CN109745977A - 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 sphericity mesoporous silicon dioxide, the sphericity mesoporous silicon dioxide has body-centred cubic structure, the compression strength of the sphericity mesoporous silicon dioxide is 12-16MPa, average grain diameter is 2-10 μm, specific surface area 700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.Propane dehydrogenation catalyst compression strength with higher, for showing good catalytic performance when preparing propylene by dehydrogenating propane reaction, 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
The purpose of the invention is to overcome the existing bar-shaped ordered mesopore material as propane dehydrogenation catalyst carrier
Mobility is poor, easy to reunite, be unfavorable for its store, transport, postorder processing and application, and then cause by existing support type propane
The defects of poor catalytic activity of the support type propane dehydrogenation catalyst of catalysis dehydrogenation agent carrier preparation, a kind of dehydrogenating propane is provided and is urged
The method of agent and preparation method thereof and preparing propylene by dehydrogenating propane.
To achieve the goals above, the present inventor after research by having found, Jie of the geometric shape with microballoon
Hole silica has apparent advantage in terms of reducing the reunion of powder, improving its, therefore will be spherical ordered mesoporous
Material can combine microballoon with the advantages of ordered mesoporous material as propane dehydrogenation catalyst carrier, can remain with
The characteristics of high-specific surface area, the macropore of sequence mesoporous material hold, aperture is big and narrowly distributing, and the group of ordered mesoporous material can be reduced
It is poly-, increase its mobility.In addition, sphericity mesoporous silicon dioxide of the invention compression strength with higher, can effectively prevent
Sphere is broken in load active component, improves the stability of the carrier, extends the service life of catalyst.Using this hair
The bright sphericity mesoporous silicon dioxide can effectively mention the negative of propane dehydrogenation catalyst as the carrier of propane dehydrogenation catalyst
Load rate and catalytic activity, so that the propane dehydrogenation catalyst made of the carrier in preparing propylene by dehydrogenating propane reaction for can get
The reaction raw materials conversion ratio significantly improved, so as to complete the present invention.
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 spherical mesoporous
Silica, the sphericity mesoporous silicon dioxide have body-centred cubic structure, the compression strength of the sphericity mesoporous silicon dioxide
For 12-16MPa, average grain diameter is 2-10 μm, specific surface area 700-900m2/ g, pore volume 0.5-1mL/g, most probable hole
Diameter is 1-5nm.
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 sphericity mesoporous silicon dioxide, described spherical mesoporous two
Silica has body-centred cubic structure, and the compression strength of the sphericity mesoporous silicon dioxide is 12-16MPa, average grain diameter 2-
10 μm, specific surface area 700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.
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 sphericity mesoporous silicon dioxide, the meso-porous titanium dioxide
Silicon combines the unique framework structure of spherical geometrical characteristic and body-centred cubic, mesopore orbit structure distribution uniformly, pore size
Be suitable for, Kong Rong great, mechanical strength it is good, have good structural stability, therefore, the sphericity mesoporous silicon dioxide is suitable as
The carrier of loaded catalyst, the load be especially suitable for loaded catalyst used in being reacted in preparing propylene by dehydrogenating propane
Body.
In the propane dehydrogenation catalyst of the invention, use the sphericity mesoporous silicon dioxide as carrier, load
There are Pt component, Sn component and Na component, so that the loaded catalyst had both had the advantages that loaded catalyst such as catalytic activity
It is high, side reaction is few, post-processing is simple etc., and with stronger catalytic activity, so that the loaded catalyst takes off for propane
There is better dehydrogenation activity and selectivity in hydrogen reaction, significantly improve the conversion ratio of reaction raw materials, specifically, use the load
Type catalyst carries out in the reaction of preparing propylene by dehydrogenating propane, and conversion of propane is up to 40%, 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
Fig. 1 is X-ray diffraction (XRD) spectrogram of the sphericity mesoporous silicon dioxide of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the sphericity mesoporous silicon dioxide 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 carrier is sphericity mesoporous silicon dioxide, described spherical mesoporous
Silica has body-centred cubic structure, and the compression strength of the sphericity mesoporous silicon dioxide is 12-16MPa, and average grain diameter is
2-10 μm, specific surface area 700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.
According to the present invention, the carrier combines the advantages of spherical geometry and special body-centred cubic structure,
Mesopore orbit structure distribution is uniform, proper pore size, Kong Rong great, mechanical strength are good, has good structural stability, favorably
In fine dispersion of the metal component inside its duct.Use the sphericity mesoporous silicon dioxide as carrier, supporting Pt component,
The loaded catalyst that Sn component and Na component obtain both had had the advantages that loaded catalyst such as catalytic activity height, side reaction
Less, post-processing is simple etc., and has stronger catalytic activity and higher stability, so that the loaded catalyst is being used for third
There is better dehydrogenation activity and selectivity in alkane dehydrogenation reaction, significantly improve the conversion ratio of reaction raw materials.
According to the present invention, the average grain diameter of the particle of the carrier is measured using laser fineness gage, specific surface area, hole
Volume and most probable pore size are measured according to nitrogen adsorption methods.
According to the present invention, by by the structural parameter control of the sphericity mesoporous silicon dioxide within above range, can
To ensure that the sphericity mesoporous silicon dioxide is not susceptible to reunite, and being used as loaded catalyst made of carrier can be with
Improve the reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.When the specific surface area of the sphericity mesoporous silicon dioxide
Less than 700m2When/g and/or pore volume are less than 0.5mL/g, it is used as the catalytic activity of loaded catalyst made of carrier
It can significantly reduce；When the specific surface area of the sphericity mesoporous silicon dioxide is greater than 900m2When/g and/or pore volume are greater than 1mL/g,
It is used as loaded catalyst made of carrier and is easy to happen reunion in preparing propylene by dehydrogenating propane reaction process, to influence
Reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.
Under preferable case, the compression strength of the carrier is 14-16MPa, and average grain diameter is 3-9 μm, and specific surface area is
750-850m2/ g, pore volume 0.6-0.8mL/g, most probable pore size 1.5-4.5nm；
It is highly preferred that the mesoporous silicon oxide is SBA-16.
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 compression strength of the propane dehydrogenation catalyst is 14-16MPa, and average grain diameter is 3-9 μm, specific surface
Product is 730-830m2/ g, pore volume 0.5-0.7mL/g, most probable pore size 1.5-4.5nm.
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 sphericity mesoporous silicon dioxide, the sphericity mesoporous silicon dioxide tool
There is body-centred cubic structure, the compression strength of the sphericity mesoporous silicon dioxide is 12-16MPa, and average grain diameter is 2-10 μm, compares table
Area is 700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.
According to the present invention, the sphericity mesoporous silicon dioxide carried metal component can be by the way of dipping, by institute
State the hole that the capillary pressure of the cellular structure of sphericity mesoporous silicon dioxide makes metal component enter the sphericity mesoporous silicon dioxide
In road, while metal component can also be in the adsorption of the sphericity mesoporous silicon dioxide, until metal component is in the spherical shape
The surface of mesoporous silicon oxide reaches adsorption equilibrium.The impregnation can be handled for co-impregnation, or step impregnation
Processing.In order to save preparation cost, simplify experimental technique, the impregnation is preferably co-impregnation processing；It is further preferred that
The condition of the co-impregnation processing includes: that spherical shape mesopore molecular sieve containing the aluminium material silica gel composite after thermal activation is being contained Pt group
The solution of presoma, Sn component presoma and Na component presoma is divided to be mixed, the temperature of the dipping can be 25-
50 DEG C, 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) in the presence of template, silicon source is contacted with sour agent, and by the mixture obtained after contact successively into
Row crystallization and filtering, obtain mesoporous material raw powder；
(b) mesoporous material raw powder is subjected to Template removal processing, obtains sphericity mesoporous silicon dioxide.
In the forming process of above-mentioned carrier, the control of main dosage and contact conditions by controlling each reaction raw materials,
The common raw material being easy to get can be used, synthesize that specific surface area is larger, pore volume is larger in next step in easy operating condition
Sphericity mesoporous silicon dioxide.
According to the present invention, in order to enable the mesoporous silicon oxide arrived has spherical shape characteristic and body-centred cubic structure special
Sign, the template is preferably triblock copolymer polyoxyethylene ether-polyethenoxy ether-polyoxyethylene ether F127, the template
Agent can be commercially available (for example, can be purchased from Aldrich, trade name F127, molecular formula EO106PO70EO106,
Average molecular mass Mn is that 12600), can also be prepared by existing various methods.When the template is polyoxyethylene
When ether-polyethenoxy ether-polyoxyethylene ether, the molal quantity of the template is according to polyoxyethylene ether-polyethenoxy ether-polyoxy second
The average molecular weight of alkene ether calculates to obtain.
According to the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, for example, can be salt
At least one of acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution, preferably aqueous hydrochloric acid solution.
There is no particular limitation for the dosage of the acid agent, can change in a big way, it is preferable that the mixing connects
The pH value of touching is 1-6.
Under preferable case, in step (a), the condition of the contact include: temperature be 10-60 DEG C, the time be 25min with
On, pH 1-6.In order to be more advantageous to the uniform mixing between each substance, a kind of preferred embodiment, described mixed according to the present invention
Splice grafting touching carries out under agitation.
In the present invention, the dosage of the template and the silicon source can change in a big way, such as the mould
The molar ratio of plate agent and the silicon source dosage can be 1:200-300；Preferably 1:225-275.
In the present invention, the silicon source can be various silicon sources commonly used in the art, and the preferably described silicon source is positive silicon
At least one of acetoacetic ester, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution, more preferably ethyl orthosilicate.
According to the present invention, it is 30-150 DEG C that the condition of the crystallization, which may include: temperature, and the time is that 10-72h is, preferably
Ground, the condition of the crystallization include: that temperature is 50-120 DEG C, time 10-40h.It is described according to a kind of preferred embodiment
Crystallization is implemented by hydrothermal crystallization method.
It according to the present invention, may include: after filtration, with distillation with the process for obtaining mesoporous material raw powder by filtering
Water washs (washing times can be 2-10) repeatedly, is then filtered.
According to the present invention, in step (b), the method for Template removal processing is that alcohol washes method, at the Template removal
The process of reason includes: to wash the mesoporous material raw powder with alcohol, wash time 10-40h at 90-120 DEG C.
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 ether-polyethenoxy ether-polyoxyethylene ether F127 is purchased from
Aldrich is abbreviated as F127, molecular formula EO106PO70EO106, average molecular mass Mn 12600.
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；The particle diameter distribution of sample is in Malvern laser grain
It is carried out on degree instrument；Rotary Evaporators are the production of IKA company, Germany, model RV10digital；The activity of propane dehydrogenation catalyst
Component load capacity is on the wavelength dispersion X-ray fluorescence spectrometer for being Axios-Advanced purchased from Dutch Panaco company model
Measurement；The analysis of reaction product ingredient carries out on the gas chromatograph purchased from agilent company model 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
2g template F127 is added in the solution of the hydrochloric acid (2.9g) containing 37 weight % and water (56g), at 40 DEG C
It stirs to F127 and is completely dissolved；8.2g (0.04mol) ethyl orthosilicate is added in above-mentioned solution again later, is stirred at 40 DEG C
Mix 45min, then obtained solution be transferred in the reaction kettle of polytetrafluoroethyllining lining, at 100 DEG C crystallization for 24 hours, then
Be filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；It will be described mesoporous
Material original powder is washed for 24 hours under reflux conditions with ethyl alcohol, and removed template method obtains sphericity mesoporous silicon dioxide C1.
(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, above-mentioned sphericity mesoporous silicon dioxide C1 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 sphericity mesoporous silicon dioxide C1 and third
Alkane dehydrogenation Cat-1 is characterized；
Fig. 1 is X-ray diffraction (XRD) spectrogram of the sphericity mesoporous silicon dioxide C1, wherein abscissa is 2 θ, indulges and sits
It is designated as intensity, the low-angle spectral peak occurred from XRD spectra is it is found that the sphericity mesoporous silicon dioxide C1 is mesoporous material SBA-
Body-centred cubic cellular structure specific to 16；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the sphericity mesoporous silicon dioxide C1, as seen from the figure, described spherical mesoporous
The microscopic appearance of silica C1 is the microballoon that partial size is 3-9 μm, and monodispersity is preferable.
Table 1 is the pore structure parameter of sphericity mesoporous silicon dioxide C1 and propane dehydrogenation catalyst Cat-1.
Table 1
It can be seen from the data of table 1 as the sphericity mesoporous silicon dioxide C1 of carrier load chief active Pt component,
After auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is during load-reaction
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of sphericity mesoporous silicon dioxide 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 sphericity mesoporous silicon dioxide C1 with body-centred cubic structure is substituted using commercially available ES955 silica gel (GRACE company) to make
For 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 sphericity mesoporous silicon dioxide C1 of core structure is as carrier D2, so that carrier D2 and propane dehydrogenation catalyst Cat-D- be made respectively
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 sphericity mesoporous silicon dioxide as carrier by co-impregnation, thus
Propane dehydrogenation catalyst Cat-D-3 is made, on the basis of the total weight of propane dehydrogenation catalyst Cat-D-3, Pt component is with Pt member
It is 1 weight % that the content of element meter, which is content of 0.5 weight %, the Sn component in terms of Sn element, remaining is carrier).
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
2g template F127 is added in the solution of the hydrochloric acid (2.9g) containing 37 weight % and water (56g), at 40 DEG C
It stirs to F127 and is completely dissolved；9.09g (0.044mol) ethyl orthosilicate is added in above-mentioned solution again later, at 60 DEG C
20h is stirred, then obtained solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, the crystallization 20h at 120 DEG C, then
Be filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；It will be described mesoporous
Material original powder is washed for 24 hours under reflux conditions with ethyl alcohol, and removed template method obtains sphericity mesoporous silicon dioxide 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, above-mentioned sphericity mesoporous silicon dioxide C2 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 sphericity mesoporous silicon dioxide C2 and propane dehydrogenation catalyst Cat-2.
Table 2
It can be seen from the data of table 2 as the sphericity mesoporous silicon dioxide C2 of carrier load chief active Pt component,
After auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is during load-reaction
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of sphericity mesoporous silicon dioxide C2.
Embodiment 3
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
2g template F127 is added in the solution of the hydrochloric acid (2.9g) containing 37 weight % and water (56g), at 40 DEG C
It stirs to F127 and is completely dissolved；7.44g (0.036mol) ethyl orthosilicate is added in above-mentioned solution again later, at 50 DEG C
Stirring for 24 hours, then obtained solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, the crystallization 36h at 90 DEG C, then into
Row filtering and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；By the mesoporous material
Material original powder is washed for 24 hours under reflux conditions with ethyl alcohol, and removed template method obtains sphericity mesoporous silicon dioxide 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, above-mentioned sphericity mesoporous silicon dioxide C3 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 sphericity mesoporous silicon dioxide C3 and propane dehydrogenation catalyst Cat-3.
Table 3
It can be seen from the data of table 3 as the sphericity mesoporous silicon dioxide C3 of carrier load chief active Pt component,
After auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is during load-reaction
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of sphericity mesoporous silicon dioxide 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 | 40% | 87% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 39.5% | 86.7% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 38.7% | 86.6% |
| Experimental comparison's example 1 | Cat-D-1 | 19.4% | 21.2% |
| Experimental comparison's example 2 | Cat-D-2 | 20.5% | 25.7% |
| Experimental comparison's example 3 | Cat-D-3 | 18.5% | 38.7% |
From table 4, it can be seen that using propane dehydrogenation catalyst prepared by sphericity mesoporous silicon dioxide of the invention have compared with
High compression strength, when for preparing propylene by dehydrogenating propane reaction, after reacting 50h, still available higher conversion of propane
And Propylene Selectivity, illustrating propane dehydrogenation catalyst of the invention 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 be sphericity mesoporous silicon dioxide, described spherical mesoporous two
Silica has body-centred cubic structure, and the compression strength of the sphericity mesoporous silicon dioxide is 12-16MPa, average grain diameter 2-
10 μm, specific surface area 700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.
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 compression strength of the carrier is 14-16MPa, and average grain diameter is 3-9 μm, specific surface area 750-850m2/ g,
Pore volume is 0.6-0.8mL/g, most probable pore size 1.5-4.5nm；
It is highly preferred that the mesoporous silicon oxide is SBA-16.
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 sphericity mesoporous silicon dioxide, and the sphericity mesoporous silicon dioxide has cube
Body-centred structure, the compression strength of the sphericity mesoporous silicon dioxide are 12-16MPa, and average grain diameter is 2-10 μm, and specific surface area is
700-900m2/ g, pore volume 0.5-1mL/g, most probable pore size 1-5nm.
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 compression strength of the carrier is 14-16MPa, and average grain diameter is 3-9 μm, specific surface area 750-850m2/ g,
Pore volume is 0.6-0.8mL/g, most probable pore size 1.5-4.5nm；
It is highly preferred that the mesoporous silicon oxide is SBA-16.
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) in the presence of template, silicon source is contacted with sour agent, and the mixture obtained after contact is successively subjected to crystalline substance
Change and filter, obtains mesoporous material raw powder；
(b) mesoporous material raw powder is subjected to Template removal processing, obtains sphericity mesoporous silicon dioxide.
7. according to the method described in claim 6, wherein, in step (a), the condition of the contact includes: that temperature is 10-60
DEG C, the time is 25min or more, pH 1-6；The condition of the crystallization includes: that temperature is 30-150 DEG C, time 10-72h；
In step (b), the process of the Template removal processing includes: to use the mesoporous material raw powder at 90-120 DEG C
Alcohol is washed, wash time 10-40h.
8. according to the method described in claim 6, wherein, the template is triblock copolymer polyoxyethylene ether-polyoxy third
Alkene ether-polyoxyethylene ether, the acid agent are at least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably hydrochloric acid, described
Silicon source is at least one of ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution, is preferably positive
Silester；
Preferably, the molar ratio of the template and the silicon source dosage is 1:200-300.
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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