CN109382129A - 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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- CN109382129A CN109382129A CN201710665919.6A CN201710665919A CN109382129A CN 109382129 A CN109382129 A CN 109382129A CN 201710665919 A CN201710665919 A CN 201710665919A CN 109382129 A CN109382129 A CN 109382129A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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 spherical double mesoporous zeolite complex carriers, spherical double mesoporous zeolite complex carriers contain zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the average grain diameter of spherical double mesoporous zeolite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-50nm.The propane dehydrogenation catalyst shows good catalytic performance when reacting for preparing propylene by dehydrogenating propane, conversion of propane is high, and Propylene Selectivity is high, and catalyst stability is good.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of propane dehydrogenation catalyst and preparation method thereof and third
The method of alkane dehydrogenation producing propylene.
Background technique
Natural zeolite is aqueous, rack-like structure porosity aluminosilicate mineral substance, is the general name of zeolite race mineral.Boiling
Stone is mainly by SiO2、Al2O3、H2The part such as O and alkali, alkaline-earth metal ions forms, and great changes have taken place for four fractions, thus structure
At a variety of zeolite group minerals.40 kinds of natural zeolite mineral are being had found, with analcime, chabasie, clinoptilolite, heulandite, hair
Zeolite, ferrierite, laumontite, modenite, phillipsite are relatively conventional.China's discovery at present has analcime, tiltedly hair boiling
More than the 10 kinds of natural zeolite mineral products such as stone, modenite, ferrierite, phillipsite, epidesmine.It largely utilizes, mainly
It is clinoptilolite, modenite, next has analcime, epidesmine.The specific physical property of zeolite depends on the lattice of zeolite
Structure, zeolite is by SiO2And Al2O3Tetrahedron element is staggered to opening of the spatial network due to crystal structure.Zeolite contains
There are many non-uniform duct of size and cavitys.Due to compensating positive charge caused by aluminium displacement silicon electricity price imbalance in tetrahedron
Needs, in these ducts and cavity often occupied by alkali or alkaline earth metal ion and zeolite hydrone.The structure of zeolite
Determine that it has the unique physical and chemical performance such as ion exchangeable and adsorptive selectivity.In addition, zeolite also has good heat steady
Qualitative, acid resistance, can the characteristics such as dehydration property, the catalytic cracking of chemical reaction, radiation resistance and low bulk density, porosity.
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 existing propane dehydrogenation catalyst preparation process complexity, preparation process to be easy to make
At environmental pollution, conversion of propane and the lower defect of Propylene Selectivity, a kind of propane dehydrogenation catalyst and its preparation side are provided
The method of method and preparing propylene by dehydrogenating propane.
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 double Jie
Hole zeolite complex carrier, spherical double mesoporous zeolite complex carriers contain zeolite and with one-dimensional hexagonal hole road distributed architecture
The average grain diameter of meso-porous molecular sieve material, spherical double mesoporous zeolite complex carriers is 30-60 μm, specific surface area 150-
350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is distinguished
For 5-15nm and 30-50nm.
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 and the carrier is spherical double mesoporous zeolite complex carriers,
Spherical double mesoporous zeolite complex carriers contain zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture,
The average grain diameter of spherical double mesoporous zeolite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume are
0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-
50nm。
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.
Spherical double mesoporous zeolite complex carriers according to the present invention, combine with one-dimensional hexagonal hole road distributed architecture
Meso-porous molecular sieve material, zeolite and the advantages of ball type carrier so that the double mesoporous zeolite complex carriers of the spherical shape are suitable as
The carrier of loaded catalyst is especially suitable as the load of loaded catalyst used in reacting in preparing propylene by dehydrogenating propane
Body.
In the loaded catalyst of the invention, spherical double mesoporous zeolite complex carriers have mesopore molecular sieve
The larger feature of porous structure, large specific surface area, the pore volume of material, in conjunction with natural zeolite due to biggish specific surface area
The strong adsorption capacity having with microcellular structure is conducive to metal component in the fine dispersion of carrier surface, and the carrier
It is also loaded the Pt component as chief active metal component, the Sn component as auxiliary agent and Na component, so that the support type is urged
Agent had not only had the advantages that loaded catalyst such as catalytic activity is high, side reaction is few, post-processing is simple etc., but also had stronger urge
Change activity, so that the loaded catalyst has better dehydrogenation activity and selectivity in for dehydrogenating propane reaction, significantly
The conversion ratio of reaction raw materials is improved, specifically, in the reaction that preparing propylene by dehydrogenating propane is carried out using the loaded catalyst, propane
Conversion ratio is up to 24.7%, and the selectivity of propylene is up to 80%.
Also, when the method by spray drying prepares the loaded catalyst, the loaded catalyst can be with
It is reused, and still can obtain higher reaction raw materials conversion ratio during recycling.
In addition, the substep leaching that the preparation method of propane dehydrogenation catalyst of the invention is conventional using the method substitution of co-impregnation
Stain method, preparation process is simple, and preparation cost is low, good economy performance.
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 the X-ray diffraction spectrogram of the double mesoporous zeolite complex carriers of spherical shape of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the double mesoporous zeolite complex carriers of spherical shape 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 spherical double mesoporous zeolite complex carriers, the ball
The double mesoporous zeolite complex carriers of shape contain zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the ball
The average grain diameter of the double mesoporous zeolite complex carriers of shape is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-
1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-50nm.
According to the present invention, spherical double mesoporous zeolite complex carriers have special one-dimensional hexagonal hole road distributed architecture,
The average grain diameter of its particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are inhaled according to nitrogen
Attached method measures.In the present invention, partial size refers to the particle size of feed particles, the then granularity sphere when feed particles are sphere
Diameter indicate that the side length of then granularity cube indicates when feed particles are cube, when feed particles are irregular
Then granularity is indicated with the mesh size for the sieve that can screen out the feed particles just when shape.
According to the present invention, by by the structural parameter control of the spherical double mesoporous zeolite complex carriers above range it
It is interior, it can be ensured that spherical double mesoporous zeolite complex carriers are not susceptible to reunite, and are used as load made of carrier
The reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process can be improved in type catalyst.When spherical double mesoporous zeolites
The specific surface area of complex carrier is less than 150m2When/g and/or pore volume are less than 0.5mL/g, it is used as load made of carrier
The catalytic activity of type catalyst can significantly reduce；When the specific surface area of spherical double mesoporous zeolite complex carriers is greater than 350m2/
When g and/or pore volume are greater than 1.5mL/g, it is used as loaded catalyst made of carrier and is reacted in preparing propylene by dehydrogenating propane
It is easy to happen reunion in the process, to influence the reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.
In the preferred case, the average grain diameter of spherical double mesoporous zeolite complex carriers is 35-55 μm, and specific surface area is
250-310m2/ g, pore volume 1-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size divides
It Wei not 7-10nm and 35-45nm.
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, spherical double mesoporous zeolites are compound
The content of carrier is 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %, the Sn
Content of the 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
Measure %.
Preferably, the average particle diameter of the propane dehydrogenation catalyst is 30-60 μm, specific surface area 120-300m2/
G, pore volume 0.3-1.3mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 7-
12nm and 35-45nm.
According to the present invention, in spherical double mesoporous zeolite complex carriers, to have one-dimensional six described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of square duct distributed architecture, the weight of the zeolite is 1-50 parts by weight, preferably
20-50 parts by weight.
According to the present invention, spherical double mesoporous zeolite complex carriers can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced by silica gel " refers in the preparation process of spherical double mesoporous zeolite complex carriers, by silicon
Glue is as the silica component for preparing raw material and bringing into the double mesoporous zeolite complex carriers of spherical shape finally prepared.In the spherical shape
In double mesoporous zeolite complex carriers, relative to the mesoporous molecular described in 100 parts by weight with one-dimensional hexagonal hole road distributed architecture
The weight of material is sieved, the content of the silica introduced by silica gel can be 1-200 parts by weight, preferably 50-150 weight
Measure part.
According to the present invention, the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture can be normal for this field
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
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 spherical double mesoporous zeolite complex carriers, the spherical shape
Double mesoporous zeolite complex carriers contain zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the spherical shape
The average grain diameter of double mesoporous zeolite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-
1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-50nm.
According to the present invention, in order to remove the hydroxyl and Residual water of the spherical double mesoporous zeolite complex carriers, described
Firstly the need of progress thermal activation treatment, the item of the thermal activation treatment before spherical double mesoporous zeolite composite carrier load metal components
Part may include: in the presence of nitrogen, to carry out calcining 7-10h at being 300-900 DEG C in temperature by carrier.
According to the present invention, by the way of the spherical double mesoporous zeolite composite carrier load metal components can be using impregnating,
Make metal component enter described spherical pair by the capillary pressure of the cellular structure of spherical double mesoporous zeolite complex carriers to be situated between
In the duct of hole zeolite complex carrier, at the same metal component can also the surfaces of spherical double mesoporous zeolite complex carriers again inhale
It is attached, until metal component reaches adsorption equilibrium on the surface of spherical double mesoporous zeolite complex carriers.Preferably, the dipping
Processing carry out after thermal activation treatment in spherical double mesoporous zeolite complex carriers, and the impregnation can be total immersion
Stain processing, 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: to contain the hexagonal mesoporous material after thermal activation
There is the solution of Pt component presoma, Sn component presoma and Na component presoma to be mixed, the temperature of the dipping can
Think 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, spherical double mesoporous zeolite complex carriers, Pt component presoma, Sn component presoma and Na group
The dosage for dividing presoma can be so that in the propane dehydrogenation catalyst of preparation, and the total weight with the propane dehydrogenation catalyst is
Benchmark, it is 0.2-0.5 weight %, Sn that the content of the carrier, which is content of 97.5-99.3 weight %, the Pt component in terms of Pt element,
Content of the component in terms of Sn element 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 spherical double mesoporous zeolite complex carriers forming method the following steps are included:
(a) in the presence of template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane is contacted with sour agent, and
It by the product crystallization obtained after contact and filters, obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake, silica gel filter cake and zeolite are mixed into simultaneously ball milling, and the solid powder that will be obtained after ball milling
It is spray-dried after the water slurrying of end, then by the template removal in obtained product.
In the forming process of above-mentioned spherical double mesoporous zeolite complex carriers, the mesoporous material filter cake is with one-dimensional six
The meso-porous molecular sieve material of square duct distributed architecture.
It is main to pass through control mesoporous material filter cake, silicon in the forming process of above-mentioned spherical double mesoporous zeolite complex carriers
The composition of glue filter cake and zeolite controls pore-size distribution for bimodal distribution, and the double mesoporous zeolite complex carriers of the spherical shape is made to have diplopore
Distributed architecture, and by control forming method (that is, mesoporous material filter cake, silica gel filter cake and zeolite are first mixed simultaneously ball milling, so
To be spray-dried after the water slurrying of obtained solid powder afterwards) by the microscopic appearance control of the spherical double mesoporous zeolite complex carriers
It is made as spherical shape.
According to the present invention, during preparing mesoporous material filter cake, the dosage of each substance can be in a wider scope
It is selected and is adjusted.For example, in step (a), the template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
Your ratio can be 1:100-500:200-600:50-200, preferably 1:200-400:250-400:70-150.
According to the present invention, the type of the template is not particularly limited, as long as the spherical shape that can make is double mesoporous
Zeolite complex carrier has above-mentioned pore structure, it is preferable that the template can be poly- for triblock copolymer polyoxyethylene-
Oxypropylene-polyoxyethylene.Wherein, which can be commercially available (for example, can be purchased from Aldrich, trade name
For P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods.When the template is poly-
When ethylene oxide-polyoxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-poly-oxypropylene polyoxyethylene
Average molecular weight calculates to obtain.
According to the present invention, the type of the sour agent is not particularly limited, and can be the conventional selection of this field, Ke Yiwei
The mixture of existing various acid or acid.Wherein, the mixture of the acid or acid can be used with pure state, can also be water-soluble with its
The form of liquid uses, and preferably uses in form of an aqueous solutions.Preferably, the sour agent is the buffer solution of acetic acid and sodium acetate；
It is highly preferred that the pH value of the acid agent is 1-6；It is further preferred that the pH value of the acid agent is 3-5.
According to the present invention, the condition that the tetramethoxy-silicane is contacted with sour agent is not particularly limited, for example, described four
The condition that methoxy silane is contacted with sour agent may include: that temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-7；It is excellent
In the case of choosing, the condition that the tetramethoxy-silicane is contacted with sour agent may include: that temperature is 10-30 DEG C, and the time is that 20-40 is small
When, pH value 3-6.In order to be more advantageous to the uniform mixing between each substance, the tetramethoxy-silicane is contacted with sour agent preferably to exist
It is carried out under stirring condition.The dosage of the acid agent preferably so that the tetramethoxy-silicane and sour agent haptoreaction system pH value
For 1-7, more preferably 3-6.
There is no particular limitation for condition of the present invention to the crystallization, what the condition of the crystallization can be conventional for this field
Selection, for example, it is 30-150 DEG C that the condition of the crystallization, which may include: temperature, the time is 10-72 hours, under preferable case, institute
It is 40-80 DEG C that the condition for stating crystallization, which includes: temperature, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
In addition, the present invention is to the contact between the template, ethyl alcohol, sour agent, trimethylpentane and tetramethoxy-silicane
Mode is not particularly limited, for example, above-mentioned five kinds of substances can be mixed simultaneously, it can also be by several substances therein
It is first mixed, will continue to be mixed in mixture that remaining substance is added again.Under preferable case, the contact side
Formula is after being stirred template, ethyl alcohol, sour agent and trimethylpentane, then to add four methoxies first at 10-100 DEG C
Base silane simultaneously continues to be stirred.
The condition that the present invention contacts the waterglass with inorganic acid is not particularly limited, for example, in step (b),
The condition that the waterglass is contacted with inorganic acid generally includes: temperature can be 10-60 DEG C, preferably 20-40 DEG C；Time can be with
It is 1-5 hours, preferably 1.5-3 hours, pH value 2-4.In order to be more advantageous to the uniform mixing between each substance, the waterglass
It contacts with inorganic acid and preferably carries 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, it is above-mentioned prepare mesoporous material filter cake and silica gel filter cake during, the mistake of filter cake is obtained by filtering
Journey may include: after filtration, washs (washing times can be 2-10) repeatedly with distilled water, is then filtered.It is preferred that
Ground prepares the washing during mesoporous material filter cake so that filter cake PH is 7, prepare 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), the dosage of the mesoporous material filter cake, silica gel filter cake and zeolite can basis
It is expected that the component of the double mesoporous zeolite complex carriers of obtained spherical shape is selected, under preferable case, with being given an account of for 100 parts by weight
On the basis of the dosage of Porous materials filter cake, the dosage of the silica gel filter cake can be 1-200 parts by weight, preferably 50-150 weight
Part；The dosage of the zeolite can be 1-50 parts by weight, preferably 20-50 parts by weight.
According to the present invention, the concrete operation method of the ball milling and condition are not particularly limited, not destroy or substantially
The structure of mesoporous material is not destroyed and enters silica gel and zeolite subject to mesoporous material duct.Those skilled in the art can basis
Mentioned above principle selects various suitable conditions to implement the present invention.Specifically, the ball milling carries out in the ball mill, wherein ball
The diameter of abrading-ball can be 2-3mm in grinding machine；The quantity of abrading-ball can reasonably be selected according to the size of ball grinder, for
Size is the ball grinder of 50-150mL, and 1 abrading-ball usually can be used；The material of the abrading-ball can be agate, polytetrafluoroethyl-ne
Alkene etc., preferably agate.The condition of the ball milling includes: that the revolving speed of abrading-ball can be 300-500r/min, the temperature in ball grinder
Degree can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
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 10-80 hours, preferably 20-30 hours, most preferably 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 following embodiment and comparative example, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, is abbreviated as
P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular weight is
5800；
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is in the ASAP2020-M+C purchased from the production of U.S. Micromeritics company
It is carried out on type adsorption instrument, the specific surface area and pore volume of sample, which calculate, uses BET method；The particle diameter distribution of sample swashs in Malvern
It is carried out on light particle size analyzer；Rotary Evaporators are the production of IKA company, Germany, model RV10digital；Propane dehydrogenation catalyst
Activity component load quantity is in the Wavelength Dispersive-X-Ray fluorescence spectrum for being Axios-Advanced purchased from Dutch Panaco company model
It is measured on instrument；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 spherical double mesoporous zeolite complex carriers
1g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
6g (0.053mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) tetramethyl is added thereto
Oxysilane stirs 20h under conditions of 15 DEG C, pH value are 4.5, obtained solution is then transferred to polytetrafluoroethyllining lining
Reaction kettle in, at 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filtering is had
The meso-porous molecular sieve material filter cake A1 of one-dimensional hexagonal hole road single hole distributed architecture；
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 5:1 is mixed
Merge the haptoreaction 1.5h at 30 DEG C, it is then anti-to what is obtained then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 3
Material is answered to be filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B1.
10g filter cake A1,10g filter cake B1 and 10g zeolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is to obtain 30g solid powder ball milling 1 hour at 60 DEG C in ball grinder；The solid powder is molten
Solution is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min in 30 grams of deionized waters；The production that will be obtained after spray drying
Object is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method, obtains 30g with one-dimensional hexagonal hole road diplopore distribution knot
The double mesoporous zeolite complex carrier C1 of the spherical shape of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the double mesoporous zeolite complex carrier C1 of spherical shape that step (1) obtains are immersed in the mixture solution
In, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 6 hours, obtain in 600 DEG C of Muffle furnaces
To propane dehydrogenation catalyst Cat-1, (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, Pt component is in terms of Pt element
It is content of 0.7 weight %, the Na component in terms of Na element is 0.5 that content, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to spherical double mesoporous zeolite complex carriers
C1 and propane dehydrogenation catalyst Cat-1 are characterized；
Fig. 1 is the X-ray diffracting spectrum of spherical double mesoporous zeolite complex carrier C1, wherein abscissa is 2 θ, ordinate
For intensity, the low-angle spectral peak occurred by XRD spectra is it is found that the XRD spectra a of spherical double mesoporous zeolite complex carrier C1 has Jie
One-dimensional hexagonal hole road structure specific to Porous materials；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of spherical double mesoporous zeolite complex carrier C1, as seen from the figure, spherical double mesoporous zeolites
The microscopic appearance of complex carrier C1 is the Mesoporous Spheres that granularity is 30-60 μm；
Table 1 is the pore structure parameter of spherical double mesoporous zeolite complex carrier C1 and propane dehydrogenation catalyst Cat-1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C1 | 290 | 1.1 | 8,40 | 30-60 |
| Catalyst Cat-1 | 258 | 0.8 | 7.5,36.7 | 30-60 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous zeolite complex carriers are in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 1
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous zeolite complex carriers.
Comparative example 1
Carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier not
Zeolite is added, so that carrier D1 and loaded catalyst Cat-D-1 be made respectively.
Comparative example 2
Carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier not
Mesoporous material is added, so that carrier D2 and loaded catalyst Cat-D-2 be made respectively.
Comparative example 3
According to the spherical double mesoporous zeolite complex carrier D3 and loaded catalyst Cat-D-3 of the method for embodiment 1 preparation, institute
Different, during preparing loaded catalyst, (Jilin is purchased from the rodlike mesoporous silicon oxide SBA-15 of identical weight
High-tech limited liability company, university) meso-porous molecular sieve material filter cake A1 is replaced, so that it is multiple that spherical double mesoporous zeolites are made respectively
Close carrier D3 and loaded catalyst Cat-D-3.
Comparative example 4
It is different according to the spherical double mesoporous zeolite complex carriers of the method for embodiment 1 preparation and loaded catalyst,
The step of not being spray-dried during preparing loaded catalyst, and only by the method for dipping by Pt component, Sn component
It is supported on spherical double mesoporous zeolite complex carriers with Na component, so that loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of spherical double mesoporous zeolite complex carriers
1g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 5, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 3.04g (0.02mol) four is added thereto
Methoxy silane stirs 15h under conditions of 25 DEG C, pH value are 5.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, the crystallization 10h at 100 DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain
Meso-porous molecular sieve material filter cake A2 with one-dimensional hexagonal hole road single hole distributed architecture；
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 4:1 is mixed
Merge the haptoreaction 1.5h at 40 DEG C, it is then anti-to what is obtained then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 2
Material is answered to be filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B2.
20g filter cake A2,10g filter cake B2 and 8g zeolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 300r/
min.Ball grinder is closed, temperature is to obtain 38g solid powder ball milling 0.5 hour at 80 DEG C in ball grinder；By the solid powder
It is dissolved in 12g deionized water, is spray-dried at 250 DEG C in the case where revolving speed is 11000r/min；By what is obtained after spray drying
Product is calcined 15 hours at 500 DEG C in Muffle furnace, removed template method, is obtained 35g and is distributed with one-dimensional hexagonal hole road diplopore
The double mesoporous zeolite complex carrier C2 of the spherical shape of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the double mesoporous zeolite complex carrier C2 of spherical shape that step (1) obtains are immersed in the mixture solution
In, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 6 hours, obtain in 600 DEG C of Muffle furnaces
To propane dehydrogenation catalyst Cat-2, (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, Pt component is in terms of Pt element
It is content of 0.7 weight %, the Na component in terms of Na element is 0.5 that content, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Weight %, remaining is carrier).
Table 2 is the pore structure parameter of spherical double mesoporous zeolite complex carrier C2 and propane dehydrogenation catalyst Cat-2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C2 | 275 | 1 | 8.3,37.5 | 35-50 |
| Catalyst Cat-2 | 235 | 0.7 | 7.2,32.7 | 35-50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous zeolite complex carriers are in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 2
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous zeolite complex carriers.
Embodiment 3
1g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 3, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 10h under conditions of 40 DEG C, pH value are 3.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, the crystallization 40h at 40 DEG C, be then filtered and and be washed with deionized 4 times, then filter and had
There is the meso-porous molecular sieve material filter cake A3 of one-dimensional hexagonal hole road single hole distributed architecture；
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 6:1 is mixed
Merge the haptoreaction 3h at 20 DEG C, then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 4, the then reaction to obtaining
Material is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B3.
20g filter cake A3,30g filter cake B3 and 12g zeolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball
The material of grinding jar is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 550r/
min.Ball grinder is closed, temperature is to obtain 55g solid powder ball milling 10 hours at 40 DEG C in ball grinder；By the solid powder
It is dissolved in 30g deionized water, is spray-dried at 150 DEG C in the case where revolving speed is 13000r/min；By what is obtained after spray drying
Product is calcined 70 hours at 450 DEG C in Muffle furnace, removed template method, is obtained 53g and is distributed with one-dimensional hexagonal hole road diplopore
The double mesoporous zeolite complex carrier C3 of the spherical shape of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the double mesoporous zeolite complex carrier C3 of spherical shape that step (1) obtains are immersed in the mixture solution
In, after being impregnated 5 hours at 30 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 150 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 5h in 650 DEG C of Muffle furnaces, obtain third
Alkane dehydrogenation Cat-3 (on the basis of the total weight of propane dehydrogenation catalyst Cat-3, content of the Pt component in terms of Pt element
It is content of 0.7 weight %, the Na component in terms of Na element for content of 0.3 weight %, the Sn component in terms of Sn element is 0.5 weight
% is measured, remaining is carrier).
Table 3 is the pore structure parameter of spherical double mesoporous zeolite complex carrier C3 and propane dehydrogenation catalyst Cat-3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C3 | 295 | 1.3 | 8.9,37.3 | 40-55 |
| Catalyst Cat-3 | 263 | 0.9 | 7.4,35.5 | 40-55 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous zeolite complex carriers are in load chief active Pt component, auxiliary agent Sn it can be seen from the data of table 3
After component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous zeolite complex carriers.
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 1-4
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 and propane dehydrogenation catalyst Cat-D-4
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 | 24.7% | 80% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 24.2% | 79.1% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 23.8% | 78.5% |
| Experimental comparison's example 1 | Cat-D-1 | 10.3% | 41.1% |
| Experimental comparison's example 2 | Cat-D-2 | 9.9% | 42.2% |
| Experimental comparison's example 3 | Cat-D-3 | 13.5% | 50.5% |
| Experimental comparison's example 4 | Cat-D-4 | 14.6% | 66.7% |
From table 4, it can be seen that using the propane dehydrogenation catalyst of the double mesoporous zeolite complex carrier preparations of spherical shape of the invention
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 stability is good.
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 spherical double mesoporous zeolite complex carriers, the spherical shape
Double mesoporous zeolite complex carriers contain zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the spherical shape
The average grain diameter of double mesoporous zeolite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-
1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-50nm.
2. propane dehydrogenation catalyst according to claim 1, wherein the dehydrogenating propane relative to 100 parts by weight is urged
The content of agent, spherical double mesoporous zeolite complex carriers is 97.5-99.3 weight %, and the Pt component is in terms of Pt element
Content is 0.2-0.5 weight %, and content of the Sn component in terms of Sn element is 0.2-1.2 weight %, and the Na component is with Na
The content of element meter is 0.3-0.8 weight %；
Preferably, the average particle diameter of the propane dehydrogenation catalyst is 30-60 μm, specific surface area 120-300m2/ g, hole
Volume is 0.3-1.3mL/g, and pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size be respectively 7-12nm and
35-45nm。
3. propane dehydrogenation catalyst according to claim 1, wherein to have one-dimensional hexagonal hole described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of road distributed architecture, the weight of the zeolite is 1-50 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 spherical double mesoporous zeolite complex carriers, described spherical double mesoporous
Zeolite complex carrier contains zeolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, described spherical double mesoporous
The average grain diameter of zeolite complex carrier is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-1.5mL/g, hole
Diameter is distributed as bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 30-50nm.
5. method according to claim 4, wherein spherical double mesoporous zeolite complex carriers, Pt component presoma, Sn component
The dosage of presoma and Na component presoma makes in the propane dehydrogenation catalyst of preparation, with the total of the propane dehydrogenation catalyst
On the basis of weight, the content of the carrier is that content of 97.5-99.3 weight %, the Pt component in terms of Pt element is 0.2-0.5 weight
% is measured, content of the Sn component in terms of Sn element is that content of 0.2-1.2 weight %, the Na component in terms of Na element is 0.3-0.8 weight
Measure %；
Preferably, the partial size of the propane dehydrogenation catalyst is 30-60 μm, specific surface area 120-300m2/ g, pore volume are
0.3-1.3mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 7-12nm and 35-
45nm；
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. the forming method of method according to claim 4 or 5, spherical double mesoporous zeolite complex carriers includes following
Step:
(a) in the presence of template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane is contacted with sour agent, and will connect
The product crystallization that obtains after touch simultaneously filters, and obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake, silica gel filter cake and zeolite are mixed into simultaneously ball milling, and the solid powder obtained after ball milling is used
It is spray-dried after water slurrying, then by the template removal in obtained product.
7. according to the method described in claim 6, wherein, in step (a), the template, ethyl alcohol, trimethylpentane and four
The molar ratio of methoxy silane is 1:100-500:200-600:50-200；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and the acid agent is pH value
For the acetic acid of 1-6 and the buffer solution of sodium acetate；
It is further preferred that it is 10-60 DEG C that the condition that tetramethoxy-silicane is contacted with sour agent, which includes: temperature, the time is that 10-72 is small
When, pH value 1-7；The condition of the crystallization includes: that temperature is 30-150 DEG C, and the time is 10-72 hours.
8. preparation method according to claim 6 or 7, wherein in step (b), the waterglass is contacted with inorganic acid
Condition include: temperature be 10-60 DEG C, the time be 1-5 hours, pH value 2-4；The inorganic acid is sulfuric acid, nitric acid and hydrochloric acid
One of or it is a variety of；
Preferably, in step (c), on the basis of the dosage of the mesoporous material filter cake of 100 parts by weight, the silica gel filter cake
Dosage be 1-200 parts by weight, preferably 50-150 parts by weight；The dosage of the zeolite is 1-50 parts by weight, preferably 20-50
Parts by weight.
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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| WO2021112913A1 (en) * | 2019-12-02 | 2021-06-10 | Saudi Arabian Oil Company | Dual functional composite catalyst for olefin metathesis and cracking |
| CN113304772A (en) * | 2020-02-27 | 2021-08-27 | 中国石油化工股份有限公司 | Light gasoline cracking propylene yield-increasing catalyst containing short rod-shaped mesoporous material and preparation method and application thereof |
| CN114425435A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for cracking methyl tert-butyl ether to prepare propylene, preparation method and application thereof |
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| WO2021112913A1 (en) * | 2019-12-02 | 2021-06-10 | Saudi Arabian Oil Company | Dual functional composite catalyst for olefin metathesis and cracking |
| US11185850B2 (en) | 2019-12-02 | 2021-11-30 | Saudi Arabian Oil Company | Dual functional composite catalyst for olefin metathesis and cracking |
| CN114667186A (en) * | 2019-12-02 | 2022-06-24 | 沙特阿拉伯石油公司 | Bifunctional composite catalysts for olefin metathesis and cracking |
| CN113304772A (en) * | 2020-02-27 | 2021-08-27 | 中国石油化工股份有限公司 | Light gasoline cracking propylene yield-increasing catalyst containing short rod-shaped mesoporous material and preparation method and application thereof |
| CN113304772B (en) * | 2020-02-27 | 2023-08-15 | 中国石油化工股份有限公司 | Light gasoline cracking yield-increasing propylene catalyst containing short rod-like mesoporous material, and preparation method and application thereof |
| CN114425435A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for cracking methyl tert-butyl ether to prepare propylene, preparation method and application thereof |
| CN114425435B (en) * | 2020-09-25 | 2023-10-10 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by cracking methyl tertiary butyl ether, preparation method and application thereof |
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| CN109382129B (en) | 2019-11-12 |
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