CN105728013B - Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof - Google Patents
Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof Download PDFInfo
- Publication number
- CN105728013B CN105728013B CN201610124322.6A CN201610124322A CN105728013B CN 105728013 B CN105728013 B CN 105728013B CN 201610124322 A CN201610124322 A CN 201610124322A CN 105728013 B CN105728013 B CN 105728013B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- solution
- catalyst
- kit
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention provides a kind of vanadium dopings to aoxidize silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof, the catalyst using pure silicon mesopore molecular sieve KIT-6 as carrier, using barium oxide as active component, the barium oxide doping enters in the skeleton of the pure silicon mesopore molecular sieve KIT-6, and the molar ratio of V, Si are 0.1:100-8:100.Application the present invention also provides the preparation method of above-mentioned catalyst and its in selective oxidation of propane dehydrogenation alkene.The dispersion degree higher of active component vanadium, the concentration bigger of active sites, and the stability higher of active sites in vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst provided by the present invention, therefore, the catalytic activity of the catalyst is higher.The catalyst is applied in the reaction of selective oxidation of propane dehydrogenation alkene, the product propylene of selective oxidation of propane reaction and the molar yield of alkene can reach 35.6% and 38.6% respectively.
Description
Technical field
The present invention relates to a kind of vanadium dopings to aoxidize silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof, belongs to stone
Oiling work catalysis technical field.
Background technology
Since 1992, the scientists of Mobil companies (J.S.Beck, J.C.Vartuli, W.J.Roth, et al.,
J.Am.Chem.Soc.,1992,114:10834-10843) prepared for the first time with uniform with nanostructure self-assembling technique
Since duct, the adjustable mesopore silicon oxide MCM-41 in aperture, mesopore molecular sieve has caused the extensive concern of people.But pure silica
Mesoporous material to the overwhelming majority reaction for be inert, it is therefore desirable to by active sites is introduced into aoxidize silicon-based mesoporous material in,
Make it have catalytic activity.The coordination of active specy and the state of oxidation have a great impact to its catalytic performance, and synthesis is containing equal
The oxidation silicon substrate meso-porous molecular sieve material of one species is very heavy for establishing the structure-activity relationship between active specy and catalytic activity
It wants.The method that active sites are introduced in mesopore molecular sieve common at present can be divided into two kinds：Post synthesis method and in-situ synthesis.
Post synthesis method includes mainly infusion process, grafting and ion-exchange etc..These methods are often complex for operation step, active specy
Mesopore surfaces are generally formed in, the interaction between carrier is weaker, therefore active specy is easy polymerization.And in-situ synthesis
It is that active component is introduced in sieve synthesis procedure, the metal-doped mesopore molecular sieve of direct hydrothermal synthesis.Such active sites
It is introduced directly into the skeleton of molecular sieve, enhances its interaction with carrier, and be easier to obtain high dispersive isolation
Active sites.
There is KIT-6 mesoporous materials typical three-dimensional cubic double helix to intersect pore passage structure, be that high-sequential Ia3d is mesoporous
Structure, pore passage structure are similar to MCM-48 structures.The specific surface area of typical KIT-6 materials is 750m2·g-1-800m2·g-1,
Pore-size distribution is in 6.0nm-8.0nm, pore volume 0.8cm3·g-1-0.95cm3·g-1, pore wall thickness 3.0nm-4.0nm, heat
Excellent in stability, pore passage structure is held essentially constant at 900 DEG C.The ducts KIT-6 are three-dimensional cubic structure, and there are two types of spiral shells for tool
The main aperture road of rotation, the two each other hand-type it is symmetrical and be about between each other 1.7nm by aperture micropore be connected, and then formed
Interactive reticular structure；The main aperture road for being wherein more than 5nm combines the microchannel of auxiliary, it is made to be very beneficial for the absorption of reactant
The diffusion of the desorption of diffusion and reactant and product.Since the mesoporous materials such as KIT-6 typically synthesize (pH under strongly acidic conditions<
1) it obtains, and the vanadium solution of high concentration is easy to form V under strongly acidic conditions2O5(c) sediment (I.E.Wachs, Dalton
Trans., 2013,42,11762-11769), cause it to cannot be introduced into the skeleton of mesopore molecular sieve, have document report in alkali at present
The vanadium species of high level can be introduced into the skeleton of MCM-41 mesopore molecular sieves under the conditions of property.However, in pH>3 condition
Lower synthesis KIT-6 materials are extremely difficult.Therefore, vanadium species are introduced into the skeleton of mesopore molecular sieve and keep high-sequential
Meso-hole structure is still a prodigious challenge.
In the reaction of preparing propene by oxidative dehydrogenation of propane and preparing propylene by propane selective oxidization, barium oxide kind is using most
Wide active component, it is considered that the coordination environment of transition metal has selective oxidation of propane critically important influence.With octahedron
The oxide of coordination is compared, and vanadium oxygen tetrahedron, the molybdenum oxygen tetrahedron of high dispersive prepare propylene, methacrylaldehyde etc. to selective oxidation of propane
Reaction may have preferable selectivity.Mesopore molecular sieve has regular pore passage structure, controllable aperture and larger specific surface
Product.Si in mesoporous molecular sieve framework can be replaced by hetero atoms such as Al, V, by the way that transition metal oxide confinement is being situated between
In the skeleton of porous molecular sieve, effectively it can be disperseed, replace the transition metal ions of Si due in structure, it must
It is in so the structure of mutually isolated four-coordination.
Invention content
In order to solve above-mentioned disadvantage and deficiency, the purpose of the present invention is to provide a kind of vanadium dopings to aoxidize silicon-based mesoporous point
Sub- sieve catalyst.
The preparation method for aoxidizing silicon substrate mesoporous molecular sieve catalyst the present invention also aims to provide above-mentioned vanadium doping.
The present invention also aims to provide above-mentioned vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst to select oxygen in propane
Application in fluidized dehydrogenation alkene.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst,
Be using pure silicon mesopore molecular sieve KIT-6 as carrier, using barium oxide as active component, barium oxide doping enters described pure
In the skeleton of silicone metapore molecular sieve KIT-6, and the molar ratio of V, Si are 0.1:100-8:100.
Wherein barium oxide is the VO of high dispersive isolationxSpecies.
Catalyst according to the present invention, it is preferable that the barium oxide doping enters the pure silicon mesopore molecular sieve
It is to use Direct Hydrothermal by raw material of hydrochloric acid, vanadium source and silicon source using triblock copolymer P123 as template in the skeleton of KIT-6
What synthetic method was realized, the KIT-6 mesopore molecular sieves being prepared are the V-KIT-6 mesopore molecular sieves containing vanadium in skeleton.
The wherein described vanadium source and silicon source may be used vanadium source commonly used in the art and silicon source, and present invention preferably uses
Vanadium source include vanadate, the more preferable vanadate includes ammonium metavanadate (molecular formula NH4VO3)。
Present invention preferably uses silicon source include tetraethyl orthosilicate.
Catalyst according to the present invention, it is preferable that the BET specific surface area of the catalyst is 600-1000m2/ g,
Pore volume is 0.80-1.20cm2/ g, aperture 8.0-10.0nm；
It is highly preferred that the BET specific surface area of the catalyst is 843-1000m2/ g, pore volume 1.14-1.20cm2/ g,
Aperture is 9.2-10.0nm.
Catalyst according to the present invention, it is preferable that the catalyst is prepared by the method included the following steps：
(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring is total to three block
Polymers P123 templates are completely dissolved, and obtain template solution；
(2) vanadium source solution is prepared：Vanadium source is dissolved in deionized water, stirring is completely dissolved to vanadium source, obtains vanadium source solution；
(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred, and positive fourth is added
Alcohol continues to stir, and obtains homogeneous phase solution, then instills silicon source, then agitated gets a uniform mixture；
(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；
(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation
Separation is filtered, is washed, dry, calcination process, obtains the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium in skeleton, i.e., described
Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst.
Catalyst according to the present invention, it is preferable that step (1) prepares template solution and is：By the three of 1-3 parts by weight
Block copolymer P123 templates are dissolved in the dilute hydrochloric acid that 17-21 parts by weight molar concentrations are 1.0-3.0mol/L, stirring to three
Block copolymer P123 templates are completely dissolved, and obtain template solution；
The wherein described dilute hydrochloric acid can be dilute hydrochloric acid solution commonly used in the art, wherein it is understood that described
Hydrochloric acid solution is generally aqueous hydrochloric acid solution.
Wherein the present invention stirs 4-6h preferably in 30-40 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template complete
Fully dissolved obtains template solution.
In addition, in preferred embodiment of the invention, the addition of triblock copolymer P123 template in step (1)
Amount is 2 parts by weight, and the molar concentration of the dilute hydrochloric acid is 2.0mol/L, and additive amount is 19 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C, and the mixing time of the stirring is 4h.
The present invention does not have particular/special requirement, any commercially available triblock copolymer to triblock copolymer P123 template used
Object P123 templates can be applied to the present invention, and aoxidize silicon substrate mesoporous molecular sieve catalyst being applied to vanadium doping
Preparation process in, it need not be purified；In the preferred embodiment of the invention, the triblock copolymer P123 that uses
Template is the triblock copolymer P123 template that the average molecular weight of Sigma Co., USA's production is 5800.
Catalyst according to the present invention, it is preferable that step (2) prepares vanadium source solution and is：Vanadium source is dissolved in deionization
In water, 3-5h is stirred in 30-40 DEG C of water bath with thermostatic control, forms it into uniform solution, obtains vanadium source solution.
In preferred embodiment of the invention, the temperature of the water bath with thermostatic control is 35 DEG C.
Catalyst according to the present invention, it is preferable that step (3) described mixing step is：By template solution and vanadium
Source solution is stirred 1-3h in 30-40 DEG C of water bath with thermostatic control, and n-butanol is added, and continues to stir 1-2h, then instills silicon source,
It is further continued for stirring 24-36h, is got a uniform mixture.
Catalyst according to the present invention, it is preferable that n-butanol described in step (3) and triblock copolymer P123
Weight ratio is 1.0:1-1.6:1.
In preferred embodiment of the invention, step (3) described mixing step is：Template solution and vanadium source is molten
Liquid is stirred 1-3h in 35 DEG C of water bath with thermostatic control, and n-butanol is added, and continues to stir 1h, then instills silicon source, be further continued for stirring
It mixes for 24 hours, gets a uniform mixture.It is that vanadium source solution is added to mould in the preferred embodiment of the present invention, in step (3)
In plate agent solution, it is stirred for mixing.
Catalyst according to the present invention, the n-butanol described in step (3) are structure directing agent, and n-butanol is as knot
Structure directed agents are techniques known common sense.
Catalyst according to the present invention, it is preferable that for pH value is adjusted to 5-6 in step (4), the present invention is more preferable
For pH value is adjusted to 5.
Catalyst according to the present invention, it is preferable that step (5) described crystallization is：By pH value after the adjustment in step (4)
Mixed solution afterwards, which is put into high pressure crystallization kettle at 80-120 DEG C, carries out crystallization 24-48h；
It is wherein more preferably described to be cooled to be cooled to room temperature；
It is centrifuged as with the rotating speed of 3000-5000r/min centrifugation 5-15min even more preferably from described；
It is to be rinsed filtrate to non-foam with deionized water even more preferably from the washing；
It is 80-120 DEG C of dry 6-12h even more preferably from the drying；
It is roasted to 530-580 DEG C of roasting 4-8h even more preferably from described.
The temperature of the further preferred step of the present invention (5) described crystallization is 100 DEG C；Dry temperature is 100 DEG C, is done
The dry time is 10h, and the temperature of roasting is 550 DEG C, and the time of roasting is 6h, and the heating rate control of roasting is 1-2 DEG C/min.
On the other hand, the present invention also provides a kind of sides for preparing the vanadium doping and aoxidizing silicon substrate mesoporous molecular sieve catalyst
Method, this method are in-situ synthesis, i.e., in the building-up process of pure silicon mesopore molecular sieve KIT-6, introduce the presoma of vanadium, and lead to
The pH value for overregulating system makes vanadium doping into such as skeleton of KIT-6 mesopore molecular sieves；
Described method includes following steps：
(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring is total to three block
Polymers P123 templates are completely dissolved, and obtain template solution；
(2) vanadium source solution is prepared：Vanadium source is dissolved in deionized water, stirring is completely dissolved to vanadium source, obtains vanadium source solution；
(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred, and positive fourth is added
Alcohol continues to stir, and obtains homogeneous phase solution, then instills silicon source, then agitated gets a uniform mixture；
(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；
(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation
Separation is filtered, is washed, dry, calcination process, obtains the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium in skeleton, i.e., described
Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst.
Wherein, vanadium source (ammonium metavanadate) and the additive amount of silicon source (tetraethyl orthosilicate) are changed with the material molar ratio of V and Si
It obtains.
Method according to the present invention, preferred steps (1) prepare template solution and are：By the three block of 1-3 parts by weight
123 template of copolymer p is dissolved in the dilute hydrochloric acid that 17-21 parts by weight molar concentrations are 1.0-3.0mol/L, stirring to three block
123 template of copolymer p is completely dissolved, and obtains template solution；
The wherein described dilute hydrochloric acid can be dilute hydrochloric acid solution commonly used in the art, wherein it is understood that described
Hydrochloric acid solution is generally aqueous hydrochloric acid solution.
Wherein the present invention stirs 4-6h preferably in 30-40 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template complete
Fully dissolved obtains template solution.
In addition, in preferred embodiment of the invention, the addition of triblock copolymer P123 template in step (1)
Amount is 2 parts by weight, and the molar concentration of the dilute hydrochloric acid is 2.0mol/L, and additive amount is 19 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C, and the mixing time of the stirring is 4h.
Method according to the present invention, preferred steps (2) prepare vanadium source solution and are：Vanadium source is dissolved in deionized water,
3-5h is stirred in 30-40 DEG C of water bath with thermostatic control, forms it into uniform solution, obtains vanadium source solution.
In preferred embodiment of the invention, the temperature of the water bath with thermostatic control is 35 DEG C.
Method according to the present invention, preferred steps (3) described mixing step are：By template solution and vanadium source solution
It is stirred 1-3h in 30-40 DEG C of water bath with thermostatic control, n-butanol is added, continues to stir 1-2h, then instills silicon source, be further continued for
24-36h is stirred, is got a uniform mixture.It is to add vanadium source solution in the preferred embodiment of the present invention, in step (3)
Enter into template solution, is stirred for mixing.
In preferred embodiment of the invention, step (3) described mixing step is：Template solution and vanadium source is molten
Liquid is stirred 1-3h in 35 DEG C of water bath with thermostatic control, and n-butanol is added, and continues to stir 1h, then instills silicon source, be further continued for stirring
It mixes for 24 hours, gets a uniform mixture.
Catalyst according to the present invention, it is preferable that n-butanol described in step (3) and triblock copolymer P123
Weight ratio is 1.0:1-1.6:1.
Method according to the present invention, for pH value is adjusted to 5-6 in preferred steps (4), the present invention more preferably will
PH value is adjusted to 5.
Method according to the present invention, preferred steps (5) described crystallization are：It will be in step (4) after the adjustment after pH value
Mixed solution, which is put into high pressure crystallization kettle at 80-120 DEG C, carries out crystallization 24-48h；
It is wherein more preferably described to be cooled to be cooled to room temperature；
It is centrifuged as with the rotating speed of 3000-5000r/min centrifugation 5-15min even more preferably from described；
It is to be rinsed filtrate to non-foam with deionized water even more preferably from the washing；
It is 80-120 DEG C of dry 6-12h even more preferably from the drying；
It is roasted to 530-580 DEG C of roasting 4-8h even more preferably from described.
The temperature of the further preferred step of the present invention (5) described crystallization is 100 DEG C；Dry temperature is 100 DEG C, is done
The dry time is 10h, and the temperature of roasting is 550 DEG C, and the time of roasting is 6h, and the heating rate control of roasting is 1-2 DEG C/min.
Involved " the weight in the preparation method that vanadium doping of the present invention aoxidizes silicon substrate mesoporous molecular sieve catalyst
Part " be carried out using same weight standard it is quantitative.
In another aspect, the present invention also provides above-mentioned vanadium doping oxidation silicon substrate mesoporous molecular sieve catalysts oxygen is selected in propane
Application in fluidized dehydrogenation alkene.
The present invention provides a kind of vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst, is with pure silicon mesopore molecular sieve KIT-
6 be carrier, using barium oxide as active component, and the barium oxide doping enters the bone of the pure silicon mesopore molecular sieve KIT-6
In frame, and the molar ratio of V, Si are 0.1:100-8:100.
Catalyst according to the present invention, it is preferable that the barium oxide doping enters the pure silicon mesopore molecular sieve
It is to use Direct Hydrothermal by raw material of hydrochloric acid, vanadium source and silicon source using triblock copolymer P123 as template in the skeleton of KIT-6
What synthetic method was realized, the KIT-6 mesopore molecular sieves being prepared are the V-KIT-6 mesopore molecular sieves containing vanadium in skeleton；
The vanadium source that wherein present invention uses is vanadate, which is ammonium metavanadate (molecular formula NH4VO3),
The silicon source that the present invention uses is tetraethyl orthosilicate.
Catalyst according to the present invention, it is preferable that the BET specific surface area of the catalyst is 600-1000m2/ g,
Pore volume is 0.80-1.20cm2/ g, aperture 8.0-10.0nm；
It is highly preferred that the BET specific surface area of the catalyst is 843-1000m2/ g, pore volume 1.14-1.20cm2/ g,
Aperture is 9.2-10.0nm.
Catalyst according to the present invention, it is preferable that the catalyst is prepared by the method included the following steps：
(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring is total to three block
Polymers P123 templates are completely dissolved, and obtain template solution；
(2) vanadium source solution is prepared：Ammonium metavanadate is dissolved in deionized water, stirring is completely dissolved to ammonium metavanadate, is obtained
Vanadium source solution；
(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred, and positive fourth is added
Alcohol continues to stir, and obtains homogeneous phase solution, then instills tetraethyl orthosilicate, then agitated gets a uniform mixture；
(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；
(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation
Separation is filtered, is washed, dry, calcination process, obtains the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium in skeleton, i.e., described
Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst.
Catalyst according to the present invention, it is preferable that step (1) prepares template solution and is：By the three of 1-3 parts by weight
Block copolymer P123 templates are dissolved in the dilute hydrochloric acid that 17-21 parts by weight molar concentrations are 1.0-3.0mol/L, stirring to three
Block copolymer P123 templates are completely dissolved, and obtain template solution.
Wherein the present invention stirs 4-6h preferably in 30-40 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template complete
Fully dissolved obtains template solution.
In addition, in preferred embodiment of the invention, the addition of triblock copolymer P123 template in step (1)
Amount is 2 parts by weight, and the molar concentration of the dilute hydrochloric acid is 2.0mol/L, and additive amount is 19 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C, and the mixing time of the stirring is 4h.
Catalyst according to the present invention, it is preferable that step (2) prepares vanadium source solution and is：By 0.004-0.288 weight
The ammonium metavanadate solid of part is dissolved in the deionized water of 55-59 parts by weight, is stirred 3-5h in 30-40 DEG C of water bath with thermostatic control, is made
It forms uniform solution, obtains vanadium source solution.In preferred embodiment of the invention, deionized water described in step (2)
Dosage be 57 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C.
Catalyst according to the present invention, it is preferable that step (3) described mixing step is：By template solution and vanadium
Source solution is stirred 1-3h in 30-40 DEG C of water bath with thermostatic control, and the n-butanol of 2.0-3.2 parts by weight is added, and continues to stir 1-
Then 2h instills the tetraethyl orthosilicate of 4.2-9.6 parts by weight, be further continued for stirring 24-36h, get a uniform mixture.At this
It is that vanadium source solution is added in template solution in invention preferred embodiment, in step (3), is stirred for mixing.
In preferred embodiment of the invention, step (3) described mixing step is：Template solution and vanadium source is molten
Liquid is stirred 1-3h in 35 DEG C of water bath with thermostatic control, and the n-butanol of 2.5 parts by weight is added, and continues to stir 1h, then instills 6.4
The tetraethyl orthosilicate of parts by weight is further continued for stirring for 24 hours, gets a uniform mixture.
Catalyst according to the present invention, it is preferable that for pH value is adjusted to 5-6 in step (4), the present invention is more preferable
For pH value is adjusted to 5.
Catalyst according to the present invention, it is preferable that step (5) described crystallization is：By pH value after the adjustment in step (4)
Mixed solution afterwards, which is put into high pressure crystallization kettle at 80-120 DEG C, carries out crystallization 24-48h；
It is wherein more preferably described to be cooled to be cooled to room temperature；
It is centrifuged as with the rotating speed of 3000-5000r/min centrifugation 5-15min even more preferably from described；
It is to be rinsed filtrate to non-foam with deionized water even more preferably from the washing；
It is 80-120 DEG C of dry 6-12h even more preferably from the drying；
It is roasted to 530-580 DEG C of roasting 4-8h even more preferably from described.
The temperature of the further preferred step of the present invention (5) described crystallization is 100 DEG C；Dry temperature is 100 DEG C, is done
The dry time is 10h, and the temperature of roasting is 550 DEG C, and the time of roasting is 6h, and the heating rate control of roasting is 1-2 DEG C/min.
The present invention also provides a kind of method for preparing the vanadium doping and aoxidizing silicon substrate mesoporous molecular sieve catalyst, this method
The presoma of vanadium is introduced, and by adjusting body that is, in the building-up process of pure silicon mesopore molecular sieve KIT-6 for in-situ synthesis
The pH value of system makes vanadium doping into such as skeleton of KIT-6 mesopore molecular sieves；
Described method includes following steps：
(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring is total to three block
Polymers P123 templates are completely dissolved, and obtain template solution；
(2) vanadium source solution is prepared：Ammonium metavanadate is dissolved in deionized water, stirring is completely dissolved to ammonium metavanadate, is obtained
Vanadium source solution；
(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred, and positive fourth is added
Alcohol continues to stir, and obtains homogeneous phase solution, then instills tetraethyl orthosilicate, then agitated gets a uniform mixture；
(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；
(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation
Separation is filtered, is washed, dry, calcination process, obtains the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium in skeleton, i.e., described
Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst.
Wherein, the additive amount of ammonium metavanadate and tetraethyl orthosilicate converts to obtain with the material molar ratio of V and Si.
Method according to the present invention, preferred steps (1) prepare template solution and are：By the three block of 1-3 parts by weight
123 template of copolymer p is dissolved in the dilute hydrochloric acid that 17-21 parts by weight molar concentrations are 1.0-3.0mol/L, stirring to three block
123 template of copolymer p is completely dissolved, and obtains template solution；
The wherein described dilute hydrochloric acid can be dilute hydrochloric acid solution commonly used in the art, wherein it is understood that described
Hydrochloric acid solution is generally aqueous hydrochloric acid solution.
Wherein the present invention stirs 4-6h preferably in 30-40 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template complete
Fully dissolved obtains template solution.
In addition, in preferred embodiment of the invention, the addition of triblock copolymer P123 template in step (1)
Amount is 2 parts by weight, and the molar concentration of the dilute hydrochloric acid is 2.0mol/L, and additive amount is 19 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C, and the mixing time of the stirring is 4h.
Method according to the present invention, preferred steps (2) prepare vanadium source solution and are：By 0.004-0.288 parts by weight
Ammonium metavanadate solid is dissolved in the deionized water of 55-59 parts by weight, and 3-5h is stirred in 30-40 DEG C of water bath with thermostatic control, makes its shape
At uniform solution, vanadium source solution is obtained.
In preferred embodiment of the invention, the dosage of deionized water described in step (2) is 57 parts by weight；
The temperature of the water bath with thermostatic control is 35 DEG C.
Method according to the present invention, preferred steps (3) described mixing step are：By template solution and vanadium source solution
It is stirred 1-3h in 30-40 DEG C of water bath with thermostatic control, the n-butanol of 2.0-3.2 parts by weight is added, continues to stir 1-2h, then
The tetraethyl orthosilicate for instilling 4.2-9.6 parts by weight is further continued for stirring 24-36h, gets a uniform mixture.It is excellent in the present invention
It is that vanadium source solution is added in template solution in the embodiment of choosing, in step (3), is stirred for mixing.
In preferred embodiment of the invention, step (3) described mixing step is：Template solution and vanadium source is molten
Liquid is stirred 1-3h in 35 DEG C of water bath with thermostatic control, and the n-butanol of 2.5 parts by weight is added, and continues to stir 1h, then instills 6.4
The tetraethyl orthosilicate of parts by weight is further continued for stirring for 24 hours, gets a uniform mixture.
Method according to the present invention, for pH value is adjusted to 5-6 in preferred steps (4), the present invention more preferably will
PH value is adjusted to 5.
Method according to the present invention, preferred steps (5) described crystallization are：It will be in step (4) after the adjustment after pH value
Mixed solution, which is put into high pressure crystallization kettle at 80-120 DEG C, carries out crystallization 24-48h；
It is wherein more preferably described to be cooled to be cooled to room temperature；
It is centrifuged as with the rotating speed of 3000-5000r/min centrifugation 5-15min even more preferably from described；
It is to be rinsed filtrate to non-foam with deionized water even more preferably from the washing；
It is 80-120 DEG C of dry 6-12h even more preferably from the drying；
It is roasted to 530-580 DEG C of roasting 4-8h even more preferably from described.
The temperature of the further preferred step of the present invention (5) described crystallization is 100 DEG C；Dry temperature is 100 DEG C, is done
The dry time is 10h, and the temperature of roasting is 550 DEG C, and the time of roasting is 6h, and the heating rate control of roasting is 1-2 DEG C/min.
Preparation method according to the present invention, the oxidation silicon substrate KIT-6 mesoporous moleculars containing vanadium active component in skeleton
The preparation process of sieve is triblock copolymer P123 template to be dissolved in hydrochloric acid first, then ammonium metavanadate is dissolved in deionized water
In (dosage of deionized water is the molten required water of triblock copolymer P123 template of script), triblock copolymer is waited for
P123 templates, ammonium metavanadate again mix the two after dissolving, and both ensure that the two can fully dissolve in this way, while also not having
There is the proportioning for changing KIT-6 synthesis materials.Then, the pH value for adjusting mixed solution after stirring 24-36h again, because of KIT-6 at this time
Three-dimensional cubic duct structure basically formed, at this moment adjust pH value again, can not only make vanadium active component doping enter point
In the skeleton of son sieve silicon, and the pore passage structure that can also keep mesopore molecular sieve original well.
In conclusion the present invention provides a kind of vanadium doping aoxidize silicon substrate mesoporous molecular sieve catalyst and preparation method thereof and
Its application in selective oxidation of propane dehydrogenation alkene.The vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst of the present invention has
Following advantage：
Active component is directly anchored in KIT-6 mesopore molecular sieve building-up processes by direct hydrothermal synthesis by the present invention
In the lattice of framework of molecular sieve, the degree of order higher of the silicon substrate KIT-6 mesopore molecular sieves containing vanadium in obtained skeleton, more favorably
In the transmission of reactants and products；Meanwhile activity in vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst provided by the present invention
The dispersion degree higher of component vanadium, the concentration bigger of active sites, and the stability higher of active sites, therefore, the catalysis of the catalyst
Activity is higher.
Vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst provided by the invention with three-dimensional spiral to intersect pore passage structure
Pure silicon KIT-6 mesopore molecular sieves be carrier, wherein three-dimensional spiral intersects pore passage structure and is conducive to dispersion and the object of active component
The transmission of material；With SiO2, the carriers such as SBA-15 and MCM-41 compare, will be using the pure silicon KIT-6 mesopore molecular sieves as carrier
When catalyst obtained is used for selective oxidation of propane alkene, with higher selective oxidation of propane activity；
Meanwhile catalyst provided by the invention as active component and is adulterated into pure using the oxide of Transition Metals V
In the skeleton of silicon KIT-6 mesopore molecular sieves, the oxide active component of Transition Metals V is doped into pure silicon KIT-6 mesoporous moleculars
The catalyst is being used for selective oxidation of propane dehydrogenation system by the dispersion degree and stability that can promote active sites in sieve carrier framework
In alkene, the catalytic activity of propane can further improve.
Vanadium doping provided by the invention oxidation silicon substrate mesoporous molecular sieve catalyst is applied to selective oxidation of propane dehydrogenation system
In the reaction of alkene, in the preferred embodiment of the invention, the product propylene of selective oxidation of propane reaction and alkene (ethylene and third
Alkene) molar yield can reach 35.6% and 38.6% respectively, the high degree of dispersion due to active metal vanadium and special part
Chemical environment causes catalyst to have excellent reactivity worth in selective oxidation of propane dehydrogenation reaction.
Description of the drawings
Fig. 1 is in embodiment 1 under different pH value, and V, Si molar ratio are 1:The V-KIT-6 catalyst synthesized under the conditions of 100
Small angle XRD spectra；
Fig. 2 is in embodiment 1 under different pH value, and V, Si molar ratio are 1:The V-KIT-6 catalyst synthesized under the conditions of 100
UV-vis DRS spectrogram；
Fig. 3 is that the V-KIT-6 catalyst synthesized under conditions of difference V, Si molar ratio in embodiment 2 and pure silicon KIT-6 are situated between
The small angle XRD spectra of porous molecular sieve；
Fig. 4 is that the V-KIT-6 catalyst synthesized under conditions of difference V, Si molar ratio in embodiment 2 and pure silicon KIT-6 are situated between
The transmission electron microscope picture of porous molecular sieve；
Fig. 5 is that the UV, visible light of the V-KIT-6 catalyst synthesized under conditions of difference V, Si molar ratio in embodiment 2 is unrestrained anti-
Penetrate spectrogram；
Fig. 6 is mesoporous for V-KIT-6 catalyst, the pure silicon KIT-6 synthesized under conditions of difference V, Si molar ratio in embodiment 2
The ultraviolet raman spectrum of molecular sieve and the KIT-6 mesoporous molecular sieve catalysts being prepared using existing infusion process.
Fig. 7 is that V, Si molar ratio are respectively 3 in application examples:100,5:100,8:100 V-KIT-6 catalyst is in propane oxygen
The front and back ultraviolet raman spectrum of fluidized dehydrogenation reaction.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction in detail below
Embodiment and Figure of description carry out following detailed description to technical scheme of the present invention, but should not be understood as can to of the invention
The restriction of practical range.
Embodiment 1
It present embodiments provides under six kinds of different pH value, V, Si molar ratio are 1:The preparation side of 100 V-KIT-6 catalyst
Method is prepared according to the following steps：
(1) template solution is prepared：The triblock copolymer P123 template of 2g, which is dissolved in 19g molar concentrations, is
In the hydrochloric acid of 2.0mol/L, the magnetic agitation 4h in 35 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template completely molten
Solution forms homogeneous phase solution, obtains triblock copolymer P123 template solution；
Six parts of identical homogeneous triblock copolymer P123 template solutions are prepared using identical operating condition.
(2) vanadium source solution is prepared：The ammonium metavanadate for weighing 0.036g mixes it with 57g deionized water water, at 35 DEG C
Magnetic agitation in water bath with thermostatic control, makes to form uniform solution, obtains ammonium metavanadate solution；
Six parts of identical ammonium metavanadate solutions are prepared using identical operating condition.
(3) it mixes：By above-mentioned six parts homogeneous triblock copolymer P123 template solutions respectively with corresponding six parts of inclined vanadium
2h is stirred in 35 DEG C of waters bath with thermostatic control after acid ammonium solution mixing, is then slowly dropped into 2.5g n-butanols respectively, is continued after stirring 1h,
6.4g tetraethyl orthosilicates are added dropwise respectively again, then lasting stirring for 24 hours, obtains six parts of identical mixed solutions；
Above-mentioned ammonium metavanadate, tetraethyl orthosilicate quality be with V, Si molar ratio be 1:What 100 conversions obtained.
(4) pH is adjusted：Continue agitating solution, ammonium hydroxide is added dropwise in five parts of mixed solutions thereto with by mixed solution
PH value be adjusted to 2,3,5,8,10 respectively；Ammonium hydroxide is added without in another mixed solution, as a control group.
(5) crystallization：Six parts of mixed solutions that above-mentioned steps (4) obtain are poured into respectively in six high pressure crystallization kettles,
The Crystallizing treatment of 48h is carried out at 100 DEG C, is cooled to room temperature after Crystallizing treatment, again with the centrifugation of the rotating speed of 4000 turns/min
10min is filtered, is reused deionized water and rinse filtrate to non-foam, finally the dry 10h at 100 DEG C, is roasted at 550 DEG C
6h obtains the six kinds of vanadium doping synthesized at various ph values oxidation silicon substrates and is situated between wherein the heating rate of the roasting is 2 DEG C/min
Pore zeolite catalyst V-KIT-6.
Above-mentioned six kinds of V-KIT-6 molecular sieve catalysts are detected using X-ray small angle powder diffractometer, according to difference
The diffraction maximum of position and the intensity of diffraction maximum may determine that whether meso-porous molecular sieve material is formed and its degree of order.
The small angle XRD spectra of above-mentioned six kinds of V-KIT-6 molecular sieve catalysts is as shown in Figure 1.As shown in Figure 1, small in pH value
The catalyst synthesized under conditions of 8 can belong to respectively 2 θ are about 0.9 °, apparent diffraction maximum occurs in 1.1 ° of position
In the characteristic diffraction peak of (211) (220) crystal face of KIT-6 molecular sieves, this shows that the V-KIT-6 molecular sieves of skeleton doping vanadium are kept
Original meso-hole structure and there is a preferable degree of order, and the catalyst synthesized under conditions of pH value is more than 8 is in low-angle
Without apparent diffraction maximum in range, this shows compared with not forming the orderly mesoporous knot of KIT-6 molecular sieves under strong alkaline condition
Structure.
UV-vis DRS spectrogram such as Fig. 2 of the V-KIT-6 of the pure silicon KIT-6 mesopore molecular sieves of above-mentioned six kinds of vanadium dopings
It is shown.As shown in Figure 2, when pH value is more than 2, there are two apparent diffraction maximums at 230nm and 320nm, can be respectively belonging to four and match
The vanadium oxygen species of position and hexa-coordinate；And pH value is when being less than or equal to 2, without apparent diffraction maximum, this illustrates that vanadium is not doped into point
In the skeleton of son sieve.Simultaneously it is also found that when pH value is 5 from Fig. 2, the diffraction maximum at 230nm becomes apparent, and illustrates high score
Proportion is maximum in the catalyst for the oxidation vanadium species of scattered four-coordination, it is preferable that the catalyst of the present invention is in pH
Value synthesizes under conditions of being 5, but without apparent absorption peak after 450nm, this illustrates the oxygen for not having crystalline phase in catalyst
Change vanadium to exist.
Embodiment 2
Present embodiments providing six kinds of difference V, Si molar ratios, (V, Si molar ratio are respectively 0.1:100,0.5:100,1:
100,3:100,5:100,8:100) preparation method of the KIT-6 mesoporous molecular sieve catalysts of vanadium doping, preparation method packet
Include following steps：
(1) template solution is prepared：The triblock copolymer P123 template of 2g, which is dissolved in 19g molar concentrations, is
In the hydrochloric acid of 2.0mol/L, the magnetic agitation 4h in 35 DEG C of water bath with thermostatic control keeps triblock copolymer P123 template completely molten
Solution forms homogeneous phase solution, obtains triblock copolymer P123 template solution；
Six parts of identical homogeneous triblock copolymer P123 template solutions are prepared using identical operating condition.
(2) vanadium source solution is prepared：0.004g, 0.018g, 0.036g, 0.108g, 0.180g and 0.288g are weighed respectively
Ammonium metavanadate respectively mixes it with 57g deionized waters, and the magnetic agitation in 35 DEG C of water bath with thermostatic control makes to form uniform solution,
Obtain six parts of ammonium metavanadate solutions.
(3) it mixes：By six parts of homogeneous triblock copolymer P123 template solutions in step (1) respectively with step (2)
In 2h is stirred in 35 DEG C of waters bath with thermostatic control after the mixing of corresponding six parts of ammonium metavanadate solutions, be then slowly dropped into the positive fourths of 2.5g respectively
Alcohol continues after stirring 1h, then 6.4g tetraethyl orthosilicates is added dropwise respectively, and then lasting stirring for 24 hours, it is molten to obtain six parts of mixing
Liquid；
Above-mentioned ammonium metavanadate, tetraethyl orthosilicate quality convert to obtain according to V, Si molar ratio.
(4) pH is adjusted：Continue agitating solution, it is molten will mix that ammonium hydroxide is added dropwise into above-mentioned six parts of mixed solutions respectively
The pH value of liquid is adjusted to 5.
(5) crystallization：Six parts of mixed solutions that above-mentioned steps (4) obtain are poured into respectively in six high pressure crystallization kettles,
The Crystallizing treatment of 48h is carried out at 100 DEG C, is cooled to room temperature after Crystallizing treatment, again with the centrifugation of the rotating speed of 4000 turns/min
10min is filtered, is reused deionized water and rinse filtrate to non-foam, finally the dry 10h at 100 DEG C, is roasted at 550 DEG C
6h obtains the pure silicon KIT-6 mesopore molecular sieves of six kinds of different vanadium doping amounts wherein the heating rate of the roasting is 2 DEG C/min,
It is denoted as 0.1V-KIT-6,0.5V-KIT-6,1V-KIT-6,3V-KIT-6,5V-KIT-6,8V-KIT-6 respectively.
Six kinds of V-KIT-6 molecular sieve catalysts in the present embodiment are detected using X-ray small angle powder diffractometer,
The pure silicon KIT-6 mesopore molecular sieves of obtained in embodiment 2 six kinds different vanadium doping amounts and pure silicon KIT-6 mesopore molecular sieves it is small
Angle XRD spectra is as shown in Figure 3.From the figure 3, it may be seen that being less than or equal to 5 in V, Si molar ratio:The catalyst synthesized under the conditions of 100 is 2
θ is about 0.9 °, apparent diffraction maximum occurs in 1.1 ° of position, can be respectively belonging to (211) (220) of KIT-6 molecular sieves
The characteristic diffraction peak of crystal face, this show skeleton doping vanadium V-KIT-6 molecular sieves maintain original meso-hole structure and have compared with
The good degree of order.And it is equal to 8 in V, Si molar ratio:The catalyst synthesized under conditions of 100 is in small angle range without apparent
Diffraction maximum, this shows the KIT-6 molecular sieve meso-hole structures that long-range order is not formed under conditions of introducing a large amount of vanadium.With
The introducing of V, the peak positions of XRD diffraction maximums also demonstrate vanadium doping into the skeleton of KIT-6 molecular sieves to low-angle offset.
V, Si molar ratio are 0 in embodiment 2:100 (pure silicon mesopore molecular sieve KIT-6), 3:100,5:100,8:100 V-
The transmission electron microscope picture of KIT-6 catalyst is as shown in figure 4, it distinguishes a, b, c, d in corresponding diagram 4.As shown in Figure 4, it rubs in V, Si
You are than being not more than 5:When 100, V-KIT-6 mesoporous molecular sieve catalysts have well-regulated orderly pore passage structure, and pore passage structure is clear
As it can be seen that the oxide particle of vanadium does not exist.It is 8 in V, Si molar ratio:When 100, V-KIT-6 mesoporous molecular sieve catalysts by
Partial destruction.The characterization result of transmission electron microscope proves that the V-KIT-6 molecular sieve catalysts of synthesis maintain KIT-6 mesopore molecular sieves
Three-dimensional open-framework feature, and vanadium active component is all high dispersive.
The UV, visible light of the pure silicon KIT-6 mesoporous molecular sieve catalysts of the six kinds of different vanadium doping amounts obtained in embodiment 2
Diffusing reflection spectrogram is as shown in Figure 5.From figure 5 it can be seen that after Transition Metals V is added, there are two apparent at 230nm and 320nm
Diffraction maximum, four-coordination and the vanadium oxygen species of hexa-coordinate can be respectively belonging to.With the increase of V dopings, absorption peak strength
Increasing, the absorption peak strength at especially 320nm becomes apparent compared with the absorption peak strength increase at 230nm, this explanation is oligomeric
Ratio gradually increases the oxidation vanadium species of conjunction state in the catalyst, but the four-coordination vanadium oxygen species of high dispersive still account for the overwhelming majority
's.Until V:Si molar ratios reach 8:After 100, there is apparent absorption peak in 450nm, this illustrates occur crystalline phase in catalyst
Vanadium oxide.
Pure silicon KIT-6 mesoporous molecular sieve catalysts, the pure silicon KIT-6 of the six kinds of different vanadium doping amounts obtained in embodiment 2
Mesopore molecular sieve and KIT-6 mesoporous molecular sieve catalysts (0.1V/KIT-6, the 0.5V/ being prepared using existing infusion process
KIT-6,1V/KIT-6,1.8V/KIT-6) ultraviolet raman spectrum it is as shown in Figure 6.From fig. 6 it can be seen that vanadium skeleton adulterates
Apparent 920 and 1060 the two absorption peaks of individualism of molecular sieve, the two absorption peaks are respectively belonging to V-O-Si stretching vibrations
And the vibration that silicon skeleton is interfered, this shows that vanadium atom is doped into the skeleton of silicon；And existing infusion process is used to prepare
There is no 920 and 1060 the two suctions for obtained 0.1V/KIT-6,0.5V/KIT-6,1V/KIT-6,1.8V/KIT-6 catalyst
Peak is received, this shows that doping does not enter in the skeleton of silicon vanadium atom, and is only to be supported on its surface.
The respective physical chemical parameters such as table 1 of the V-KIT-6 catalyst for six kinds of difference V, Si molar ratios that embodiment 2 obtains
It is shown, in table 1, SBETIndicate the BET specific surface area of catalyst, VPIndicate that the pore volume of catalyst, D indicate the aperture of catalyst.
The structural parameters of table 1KIT-6 and V-KIT-6 catalyst
| Sample | SBET,m2/g | VP,cm3/g | D,nm |
| KIT-6 | 816 | 1.10 | 8.9 |
| 0.1V-KIT-6 | 954 | 1.16 | 9.2 |
| 0.5V-KIT-6 | 880 | 1.15 | 9.3 |
| 1V-KIT-6 | 868 | 1.14 | 9.6 |
| 3V-KIT-6 | 843 | 1.14 | 9.5 |
| 5V-KIT-6 | 846 | 1.15 | 9.7 |
| 8V-KIT-6 | 618 | 0.86 | 8.9 |
From table 1 it follows that compared with pure KIT-6, it is doped with the ratio of the KIT-6 catalyst (in addition to 8V-KIT-6) of vanadium
Surface area, hole hold and aperture have it is different degrees of become larger, this illustrates that the addition of vanadium is conducive to the raising of the degree of order of KIT-6,
This is consistent with small angle XRD data and transmission electron microscope picture.
Application examples 1
The application example is de- to the selective oxidation of propane for six kinds of V-KIT-6 molecular sieve catalysts being prepared in embodiment 2
Hydrogen reactivity has carried out evaluation test, wherein：
Six kinds of V-KIT-6 molecular sieve catalysts performance evaluations carry out on miniature fixed-bed reactor, reaction knot
On-line quantitative analysis is carried out to the gas composition after reaction using gas chromatograph (SP-3420, Beijing Analytical Instrument Factory) after beam.
Wherein reactor is transparent fixed bed crystal reaction tube, bore 6mm, thickness of pipe wall 1mm.Catalyst is placed in heating furnace
Constant temperature fragment position, is fixed with silica wool up and down.Temperature is controlled using accurate temperature controller in experimentation, heating furnace uses
Program control heating.Catalyst filling amount is 0.1g, and unstripped gas total flow is 40mLmin-1(C3H8:O2:N2=1:1:8, body
Product ratio), the pressure of reaction gas is 0.4MPa, and the granularity of catalyst sample is 60 mesh to 100 mesh.
1, reactor outlet gas phase composition analysis
With the gas-phase product of gas chromatograph (SP-3420, Beijing Analytical Instrument Factory) separate reactor outlet and detection.Profit
The gas composition exported with double FID hydrogen flame detectors analysis reactors：With Porapack-Q columns (3m) separation propylene, propane,
Ethylene, ethane, acetaldehyde, methacrylaldehyde, acetone and propyl alcohol, and detected with flame ionization ditector；It is filled with the TDX-01 of 1m
Post separation CO, CH4、CO2、HCHO、C2H4And C2H6, wherein CO and CO2Hydrogen is added to be changed into CH by nickel reburner4Afterwards with hydrogen flame
Ionization detector detects.
2, gas-chromatography separation detection condition
Six-way valve and injector temperature are 150 DEG C, and methane reborner and detector temperature are 380 DEG C, chromatograph box temperature
Using temperature programming, initial temperature is 70 DEG C, and it is 150 DEG C to keep 15min, final temperature, and heating rate is 40 DEG C of min-1；Chromatographic column nitrogen
Carrier gas current stabilization flow velocity is 10mLmin-1.The hydrogen flowing quantity of detector is 30mLmin-1, air velocity 300mLmin-1。
3, analysis method
Conversion of propane, selectivity of product and yield are calculated using area normalization method；The specific method is as follows：
(1) carbon number of the peak areas × reactant or product obtained in effective peak area=chromatography of product × with third
Relative correction factor on the basis of alkane, i.e. Ai=A × Cn × fr；
(2) the sum of effective peak area of the effective peak area/gross product of selectivity of product=a certain product,
That is Selectivity i%=Ai/ ∑s Ai × 100%；
(3) conversion of propane=(the effective peak area of the unreacted propane of the effective peak area-of propane feed)/propane feed has
Imitate peak area × 100%；
(4) selectivity × conversion of propane of the yield of product=a certain component,
That is Yield i%=Selectivity i × Conversion C3H8× 100%.
(V, Si molar ratio are 0.1 to six kinds of V-KIT-6 molecular sieves that embodiment 2 provides:100,0.5:100,1:100,3:
100,5:100,8:100) activity data of the catalyst in being catalyzed selective oxidation of propane dehydrogenation reaction is as shown in table 2, reaction
Temperature is 600 DEG C.
The selective oxidation of propane performance of table 2V-KIT-6 catalyst
As shown in table 2, as the raising of the doping of vanadium, the conversion of propane take the lead in reducing after increasing, V, Si molar ratio are
5:When 100 or so, the conversion ratio of propane reaches highest, and maximum conversion reaches 55.0%；The selectivity of propylene also reaches at this time
Maximum, the molar yield and ethylene of propylene and the total moles yield of propylene respectively reach 35.6% and 38.6%.
V, Si molar ratio are respectively 3 in the application example:100,5:100,8:100 V-KIT-6 catalyst is in oxidation of propane
Ultraviolet raman spectrum before and after dehydrogenation reaction is as shown in Figure 7.It can be seen from figure 7 that before and after reaction, catalysis provided by the invention
The raman spectrum of agent does not have significant change, this illustrates that the active sites stability of the catalyst is preferable.
Comparative example
This comparative example each provides 5V-KIT-6 catalyst, the SiO that embodiment 2 is prepared2Carrier loaded vanadium base is urged
Agent (V-SiO2), the carrier loaded catalytic component based on vanadium of SBA-15 (V-SBA-15) and the carrier loaded catalytic component based on vanadium of MCM-41
(V-MCM-41) selective oxidation of propane dehydrogenation reaction activity has carried out evaluation test, wherein：V-SiO2、V-SBA-15、V-
MCM-41 catalyst (Y.Liu, Y.Cao, N.Yi, et al., J.Catal., 2004,224:417-428) it is this field routine
Catalyst, in addition, the test method and data method in this comparative example are identical as the corresponding method in application examples, herein not
It repeats；5V-KIT-6,V-SiO2, V-SBA-15 and V-MCM-41 these four catalyst selective oxidation of propane performance data such as table
Shown in 3.
Table 3
As shown in table 3, by with SiO2, the carriers such as SBA-15, MCM-41 catalytic component based on vanadium compare, the present invention is prepared into
To V-KIT-6 catalyst show more excellent oxidative dehydrogenation of propane performance, the either conversion ratio of propane or third
The total moles yield of alkene and ethylene and propylene, which is obtained for, to be increased substantially.
Claims (22)
- It is using pure silicon mesopore molecular sieve KIT-6 as carrier, with vanadium 1. a kind of vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst Oxide is active component, and the barium oxide doping enters in the skeleton of the pure silicon mesopore molecular sieve KIT-6, and V, Si Molar ratio be 0.1:100-8:100；It is to be with triblock copolymer P123 that the barium oxide, which adulterates in the skeleton for entering the pure silicon mesopore molecular sieve KIT-6, Template is realized as raw material using direct hydrothermal synthesis method, mesoporous point of the KIT-6 being prepared using hydrochloric acid, vanadium source and silicon source Son sieve is the V-KIT-6 mesopore molecular sieves containing vanadium in skeleton；Vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst is prepared using the method included the following steps：(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring to triblock copolymer P123 templates are completely dissolved, and obtain template solution；(2) vanadium source solution is prepared：Vanadium source is dissolved in deionized water, stirring is completely dissolved to vanadium source, obtains vanadium source solution；(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred 1-3h, and positive fourth is added Alcohol continues to stir 1-2h, obtains homogeneous phase solution, then instill silicon source, is further continued for stirring 24-36h, gets a uniform mixture；(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation point From, filter, washing, dry, calcination process, obtain the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium, i.e., the described vanadium in skeleton Doped silicon oxide base mesoporous molecular sieve catalyst.
- 2. catalyst according to claim 1, which is characterized in that the vanadium source includes vanadate.
- 3. catalyst according to claim 2, which is characterized in that the vanadate includes ammonium metavanadate.
- 4. catalyst according to claim 1, which is characterized in that the silicon source includes tetraethyl orthosilicate.
- 5. catalyst according to claim 1, which is characterized in that the weight of the n-butanol and triblock copolymer P123 Than being 1.0:1-1.6:1.
- 6. catalyst according to claim 1, which is characterized in that the pH value is 5-6.
- 7. catalyst according to claim 1, which is characterized in that step (1) prepares template solution and is：By 1-3 weight The triblock copolymer P123 template of part is dissolved in the dilute hydrochloric acid that 17-21 parts by weight molar concentrations are 1.0-3.0mol/L, is stirred It mixes to triblock copolymer P123 template and is completely dissolved, obtain template solution.
- 8. catalyst according to claim 7, which is characterized in that stirring 4-6h in 30-40 DEG C of water bath with thermostatic control makes three Block copolymer P123 templates are completely dissolved, and obtain template solution.
- 9. catalyst according to claim 1, which is characterized in that step (2) prepares vanadium source solution and is：Vanadium source is dissolved in In ionized water, 3-5h is stirred in 30-40 DEG C of water bath with thermostatic control, forms it into uniform solution, obtains vanadium source solution.
- 10. catalyst according to claim 1, which is characterized in that step (5) described crystallization is：By in step (4) through adjust Mixed solution after section pH value, which is put into high pressure crystallization kettle at 80-120 DEG C, carries out crystallization 24-48h.
- 11. catalyst according to claim 1, which is characterized in that described to be cooled to be cooled to room temperature.
- 12. catalyst according to claim 1, which is characterized in that described to centrifuge as with 3000-5000r/min's Rotating speed centrifuges 5-15min.
- 13. catalyst according to claim 1, which is characterized in that it is described washing for deionized water by filtrate rinse to Non-foam.
- 14. catalyst according to claim 1, which is characterized in that the drying is 80-120 DEG C of dry 6-12h.
- 15. catalyst according to claim 1, which is characterized in that described to be roasted to 530-580 DEG C of roasting 4-8h.
- 16. catalyst according to claim 15, which is characterized in that the control of the heating rate of the roasting for 1-2 DEG C/ min。
- 17. according to the catalyst described in claim 1-16 any one, which is characterized in that the BET specific surfaces of the catalyst Product is 600-1000m2/ g, pore volume 0.80-1.20cm3 / g, aperture 8.0-10.0nm.
- 18. catalyst according to claim 17, which is characterized in that the BET specific surface area of the catalyst is 843- 1000m2/ g, pore volume 1.14-1.20cm3 / g, aperture 9.2-10.0nm.
- 19. a kind of method preparing vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst described in claim 1-18 any one, Described method includes following steps：(1) template solution is prepared：Triblock copolymer P123 template is dissolved in dilute hydrochloric acid, stirring to triblock copolymer P123 templates are completely dissolved, and obtain template solution；(2) vanadium source solution is prepared：Vanadium source is dissolved in deionized water, stirring is completely dissolved to vanadium source, obtains vanadium source solution；(3) it mixes：By vanadium source solution and template solution by weight 0.3:1-0.43:1 is stirred, and n-butanol is added, after Continuous stirring, obtains homogeneous phase solution, then instills silicon source, then agitated gets a uniform mixture；(4) pH value is adjusted：The mixed solution and dripping ammonium hydroxide obtained to step (3), 3-8 is adjusted to by its pH value；(5) crystallization：By the mixed solution after pH value carries out crystallization after the adjustment in step (4), then through cooling, centrifugation point From, filter, washing, dry, calcination process, obtain the oxidation silicon substrate KIT-6 mesopore molecular sieves containing vanadium, i.e., the described vanadium in skeleton Doped silicon oxide base mesoporous molecular sieve catalyst.
- 20. according to the method for claim 19, which is characterized in that the weight of the n-butanol and triblock copolymer P123 Than being 1.0:1-1.6:1.
- 21. according to the method for claim 19, which is characterized in that the pH value is 5-6.
- 22. the vanadium doping described in claim 1-18 any one aoxidizes silicon substrate mesoporous molecular sieve catalyst in selective oxidation of propane Application in dehydrogenation alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610124322.6A CN105728013B (en) | 2016-03-04 | 2016-03-04 | Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610124322.6A CN105728013B (en) | 2016-03-04 | 2016-03-04 | Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105728013A CN105728013A (en) | 2016-07-06 |
| CN105728013B true CN105728013B (en) | 2018-11-02 |
Family
ID=56249813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610124322.6A Active CN105728013B (en) | 2016-03-04 | 2016-03-04 | Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105728013B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126687B (en) * | 2017-12-28 | 2020-10-16 | 沈阳师范大学 | Molybdenum and molybdenum-vanadium co-doped nano silicon oxide-based catalyst, and preparation method and application thereof |
| CN108160068A (en) * | 2017-12-28 | 2018-06-15 | 沈阳师范大学 | A kind of second of high activity, selective oxidation of propane catalyst and its preparation method and application |
| CN108325496B (en) * | 2018-02-07 | 2021-06-01 | 苏州科技大学 | Method for synthesizing efficient catalytic degradation methylene blue metal mesoporous silicon oxide through grinding-assisted self-permeation |
| CN108906114B (en) * | 2018-07-19 | 2021-02-09 | 北京石油化工学院 | Vanadium-containing mesoporous silica ball catalyst and preparation method and application thereof |
| CN111054431B (en) * | 2018-10-17 | 2022-08-12 | 中国石油化工股份有限公司 | Mesoporous silica microsphere with high catalytic activity |
| CN112756009B (en) * | 2019-11-04 | 2023-09-08 | 中国石油化工股份有限公司 | C4 olefin cracking catalyst containing three-dimensional cubic mesoporous molecular sieve, and preparation method and application thereof |
| CN115430455B (en) * | 2021-06-03 | 2024-06-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dehydrogenating V-base propane and preparation method thereof |
| CN113559923B (en) * | 2021-07-23 | 2023-08-29 | 陕西师范大学 | VOx/Zr-TUD-1 catalyst and method for preparing fluorine-containing epoxy oligomer-based styrene by catalytic dehydrogenation |
| CN114272949B (en) * | 2021-12-31 | 2023-11-21 | 上海复翼环保科技有限公司 | M1 type molybdenum molecular sieve denitration catalyst resistant to ABS poisoning at low temperature and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537314A (en) * | 2013-09-26 | 2014-01-29 | 中国石油大学(北京) | Catalyst for producing aldehyde and ethylene through selective oxidation of ethane, and preparation and application thereof |
| CN103816933A (en) * | 2014-02-13 | 2014-05-28 | 中国石油大学(北京) | Dehydrogenation catalyzing material as well as preparation method and application thereof |
| CN104003414A (en) * | 2014-05-20 | 2014-08-27 | 上海师范大学 | Vanadium-containing MCM-41 heteroatom molecular sieve catalyst as well as preparation method and application thereof |
-
2016
- 2016-03-04 CN CN201610124322.6A patent/CN105728013B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537314A (en) * | 2013-09-26 | 2014-01-29 | 中国石油大学(北京) | Catalyst for producing aldehyde and ethylene through selective oxidation of ethane, and preparation and application thereof |
| CN103816933A (en) * | 2014-02-13 | 2014-05-28 | 中国石油大学(北京) | Dehydrogenation catalyzing material as well as preparation method and application thereof |
| CN104003414A (en) * | 2014-05-20 | 2014-08-27 | 上海师范大学 | Vanadium-containing MCM-41 heteroatom molecular sieve catalyst as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105728013A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105728013B (en) | Vanadium doping aoxidizes silicon substrate mesoporous molecular sieve catalyst and the preparation method and application thereof | |
| CN108906114B (en) | Vanadium-containing mesoporous silica ball catalyst and preparation method and application thereof | |
| CN110256376A (en) | A kind of fluidization reaction method of propylene and hydrogen peroxide gas-phase epoxidation synthesizing epoxypropane | |
| CN105712379B (en) | A kind of synthetic method of multi-stage porous ZSM-5 molecular sieve | |
| Lin et al. | Synthesis and catalytic activity of Ti-MCM-41 nanoparticles with highly active titanium sites | |
| CN106925344A (en) | Including the mechanograph containing Ti and the zeolitic material of Zn | |
| CN106745036B (en) | Multi-stage porous SSZ-13 molecular sieve and its synthetic method and application with micropore-mesopore | |
| CN108126687B (en) | Molybdenum and molybdenum-vanadium co-doped nano silicon oxide-based catalyst, and preparation method and application thereof | |
| CN104709920B (en) | Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof | |
| CN104556125B (en) | A kind of isomorphous composite molecular screen and its preparation method and application | |
| CN106140245B (en) | Preparing propylene by propane selective oxidization and alkene catalyst and its preparation and application | |
| Rahman et al. | Aerobic Baeyer–Villiger oxidation of cyclic ketones over periodic mesoporous silica Cu/Fe/Ni/Co-HMS-X | |
| CN104556113A (en) | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent | |
| CN106904632A (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN105712378A (en) | Synthetic method for nanometer ZSM-5 molecular sieve | |
| CN105621449B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| Wang et al. | Preparation of bifunctional core-shell structured Cu/TS-1@ MCM-41 molecular sieves for synthesis of aniline by benzene in one step amination | |
| CN102125869A (en) | Catalyst for preparing acetaldehyde by ethane selective oxidation and preparation method thereof | |
| CN105217650B (en) | Mesoporous titanium silicate molecular sieve, synthetic method therefor and application thereof as well as method for oxidizing 2,6-di-tert-butylphenol | |
| CN105293515B (en) | A kind of MWW structure molecular screens and its synthetic method | |
| Tang et al. | Regulation of framework titanium siting in MWW-type titanosilicates by boron and aluminum incorporation and its effect on the catalytic performance | |
| CN101205075B (en) | Method for synthesizing titanium-containing molecular sieve material | |
| CN107879355B (en) | Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation | |
| CN101519213A (en) | Synthetic method of titanium-containing mesoporous materials | |
| CN105293517B (en) | HTS and its preparation method and application and a kind of method of alkene direct oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |