CN108906114B - Vanadium-containing mesoporous silica ball catalyst and preparation method and application thereof - Google Patents
Vanadium-containing mesoporous silica ball catalyst and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 71
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000001294 propane Substances 0.000 claims abstract description 29
- 239000002077 nanosphere Substances 0.000 claims abstract description 19
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 41
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 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 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229960004025 sodium salicylate Drugs 0.000 claims description 7
- 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
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims 1
- 229940041260 vanadyl sulfate Drugs 0.000 claims 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 239000002808 molecular sieve Substances 0.000 description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002349 favourable effect Effects 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
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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Abstract
The invention provides a vanadium-containing mesoporous silica nanosphere catalyst as well as a preparation method and application thereof. The invention also provides a preparation method of the catalyst and application of the catalyst in preparation of olefin by oxidative dehydrogenation of propane. The vanadium-doped mesoporous silicon oxide nanosphere catalyst provided by the invention has the advantages of uniform particle size, larger dendritic mesoporous structure, higher dispersion degree of vanadium serving as an active component and higher concentration of active sites. The catalyst is applied to the reaction of preparing olefin by oxidative dehydrogenation of propane, and when the conversion rate of propane is 20 percent, the selectivity of propylene and olefin (ethylene and propylene) can reach 71.3 percent and 77.6 percent respectively.
Description
Technical Field
The invention belongs to the technical field of petrochemical catalysis, and relates to a vanadium-containing mesoporous silica sphere catalyst, and a preparation method and application thereof.
Background
Mesoporous molecular sieves have attracted considerable attention since the first time that scientists of Mobil corporation (j.s.beck, j.c.vartuli, w.j.roth, et al., j.am.chem.soc.,1992,114:10834-10843) used nanostructure self-assembly technology to prepare mesoporous silica MCM-41 with uniform and adjustable pore size in 1992. However, the mesoporous material of pure silica is inert to most reactions, so that active sites need to be introduced into the silica-based mesoporous material to make it catalytically active. The coordination and oxidation state of the active species have great influence on the catalytic performance of the active species, and the synthesis of the silica-based mesoporous molecular sieve material containing uniform species is very important for establishing the structure-activity relationship between the active species and the catalytic activity. The vanadium-based catalyst has good catalytic effect on the reaction of preparing propylene by oxidative dehydrogenation of propane, and the catalytic performance of the vanadium-based catalyst is closely related to the existence form of vanadium oxide species and the structure of a carrier. The support can disperse the vanadium oxide species well to form active sites with specific physicochemical characteristics, thereby improving the catalyst activity of the catalyst. The mesoporous molecular sieve has a special pore structure and a special morphology structure, is beneficial to adsorption, desorption, diffusion, shape-selective catalysis and the like of reactant molecules, and has certain effect and influence on the existing form of active species of the catalyst. The currently common methods for introducing active sites into mesoporous molecular sieves can be divided into two types: post-synthesis and in-situ synthesis. The post-synthesis method mainly comprises an impregnation method, a grafting method, an ion exchange method and the like. These methods are often complicated in operation steps, and the active species are usually formed on the surface of the mesopores and have weak interaction with the carrier, so that the active species are easily polymerized. The in-situ synthesis method is to introduce active components in the synthesis process of the molecular sieve and directly hydrothermally synthesize the metal-doped mesoporous molecular sieve. Thus, the active sites are directly introduced into the framework of the molecular sieve, the interaction between the molecular sieve and the carrier is enhanced, and the highly dispersed and isolated active sites are easier to obtain.
The nanometer silicon oxide ball with super large mesopores is used as a novel nanometer material, and the nanometer silicon oxide ball with larger mesopore diameter, smaller particle size and dendritic mesoporous structure is more favorable for the diffusion of reactants and products. The catalyst is used as a carrier to be doped into vanadium atoms and applied to the oxidative dehydrogenation reaction of propane, and is not reported in the literature. The vanadium-doped mesoporous silica sphere catalyst is synthesized by taking mesoporous silica spheres as a carrier and vanadium-oxygen species as an active component by utilizing a novel dendritic mesoporous silica nanosphere synthesis technology, and is applied to propane oxidative dehydrogenation reaction.
Disclosure of Invention
The invention aims to provide a vanadium-containing mesoporous silica nanosphere catalyst.
The invention also aims to provide a preparation method of the vanadium-containing mesoporous silica nanosphere catalyst.
The invention also aims to provide the application of the vanadium-containing mesoporous silica nanosphere catalyst in the preparation of olefin through propane oxidative dehydrogenation.
In order to achieve the above object, in one aspect, the present invention provides a vanadium-containing mesoporous silica nanosphere catalyst, which uses a dendritic ultra-large mesoporous silica nanosphere as a carrier and a vanadium oxide as an active component, wherein the vanadium oxide is doped into a skeleton of the mesoporous silica nanosphere, and the vanadium oxide is a highly dispersed vanadium oxide species.
According to the catalyst provided by the invention, preferably, the vanadium oxide is doped into the framework of the vanadium-containing mesoporous silica nanosphere, and the prepared oversized mesoporous silica nanosphere with the framework containing vanadium oxide is realized by taking a hexadecyl trimethyl ammonium bromide (CTAB) ionic surfactant as a template agent, taking sodium salicylate as a structure directing agent, taking triethanolamine as a synthesis catalyst, taking a vanadium source and a silicon source as raw materials and adopting a direct hydrothermal synthesis method.
The vanadium source and the silicon source can be vanadium source and silicon source which are conventionally used in the field, the vanadium source which is preferably used in the invention is vanadate, and the vanadate is ammonium metavanadate (the molecular formula is NH)4VO3)。
Preferred silicon sources for use in the present invention include tetraethyl orthosilicate.
The preparation method of the catalyst comprises the following steps:
(1) preparing a triethanolamine solution: dissolving triethanolamine with required amount in a certain amount of water, and stirring until the triethanolamine is completely dissolved to obtain a triethanolamine solution;
(2) adding a template agent and a structure directing agent: adding a CTAB template agent with required amount into the solution obtained in the step (1), adding sodium salicylate with required amount after dissolving until completely dissolving and uniformly mixing, and stirring for 1-3 h;
(3) adding a silicon source: adding a required amount of silicon source into the solution obtained in the step (2), and continuously stirring for 2-6 h;
(4) preparing a vanadium source solution: dissolving a vanadium source in deionized water, and stirring until the vanadium source is completely dissolved to obtain a vanadium source solution;
(5) adding the vanadium source solution obtained in the step (4) into the solution obtained in the step (3), and continuously stirring for 0.5-1 h;
(6) settling and crystallizing: and (3) putting the mixed solution obtained in the step (5) into a crystallization kettle with a polytetrafluoroethylene lining for settlement and crystallization reaction, and then carrying out cooling, suction filtration, washing, drying and roasting treatment to obtain vanadium-containing mesoporous silica spheres, namely the vanadium-containing mesoporous silica sphere catalyst.
Preferably, the step (1) of preparing the template solution is: dissolving 1-2 parts by weight of triethanolamine in 800 parts by weight of deionized water, and stirring until the triethanolamine is completely dissolved to obtain a triethanolamine solution.
Wherein the invention preferably stirs in the thermostatic water bath of 60-90 ℃ for 0.5-2h to completely dissolve the triethanolamine and obtain the triethanolamine solution, and the stirring speed is 200-.
In addition, in a more preferred embodiment of the present invention, the amount of triethanolamine added in step (1) is 1.5 parts by weight, and the amount of deionized water added is 550 parts by weight; the temperature of the constant-temperature water bath is 80 ℃, and the stirring time of the stirring is 1 h.
Preferably, the adding of the template agent and the structure directing agent in the step (2) comprises the following steps: adding 5-10 parts by weight of CTAB template agent into the triethanolamine solution obtained in the step (1), after completely dissolving, adding 2.5-5 parts by weight of sodium salicylate, and continuously stirring for 1-3h in a constant-temperature water bath at 60-90 ℃, wherein the stirring speed is 200-.
Further, in a more preferred embodiment of the present invention, the amount of the CTAB template added in step (2) is 7.5 parts by weight, and the amount of sodium salicylate added is 4 parts by weight; the temperature of the constant-temperature water bath is 80 ℃, and the stirring time of the stirring is 2 hours.
Preferably, the step (3) of adding the silicon source comprises the following steps: adding 55-100 parts by weight of silicon source into the mixed solution obtained in the step (2), and continuously stirring for 2-6h in a constant-temperature water bath at the temperature of 60-90 ℃, wherein the stirring speed is 200-.
Further, in a more preferred embodiment of the present invention, the silicon source used in step (3) is tetraethyl orthosilicate, and the amount of tetraethyl orthosilicate added is 84 parts by weight; the temperature of the constant-temperature water bath is 80 ℃, and the stirring time of the stirring is 4 h.
Preferably, the vanadium source solution preparation process in the step (4) is as follows: dissolving 0.03-2.5 parts by weight of a vanadium source in 5-15 parts by weight of deionized water, and stirring for 3-5 hours in a constant-temperature water bath at 60-90 ℃ to form a uniform solution to obtain a vanadium source solution;
in a more preferred embodiment of the present invention, the vanadium source is ammonium metavanadate, the temperature of the thermostatic water bath is 80 ℃, and the stirring time of the stirring is 4 hours.
Preferably, the adding of the vanadium source solution in the step (5) is carried out by the following steps: adding the vanadium source solution obtained in the step (4) into the mixed solution obtained in the step (3), and stirring in a constant-temperature water bath at the temperature of 60-90 ℃ for 0.5-1h at the stirring speed of 200-;
in a more preferred embodiment of the present invention, the temperature of the thermostatic waterbath is 80 ℃, the stirring time of the stirring is 0.75h, and the stirring speed is 350 rpm.
Preferably, the crystallization in step (6) is: putting the vanadium-containing mixed solution obtained in the step (5) into a crystallization reaction kettle with a polytetrafluoroethylene lining for crystallization reaction at 60-120 ℃ for 2-24 h; then cooling, filtering and washing; then drying for 6-12h at the temperature of 60-100 ℃; finally, roasting for 4-8h at the temperature of 500-600 ℃, wherein the heating rate of roasting is controlled to be 1-2 ℃/min.
Obtaining vanadium-containing mesoporous silica spheres after roasting, namely the vanadium-containing mesoporous silica sphere catalyst.
Wherein in a more preferred embodiment of the present invention, the crystallization temperature is 80 ℃ and the crystallization time is 4 hours;
the cooling is to cool to room temperature;
the washing is to wash the filtrate by deionized water until no foam exists;
the drying is drying for 10 hours at 80 ℃;
the roasting is carried out for 6h at 550 ℃, and the heating rate is 1 ℃/min.
The addition amounts of the vanadium source (ammonium metavanadate) and the silicon source (tetraethyl orthosilicate) were calculated as the raw material molar ratio of V to Si.
The invention also provides the application of the vanadium doped silica-based mesoporous molecular sieve catalyst in the preparation of olefin by selective oxidative dehydrogenation of propane.
In conclusion, the invention provides a vanadium-doped silicon oxide-based mesoporous molecular sieve catalyst, a preparation method thereof and application thereof in preparing olefin through selective oxidative dehydrogenation of propane. The vanadium doped silica-based mesoporous molecular sieve catalyst has the following advantages:
according to the vanadium-containing mesoporous silica nanosphere catalyst, in the process of synthesizing the nano silica spheres, the active component is directly fixed in the crystal lattice of the molecular sieve framework through direct hydrothermal synthesis, so that the obtained nano silica spheres containing vanadium in the framework have higher order degree, and the transmission of reactants and products is facilitated; meanwhile, the vanadium-doped silicon oxide-based mesoporous molecular sieve catalyst provided by the invention has the advantages of higher dispersion degree of the active component vanadium, higher concentration of active sites and higher stability of the active sites, so that the catalyst has higher catalytic activity.
The nanometer silicon oxide ball with the super large mesopores provided by the invention is used as a novel nanometer material, and the nanometer silicon oxide ball with the larger mesopore diameter, the smaller particle size and the dendritic mesoporous structure are more favorable for the diffusion of reactants and products. The catalyst is used as a carrier to be doped into vanadium atoms and applied to the oxidative dehydrogenation reaction of propane, and is not reported in the literature.
Meanwhile, the catalyst provided by the invention takes the oxide of the transition metal vanadium as an active component and is doped into the skeleton of the nano silicon oxide spheres, so that the dispersion degree and stability of active sites can be promoted, and the catalytic activity of propane can be improved when the catalyst is used for preparing olefin by selective oxidative dehydrogenation of propane.
The vanadium-doped silica-based mesoporous molecular sieve catalyst provided by the invention is applied to the reaction of preparing olefin by selective oxidative dehydrogenation of propane, in the preferred embodiment of the invention, when the conversion rate of propane is 20%, the selectivity of propylene and olefin (ethylene and propylene) which are products of the oxidation reaction can reach 71.3% and 77.6% respectively, and the catalyst has excellent reaction performance in the selective oxidative dehydrogenation reaction of propane due to the high dispersion of active metal vanadium and the special local chemical environment.
Drawings
FIG. 1 is a scanning electron microscope image of a V-doped mesoporous sphere catalyst synthesized under the condition that the molar ratio of V, Si is 3:100 in example 1 of the invention;
FIG. 2 is a scanning electron microscope image of a V-doped mesoporous sphere catalyst synthesized under the condition that the molar ratio of V, Si is 8:100 in example 1 of the invention;
FIG. 3 is a nitrogen desorption isotherm diagram of V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios in example 1 of the present invention;
FIG. 4 is a nitrogen adsorption and desorption pore size distribution diagram of V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios in example 1 of the present invention;
FIG. 5 is a wide-angle XRD diagram of a V-doped mesoporous sphere catalyst synthesized under the conditions of V, Si molar ratios of 0:100, 3:100, 5:100 and 8:100 in example 1 of the invention;
FIG. 6 is a graph showing the relationship between the conversion rate of propane and the reaction temperature in the oxidative dehydrogenation of propane using V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios in example 1 of the present invention;
FIG. 7 is a graph of propylene selectivity versus reaction temperature for the oxidative dehydrogenation of propane using V-doped mesoporous sphere catalysts synthesized under different V, Si mole ratios in example 1 according to the present invention;
FIG. 8 is a graph of the total selectivity of propylene and ethylene in the oxidative dehydrogenation of propane versus reaction temperature for V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios in example 1 of the present invention.
Detailed Description
For a better understanding of the technical features, objects and advantages of the present invention, reference will now be made in detail to the present embodiments of the invention, which are illustrated in the accompanying drawings, and the following detailed description of the invention is not to be construed as limiting the scope of the invention.
Example 1
This example provides a preparation method of six vanadium-doped mesoporous silica nanosphere catalysts with different V, Si molar ratios (V, Si molar ratios are 0.1:100, 0.5:100, 1:100, 3:100, 5:100, and 8:100, respectively), the preparation method includes the following steps:
(1) preparing a triethanolamine solution: dissolving 0.41g of triethanolamine in 150g of deionized water, stirring for 1 hour at 80 ℃ until the triethanolamine is completely dissolved to obtain a triethanolamine solution, wherein the stirring speed is 350 r/min;
(2) adding a template agent and a structure directing agent: adding 2.28g of CTAB template agent into the solution obtained in the step (1), adding 1.00g of sodium salicylate after dissolving until completely dissolving and uniformly mixing, wherein the stirring time is 2h, and the stirring speed is 350 r/min;
(3) adding a silicon source: adding 22.43g of tetraethyl orthosilicate into the solution obtained in the step (2), and continuing stirring at 80 ℃ for 4 hours at the stirring speed of 350 r/min;
six identical parts of the above solution were prepared using the same operating conditions.
(4) Preparing a vanadium source solution: 0.013g, 0.063g, 0.126g, 0.378g, 0.630g and 1.007g of ammonium metavanadate are weighed respectively and mixed with 10g of deionized water respectively, and the mixture is magnetically stirred for 4 hours in a constant-temperature water bath at 75 ℃ to form a uniform solution, so that six parts of ammonium metavanadate solution are obtained, and the stirring speed is 350 revolutions per minute.
(5) Adding the six parts of vanadium source solution obtained in the step (4) into the six parts of solution obtained in the step (3) respectively, and continuously stirring for 1h at the temperature of 80 ℃, wherein the stirring speed is 350 revolutions per minute;
(6) settling and crystallizing: and (3) putting the mixed solution obtained in the step (5) into a crystallization kettle with a polytetrafluoroethylene lining for sedimentation and crystallization reaction, wherein the crystallization temperature is 80 ℃, the crystallization time is 4h, then cooling to room temperature, carrying out suction filtration and washing until no obvious foam exists, then drying at 80 ℃ for 10h, and finally roasting at 550 ℃ for 6h, wherein the heating rate is 1 ℃/min. Finally obtaining the vanadium-containing mesoporous silica nanospheres, namely the vanadium-containing mesoporous silica nanosphere catalyst.
The vanadium doped mesoporous sphere catalyst was characterized by Scanning Electron Microscopy (SEM), and representative V, Si molar ratios of 3:100 and 8:100 were selected for the results shown in fig. 1 and 2. As can be seen from fig. 1 and 2, the vanadium-doped mesoporous sphere catalyst is monodisperse spherical nanoparticles, the particle size of the nanoparticles is uniform, and the surface of the nanoparticles presents a wrinkled spatial topology, so that the mesoporous pore of the catalyst is clearly seen to be wider.
The vanadium-doped mesoporous sphere catalyst was characterized by structural parameters by a nitrogen adsorption and desorption method, and the results are shown in fig. 3, fig. 4, and table 1. Fig. 3 is a nitrogen adsorption and desorption isotherm diagram of V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios, and fig. 4 is a nitrogen adsorption and desorption pore size distribution diagram of V-doped mesoporous sphere catalysts synthesized under different V, Si molar ratios. From fig. 3, it can be observed that catalysts with different V, Si molar ratios exhibited typical type IV isotherms according to IUPAC isotherm classification, indicating that the catalysts had regular mesoporous channel structures. The adsorption desorption isotherms of the samples all show obvious hysteresis loops, indicating that the capillary condensation phenomenon occurs. Relative pressure P/P0The H3 type hysteresis loop is shown in the range of more than 0.8, which also proves that the dendritic mesoporous silica nano-particles have larger mesoporous channels. As can be seen from FIG. 4, the catalysts with different V contents have uniform pore diameters, which are concentrated around 10-20 nm. As can be seen from the specific parameters in Table 1, the catalyst has higher specific surface area and pore volume, and the increase of the vanadium content has less influence on the structural parameters of the catalyst.
TABLE 1 structural parameters of dendritic mesoporous silica supports and vanadium-doped catalysts
| 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 SBETIs the specific surface area of the sample, VtTo total pore volume, DmIs the average pore diameter.
The results of the examination of a part of the catalyst in example 1 by a wide-angle X-ray powder diffractometer are shown in fig. 5. As can be seen from the figure, as the vanadium loading was gradually increased, no distinct diffraction peak attributable to the crystalline phase vanadium oxide was present in the catalyst, indicating that the vanadyl species was present in a highly dispersed form in the catalyst.
Application example 1
The application example evaluates and tests the activity of the selective oxidative dehydrogenation reaction of propane of the six vanadium-doped mesoporous sphere catalysts prepared in example 1, wherein:
the catalyst performance evaluation was carried out on a miniature fixed bed reaction apparatus, and after the reaction was completed, the gas composition after the reaction was quantitatively analyzed on line using a gas chromatograph (GC490, agilent). Wherein the reactor is a transparent fixed bed quartz reaction tube, the inner diameter of the tube is 6mm, and the wall thickness of the tube is 2 mm. The catalyst is arranged at the position of a constant temperature section of the heating furnace and fixed by quartz wool up and down. In the experimental process, a precise temperature controller is adopted to control the temperature, and the heating furnace is controlled to heat up by a program. The catalyst packing amount was 0.15g, and the total flow rate of the feed gas was 72 mL/min-1(C3H8:O2:N22:1:15, molar ratio), the particle size of the catalyst sample was 40 mesh to 80 mesh.
The method for calculating the conversion rate of propane and the selectivity of the product is as follows:
(1) product selectivity is the content of a certain product/total content of all products x 100%,
(2) propane conversion ═ feed flow × propane content-reaction off-gas flow × unreacted propane content)/feed flow × propane content × 100%;
the results of the catalytic reaction of the catalyst in the oxidative dehydrogenation of propane are shown in fig. 6, 7 and 8. As can be seen from fig. 6, the propane conversion of each catalyst increased with increasing temperature, with higher vanadium content indicating higher propane conversion at the same temperature. However, as can be seen from FIGS. 7 and 8, moderate vanadium content favors the formation of products such as propylene.
Claims (4)
1. The vanadium-containing mesoporous silicon oxide nanosphere catalyst applied to preparation of olefin by oxidative dehydrogenation of propane is characterized in that the catalyst takes dendritic ultra-large mesoporous silicon oxide nanospheres as carriers and vanadium oxide as an active component, the vanadium oxide is doped into the skeleton of the mesoporous silicon oxide nanospheres, and the vanadium oxide is a high-dispersion vanadium oxide species; the preparation method of the catalyst comprises the following steps:
(1) preparing a triethanolamine solution: dissolving triethanolamine in water, and stirring to obtain triethanolamine solution;
(2) adding a template agent and a structure directing agent: adding a CTAB template into the solution obtained in the step (1), adding sodium salicylate, and stirring;
(3) adding a silicon source: adding 55-100 parts by weight of silicon source into the solution obtained in the step (2), and continuously stirring for 2-6 h; the silicon source is tetraethyl orthosilicate;
(4) preparing a vanadium source solution: dissolving 0.03-2.5 parts by weight of vanadium source in 5-15 parts by weight of deionized water, and continuously stirring for 3-5 hours until the vanadium source is completely dissolved; the vanadium source is ammonium metavanadate or vanadyl sulfate;
(5) adding a vanadium source: adding the vanadium source solution obtained in the step (4) into the solution obtained in the step (3), and continuously stirring;
(6) settling and crystallizing: putting the solution obtained in the step (5) into a reaction kettle for reaction, and then carrying out post-treatment to obtain the vanadium-containing mesoporous silica nanosphere catalyst; the reaction kettle is a crystallization reaction kettle with a polytetrafluoroethylene lining, and the reaction is carried out for 2-4h at the temperature of 60-120 ℃;
the steps (1) to (5) are stirred in a constant-temperature water bath at the temperature of 80-90 ℃, and the stirring speed is 350-500 r/min.
2. The catalyst according to claim 1, wherein the triethanolamine solution in step (1) is: 1-2 parts by weight of triethanolamine is dissolved in 800 parts by weight of deionized water.
3. The catalyst according to claim 1, wherein in the step (2), 5 to 10 parts by weight of CTAB template is added into the triethanolamine solution obtained in the step (1), and after complete dissolution, 2.5 to 5 parts by weight of sodium salicylate is added, and the mixture is continuously stirred for 1 to 3 hours.
4. The catalyst of claim 1, wherein the post-treatment comprises cooling, suction filtration, washing, drying, calcining; the drying is carried out for 6-12h at 60-100 ℃, the roasting is carried out for 4-8h at 600 ℃ and the heating rate of the roasting is controlled to be 1-2 ℃/min.
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