:
Course of reaction with embodiment 4, but now with mixture of ice and water hierarchy of control temperature at zero degrees celsius.Accompanying drawing 7 is reactivity under this condition and selective.Even if result shows also demonstrate higher catalytic activity (being greater than 60%) at zero degrees celsius catalyst to 1,5-cyclo-octadiene catalytic hydrogenation reaction and keep being greater than 98% to the selective of cyclo-octene.Illustrate that Pd/S-C_300 catalyst has good activity and selectivity to this hydrogenation reaction.
Embodiment 6:
Can reusing in order to what detect Pd/S-C_300, stability test has been carried out to this catalyst.By in embodiment 4 reaction terminate after catalyst after filtration, 100 DEG C dry 6 hours, again carry out active testing.Process is with embodiment 4.Result is as shown in Figure 8: catalyst after circulation five times conversion ratio only comparatively first time (fresh catalyst) reduces 13%, period keeps selective constant.Illustrate that catalyst not only has good activity and selectivity, also there is higher stability simultaneously.
Embodiment 7:
Test in catalytic reaction that different solvents is on the impact of Pd/S-C_300 catalyst reaction activity, experimentation, with embodiment 4, only converts solvent, and result is as shown in table 1.More known, oxolane and normal heptane are all the more suitable solvents of this reaction, but consider the initial activity of catalyst, take normal heptane as optimum solvent.
Table 1: in embodiment 7, the impact of different solvents on Pd/S-C_300 catalyst activity is compared.
Claims (7)
1. a preparation method for Pd/S-C catalyst, its step is as follows:
(1) cyanamid dimerization is dissolved in the mixed solvent be made up of distilled water and absolute ethyl alcohol, is heated to 80 DEG C, after dissolving, add the SBA-15 with the quality such as cyanamid dimerization again, keep 80 DEG C and stirring to volatilize completely to the solvent of system;
Described mixed solvent is that distilled water and absolute ethyl alcohol mix according to the volume ratio of 1:4;
Described cyanamid dimerization and mixed solvent solid-to-liquid ratio are 3g:(40-50) mL;
(2) product drying that step (1) obtains is spent the night, then from room temperature to 300-500 DEG C in nitrogen atmosphere, heat preservation hot process 4 h, then cools, takes out, obtain catalyst carrier;
(3) catalyst carrier is joined the PdCl of 0.001M by solid-to-liquid ratio 0.5g:50mL
2in solution, ultrasonic 5 minutes, then flood absorption 4 h, suction filtration, washing, vacuum drying, the sample obtained was again in H
2from room temperature to 300 DEG C heat preservation hot process 3 h under atmosphere.
2. preparation method according to claim 1, is characterized in that: the temperature being warming up to 300-500 DEG C in described step (2) is set as 300 DEG C.
3. the application of Pd/S-C catalyst in selective catalysis hydrogenation reaction that obtain of preparation method according to claim 1 and 2.
4. the application of Pd/S-C catalyst in selective catalysis 1,5-cyclo-octadiene hydrogenation that obtain of preparation method according to claim 1 and 2.
5. the application in cyclo-octene prepared by the Pd/S-C catalyst that preparation method according to claim 1 and 2 obtains in the selective hydrogenation of catalysis 1,5-cyclo-octadiene.
6. application according to claim 5, is characterized in that: the reaction that cyclo-octene is prepared in the selective hydrogenation of described catalysis 1,5-cyclo-octadiene is carried out in normal heptane solvent.
7. application according to claim 5, is characterized in that: the reaction that cyclo-octene is prepared in the selective hydrogenation of described catalysis 1,5-cyclo-octadiene is carried out under normal temperature and pressure conditions.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN103641673A (en) * | 2013-12-12 | 2014-03-19 | 上海交通大学 | Method for catalytic reduction of carbon-carbon double bond by carbon nitride supported metal nanoparticles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN103641673A (en) * | 2013-12-12 | 2014-03-19 | 上海交通大学 | Method for catalytic reduction of carbon-carbon double bond by carbon nitride supported metal nanoparticles |
Non-Patent Citations (2)
| Title |
|---|
| PING XIAO ET.AL.: "Polymeric Carbon Nitride/Mesoporous Silica Composites as Catalyst Support for Au and Pt Nanoparticles", 《CHEM.EUR.J.》 * |
| 黄天松: "温控PEG两相体系中过渡金属纳米催化剂的制备与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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