CN108906114A - One kind sphere catalyst of mesopore silicon oxide containing vanadium and the preparation method and application thereof - Google Patents
One kind sphere catalyst of mesopore silicon oxide containing vanadium and the preparation method and application thereof Download PDFInfo
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- CN108906114A CN108906114A CN201810796290.3A CN201810796290A CN108906114A CN 108906114 A CN108906114 A CN 108906114A CN 201810796290 A CN201810796290 A CN 201810796290A CN 108906114 A CN108906114 A CN 108906114A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 84
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 title abstract description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000001294 propane Substances 0.000 claims abstract description 26
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 10
- 241000555268 Dendroides Species 0.000 claims abstract description 5
- -1 propane alkene Chemical class 0.000 claims abstract 4
- 229910052710 silicon Inorganic materials 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 6
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229960004025 sodium salicylate Drugs 0.000 claims description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 239000002808 molecular sieve Substances 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical group [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of catalyst of mesoporous monox nanometer ball containing vanadium and the preparation method and application thereof, the catalyst using the super large mesoporous monox nanometer ball of dendroid as carrier, using barium oxide as active component, barium oxide doping enters in the skeleton of mesopore silicon oxide spheres.The present invention also provides the preparation method of above-mentioned catalyst and its applications in oxidative dehydrogenation of propane alkene.Vanadium doping mesoporous monox nanometer ball catalyst particle size provided by the present invention is uniform, has the biggish meso-hole structure of dendroid, the dispersion degree of active component vanadium is higher, and the concentration of active sites is larger.The catalyst is applied in the reaction of oxidative dehydrogenation of propane alkene, when conversion of propane is 20%, the selectivity of propylene and alkene (ethylene and propylene) can achieve 71.3% and 77.6% respectively.
Description
Technical field
The invention belongs to petrochemical industry catalysis technical fields, are related to one kind sphere catalyst of mesopore silicon oxide containing vanadium and its preparation
Method and application.
Background technique
Since 1992, the scientists of Mobil company (J.S.Beck, J.C.Vartuli, W.J.Roth, et al.,
J.Am.Chem.Soc.,1992,114:10834-10843) preparing for the first time with nanostructure self-assembling technique has uniformly
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.Catalytic component based on vanadium has good catalytic effect, catalytic performance and vanadium oxygen species for preparing propene by oxidative dehydrogenation of propane reaction
Existing forms and carrier structure it is closely related.Carrier can disperse barium oxide kind well, and being formed has specific physical
Thus the catalyst activity of catalyst can be improved in the activated centre of chemical characteristic.Mesopore molecular sieve has special cellular structure
And appearance structure, be conducive to suction adsorption desorption, diffusion and shape selective catalysis of reactant molecule etc., to depositing for the active specy of catalyst
It also has certain effect and influences in form.The method that active sites are introduced in mesopore molecular sieve common at present can be divided into two
Kind：Post synthesis method and in-situ synthesis.Post synthesis method mainly includes infusion process, grafting and ion-exchange etc..These methods
Often complex for operation step, active specy is generally formed in mesopore surfaces, and the interaction between carrier is weaker, therefore activity
Species are easy polymerization.And in-situ synthesis is that active component is introduced in sieve synthesis procedure, direct hydrothermal synthesis metal is mixed
Miscellaneous mesopore molecular sieve.Active sites are introduced directly into the skeleton of molecular sieve in this way, enhance its interaction with carrier, and
And it is easier to obtain the active sites of high dispersive isolation.
With super large mesoporous nanosilica white sphere as a kind of novel nano material, biggish mesoporous pore size, compared with
Small particle size, dendritic meso-hole structure are more advantageous to the diffusion of reactant and product.It enters vanadium as carrier doping
Atom is simultaneously applied in oxidative dehydrogenation of propane reaction, is had no and is had been reported that in document.The present invention is using mesopore silicon oxide spheres as carrier, vanadium
Oxygen species are active component, utilize the mesoporous oxidation of novel dendritic mesoporous silica nanospheres synthetic technology synthesis vanadium doping
Silicon ball catalyst, and be applied in oxidative dehydrogenation of propane reaction.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst of mesoporous monox nanometer ball containing vanadium.
The object of the invention is also to provide the preparation methods of the above-mentioned catalyst of mesoporous monox nanometer ball containing vanadium.
The object of the invention is also to provide the above-mentioned catalyst of mesoporous monox nanometer ball containing vanadium in oxidative dehydrogenation of propane system
Application in alkene.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of catalyst of mesoporous monox nanometer ball containing vanadium, with tree
Dendritic super large mesoporous monox nanometer ball is carrier, using barium oxide as active component, described in the barium oxide doping entrance
In the skeleton of mesoporous monox nanometer ball, the barium oxide is the vanadium oxygen species of high dispersive.
Catalyst according to the present invention, it is preferable that the barium oxide doping enters the mesopore silicon oxide containing vanadium
It is using cetyl trimethylammonium bromide (CTAB) ionic surfactant as template, with salicylic acid in the skeleton of nanosphere
Sodium is structure directing agent, real using direct hydrothermal synthesis method using vanadium source and silicon source as raw material using triethanolamine as synthetic catalyst
Existing, the super large mesoporous silicon oxide ball being prepared is the monox nanometer ball containing vanadium oxygen species in skeleton.
Wherein the vanadium source and silicon source can use vanadium source commonly used in the art and silicon source, present invention preferably uses
Vanadium source is vanadate, and the more preferable vanadate is ammonium metavanadate (molecular formula NH4VO3)。
Present invention preferably uses silicon source include tetraethyl orthosilicate.
Catalyst according to the present invention, preparation method include the following steps：
(1) triethanolamine solution is prepared：The desired amount of triethanolamine is dissolved in a certain amount of water, stirring to triethanolamine
It is completely dissolved, obtains the solution of triethanolamine；
(2) template and structure directing agent is added：The desired amount of CTAB template is added to the solution that step (1) obtains
In, the desired amount of sodium salicylate is added after to be dissolved, until being completely dissolved uniformly mixed, mixing time 1-3h；
(3) silicon source is added：The desired amount of silicon source is added to step (2) to obtain in solution, continues to stir 2-6h；
(4) vanadium source solution is prepared：Vanadium source is dissolved in deionized water, stirring is completely dissolved to vanadium source, obtains vanadium source solution；
(5) the vanadium source solution that step (4) obtains is added in the solution that step (3) obtains, continues to stir 0.5-1h；
(6) sedimentation and crystallization：The mixed solution that step (5) obtains is put into the crystallizing kettle with polytetrafluoroethyllining lining
It carries out sedimentation and crystallization and obtains mesopore silicon oxide spheres containing vanadium, i.e., then through cooling, suction filtration, washing, drying, calcination process
The sphere catalyst of mesopore silicon oxide containing vanadium.
Preferably, step (1) prepares template solution and is：The triethanolamine of 1-2 parts by weight is dissolved in 300-800 parts by weight
Deionized water in, stirring be completely dissolved to triethanolamine, obtain triethanolamine solution.
Wherein the present invention stirs 0.5-2h preferably in 60-90 DEG C of water bath with thermostatic control is completely dissolved triethanolamine, obtains
Triethanolamine solution, mixing speed are 200-500 revs/min.
In addition, the additive amount of triethanolamine is 1.5 parts by weight in step (1) in preferred embodiment of the invention,
The deionized water additive amount is 550 parts by weight；The temperature of the water bath with thermostatic control is 80 DEG C, and the mixing time of the stirring is
1h。
Preferably, template is added in step (2) and structure directing agent process is：The CTAB template of 5-10 parts by weight is added
Enter in the triethanolamine solution obtained to step (1), after being completely dissolved, the sodium salicylate of 2.5-5 parts by weight is added, in 60-90
DEG C water bath with thermostatic control in continuously stir 1-3h, mixing speed is 200-500 revs/min.
In addition, CTAB template additive amount is 7.5 parts by weight in step (2) in preferred embodiment of the invention,
The additive amount of sodium salicylate is 4 parts by weight；The temperature of the water bath with thermostatic control is 80 DEG C, and the mixing time of the stirring is 2h.
Preferably, step (3) addition silicon source process is：The silicon source of 55-100 parts by weight is added to what step (2) obtained
Mixed solution, continuously stirs 2-6h in 60-90 DEG C of water bath with thermostatic control, and mixing speed is 200-500 revs/min.
In addition, silicon source used in step (3) is tetraethyl orthosilicate, just in preferred embodiment of the invention
Tetraethyl orthosilicate additive amount is 84 parts by weight；The temperature of the water bath with thermostatic control is 80 DEG C, and the mixing time of the stirring is 4h.
Preferably, step (4) preparation vanadium source solution processes are：0.03-2.5 parts by weight vanadium source is dissolved in 5-15 parts by weight
In deionized water, 3-5h is stirred in 60-90 DEG C of water bath with thermostatic control, forms it into uniform solution, obtains vanadium source solution；
In preferred embodiment of the invention, the vanadium source is ammonium metavanadate, and the temperature of the water bath with thermostatic control is 80
DEG C, the mixing time of the stirring is 4h.
Preferably, step (5) addition vanadium source solution processes are：The vanadium source solution that step (4) obtains is added to step (3)
In obtained mixed solution, 0.5-1h is stirred in 60-90 DEG C of water bath with thermostatic control, mixing speed is 200-500 revs/min；
In embodiment of the invention preferred, the temperature of the water bath with thermostatic control is 80 DEG C, when the stirring of the stirring
Between be 0.75h, the mixing speed be 350 revs/min.
Preferably, step (6) described crystallization is：The mixed solution containing vanadium that step (5) obtains is put into polytetrafluoro
Crystallization 2-24h is carried out in the crystallization kettle of ethylene liner at 60-120 DEG C；Then through cooling, suction filtration, carrying out washing treatment；
Then dry 6-12h at a temperature of 60-100 DEG C；4-8h is finally roasted at 500-600 DEG C, the heating rate control of roasting is
1-2℃/min。
Mesopore silicon oxide spheres containing vanadium are obtained after having roasted, i.e., the described sphere catalyst of mesopore silicon oxide containing vanadium.
Wherein in preferred embodiment of the invention, the crystallization temperature is 80 DEG C, crystallization time 4h；
It is described to be cooled to be cooled to room temperature；
The washing is to be rinsed filtrate to non-foam with deionized water；
The drying is 80 DEG C of dry 10h；
Described to be roasted to 550 DEG C of roasting 6h, heating rate is 1 DEG C/min.
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.
The present invention also provides above-mentioned vanadium doping oxidation silicon substrate mesoporous molecular sieve catalysts in selective oxidation of propane dehydrogenation system
Application in alkene.
In conclusion the present invention provides a kind of vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst and preparation method thereof and
Its application in selective oxidation of propane dehydrogenation alkene.Vanadium doping oxidation silicon substrate mesoporous molecular sieve catalyst of the invention has
Following advantage：
The catalyst of mesoporous monox nanometer ball containing vanadium of the invention passes through direct water in nanosilica white sphere synthesis process
Active component is directly anchored in the lattice of framework of molecular sieve by thermal synthesis, and the nanosilica white sphere of vanadium is contained in obtained skeleton
The degree of order it is higher, be more advantageous to the transmission of reactants and products；Meanwhile vanadium doping provided by the present invention oxidation is silicon-based mesoporous
The dispersion degree of active component vanadium is higher in molecular sieve catalyst, and the concentration of active sites is bigger, and the stability of active sites is higher, because
This, the catalytic activity of the catalyst is higher.
The nano material novel as one kind with super large mesoporous nanosilica white sphere provided by the invention, it is biggish
Mesoporous pore size, lesser particle size, dendritic meso-hole structure are more advantageous to the diffusion of reactant and product.It is as carrier
Doping enters vanadium atom and is applied in oxidative dehydrogenation of propane reaction, has no and has been reported that in document.
Meanwhile catalyst provided by the invention as active component and is adulterated into receiving using the oxide of Transition Metals V
In the skeleton of rice silicon oxide ball, this can promote the dispersion degree and stability of active sites, which is being used for propane selection
In oxidative dehydrogenation alkene, the catalytic activity of propane can be improved.
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, when conversion of propane is 20%, the product propylene and alkene of oxidation reaction
The selectivity of hydrocarbon (ethylene and propylene) can achieve 71.3% and 77.6% respectively, high degree of dispersion and spy due to active metal vanadium
Different localized chemical environment causes catalyst to have excellent reactivity worth in selective oxidation of propane dehydrogenation reaction.
Detailed description of the invention
Fig. 1 is that V, Si molar ratio are 3 in the embodiment of the present invention 1:The doped meso-porous sphere catalyst of the V synthesized under the conditions of 100
Scanning electron microscope (SEM) photograph；
Fig. 2 is that V, Si molar ratio are 8 in the embodiment of the present invention 1:The doped meso-porous sphere catalyst of the V synthesized under the conditions of 100
Scanning electron microscope (SEM) photograph；
Fig. 3 is the nitrogen of the doped meso-porous sphere catalyst of V synthesized under conditions of difference V, Si molar ratio in the embodiment of the present invention 1
Aspiration desorption isotherm figure；
Fig. 4 is the nitrogen of the doped meso-porous sphere catalyst of V synthesized under conditions of difference V, Si molar ratio in the embodiment of the present invention 1
Graph of pore diameter distribution is desorbed in aspiration；
Fig. 5 is that V, Si molar ratio are 0 in the embodiment of the present invention 1:100,3:100,5:100,8:The V synthesized under the conditions of 100
The wide-angle XRD diagram of doped meso-porous sphere catalyst；
Fig. 6 is the doped meso-porous sphere catalyst of V that synthesizes under conditions of difference V, Si molar ratio in the embodiment of the present invention 1 third
Conversion of propane and reaction temperature relational graph in alkoxide dehydrogenation reaction；
Fig. 7 is the doped meso-porous sphere catalyst of V that synthesizes under conditions of difference V, Si molar ratio in the embodiment of the present invention 1 third
Propylene Selectivity and reaction temperature relational graph in alkoxide dehydrogenation reaction；
Fig. 8 is the doped meso-porous sphere catalyst of V that synthesizes under conditions of difference V, Si molar ratio in the embodiment of the present invention 1 third
Propylene and ethylene overall selectivity and reaction temperature relational graph in alkoxide dehydrogenation reaction.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction in detail below
Technical solution of the present invention is described in detail in embodiment and Figure of description, but should not be understood as to of the invention implementable
The restriction of range.
Embodiment 1
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 mesoporous monox nanometer ball catalyst of vanadium doping, preparation method packet
Include following steps：
(1) triethanolamine solution is prepared：The triethanolamine of 0.41g is dissolved in the deionized water of 150g, is stirred at 80 DEG C
It mixes 1h to be completely dissolved to triethanolamine, obtains the solution of triethanolamine, mixing speed is 350 revs/min；
(2) template and structure directing agent is added：The CTAB template of 2.28g is added to the solution that step (1) obtains
In, the sodium salicylate of 1.00g is added after to be dissolved, until being completely dissolved uniformly mixed, mixing time 2h, mixing speed is
350 revs/min；
(3) silicon source is added：The tetraethyl orthosilicate of 22.43g is added to step (2) to obtain in solution, at 80 DEG C after
Continuous stirring 4h, mixing speed are 350 revs/min；
Six parts of identical above-mentioned solution are prepared using identical operating condition.
(4) vanadium source solution is prepared：0.013g, 0.063g, 0.126g, 0.378g, 0.630g and 1.007g are weighed respectively
Ammonium metavanadate respectively mixes it with 10g deionized water, and the magnetic agitation 4h in 75 DEG C of water bath with thermostatic control makes to be formed uniform molten
Liquid, obtains six parts of ammonium metavanadate solutions, and mixing speed is 350 revs/min.
(5) six parts of vanadium source solution for obtaining step (4) are added separately in six parts of solution that step (3) obtains, 80
Continue to stir 1h at DEG C, mixing speed is 350 revs/min；
(6) sedimentation and crystallization：The mixed solution that step (5) obtains is put into the crystallizing kettle with polytetrafluoroethyllining lining
Carry out sedimentation and crystallization, crystallization temperature be 80 DEG C, crystallization time 4h is then cooled to room temperature, through suction filtration, wash to
Without obvious foam, then the dry 10h at 80 DEG C, finally roasts 6h at 550 DEG C, and heating rate is 1 DEG C/min.It finally obtains
Mesoporous monox nanometer ball containing vanadium, i.e., the described catalyst of mesoporous monox nanometer ball containing vanadium.
The mesoporous sphere catalyst of above-mentioned vanadium doping is characterized using scanning electron microscope (SEM), choose representative V,
Si molar ratio is respectively 3:100 and 8:100 two sample results are as depicted in figs. 1 and 2.It can see from Fig. 1 and Fig. 2, vanadium
Doped meso-porous sphere catalyst is monodisperse spherical nano particle, and nano particle diameter is uniform, and its surface shows fold
Space expanding is clear that the mesopore orbit of catalyst is openr.
Structural parameters characterization is carried out to the mesoporous sphere catalyst of above-mentioned vanadium doping using nitrogen adsorption desorption method, result is such as
Shown in Fig. 3, Fig. 4 and table 1.Fig. 3 inhales de- for the nitrogen of the doped meso-porous sphere catalyst of V synthesized under conditions of different V, Si molar ratios
Attached isollaothermic chart, Fig. 4 are the nitrogen adsorption desorption aperture of the doped meso-porous sphere catalyst of V synthesized under conditions of different V, Si molar ratios
Distribution map.From Fig. 3 it is observed that being classified according to IUPAC thermoisopleth, the catalyst of different V, Si molar ratios shows typical case
IV type thermoisopleth, this illustrates that catalyst has well-regulated mesopore orbit structure.The de- thermoisopleth of paying of the absorption of each sample goes out
Hysteresis loop is showed obvious, has illustrated that capillary condensation phenomenon has occurred.Relative pressure P/P0It is being greater than in 0.8 range the H3 type that presents
Hysteresis loop, this also demonstrates dendroid mesoporous silica nano-particle with biggish mesopore orbit.It can from Fig. 4
Out, the catalyst of different V contents has more uniform aperture, concentrates on 10~20nm or so.Design parameter can be with from table 1
Find out, catalyst specific surface area with higher and Kong Rong, and the raising of content of vanadium to the structure parameters influence of catalyst compared with
It is small.
The structural parameters of 1 dendroid meso-porous titanium dioxide silicon carrier of table and vanadium doping catalyst
| Sample | SBET/m2g-1 | Vt/m3g-1 | Dm/nm |
| DMSNs | 511 | 1.97 | 15.4 |
| 0.1V-DMSNs | 499 | 1.89 | 15.2 |
| 0.5V-DMSNs | 515 | 2.01 | 15.6 |
| 1V-DMSNs | 519 | 1.83 | 14.1 |
| 2V-DMSNs | 584 | 2.24 | 15.3 |
| 3V-DMSNs | 584 | 2.17 | 14.9 |
| 5V-DMSNs | 530 | 1.52 | 11.5 |
| 8V-DMSNs | 577 | 1.42 | 9.9 |
Wherein SBETFor the specific surface area of sample, VtFor total pore volume, DmFor average pore size.
Partial catalyst in embodiment 1 is detected using wide-angle x-ray powder diffractometer, as a result as shown in Figure 5.From
It can be seen that, as vanadium carrying capacity is gradually increased, there is no the diffraction maximum for occurring significantly belonging to crystal phase vanadium oxide in catalyst in figure,
This illustrates that vanadium oxygen species exist in the form of compared with high dispersive in the catalyst.
Application examples 1
Selective oxidation of propane dehydrogenation of the application example to six kinds of mesoporous sphere catalysts of vanadium doping being prepared in embodiment 1
Reactivity has carried out evaluation test, wherein：
Catalyst performance evaluation is carried out on miniature fixed-bed reactor, uses gas chromatograph after reaction
(GC490, Agilent) carries out on-line quantitative analysis to the gas composition after reaction.Wherein reactor is transparent fixed bed quartz
Reaction tube, bore 6mm, thickness of pipe wall 2mm.Catalyst is placed in the constant temperature fragment position of heating furnace, is fixed up and down with silica wool.
Temperature is controlled using accurate temperature controller in experimentation, heating furnace is heated up using process control.Catalyst filling amount is
0.15g, unstripped gas total flow are 72mLmin-1(C3H8:O2:N2=2:1:15, molar ratio), the granularity of catalyst sample is 40
Mesh is to 80 mesh.
Conversion of propane, selectivity of product calculation method are as follows：
(1) selectivity of product=a certain product assay/all products total content × 100%,
(2) conversion of propane=(raw material flow × propane content-reaction end gas flow × unreacted propane content)/original
Stream amount × propane content × 100%；
Catalysis reaction result of the catalyst in oxidative dehydrogenation of propane reaction is as shown in Fig. 6, Fig. 7 and Fig. 8.It can be with from Fig. 6
Find out, with the raising of temperature, the conversion of propane of each catalyst is increased, and at the same temperature, content of vanadium is higher
Show higher conversion of propane.But as can be seen from Figures 7 and 8, it is raw to be conducive to the products such as propylene for moderate content of vanadium
At.
Claims (10)
1. a kind of catalyst of mesoporous monox nanometer ball containing vanadium, which is characterized in that with the super large mesoporous monox nanometer ball of dendroid
For carrier, using barium oxide as active component, barium oxide doping enters in the skeleton of the mesoporous monox nanometer ball,
The barium oxide is the vanadium oxygen species of high dispersive.
2. the preparation method of the catalyst of mesoporous monox nanometer ball containing vanadium described in claim 1, which is characterized in that including walking as follows
Suddenly：
(1) triethanolamine solution is prepared：Triethanolamine is soluble in water, and stirring obtains triethanolamine solution；
(2) template and structure directing agent is added：CTAB template is added in step (1) acquired solution, salicylic acid is added
Sodium, stirring；
(3) silicon source is added：Silicon source is added in step (2) acquired solution, continues to stir；
(4) vanadium source solution is prepared：Vanadium source presoma is dissolved in deionized water, stirs, obtains vanadium source solution；
(5) vanadium source is added：Vanadium source solution obtained by step (4) is added in step (3) acquired solution, continues to stir；
(6) sedimentation and crystallization：Step (5) acquired solution is put into reaction kettle and is reacted, it is then post-treated, it obtains mesoporous containing vanadium
Monox nanometer ball catalyst.
3. according to the method described in claim 2, it is characterized in that, triethanolamine solution described in step (1) is：1-2 weight
The triethanolamine of part is dissolved in the deionized water of 300-800 parts by weight.
4. according to the method described in claim 3, it is characterized in that, 5-10 parts by weight CTAB template is added in step (2)
In triethanolamine solution obtained by step (1), after being completely dissolved, the sodium salicylate of 2.5-5 parts by weight is added, 1- is continuously stirred
3h。
5. according to the method described in claim 4, it is characterized in that, the silicon source of 55-100 parts by weight is added in step (3)
Step (2) acquired solution, continuously stirs 2-6h；The silicon source is tetraethyl orthosilicate.
6. according to the method described in claim 2, it is characterized in that, the vanadium source of 0.03-2.5 parts by weight is dissolved in step (4)
In the deionized water of 5-15 parts by weight, 3-5h is continuously stirred to being completely dissolved；The vanadium source is ammonium metavanadate or vanadic sulfate.
7. according to the method described in claim 2, it is characterized in that, step (1) to (5) is stirred in 60-90 DEG C of water bath with thermostatic control
Progress is mixed, mixing speed is 200-500 revs/min.
8. according to the method described in claim 2, it is characterized in that, step (6) reaction kettle is in polytetrafluoroethylene (PTFE)
The crystallization kettle of lining, carries out reaction 2-24h at 60-120 DEG C.
9. according to the method described in claim 2, it is characterized in that, described and processing includes cooling, suction filtration, washing, dry, roasting
It burns；The drying is controlled in 60-100 DEG C of dry 6-12h, the roasting in 500-600 DEG C of roasting 4-8h, the heating rate of roasting
For 1-2 DEG C/min.
10. application of the catalyst of mesoporous monox nanometer ball containing vanadium described in claim 1 in oxidative dehydrogenation of propane alkene.
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