CN109745978A - The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane - Google Patents
The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane Download PDFInfo
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Abstract
The present invention relates to catalyst field, the method for a kind of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane is disclosed.The propane dehydrogenation catalyst includes Pt component, Sn component and the Na component of carrier and load on the carrier, wherein, the carrier is meso-porous carbon material, the meso-porous carbon material has the cellular structure of six side's symbiosis of sum of cubes of body-centred cubic structure, and the specific surface area of the meso-porous carbon material is 300-450m2/ g, pore volume 0.1-0.5mL/g, most probable pore size 2-5nm.The propane dehydrogenation catalyst shows good catalytic performance when reacting for preparing propylene by dehydrogenating propane, conversion of propane is high, and Propylene Selectivity is high, and catalyst stability is good.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of propane dehydrogenation catalyst and preparation method thereof and third
The method of alkane dehydrogenation producing propylene.
Background technique
Propylene is the base stock of petrochemical industry, mainly for the production of polypropylene, acrylonitrile, acetone, propylene oxide, propylene
Acid and octyl alconyl etc..The supply half of propylene comes from refinery's by-product, separately has about 45% to come from steam cracking, a small amount of other substitution skills
Art.In recent years, the demand of propylene increases year by year, and traditional production of propylene has been unable to meet demand of the chemical industry to propylene,
Therefore propylene enhancing becomes a big hot spot of research.Wherein, preparing propylene by dehydrogenating propane is a major technique of propylene volume increase.10
For many years, preparing propylene by dehydrogenating propane has become the important process process of industrialization production of propylene.The major catalytic of dehydrogenating propane
Agent has in chromium oxide/aluminum oxide catalyst and Uop Inc.'s Oleflex technique in ABB Lummus company CYLofin technique
Platinum tin/aluminium oxide catalyst.Requirement of the chromium-based catalysts to raw material impurity is relatively low, on the low side compared with noble metal；But this
Class catalyst is easy carbon distribution inactivation, will regenerate every 15-30 minutes once, and since the chromium in catalyst is heavy metal,
Environmental pollution is serious.Platinum-tin catalyst activity is high, and selectivity is good, can reach reaction time several days, can bear more harsh
Process conditions, and to more environment-friendly；But since noble metal platinum is expensive, lead to catalyst higher cost.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst is not still high there is conversion of propane and is easy to the defects of inactivating, and requires further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.In order to improve the reactivity worth of propane dehydrogenation catalyst, people is studied
Member has done many work.Such as: traditional γ-Al2O3 carrier is substituted using molecular sieve carrier, effect preferably includes MFI
Type micro porous molecular sieve (CN104307555A, CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41
Molecular sieve (CN102389831A) and mesoporous SBA-15 molecular sieve (CN101972664A, CN101972664B) etc..However at present
Common mesoporous material aperture is smaller (6~9nm of average pore size), if carrying out bulky molecular catalysis reaction, macromolecular is more difficult to get access
Duct, so that influencing catalytic effect.Therefore, it selects a kind of excellent carrier to be that one, dehydrogenating propane field is urgently to be resolved to ask
Topic.
Summary of the invention
Propane dehydrogenation catalyst in the prior art is usually with Pt for main metal active constituent, with γ-Al2O3For carrier,
The active component poor dispersion of the catalyst, catalytic activity and the poor defect of stability.It is existing the purpose of the present invention is overcoming
Technical agency's pore structure is unstable, further result in conversion of propane and Propylene Selectivity it is not high and be easy to the defects of inactivating lack
It falls into, the method for a kind of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane is provided.
To achieve the goals above, one aspect of the present invention provides a kind of propane dehydrogenation catalyst, the dehydrogenating propane catalysis
Agent includes Pt component, Sn component and the Na component of carrier and load on the carrier, wherein the carrier is mesoporous carbon materials
Material, the meso-porous carbon material have the cellular structure of six side's symbiosis of sum of cubes of body-centred cubic structure, the meso-porous carbon material
Specific surface area is 300-450m2/ g, pore volume 0.1-0.5mL/g, most probable pore size 2-5nm.
Second aspect of the present invention provides a kind of method for preparing above-mentioned propane dehydrogenation catalyst, this method comprises: by carrier
Carry out impregnation in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma, then according to
It is secondary to be removed solvent processing, dry and roasting, wherein the carrier is meso-porous carbon material, and the meso-porous carbon material has vertical
The cellular structure of six side's symbiosis of sum of cubes of cube core structure, the specific surface area of the meso-porous carbon material are 300-450m2/ g, hole
Volume is 0.1-0.8mL/g, most probable pore size 2-5nm.
Third aspect present invention provides a kind of propane dehydrogenation catalyst prepared by the above method.
Fourth aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, which comprises in catalyst and hydrogen
In the presence of gas, propane is subjected to dehydrogenation reaction, wherein the catalyst be propane dehydrogenation catalyst provided by the invention or by
The propane dehydrogenation catalyst that method provided by the invention is prepared.
The carrier of propane dehydrogenation catalyst according to the present invention is meso-porous carbon material, and the meso-porous carbon material has vertical
The cellular structure of six side's symbiosis of sum of cubes of cube core structure, and there is biggish pore size, in addition, the meso-porous carbon material
Skeleton be made of phenolic resin, a large amount of aromatic rings are contained in skeleton structure, therefore hydrophobicity is stronger, steady with excellent hydro-thermal
It is qualitative.Therefore, the meso-porous carbon material is suitable as the carrier of loaded catalyst, be especially suitable in dehydrogenating propane system third
The carrier of loaded catalyst used in alkene reaction.
In the propane dehydrogenation catalyst of the invention, use the meso-porous carbon material as carrier, load has Pt group
Point, Sn component and Na component so that the loaded catalyst had both had the advantages that loaded catalyst such as catalytic activity was high, secondary anti-
Should less, post-processing it is simple etc., and there is stronger catalytic activity, so that the loaded catalyst is in for dehydrogenating propane reaction
With better dehydrogenation activity and selectivity, the conversion ratio of reaction raw materials is significantly improved, specifically, uses the loaded catalyst
In the reaction for carrying out preparing propylene by dehydrogenating propane, conversion of propane is up to 31%, and the selectivity of propylene is up to 87%.
In addition, the step impregnation method that the present invention is conventional using co-impregnation method substitution, preparation process is simple, and condition is easy to
Control, good repetitiveness.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is X-ray diffraction (XRD) spectrogram of the meso-porous carbon material of embodiment 1；
Fig. 2 is the nitrogen Adsorption and desorption isotherms of the meso-porous carbon material of embodiment 1；
Fig. 3 is the pore size distribution curve figure of the meso-porous carbon material of embodiment 1；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the meso-porous carbon material of embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of propane dehydrogenation catalyst, the propane dehydrogenation catalyst includes carrier and is supported on institute
State Pt component, Sn component and the Na component on carrier, wherein the propane dehydrogenation catalyst includes carrier and is supported on described
Pt component, Sn component and Na component on carrier, wherein the carrier is meso-porous carbon material, and the meso-porous carbon material has vertical
The cellular structure of six side's symbiosis of sum of cubes of cube core structure, the specific surface area of the meso-porous carbon material are 300-450m2/ g, hole
Volume is 0.1-0.5mL/g, most probable pore size 2-5nm.
According to the present invention, the carrier has the cellular structure of six side's symbiosis of sum of cubes of special body-centred cubic structure,
This unique skeleton structure has broken limitation of the one-dimensional channels for molecular transport, and the mesoporous hole of the meso-porous carbon material
Road structure distribution is uniform, proper pore size, Kong Rong great, mechanical strength are good, has good structural stability, is conducive to metal
Fine dispersion of the component inside its duct.The support type obtained using the carrier loaded Pt component, Sn component and Na component
Catalyst had not only had the advantages that loaded catalyst such as catalytic activity is high, side reaction is few, post-processing is simple etc., but also had stronger
Catalytic activity and higher stability, so that the loaded catalyst has better dehydrogenation living in for dehydrogenating propane reaction
Property and selectivity, significantly improve the conversion ratio of reaction raw materials.
According to the present invention, the specific surface area of the carrier, pore volume and most probable pore size are measured according to nitrogen adsorption methods.
It is further preferred that the meso-porous carbon material is order mesoporous resin material FDU-14.The skeleton of FDU-14 is by phenol
Urea formaldehyde forms, and a large amount of aromatic rings is contained in skeleton structure, therefore hydrophobicity is stronger, has excellent hydrothermal stability.Also,
FDU-14 meets the cellular structure with six side's symbiosis of sum of cubes, has biggish pore size.
According to the present invention, the most probable pore size of the carrier can be 2-5nm, preferably 2-4nm, more preferably 3nm.Root
According to the present invention, the specific surface area of the carrier can be 300-450m2/ g, preferably 350-400m2/ g, most preferably 375m2/
g.According to the present invention, the pore volume of the carrier can be 0.1-0.5mL/g, preferably 0.1-0.3mL/g, more preferably
0.2mL/g.In the present invention, the most probable pore size, specific surface area and pore volume are using nitrogen adsorption-detachment assays measurement
's.
According to the present invention, by by the structural parameter control of the meso-porous carbon material within above range, it can be ensured that
The meso-porous carbon material is not susceptible to reunite, and is used as loaded catalyst made of carrier and dehydrogenating propane can be improved
Reaction raw materials conversion ratio in propylene reaction process processed.When the meso-porous carbon material specific surface area is less than 300m2/ g and/or hole body
When product is less than 0.1mL/g, the catalytic activity for being used as loaded catalyst made of carrier can be significantly reduced；When described mesoporous
The specific surface area of carbon material is greater than 450m2When/g and/or pore volume are greater than 0.5mL/g, it is used as support type made of carrier
Catalyst is easy to happen reunion in preparing propylene by dehydrogenating propane reaction process, to influence in preparing propylene by dehydrogenating propane reaction process
Reaction raw materials conversion ratio.
According to the present invention, the propane dehydrogenation catalyst includes carrier and load Pt component on the carrier, Sn
Component and Na component, wherein the Pt group is divided into active metal component, and the Sn component and Na group are divided into metal promoter.
According to the present invention, relative to the propane dehydrogenation catalyst of 100 parts by weight, the content of the carrier is 97.5-
99.3 weight %, content of the Pt component in terms of Pt element are 0.2-0.5 weight %, Sn component the containing in terms of Sn element
Amount is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8 weight %.
Preferably, the specific surface area of the propane dehydrogenation catalyst is 330-380m2/ g, pore volume 0.05-0.25mL/
G, most probable pore size 2-4nm.
The present invention also provides a kind of methods for preparing propane dehydrogenation catalyst, this method comprises: carrier is being contained Pt
Impregnation is carried out in the mixed solution of component presoma, Sn component presoma and Na component presoma, is then successively gone
Except solvent processing, dry and roasting, wherein the carrier is meso-porous carbon material, and the meso-porous carbon material has cube hearty cord
The cellular structure of six side's symbiosis of sum of cubes of structure, the specific surface area of the meso-porous carbon material are 300-450m2/ g, pore volume are
0.1-0.8mL/g, most probable pore size 2-5nm.
According to the present invention, the meso-porous carbon material carried metal component can be by the way of dipping, by described mesoporous
The capillary pressure of the cellular structure of carbon material enters metal component in the duct of the meso-porous carbon material, while metal component is also
It can be in the adsorption of the meso-porous carbon material, until metal component reaches adsorption equilibrium on the surface of the meso-porous carbon material.
The impregnation can be handled for co-impregnation, or step impregnation processing.In order to save preparation cost, simplify experiment work
Skill, the impregnation are preferably co-impregnation processing；It is further preferred that the condition of the co-impregnation processing includes: that heat is living
Spherical shape mesopore molecular sieve containing aluminium material silica gel composite after change is before containing Pt component presoma, Sn component presoma and Na component
The solution for driving body is mixed, and the temperature of the dipping can be 25-50 DEG C, and the time of the dipping can be 2-6h.
According to the present invention, the solution of the Pt component presoma, Sn component presoma and Na component presoma is not special
Restriction as long as water-soluble can be the conventional selection of this field.For example, the Pt component presoma can be
H2PtCl6, the Sn component presoma can be SnCl4, the Na component presoma can be NaNO3。
The present invention does not have the concentration of the solution containing Pt component presoma, Sn component presoma and Na component presoma
There is special restriction, can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.1-
The concentration of 0.3mol/L, the Sn component presoma can be 0.15-1mol/L, and the concentration of the Na component presoma can be
1-3.5mol/L。
According to the present invention, the dosage of the carrier, Pt component presoma, Sn component presoma and Na component presoma can be with
In propane dehydrogenation catalyst to make preparation, on the basis of the total weight of the propane dehydrogenation catalyst, the carrier contains
It is 0.2-0.5 weight %, Sn component in terms of Sn element that amount, which is content of 97.5-99.3 weight %, the Pt component in terms of Pt element,
Content is that content of 0.2-1.2 weight %, the Na component in terms of Na element is 0.3-0.8 weight %.
According to the present invention, the process of the removal solvent processing can adopt with the conventional methods in the field, such as can adopt
With the solvent in Rotary Evaporators removal system.
According to the present invention, in the preparation process of the propane dehydrogenation catalyst, the drying can in drying box into
Row, the roasting can carry out in Muffle furnace.Also there is no particular limitation for condition of the present invention to the drying and roasting, can
Think the conventional selection of this field, for example, it is 110-150 DEG C that the condition of the drying, which may include: temperature, time 3-6h；
The condition of the roasting may include: that temperature is 600-650 DEG C, time 5-8h.
According to the present invention, the carrier forming method the following steps are included:
(a) under heating conditions, phenol, formaldehyde and NaOH are subjected to the first contact, the production obtained after the first contact
Object is cooled to room temperature, and obtains the first product of contact；
(b) under heating conditions, first product of contact is carried out second with template to contact, after the second contact
Obtained product is cooled to room temperature, and obtains the second product of contact, and then the second product of contact is successively centrifuged and is done
It is dry, obtain meso-porous carbon material original powder；
(c) the meso-porous carbon material original powder is subjected to Template removal processing, obtains meso-porous carbon material.
In the forming process of above-mentioned carrier, the main dosage by controlling each reaction raw materials, feeding sequence and reaction temperature
The control of degree can use the common raw material being easy to get, synthesize that specific surface area is larger, hole in next step in easy operating condition
The biggish meso-porous carbon material of volume.
According to the present invention, in order to enable the meso-porous carbon material arrived has six side of sum of cubes of special body-centred cubic structure total
Raw cellular structure, the template is preferably triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123, described
Template can be commercially available that (for example, can be purchased from Aldrich, trade name P123, molecular formula be
EO20PO70EO20, average molecular mass Mn 5800), it can also be prepared by existing various methods.When the template
When for polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to PULLRONIC F68-polyoxy second
The average molecular weight of alkene calculates to obtain.
According to the present invention, in step (a), there is no particular limitation for the sequence of first contact, can be by phenol, first
Aldehyde and NaOH are mixed simultaneously, any two kinds can also be mixed, and are added other components and are uniformly mixed.According to a kind of preferred
Embodiment, the phenol, formaldehyde and NaOH are mixed simultaneously.It is 50- that the condition of first contact, which includes: temperature,
100 DEG C, time 1-3h, in order to be more advantageous to the uniform mixing between each substance, first contact is preferably under agitation
It carries out.
According to the present invention, in step (b), second contact includes the first heating period and the second heating period, excellent
Selection of land, the temperature of second heating period are higher than the temperature of the first heating period, specifically,
The condition of first heating period may include: that temperature is 50-65 DEG C, time 100-150h,
The condition of second heating period may include: that temperature is 66-100 DEG C, time 24-100h.
According to the present invention, in the forming process of the carrier, the condition of the drying can carry out in drying box, institute
State dry condition may include: temperature be 25-100 DEG C, time 3-5h.
According to the present invention, the method for the removed template method is usually calcination method.The condition of the removed template method can be with
For this field conventional selection, for example, the condition of the removed template method includes: the condition with 0.5-5 DEG C per minute by 10-50 DEG C
(such as room temperature) rises to 300-600 DEG C, preferably 350-550 DEG C, most preferably 500 DEG C, after keep the temperature 3-20 hours again.
According to the present invention, the dosage of the phenol, formaldehyde, NaOH and template can be according to expected obtained mesoporous carbon materials
The skeleton structure of material is selected, under preferable case, the phenol, formaldehyde, NaOH and template dosage molar ratio be 1:
2-10:200-500:0.1-5.
The forming method of a kind of specific embodiment according to the present invention, the carrier may comprise steps of: by benzene
The formalin that phenol, concentration are 20-50 weight % and the NaOH aqueous solution that concentration is 0.05-0.2mol/L are according to phenol: formaldehyde:
The mass ratio of NaOH is that 1:0.5-2:0.05-0.2 is stirred 1-3 hours at 50-100 DEG C, after being down to 10-45 DEG C (such as room temperature),
It is added by ethylene oxide-propylene oxide-ethylene oxide triblock copolymer template (such as P123, number-average molecular weight Mn=5800)
(U.S. chemical abstract registration number be 9003-11-6) and deionized water form mixed solution in, template and deionization
The mass ratio of water is 1:5-20,66-100 DEG C is warming up to after being again heated to 50-65 DEG C and heating stirring 100-150 hours, stirring
It is down to 10-50 DEG C (such as room temperature) after 24-100 hours, solid sample is obtained after centrifuge separation, then solid sample is put into 25-100
DEG C baking oven in dry, obtain original powder mesoporous material polymer；Later, by original powder mesoporous material polymer in muffle furnace with every
The condition of 0.5-5 DEG C of minute keeps the temperature 3-20 hours, after removed template method after rising to 300-600 DEG C by 10-50 DEG C (such as room temperature) again
Obtain mesoporous material polymer FDU-14.
The present invention also provides the propane dehydrogenation catalysts being prepared by the method for the invention.
The present invention also provides a kind of methods of preparing propylene by dehydrogenating propane, which comprises in catalyst and hydrogen
In the presence of, propane is subjected to dehydrogenation reaction, wherein the catalyst is propane dehydrogenation catalyst of the present invention.
According to the present invention, in order to improve conversion of propane and prevent catalyst coking, under preferable case, the dosage of propane with
The molar ratio of the dosage of hydrogen is 0.5-1.5:1.
There is no particular limitation for condition of the present invention to the dehydrogenation reaction, can be the conventional selection of this field, for example,
The condition of the dehydrogenation reaction may include: that reaction temperature is 600-650 DEG C, reaction pressure 0.05-0.2MPa, the reaction time
For 40-60h, propane mass space velocity is 2-5h-1。
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene P123 is purchased from Aldrich,
It is abbreviated as P123, molecular formula EO20PO70EO20, average molecular mass Mn 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled in the ASAP2020-M+C type that Micromeritics company, the U.S. produces
It is carried out on attached instrument；The specific surface area and pore volume of sample, which calculate, uses BET method；Rotary Evaporators are the production of IKA company, Germany,
Model RV10digital；The activity component load quantity of propane dehydrogenation catalyst is being purchased from Dutch Panaco company model
It is measured on the wavelength dispersion X-ray fluorescence spectrometer of Axios-Advanced；The analysis of reaction product ingredient is being purchased from Agilent
It is carried out on the gas chromatograph that company model is 7890A.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio (%) of propane=(in dosage-reaction product of propane
The content of propane) ÷ propane dosage × 100%；
Theoretical yield × 100% of selectivity (%)=propylene actual production ÷ propylene of propylene.
Embodiment 1
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
The NaOH aqueous solution of 2.8 grams of phenol, the formalin of 7.1 gram of 38 weight % and 69 grams of 0.1mol/L is sequentially added
Into the single-necked flask of 250mL, 72 DEG C heating stirring 1.5 hours, after being down to 25 DEG C, addition gone by 6.72 grams P123 and 70 gram
The mixed solution of ionized water composition, then obtained mixture is heated to 64 DEG C, heating stirring 120 hours at 64 DEG C, then
72 DEG C are warming up to, stirring was down to 25 DEG C after 48 hours, and obtained reaction product is centrifugated, and obtained solid product, and incite somebody to action
The solid product arrived was oven drying 4 hours of 80 DEG C；By the solid product being dried to obtain with 1 DEG C of rate per minute by 25 DEG C
350 DEG C are risen to, and keeps the temperature 6 hours, obtains the mesoporous carbon of the cellular structure of six side's symbiosis of sum of cubes with body-centred cubic structure
Material C 1.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the meso-porous carbon material C1 of above-mentioned preparation is immersed in the mixture solution, is impregnated at 25 DEG C
After 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 DEG C that solid product, which is placed in temperature,
In drying box, dry 3h, being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, obtain propane dehydrogenation catalyst Cat-1 (with
On the basis of the total weight of propane dehydrogenation catalyst Cat-1, content of the Pt component in terms of Pt element be 0.3 weight %, Sn component with
The content of Sn element meter is that content of 0.7 weight %, the Na component in terms of Na element is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to meso-porous carbon material C1 and dehydrogenating propane
Catalyst Cat-1 is characterized；
Fig. 1 is X-ray diffraction (XRD) spectrogram of the meso-porous carbon material C1, wherein abscissa is 2 θ, and ordinate is strong
Degree, the low-angle spectral peak occurred from XRD spectra is it is found that the meso-porous carbon material C1 has special six side's symbiosis of sum of cubes
Cellular structure；
Fig. 2 is the nitrogen Adsorption and desorption isotherms of the meso-porous carbon material C1, wherein abscissa is relative pressure (p/p0),
Curve shape in Fig. 2 is typical IV type thermoisopleth, it was demonstrated that the meso-porous carbon material C1 has the spy of typical mesoporous material
Sign；
Fig. 3 is the pore size distribution curve figure of the meso-porous carbon material C1, wherein the hole diametal curve of the meso-porous carbon material C1
It is evenly distributed, peak shape is symmetrical；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the meso-porous carbon material C1, as seen from the figure, the mesoporous carbon materials
The microscopic appearance for expecting C1 is 1~3 μm of spheric granules, and monodispersity is preferable.
Table 1 is the pore structure parameter of the meso-porous carbon material C1 and propane dehydrogenation catalyst Cat-1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size (nm) |
| Meso-porous carbon material C1 | 375 | 0.2 | 3 |
| Catalyst Cat-1 | 350 | 0.14 | 2.7 |
As the meso-porous carbon material C1 of carrier in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 1
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of meso-porous carbon material C1.
Comparative example 1
This comparative example is for illustrating propane dehydrogenation catalyst of reference and preparation method thereof.
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
The duct of six side's symbiosis of sum of cubes with body-centred cubic structure is substituted using commercially available ES955 silica gel (GRACE company)
The meso-porous carbon material C1 of structure is as carrier D1, so that carrier D1 and propane dehydrogenation catalyst Cat-D-1 be made respectively.
Comparative example 2
This comparative example is for illustrating propane dehydrogenation catalyst of reference and preparation method thereof.
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
There is cube using commercially available mesoporous SBA-15 molecular sieve (being purchased from Jilin University's high-tech limited liability company) substitution is described
The meso-porous carbon material C1 of the cellular structure of six side's symbiosis of sum of cubes of core structure as carrier D2, thus respectively be made carrier D2 and
Propane dehydrogenation catalyst Cat-D-2.
Comparative example 3
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, the difference is that preparing dehydrogenating propane type
In the dipping process of catalyst, NaNO is not added3, 0.133g H is only added2PtCl6·6H2O and 0.295g SnCl4·5H2O,
Only active component Pt and metal promoter Sn are supported on the meso-porous carbon material as carrier after thermal activation by co-impregnation,
To be made propane dehydrogenation catalyst Cat-D-3, on the basis of the total weight of propane dehydrogenation catalyst Cat-D-3, Pt component with
The content of Pt element meter is that content of 0.5 weight %, the Sn component in terms of Sn element is 1 weight %, remaining is carrier).
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
The NaOH aqueous solution of 2.8 grams of phenol, the formalin of 23.7 gram of 38 weight % and 120 grams of 0.1mol/L is successively added
Enter into the single-necked flask of 250mL, 75 DEG C heating stirring 2.5 hours, after being down to 25 DEG C, be added by 9.97 grams P123 and 70 gram
The mixed solution of deionized water composition, then obtained mixture is heated to 60 DEG C, heating stirring 150 hours at 60 DEG C, so
After be warming up to 80 DEG C, stirring was down to 25 DEG C after 36 hours, and obtained reaction product is centrifugated, and obtained solid product, and will
Obtained solid product was oven drying 3.5 hours of 90 DEG C；By the solid product being dried to obtain with 1 DEG C of rate per minute by
25 DEG C rise to 500 DEG C, and keep the temperature 4 hours, obtain Jie of the cellular structure of six side's symbiosis of sum of cubes with body-centred cubic structure
Hole carbon material C2.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the meso-porous carbon material C2 of above-mentioned preparation is immersed in the mixture solution, is impregnated at 25 DEG C
After 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 DEG C that solid product, which is placed in temperature,
In drying box, dry 3h, being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, obtain propane dehydrogenation catalyst Cat-2 (with
On the basis of the total weight of propane dehydrogenation catalyst Cat-2, content of the Pt component in terms of Pt element be 0.3 weight %, Sn component with
The content of Sn element meter is that content of 0.7 weight %, the Na component in terms of Na element is 0.5 weight %, remaining is carrier).
Table 2 is the pore structure parameter of the meso-porous carbon material C2 and propane dehydrogenation catalyst Cat-2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size (nm) |
| Meso-porous carbon material C2 | 400 | 0.3 | 4 |
| Catalyst Cat-2 | 380 | 0.18 | 3.6 |
As the meso-porous carbon material C2 of carrier in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 2
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of meso-porous carbon material C2.
Embodiment 3
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
The NaOH aqueous solution of 2.8 grams of phenol, the formalin of 11.6 gram of 38 weight % and 90 grams of 0.1mol/L is successively added
Enter into the single-necked flask of 250mL, 70 DEG C heating stirring 3 hours, after being down to 25 DEG C, addition gone by 13.3 grams P123 and 70 gram
The mixed solution of ionized water composition, then obtained mixture is heated to 65 DEG C, heating stirring 110 hours at 65 DEG C, then
75 DEG C are warming up to, stirring was down to 25 DEG C after 40 hours, and obtained reaction product is centrifugated, and obtained solid product, and incite somebody to action
The solid product arrived was oven drying 3 hours of 100 DEG C；By the solid product being dried to obtain with 1 DEG C of rate per minute by 25
450 DEG C DEG C are risen to, and keeps the temperature 5 hours, obtains the mesoporous of the cellular structure of six side's symbiosis of sum of cubes with body-centred cubic structure
Carbon material C3.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the meso-porous carbon material C3 of above-mentioned preparation is immersed in the mixture solution, is impregnated at 25 DEG C
After 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 DEG C that solid product, which is placed in temperature,
In drying box, dry 3h, being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, obtain propane dehydrogenation catalyst Cat-3 (with
On the basis of the total weight of propane dehydrogenation catalyst Cat-3, content of the Pt component in terms of Pt element be 0.3 weight %, Sn component with
The content of Sn element meter is that content of 0.7 weight %, the Na component in terms of Na element is 0.5 weight %, remaining is carrier).
Table 3 is the pore structure parameter of the meso-porous carbon material C3 and propane dehydrogenation catalyst Cat-3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (mL/g) | Most probable pore size (nm) |
| Meso-porous carbon material C3 | 350 | 0.1 | 2 |
| Catalyst Cat-3 | 330 | 0.07 | 1.7 |
As the meso-porous carbon material C3 of carrier in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 3
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of meso-porous carbon material C3.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the method for illustrating to prepare propylene using propane dehydrogenation catalyst of the invention
0.5g propane dehydrogenation catalyst Cat-1 is fitted into fixed-bed quartz reactor, control reaction temperature is 610 DEG C,
Reaction pressure is 0.1MPa, and propane: the molar ratio of hydrogen is 1:1, and reaction time 50h, propane mass space velocity is 3h-1.Propane
Conversion ratio and Propylene Selectivity are as shown in table 4.
EXPERIMENTAL EXAMPLE 2-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-2 and propane dehydrogenation catalyst Cat-3 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are such as
Shown in table 4.
Experimental comparison's example 1-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-D-1, propane dehydrogenation catalyst Cat-D-2 and propane dehydrogenation catalyst Cat-D-3, instead of propane dehydrogenation catalyst Cat-
1.Conversion of propane and Propylene Selectivity are as shown in table 4.
Table 4
| Dehydrogenation | Conversion of propane | Propylene Selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 31% | 87% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 30.7% | 86.8% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 30.8% | 86.5% |
| Experimental comparison's example 1 | Cat-D-1 | 20.5% | 22.6% |
| Experimental comparison's example 2 | Cat-D-2 | 21.7% | 23.5% |
| Experimental comparison's example 3 | Cat-D-3 | 22.3% | 43.3% |
From table 4, it can be seen that being used for dehydrogenating propane using propane dehydrogenation catalyst prepared by meso-porous carbon material of the invention
When propylene processed reacts, after reacting 50h, still available higher conversion of propane and Propylene Selectivity illustrate of the invention
Propane dehydrogenation catalyst not only has preferable catalytic performance, but also has excellent stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of propane dehydrogenation catalyst, which is characterized in that the propane dehydrogenation catalyst includes carrier and is supported on described
Pt component, Sn component and Na component on carrier, wherein the carrier is meso-porous carbon material, and the meso-porous carbon material has vertical
The cellular structure of six side's symbiosis of sum of cubes of cube core structure, the specific surface area of the meso-porous carbon material are 300-450m2/ g, hole
Volume is 0.1-0.5mL/g, most probable pore size 2-5nm.
2. propane dehydrogenation catalyst according to claim 1, wherein using the total weight of the propane dehydrogenation catalyst as base
Standard, the content of the carrier are 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %,
Content of the Sn component in terms of Sn element is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8
Weight %；
Preferably, the specific surface area of the carrier is 350-400m2/ g, pore volume 0.1-0.3mL/g, most probable pore size 2-
4nm；
It is highly preferred that the meso-porous carbon material is FDU-14.
3. a kind of method for preparing propane dehydrogenation catalyst, which is characterized in that this method comprises: by carrier before containing Pt component
It drives in the mixed solution of body, Sn component presoma and Na component presoma and carries out impregnation, be then successively removed solvent
Processing, dry and roasting, wherein the carrier is meso-porous carbon material, and the meso-porous carbon material has the vertical of body-centred cubic structure
The cellular structure of side and six side's symbiosis, the specific surface area of the meso-porous carbon material are 300-450m2/ g, pore volume 0.1-
0.8mL/g, most probable pore size 2-5nm.
4. according to the method in claim 3, wherein the carrier, Pt component presoma, Sn component presoma and Na component forerunner
The dosage of body makes in the propane dehydrogenation catalyst of preparation, on the basis of the total weight of the propane dehydrogenation catalyst, the load
The content of body is that content of 97.5-99.3 weight %, the Pt component in terms of Pt element is 0.2-0.5 weight %, Sn component with Sn member
It is 0.3-0.8 weight % that the content of element meter, which is content of 0.2-1.2 weight %, the Na component in terms of Na element,；
Preferably, the specific surface area of the carrier is 350-400m2/ g, pore volume 0.1-0.5mL/g, most probable pore size 2-
4nm；
It is highly preferred that the meso-porous carbon material is FDU-14.
5. according to the method in claim 3, wherein the condition of the impregnation includes: that temperature is 25-50 DEG C, time 2-
6h。
6. the method according to any one of claim 3-5, the forming method of the carrier the following steps are included:
(a) under heating conditions, phenol, formaldehyde and NaOH are subjected to the first contact, the product obtained after the first contact is cold
But to room temperature, the first product of contact is obtained；
(b) under heating conditions, first product of contact is carried out second with template to contact, is obtained after the second contact
Product be cooled to room temperature, obtain the second product of contact, then the second product of contact be successively centrifuged and dried, is obtained
To meso-porous carbon material original powder；
(c) the meso-porous carbon material original powder is subjected to Template removal processing, obtains meso-porous carbon material.
7. according to the method described in claim 6, wherein, in step (a), the condition of first contact includes: that temperature is
50-100 DEG C, time 1-3h；
In step (b), second contact includes the first heating period and the second heating period,
The condition of first heating period includes: that temperature is 50-65 DEG C, time 100-150h,
The condition of second heating period includes: that temperature is 66-100 DEG C, time 24-100h.
8. according to the method described in claim 6, wherein, the phenol, formaldehyde, NaOH and template the molar ratio of dosage be
1:2-10:200-500:0.1-5；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；
It is highly preferred that the process of the Template removal processing includes: to calcine 3-20h at 300-600 DEG C.
9. the propane dehydrogenation catalyst that method described in any one of claim 4-8 is prepared.
10. a kind of method of preparing propylene by dehydrogenating propane, which comprises in the presence of catalyst and hydrogen, by propane into
Row dehydrogenation reaction, which is characterized in that the catalyst is dehydrogenating propane catalysis described in any one of claim 1-2 and 9
Agent.
11. according to the method described in claim 10, wherein, the molar ratio of the dosage of the dosage and hydrogen of propane is 0.5-1.5:
1；
Preferably, it is 600-650 DEG C, reaction pressure 0.05-0.2MPa that the condition of the dehydrogenation reaction, which includes: reaction temperature,
Reaction time is 40-60h, and propane mass space velocity is 2-5h-1。
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