CN109748294A - The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
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Abstract
The present invention relates to catalyst field, a kind of spherical mesoporous molecular screen material and preparation method thereof, catalyst containing aforementioned spherical mesoporous molecular screen material and its preparation method and application and a kind of method of preparing propylene by dehydrogenating propane are disclosed.The method for preparing spherical mesoporous molecular screen material includes: (a) under solution condition, template, nonionic surfactant, sour agent and industrial metasilicate are mixed to obtain solution A, wherein, the template is cetyl trimethylammonium bromide, and the nonionic surfactant is Triton X-100；(b) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；(c) mesoporous material raw powder is subjected to Template removal processing, obtains spherical mesoporous molecular screen material.This method synthesizes the spherical mesoporous molecular screen material of high-specific surface area using low-cost silicon source, is suitable as supported catalyst agent carrier.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of spherical mesoporous molecular screen material and preparation method thereof contains
There are catalyst of aforementioned spherical mesoporous molecular screen material and its preparation method and application and a kind of side of preparing propylene by dehydrogenating propane
Method.
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 Catofin 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, researcher has done many work.Such as: use molecular sieve
Class carrier substitutes traditional γ-Al2O3 carrier, effect preferably include 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 currently used mesoporous material aperture is smaller (average
3~7nm of aperture), if carrying out bulky molecular catalysis reaction, macromolecular duct more difficult to get access, so that influencing catalytic effect.Cause
This, selecting a kind of excellent carrier is one, dehydrogenating propane field urgent problem to be solved.
Summary of the invention
The purpose of the invention is to overcome existing preparation cost height, pattern as propane dehydrogenation catalyst carrier to be
Rodlike ordered mesoporous material mobility is poor, easy to reunite, be unfavorable for its store, transport, postorder processing and application, and then cause
By existing support type propane dehydrogenation catalyst carrier preparation support type propane dehydrogenation catalyst poor catalytic activity the defects of,
There is provided a kind of spherical mesoporous molecular screen material and preparation method thereof, the catalyst containing aforementioned spherical mesoporous molecular screen material and its
Preparation method and application and a kind of method of preparing propylene by dehydrogenating propane.
To achieve the goals above, the present inventor, can using low-cost silicon source by finding after research
To synthesize the spherical mesoporous molecular screen material of high-specific surface area, the spherical mesoporous molecular screen material has outside the geometry of microballoon
The spherical mesoporous molecular screen material of shape has apparent advantage in terms of reducing the reunion of powder, improving its, therefore will
Spherical ordered mesoporous material can play microballoon in conjunction with the advantages of ordered mesoporous material as propane dehydrogenation catalyst carrier
Come, the high-specific surface area of ordered mesoporous material can be retained, the characteristics of macropore holds, aperture is big and narrowly distributing and reduced orderly
The reunion of mesoporous material increases its mobility.It is urged using spherical mesoporous molecular screen material of the present invention as dehydrogenating propane
The carrier of agent can effectively propose the load factor and catalytic activity of propane dehydrogenation catalyst, so that the propane made of the carrier takes off
Hydrogen catalyst is for can get the reaction raw materials conversion ratio significantly improved in preparing propylene by dehydrogenating propane reaction, so as to complete this hair
It is bright.
To achieve the goals above, one aspect of the present invention provides a kind of method for preparing spherical mesoporous molecular screen material, institute
The method of stating includes:
(a) under solution condition, template, nonionic surfactant, sour agent and industrial metasilicate is subjected to mixing and connect
Touching is to obtain solution A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is poly-
Ethylene glycol octyl phenyl ether；
(b) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(c) mesoporous material raw powder is subjected to Template removal processing, obtains spherical mesoporous molecular screen material.
Second aspect of the present invention provides a kind of spherical mesoporous molecular screen material prepared by the above method.
Third aspect present invention provides a kind of catalyst, the Pt in the catalyst containing carrier and load on the carrier
Component, Sn component and Na component, wherein the carrier is spherical mesoporous molecular screen material above-mentioned.
Fourth aspect present invention provides a kind of method for preparing aforementioned catalytic agent, this method comprises: carrier is successively carried out
Thermal activation treatment, impregnation, the processing of removal solvent, dry and roasting, make the supported on carriers Pt component, Sn component and Na
Component, wherein the carrier is spherical mesoporous molecular screen material above-mentioned.
Fifth aspect present invention provides a kind of catalyst prepared by the above method.
Sixth aspect present invention provides a kind of application of aforementioned catalytic agent in catalysis dehydrogenating propane.
Seventh aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, this method comprises: in catalyst and hydrogen
In the presence of, propane is subjected to dehydrogenation reaction, wherein the catalyst provides for catalyst provided by the invention or by the present invention
Method preparation catalyst.
Spherical, specific surface area is larger, biggish Jie of pore volume using being synthesized using low-cost silicon source by the present invention
Porous molecular sieve material is conducive to metal component in carrier surface fine dispersion, and the carrier has been also loaded Pt component, Sn group
Point and Na component so that the loaded catalyst both had the advantages that loaded catalyst such as catalytic activity are high, side reaction is few, after
Processing is simple etc., and has stronger catalytic activity, so that the loaded catalyst has more in for dehydrogenating propane reaction
Good dehydrogenation activity and selectivity, significantly improves the conversion ratio of reaction raw materials, specifically, carries out third using the loaded catalyst
In the reaction of alkane dehydrogenation producing propylene, conversion of propane is up to 34%, and the selectivity of propylene is up to 90%.
In addition, the step impregnation method that the present invention is conventional using co-impregnation method substitution, preparation process is simple, and condition is easy to
Control, good repetitiveness.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffracting spectrum of the spherical mesoporous molecular screen material of embodiment 1；
Fig. 2 is nitrogen adsorption-desorption curve figure of the spherical mesoporous molecular screen material of embodiment 1；
Fig. 3 is the graph of pore diameter distribution of the spherical mesoporous molecular screen material of embodiment 1；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical mesoporous molecular screen material of embodiment 1；
Fig. 5 is the TEM transmission electron microscope picture of the microscopic appearance of the spherical mesoporous molecular screen material of embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously shown, the present invention provides a kind of methods for preparing spherical mesoporous molecular screen material, which comprises
(a) under solution condition, template, nonionic surfactant, sour agent and industrial metasilicate is subjected to mixing and connect
Touching is to obtain solution A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is poly-
Ethylene glycol octyl phenyl ether；
(b) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(c) mesoporous material raw powder is subjected to Template removal processing, obtains spherical mesoporous molecular screen material.
The solution condition of the invention can be aqueous conditions.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, for example, can be salt
At least one of acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution, preferably aqueous hydrochloric acid solution.
There is no particular limitation for the dosage of the acid agent, can change in a big way, it is preferable that the mixing connects
The pH value of touching is 1-7.
Under preferable case, in step (a), the condition being mixed includes: that temperature is 25-60 DEG C, and the time is
0.1-48h.In order to be more advantageous to the uniform mixing between each substance, a kind of preferred embodiment according to the present invention, the mixing
Contact carries out under agitation.
In the present invention, the dosage of the template, nonionic surfactant and industrial metasilicate can be in larger model
Interior variation is enclosed, such as the molar ratio of the template, the nonionic surfactant and the industrial metasilicate dosage is
0.1-0.6:0.1-0.5:1；It is highly preferred that institute's template, the nonionic surfactant and the industrial metasilicate dosage
Molar ratio be 0.1-0.3:0.1-0.3:1.
In the present invention, the industrial metasilicate refers to the work with standard No. for parameter specified in GB/T 4209-2008
Industry sodium metasilicate.
Preferably, in step (b), the condition of the crystallization includes: that temperature is 90-180 DEG C, time 4-40h.According to
A kind of preferred embodiment, the crystallization are implemented by hydrothermal crystallization method.
Preferably, in step (c), the process of the washing may include: after filtration, to be washed repeatedly with deionized water
(washing times can be 2-10) is washed, is then filtered.
Preferably, in step (d), the mode of the drying is spray drying, and the spray drying can be according to routine
Mode implement, can be selected from least one in pressure spray dryer method, the gentle flow type spray seasoning of centrifugal spray drying method
Kind.A kind of preferred embodiment according to the present invention, the spray drying use centrifugal spray drying method.The spray drying can
To be carried out in atomizer.The condition of the spray drying may include: that temperature is 150-600 DEG C, revolving speed 10000-
15000r/min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is
11000-13000r/min。
Preferably, in step (c), the method for the removed template method is calcination method, the mistake of the Template removal processing
Journey includes: that the mesoporous material raw powder is calcined 5-40h at 300-800 DEG C.
Of the invention additionally provides the spherical mesoporous molecular screen material prepared by the above method.
It according to the present invention, is 0.5-1.5mL/g by the pore volume of the spherical mesoporous molecular screen material of above method preparation, than
Surface area is 1000-1500m2/ g, most probable pore size 1-2.5nm, average grain diameter are 1-20 μm.
According to the present invention, the average grain diameter of the spherical mesoporous molecular screen material is measured using laser fineness gage, than
Surface area, pore volume and average pore size are measured according to nitrogen adsorption methods.In the present invention, partial size refers to the particle ruler of feed particles
Very little, when feed particles are sphere, the diameter of then granularity sphere is indicated, when feed particles are cube then granularity with cube
The side length of body indicates that then granularity uses just the sieve that can screen out the feed particles when feed particles are irregular shape
Mesh size indicate.
According to the present invention, it by controlling the dosage of each reaction raw materials and the control of contact conditions, can use common easy
Raw material, synthesize in easy operating condition that specific surface area is larger, the biggish spherical mesoporous molecular sieve of pore volume in next step
Material, and by the structural parameter control of the spherical mesoporous molecular screen material within above range, it can be ensured that it is described spherical
Meso-porous molecular sieve material is not susceptible to reunite, and is used as loaded catalyst made of carrier and dehydrogenating propane can be improved
Reaction raw materials conversion ratio in propylene reaction process processed.When the specific surface area of the spherical mesoporous molecular screen material is less than
1000m2When/g and/or pore volume are less than 0.5mL/g, the catalytic activity for being used as loaded catalyst made of carrier can be shown
Writing reduces；When the specific surface area of the spherical mesoporous molecular screen material is greater than 1500m2/ g and/or pore volume are greater than 1.5mL/g
When, it is used as loaded catalyst made of carrier and is easy to happen reunion in catalytic process, to influence catalysis reaction
Feed stock conversion.
Under preferable case, the pore volume of the spherical mesoporous molecular screen material is 0.5-0.8mL/g, and specific surface area is
1200-1400m2/ g, average pore size 1.5-2nm, partial size are 4-15 μm.
Spherical mesoporous molecular screen material provided by the invention has the specific surface area of superelevation, while also having spherical geometry
The larger advantage of feature, stable structure, pore volume facilitates the degree of scatter for improving the metal component in catalyst, to make
The carrier that the spherical mesoporous molecular screen material is particularly suitable for application as loaded catalyst is obtained, the loaded catalyst of formation exists
There is more excellent catalytic performance, and the beneficial effect high thus to obtain feed stock conversion height and selectivity of product in catalysis reaction
Fruit.
A kind of Pt group the present invention also provides catalyst, in the catalyst containing carrier and load on the carrier
Divide, Sn component and Na component, the carrier are spherical mesoporous molecular screen material above-mentioned.
According to the present invention, in the catalyst, the Pt group is divided into active metal component, the Sn component and Na component
The strong acid center of carrier surface can be effectively neutralized, is improved when three's cooperation loads on the carrier for metal promoter
The dispersion degree of active metal component Pt, to improve the selectivity and reaction stability of catalyst.
According to the present invention, on the basis of the total weight of the catalyst, the content of the carrier is 97.5-99.3 weight
% is measured, content of the Pt component in terms of Pt element is 0.2-0.5 weight %, and content of the Sn component in terms of Sn element is
0.2-1.2 weight %, content of the Na component in terms of Na element are 0.3-0.8 weight %.
The present invention also provides a kind of method for preparing aforementioned catalytic agent, this method includes；It is living that carrier is successively carried out to heat
Change processing, impregnation, the processing of removal solvent, dry and roasting, make the supported on carriers Pt component, Sn component and Na group
Point, wherein the carrier is spherical mesoporous molecular screen material provided by the invention.
According to the present invention, in order to remove the hydroxyl and Residual water of the spherical mesoporous molecular screen material, described spherical
It needs to carry out thermal activation treatment before meso-porous molecular sieve material carried metal component, the condition of the thermal activation treatment may include:
In the presence of nitrogen, by carrier temperature be 300-900 DEG C at carry out calcining 7-10h.
According to the present invention, the spherical mesoporous molecular screen material carried metal component can be relied on by the way of dipping
The capillary pressure of the cellular structure of the spherical mesoporous molecular screen material makes metal component enter spherical Jie as carrier
In the duct of porous molecular sieve material, at the same metal component can also the spherical mesoporous molecular screen material again adsorption, until
Metal component reaches adsorption equilibrium on the surface of the spherical mesoporous molecular screen material.Preferably, the impregnation is described
Spherical mesoporous molecular screen material carry out after thermal activation treatment, and the impregnation can be handled for co-impregnation, can also be with
For step impregnation processing.In order to save preparation cost, simplify experimental technique, the impregnation is preferably co-impregnation processing；Into
Preferably, the condition of the co-impregnation processing includes: that the spherical mesoporous molecular screen material after thermal activation is being contained Pt group to one step
The solution of presoma, Sn component presoma and Na component presoma is divided to be mixed, the temperature of the dipping can be 25-
50 DEG C, the time of the dipping can be 2-6h.
According to the present invention, the solution of the Pt component presoma, Sn component presoma and Na component presoma is not special
Restriction as long as water-soluble can be the conventional selection of this field.For example, the Pt component presoma can be
H2PtCl6, the Sn component presoma can be SnCl4, the Na component presoma can be NaNO3。
The present invention does not have the concentration of the solution containing Pt component presoma, Sn component presoma and Na component presoma
There is special restriction, can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.1-
The concentration of 0.3mol/L, the Sn component presoma can be 0.15-1mol/L, and the concentration of the Na component presoma can be
1-3.5mol/L。
According to the present invention, the dosage of the Pt component presoma, Sn component presoma and Na component presoma to prepare
In obtained propane dehydrogenation catalyst, on the basis of the total weight of the propane dehydrogenation catalyst, the spherical mesoporous molecular sieve
The content of material support 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
It is 0.3-0.8 weight % that content in terms of Sn element, which is content of 0.2-1.2 weight %, the Na component in terms of Na element,.
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.
The present invention also provides a kind of catalyst prepared by preceding method.
The present invention also provides a kind of application of aforementioned catalytic agent in catalysis dehydrogenating propane.
When being used for catalyst provided by the invention to be catalyzed dehydrogenating propane, the choosing of the conversion ratio and propylene of propane is enabled to
Selecting property is improved largely.
The present invention also provides a kind of methods of preparing propylene by dehydrogenating propane, this method comprises: in the presence of catalyst and hydrogen
Under, propane is subjected to dehydrogenation reaction, wherein the catalyst is catalyst provided by the invention or method provided by the present invention
The catalyst of preparation.
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, Triton X-100 is purchased from Beijing Bellingwell company, trade name
Triton x-100, molecular formula C34H62O11；
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 carrier
By the poly- of 1.5g (0.004mol) template CTAB (cetyl trimethylammonium bromide) and 1.5ml (0.002mol)
Ethylene glycol octyl phenyl ether (Bio-Rad-Laboratories) is added to the solution of the hydrochloric acid (29.6g) containing 37 weight % and water (75g)
In, it is completely dissolved in 40 DEG C of stirrings to CTAB；4.6g industrial metasilicate is added in above-mentioned solution again later, is stirred at 40 DEG C
Mix 15 minutes, then obtained solution be transferred in the reaction kettle of polytetrafluoroethyllining lining, at 120 DEG C crystallization for 24 hours, then
Be filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；It will be described mesoporous
Material original powder is calcined for 24 hours at 600 DEG C, removed template method, obtains spherical mesoporous molecular screen material C1.
(2) preparation of propane dehydrogenation catalyst
The 30g spherical mesoporous molecular screen material C1 that step (1) is obtained calcines 10h at 400 DEG C under the protection of nitrogen
Thermal activation treatment is carried out, the hydroxyl and Residual water of spherical mesoporous molecular screen material C1 are removed；
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 mesoporous molecular screen material C1 by thermal activation treatment is immersed in the mixture
In solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 120 DEG C, dry 3h, and being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, obtain third
Alkane dehydrogenation Cat-1 (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, 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).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to spherical mesoporous molecular screen material C1 and
Propane dehydrogenation catalyst Cat-1 is characterized；
Fig. 1 is the x-ray diffraction pattern of spherical mesoporous molecular screen material C1, wherein abscissa is 2 θ, and ordinate is intensity,
By XRD spectra, it is apparent that spherical mesoporous molecular screen material C1 3 diffraction maximums occurs in small angular region, illustrate spherical mesoporous
Molecular screen material C1 has good mesoporous phase structure, this (Xuelei consistent with mesoporous material XRD spectra reported in the literature
Pang, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1~6)；
Fig. 2 is nitrogen adsorption-desorption curve figure of spherical mesoporous molecular screen material C1, wherein abscissa is relative pressure,
Unit is p/p0, nitrogen adsorption-desorption isotherm shows that spherical mesoporous molecular sieve C1 is that the Section IV class that defines of typical IUPAC is inhaled
Attached-desorption isotherm, the specific surface area with superelevation, it was demonstrated that spherical mesoporous molecular screen material C1 has reported in the literature peculiar
Cube cage structure meso-hole structure (Xuelei Pang, Fangqiong Tang, Microporous and
Mesoporous Materials, 2005 (85): 1~6；Chengzhong Yu,Bozhi Tian,Jie Fan,Galen
D.Stucky, Dongyuan Zhao, J.Am.Chem.Soc.2002,124,4556-4557)；
Fig. 3 is the graph of pore diameter distribution of spherical mesoporous molecular screen material C1, wherein abscissa is aperture, unit nm, described
Graph of pore diameter distribution shows that the spherical mesoporous molecular screen material C1 has narrow pore-size distribution, and duct is highly uniform；
Fig. 4 is the SEM stereoscan photograph of the microscopic appearance of spherical mesoporous molecular screen material C1, this illustrates spherical Jie
The microscopic appearance of porous molecular sieve material C 1 is the microballoon that partial size is 1-20 μm, and monodispersity is preferable.
Fig. 5 is the TEM transmission electron microscope photo of the microscopic appearance of spherical mesoporous molecular screen material C1, transmits electricity from the TEM
Spherical mesoporous molecular screen material C1 sample is clearly visible in mirror photo with relatively regular pore-size distribution, this and XRD above-mentioned
The conclusion that diffracting spectrum obtains is consistent.
Table 1 is the pore structure parameter of spherical mesoporous molecular screen material C1 and propane dehydrogenation catalyst Cat-1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Partial size (μm) |
| Meso-porous molecular sieve material C1 | 1345 | 0.6 | 1.8 | 8 |
| Catalyst Cat-1 | 1180 | 0.5 | 1.1 | 8 |
As the spherical mesoporous molecular screen material C1 of carrier in load chief active Pt group it can be seen from the data of table 1
Divide, after auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is in load-reaction process
Middle chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical mesoporous molecular screen 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
Analytically pure ethyl orthosilicate is used to substitute the industrial metasilicate as silicon source, so that carrier D1 and dehydrogenating propane be made respectively
Catalyst Cat-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
Commercially available ES955 silica gel (GRACE company) is used to substitute the spherical mesoporous molecular screen material C1 as carrier D2, thus respectively
Carrier D2 and propane dehydrogenation catalyst Cat-D-2 is made.
Comparative example 3
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, the difference is that preparing dehydrogenating propane type
In the dipping process of catalyst, NaNO is not added3, 0.133g H is only added2PtCl6·6H2O and 0.295g SnCl4·5H2O,
Only active component Pt and metal promoter Sn are supported on the sphericity mesoporous silicon dioxide as carrier by co-impregnation, thus
Propane dehydrogenation catalyst Cat-D-3 is made, on the basis of the total weight of propane dehydrogenation catalyst Cat-D-3, Pt component is with Pt member
It is 1 weight % that the content of element meter, which is content of 0.5 weight %, the Sn component in terms of Sn element, remaining is carrier).
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
By the poly- of 0.75g (0.002mol) template CTAB (cetyl trimethylammonium bromide) and 3ml (0.004mol)
Ethylene glycol octyl phenyl ether (Bio-Rad-Laboratories) is added to the solution of the hydrochloric acid (29.6g) containing 37 weight % and water (75g)
In, it is completely dissolved in 40 DEG C of stirrings to CTAB；4.35g industrial metasilicate is added in above-mentioned solution again later, at 40 DEG C
Obtained solution, is then transferred in the reaction kettle of polytetrafluoroethyllining lining, crystallization for 24 hours, connects at 100 DEG C by stirring 15 minutes
Be filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；It will be given an account of
Porous materials original powder is calcined for 24 hours at 600 DEG C, removed template method, obtains spherical mesoporous molecular screen material C2.
(2) preparation of propane dehydrogenation catalyst
The 30g spherical mesoporous molecular screen material C2 that step (1) is obtained calcines 10h at 400 DEG C under the protection of nitrogen
Thermal activation treatment is carried out, the hydroxyl and Residual water of spherical mesoporous molecular screen material C2 are removed；
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 mesoporous molecular screen material C2 by thermal activation treatment is immersed in the mixture
In solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 120 DEG C, dry 3h, and being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, obtain third
Alkane dehydrogenation Cat-2 (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, 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 2 is the pore structure parameter of spherical mesoporous molecular screen material C2 and propane dehydrogenation catalyst Cat-2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Partial size (μm) |
| Meso-porous molecular sieve material C2 | 1300 | 0.7 | 2 | 10 |
| Catalyst Cat-2 | 1075 | 0.5 | 1.4 | 10 |
As the spherical mesoporous molecular screen material C2 of carrier in load chief active Pt group it can be seen from the data of table 2
Divide, after auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is in load-reaction process
Middle chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical mesoporous molecular screen material C2.
Embodiment 3
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
By the poly- second of 1.5g (0.004mol) template CTAB (cetyl trimethylammonium bromide) and 3ml (0.004mol)
Glycol octyl phenyl ether (Bio-Rad-Laboratories) is added in the solution of the hydrochloric acid (29.6g) containing 37 weight % and water (75g),
It is completely dissolved in 40 DEG C of stirrings to CTAB；4.35g industrial metasilicate is added in above-mentioned solution again later, is stirred at 40 DEG C
15 minutes, then obtained solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, at 110 DEG C crystallization for 24 hours, then into
Row filtering and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw powder；By the mesoporous material
Material original powder is calcined for 24 hours at 600 DEG C, and removed template method obtains spherical mesoporous molecular screen material C3.
(2) preparation of propane dehydrogenation catalyst
The 30g spherical mesoporous molecular screen material C3 that step (1) is obtained calcines 10h at 400 DEG C under the protection of nitrogen
Thermal activation treatment is carried out, the hydroxyl and Residual water of spherical mesoporous molecular screen material C3 are removed；
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 mesoporous molecular screen material C2 by thermal activation treatment is immersed in the mixture
In solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 120 DEG C, dry 3h, and being subsequently placed in temperature is to roast 6h in 600 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 mesoporous molecular screen material C3 and propane dehydrogenation catalyst Cat-3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Partial size (μm) |
| Meso-porous molecular sieve material C3 | 1310 | 1 | 1.9 | 8.5 |
| Catalyst Cat-3 | 1105 | 0.7 | 1.3 | 8.5 |
As the spherical mesoporous molecular screen material C3 of carrier in load chief active Pt group it can be seen from the data of table 3
Divide, after auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is in load-reaction process
Middle chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical mesoporous molecular screen material C3.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the method for illustrating to prepare propylene using propane dehydrogenation catalyst of the invention
0.5g propane dehydrogenation catalyst Cat-1 is fitted into fixed-bed quartz reactor, control reaction temperature is 610 DEG C,
Reaction pressure is 0.1MPa, and propane: the molar ratio of hydrogen is 1:1, and reaction time 50h, propane mass space velocity is 3h-1.Propane
Conversion ratio and Propylene Selectivity are as shown in table 4.
EXPERIMENTAL EXAMPLE 2-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-2 and propane dehydrogenation catalyst Cat-3 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are such as
Shown in table 4.
Experimental comparison's example 1-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-D-1, propane dehydrogenation catalyst Cat-D-2 and propane dehydrogenation catalyst Cat-D-3, instead of propane dehydrogenation catalyst Cat-
1.Conversion of propane and Propylene Selectivity are as shown in table 4.
Table 4
| Dehydrogenation | Conversion of propane | Propylene Selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 34% | 90% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 33.7% | 88.7% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 33.5% | 89.3% |
| Experimental comparison's example 1 | Cat-D-1 | 18.2% | 20.5% |
| Experimental comparison's example 2 | Cat-D-2 | 19.2% | 21.4% |
| Experimental comparison's example 3 | Cat-D-3 | 16.8% | 35.4% |
From table 4, it can be seen that being used for third using propane dehydrogenation catalyst prepared by sphericity mesoporous silicon dioxide of the invention
When alkane dehydrogenation producing propylene reacts, after reacting 50h, still available higher conversion of propane and Propylene Selectivity illustrate this
The propane dehydrogenation catalyst of invention not only has preferable catalytic performance, but also has excellent stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of method for preparing spherical mesoporous molecular screen material, which is characterized in that the described method includes:
(a) under solution condition, by template, nonionic surfactant, sour agent and industrial metasilicate be mixed with
Obtain solution A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is poly- second two
Alcohol octyl phenyl ether；
(b) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(c) mesoporous material raw powder is subjected to Template removal processing, obtains spherical mesoporous molecular screen material.
2. according to the method described in claim 1, wherein, in step (a), the condition being mixed includes: that temperature is
25-60 DEG C, time 0.1-48h；
Preferably, the molar ratio of the template, the nonionic surfactant and the industrial metasilicate dosage is 0.1-
0.6:0.1-0.5:1；
Preferably, in step (b), the condition of the crystallization includes: that temperature is 90-180 DEG C, time 4-40h；
Preferably, in step (c), the process of the Template removal processing includes: at 300-800 DEG C, by the mesoporous material
Expect that original powder calcines 5-40h.
3. the spherical mesoporous molecular screen material prepared by method of any of claims 1 or 2.
4. spherical mesoporous molecular screen material according to claim 3, wherein the hole body of the spherical mesoporous molecular screen material
Product is 0.5-1.5mL/g, specific surface area 1000-1500m2/ g, most probable pore size 1-2.5nm, average grain diameter are 1-20 μm.
5. spherical mesoporous molecular screen material according to claim 4, wherein the hole body of the spherical mesoporous molecular screen material
Product is 0.5-0.8mL/g, specific surface area 1200-1400m2/ g, average pore size 1.5-2nm, partial size are 4-15 μm.
6. a kind of catalyst, Pt component, Sn component and Na component in the catalyst containing carrier and load on the carrier,
It is characterized in that, the carrier is spherical mesoporous molecular screen material described in any one of claim 3-5.
7. catalyst according to claim 6, wherein on the basis of the total weight of the catalyst, the carrier contains
Amount is 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %, and the Sn component is with Sn
The content of element meter is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8 weight %.
8. a kind of method for preparing catalyst described in claim 6 or 7, this method comprises: carrier is successively carried out thermal activation
Processing, impregnation, the processing of removal solvent, dry and roasting, make the supported on carriers Pt component, Sn component and Na component,
It is characterized in that, the carrier is spherical mesoporous molecular screen material described in any one of claim 3-5.
9. the catalyst prepared by method according to any one of claims 8.
10. application of the catalyst described in any one of claim 6,7 and 9 in catalysis dehydrogenating propane.
11. a kind of method of preparing propylene by dehydrogenating propane, this method comprises: carrying out propane in the presence of catalyst and hydrogen
Dehydrogenation reaction, which is characterized in that the catalyst is catalyst described in any one of claim 6,7 and 9.
12. according to the method for claim 11, 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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| CN112221491A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with modified spherical mesoporous material as carrier and preparation method and application thereof |
| CN112221492A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst with Mg and/or Ti modified spherical mesoporous material as carrier and preparation method and application thereof |
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