CN115400748B - Isobutane CO 2 Vanadium-based catalyst for oxidative dehydrogenation to prepare isobutene and preparation thereof - Google Patents
Isobutane CO 2 Vanadium-based catalyst for oxidative dehydrogenation to prepare isobutene and preparation thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000001282 iso-butane Substances 0.000 title claims abstract description 22
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 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 abstract description 48
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 48
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 83
- 239000002002 slurry Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000004448 titration Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 11
- 229910052734 helium Inorganic materials 0.000 claims description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 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 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010992 reflux Methods 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
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 235000011044 succinic acid Nutrition 0.000 claims description 4
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 4
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 4
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- -1 ceO 2 Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 238000011156 evaluation Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 238000005303 weighing Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910001456 vanadium ion Chemical group 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003795 desorption Methods 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
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Abstract
The invention relates to the technical field of catalyst preparation, in particular to isobutane CO 2 Vanadium-based catalyst for preparing isobutene by oxidative dehydrogenation and preparation thereof. From ZrO 2 The vanadium-based catalyst is formed by taking the catalyst as a carrier and adding an active component and a metal oxide auxiliary agent in an impregnation mode, wherein the specific surface area of the vanadium-based catalyst is 100-350 m 2 g ‑1 The pore diameter of the mesoporous structure is 11-18 nm, and the pore volume is 0.31-0.46 cm 3 g ‑1 . The catalyst of the invention contains a large amount of oligomer vanadium oxide, and can improve the activity and stability of the catalyst. Simple preparation, can generate a large amount of oligomeric and isolated vanadium oxides, and effectively utilizes CO 2 Has excellent anti-carbon property, high isobutane conversion rate, high isobutene selectivity and excellent stability.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to isobutane CO 2 Vanadium-based catalyst for preparing isobutene by oxidative dehydrogenation and preparation thereof.
Background
In recent years, a new interest has been raised by researchers in the related art for producing isobutene by catalytic dehydrogenation of isobutane, mainly due to the increase in isobutane supply and the expansion of the demand gap of the deep processing industry of isobutene caused by the rise of petroleum cracking processes. Compared with the traditional isobutane direct dehydrogenation process, the method has the advantages that the energy consumption is high, the catalyst is easy to deactivate, and the greenhouse gas CO 2 Is effective in utilizing isobutane CO 2 Oxidative dehydrogenation (CO) 2 BDH) becomes a green and efficient isobutene production process.
Vanadium oxide is considered to be one of the most important metal oxides in catalytic dehydrogenation. The catalytic activity and selectivity of vanadium oxide depends on its structure and partitionDispersibility and the nature of the carrier material thereof. The high polymer vanadium oxide has poor dehydrogenation activity and high olefin isomerization capability, butadiene formed by isobutene isomerization is further polymerized to be a main source of carbon deposition, and the carbon deposition is a key factor affecting the stability of the catalyst, and oligomerization (or orphan) is carried out<5V/nm 2 ) The vanadium oxide of (c) appears to be very active and detrimental to the isomerisation of isobutene. Therefore, the realization of more oligomerization and island distribution of vanadium oxide can effectively improve the activity, selectivity and stability of the catalyst.
Research has shown that the introduction of the metal oxide auxiliary agent can play a role in structure regulation and control to promote the dispersion of vanadium oxide, and the doping of the auxiliary agent is often beneficial to carbon deposition elimination. Furthermore, the support material has an important influence on the catalytic properties. The traditional zeolite molecular sieve is easy to break carbon-carbon bonds due to the excessive exposure of strong acid sites in the zeolite molecular sieve, and the long and narrow micropore channels are easy to cause isomerization reaction in isobutene passing, thereby reducing isobutene selectivity, while ZrO 2 The typical metal oxide carrier has the characteristics of good thermal stability and large specific surface area, the excellent texture characteristics allow the high dispersion of vanadium oxide and the timely diffusion of reactants, and the carrier surface modified by the auxiliary agent has moderate acid-base property and can be used as a proper carrier of an isobutane dehydrogenation catalyst.
Disclosure of Invention
The invention aims to provide isobutane CO 2 The vanadium-based catalyst for the reaction of preparing isobutene by oxidative dehydrogenation has simple preparation, can generate a large amount of oligomeric (and isolated) vanadium oxide, and effectively utilizes CO 2 Has excellent anti-carbon property, high isobutane conversion rate, high isobutene selectivity and excellent stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
isobutane CO 2 The vanadium-based catalyst for the reaction of preparing isobutene through oxidative dehydrogenation comprises a carrier, an active component and an auxiliary agent, and is obtained through an impregnation method; the specific surface area of the vanadium-based catalyst is 100-350 m 2 g -1 The pore diameter of the mesoporous structure is 11 to the ultra18nm, pore volume of 0.31-0.46 cm 3 g -1 。
Further, the carrier is ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The active component is vanadium oxide; the auxiliary agent is MnO, ceO 2 、Fe 2 O 3 、Y 2 O 3 、MoO 3 One or two of the following components; the vanadium-based catalyst comprises the following components in percentage by weight: 5.8 to 24.3 weight percent of vanadium oxide, 2.1 to 24.1 weight percent of auxiliary agent and ZrO 2 59.7% -90%.
Under the double physical barriers of the space limiting effect formed by the three-dimensional crossed mesoporous structure and the molecular fence effect formed by the metal oxide auxiliary agent, the catalyst generates a large amount of oligomeric and isolated vanadium oxides, provides an isolated protection mechanism for effectively resisting vanadium oxide aggregation while realizing exposure of more active sites, and improves the activity of the catalyst. Support ZrO 2 And the rapid conversion capability of the 'lattice oxygen-active oxygen' of the auxiliary agent to enable CO 2 The activation utilization of the catalyst is improved, and the sufficient free oxygen supply can not only effectively avoid carbon accumulation, but also break the reaction balance, stabilize the redox cycle on the active site, improve the conversion rate of isobutane and prolong the service life.
Isobutane CO 2 The preparation of the vanadium-based catalyst for the reaction of preparing isobutene by oxidative dehydrogenation comprises the following steps:
step 1, preparing ZrO 2 And (3) a carrier: dissolving soluble salt containing a carrier in deionized water, and uniformly stirring to obtain a solution A; preparing an aqueous solution of soluble alkali as a solution B; at the crystallization temperature of 50-70 ℃, adopting a parallel flow titration mode, simultaneously co-titrating the solution A and the solution B into a large beaker while stirring, continuously stirring and aging the slurry obtained after the dripping is finished for 1-7 hours, washing with deionized water, centrifuging, and placing the precipitate obtained by centrifuging for 2-12 hours; placing the slurry obtained by uniformly stirring the precipitate and deionized water together with a porcelain ring into a round bottom flask, heating the slurry to a state that the slurry boils and a large amount of bubbles are generated by using a heating sleeve or an oil bath pot, heating for 24-72 h, cooling the heated slurry to room temperature, washing the slurry with deionized water for multiple times, and centrifugingUntil the pH is neutral, drying the precipitate obtained by centrifugation at 70-120 ℃ for 12-36 h, and finally calcining at 500-650 ℃ for 2-6 h to obtain the ZrO 2 A carrier;
step 2, dipping the active components and the auxiliary agents: dissolving soluble salt containing active components and auxiliary agents and organic acid in deionized water, uniformly stirring to obtain solution C, and obtaining ZrO in the step 1 2 Immersing the carrier in the solution C, stirring and drying at 80-120 ℃, drying the obtained product at 70-110 ℃ for 12-24 h, carbonizing at 350-400 ℃ for 20-60 min in helium atmosphere to form an oligomeric vanadium oxide catalyst precursor with an isolated coated carbon layer, and calcining at 500-650 ℃ in air atmosphere for 2-6 h to obtain the vanadium-based catalyst.
The vanadium-based catalyst may be expressed as V-M/ZrO 2 Wherein V is vanadium oxide, M is MnO, ceO 2 、Fe 2 O 3 、Y 2 O 3 、MoO 3 One or two of them.
Further, the soluble salt of the carrier is zirconium nitrate or zirconyl nitrate; the soluble salt of the active component is one of ammonium metavanadate, vanadyl sulfate and vanadyl oxalate; the soluble salt of the auxiliary agent is one or two of cerium nitrate, ferric nitrate, manganese nitrate, yttrium nitrate and ammonium molybdate; the soluble alkali is one of sodium hydroxide, sodium carbonate and potassium hydroxide; the organic acid is one of oxalic acid, tartaric acid and succinic acid.
Further, the mole ratio of the soluble salt of the active component, the soluble salt of the auxiliary agent, the organic acid and the deionized water in the solution C is 0.0009-0.0036: 0.00036 to 0.0018:0.0036 to 0.0072:1.
further, the concentration of the solution A in the step 1 is 0.08-0.2 mol/L; the concentration of the solution B is 0.5-2 mol/L; the drop ratio of the solution A to the solution B is 3-7:1, and the titration duration is 1-12 h.
Further, the deionized water content in the slurry in the step 1 is 200-350 mL.
Further, in the step 1, the ceramic ring is a ceramic Raschig ring with the outer diameter of 6-12 mm, the height of 6-12 mm and the wall thickness of 1.5-2.5 mm, and the filler amount of the ceramic ring is 5-10 g.
Further, the heating temperature of the heating sleeve or the oil bath in the step 1 is 135-185 ℃.
Isobutane CO 2 The method for preparing isobutene by oxidative dehydrogenation adopts the catalyst, the catalyst is evaluated in a fixed bed, the calcined catalyst is ground into powder, particles with 20-40 or 40-60 meshes are screened out by tabletting and used for filling a reaction tube, the catalyst dosage is 0.2-1 g, and C in raw material gas 4 H 10 The volume concentration is 9-11%, CO 2 The volume concentration is 40-50%, N 2 The volume concentration is 40-50%, the reaction pressure is 0.08-0.12 Mpa, the flow rate is 30-80 mL/min, and the reaction temperature is 550-650 ℃.
The catalyst provided by the invention is used for isobutane CO 2 Oxidative dehydrogenation reaction, the conversion rate of the isobutene reaches 36-49%, the selectivity of the isobutene reaches 87-92%, and CO 2 The conversion rate reaches 12-22%.
Compared with the prior art, the invention has the following advantages:
(1) ZrO used in the present invention 2 The carrier preparation method has a unique pore-increasing effect, the slurry in the round-bottom flask is heated to be in a boiling state, gas in micropores of the ultra-dense pore ceramic Raschig ring is heated, expanded and overflowed to form a plurality of gasification centers, so that a plurality of vapor bubbles are formed and float upwards to escape to the surface of the slurry, the pore-increasing effect is achieved while the formation of the bubbles prevents the slurry from overheating, and finally ZrO with a high specific surface area and rich three-dimensional cross mesoporous structure is formed 2 A carrier.
(2) In the preparation process of the material, the added organic acid has the special effects that the acid group can promote the dissolution of vanadium precursor salt, and simultaneously the organic group and vanadium ion form a metal ion-organic ligand composite group which is uniformly adsorbed and then dispersed and deposited on ZrO in the stirring and drying processes 2 The surface of the carrier. In the low-temperature calcination process, the organic ligand is carbonized preferentially, namely, the coated carbon framework formed by in-situ pyrolysis of the organic ligand under inert atmosphere generates anchoring to the vanadium oxideActing; during the subsequent high temperature calcination treatment, it acts as an isolation layer to limit the growth of the vanadium oxide, and the final carbon framework is removed in an air atmosphere and an oligomeric distribution of the vanadium oxide on the catalyst is achieved. In addition, in the material synthesis system, the vanadium species preferably form a metal ion-organic ligand composite group, and then are strongly adsorbed on a carrier interface through the electrophilic action of the organic group and the hydroxyl group on the surface of the carrier, while the auxiliary species are only impregnated and attached to the surface of the carrier through inorganic groups of metal ions such as cerium, iron, manganese, yttrium, ammonium and the like, and the competitive adsorption and impregnation mode promotes the formation of a 'molecular fence' of the vanadium-auxiliary species.
(3) ZrO used in the present invention 2 The support has a high specific surface area, allows the formation of more oligomeric active components, simultaneously due to ZrO 2 The catalyst has certain oxygen supply capacity for eliminating carbon deposition, so that the activity and the service life of the catalyst are improved; the abundant three-dimensional crossed mesoporous structure can form a space limiting domain effect, and aggregation of active components is prevented in a physical barrier mode, so that loss of active sites is avoided; in addition, the three-dimensional cross mesoporous structure allows isobutene molecules to escape from the catalyst to the outside in time, so that the risk that isobutene molecules encounter active sites to react secondarily in the process of passing through the pore canal due to long and narrow pore canal of the traditional microporous molecular sieve is avoided, and the selectivity of isobutene is improved.
(4) The addition of the metal oxide auxiliary agent can achieve the effect of dispersing and isolating the vanadium oxide, and the change of the vanadium oxide from the oligomer to the high polymer is hindered by forming a molecular fence, so that more high-dispersion oligomer vanadium oxide is promoted to be formed, the number of active sites is increased, and aggregation sintering under high-temperature reaction is prevented. Meanwhile, the addition of the auxiliary agent improves the acid-base property of the surface of the catalyst and enhances CO 2 And interact with adjacent vanadium oxides to form interfacial synergistic catalysis for carbon deposit elimination to maintain stable catalyst operation and sufficient free oxygen species to consume H generated by isobutane dehydrogenation through RWGS reaction 2 To break the reaction equilibrium and thereby increase the conversion of isobutane.
(5) The catalyst provided by the invention containsA large amount of oligomer vanadium oxide can improve the activity and stability of the catalyst. As the size of the vanadium oxide increases, the probability of simultaneously adsorbing multiple olefin molecules and condensing into a regular graphite structure through polymerization or cyclization reactions increases, resulting in a higher carbon deposition rate, which is more difficult to achieve for oligomeric vanadium oxides. In addition, the oxygen of the V=O group in the oligomeric vanadium oxide has stronger oxidative dehydrogenation induction activity, and the oligomeric vanadium oxide can be combined with an auxiliary agent or ZrO 2 More contact interfaces are formed so that the active oxygen species are more quickly taken up to reoxidize the partially reduced lower vanadium ions to higher vanadium ions, thereby allowing for continued redox cycling at the active site.
Drawings
FIG. 1 is a simplified flow chart of the catalyst preparation of example 3 of the present invention;
FIG. 2 is a schematic representation of the redox cycling at the active site of the catalyst of example 9 of the present invention;
FIG. 3 is a wide-angle XRD spectrum of the catalyst of example 6 of the invention;
FIG. 4 is a catalyst N according to example 6 of the present invention 2 Adsorption and desorption graph.
Detailed Description
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.05 mol of zirconium nitrate into 0.1 mol/L of solution A; an aqueous sodium carbonate solution of 0.5 mol/l was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker with stirring in a 70℃water bath at a 4:1 drop ratio by co-current titration, and after approximately 3h of the dropwise addition, the resulting slurry was stirred for a further 2h, washed with deionized water, centrifuged and the resulting precipitate was left for 12h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 300mL of deionized water into a round bottom flask, placing 5g of porcelain ring with the outer diameter of 6mm, the height of 6mm and the wall thickness of 1.5mm into the round bottom flask, heating to 145 ℃ by using an oil bath pot, refluxing and aging for 48 hours, cooling the slurry to room temperature after the reaction is finished, washing the slurry with deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 120 ℃ for 12 hours, and calcining the slurry at 600 ℃ for 4 hours to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.003 mol of ammonium metavanadate, 0.001 mol of cerium nitrate and 0.004 mol of succinic acid are dissolved in 20mL of deionized water, and then stirred uniformly to obtain solution C. 1g of ZrO obtained in step 1 was weighed out 2 Immersing a carrier in the solution C, stirring and drying at 100 ℃, drying the obtained product at 100 ℃ for 24 hours, carbonizing the product at 350 ℃ in helium atmosphere for 30 minutes to form an isolated oligomeric vanadium oxide catalyst precursor coated with a carbon layer, and calcining the product at 650 ℃ in air atmosphere for 3 hours to obtain the catalyst 1, wherein the actual composition of the catalyst 1 is 17.6wt% vanadium oxide, 12.1wt% auxiliary agent and 70.3wt% ZrO 2 Specific surface area of 350m 2 g -1 Pore diameter of 11.3nm and pore volume of 0.46cm 3 g -1 The texture and structural parameters of catalyst 1 are shown in Table 2.
Step 3 Activity evaluation
Weighing 0.6g of a 40-60-mesh catalyst 1 sample, and introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 600 ℃ at a flow rate of 30mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 40%, N 2 The reaction was started with a mixture of 50% by volume. The evaluation results are shown in Table 1.
Example 2
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.1 mol of zirconyl nitrate into 0.2 mol/L of solution A; an aqueous sodium hydroxide solution of 2 mol/liter was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker at a 7:1 drop rate by co-current titration in a 70℃water bath with stirring, and after approximately 1h of the drop was completed, the resulting slurry was stirred for a further 7h, then washed with deionized water, centrifuged, and the resulting precipitate was allowed to stand for 2h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 200mL of deionized water into a round bottom flask, placing 10g of ceramic ring with the outer diameter of 12mm, the height of 12mm and the wall thickness of 2.5mm into the round bottom flask, heating to 135 ℃ by using an oil bath pot, refluxing and aging for 72h, cooling the slurry to room temperature after the reaction is finished, washing the slurry with deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 70 ℃ for 36h, and roasting the slurry at 650 ℃ for 2h to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.003 mol of ammonium metavanadate, 0.0008 mol of manganese nitrate and 0.008 mol of oxalic acid were dissolved in 40mL of deionized water, and then stirred uniformly to obtain solution C. 2g of ZrO obtained in step 1 were weighed out 2 Immersing the carrier in the solution C, stirring and drying at 80 ℃, drying the obtained product at 110 ℃ for 12 hours, carbonizing the product at 350 ℃ in helium atmosphere for 20 minutes to form an isolated oligomeric vanadium oxide catalyst precursor coated with a carbon layer, and calcining the product at 500 ℃ in air atmosphere for 6 hours to obtain the catalyst 2, wherein the actual composition of the catalyst 2 is 10.8wt% of vanadium oxide, 2.5wt% of auxiliary agent and 86.7wt% of ZrO 2 A specific surface area of 258m 2 g -1 Pore diameter of 15.5nm and pore volume of 0.34cm 3 g -1 The texture and structural parameters of catalyst 2 are shown in table 2.
Step 3: activity evaluation
Weighing 0.2g of 20-40 mesh catalyst 1 sample, and introducing C at a reaction pressure of 0.12MPa and a reaction temperature of 650 ℃ at a flow rate of 30mL/min 4 H 10 The volume concentration is 9%, CO 2 The volume concentration is 45%, N 2 The reaction was started with a mixture of 46% by volume. The evaluation results are shown in Table 1.
Example 3
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.04 mol of zirconium nitrate into 0.08 mol/L of solution A; an aqueous potassium hydroxide solution (0.5 mol/l) was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker with stirring in a 50℃water bath at a 3:1 drop rate by co-current titration, and after approximately 6h of the dropwise addition, the resulting slurry was stirred for a further 1h, washed with deionized water, centrifuged and the resulting precipitate was left for 12h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 250mL of deionized water into a round bottom flask, placing 5g of porcelain ring with the outer diameter of 6mm, the height of 6mm and the wall thickness of 1.5mm into the round bottom flask, heating to 155 ℃ by using an oil bath pot, refluxing and aging for 24 hours, cooling the slurry to room temperature after the reaction is finished, washing the slurry with deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 120 ℃ for 12 hours, and roasting the slurry at 500 ℃ for 6 hours to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.001 mol of ammonium metavanadate, 0.002 mol of ferric nitrate and 0.008 mol of tartaric acid were dissolved in 20mL of deionized water, and then stirred uniformly to obtain solution C. 1g of ZrO obtained in step 1 was weighed out 2 The support was immersed in the solution C and dried with stirring at a temperature of 110 ℃. Drying the obtained product at 110deg.C for 24 hr, carbonizing at 350deg.C under helium atmosphere for 25min to form oligomeric vanadium oxide catalyst precursor with carbon-coated layer isolation, and calcining at 650deg.C under air atmosphere for 2 hr to obtain the catalyst 3, wherein FIG. 1 is a simple preparation flow chart of catalyst 3, and the actual composition of catalyst 3 is 6.6wt% vanadium oxide, 12.8wt% adjuvant and 80.6wt% ZrO 2 A specific surface area of 116m 2 g -1 Pore diameter of 17.6nm and pore volume of 0.31cm 3 g -1 The texture and structural parameters of catalyst 3 are shown in table 2.
Step 3: activity evaluation
Weighing 0.3g of 40-60 mesh catalyst 3 sample, introducing C at a reaction pressure of 0.08MPa and a reaction temperature of 600 ℃ at a flow rate of mL/min 4 H 10 The volume concentration is 11%, CO 2 The volume concentration is 50%, N 2 The reaction was started with a 39% by volume mixture. The evaluation results are shown in Table 1.
Example 4
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.06 mol of zirconium nitrate into 0.12 mol/L of solution A; an aqueous sodium hydroxide solution of 1 mol/liter was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker at a 5:1 drop rate by co-current titration in a 50℃water bath with stirring, and after approximately 12h of the dropwise addition, the resulting slurry was stirred for a further 7h, washed with deionized water, centrifuged and the resulting precipitate was left for 12h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 200mL of deionized water into a round bottom flask, placing 0.5g of ceramic ring with the outer diameter of 12mm, the height of 12mm and the wall thickness of 2.5mm into the round bottom flask, heating the mixture to 185 ℃ by using a heating sleeve, refluxing and aging for 72 hours, and cooling the slurry to room temperature after the reaction is finishedWashing with deionized water, centrifuging to neutrality, drying at 100deg.C for 24 hr, and calcining at 500deg.C for 6 hr to obtain ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.006 mol of vanadyl oxalate, 0.006 mol of yttrium nitrate and 0.012 mol of oxalic acid are dissolved in 60mL of deionized water, and then stirred uniformly to obtain a solution C. 3g of ZrO obtained in step 1 were weighed 2 The support was immersed in solution C and dried with stirring at a temperature of 120 ℃. Drying the obtained product at 70 ℃ for 24 hours, carbonizing the product at 350 ℃ in helium atmosphere for 60 minutes to form an oligomeric vanadium oxide catalyst precursor with a carbon-coated layer isolated, and calcining the product at 600 ℃ in air atmosphere for 4 hours to obtain the catalyst 4, wherein the actual composition of the catalyst 4 comprises 11.9 weight percent of vanadium oxide, 16.2 weight percent of auxiliary agent and 71.9 weight percent of ZrO 2 Specific surface area of 153m 2 g -1 Pore diameter of 16.5nm and pore volume of 0.33cm 3 g -1 The texture and structural parameters of catalyst 4 are shown in table 2.
Step 3: activity evaluation
Weighing 0.2g of 40-60 mesh catalyst 4 sample, and introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 580 ℃ at a flow rate of mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 50%, N 2 The reaction was started with a mixture of 40% by volume. The evaluation results are shown in Table 1.
Example 5
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.045 mol of zirconium nitrate into 0.1 mol/L of solution A; an aqueous sodium carbonate solution of 0.5 mol/l was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker with stirring in a 50℃water bath at a 3:1 drop rate by co-current titration, and after approximately 12h of the dropwise addition, the resulting slurry was stirred for a further 5h, washed with deionized water, centrifuged and the resulting precipitate was allowed to stand for 10h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 250mL of deionized water into a round bottom flask, placing 0.5g of porcelain ring with the outer diameter of 9mm, the height of 9mm and the wall thickness of 2mm into the flask, heating to 155 ℃ by an oil bath pot, refluxing and aging for 60 hours, and reacting to obtain the final productCooling the slurry to room temperature, washing with deionized water, centrifuging to neutrality, drying at 110deg.C for 12 hr, and calcining at 550deg.C for 6 hr to obtain the final product 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.004 mol of vanadyl sulfate, 0.002 mol of ammonium molybdate and 0.01 mol of tartaric acid are dissolved in 40mL of deionized water, and then stirred uniformly to obtain solution C. 2g of ZrO obtained in step 1 were weighed out 2 The support was immersed in the solution C and dried with stirring at a temperature of 80 ℃. Drying the obtained product at 70 ℃ for 24 hours, carbonizing at 370 ℃ in helium atmosphere for 35 minutes to form an oligomeric vanadium oxide catalyst precursor with a carbon-coated layer isolated, and calcining at 600 ℃ in air atmosphere for 2 hours to obtain the catalyst 5, wherein the actual composition of the catalyst 5 comprises 12.7 weight percent of vanadium oxide, 11 weight percent of auxiliary agent and 76.3 weight percent of ZrO 2 Specific surface area of 298m 2 g -1 Pore diameter of 15.3nm and pore volume of 0.38cm 3 g -1 The texture and structural parameters of catalyst 5 are shown in table 2.
Step 3: activity evaluation
Weighing 0.4g of 40-60 mesh catalyst 5 sample, and introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 600 ℃ at a flow rate of 40mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 40%, N 2 The reaction was started with a mixture of 50% by volume. The evaluation results are shown in Table 1.
Example 6
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.05 mol of zirconium nitrate into 0.1 mol/L of solution A; an aqueous sodium hydroxide solution of 1 mol/liter was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker with stirring in a 60℃water bath at a 4:1 drop ratio by co-current titration, and after approximately 6h of the dropwise addition, the resulting slurry was stirred for a further 3h, washed with deionized water, centrifuged and the resulting precipitate was left for 6h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 300mL of deionized water into a round bottom flask, placing 1g of porcelain ring with the outer diameter of 9mm, the height of 9mm and the wall thickness of 2mm into the flask, and heating to 165 ℃ by using an oil bath potAfter the back flow aging for 36 hours, cooling the slurry to room temperature after the reaction is finished, washing the slurry with deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 70 ℃ for 36 hours, and roasting the slurry at 650 ℃ for 2 hours to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.004 mol of vanadyl sulfate, 0.002 mol of yttrium nitrate and 0.005 mol of tartaric acid are dissolved in 20mL of deionized water, and then stirred uniformly to obtain solution C. 1g of ZrO obtained in step 1 was weighed out 2 The support was immersed in the solution C and dried with stirring at a temperature of 90 ℃. Drying the obtained product at 100deg.C for 24 hr, carbonizing at 370deg.C under helium atmosphere for 20min to form oligomeric vanadium oxide catalyst precursor with carbon-coated layer isolation, and calcining at 500deg.C under air atmosphere for 6 hr to obtain the catalyst 6, wherein figure 3 shows wide angle XRD spectrum of catalyst 6, and the actual composition of catalyst 6 comprises 21.3wt% vanadium oxide, 14.5wt% adjuvant and 64.2wt% ZrO 2 A specific surface area of 332m 2 g -1 Pore diameter of 12.8nm and pore volume of 0.43cm 3 g -1 The texture and structural parameters of catalyst 6 are shown in Table 2.
Step 3 Activity evaluation
Weighing 0.5g of 40-60 mesh catalyst 6 sample, and introducing C at a reaction pressure of 0.12MPa and a reaction temperature of 610 ℃ at a flow rate of 50mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 45%, N 2 The reaction was started with a mixture having a volume concentration of 45%, and FIG. 4 shows N of catalyst 6 2 Adsorption and desorption graph. The evaluation results are shown in Table 1.
Example 7
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.05 mol of zirconyl nitrate into 0.1 mol/L of solution A; an aqueous sodium carbonate solution of 2 mol/l was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker at a 4:1 drop rate by co-current titration in a 70℃water bath with stirring, and after approximately 1h of the drop was completed, the resulting slurry was stirred for a further 4h, then washed with deionized water, centrifuged, and the resulting precipitate was allowed to stand for 10h. Mixing and stirring the precipitate and 200mL deionized waterPlacing the homogenized slurry into a round-bottom flask, placing 1g of porcelain ring with outer diameter of 6mm, height of 6mm and wall thickness of 1.5mm, heating to 135 ℃ by a heating sleeve, refluxing and aging for 48h, cooling the slurry to room temperature after the reaction is finished, washing with deionized water for multiple times, centrifuging to neutrality, drying at 90 ℃ for 24h, and roasting at 600 ℃ for 4h to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.009 mol ammonium metavanadate, 0.002 mol ferric nitrate and 0.015 mol tartaric acid were dissolved in 60mL deionized water, and then stirred well to obtain solution C. 3g of ZrO obtained in step 1 were weighed 2 The support was immersed in the solution C and dried with stirring at a temperature of 100 ℃. Drying the obtained product at 80 ℃ for 24 hours, carbonizing the product at 400 ℃ for 50 minutes in helium atmosphere to form an oligomeric vanadium oxide catalyst precursor with a carbon-coated layer isolated, and calcining the product at 650 ℃ in air atmosphere for 2 hours to obtain the catalyst 7, wherein the actual composition of the catalyst 7 comprises 19.1 weight percent of vanadium oxide, 4.1 weight percent of auxiliary agent and 76.8 weight percent of ZrO 2 A specific surface area of 226m 2 g -1 Pore diameter of 16.1nm and pore volume of 0.34cm 3 g -1 The texture and structural parameters of catalyst 7 are shown in Table 2.
Step 3: activity evaluation
Weighing 0.3g of a catalyst 7 sample with 40-60 meshes, and introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 570 ℃ at a flow rate of 60mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 50%, N 2 The reaction was started with a mixture of 40% by volume. The evaluation results are shown in Table 1.
Example 8
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.08 mol of zirconyl nitrate into 0.15 mol/L of solution A; an aqueous sodium carbonate solution of 2 mol/l was prepared and designated as solution B. Solution A and solution B were titrated into a large beaker at a 5:1 drop rate by co-current titration with stirring in a 70℃water bath, the resulting slurry was stirred for 2h after approximately 3h, then washed with deionized water, centrifuged and the resulting precipitate was left for 5h. Will precipitatePlacing the slurry which is uniformly mixed and stirred with 200mL of deionized water into a round-bottom flask, placing 0.5g of ceramic ring with the outer diameter of 12mm, the height of 12mm and the wall thickness of 2.5mm into the round-bottom flask, heating to 165 ℃ by an oil bath pot, refluxing and aging for 24 hours, cooling the slurry to room temperature after the reaction is finished, washing the slurry with deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 70 ℃ for 36 hours, and roasting the slurry at 550 ℃ for 4 hours to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.005 mol of ammonium metavanadate, 0.002 mol of ferric nitrate, 0.001 mol of yttrium nitrate and 0.01 mol of succinic acid were dissolved in 40mL of deionized water, and then stirred uniformly to obtain solution C. 2g of ZrO obtained in step 1 were weighed out 2 The support was immersed in the solution C and dried with stirring at a temperature of 110 ℃. Drying the obtained product at 100 ℃ for 12 hours, carbonizing at 350 ℃ in helium atmosphere for 40 minutes to form an oligomeric vanadium oxide catalyst precursor with a carbon-coated layer isolated, and calcining at 600 ℃ in air atmosphere for 4 hours to obtain the catalyst 8, wherein the actual composition of the catalyst 8 comprises 15.5 weight percent of vanadium oxide, 10.1 weight percent of auxiliary agent and 74.4 weight percent of ZrO 2 Specific surface area of 312m 2 g -1 Pore diameter of 12.5nm and pore volume of 0.41cm 3 g -1 The texture and structural parameters of catalyst 8 are shown in table 2.
Step 3: activity evaluation
Weighing 0.3g of 40-60 mesh catalyst 8 sample, and introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 600 ℃ at a flow rate of 30mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 40%, N 2 The reaction was started with a mixture of 50% by volume. The evaluation results are shown in Table 1.
Example 9
Step 1: zrO (ZrO) 2 Carrier preparation
Preparing 0.05 mol of zirconium nitrate into 0.1 mol/L of solution A; an aqueous solution of potassium hydroxide was prepared at a concentration of 2 mol/liter and designated as solution B. Solution A and solution B were titrated into a large beaker at a 6:1 drop rate by co-current titration with stirring in a 60℃water bath, and after approximately 6h of the drop was completed, the resulting slurry was stirred for a further 5h and then used upWashing with ionized water, centrifuging, and standing the obtained precipitate for 10h. Placing the slurry obtained by uniformly mixing and stirring the precipitate and 300mL of deionized water into a round bottom flask, placing 1g of ceramic ring with the outer diameter of 9mm, the height of 9mm and the wall thickness of 2mm into the round bottom flask, heating to 155 ℃ by using an oil bath pot, refluxing and aging for 48 hours, cooling the slurry to room temperature after the reaction is finished, washing the slurry by using deionized water for multiple times, centrifuging the slurry to be neutral, drying the slurry at 100 ℃ for 24 hours, and roasting the slurry at 650 ℃ for 3 hours to obtain the required ZrO 2 A carrier.
Step 2: impregnating active components and auxiliary agents
0.002 mol of ammonium metavanadate, 0.001 mol of cerium nitrate and 0.015 mol of oxalic acid were dissolved in 40mL of deionized water, and then stirred uniformly to obtain solution C. 2g of ZrO obtained in step 1 were weighed out 2 The support was immersed in the solution C and dried with stirring at a temperature of 100 ℃. Drying the obtained product at 110 ℃ for 12 hours, carbonizing the product at 370 ℃ in helium atmosphere for 30 minutes to form an oligomeric vanadium oxide catalyst precursor with an isolated coated carbon layer, and calcining the product at 600 ℃ in air atmosphere for 4 hours to obtain the catalyst 9, wherein the actual composition of the catalyst 9 comprises 7 weight percent of vanadium oxide, 7.3 weight percent of auxiliary agent and 85.7 weight percent of ZrO 2 Specific surface area of 308m 2 g -1 Pore diameter of 14.1nm and pore volume of 0.39cm 3 g -1 The texture and structural parameters of catalyst 9 are shown in table 2.
Step 3: activity evaluation FIG. 2 is a schematic representation of the redox cycle at the active site of catalyst 9.
Weighing 1g of catalyst 9 sample with 40-60 meshes, introducing C at a reaction pressure of 0.1MPa and a reaction temperature of 550 ℃ at a flow rate of 80mL/min 4 H 10 The volume concentration is 10%, CO 2 The volume concentration is 50%, N 2 The reaction was started with a mixture of 40% by volume. The evaluation results are shown in Table 1.
Table 1 vanadium-based catalysts, isobutane CO, prepared by catalysts 1 to 9 2 Oxidative dehydrogenation Activity evaluation results
Table 2 texture and Structure parameters of vanadium-based catalysts prepared from catalysts 1 to 9
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (7)
1. Isobutane CO 2 The preparation method of the vanadium-based catalyst for the reaction of preparing isobutene by oxidative dehydrogenation is characterized in that the vanadium-based catalyst consists of a carrier, an active component and an auxiliary agent, and is obtained by an impregnation method; the specific surface area of the vanadium-based catalyst is 100-350 m 2 g -1 The pore diameter of the mesoporous structure is 11-18 nm, and the pore volume is 0.31-0.46 cm 3 g -1 ；
The carrier is ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The active component is vanadium oxide; the auxiliary agent is MnO, ceO 2 、Fe 2 O 3 、Y 2 O 3 、MoO 3 One or two of the following components; the vanadium-based catalyst comprises the following components in percentage by weight: 5.8 to 24.3 weight percent of vanadium oxide, 2.1 to 24.1 weight percent of auxiliary agent and ZrO 2 59.7% -90%;
the preparation method comprises the following steps:
step 1, preparing ZrO 2 And (3) a carrier: solubility of the carrierDissolving salt in deionized water, and uniformly stirring to obtain a solution A; preparing an aqueous solution of soluble alkali as a solution B; titrating the solution A and the solution B into a large beaker in a parallel flow titration mode in a water bath with the temperature of 50-70 ℃ while stirring, continuously stirring the slurry obtained after the dripping is finished for 1-7 h, washing with deionized water, centrifuging, and placing a precipitate obtained by centrifuging for 2-12 h; placing the slurry obtained by uniformly mixing and stirring the precipitate and deionized water into a round-bottom flask, placing the round-bottom flask into a ceramic ring, heating the ceramic ring to 135-185 ℃ by using a heating sleeve or an oil bath pot, refluxing and ageing the ceramic ring for 24-72 h, cooling the slurry to room temperature after the reaction is finished, washing the ceramic ring by using deionized water for multiple times, centrifuging the ceramic ring until the pH value is neutral, drying the precipitate obtained by centrifuging at 70-120 ℃ for 12-36 h, and calcining at 500-650 ℃ for 2-6 h to obtain the ZrO 2 A carrier;
step 2, dipping the active components and the auxiliary agents: dissolving soluble salt containing active components and auxiliary agents and organic acid in deionized water, uniformly stirring to obtain solution C, and obtaining ZrO in the step 1 2 Immersing the carrier in the solution C, stirring and drying the carrier at the temperature of 80-120 ℃, drying the obtained product at the temperature of 70-110 ℃ for 12-24 hours, carbonizing the product at the temperature of 350-400 ℃ for 20-60 minutes in helium atmosphere to form an oligomeric vanadium oxide catalyst precursor with an isolated coated carbon layer, and calcining the product at the temperature of 500-650 ℃ for 2-6 hours in air atmosphere to obtain the vanadium-based catalyst;
the ceramic ring in the step 1 is a ceramic Raschig ring with the outer diameter of 6-12 mm, the height of 6-12 mm and the wall thickness of 1.5-2.5 mm, and the filler amount of the ceramic ring is 5-10 g.
2. The preparation of the vanadium-based catalyst according to claim 1, wherein the soluble salt of the carrier is zirconium nitrate or zirconyl nitrate; the soluble salt of the active component is one of ammonium metavanadate, vanadyl sulfate and vanadyl oxalate; the soluble salt of the auxiliary agent is one or two of cerium nitrate, ferric nitrate, manganese nitrate, yttrium nitrate and ammonium molybdate; the soluble alkali is one of sodium hydroxide, sodium carbonate and potassium hydroxide; the organic acid is one of oxalic acid, tartaric acid and succinic acid.
3. The preparation of the vanadium-based catalyst according to claim 1, wherein the molar ratio of the soluble salt of the active component, the soluble salt of the auxiliary agent, the organic acid and the deionized water in the solution C is 0.0009-0.0036: 0.00036 to 0.0018:0.0036 to 0.0072:1.
4. the preparation of the vanadium-based catalyst according to claim 1, wherein the concentration of the solution a in step 1 is 0.08 to 0.2 mol/l; the concentration of the solution B is 0.5-2 mol/L; the drop ratio of the solution A to the solution B is 3-7:1, and the titration duration is 1-12 h.
5. The method of claim 1, wherein the deionized water content of the slurry in step 1 is 200-350 mL.
6. The preparation of the vanadium-based catalyst according to claim 1, wherein the heating temperature of the heating jacket or the oil bath in step 1 is 135-185 ℃.
7. Isobutane CO 2 A process for preparing isobutene by oxidative dehydrogenation, which comprises the steps of using the vanadium-based catalyst prepared by the method of claim 1, evaluating the vanadium-based catalyst in a fixed bed, grinding the calcined catalyst into powder, tabletting and screening particles with 20-40 or 40-60 meshes for filling reaction tubes, wherein the catalyst dosage is 0.2-1 g, and C in raw gas 4 H 10 The volume concentration is 9-11%, CO 2 The volume concentration is 40-50%, N 2 The volume concentration is 40-50%, the reaction pressure is 0.08-0.12 Mpa, the flow rate is 30-80 mL/min, and the reaction temperature is 550-650 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549219A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst for preparing olefin by dehydrogenating isobutane and application of supported catalyst |
| CN104549415A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenizing light alkane and using method of catalyst |
| CN106944087A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549219A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst for preparing olefin by dehydrogenating isobutane and application of supported catalyst |
| CN104549415A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenizing light alkane and using method of catalyst |
| CN106944087A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst |
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