CN109746031A - 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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- CN109746031A CN109746031A CN201711069002.6A CN201711069002A CN109746031A CN 109746031 A CN109746031 A CN 109746031A CN 201711069002 A CN201711069002 A CN 201711069002A CN 109746031 A CN109746031 A CN 109746031A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 the spherical material silica gel composite of mesopore molecular sieve containing aluminium, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contains aluminium component, meso-porous molecular sieve material and silica gel with hexagonal hole road structure, the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average grain diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture is distributed in four peaks, and corresponding first most probable pore size in four peak, the second most probable pore size, third most probable pore size and the 4th most probable pore size are respectively 1-1.8nm, 2-2.8nm, 3-5nm and 20-40nm.The propane dehydrogenation catalyst shows good catalytic performance when reacting for preparing propylene by dehydrogenating propane.
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 spherical containing aluminium
Mesopore molecular sieve material silica gel composite, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, have six sides
The compression strength of the meso-porous molecular sieve material and silica gel of cellular structure, spherical shape mesopore molecular sieve containing the aluminium material silica gel composite is
12-16MPa, average grain diameter are 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture are in four
Peak distribution, and corresponding first most probable pore size in four peak, the second most probable pore size, third most probable pore size and the 4th most may be used
Several apertures are respectively 1-1.8nm, 2-2.8nm, 3-5nm and 20-40nm.
Second aspect of the present invention provides a kind of method for preparing above-mentioned propane dehydrogenation catalyst, this method comprises: by carrier
It is carried out at dipping in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma after thermal activation
Then reason is successively removed solvent processing, dry and roasting, wherein the carrier is the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, with the mesoporous of hexagonal hole road structure
The compression strength of molecular screen material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average
Partial size is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture are distributed in four peaks, and described
Corresponding first most probable pore size in four peaks, the second most probable pore size, third most probable pore size and the 4th most probable pore size are respectively
1-1.8nm, 2-2.8nm, 3-5nm and 20-40nm.
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 the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
Combine mesopore molecular sieve with hexagonal hole road distributed architecture, the regular mesoporous spatial character of silica gel and spherical shape
Pattern advantage not only remains the high-specific surface area of ordered mesoporous material, the characteristics of macropore holds, and it is big and be distributed to also add aperture
Narrow advantage, and unique four peaks distribution is presented in its pore-size distribution, is dexterously distributed micro-sphere structure and aperture with four peaks
Ordered mesoporous material the advantages of combine, the more conducively load of active component.In addition, introducing of the aluminium component in mechanical milling process
So that the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium increases, sphere can be effectively prevent to live in load
Property group timesharing it is broken, improve the stability of the carrier, extend the service life of catalyst.The propane dehydrogenation catalyst
Carrier has spherical porous material, has the characteristics that nontoxic, odorless, not dusting, not soluble in water and ethyl alcohol, also has unique
Skeleton structure, so the affinity with active component is extremely strong, the mesopore orbit structure distribution of the composite material uniformly, pore size
Be suitable for, Kong Rong great, mechanical strength it is good, have good structural stability, therefore, it is described spherical shape the silica gel of mesopore molecular sieve containing aluminium answer
Condensation material is suitable as the carrier of loaded catalyst, be especially suitable for load used in reacting in preparing propylene by dehydrogenating propane
The carrier of type catalyst.
In the propane dehydrogenation catalyst of the invention, the spherical material silica gel composite of mesopore molecular sieve containing aluminium is used
As carrier, load has Pt component, Sn component and Na component, so that the loaded catalyst had both had the excellent of loaded catalyst
Point such as catalytic activity is high, side reaction is few, post-processing is simple, and has stronger catalytic activity, so that the loaded catalyst
There is better dehydrogenation activity and selectivity in for dehydrogenating propane reaction, significantly improve the conversion ratio of reaction raw materials, specifically
Ground, in the reaction that preparing propylene by dehydrogenating propane is carried out using the loaded catalyst, conversion of propane is up to 27%, the selection of propylene
Property is up to 82%.
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.
Also, when the method by spray drying prepares the propane dehydrogenation catalyst, the propane dehydrogenation catalyst
It may be repeated utilization, and still can obtain higher reaction raw materials conversion ratio during recycling.
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 spherical material silica gel composite of mesopore molecular sieve containing aluminium of embodiment 1；
Fig. 2 is the SEM scanning electron microscope of the microscopic appearance of the spherical material silica gel composite of mesopore molecular sieve containing aluminium of embodiment 1
Figure；
Fig. 3 is the pore size distribution curve figure of the spherical material silica gel composite of mesopore molecular sieve containing aluminium 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 the spherical silica gel composite wood of mesopore molecular sieve containing aluminium
Material, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, the mesopore molecular sieve with hexagonal hole road structure
The compression strength of material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, and average grain diameter is
10-80 μm, specific surface area 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture is distributed in four peaks, and four peak pair
The first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most probable pore size answered are respectively 1-
1.8nm, 2-2.8nm, 3-5nm and 20-40nm.
According to the present invention, the carrier has special hexagonal hole road distributed architecture, and this unique skeleton structure is broken
Limitations of the one-dimensional channels for molecular transport, the carrier have spherical porous material, and mesopore orbit structure distribution is equal
Even, proper pore size, Kong Rong great, mechanical strength are good, have good structural stability, orderly in conjunction with special hexagonal hole road
The cellular structure of mesopore orbit distributed architecture and silica gel is conducive to fine dispersion of the metal component inside its duct.In addition, institute
The aluminium component that the spherical material silica gel composite of mesopore molecular sieve containing aluminium contains is stated, so that the spherical shape silica gel of mesopore molecular sieve containing aluminium is multiple
The compression strength of condensation material significantly increases, and sphere can be effectively prevent broken in load active component, improve the carrier
Stability.Use the spherical material silica gel composite of mesopore molecular sieve containing aluminium as carrier, supporting Pt component, Sn component and Na
The loaded catalyst that component obtains both had had the advantages that loaded catalyst such as catalytic activity was high, side reaction is few, post-processing is simple
It is single etc., and there is stronger catalytic activity and higher stability, so that the loaded catalyst is reacted for dehydrogenating propane
In have better dehydrogenation activity and selectivity, 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 spherical material silica gel composite of mesopore molecular sieve containing aluminium upper
Within the scope of stating, it can be ensured that the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is not susceptible to reunite, and is used
Making loaded catalyst made of carrier can be improved reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.Work as institute
The specific surface area for stating the spherical material silica gel composite of mesopore molecular sieve containing aluminium is less than 100m2/ g and/or pore volume are less than 0.4mL/g
When, the catalytic activity for being used as loaded catalyst made of carrier can significantly reduce；When the spherical mesoporous molecular containing aluminium
The specific surface area for sieving material silica gel composite is greater than 180m2When/g and/or pore volume are greater than 1.5mL/g, it is used as carrier and is made
Loaded catalyst reunion is easy to happen in preparing propylene by dehydrogenating propane reaction process, so that it is anti-to influence preparing propylene by dehydrogenating propane
Reaction raw materials conversion ratio during answering.
Under preferable case, the compression strength of the carrier is 14-16MPa, and average grain diameter is 20-70 μm, and specific surface area is
110-140m2/ g, pore volume 0.4-1mL/g, and the first most probable pore size, the second most probable pore size, third most probable pore size
It is respectively 1.2-1.6nm, 2.2-2.8nm, 3-4nm and 25-35nm with the 4th most probable pore size.
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 20-70 μm, compares table
Area is 90-120m2/ g, pore volume 0.3-0.9mL/g, and the first most probable pore size, the second most probable pore size, third most may be used
Several apertures and the 4th most probable pore size are respectively 1.2-1.6nm, 2.2-2.8nm, 3-4nm and 25-35nm.
According to the present invention, the increase of aluminium constituent content is conducive to improve the compression strength of the carrier, the mesoporous molecular
The cellular structure of the adjustable carrier of content of material and silica gel is sieved, in order to make the carrier have both higher compression strength
Preferably cellular structure parameter, in the spherical material silica gel composite of mesopore molecular sieve containing aluminium, relative to 100 parts by weight
The meso-porous molecular sieve material with hexagonal hole road structure, the content of the aluminium component are 1-20 parts by weight, preferably 5-19
Parts by weight, the content of the silica gel are 1-90 parts by weight, preferably 2-85 parts by weight.
The present invention also provides a kind of methods for preparing propane dehydrogenation catalyst, this method comprises: by after carrier thermal activation
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 the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
The compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, and average grain diameter is 10-80 μm, compares table
Area is 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture is distributed in four peaks, and four peak corresponding first most may be used
Several apertures, the second most probable pore size, third most probable pore size and the 4th most probable pore size are respectively 1-1.8nm, 2-2.8nm, 3-
5nm and 20-40nm.
According to the present invention, in order to remove the hydroxyl and remaining water of the spherical material silica gel composite of mesopore molecular sieve containing aluminium
Point, firstly the need of progress thermal activation treatment before the spherical material silica gel composite carried metal component of mesopore molecular sieve containing aluminium,
The condition of the thermal activation treatment may include: in the presence of nitrogen, to calcine at being 300-900 DEG C in temperature by carrier
7-10h。
According to the present invention, the spherical material silica gel composite carried metal of mesopore molecular sieve containing the aluminium component can be using dipping
Mode, by the capillary pressure of the cellular structure of the spherical material silica gel composite of mesopore molecular sieve containing aluminium make metal component into
In the duct for entering the spherical material silica gel composite of mesopore molecular sieve containing aluminium, while metal component can also be described spherical containing aluminium Jie
The adsorption of porous molecular sieve material silica gel composite, until metal component is in the spherical silica gel composite wood of mesopore molecular sieve containing aluminium
The surface of material reaches adsorption equilibrium.Preferably, the impregnation is in the spherical material silica gel composite of mesopore molecular sieve containing aluminium
Carry out after thermal activation treatment, the impregnation can be handled for co-impregnation, or step impregnation processing.In order to
Preparation cost is saved, experimental technique is simplified, the impregnation is preferably co-impregnation processing；It is further preferred that the total immersion
The condition of stain processing includes: that spherical shape mesopore molecular sieve containing the aluminium material silica gel composite after thermal activation is being contained Pt component forerunner
The solution of body, Sn component presoma and Na component presoma is mixed, and 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, the drying can carry out in drying box, and the roasting can carry out in Muffle furnace.This hair
Also there is no particular limitation for the bright condition to the drying and roasting, can be the conventional selection of this field, for example, the drying
Condition may include: temperature be 110-150 DEG C, 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 the first template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane and sour agent are carried out first
Contact, and the mixture obtained after contact is successively subjected to the first crystallization and filtering, obtain No. 1 mesopore molecular sieve filter cake；?
In the presence of two templates, silicon source and ammonia spirit are subjected to the second contact, and the mixture obtained after contact is subjected to the second crystalline substance
Change and filter, obtains No. 2 mesopore molecular sieve filter cakes；
(b) waterglass is contacted with inorganic acid and n-butanol, and the mixture obtained after contact is filtered, obtained
To silica gel filter cake；
(c) No. 1 mesopore molecular sieve filter cake, No. 2 mesopore molecular sieve filter cakes and silica gel filter cake are mixed and is made pottery in high alumina
Ball milling, and the solid powder water slurrying that will be obtained after ball milling are carried out in porcelain jar, are then spray-dried obtained slurry,
Again by the template removal in obtained product.
In the forming process of above-mentioned carrier, No. 1 mesopore molecular sieve filter cake is with hexagonal hole road distributed architecture
Mesopore molecular sieve filter cake, No. 2 mesopore molecular sieve filter cakes are the mesopore molecular sieve filter cake with hexagonal hole road distributed architecture.
It is main to pass through control No. 1 mesopore molecular sieve filter cake, No. 2 mesoporous molecular sievings in the forming process of above-mentioned carrier
The pore-size distribution control of the carrier is that four peaks are distributed by the composition of cake and silica gel filter cake, makes the spherical mesopore molecular sieve containing aluminium
Material silica gel composite has porous distributed architecture, and by control forming method, first by No. 1 mesopore molecular sieve filter cake, No. 2 Jie
Porous molecular sieve filter cake and silica gel filter cake mix and carry out ball milling in high alumina ceramic tank, the solid powder water system that then will be obtained
It is spray-dried after slurry, the microscopic appearance control of the spherical material silica gel composite of mesopore molecular sieve containing aluminium for spherical shape and is made described
The spherical material silica gel composite of mesopore molecular sieve containing aluminium introduces aluminium component.
According to the present invention, in step (a), the process for preparing No. 1 mesopore molecular sieve filter cake may include: by first
Template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane carry out the first contact, and obtained mixture is carried out the first crystallization
And filtering.There is no particular limitation for the sequence of first contact, can be by the first template, ethyl alcohol, trimethylpentane and four
Methoxy silane is mixed simultaneously, any two or three can also be mixed, and is added other components and is uniformly mixed.According to
First template, ethyl alcohol, sour agent and trimethylpentane are first uniformly mixed, then add four by a kind of preferred embodiment
Methoxy silane.The mode of first contact is first to be uniformly mixed first template, ethyl alcohol and sour agent, and will obtain
Mixture be placed in 10-60 DEG C of water-bath, then keep temperature-resistant, then trimethylpentane is slowly dropped to above-mentioned mixing
In object, and it is stirred to react 5-20h, then keeps temperature-resistant, then tetramethoxy-silicane is slowly dropped in said mixture,
And it is stirred to react 20-40h.On the basis of the first template of 1g, the drop rate of the trimethylpentane can be 0.1-1g/
Min, the drop rate of the tetramethoxy-silicane can be 0.1-1g/min.
According to the present invention, during preparing No. 1 mesopore molecular sieve filter cake, the dosage of each substance can be in wider model
It encloses and interior selected and adjusted.For example, the dosage of first template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane
Molar ratio is 1:100-500:200-500:50-200, preferably 1:200-400:250-400:70-150.
According to the present invention, in order to enable there is No. 1 mesoporous sieving cake arrived the hexagonal hole road of aperture size above-mentioned to be distributed
Structure, first template are preferably triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 and F127, on
Stating the first template can be commercially available (for example, can be purchased from Aldrich, trade name P123 and F127, molecule
Formula is respectively EO20PO70EO20, average molecular mass Mn is 5800 and EO106PO70EO106, average molecular mass Mn 12600), it can also
To be prepared by existing various methods.When first template is polyoxyethylene-poly-oxypropylene polyoxyethylene,
The molal quantity of the template calculates to obtain according to the average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.Further
Ground, in the preferred case, when first template is P123 and F127, the weight ratio of the P123 and F127 can be 1:
0.5-2, preferably 1:1.
According to the present invention, the sour agent can be used for adjusting for various routines pH value substance or mixture it is (such as molten
Liquid).The acid agent preferably uses in form of an aqueous solutions, and pH value can be 1-6, preferably 3-5.It is highly preferred that the acid
Agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6 (more preferable 3-5).
According to the present invention, it is 10-60 that the condition that tetramethoxy-silicane is contacted with sour agent progress first, which may include: temperature,
DEG C, time 10-72h, pH value 1-7.In order to be more advantageous to the uniform mixing between each substance, the tetramethoxy-silicane and acid
First contact of agent preferably carries out under agitation.The dosage of the acid agent preferably so that tetramethoxy-silicane and sour agent the
The pH value of one haptoreaction system is 1-7.
According to the present invention, it is 30-150 DEG C that the condition of first crystallization, which may include: temperature, time 10-72h.It is excellent
In the case of choosing, the condition of first crystallization includes: that temperature is 40-100 DEG C, time 20-40h.First crystallization can be with
Implemented by hydrothermal crystallization method.
According to the present invention, in step (a), the process for preparing No. 2 mesopore molecular sieve filter cakes may include: by second
Template, silicon source and ammonia spirit carry out the second contact, and the mixture obtained after contact is carried out the second crystallization and filtering.Institute
Stating the sequence of the second contact, there is no particular limitation, the second template, silicon source and ammonia spirit can be mixed simultaneously,
Any two kinds can be mixed, add other components and be uniformly mixed.According to a kind of preferred embodiment, by the second template
It is added in ammonia spirit and is uniformly mixed together with silicon source.The mode of second contact is first by second template and silicon
Source is added in ammonia spirit together and is uniformly mixed, and obtained mixture is placed in 25-100 DEG C of stirred in water bath to molten
Solution, then keeps temperature-resistant, and be stirred to react 20-40h.
According to the present invention, during preparing No. 2 mesopore molecular sieve filter cakes, the dosage of each substance can be in wider model
It encloses and interior selected and adjusted.For example, the silicon source, the second template, the ammonia in ammonium hydroxide and water dosage molar ratio be 1:
0.1-1:0.1-5:100-200, preferably 1:0.2-0.5:1.5-3.5:120-180.
According to the present invention, in order to enable there is No. 2 mesoporous sieving cakes arrived the hexagonal hole road of aperture size above-mentioned to be distributed
Structure, second template is preferably cetyl trimethylammonium bromide, and the silicon source can be commonly used in the art
Various silicon sources, the preferably described silicon source are in ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution
At least one, more preferably ethyl orthosilicate.
According to the present invention, it is 25-100 DEG C that the condition of the second contact of silicon source and ammonia spirit progress, which may include: temperature, when
Between be 10-72h.In order to be more advantageous to the uniform mixing between each substance, the second contact of the silicon source, the second template and ammonium hydroxide
It is preferred that carrying out under agitation.
According to the present invention, it is 30-150 DEG C that the condition of second crystallization, which may include: temperature, time 10-72h.It is excellent
In the case of choosing, the condition of second crystallization includes: that temperature is 40-100 DEG C, time 20-40h.Second crystallization can be with
Implemented by hydrothermal crystallization method.
The condition that the present invention contacts the waterglass, inorganic acid and n-butanol is not particularly limited, for example, in step
(b) in, the condition of the waterglass, inorganic acid and n-butanol contact is generally included: temperature can be 10-60 DEG C, preferably 20-
40℃；Time can be 1-5h, preferably 1.5-3h, pH value 2-4.In order to increase preparation silica gel aperture size, preferably
Ground, waterglass, inorganic acid and n-butanol the weight ratio of dosage can be 3-6:1:1.It is equal between each substance in order to be more advantageous to
Even mixing, the waterglass, inorganic acid and n-butanol contact preferably carry out under agitation.
According to the present invention, the waterglass is the aqueous solution of the sodium metasilicate of this field routine, and concentration can be 10-50 weight
Measure %, preferably 12-30 weight %.
According to the present invention, the type of the inorganic acid can be the conventional selection of this field, for example, can be sulfuric acid, nitre
One of acid and hydrochloric acid are a variety of.The inorganic acid can use in pure form, can also be in the form of its aqueous solution
It uses.The dosage of the inorganic acid is preferably so that the pH value of the contact conditions reaction system of waterglass and inorganic acid is 2-4.
In addition, during No. 1 mesopore molecular sieve filter cake of above-mentioned preparation, No. 2 mesopore molecular sieve filter cakes and silica gel filter cake,
It with the process for obtaining filter cake may include: after filtration by filtering, wash that (washing times can be 2- repeatedly with distilled water
10) it, is then filtered.Preferably, washing during No. 1 mesopore molecular sieve filter cake and No. 2 mesopore molecular sieve filter cakes is prepared
It washs so that filter cake pH is 7, prepares the washing during silica gel filter cake so that sodium ions content is lower than 0.02 weight %.
According to the present invention, in step (c), No. 1 mesopore molecular sieve filter cake, No. 2 mesopore molecular sieve filter cakes and silica gel
The dosage of filter cake can be selected according to the component of the expected obtained spherical material silica gel composite of mesopore molecular sieve containing aluminium, preferably
In the case of, total dosage of No. 1 mesopore molecular sieve filter cake and No. 2 mesopore molecular sieve filter cakes relative to 100 parts by weight is described
The dosage of silica gel filter cake is 1-90 parts by weight, preferably 2-85 parts by weight；No. 1 mesopore molecular sieve filter cake and No. 2 mesoporous point
The weight ratio of the dosage of sub- sieving cake is 1:0.5-2, preferably 1:0.6-1.5.
According to the present invention, before in order to make to contain in the final spherical material silica gel composite of mesopore molecular sieve containing aluminium obtained
The aluminium component of content is stated, to improve its mechanical strength, and not destroy or not destroy carrier structure substantially and silica gel is made to enter load
Subject in body opening road, powder segregation after ball milling is prevented, in step (c), the concrete operation method and condition of the ball milling are preferred
It is carried out in high alumina ceramic ball grinder, wherein the diameter of abrading-ball can be 2-3mm in high alumina ceramic ball grinder；The quantity of abrading-ball
It can reasonably be selected according to the size of high alumina ceramic ball grinder, the high alumina ceramic ball milling for being 50-150mL for size
1 abrading-ball usually can be used in tank；The material of the abrading-ball is high alumina ceramic ball.The condition of the high alumina ceramic ball milling includes:
The revolving speed of abrading-ball can be 300-500r/min, and the temperature in high alumina ceramic ball grinder can be 15-100 DEG C, high alumina ceramic ball
The time of mill can be 0.1-100h.
In the present invention, the solid powder obtained after ball milling can be carried out with the process of water slurrying in 25-60 DEG C lower.
In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.5-5, preferably 1:1-2.
In the present invention, the concrete operation method and condition of the spray drying are the conventional selection of this field.Specifically, will
High speed rotation is added in atomizer by the slurry that the solid powder and water are made into realize spray drying.Wherein, the spray
The dry condition of mist includes: that temperature can be 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；It is preferred that feelings
Under condition, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min；It is optimal
In the case of choosing, the condition of the spray drying includes: that temperature is 200 DEG C, and the revolving speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is usually calcination method.The condition of the removed template method can be this
Field conventional selection, for example, the condition of the removed template method, which includes: temperature, to be 300-600 DEG C, preferably 350-550
DEG C, most preferably 500 DEG C；Time can be 10-80h, preferably 20-30h, most preferably for 24 hours.
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；Polyoxyethylene-poly-oxypropylene polyoxyethylene
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；Aluminium content result is by XPS Analysis instrument
It measures；The particle diameter distribution of sample carries out on Malvern laser particle analyzer；Rotary Evaporators are the production of IKA company, Germany, model
For RV10digital；The activity component load quantity of propane dehydrogenation catalyst is being Axios- purchased from Dutch Panaco company model
It is measured on the wavelength dispersion X-ray fluorescence spectrometer of Advanced；The analysis of reaction product ingredient is being purchased from agilent company type
Number for 7890A gas chromatograph on carry out.
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
0.5g triblock copolymer P123 and 0.5g triblock copolymer F127 and 1.69g (0.037mol) ethyl alcohol are added
To 28ml acetic acid and sodium acetate buffer solution (pH=4.4) in, stirring is poly- to polyethylene glycol glycerine-at 15 DEG C
Ethylene glycol is completely dissolved, and the trimethylpentane of 6g (0.053mol) is added in above-mentioned solution later, after 15 DEG C of stirring 8h, then
2.13g (0.014mol) tetramethoxy-silicane is added in above-mentioned solution, after 15 DEG C of stirring 20h, transfers the solution into poly- four
In the reaction kettle of vinyl fluoride liner, baking oven crystallization is for 24 hours afterwards by filtering at 60 DEG C, and is washed with deionized 4 times to pH and is
7, obtain No. 1 mesopore molecular sieve filter cake X1 with hexagonal hole road structure；
Cetyl trimethylammonium bromide and ethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %,
In, the additional amount of ethyl orthosilicate is 1g, by molar feed ratio, ethyl orthosilicate: cetyl trimethylammonium bromide: ammonium hydroxide
(25%): deionized water=1:0.37:2.8:142, solution is filtered to dissolving and obtains mesoporous material by stirring at a temperature of 80 DEG C
Expect filter cake, it is 7 that solution, which is filtered, and is washed with deionized 4 times to pH, obtains No. 2 mesoporous moleculars with hexagonal hole road structure
Sieving cake Y1；
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, and press water glass
Glass: sulfuric acid: n-butanol weight ratio=5:1:1 progress sufficiently reacts 1.5h at 30 DEG C, the sulfuric acid tune for being 98 weight % with concentration
Whole pH is 3, and is 0.02 weight % by filtering, distilling water washing to be washed till sodium ions content by reaction mass, obtains silica gel filter
Cake B1.
10g filter cake X1,10g filter cake Y1 and 10g filter cake B1 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
Ball grinder material is high alumina ceramic, and Material quality of grinding balls is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is ball milling 1h at 60 DEG C in ball grinder, obtains 30g solid powder；The solid powder is dissolved
In 30g deionized water, it is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；The product that will be obtained after spray drying
For 24 hours, removed template method obtains the target product spherical shape mesoporous molecular containing aluminium of 30g removed template method for 500 DEG C of calcinings in Muffle furnace
Sieve material silica gel composite C1.According to XPS Analysis as a result, the content of aluminium is 7 weight % in C1.
(2) preparation of propane dehydrogenation catalyst
30g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C1 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1 hydroxyl and
Residual water；
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 above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-1, (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material C1 and propane dehydrogenation catalyst Cat-1 are characterized；
Fig. 1 is X-ray diffraction (XRD) spectrogram of the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1, wherein
Abscissa is 2 θ, and ordinate is intensity, and the low-angle spectral peak occurred from XRD spectra is it is found that the spherical shape mesoporous molecular containing aluminium
The XRD spectra for sieving material silica gel composite C1 has two dimension hexagonal hole cave structure specific to mesoporous material；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1, as seen from the figure, institute
The microscopic appearance for stating the spherical material silica gel composite of mesopore molecular sieve containing aluminium C1 is microballoon that partial size is 10-80 μm, monodispersity
Preferably；
Fig. 3 is the graph of pore diameter distribution of the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1, as seen from the figure, the ball
Shape mesopore molecular sieve containing aluminium material silica gel composite C1 is in porous distribution.
Table 1 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C1 and propane dehydrogenation catalyst Cat-1
Structure parameter.
Table 1
*: the first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most probable pore size comma
It separates: being successively the first most probable pore size, the second most probable pore size, third most probable pore size and according to sequence from left to right
Four most probable pore sizes.
Spherical shape mesopore molecular sieve containing aluminium material silica gel composite C1 it can be seen from the data of table 1 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite 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 meso-porous molecular sieve material with hexagonal hole road structure is not added, so that carrier D1 and propane dehydrogenation catalyst Cat- be made respectively
D-1。
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
Silica gel is not added, so that carrier D2 and propane dehydrogenation catalyst Cat-D-2 be made respectively.
Comparative example 3
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
Aluminium component is not introduced, and the material of ball grinder used in mechanical milling process is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, thus respectively
Carrier D3 and propane dehydrogenation catalyst Cat-D-3 is made.
Comparative example 4
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, 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,
It is mesoporous containing aluminium that active component Pt and metal promoter Sn are only supported on the spherical shape as carrier after thermal activation by co-impregnation
In molecular sieve material silica gel composite, so that propane dehydrogenation catalyst Cat-D-4 is made, with propane dehydrogenation catalyst Cat-D-4's
On the basis of total weight, content of the Pt component in terms of Pt element is that content of 0.5 weight %, the Sn component in terms of Sn element is 1 weight
% is measured, remaining is carrier).
Comparative example 5
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
The step of not being spray-dried, and only Pt component, Sn component and Na component are supported on as carrier by the method impregnated
In the spherical material silica gel composite of mesopore molecular sieve containing aluminium, so that propane dehydrogenation catalyst Cat-D-5 be made.
Embodiment 2
(1) preparation of carrier
0.5g triblock copolymer P123 and 0.5g triblock copolymer F127 and 1.84g (0.04mol) ethyl alcohol are added
To 28ml acetic acid and sodium acetate buffer solution (pH=5) in, stirring is to polyethylene glycol glycerine-poly- second at 15 DEG C
Glycol is completely dissolved, and the trimethylpentane of 9.12g (0.08mol) is added in above-mentioned solution later, after 15 DEG C of stirring 8h, then
3.04g (0.02mol) tetramethoxy-silicane is added in above-mentioned solution, after 25 DEG C of stirring 15h, transfers the solution into polytetrafluoro
In the reaction kettle of ethylene liner, at 100 DEG C after baking oven crystallization 10h through suction filtration, deionized water wash 4 times after and had
No. 1 mesopore molecular sieve filter cake X2 of hexagonal hole road structure；
Cetyl trimethylammonium bromide and ethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %,
In, the additional amount of ethyl orthosilicate is 1g, by molar feed ratio, ethyl orthosilicate: cetyl trimethylammonium bromide: ammonium hydroxide
(25%): deionized water=1:0.5:3.5:150, solution is filtered to dissolving and obtains mesoporous material by stirring at a temperature of 80 DEG C
Expect filter cake, is 7 by Washing of Filter Cake to pH, obtains No. 2 mesopore molecular sieve filter cake Y2 with hexagonal hole road structure；
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, and press water glass
Glass: sulfuric acid: n-butanol weight ratio=6:1:1 progress sufficiently reacts 1h at 60 DEG C, is adjusted with the sulfuric acid that concentration is 98 weight %
PH is 2, and is 0.02 weight % by filtering, distilling water washing to be washed till sodium ions content by reaction mass, obtains silica gel filter cake
B2。
10g filter cake X2,10g filter cake Y2 and 40g filter cake B2 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
Ball grinder material is high alumina ceramic, and Material quality of grinding balls is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 300r/
min.Ball grinder is closed, temperature is ball milling 0.5h at 100 DEG C in ball grinder, obtains 40g solid powder；The solid powder is molten
Solution is spray-dried at 150 DEG C in the case where revolving speed is 11000r/min in 30g deionized water；The production that will be obtained after spray drying
Object 300 DEG C of calcining 72h, removed template method in Muffle furnace obtain the target product spherical shape of 35g removed template method containing mesoporous point of aluminium
Son sieve material silica gel composite C2.According to XPS Analysis as a result, the content of aluminium is 9 weight % in C2.
(2) preparation of propane dehydrogenation catalyst
35g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C2 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C2 hydroxyl and
Residual water；
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 above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-2, (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
Table 2 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C2 and propane dehydrogenation catalyst Cat-2
Structure parameter.
Table 2
*: the first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most probable pore size comma
It separates: being successively the first most probable pore size, the second most probable pore size, third most probable pore size and according to sequence from left to right
Four most probable pore sizes.
Spherical shape mesopore molecular sieve containing aluminium material silica gel composite C2 it can be seen from the data of table 2 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite material C2.
Embodiment 3
(1) preparation of carrier
0.5g triblock copolymer P123 and 0.5g triblock copolymer F127 and 2.76g (0.06mol) ethyl alcohol are added
To 28ml acetic acid and sodium acetate buffer solution (pH=3) in, stirring is to polyethylene glycol glycerine-poly- second at 15 DEG C
Glycol is completely dissolved, and the trimethylpentane of 5.7g (0.05mol) is added in above-mentioned solution later, after 15 DEG C of stirring 8h, then
2.13g (0.014mol) tetramethoxy-silicane is added in above-mentioned solution, after 40 DEG C of stirring 10h, transfers the solution into poly- four
In the reaction kettle of vinyl fluoride liner, at 40 DEG C after baking oven crystallization 40h through suction filtration, deionized water wash 4 times after and had
There is No. 1 mesopore molecular sieve filter cake X3 of hexagonal hole road structure；
Cetyl trimethylammonium bromide and ethyl orthosilicate are added in the ammonia spirit that concentration is 25 weight %,
In, the additional amount of ethyl orthosilicate is 1g, by molar feed ratio, ethyl orthosilicate: cetyl trimethylammonium bromide: ammonium hydroxide
(25%): deionized water=1:0.4:3:130, solution is filtered to dissolving and obtains mesoporous material by stirring at a temperature of 60 DEG C
Washing of Filter Cake to pH is 7, obtains No. 2 mesopore molecular sieve filter cake Y3 with hexagonal hole road structure by filter cake；
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, and press water glass
Glass: sulfuric acid: n-butanol weight ratio=3:1:1 progress sufficiently reacts 5h at 10 DEG C, is adjusted with the sulfuric acid that concentration is 98 weight %
PH is 4, and is 0.02 weight % by filtering, distilling water washing to be washed till sodium ions content by reaction mass, obtains silica gel filter cake
B3。
10g filter cake X3,10g filter cake Y3 and 60g filter cake B3 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
Ball grinder material is high alumina ceramic, and Material quality of grinding balls is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 500r/
min.Ball grinder is closed, temperature is ball milling 10h at 25 DEG C in ball grinder, obtains 40g solid powder；The solid powder is dissolved
In 30g deionized water, it is spray-dried at 300 DEG C in the case where revolving speed is 13000r/min；The product that will be obtained after spray drying
600 DEG C of calcining 12h, removed template method in Muffle furnace, obtain the target product spherical shape mesoporous molecular containing aluminium of 30g removed template method
Sieve material silica gel composite C3.According to XPS Analysis as a result, the content of aluminium is 15 weight % in C3.
(2) preparation of propane dehydrogenation catalyst
30g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C3 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C3 hydroxyl and
Residual water；
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 above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-3, (on the basis of the total weight of propane dehydrogenation catalyst Cat-3, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
Table 3 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C3 and propane dehydrogenation catalyst Cat-3
Structure parameter.
Table 3
*: the first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most probable pore size comma
It separates: being successively the first most probable pore size, the second most probable pore size, third most probable pore size and according to sequence from left to right
Four most probable pore sizes.
Spherical shape mesopore molecular sieve containing aluminium material silica gel composite C3 it can be seen from the data of table 3 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite 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 1-5
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, propane dehydrogenation catalyst Cat-D-3, propane dehydrogenation catalyst Cat-D-4 and
Propane dehydrogenation catalyst Cat-D-5 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are as shown in table 4.
Table 4
From table 4, it can be seen that de- using the propane of the spherical material silica gel composite of mesopore molecular sieve containing aluminium preparation of the invention
Hydrogen catalyst compression strength with higher, for preparing propylene by dehydrogenating propane reaction when, react 50h after, it is still available compared with
High conversion of propane and Propylene Selectivity, illustrating propane dehydrogenation catalyst of the invention not only has preferable catalytic performance,
But also it 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 the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
The spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contains aluminium component, the meso-porous molecular sieve material with hexagonal hole road structure
And silica gel, the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average grain diameter 10-80
μm, specific surface area 100-180m2/ g, pore volume 0.4-1.5mL/g, aperture is distributed in four peaks, and four peak is corresponding
First most probable pore size, the second most probable pore size, third most probable pore size and the 4th most probable pore size are respectively 1-1.8nm, 2-
2.8nm, 3-5nm and 20-40nm.
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 10-70 μm, specific surface area 110-140m2/
G, pore volume 0.4-1mL/g, and the first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most may be used
Several apertures are respectively 1.2-1.6nm, 2.2-2.8nm, 3-4nm and 25-35nm.
3. propane dehydrogenation catalyst according to claim 1, wherein relative to described in 100 parts by weight have hexagonal hole
The meso-porous molecular sieve material of road structure, the content of the aluminium component are 1-20 parts by weight, preferably 5-19 parts by weight, the silica gel
Content be 1-90 parts by weight, preferably 2-85 parts by weight.
4. a kind of method for preparing propane dehydrogenation catalyst, which is characterized in that this method comprises: by containing after carrier thermal activation
Impregnation is carried out in the mixed solution of Pt component presoma, Sn component presoma and Na component presoma, is then successively carried out
Remove solvent processing, dry and roasting, wherein the carrier is the spherical material silica gel composite of mesopore molecular sieve containing aluminium, the ball
The compression strength of the shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, and average grain diameter is 10-80 μm, and specific surface area is
100-180m2/ g, pore volume 0.4-1.5mL/g, aperture is distributed in four peaks, and corresponding first most probable in four peaks hole
Diameter, the second most probable pore size, third most probable pore size and the 4th most probable pore size be respectively 1-1.8nm, 2-2.8nm, 3-5nm and
20-40nm。
5. method according to claim 4, 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 10-70 μm, specific surface area 110-140m2/
G, pore volume 0.4-1mL/g, and the first most probable pore size, the second most probable pore size, third most probable pore size and the 4th most may be used
Several apertures are respectively 1.2-1.6nm, 2.2-2.8nm, 3-4nm and 25-35nm；
It is highly preferred that it is 300-900 DEG C that the condition of the thermal activation, which includes: temperature, time 7-10h；The impregnation
Condition includes: that temperature is 25-50 DEG C, time 2-6h.
6. method according to claim 4 or 5, the forming method of the carrier the following steps are included:
(a) in the presence of the first template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane is carried out first with sour agent and is connect
Touching, and the mixture obtained after contact is successively subjected to the first crystallization and filtering, obtain No. 1 mesopore molecular sieve filter cake；Second
In the presence of template, silicon source and ammonia spirit are subjected to the second contact, and the mixture obtained after contact is subjected to the second crystallization
And filtering, obtain No. 2 mesopore molecular sieve filter cakes；
(b) waterglass is contacted with inorganic acid and n-butanol, and the mixture obtained after contact is filtered, obtain silicon
Glue filter cake；
(c) by the mixing of No. 1 mesopore molecular sieve filter cake, No. 2 mesopore molecular sieve filter cakes and silica gel filter cake and in high alumina ceramic tank
Obtained slurry, is then spray-dried by middle carry out ball milling, and the solid powder water slurrying that will be obtained after ball milling, then will
The template removal in obtained product.
7. according to the method described in claim 6, wherein, in step (a), first template, ethyl alcohol, trimethylpentane
Molar ratio with the dosage of tetramethoxy-silicane is 1:100-500:200-500:50-200, preferably 1:200-400:250-
400:70-150；The silicon source, the second template, the ammonia in ammonium hydroxide and water dosage molar ratio be 1:0.1-1:0.1-5:100-
200, preferably 1:0.2-0.5:1.5-3.5:120-180；
Preferably, first template include triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene P123 and
F127, the acid agent are the acetic acid and sodium acetate buffer solution that pH value is 1-6；Second template is cetyl trimethyl
Ammonium bromide, the silicon source include in ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution at least
One kind, preferably ethyl orthosilicate；
It is further preferred that it is 10-60 DEG C, time 10-72h, pH value 1-7 that the condition of first contact, which includes: temperature,
The condition of first crystallization includes: that temperature is 30-150 DEG C, time 10-72h；The condition of second contact includes: temperature
Degree is 25-100 DEG C, time 10-72h；The condition of second crystallization includes: that temperature is 30-150 DEG C, time 10-72h.
8. preparation method according to claim 6, wherein in step (b), item that the waterglass is contacted with inorganic acid
Part includes: that the condition of the waterglass, inorganic acid and n-butanol contact includes: the dosage of waterglass, inorganic acid and n-butanol
Weight ratio is 3-6:1:1, and temperature is 10-60 DEG C, time 1-5h, pH value 2-4；The inorganic acid is sulfuric acid, nitric acid and salt
One of acid is a variety of；
Preferably, in step (c), relative to No. 1 mesopore molecular sieve filter cake of 100 parts by weight and No. 2 mesopore molecular sieves
Total dosage of filter cake, the dosage of the silica gel filter cake are 1-90 parts by weight, preferably 2-85 parts by weight；No. 1 mesoporous molecular
The weight ratio of the dosage of sieving cake and No. 2 mesopore molecular sieve filter cakes is 1:0.5-2, preferably 1:0.6-1.5；
It is highly preferred that the revolving speed that the condition that ball milling is carried out in high alumina ceramic tank includes: abrading-ball is 300-500r/min, it is high
Temperature in aluminium ceramics ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100h；The condition of the spray drying includes: temperature
100-300 DEG C of degree, revolving speed 10000-15000r/min；
It is further preferred that the process of the template removal includes: to calcine 10-80h 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 1-3 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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| CN114515594A (en) * | 2020-11-19 | 2022-05-20 | 中国石油化工股份有限公司 | Light gasoline cracking propylene yield-increasing catalyst containing porous aluminum-containing silica gel mesoporous composite material and preparation method and application thereof |
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