CN105037066A - Method for achieving Pt/C catalyst preparation and methyl cyclohexane dehydrogenation through one step - Google Patents
Method for achieving Pt/C catalyst preparation and methyl cyclohexane dehydrogenation through one step Download PDFInfo
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- CN105037066A CN105037066A CN201510467908.8A CN201510467908A CN105037066A CN 105037066 A CN105037066 A CN 105037066A CN 201510467908 A CN201510467908 A CN 201510467908A CN 105037066 A CN105037066 A CN 105037066A
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Abstract
The invention discloses a method for achieving Pt/C catalyst preparation and methyl cyclohexane dehydrogenation through one step. A prepared acetylacetone platinum ethanol solution and a carbon sphere deionized water solution are mixed to obtain acetylacetone platinum/carbon sphere suspension which is leached, and after drying, acetylacetone platinum/carbon sphere powder is obtained; the acetylacetone platinum/carbon sphere powder is pressed into slices, the slices are placed in a normal-pressure fixed bed reactor, methyl cyclohexane is introduced to the normal-pressure fixed bed reactor, the temperature of the reactor ranges from 280 DEG C to 320 DEG C, and methyl cyclohexane dehydrogenation is achieved. The method is provided for solving the problems that an existing catalyst preparation technology is complex and oxidation occurs easily. The high temperature characteristic of methyl cyclohexane in the catalytic reaction is utilized, the characteristic that acetylacetone platinum is decomposed into Pt at the high temperature is combined, a Pt/C catalyst is prepared in the catalytic process through one step, and the efficient methyl cyclohexane dehydrogenation performance is obtained. The synthetic method is simple, operation is convenient, control is easy, no byproduct or impurity is produced, and the synthetic method is an in-situ synthesis and environment-friendly synthetic technology.
Description
Technical field
The invention relates to the method that a step achieves Pt/C catalyst preparing and methylcyclohexane dehydrogenation, particularly a kind ofly utilize hot conditions one step in catalytic process prepare Pt/C catalyzer and accelerate the processing method of catalyzed reaction.
Background technology
Hydrogen Energy has the advantages such as rich reserves, wide material sources, energy density height as a kind of " green energy resource ", presents good application prospect in fuel cell and substitute fossil fuels etc.Utilizing in process, it stores and transport is crucial.When hydrogen is as a kind of fuel, the dispersed and intermittent feature used must be had, therefore must can be stored and shipped to given place within for some time.International Energy Agency specifies, practical its quality hydrogen-storage density of hydrogen storage system must reach 5wt%, and volume hydrogen-storage density also requires to be greater than 40kg/m
3.
At present, report that more hydrogen storage method mainly contains low temperature liquid storage hydrogen, high-pressure gaseous storage hydrogen, metal alloy storage hydrogen, carbon material adsorption hydrogen-storing, method such as chemical hydride storage hydrogen and metal-organic framework materials (MOFs) Chu Qing etc.These methods all achieve certain progress, but also need to further consider from aspects such as quality hydrogen-storage density, volume hydrogen-storage density, energy efficiency, safety, costs.Therefore, find high efficiency, low cost and can just become crucial by the hydrogen storage method that utilizes of mass-producing again.See: Zhu Gang profit poplar uncle human relations, liquid organic hydride storage hydrogen progress. chemical progress 21 (2009) 2760-2770.
Methylcyclohexane is with its high hydrogen-storage density: quality hydrogen-storage density is for 6.1wt%, and volume hydrogen-storage density is 47Kg/m
3, and cause people's extensive concern gradually; Secondly, methylcyclohexane is industrial scale operation chemical article; Moreover, methylcyclohexane storage hydrogen is circulating and reversible process, and namely methylbenzene-methylcyclohexane can hydrogenation and dehydrogenation under the agent structure not destroying carbocyclic ring, and this is the non-sensitive reaction of structure, while c h bond fracture, do not affect the structure of C-C skeleton, and reaction is reversible.Meanwhile, because hydrogenation process is that Gibbs free energy reduces process, and absolute value is very big, and thermodynamics is very favourable, and namely hydrogenation process is very easy to carry out; And certain embodiments is strong endothermic reaction, react more difficult carrying out, need to use catalyzer to reduce reaction barrier.
Two-step approach mostly is at present about methylcyclohexane dehydrogenation catalyst preparation method, namely need first to prepare catalyzer, be applied to catalyzed reaction more afterwards, such as more common is pickling process, first adopt Platinic chloride to flood with carbon ball to mix, Pt/C catalyzer is prepared in repeated hydrogenation reduction afterwards, is finally applied in this reaction process of methylcyclohexane dehydrogenation again.See: CuiZhang, all can problem of oxidation be there is after the preparation in ShuangxiLiuetal.Hydrogenproductionbycatalyticdehydrogena tionofmethylcyclohexaneoverPtcatalystssupportedonpyrolyt icwastetirechar.InternationalJournalOfHydrogenEnergy36 (2011) 8902-8907. but catalyzer in participation reaction put procedure, even precious metals pt is also can hardly be avoided, and in catalytic process, only have atomic state Pt just can play katalysis, and oxidation state Pt can not play katalysis.So be badly in need of a kind of novel technological method, can a step realize catalyst preparing and in-situ applications in methylcyclohexane dehydrogenation.Single stage method prepares catalyzer in methylcyclohexane catalysis dehydrogenation reaction process, feed back simultaneously and accelerate methylcyclohexane dehydrogenation, centre does not relate to first prepares catalyzer, transfer to again in reaction unit, be different from common two-step approach, effectively can avoid catalyst oxidation and obtain efficient methylcyclohexane dehydrogenation.
Summary of the invention
Object of the present invention is for existing Kaolinite Preparation of Catalyst complex process, easily the problems such as oxidation occurs.Utilize the feature of high temperature in methylcyclohexane catalytic reaction process, generate Pt characteristic in conjunction with methyl ethyl diketone platinum pyrolytic decomposition, in catalytic process, a step prepares Pt/C catalyzer, and obtains efficient methylcyclohexane dehydrogenation simultaneously.
The present invention is achieved by following technical solution.
One step achieves the method for Pt/C catalyst preparing and methylcyclohexane dehydrogenation, and step is as follows:
(1) will configure methyl ethyl diketone platinum ethanolic soln and the mixing of carbon ball deionized water solution, obtained methyl ethyl diketone platinum/carbon ball suspension suction filtration, obtains methyl ethyl diketone platinum/carbon ball powder through super-dry;
(2) by methyl ethyl diketone platinum/carbon ball pressed powder, be placed in atmospheric fixed bed reactor, pass into methylcyclohexane, entering temperature of reactor is 280 DEG C-320 DEG C, methylcyclohexane dehydrogenation.
The mass concentration of described methyl ethyl diketone platinum ethanolic soln is preferably: 0.25g/L-1.5g/L.
Described carbon ball deionized water solution mass concentration is preferably: 20g/L-50g/L.
Described methyl ethyl diketone platinum ethanolic soln is added drop-wise in carbon ball deionized water solution.Methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are preferably 1:1-2:1.
Described methylcyclohexane input speed is preferably 0.03mL/min-0.05ml/min.
During described methylcyclohexane charging, pass into nitrogen, N2 flow is preferably 5mL/min-7ml/min.
Described its purity of methyl ethyl diketone platinum is preferably 99.999%.
Agilent7700x type proton inductivity coupled plasma mass spectrometry combined instrument can be adopted, the content of Pt in analytic sample.
GC-7800 type gas chromatograph can be adopted to analyze, in assay products, methylcyclohexane and hydrogen content .GC-7800 type gas chromatograph are SE-54 capillary column, use flame ionization ditector (FID), constant temperature 80 DEG C, vaporizing chamber 230 DEG C, detector 230 DEG C.
The present invention for Pt source, utilizes methyl ethyl diketone platinum high temperature to occur to decompose the characteristic generating catalyst Pt with methyl ethyl diketone platinum; Secondly, hot properties in methylcyclohexane certain embodiments is utilized.Ingeniously both combined, when methylcyclohexane dehydrogenation reaction, single stage method prepares Pt/C catalyzer, and completes methylcyclohexane dehydrogenation reaction.One-step synthesis in reaction process, namely catalyzer one prepares, and immediately comes into operation, do not relate to catalyzer transfer, effectively prevent catalyst oxidation, thus obtain an efficient catalytic performance, namely methylcyclohexane hydrogen-producing speed and transformation efficiency all reach one very high-level.
The present invention has following effect:
(1) instant invention overcomes existing preparation technology and prepare the deficiencies such as catalyzer is oxidizable, surface is unclean, provide an a kind of step and prepare Pt/C catalyzer and complete methylcyclohexane dehydrogenation.In methylcyclohexane catalytic reaction process, a step high-temp in-situ prepares Pt/C catalyzer, and feedback accelerates methylcyclohexane dehydrogenation simultaneously.Centre does not relate to catalyzer transfer, effectively prevent catalyzer in use problem of oxidation.In addition, synthetic method of the present invention is simple, easy to operate, be easy to control, no coupling product and impurity, belongs to fabricated in situ and eco-friendly green synthesis process.
(2) the present invention is a kind of universality method, can be suitable for the high-temperature catalytic reaction that other take Pt as catalyzer.
Accompanying drawing explanation
Fig. 1 is the thermal multigraph that the present invention prepares Pt/C loaded catalyst;
Fig. 2 is Pt/C loaded catalyst high power transmission electron microscope photo of the present invention;
Fig. 3 is Pt/C loaded catalyst size distribution of the present invention statistics;
Fig. 4 is Pt/C loaded catalyst of the present invention whole x-ray photoelectron energy spectrogram;
Fig. 5 is hydrogen-producing speed figure under Pt/C loading type different loads amount of the present invention;
Fig. 6 is turnover ratio figure under Pt/C loading type different loads amount of the present invention.
Embodiment
The present invention's raw material used is commercially available analytical pure raw material
Embodiment 1:
Taking 5mg purity is 99.999% methyl ethyl diketone platinum, is dissolved in 20ml ethanolic soln, stirs 30min, is mixed with 0.25g/L methyl ethyl diketone platinum ethanolic soln; Take 1g carbon ball, be scattered in 20ml deionized water, ultrasonic 30min, be mixed with the 50g/L carbon ball aqueous solution; Methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are 1:1; Dropping mode is adopted to be added drop-wise in the carbon ball aqueous solution by methyl ethyl diketone platinum ethanolic soln afterwards, fully stir 3h afterwards, guarantee the many as far as possible absorption of methyl ethyl diketone platinum, suction filtration afterwards, dry 5h at 80 DEG C, through ICP-MS test in methyl ethyl diketone platinum/carbon ball platinum charge capacity be 0.18%.Get 0.3g methyl ethyl diketone platinum/carbon ball afterwards, compressing tablet, be placed in fixation reaction bed apparatus, methylcyclohexane input speed is 0.03ml/min, N2 flow is 5mL/min, and vaporizing chamber, preheater, temperature of reactor are 280 DEG C, and in catalytic process, high temperature facilitates the decomposition of methyl ethyl diketone platinum and generates Pt nano particle, feed back the dehydrogenation of catalysis methylcyclohexane, a step achieves catalyst preparing and dehydrogenation test simultaneously.
Embodiment 2:
Taking 15mg purity is 99.999% methyl ethyl diketone platinum, is dissolved in 40ml ethanolic soln, stirs 30min, is mixed with 0.375g/L methyl ethyl diketone platinum ethanolic soln; Take 1g carbon ball, be scattered in 30ml deionized water, ultrasonic 30min, be mixed with the 33.3g/L carbon ball aqueous solution; Methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are 1.33:1; Dropping mode is adopted to be added drop-wise in the carbon ball aqueous solution by methyl ethyl diketone platinum ethanolic soln, fully stir 3h afterwards, guarantee the many as far as possible absorption of methyl ethyl diketone platinum, suction filtration afterwards, dry 5h at 80 DEG C, through ICP-MS test in methyl ethyl diketone platinum/carbon ball platinum charge capacity be 0.37%.Get 0.3g methyl ethyl diketone platinum/carbon ball afterwards, compressing tablet, be placed in fixation reaction bed apparatus, methylcyclohexane input speed is 0.04ml/min, N2 flow is 6mL/min, and vaporizing chamber, preheater, temperature of reactor are 300 DEG C, and in catalytic process, high temperature facilitates the decomposition of methyl ethyl diketone platinum and generates Pt nano particle, feed back the dehydrogenation of catalysis methylcyclohexane, a step achieves catalyst preparing and dehydrogenation test simultaneously.Wherein, methyl ethyl diketone platinum purity is 99.999%.
Embodiment 3:
Taking 25mg purity is 99.999% methyl ethyl diketone platinum, is dissolved in 60ml ethanolic soln, stirs 30min, is mixed with 0.417g/L methyl ethyl diketone platinum ethanolic soln; Take 1g carbon ball, be scattered in 40ml deionized water, ultrasonic 30min, be mixed with the 25g/L carbon ball aqueous solution; Methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are 1.5:1; Dropping mode is adopted to be added drop-wise in the carbon ball aqueous solution by methyl ethyl diketone platinum ethanolic soln, fully stir 3h afterwards, guarantee the many as far as possible absorption of methyl ethyl diketone platinum, suction filtration afterwards, dry 5h at 80 DEG C, through ICP-MS test in methyl ethyl diketone platinum/carbon ball platinum charge capacity be 0.68%.Get 0.3g methyl ethyl diketone platinum/carbon ball afterwards, compressing tablet, be placed in fixation reaction bed apparatus, methylcyclohexane input speed is 0.05ml/min, N2 flow is 7mL/min, and vaporizing chamber, preheater, temperature of reactor are 320 DEG C, and in catalytic process, high temperature facilitates the decomposition of methyl ethyl diketone platinum and generates Pt nano particle, feed back the dehydrogenation of catalysis methylcyclohexane, a step achieves catalyst preparing and dehydrogenation test simultaneously.
Embodiment 4:
Taking 150mg purity is 99.999% methyl ethyl diketone platinum, is dissolved in 100ml ethanolic soln, stirs 30min, is mixed with 1.5g/L methyl ethyl diketone platinum ethanolic soln; Take 1g carbon ball, be scattered in 50ml deionized water, ultrasonic 30min, be mixed with the 20g/L carbon ball aqueous solution; Methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are 2:1; Dropping mode is adopted to be added drop-wise in the carbon ball aqueous solution by methyl ethyl diketone platinum ethanolic soln, fully stir 3h afterwards, guarantee the many as far as possible absorption of methyl ethyl diketone platinum, suction filtration afterwards, dry 5h at 80 DEG C, through ICP-MS test in methyl ethyl diketone platinum/carbon ball platinum charge capacity be 2.83%.Get 0.3g methyl ethyl diketone platinum/carbon ball afterwards, compressing tablet, be placed in fixation reaction bed apparatus, methylcyclohexane input speed is 0.05ml/min, N2 flow is 5mL/min, and vaporizing chamber, preheater, temperature of reactor are 320 DEG C, and in catalytic process, high temperature facilitates the decomposition of methyl ethyl diketone platinum and generates Pt nano particle, feed back the dehydrogenation of catalysis methylcyclohexane, a step achieves catalyst preparing and dehydrogenation test simultaneously.
Below in conjunction with accompanying drawing, the invention will be further described.
Show from Fig. 1 heavy load amount 2.83% methyl ethyl diketone platinum/carbon ball sample thermogravimetric analysis, methyl ethyl diketone platinum there occurs change really at 220 DEG C-320 DEG C, but can not determine what change methyl ethyl diketone platinum there occurs on earth.
Fig. 2 (a) (c) is sample after charge capacity 0.45% methyl ethyl diketone platinum/320 DEG C, carbon ball annealing 1h and 320 DEG C of 10h dehydrogenation, and (b) (d) is sample after charge capacity 0.68% methyl ethyl diketone platinum/320 DEG C, carbon ball annealing 1h and 320 DEG C of 10h dehydrogenation.Demonstrating high temperature action impels methyl ethyl diketone platinum to be decomposed to form Pt nano particle.
Fig. 3 is heavy load amount 2.83% methyl ethyl diketone platinum/320 DEG C, carbon ball sample annealing 1h size distribution statistics, and particle mean size is 1.28nm.
Fig. 4 is heavy load amount 2.83% methyl ethyl diketone platinum/carbon ball x-ray photoelectron energy spectrogram, is respectively the x-ray photoelectron energy spectrogram after dehydrogenation reaction, the x-ray photoelectron energy spectrogram of 320 DEG C of annealing 1h and methyl ethyl diketone platinum x-ray photoelectron energy spectrogram.Wherein after 320 DEG C of annealing 1h, show that methyl ethyl diketone platinum there occurs decomposition, generate 0 valency Pt, but this part 0 valency Pt exposure there occurs oxidation in atmosphere and then generates Pt II with Pt IV; Sample after dehydrogenation, methyl ethyl diketone platinum is decomposed to form 0 valency Pt completely, exposes some generation oxidation in atmosphere and generates Pt II.
Fig. 1,2,3,4 demonstrate high temperature action has impelled methyl ethyl diketone platinum to be decomposed to form Pt nanometer really, and mean sizes is 1.28nm.
Under being respectively different loads amount by Fig. 5, Fig. 6, hydrogen-producing speed is with turnover ratio, reaches maximum hydrogen-producing speed 570mmol/g/min when charge capacity is 0.37%.Turnover ratio also increases along with charge capacity, increases gradually, when charge capacity is 0.68% close to 100% turnover ratio.
Open and all methods that propose of the present invention and technology of preparing, those skilled in the art are by using for reference present disclosure, the links such as appropriate change raw material and operational path realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (8)
1. a step achieves the method for Pt/C catalyst preparing and methylcyclohexane dehydrogenation, it is characterized in that step is as follows:
(1) will configure methyl ethyl diketone platinum ethanolic soln and the mixing of carbon ball deionized water solution, obtained methyl ethyl diketone platinum/carbon ball suspension suction filtration, obtains methyl ethyl diketone platinum/carbon ball powder through super-dry;
(2) by methyl ethyl diketone platinum/carbon ball pressed powder, be placed in atmospheric fixed bed reactor, pass into methylcyclohexane, entering temperature of reactor is 280 DEG C-320 DEG C, methylcyclohexane dehydrogenation.
2. the method for claim 1, is characterized in that the mass concentration of methyl ethyl diketone platinum ethanolic soln is: 0.25g/L-1.5g/L.
3. the method for claim 1, is characterized in that carbon ball deionized water solution mass concentration is: 20g/L-50g/L.
4. the method for claim 1, is characterized in that methyl ethyl diketone platinum ethanolic soln is added drop-wise in carbon ball deionized water solution.
5. the method for claim 1, is characterized in that methyl ethyl diketone platinum ethanolic soln and carbon ball deionized water solution volume ratio are 1:1-2:1.
6. the method for claim 1, is characterized in that methylcyclohexane input speed is 0.03mL/min-0.05ml/min.
7. the method for claim 1, when it is characterized in that methylcyclohexane charging, passes into nitrogen, and N2 flow is 5mL/min-7ml/min.
8. the method for claim 1, is characterized in that its purity of methyl ethyl diketone platinum is 99.999%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250532A (en) * | 2016-06-16 | 2021-01-22 | 国际香料和香精公司 | Cyclic economic process for the preparation of unsaturated compounds |
Citations (1)
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| CN102029151A (en) * | 2010-10-27 | 2011-04-27 | 贵研铂业股份有限公司 | Modified polyol method for preparing Pt/C catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102029151A (en) * | 2010-10-27 | 2011-04-27 | 贵研铂业股份有限公司 | Modified polyol method for preparing Pt/C catalyst |
Non-Patent Citations (4)
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| C. MERCADO-ZÚñIGA ET AL.: "Synthesis of highly dispersed platinum particles on carbon nanotubes by an in situ vapor-phase method", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| CUI ZHANG ET AL.: "Hydrogen production by catalytic dehydrogenation of methylcyclohexane over Pt catalysts supported on pyrolytic waste tire char", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| PHAM DUNG TIEN ET AL.: "Continuous hydrogen evolution from cyclohexanes over platinum catalysts supported on activated carbon fibers", 《FUEL PROCESSING TECHNOLOGY》 * |
| 李晓芸等: "不同活性炭上Pt催化剂的分散性及其在甲基环己烷脱氢反应中的催化性能", 《催化学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250532A (en) * | 2016-06-16 | 2021-01-22 | 国际香料和香精公司 | Cyclic economic process for the preparation of unsaturated compounds |
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