CN116099543A - Vanadium-iron-based bimetallic oxide catalyst and preparation method and application thereof - Google Patents
Vanadium-iron-based bimetallic oxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000002356 single layer Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 239000001294 propane Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000628 Ferrovanadium Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 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
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- 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 belongs to the technical field of chemical chain low-carbon alkane dehydrogenation catalysts, and discloses a vanadium iron-based bimetallic oxide catalyst, a preparation method and application thereof, wherein the catalyst is FeVO with single-layer dispersion supported on a carrier 4 Monolayer dispersed FeVO 4 FeVO loaded with bulk phase 4 A nanoparticle; monolayer dispersed FeVO 4 FeVO as a direct dehydrogenation catalytic site 4 The nanoparticles act as hydrogen selective combustion sites; the preparation method comprises the steps of firstly dissolving and uniformly mixing precursor salt of iron and precursor salt of vanadium; then impregnating the uniformly mixed salt solutionDrying on a carrier; finally, roasting, and tabletting, forming and sieving the roasted catalyst for standby. The catalyst is applied to the chemical chain dehydrogenation of the low-carbon alkane, and has the outstanding advantages of high single-pass conversion rate of the low-carbon alkane and high selectivity of the target product alkene; meanwhile, the problem of sintering of pure ferric oxide in the oxidation-reduction process can be effectively solved, and the performance and the structure of the pure ferric oxide can be kept stable after a plurality of reduction-oxidation regeneration cycles are realized.
Description
Technical Field
The invention belongs to the technical field of chemical chain low-carbon alkane dehydrogenation catalysts, and particularly relates to a supported ferrovanadium-based bimetallic oxide catalyst, a preparation method and application thereof.
Background
Propylene is one of the three basic synthetic materials, and its demand gap is continuously expanding worldwide. The traditional propylene production technology based on light oil cracking and heavy oil catalytic cracking cannot meet the market requirements and low-carbon economic development due to high energy consumption and large carbon emission. The development of novel propylene production technology is therefore urgent. The success of the united states "shale gas revolution" provides a new opportunity for low carbon economic strategic development. The shale gas is developed to obtain a large amount of cheap low-carbon alkane, and the method brings dawn to the preparation of the corresponding high-added-value alkene.
Propane is taken as a raw material, and oxygen-free dehydrogenation (PDH for short) of propane is taken as a new production method of on-purcose propylene, which is paid attention to by vast researchers. In the current commercial PDH process (mainly Catofin and Oleflex processes) at home and abroad, chromium oxide and platinum-based catalysts are used, respectively. However, toxic CrO x And expensive Pt-based catalyst, and the defects of intrinsic thermodynamic equilibrium limitation and high energy consumption of endothermic reaction, and promote researchers to search for new technology for preparing propylene from propane, which is more efficient, environment-friendly, low-carbon and economical. Propane oxidative dehydrogenation (ODHP for short) can effectively break thermodynamic limitations by introducing an oxidant (such as oxygen, carbon dioxide and nitrous oxide) into a reaction system, and is a potential propylene production mode. However, the reactant propane and product propylene tend to over oxidize to CO 2 And the potential safety hazard of blending the reducing gas and the oxidizing gas draws a large question mark on the feasibility of industrial production of the gas.
Chemical Looping (Chemical Looping) is used as an efficient and promising energy conversion technology, and can realize efficient clean utilization of low-carbon alkane by decoupling one Chemical reaction into two or more independent reactions. In the oxidative dehydrogenation (CL-ODHP) process of chemical chain propane, the metal oxide (also called oxygen carrier) is used as a medium, and lattice oxygen of the oxygen carrier is recycled and supplemented between a reduction bed and an oxidation bed, so that the oxygen removal and replenishment process in the lattice can be effectively separated in space or time. Compared with direct dehydrogenation and oxidative dehydrogenation, the chemical chain oxidative dehydrogenation technology has the remarkable advantages of reducing the reaction temperature, improving the selectivity of propylene, reducing side reactions, avoiding product separation and the like. The application of this technology is critical to the design and development of the oxygen carrier, as the oxygen carrier must serve multiple roles of catalyst (C-H bond activation) and reactant (lattice oxygen supply) simultaneously. The oxygen carrier used for CL-ODH at present is mainly one-component metal oxide (vanadium oxide, chromium oxide, tungsten oxide and the like), but the oxygen carrier is difficult to simultaneously realize high activity and high selectivity for activating propane into propylene.
Disclosure of Invention
The invention aims to solve the related technical problems of a chemical chain low-carbon alkane dehydrogenation catalyst, and provides a vanadium iron-based bimetallic oxide catalyst, a preparation method and application thereof, wherein the catalyst can couple a propane direct dehydrogenation site and a selective hydrogen burning site on a nanometer scale, wherein FeVO with a single-layer dispersed carrier surface is provided 4 Bulk FeVO as a direct dehydrogenation catalytic site 4 The nanoparticles act as hydrogen selective combustion sites.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the present invention, there is provided a vanadium iron-based bimetallic oxide catalyst comprising a support having a single layer of dispersed FeVO supported thereon 4 The single layer of dispersed FeVO 4 FeVO loaded with bulk phase 4 A nanoparticle; the single layer dispersed FeVO 4 As a direct dehydrogenation catalytic site, the FeVO 4 The nanoparticles act as hydrogen selective combustion sites.
Further, the carrier is Al 2 O 3 、SiO 2 、TiO 2 Or a molecular sieve.
Further, the FeVO 4 The total mass of (2) is 10-50wt.% of the total mass of the catalyst.
Further, the FeVO 4 Is 30wt.% of the total mass of the catalyst.
According to another aspect of the invention, a preparation method of the ferrovanadium-based bimetallic oxide catalyst is provided, and the preparation method comprises the following steps:
(1) Dissolving and uniformly mixing precursor salt of iron and precursor salt of vanadium;
(2) Impregnating the uniformly mixed salt solution obtained in the step (1) on the carrier, and drying;
(3) Roasting the impregnated carrier, wherein the roasting atmosphere is air, the roasting temperature is 500-600 ℃, and the roasted catalyst is pressed into tablets for shaping and sieving for standby.
Further, in the step (1), ferric nitrate is uniformly dispersed in deionized water to form an impregnating solution-1, ammonium metavanadate and oxalic acid are uniformly mixed and dissolved in the deionized water to form an impregnating solution-2, and the impregnating solution-1 and the impregnating solution-2 are uniformly mixed; wherein the mass ratio of the ammonium metavanadate to the oxalic acid is 1:2.
further, in the step (2), the drying temperature is 80-100 ℃ and the drying time is 6-12h; in the step (3), the roasting time is 1-8 hours; the mesh number of the sieve is 20-40 mesh.
According to another aspect of the invention, there is provided the use of the ferrovanadium-based bimetallic oxide catalyst as described above for the chemical chain dehydrogenation of light alkanes, the catalyst being reacted with light alkanes in the absence of an oxygen co-feed, the monolayer of dispersed FeVO 4 As a direct dehydrogenation catalytic site to convert light alkanes into corresponding olefins and hydrogen; the FeVO 4 Nanoparticles as selective hydrogen combustion sites for selectively burning byproduct hydrogen to produce product water and release heat energy, the FeVO 4 The nanoparticle is reduced to a lower valence state; introducing oxygen or air into the reacted catalyst to regenerate FeVO 4 The lattice oxygen of the nano particles is supplemented, and the carbon deposit is burnt simultaneouslyFiring and releasing heat energy; after the above cycle, the catalyst returns to the original state. .
Further, the carbon number of the lower alkane is 2-4.
Further, the catalyst and the quartz sand are physically and evenly mixed, and the mass ratio of the catalyst to the quartz sand is (0.2-1): 1, a step of; the reaction is carried out under normal pressure, the reaction temperature is 450-650 ℃, nitrogen is pre-introduced to remove air, and then propane is introduced; wherein the total flow of propane and nitrogen is 20-50 ml/min, and the volume percentage of propane is 5-30%.
The beneficial effects of the invention are as follows:
the ferrovanadium-based bimetallic oxide catalyst has a double-catalytic site structure constructed on the nano scale, and the propane dehydrogenation and selective hydrogen combustion are organically coupled on the nano scale, so that the thermodynamic limit is effectively broken; wherein, feVO with single-layer dispersion on the surface of the carrier 4 Catalytic site for direct dehydrogenation of low-carbon alkane and bulk FeVO 4 Lattice oxygen in the nano-particles participates in the selective combustion of hydrogen to generate product water; in addition, the vanadium iron-based bimetallic oxide catalyst of the invention can realize bulk FeVO 4 Surface monolayer dispersed FeVO of nanoparticles after lattice oxygen depletion 4 The method still participates in direct dehydrogenation, and keeps higher conversion rate and selectivity, so that the problem of sintering of pure ferric oxide in the oxidation-reduction process can be effectively solved.
The preparation method of the vanadium iron-based bimetallic oxide catalyst adopts an impregnation method, has low cost, is simple to operate and is easy to realize large-scale production; meanwhile, the method adopts the cheap and easily available ferric oxide with rich reserves, is nontoxic and environment-friendly.
The ferrovanadium-based bimetallic oxide catalyst is applied to low-carbon alkane chemical chain dehydrogenation, and has the outstanding advantages of low-carbon alkane single-pass high conversion rate and high selectivity of target product alkene; wherein by adjusting the carrier selection and the load, a catalyst with optimal propylene yield can be obtained; meanwhile, the problem of sintering of pure ferric oxide in the oxidation-reduction process can be effectively solved, and the performance and the structure of the pure ferric oxide can be kept stable after a plurality of reduction-oxidation regeneration cycles are realized. The catalyst after reaction is regenerated by oxygen or air, lattice oxygen of low-valence ferric vanadate nano particles is supplemented, carbon deposition is effectively combusted, generated heat is transferred through a catalyst medium, and high heat matching can be realized by adjusting the quality of the catalyst. Compared with the prior art, the method avoids the direct use of oxygen, saves the high cost of air separation, reduces the formation of deep oxidation products and eliminates the potential safety hazard of blending reducing and oxidizing gases.
Drawings
FIG. 1 is a schematic diagram of a chemical chain propane dehydrogenation process according to the present invention;
FIG. 2 is a graph of a propane conversion, propylene selectivity, and b propylene yield for the catalysts prepared in examples 1-4 during chemical chain propane dehydrogenation;
FIG. 3 is a graph showing the results of X-ray diffraction (XRD) tests of the catalysts prepared in examples 1 to 4 of the present invention;
FIG. 4 is a graph showing XRD test results of fresh catalysts prepared in examples 5 and 6 according to the present invention;
FIG. 5 shows the hydrogen temperature programmed reduction (H) of fresh catalyst prepared in examples 1-4 of the present invention 2 -TPR) test result profile;
FIG. 6 shows a process for preparing 30FeVO according to example 1 of the present invention 4 /Al 2 O 3 A high-angle annular dark field scanning transmission electron microscope (HAADF-STEM) image and an energy spectrum analysis surface scanning (EDS-MAPPING) image of the catalyst respectively show distribution graphs of Al element, O element, fe element and V element, wherein the scale of the HAADF-STEM image is 100nm;
FIG. 7 shows the use of 30FeVO in chemical looping propane dehydrogenation 4 /Al 2 O 3 And a graph of the test results of the cycle stability of the catalyst in the reaction regeneration cycle.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
Example 1:
And 4, naturally cooling the roasted catalyst to room temperature, tabletting, forming and sieving to prepare the granular catalyst with the size of 20-40 meshes for later use.
Example 2:
preparation and reaction were carried out as in example 1 except that 0.26 parts by mass of ferric nitrate was uniformly dissolved in 0.5mL of deionized water in step 1 to form an immersion liquid-1; 0.08 mass part of ammonium metavanadate and 0.16 mass part of oxalic acid are uniformly mixed and dissolved in 0.5mL of deionized water to form an impregnating solution-2. The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 10 percent, and the molecular formula is 10FeVO 4 /Al 2 O 3 。
Example 3:
preparation and reaction were carried out as in example 1 except that 2.4 parts by mass of ferric nitrate was uniformly dissolved in 0.5mL of deionized water in step 1 to form an immersion liquid-1; mixing 0.7 mass part of ammonium metavanadate and 1.5 mass parts of oxalic acid uniformly and dissolving in 0.5mL of deionized water to formImpregnating solution-2. The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 50 percent, and the molecular formula is 50FeVO 4 /Al 2 O 3 。
Example 4:
preparation and reaction were carried out as in example 1 except that 5.0 parts by mass of ferric nitrate and 2.5 parts by mass of citric acid were uniformly mixed in step 1, and dissolved in 200.0mL of deionized water to form solution-1; uniformly dissolving 1.5 parts by mass of ammonium metavanadate in 200.0mL of deionized water to form a solution-2; the difference is that in the step 2, the solution-2 is added into the solution-1, stirred, water-bath is carried out for 3-4 hours at the temperature of 100 ℃, the solution is evaporated to dryness, and then the solution is dried for 6-12 hours at the temperature of 80-100 ℃. The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 100 percent, and the molecular formula is FeVO 4 。
Example 5:
the preparation and reaction were carried out as in example 1, except that the support of step 2 was changed to SiO 2 . The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 30 percent, and the molecular formula is 30FeVO 4 /SiO 2 。
Example 6:
the preparation and reaction were carried out as in example 1, except that the support of step 2 was changed to TiO 2 . The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 30 percent, and the molecular formula is 30FeVO 4 /TiO 2 。
Example 7:
the preparation and reaction were carried out as in example 1, except that the support of step 2 was changed to a molecular sieve. The obtained catalyst is FeVO based on the mass of the carrier 4 The mass percentage of (2) is 30 percent, and the molecular formula is 30FeVO 4 /Zeolite。
Example 8:
The propane conversion is calculated from the following formula:
wherein:
The product gas phase selectivity is calculated by the following formula:
wherein:
s product A-selectivity of gas phase product A%
n production of product A-yield of gas phase product A, moL
Sigma n product-sum of the amounts of all product species in the gas phase, moL
x product A-content of gas phase product A in all gas phase products
Gas phase productionThe article A comprises: c (C) 3 H 6 ，CO x (carbon oxides, i.e. CO, CO 2 )，CH 4 ，C 2 H 6 ，C 2 H 4 。
As shown in fig. 1, the oxidative dehydrogenation process of the chemical-chain low-carbon alkane can realize the effective separation of oxygen removal and replenishment processes in the crystal lattice spatially or temporally by using metal oxide as a medium and recycling and replenishing the lattice oxygen of the catalyst. And (3) introducing oxygen or air into the oxidation bed to regenerate the catalyst after the reaction of the reduction bed, supplementing lattice oxygen of the low-valence ferric vanadate nanoparticles, effectively burning carbon deposition, transferring generated heat through a catalyst medium, and realizing high heat matching by adjusting the quality of the catalyst. The ferrovanadium-based bimetallic oxide catalyst is applied to the chemical chain dehydrogenation of low-carbon alkane, and the carbon number of the low-carbon alkane is preferably 2-4. Taking a chemical chain propane dehydrogenation reaction as an example, filling a catalyst and quartz sand which are uniformly physically mixed into a reaction bed, pre-introducing nitrogen to remove air, and then introducing propane; wherein the total flow of propane and nitrogen is 20-50 ml/min, and the volume percentage of propane is 5-30%. The performance of the catalyst at normal pressure and a reaction temperature of 450-650 ℃ is examined.
As shown in FIG. 2, the histogram shows the propane conversion, the solid line circle plot represents propylene selectivity, and the dashed triangle plot represents CO 2 Selectivity. As can be seen from fig. 2, the supported catalyst greatly improves the selectivity for propylene compared to the unsupported iron vanadate. Wherein 30FeVO 4 /Al 2 O 3 The single pass yield of propylene can be up to 42%, and the essential reason for the improved selectivity is that the supported catalyst realizes the organic combination of the catalytic site for propane dehydrogenation and the selective hydrogen combustion on the nanometer scale, so that the catalyst can maintain higher conversion rate and selectivity after the consumption of lattice oxygen. It should be noted here that unsupported ferric vanadate tends to over-oxidize propane.
The fresh catalyst prepared in the above example was subjected to XRD test, and the results are shown in fig. 3. As can be seen from FIG. 3, the unsupported iron vanadate catalystThe chemical agent has a triclinic structure and is a P1 space group. When it is loaded on the carrier, 30FeVO 4 /Al 2 O 3 And 50FeVO 4 /Al 2 O 3 All show a similarity to pure FeVO 4 And gamma-Al 2 O 3 The XRD characteristic peaks of (c) indicate that the crystal structure of the catalyst at higher loadings remains consistent with that of the unsupported catalyst. For 10FeVO 4 /Al 2 O 3 No analogy to pure FeVO was observed 4 Possibly due to smaller catalyst crystallites or highly dispersed on the support at this loading.
The research of the invention finds that the series catalyst on the nanometer scale is equally effective on other carrier supported catalysts. As shown in FIG. 4, can be extended to, for example, siO 2 、TiO 2 Molecular sieves, and the like are carriers.
The fresh catalyst prepared in the invention is subjected to H 2 TPR test, the results are shown in FIG. 5, with FeVO 4 The increase of the loading amount greatly shifts the position of the reduction peak in the low temperature direction, indicating that the catalyst is opposite to H 2 Is significantly enhanced. It should be mentioned here that a catalyst with excellent hydrogen-burning capacity, if effectively coupled with catalytic sites with dehydrogenation capacity, will be able to achieve tandem catalysis of propane dehydrogenation and selective hydrogen combustion on the nanometer scale.
From the results of the performance test, it is found that 30FeVO 4 /Al 2 O 3 The performance is optimal, and the microstructure is further explored. FIG. 6 is a 30FeVO 4 /Al 2 O 3 The HAADF-STEM diagram and the EDS-MAPPING diagram of the catalyst can observe that the grain size of the ferric vanadate is about 80nm, and the ferric vanadate is in a solid solution structure, and is consistent with XRD results. Monolayer dispersed FeVO 4 As a catalytic site for the direct dehydrogenation of propane, the catalyst is synergistic with adjacent ferric vanadate grains to realize serial catalysis on nanometer scale.
30FeVO with optimal performance 4 /Al 2 O 3 For example, the cyclic stability of the catalyst in the dehydrogenation reaction of chemical chain propane was investigated, and the results are shown in FIG. 7. It can be seen that the cycle of 10 cycles ("reaction-regeneration-reaction-regeneration" cycle)After that, the catalyst performance remained essentially unchanged. The supported ferrovanadium bimetallic oxide has good stability, can effectively solve the problem of sintering of pure ferric oxide in the oxidation-reduction process, and has practical application prospect.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (10)
1. A vanadium iron-based bimetallic oxide catalyst comprises a carrier, and is characterized in that a single-layer dispersed FeVO is loaded on the carrier 4 The single layer of dispersed FeVO 4 FeVO loaded with bulk phase 4 A nanoparticle; the single layer dispersed FeVO 4 As a direct dehydrogenation catalytic site, the FeVO 4 The nanoparticles act as hydrogen selective combustion sites.
2. A vanadium iron-based bimetallic oxide catalyst according to claim 1, wherein the support is Al 2 O 3 、SiO 2 、TiO 2 Or a molecular sieve.
3. A vanadium iron-based bimetallic oxide catalyst according to claim 1, wherein the FeVO 4 The total mass of (2) is 10-50wt.% of the total mass of the catalyst.
4. A vanadium iron-based bimetallic oxide catalyst according to claim 3, wherein the FeVO 4 Is 30wt.% of the total mass of the catalyst.
5. A process for the preparation of a vanadium iron-based bimetallic oxide catalyst as set forth in any one of claims 1 to 4, comprising the steps of:
(1) Dissolving and uniformly mixing precursor salt of iron and precursor salt of vanadium;
(2) Impregnating the uniformly mixed salt solution obtained in the step (1) on the carrier, and drying;
(3) Roasting the impregnated carrier, wherein the roasting atmosphere is air, the roasting temperature is 500-600 ℃, and the roasted catalyst is pressed into tablets for shaping and sieving for standby.
6. The method for preparing a vanadium iron-based bimetallic oxide catalyst according to claim 5, wherein in the step (1), ferric nitrate is uniformly dispersed in deionized water to form an impregnating solution-1, ammonium metavanadate and oxalic acid are uniformly mixed and dissolved in deionized water to form an impregnating solution-2, and the impregnating solution-1 and the impregnating solution-2 are uniformly mixed; wherein the mass ratio of the ammonium metavanadate to the oxalic acid is 1:2.
7. the method for preparing a vanadium iron-based bimetallic oxide catalyst according to claim 5, wherein in the step (2), the drying temperature is 80-100 ℃ and the drying time is 6-12 hours; in the step (3), the roasting time is 1-8 hours; the mesh number of the sieve is 20-40 mesh.
8. Use of a vanadium iron-based bimetallic oxide catalyst according to any one of claims 1 to 4 for the chemical chain dehydrogenation of lower alkanes, wherein the catalyst is reacted with lower alkanes in the absence of an oxygen co-feed, said single layer of dispersed FeVO 4 As a direct dehydrogenation catalytic site to convert light alkanes into corresponding olefins and hydrogen; the FeVO 4 Nanoparticles as selective hydrogen combustion sites for selectively burning byproduct hydrogen to produce product water and release heat energy, the FeVO 4 The nanoparticle is reduced to a lower valence state; introducing oxygen or air into the reacted catalyst to regenerate FeVO 4 The lattice oxygen of the nano particles is supplemented, and meanwhile, carbon deposition is combusted and heat energy is released; after the above cycle, the catalyst returns to the original state.
9. The use of the ferrovanadium-based bimetallic oxide catalyst according to claim 8 in the chemical chain dehydrogenation of lower alkanes, wherein the lower alkanes have a carbon number of 2-4.
10. The use of the ferrovanadium-based bimetallic oxide catalyst in low-carbon alkane chemical chain dehydrogenation according to claim 8, wherein the catalyst and quartz sand are physically and uniformly mixed, and the mass ratio of the catalyst to the quartz sand is (0.2-1): 1, a step of; the reaction is carried out under normal pressure, the reaction temperature is 450-650 ℃, nitrogen is pre-introduced to remove air, and then propane is introduced; wherein the total flow of propane and nitrogen is 20-50 ml/min, and the volume percentage of propane is 5-30%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB381072A (en) * | 1931-02-28 | 1932-09-29 | Bataafsche Petroleum | A process for the manufacture of hydrogen from hydrocarbons |
| CN102989467A (en) * | 2012-12-13 | 2013-03-27 | 中国科学院生态环境研究中心 | Titanium oxide supported ferric vanadate catalyst, as well as preparation method and use thereof |
| CN111229269A (en) * | 2020-03-25 | 2020-06-05 | 浙江工商大学 | FePMo/ferric vanadate composite material and preparation method and application thereof |
-
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- 2023-03-15 CN CN202310248826.9A patent/CN116099543A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB381072A (en) * | 1931-02-28 | 1932-09-29 | Bataafsche Petroleum | A process for the manufacture of hydrogen from hydrocarbons |
| CN102989467A (en) * | 2012-12-13 | 2013-03-27 | 中国科学院生态环境研究中心 | Titanium oxide supported ferric vanadate catalyst, as well as preparation method and use thereof |
| CN111229269A (en) * | 2020-03-25 | 2020-06-05 | 浙江工商大学 | FePMo/ferric vanadate composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGBO SONG ET AL.: "Chemical looping oxidative propane dehydrogenation controlled by oxygen bulk diffusion over FeVO4 oxygen carrier pellets", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》, vol. 53, 28 October 2022 (2022-10-28), pages 410 - 411 * |
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