CN109746028A - 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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- CN109746028A CN109746028A CN201711068972.4A CN201711068972A CN109746028A CN 109746028 A CN109746028 A CN 109746028A CN 201711068972 A CN201711068972 A CN 201711068972A CN 109746028 A CN109746028 A CN 109746028A
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Abstract
The present invention relates to catalyst field, the method for a kind of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane is disclosed.The propane dehydrogenation catalyst includes Pt component, Sn component and the Na component of carrier and load on the carrier, wherein, the carrier is the spherical material silica gel composite of mesopore molecular sieve containing aluminium, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contains aluminium component, meso-porous molecular sieve material and silica gel with three-dimensional cubic duct structure, the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average grain diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture is in bimodal distribution, and the bimodal corresponding most probable pore size is respectively 4-8nm and 30-40nm.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, resists poisoning strong.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of propane dehydrogenation catalyst and preparation method thereof and third
The method of alkane dehydrogenation producing propylene.
Background technique
Propylene is the base stock of petrochemical industry, mainly for the production of polypropylene, acrylonitrile, acetone, propylene oxide, propylene
Acid and octyl alconyl etc..The supply half of propylene comes from refinery's by-product, separately has about 45% to come from steam cracking, a small amount of other substitution skills
Art.In recent years, the demand of propylene increases year by year, and traditional production of propylene has been unable to meet demand of the chemical industry to propylene,
Therefore propylene enhancing becomes a big hot spot of research.Wherein, preparing propylene by dehydrogenating propane is a major technique of propylene volume increase.10
For many years, preparing propylene by dehydrogenating propane has become the important process process of industrialization production of propylene.The major catalytic of dehydrogenating propane
Agent has in chromium oxide/aluminum oxide catalyst and Uop Inc.'s Oleflex technique in ABB Lummus company CYLofin technique
Platinum tin/aluminium oxide catalyst.Requirement of the chromium-based catalysts to raw material impurity is relatively low, on the low side compared with noble metal；But this
Class catalyst is easy carbon distribution inactivation, will regenerate every 15-30 minutes once, and since the chromium in catalyst is heavy metal,
Environmental pollution is serious.Platinum-tin catalyst activity is high, and selectivity is good, can reach reaction time several days, can bear more harsh
Process conditions, and to more environment-friendly；But since noble metal platinum is expensive, lead to catalyst higher cost.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst is not still high there is conversion of propane and is easy to the defects of inactivating, and requires further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.In order to improve the reactivity worth of propane dehydrogenation catalyst, people is studied
Member has done many work.Such as: traditional γ-Al2O3 carrier is substituted using molecular sieve carrier, effect preferably includes MFI
Type micro porous molecular sieve (CN104307555A, CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41
Molecular sieve (CN102389831A) and mesoporous SBA-15 molecular sieve (CN101972664A, CN101972664B) etc..However at present
Common mesoporous material aperture is smaller (6~9nm of average pore size), if carrying out bulky molecular catalysis reaction, macromolecular is more difficult to get access
Duct, so that influencing catalytic effect.Therefore, it selects a kind of excellent carrier to be that one, dehydrogenating propane field is urgently to be resolved to ask
Topic.
Summary of the invention
Propane dehydrogenation catalyst in the prior art is usually with Pt for main metal active constituent, with γ-Al2O3For carrier,
The active component poor dispersion of the catalyst, catalytic activity and the poor defect of stability.It is existing the purpose of the present invention is overcoming
Technical agency's pore structure is unstable, further result in conversion of propane and Propylene Selectivity it is not high and be easy to the defects of inactivating lack
It falls into, the method for a kind of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane is provided.
To achieve the goals above, one aspect of the present invention provides a kind of propane dehydrogenation catalyst, the dehydrogenating propane catalysis
Agent includes Pt component, Sn component and the Na component of carrier and load on the carrier, wherein the carrier is spherical containing aluminium
Mesopore molecular sieve material silica gel composite, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, have three-dimensional
The meso-porous molecular sieve material and silica gel of cube cellular structure, the pressure resistance of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium
Degree is 12-16MPa, and average grain diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture is in
Bimodal distribution, and the bimodal corresponding most probable pore size is respectively 4-8nm and 30-40nm.
Second aspect of the present invention provides a kind of method for preparing above-mentioned propane dehydrogenation catalyst, this method comprises: by carrier
It is carried out at dipping in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma after thermal activation
Then reason is successively removed solvent processing, dry and roasting, wherein the carrier is the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, with three-dimensional cubic duct structure
The compression strength of meso-porous molecular sieve material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa,
Average grain diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture are in bimodal distribution, and institute
Stating bimodal corresponding most probable pore size is respectively 4-8nm and 30-40nm.
Third aspect present invention provides a kind of propane dehydrogenation catalyst prepared by the above method.
Fourth aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, which comprises in catalyst and hydrogen
In the presence of gas, propane is subjected to dehydrogenation reaction, wherein the catalyst be propane dehydrogenation catalyst provided by the invention or by
The propane dehydrogenation catalyst that method provided by the invention is prepared.
The carrier of propane dehydrogenation catalyst according to the present invention is the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
Combine the regular mesoporous spatial character and ball of mesopore molecular sieve with three-dimensional cubic duct distributed architecture, silica gel
The pattern advantage of shape not only remains the high-specific surface area of ordered mesoporous material, the characteristics of macropore holds, also add aperture it is big and
The advantage of narrowly distributing, and unique bimodal distribution is presented in its pore-size distribution, dexterously has micro-sphere structure with aperture bimodal
The advantages of ordered mesoporous material of distribution, combines, more conducively the load of active component.In addition, aluminium component is in mechanical milling process
The compression strength increase so that the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is introduced, sphere can be effectively prevent negative
Being crushed when carrying active component, improves the stability of the carrier, extends the service life of catalyst.Therefore, the spherical shape contains
Aluminium mesopore molecular sieve material silica gel composite is suitable as the carrier of loaded catalyst, be especially suitable in dehydrogenating propane system third
The carrier of loaded catalyst used in alkene reaction.
In the propane dehydrogenation catalyst of the invention, the spherical material silica gel composite of mesopore molecular sieve containing aluminium is used
As carrier, load has Pt component, Sn component and Na component, so that the loaded catalyst had both had the excellent of loaded catalyst
Point such as catalytic activity is high, side reaction is few, post-processing is simple, and has stronger catalytic activity, so that the loaded catalyst
There is better dehydrogenation activity and selectivity in for dehydrogenating propane reaction, significantly improve the conversion ratio of reaction raw materials, specifically
Ground, in the reaction that preparing propylene by dehydrogenating propane is carried out using the loaded catalyst, conversion of propane is up to 30%, the selection of propylene
Property is up to 82.4%.
In addition, the step impregnation method that the present invention is conventional using co-impregnation method substitution, preparation process is simple, and condition is easy to
Control, good repetitiveness.
Also, when the method by spray drying prepares the propane dehydrogenation catalyst, the propane dehydrogenation catalyst
It may be repeated utilization, and still can obtain higher reaction raw materials conversion ratio during recycling.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is X-ray diffraction (XRD) spectrogram of the spherical material silica gel composite of mesopore molecular sieve containing aluminium of embodiment 1；
Fig. 2 is the SEM scanning electron microscope of the microscopic appearance of the spherical material silica gel composite of mesopore molecular sieve containing aluminium of embodiment 1
Figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of propane dehydrogenation catalyst, the propane dehydrogenation catalyst includes carrier and is supported on institute
State Pt component, Sn component and the Na component on carrier, wherein the carrier is the spherical silica gel composite wood of mesopore molecular sieve containing aluminium
Material, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, mesoporous point with three-dimensional cubic duct structure
The compression strength of son sieve material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average grain
Diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture are in bimodal distribution, and described bimodal
Corresponding most probable pore size is respectively 4-8nm and 30-40nm.
According to the present invention, the carrier have special three-dimensional cubic duct distributed architecture, broken one-dimensional channels for
The limitation of molecular transport, the carrier combine the cellular structure of special three-dimensional cubic ordered mesoporous pore canals distributed architecture and silica gel
Be conducive to fine dispersion of the metal component inside its duct.In addition, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium
The aluminium component contained, so that the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium significantly increases, Neng Gouyou
Effect prevents sphere broken in load active component, improves the stability of the carrier.Using described spherical containing mesoporous point of aluminium
As carrier, the loaded catalyst that supporting Pt component, Sn component and Na component obtain both had had negative son sieve material silica gel composite
The advantages of supported catalyst such as catalytic activity it is high, side reaction is few, post-processing is simple, and with stronger catalytic activity and higher
Stability so that the loaded catalyst for dehydrogenating propane reaction in have better dehydrogenation activity and selectivity, show
Write the conversion ratio for improving reaction raw materials.
According to the present invention, the average grain diameter of the particle of the carrier is measured using laser fineness gage, specific surface area, hole
Volume and most probable pore size are measured according to nitrogen adsorption methods.
According to the present invention, by by the structural parameter control of the spherical material silica gel composite of mesopore molecular sieve containing aluminium upper
Within the scope of stating, it can be ensured that the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is not susceptible to reunite, and is used
Making loaded catalyst made of carrier can be improved reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.Work as institute
The specific surface area for stating the spherical material silica gel composite of mesopore molecular sieve containing aluminium is less than 100m2/ g and/or pore volume are less than 0.5mL/g
When, the catalytic activity for being used as loaded catalyst made of carrier can significantly reduce；When the spherical mesoporous molecular containing aluminium
The specific surface area for sieving material silica gel composite is greater than 180m2When/g and/or pore volume are greater than 2mL/g, it is used as made of carrier
Loaded catalyst is easy to happen reunion in preparing propylene by dehydrogenating propane reaction process, to influence preparing propylene by dehydrogenating propane reaction
Reaction raw materials conversion ratio in the process.
Under preferable case, the compression strength of the carrier is 14-16MPa, and average grain diameter is 30-60 μm, and specific surface area is
100-170m2/ g, pore volume 0.8-1.8mL/g, the corresponding most probable pore size of bimodal distribution is respectively 4-8nm and 32-39nm.
According to the present invention, the propane dehydrogenation catalyst includes carrier and load Pt component on the carrier, Sn
Component and Na component, wherein the Pt group is divided into active metal component, and the Sn component and Na group are divided into metal promoter.
According to the present invention, relative to the propane dehydrogenation catalyst of 100 parts by weight, the content of the carrier is 97.5-
99.3 weight %, content of the Pt component in terms of Pt element are 0.2-0.5 weight %, Sn component the containing in terms of Sn element
Amount is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8 weight %.
Preferably, the compression strength of the propane dehydrogenation catalyst is 14-16MPa, and average particle diameter is 30-60 μm,
Specific surface area is 80-150m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution are bimodal distribution, and described bimodal corresponding
Most probable pore size is respectively 4-8nm and 32-39nm.
According to the present invention, the increase of aluminium constituent content is conducive to improve the compression strength of the carrier, the mesoporous molecular
The cellular structure of the adjustable carrier of content of material and silica gel is sieved, in order to make the carrier have both higher compression strength
Preferably cellular structure parameter, in the spherical material silica gel composite of mesopore molecular sieve containing aluminium, relative to 100 parts by weight
The meso-porous molecular sieve material with three-dimensional cubic duct structure, the content of the aluminium component are 1-20 parts by weight, preferably
5-19 parts by weight, the content of the silica gel are 1-90 parts by weight, preferably 2-85 parts by weight.
The present invention also provides a kind of methods for preparing propane dehydrogenation catalyst, this method comprises: by after carrier thermal activation
Carry out impregnation in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma, then according to
It is secondary to be removed solvent processing, dry and roasting, wherein the carrier is the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
The spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contains containing aluminium component, mesoporous point with three-dimensional cubic duct structure
The compression strength of son sieve material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, average grain
Diameter is 10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture are in bimodal distribution, and described bimodal
Corresponding most probable pore size is respectively 4-8nm and 30-40nm.
According to the present invention, in order to remove the hydroxyl and remaining water of the spherical material silica gel composite of mesopore molecular sieve containing aluminium
Point, firstly the need of progress thermal activation treatment before the spherical material silica gel composite carried metal component of mesopore molecular sieve containing aluminium,
The condition of the thermal activation treatment may include: in the presence of nitrogen, to calcine at being 300-900 DEG C in temperature by carrier
7-10h。
According to the present invention, the spherical material silica gel composite carried metal of mesopore molecular sieve containing the aluminium component can be using dipping
Mode, by the capillary pressure of the cellular structure of the spherical material silica gel composite of mesopore molecular sieve containing aluminium make metal component into
In the duct for entering the spherical material silica gel composite of mesopore molecular sieve containing aluminium, while metal component can also be described spherical containing aluminium Jie
The adsorption of porous molecular sieve material silica gel composite, until metal component is in the spherical silica gel composite wood of mesopore molecular sieve containing aluminium
The surface of material reaches adsorption equilibrium.Preferably, the impregnation is in the spherical material silica gel composite of mesopore molecular sieve containing aluminium
Carry out after thermal activation treatment, the impregnation can be handled for co-impregnation, or step impregnation processing.In order to
Preparation cost is saved, experimental technique is simplified, the impregnation is preferably co-impregnation processing；It is further preferred that the total immersion
The condition of stain processing includes: that spherical shape mesopore molecular sieve containing the aluminium material silica gel composite after thermal activation is being contained Pt component forerunner
The solution of body, Sn component presoma and Na component presoma is mixed, and the temperature of the dipping can be 25-50 DEG C,
The time of the dipping can be 2-6h.
According to the present invention, the solution of the Pt component presoma, Sn component presoma and Na component presoma is not special
Restriction as long as water-soluble can be the conventional selection of this field.For example, the Pt component presoma can be
H2PtCl6, the Sn component presoma can be SnCl4, the Na component presoma can be NaNO3。
The present invention does not have the concentration of the solution containing Pt component presoma, Sn component presoma and Na component presoma
There is special restriction, can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.1-
The concentration of 0.3mol/L, the Sn component presoma can be 0.15-1mol/L, and the concentration of the Na component presoma can be
1-3.5mol/L。
According to the present invention, the dosage of the carrier, Pt component presoma, Sn component presoma and Na component presoma can be with
In propane dehydrogenation catalyst to make preparation, on the basis of the total weight of the propane dehydrogenation catalyst, the carrier contains
It is 0.2-0.5 weight %, Sn component in terms of Sn element that amount, which is content of 97.5-99.3 weight %, the Pt component in terms of Pt element,
Content is that content of 0.2-1.2 weight %, the Na component in terms of Na element is 0.3-0.8 weight %.
According to the present invention, the process of the removal solvent processing can adopt with the conventional methods in the field, such as can adopt
With the solvent in Rotary Evaporators removal system.
According to the present invention, the drying can carry out in drying box, and the roasting can carry out in Muffle furnace.This hair
Also there is no particular limitation for the bright condition to the drying and roasting, can be the conventional selection of this field, for example, the drying
Condition may include: temperature be 110-150 DEG C, time 3-6h；The condition of the roasting may include: that temperature is 600-
650 DEG C, time 5-8h.
According to the present invention, the carrier forming method the following steps are included:
(a) in the presence of template and butanol, mixture that silicon source is contacted with sour agent, and will obtained after contact
Crystallization and filtering are successively carried out, mesopore molecular sieve filter cake is obtained；
(b) waterglass is contacted with inorganic acid and n-butanol, and the mixture obtained after contact is filtered, obtained
To silica gel filter cake；
(c) the spherical double mesopore molecular sieve filter cake and silica gel filter cake are mixed and are carried out in high alumina ceramic tank ball milling,
And the solid powder water slurrying that will be obtained after ball milling, then obtained slurry is spray-dried, then the product that will be obtained
In the template removal.
In the forming process of above-mentioned carrier, the mesopore molecular sieve filter cake is with three-dimensional cubic duct distributed architecture
Mesopore molecular sieve filter cake.
In the forming process of above-mentioned carrier, it is main by the composition of control mesopore molecular sieve filter cake and silica gel filter cake by institute
The pore-size distribution control for stating carrier is bimodal distribution, makes the spherical material silica gel composite of mesopore molecular sieve containing aluminium with diplopore point
Cloth structure, and by control forming method, first mesopore molecular sieve filter cake and silica gel filter cake are mixed and in high alumina ceramic tank
Ball milling is carried out, then will be spray-dried after the water slurrying of obtained solid powder, by the spherical silica gel of mesopore molecular sieve containing aluminium
The microscopic appearance control of composite material is spherical shape and the spherical material silica gel composite of mesopore molecular sieve containing aluminium is made to introduce aluminium component.
According to the present invention, in step (a), prepare the mesopore molecular sieve filter cake process may include: by template,
Butanol, sour agent and silicon source are mixed, and obtained mixture is carried out crystallization and filtering.The sequence being mixed
There is no particular limitation, template, butanol, sour agent and silicon source can be mixed simultaneously, can also be by any two kinds or three
Kind mixing adds other components and is uniformly mixed.According to a kind of preferred embodiment, first template, butanol and sour agent are mixed
It closes uniformly, then adds silicon source and be uniformly mixed.The way of contact is first to mix the template, butanol and acidic aqueous solution
It closes uniformly, and obtained mixture is placed in 30-45 DEG C of water-bath, then keep temperature-resistant, then silicon source is slowly added dropwise
Into said mixture, and it is stirred to react 20-40 hours.On the basis of the template of 1g, the drop rate of the silicon source can be with
For 0.1-1g/min.
According to the present invention, during preparing mesopore molecular sieve filter cake, the dosage of each substance can be in wider range
It is inside selected and is adjusted.For example, the molar ratio of the template, butanol and silicon source can be 1:10-100:10-90, preferably
For 1:60-90:50-75, it is more selected as 1:75-85:50-70.
According to the present invention, described in order to enable the mesoporous sieving cake arrived has three-dimensional cubic duct above-mentioned distributed architecture
Template is preferably triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.The template can pass through existing ability
The method that field technique personnel are known is prepared, and can also be commercially available, for example, Aldrich, quotient can be purchased from
The name of an article is P123, molecular formula EO20PO70EO20, average molecular mass Mn 5800.Wherein, PULLRONIC F68-polyoxy
The molal quantity of ethylene calculates to obtain according to the average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In the present invention, the silicon source can be various silicon sources commonly used in the art, and the preferably described silicon source is positive silicon
At least one of acetoacetic ester, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution, more preferably ethyl orthosilicate.
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 1-6.
There is no particular limitation to the condition being mixed by the present invention, for example, the condition being mixed can be with
Include: temperature be 25-60 DEG C, time 10-72h, pH value 1-6.In order to be more advantageous to the uniform mixing between each substance, according to
A kind of preferred embodiment of the present invention, described be mixed carry out under agitation.
In a preferred embodiment, the way of contact is first by the template, butanol and acidic aqueous solution
It is uniformly mixed, and obtained mixture is placed in 30-45 DEG C of water-bath, then keep temperature-resistant, then by ethyl orthosilicate
It is slowly dropped in said mixture, and is stirred to react 20-40 hours.On the basis of the template of 1g, the ethyl orthosilicate
Drop rate can be 0.1-1g/min.
In the present invention, there is no particular limitation for the condition of the crystallization, for example, the condition of the crystallization may include:
Temperature is 30-150 DEG C, preferably 90-150 DEG C；Time is 10-72h, preferably 10-40h.According to a kind of preferred embodiment party
Formula, the crystallization are implemented by hydrothermal crystallization method.
The condition that the present invention contacts the waterglass, inorganic acid and n-butanol is not particularly limited, for example, in step
(b) in, the condition of the waterglass, inorganic acid and n-butanol contact is generally included: temperature can be 10-60 DEG C, preferably 20-
40℃；Time can be 1-5 hours, preferably 1.5-3 hours, pH value 2-4.In order to increase preparation silica gel aperture ruler
It is very little, it is preferable that waterglass, inorganic acid and n-butanol the weight ratio of dosage can be 3-6:1:1.In order to be more advantageous to each substance
Between uniform mixing, the waterglass, inorganic acid and n-butanol contact preferably carry out under agitation.
According to the present invention, the waterglass is the aqueous solution of the sodium metasilicate of this field routine, and concentration can be 10-50 weight
Measure %, preferably 12-30 weight %.
According to the present invention, the type of the inorganic acid can be the conventional selection of this field, for example, can be sulfuric acid, nitre
One of acid and hydrochloric acid are a variety of.The inorganic acid can use in pure form, can also be in the form of its aqueous solution
It uses.The dosage of the inorganic acid is preferably so that the pH value of the contact conditions reaction system of waterglass and inorganic acid is 2-4.
In addition, it is above-mentioned prepare mesopore molecular sieve filter cake and silica gel filter cake during, obtain filter cake by filtering
Process may include: after filtration, washs (washing times can be 2-10) repeatedly with distilled water, is then filtered.It is excellent
Selection of land prepares the washing during mesopore molecular sieve filter cake so that filter cake pH is 7, prepares the washing during silica gel filter cake
So that sodium ions content is lower than 0.02 weight %.
According to the present invention, in step (c), the dosage of the mesopore molecular sieve filter cake and silica gel filter cake can be according to expection
The component of the obtained spherical material silica gel composite of mesopore molecular sieve containing aluminium is selected, under preferable case, the mesopore molecular sieve
The weight ratio of the dosage of filter cake and silica gel filter cake is 1:1-3.
According to the present invention, before in order to make to contain in the final spherical material silica gel composite of mesopore molecular sieve containing aluminium obtained
The aluminium component of content is stated, to improve its mechanical strength, and not destroy or not destroy carrier structure substantially and silica gel is made to enter load
Subject in body opening road, powder segregation after ball milling is prevented, in step (c), the concrete operation method and condition of the ball milling are preferred
It is carried out in high alumina ceramic ball grinder, wherein the diameter of abrading-ball can be 2-3mm in high alumina ceramic ball grinder；The quantity of abrading-ball
It can reasonably be selected according to the size of high alumina ceramic ball grinder, the high alumina ceramic ball milling for being 50-150mL for size
1 abrading-ball usually can be used in tank；The material of the abrading-ball is high alumina ceramic ball.The condition of the high alumina ceramic ball milling includes:
The revolving speed of abrading-ball can be 300-500r/min, and the temperature in high alumina ceramic ball grinder can be 15-100 DEG C, high alumina ceramic ball
The time of mill can be 0.1-100 hours.
In the present invention, the solid powder obtained after ball milling can be carried out with the process of water slurrying in 25-60 DEG C lower.
In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.5-5, preferably 1:1-2.
In the present invention, the concrete operation method and condition of the spray drying are the conventional selection of this field.Specifically, will
High speed rotation is added in atomizer by the slurry that the solid powder and water are made into realize spray drying.Wherein, the spray
The dry condition of mist includes: that temperature can be 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；It is preferred that feelings
Under condition, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min；It is optimal
In the case of choosing, the condition of the spray drying includes: that temperature is 200 DEG C, and the revolving speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is usually calcination method.The condition of the removed template method can be this
Field conventional selection, for example, the condition of the removed template method, which includes: temperature, to be 300-600 DEG C, preferably 350-550
DEG C, most preferably 500 DEG C；Time can be 10-80 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 the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular weight
Mn 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 inhaled in the ASAP2020-M+C type that Micromeritics company, the U.S. produces
It is carried out on attached instrument；The specific surface area and pore volume of sample, which calculate, uses BET method；Aluminium content result is by XPS Analysis instrument
It measures；The particle diameter distribution of sample carries out on Malvern laser particle analyzer；Rotary Evaporators are the production of IKA company, Germany, model
For RV10digital；The activity component load quantity of propane dehydrogenation catalyst is being Axios- purchased from Dutch Panaco company model
It is measured on the wavelength dispersion X-ray fluorescence spectrometer of Advanced；The analysis of reaction product ingredient is being purchased from agilent company type
Number for 7890A gas chromatograph on carry out.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio (%) of propane=(in dosage-reaction product of propane
The content of propane) ÷ propane dosage × 100%；
Theoretical yield × 100% of selectivity (%)=propylene actual production ÷ propylene of propylene.
Embodiment 1
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
6g (0.001mol) triblock copolymer template P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL deionization is water-soluble
In liquid, 4h is stirred at 15 DEG C and forms clear solution to dissolve P123, then 6g (0.08mol) positive fourth is added into this solution
Alcohol simultaneously stirs 1h, is then placed in the solution in 30 DEG C of water-bath, and 12.9g is slowly added dropwise with the rate of 1g/min
(0.062mol) ethyl orthosilicate keeps the temperature at 30 DEG C, and pH value stirs for 24 hours under conditions of being 4.5, then again at 100 DEG C
Under the conditions of hydro-thermal process for 24 hours, finally filter after washed repeatedly with deionized water, obtained after suction filtration with three-dimensional cubic duct structure
Meso-porous molecular sieve material filter cake A1.
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, by waterglass,
Sulfuric acid and n-butanol weight ratio are uniformly mixed for 5:1:1, and 1.5h, and the reaction product that will be obtained then are stirred to react at 15 DEG C
It is 3 with the sulfuric acid adjustment pH value that concentration is 98 weight %, then filters reaction mass, distillation water washing is washed till sodium ions content
For 0.02 weight %, silica gel filter cake B1 is obtained.
The 20g filter cake A1 and 20g filter cake B1 of above-mentioned preparation is put into togerther in 100mL high alumina ceramic ball grinder (wherein, high
Aluminium ceramics ball grinder material is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min), close high alumina
Ceramic ball grinder, temperature is high alumina ceramic ball milling 1h at 60 DEG C in high alumina ceramic ball grinder, obtains 40g solid powder.It should
Solid powder is dissolved in 30g deionized water, and is spray-dried at 200 DEG C, in the case where revolving speed is 12000r/min, then will spray
The product obtained after mist is dry is calcined for 24 hours in 500 DEG C of Muffle furnace with removed template method, and the mesh of 30g removed template method is obtained
Mark the spherical shape material silica gel composite of mesopore molecular sieve containing the aluminium C1 in product high intensity macropore three-dimensional cubic duct.According to photoelectron spectroscopy
Analysis as a result, in C1 aluminium content be 6 weight %.
(2) preparation of propane dehydrogenation catalyst
30g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C1 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1 hydroxyl and
Residual water；
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-1, (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material C1 and propane dehydrogenation catalyst Cat-1 are characterized；
Fig. 1 is X-ray diffraction (XRD) spectrogram of the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1, wherein
Abscissa is 2 θ, and ordinate is intensity, and the low-angle spectral peak occurred from XRD spectra is it is found that the spherical shape mesoporous molecular containing aluminium
The XRD spectra for sieving material silica gel composite C1 has three-dimensional cubic hole structure specific to mesoporous material；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C1, as seen from the figure, institute
The microscopic appearance for stating the spherical material silica gel composite of mesopore molecular sieve containing aluminium C1 is microballoon that partial size is 10-80 μm, monodisperse
Property is preferable.
Table 1 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C1 and propane dehydrogenation catalyst Cat-1
Structure parameter.
Table 1
*: the first most probable pore size 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 shape mesopore molecular sieve containing aluminium material silica gel composite C1 it can be seen from the data of table 1 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite material C1.
Comparative example 1
This comparative example is for illustrating propane dehydrogenation catalyst of reference and preparation method thereof.
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
The mesopore molecular sieve with three-dimensional cubic duct distributed architecture is not added, so that carrier D1 and propane dehydrogenation catalyst be made respectively
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
Silica gel is not added, so that carrier D2 and propane dehydrogenation catalyst Cat-D-2 be made respectively.
Comparative example 3
This comparative example is for illustrating propane dehydrogenation catalyst of reference and preparation method thereof.
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
Aluminium component is not introduced, and the material of ball grinder used in mechanical milling process is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, thus respectively
Carrier D3 and propane dehydrogenation catalyst Cat-D-3 is made.
Comparative example 4
This comparative example is for illustrating propane dehydrogenation catalyst of reference and preparation method thereof.
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, the difference is that preparing dehydrogenating propane type
In the dipping process of catalyst, NaNO is not added3, 0.133g H is only added2PtCl6·6H2O and 0.295g SnCl4·5H2O,
It is mesoporous containing aluminium that active component Pt and metal promoter Sn are only supported on the spherical shape as carrier after thermal activation by co-impregnation
In molecular sieve material silica gel composite, so that propane dehydrogenation catalyst Cat-D-4 is made, with propane dehydrogenation catalyst Cat-D-4's
On the basis of total weight, content of the Pt component in terms of Pt element is that content of 0.5 weight %, the Sn component in terms of Sn element is 1 weight
% is measured, remaining is carrier).
Comparative example 5
Carrier and propane dehydrogenation catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier
The step of not being spray-dried, and only Pt component, Sn component and Na component are supported on as carrier by the method impregnated
In the spherical material silica gel composite of mesopore molecular sieve containing aluminium, so that propane dehydrogenation catalyst Cat-D-5 be made.
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
6g (0.001mol) triblock copolymer template P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL deionization is water-soluble
In liquid, 4h is stirred at 15 DEG C and forms clear solution to dissolve P123, then 4.5g (0.06mol) is being added just into this solution
Butanol simultaneously stirs 1h, is then placed in the solution in 30 DEG C of water-bath, and 10.4g is slowly added dropwise with the rate of 1g/min
(0.05mol) ethyl orthosilicate keeps the temperature at 60 DEG C, and pH value stirs 10h under conditions of being 6, then again in 150 DEG C of conditions
Lower hydro-thermal process for 24 hours, is washed repeatedly with deionized water after finally filtering, Jie with three-dimensional cubic duct structure is obtained after suction filtration
The filter cake A2 of porous molecular sieve material.
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, by waterglass,
Sulfuric acid and n-butanol weight ratio are uniformly mixed for 6:1:1,1h are then stirred to react at 60 DEG C, and obtained reaction product is used
The sulfuric acid adjustment pH value that concentration is 98 weight % is 2, is then filtered reaction mass, distillation water washing is washed till sodium ions content and is
0.02 weight % obtains silica gel filter cake B2.
The 20g filter cake A2 and 40g filter cake B2 of above-mentioned preparation is put into togerther in 100mL high alumina ceramic ball grinder (wherein, high
Aluminium ceramics ball grinder material is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 300r/min), close high alumina
Ceramic ball grinder, temperature is high alumina ceramic ball milling 0.5h at 100 DEG C in high alumina ceramic ball grinder, obtains 40g solid powder.It will
The solid powder is dissolved in 30g deionized water, and is spray-dried at 150 DEG C, in the case where revolving speed is 11000r/min, then will
The product obtained after spray drying calcines 72h in 300 DEG C of Muffle furnace with removed template method, obtains 35g removed template method
The spherical shape material silica gel composite of mesopore molecular sieve containing the aluminium C2 in target product high intensity macropore three-dimensional cubic duct.According to photoelectron energy
Spectrum analysis as a result, in C2 aluminium content be 9 weight %.
(2) preparation of propane dehydrogenation catalyst
35g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C2 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C2 hydroxyl and
Residual water；
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-2, (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material C2 and propane dehydrogenation catalyst Cat-2 are characterized；
Table 2 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C2 and propane dehydrogenation catalyst Cat-2
Structure parameter.
Table 2
*: the first most probable pore size 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 shape mesopore molecular sieve containing aluminium material silica gel composite C2 it can be seen from the data of table 2 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite material C2.
Embodiment 3
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of carrier
6g (0.001mol) triblock copolymer template P123 is dissolved in 10mL concentrated hydrochloric acid and 220mL deionization is water-soluble
In liquid, 4h is stirred at 15 DEG C and forms clear solution to dissolve P123, then 6.75g (0.09mol) is being added just into this solution
Butanol simultaneously stirs 1h, is then placed in the solution in 30 DEG C of water-bath, and 15.6g is slowly added dropwise with the rate of 1g/min
(0.075mol) ethyl orthosilicate keeps the temperature at 10 DEG C, and pH value stirs 72h under conditions of being 1, then again in 30 DEG C of conditions
Lower hydro-thermal process 72h is washed repeatedly with deionized water after finally filtering, Jie with three-dimensional cubic duct structure is obtained after suction filtration
The filter cake A3 of porous molecular sieve material.
By the waterglass that concentration is 15 weight % and sulfuric acid solution and n-butanol that concentration is 12 weight %, by waterglass,
Sulfuric acid and n-butanol weight ratio are uniformly mixed for 3:1:1,5h are then stirred to react at 10 DEG C, and obtained reaction product is used
The sulfuric acid adjustment pH value that concentration is 98 weight % is 4, is then filtered reaction mass, distillation water washing is washed till sodium ions content and is
0.02 weight % obtains silica gel filter cake B3.
The 20g filter cake A3 and 60g filter cake B3 of above-mentioned preparation is put into togerther in 100mL high alumina ceramic ball grinder (wherein, high
Aluminium ceramics ball grinder material is high alumina ceramic, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 500r/min), close high alumina
Ceramic ball grinder, temperature is high alumina ceramic ball milling 10h at 25 DEG C in high alumina ceramic ball grinder, obtains 40g solid powder.It should
Solid powder is dissolved in 30g deionized water, and is spray-dried at 300 DEG C, in the case where revolving speed is 13000r/min, then will spray
The product obtained after mist is dry calcines 12h in 600 DEG C of Muffle furnace with removed template method, obtains the mesh of 30g removed template method
Mark the spherical shape material silica gel composite of mesopore molecular sieve containing the aluminium C3 in product high intensity macropore three-dimensional cubic duct.According to photoelectron spectroscopy
Analysis as a result, in C3 aluminium content be 15 weight %.
(2) preparation of propane dehydrogenation catalyst
30g spherical shape mesopore molecular sieve containing the aluminium material silica gel composite C3 that step (1) is obtained under the protection of nitrogen, in
Calcine 10h at 400 DEG C and carry out thermal activation treatment, remove the spherical material silica gel composite of mesopore molecular sieve containing the aluminium C3 hydroxyl and
Residual water；
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the above-mentioned spherical shape material silica gel composite of mesopore molecular sieve containing aluminium by thermal activation treatment is immersed in
In the mixture solution, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid production
Solid product is placed in the drying box that temperature is 120 DEG C by object, dry 3h, and being subsequently placed in temperature is roasting in 600 DEG C of Muffle furnaces
6h is burnt, obtaining propane dehydrogenation catalyst Cat-3, (on the basis of the total weight of propane dehydrogenation catalyst Cat-3, Pt component is with Pt member
It is 0.7 weight %, Na component containing in terms of Na element that the content of element meter, which is content of 0.3 weight %, the Sn component in terms of Sn element,
Amount is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to the spherical silica gel of mesopore molecular sieve containing aluminium
Composite material C3 and propane dehydrogenation catalyst Cat-3 are characterized；
Table 3 is the hole knot of spherical mesopore molecular sieve containing aluminium the material silica gel composite C3 and propane dehydrogenation catalyst Cat-3
Structure parameter.
Table 3
*: the first most probable pore size 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 shape mesopore molecular sieve containing aluminium material silica gel composite C3 it can be seen from the data of table 3 as carrier is being loaded
After chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation exists
Chief active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the spherical silicon of mesopore molecular sieve containing aluminium during load-reaction
The inside of glue composite material C3.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the method for illustrating to prepare propylene using propane dehydrogenation catalyst of the invention
0.5g propane dehydrogenation catalyst Cat-1 is fitted into fixed-bed quartz reactor, control reaction temperature is 610 DEG C,
Reaction pressure is 0.1MPa, and propane: the molar ratio of hydrogen is 1:1, and reaction time 50h, propane mass space velocity is 3h-1.Propane
Conversion ratio and Propylene Selectivity are as shown in table 4.
EXPERIMENTAL EXAMPLE 2-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-2 and propane dehydrogenation catalyst Cat-3 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are such as
Shown in table 4.
Experimental comparison's example 1-5
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-D-1~Cat-D-5 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are as shown in table 4.
Table 4
From table 4, it can be seen that de- using the propane of the spherical material silica gel composite of mesopore molecular sieve containing aluminium preparation of the invention
Hydrogen catalyst compression strength with higher, for preparing propylene by dehydrogenating propane reaction when, react 50h after, it is still available compared with
High conversion of propane and Propylene Selectivity, illustrating propane dehydrogenation catalyst of the invention not only has preferable catalytic performance,
But also it has excellent stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of propane dehydrogenation catalyst, which is characterized in that the propane dehydrogenation catalyst includes carrier and is supported on described
Pt component, Sn component and Na component on carrier, wherein the carrier is the spherical material silica gel composite of mesopore molecular sieve containing aluminium,
The spherical shape material silica gel composite of mesopore molecular sieve containing aluminium contains aluminium component, the mesopore molecular sieve with three-dimensional cubic duct structure
The compression strength of material and silica gel, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium is 12-16MPa, and average grain diameter is
10-80 μm, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture are in bimodal distribution, and the bimodal correspondence
Most probable pore size be respectively 4-8nm and 30-40nm.
2. propane dehydrogenation catalyst according to claim 1, wherein using the total weight of the propane dehydrogenation catalyst as base
Standard, the content of the carrier are 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %,
Content of the Sn component in terms of Sn element is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8
Weight %；
Preferably, the compression strength of the carrier is 14-16MPa, and average grain diameter is 30-60 μm, specific surface area 100-170m2/
G, pore volume 0.8-1.8mL/g, the corresponding most probable pore size of bimodal distribution is respectively 4-8nm and 32-39nm.
3. propane dehydrogenation catalyst according to claim 1, wherein three-dimensional vertical relative to having described in 100 parts by weight
The meso-porous molecular sieve material of square duct structure, the content of the aluminium component are 1-20 parts by weight, preferably 5-19 parts by weight, described
The content of silica gel is 1-90 parts by weight, preferably 2-85 parts by weight.
4. a kind of method for preparing propane dehydrogenation catalyst, which is characterized in that this method comprises: by containing after carrier thermal activation
Impregnation is carried out in the mixed solution of Pt component presoma, Sn component presoma and Na component presoma, is then successively carried out
Remove solvent processing, dry and roasting, wherein the carrier is the spherical material silica gel composite of mesopore molecular sieve containing aluminium, the ball
The shape material silica gel composite of mesopore molecular sieve containing aluminium contain aluminium component, the meso-porous molecular sieve material with three-dimensional cubic duct structure and
Silica gel, the compression strength of the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium are 12-16MPa, and average grain diameter is 10-80 μ
M, specific surface area 100-180m2/ g, pore volume 0.5-2mL/g, aperture are in bimodal distribution, and described bimodal corresponding most may be used
Several apertures are respectively 4-8nm and 30-40nm.
5. method according to claim 4, wherein the carrier, Pt component presoma, Sn component presoma and Na component forerunner
The dosage of body makes in the propane dehydrogenation catalyst of preparation, on the basis of the total weight of the propane dehydrogenation catalyst, the load
The content of body is that content of 97.5-99.3 weight %, the Pt component in terms of Pt element is 0.2-0.5 weight %, Sn component with Sn member
It is 0.3-0.8 weight % that the content of element meter, which is content of 0.2-1.2 weight %, the Na component in terms of Na element,；
Preferably, the compression strength of the carrier is 14-16MPa, the spherical shape material silica gel composite of mesopore molecular sieve containing aluminium
Average grain diameter is 30-60 μm, specific surface area 100-170m2/ g, pore volume 0.8-1.8mL/g, aperture are in bimodal distribution, and
The bimodal corresponding most probable pore size is respectively 4-8nm and 32-39nm；
It is highly preferred that it is 300-900 DEG C that the condition of the thermal activation, which includes: temperature, time 7-10h；The impregnation
Condition includes: that temperature is 25-50 DEG C, time 2-6h.
6. method according to claim 4 or 5, the forming method of the carrier the following steps are included:
(a) in the presence of template and butanol, silicon source is contacted with sour agent, and successively by the mixture obtained after contact
Crystallization and filtering are carried out, mesopore molecular sieve filter cake is obtained；
(b) waterglass is contacted with inorganic acid and n-butanol, and the mixture obtained after contact is filtered, obtain silicon
Glue filter cake；
(c) the spherical double mesopore molecular sieve filter cake and silica gel filter cake are mixed and are carried out in high alumina ceramic tank ball milling, and will
Obtained slurry, is then spray-dried by the solid powder obtained after ball milling water slurrying, then will be in obtained product
The template removal.
7. according to the method described in claim 6, wherein, in step (a), the dosage of the template, butanol and silicon source
Molar ratio is 1:10-100:10-90, preferably 1:60-90:50-75；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and the acid agent is hydrochloric acid,
The silicon source is at least one of ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and silica solution；
It is further preferred that it is 25-60 DEG C, time 10-72h, pH value 1-6 that the condition of the contact, which includes: temperature, it is described
The condition of crystallization includes: that temperature is 30-150 DEG C, time 10-72h.
8. preparation method according to claim 6, wherein in step (b), the waterglass, inorganic acid and n-butanol
The condition of contact includes: that the weight ratio of the dosage of waterglass, inorganic acid and n-butanol is 3-6:1:1, and temperature is 10-60 DEG C, when
Between be 1-5 hours, pH value 2-4；The inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid or a variety of；
Preferably, in step (c), the weight ratio of the dosage of the spherical mesoporous molecular sieve filter cake and silica gel filter cake is 1:1-3；
It is highly preferred that the revolving speed that the condition that ball milling is carried out in high alumina ceramic tank includes: abrading-ball is 300-500r/min, it is high
Temperature in aluminium ceramics ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The condition packet of the spray drying
It includes: 100-300 DEG C of temperature, revolving speed 10000-15000r/min；
It is further preferred that the process of the template removal includes: to calcine 10-80h at 300-600 DEG C.
9. the propane dehydrogenation catalyst that method described in any one of claim 4-8 is prepared.
10. a kind of method of preparing propylene by dehydrogenating propane, which comprises in the presence of catalyst and hydrogen, by propane into
Row dehydrogenation reaction, which is characterized in that the catalyst is dehydrogenating propane catalysis described in any one of claim 1-3 and 9
Agent.
11. according to the method described in claim 10, wherein, the molar ratio of the dosage of the dosage and hydrogen of propane is 0.5-1.5:
1；
Preferably, it is 600-650 DEG C, reaction pressure 0.05-0.2MPa that the condition of the dehydrogenation reaction, which includes: reaction temperature,
Reaction time is 40-60h, and propane mass space velocity is 2-5h-1。
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| CN112473720A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application thereof |
| CN113546671A (en) * | 2020-04-26 | 2021-10-26 | 中国石油化工股份有限公司 | Light gasoline cracking yield-increasing propylene catalyst containing ultra-large pore silica gel, and preparation method and application thereof |
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| CN106632760A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method |
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| CN104248968A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for preparation of propylene by direct dehydrogenation of propane and preparation method thereof |
| CN105330767A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN106632760A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminum-containing mesoporous composite material and supported catalyst and preparation method and application thereof and ethylene polymerization method |
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| CN112473720A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application thereof |
| CN113546671A (en) * | 2020-04-26 | 2021-10-26 | 中国石油化工股份有限公司 | Light gasoline cracking yield-increasing propylene catalyst containing ultra-large pore silica gel, and preparation method and application thereof |
| CN113546671B (en) * | 2020-04-26 | 2024-02-20 | 中国石油化工股份有限公司 | Light gasoline cracking yield-increasing propylene catalyst containing ultra-macroporous silica gel, and preparation method and application thereof |
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