WO2020138600A1 - 산소 캐리어 물질 및 탈수소 촉매를 포함하는 올레핀 제조용 촉매 - Google Patents
산소 캐리어 물질 및 탈수소 촉매를 포함하는 올레핀 제조용 촉매 Download PDFInfo
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- WO2020138600A1 WO2020138600A1 PCT/KR2019/005548 KR2019005548W WO2020138600A1 WO 2020138600 A1 WO2020138600 A1 WO 2020138600A1 KR 2019005548 W KR2019005548 W KR 2019005548W WO 2020138600 A1 WO2020138600 A1 WO 2020138600A1
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- Prior art keywords
- catalyst
- carrier material
- oxygen
- oxygen carrier
- platinum
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000001301 oxygen Substances 0.000 title claims abstract description 80
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 80
- 239000012876 carrier material Substances 0.000 title claims abstract description 45
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000011651 chromium Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910017563 LaCrO Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910039444 MoC Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- IGOJMROYPFZEOR-UHFFFAOYSA-N manganese platinum Chemical compound [Mn].[Pt] IGOJMROYPFZEOR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 4
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 41
- 239000001257 hydrogen Substances 0.000 abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000007423 decrease Effects 0.000 abstract description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 90
- 239000001294 propane Substances 0.000 description 45
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- 230000009257 reactivity Effects 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910019923 CrOx Inorganic materials 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- -1 VOx Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- IYNQBRDDQSFSRT-UHFFFAOYSA-N chromium(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IYNQBRDDQSFSRT-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- 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
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a catalyst for the production of olefins with improved selectivity and conversion rate, including an oxygen carrier material.
- Olefins such as ethylene and propylene are widely used in the petrochemical industry. Typically, these olefins are obtained from the naphtha pyrolysis process. However, in the petrochemical industry, since a larger amount of olefin is required, olefin is also produced through a dehydrogenation process using a catalyst of lower hydrocarbon.
- the main difference between the fixed bed reactor and the fluidized bed reactor is the contact time between the catalyst and the reactant (propane). That is, the fluidized bed reactor is a process in which propane and a catalyst are injected together into a fluidized bed reactor at a very high speed to react, and then the catalyst enters the regeneration unit and the product enters the separation unit.
- the goal of the conventionally developed FPDH process is to set the residence time of the catalyst to 10 seconds or less. If the residence time of the catalyst is short, the injection rate of the propane supply amount is also fast, and the catalyst is regenerated and participates in the reaction again, and thus, when it is developed as a commercial process, the propylene production is greatly increased compared to the fixed bed process.
- propane dehydrogenation process technologies currently used are based on noble metal catalysts or non-continuous processes, and are known to be unsuitable for mass production of multi-million tons of propylene because of problems with the catalyst layer operation in the case of continuous processes.
- the propane dehydrogenation reaction is thermodynamically limited in the propane conversion rate due to the reversible reaction of propylene and hydrogen produced. Therefore, for effective mass production of propylene, there is a need to develop a new propane dehydrogenation process that reduces the production cost by solving the problem of the continuous process and using a low-cost non-precious metal catalyst with maximized selectivity and conversion.
- the reaction proceeds with a direct dehydrogenation mechanism in which hydrogen is adsorbed at the active point in the case of a noble metal catalyst, but in the case of a transition metal oxide, the mechanism is clearly identified due to the incompleteness of the active point due to electron mobility. It is not being done.
- the catalysts most commonly used as PDH catalysts are Pt, Pt-Sn, VOx, and CrOx catalysts, and the CrOx catalyst is very excellent in propane conversion and selectivity.
- the platinum catalyst has the disadvantages of excellent selectivity but high cost and very low conversion rate.
- the representative oxide catalyst, CrOx catalyst is a stable form of Cr 6 + and Cr 3 + , and most of the catalysts prepared by firing at high temperature are Cr 2 O 3 as Cr 3 + , but some Cr 6 + is present.
- the catalyst (new catalyst) produced in this way contributes to the production of CO 2 rather than propylene by participating in the propane dehydrogenation reaction of oxygen (from lattice oxygen of the oxidation catalyst) generated as Cr 6 + is reduced to Cr 3 + at the beginning of the reaction. Is done.
- an oxidative dehydrogenation of propane has been widely studied.
- the reaction removes hydrogen produced by water by supplying oxygen in addition to propane as a reactant.
- the advantage of the reaction is that the combustion reaction in which the oxygen reacts is an exothermic reaction, and thus the energy consumption can be reduced and the conversion rate is increased by using this heat for the dehydrogenation reaction.
- oxygen is supplied as a reactant, the selectivity of propylene is lower than that of a direct dehydrogenation reaction.
- the present inventors have developed a new concept catalyst that can solve the problems that have appeared in the prior art through continuous research, and by converting hydrogen into water using oxygen in the lattice of the oxide catalyst without additionally supplying oxygen, The conversion rate could be increased while suppressing the decrease in selectivity, which is a disadvantage of the additional oxidative dehydrogenation reaction (ODHP).
- ODHP additional oxidative dehydrogenation reaction
- the exhausted oxygen in the catalyst lattice can be supplied through rapid catalyst regeneration and recycling in the FPDH process.
- the catalyst for olefin production according to the present invention for solving the above problems includes an oxygen carrier material and a dehydrogenation catalyst.
- the oxygen carrier material contains oxygen in the lattice structure.
- the oxygen carrier material has an ABOx structure.
- a or B is independently selected from the group consisting of sodium, magnesium, manganese, yttrium, zirconium, indium, antimony, cerium, tungsten, and bismuth.
- the oxygen carrier material is Bi 2 O 3 , Sb 2 O 4 , In 2 O 3 , CeO 2 , WO x , ZrO 2 -Y 2 O 3 , Na 2 WO 4 or Mg 6 MnO 8 or their It is preferably a mixture.
- the dehydrogenation catalyst is preferably an active metal oxide supported on a support.
- the carrier includes alumina and an auxiliary carrier component.
- the auxiliary supporting component includes at least one selected from zirconium, alkali metals and alkaline earth metals.
- the active metal component is chromium, lanthanum, strontium, niobium, vanadium, gallium, cobalt, zirconium, tungsten, zinc, nickel-phosphorus, molybdenum-carbide, palladium, platinum, platinum-tin, platinum-gallium, platinum-copper, It is more preferable to include at least one selected from platinum-manganese, alkali metal and alkaline earth metal.
- the active metal component contains chromium as an essential component.
- the active metal oxide is NaCrO X , KCrO X , CaCrO X , MgCrO X , LaCrO 3 , La 0.8 Sr 0.2 CrO 3 , La 0 . 7 Ca 0 .
- Particular preference is given to at least one selected from the group consisting of 3 CrO 3 , NbCrO 4 and SrCrO 4 .
- the catalyst for olefin production according to the present invention converts hydrogen to water by using oxygen in the lattice of the oxide catalyst without additionally supplying oxygen, thereby suppressing the selectivity reduction phenomenon, which is a disadvantage of the additional oxidative dehydrogenation reaction (ODHP). Can increase.
- ODHP additional oxidative dehydrogenation reaction
- Figure 1 schematically shows the results of the experiment using a perovskite structure catalyst as an oxygen carrier material.
- Figure 2 schematically shows the results of the reactivity test of the oxygen carrier material.
- FIG. 4 schematically shows the results of the reactivity experiment of the oxygen carrier material of FIG. 3.
- FIG. 5 schematically shows the lattice oxygen utilization phenomenon of the oxygen carrier material of FIG. 3 by XRD.
- FIG. 6 schematically shows the results of a reactivity experiment using an oxygen carrier material in combination with a case in which only a dehydrogenation catalyst was used.
- the catalyst for olefin production according to the present invention for solving the above problems includes an oxygen carrier material and a dehydrogenation catalyst.
- the oxygen carrier material contains oxygen in the lattice structure.
- the oxygen carrier material has an ABOx structure.
- the dehydrogenation catalyst is preferably an active metal oxide supported on a support.
- the Perovskite structure is known to facilitate oxygen in the lattice to participate in the reaction.
- the perovskite structure directly reacts with propane and the reaction proceeds, it does not solve the disadvantage that the selectivity is lowered, such as the problem of the conventional ODHP.
- the initial selectivity of the reaction is very important.
- the selectivity of the initial reaction CO, CO 2 There was still a high problem.
- the catalyst for preparing an olefin according to the present invention includes an oxygen carrier material (OCM) and a dehydrogenation catalyst.
- OCM oxygen carrier material
- the oxygen carrier material contains oxygen in the lattice structure.
- the present invention can convert hydrogen to water by using oxygen in the lattice of the oxide catalyst without supplying additional oxygen to the hydrogen generated by dehydrogenation catalysis.
- the oxygen carrier material and the dehydrogenation catalyst each play different roles.
- the dehydrogenation catalyst contributes only to the reaction of producing propane as propylene and hydrogen, and then the produced hydrogen reacts with oxygen present in the oxygen carrier material and is selectively converted to water.
- the dehydrogenation catalyst should contribute only to the dehydrogenation reaction of propane, while the selectivity to flopilene is maximal.
- the oxygen carrier material is not reactive with propane or propylene, and only hydrogen must be selectively reacted.
- the oxygen carrier material has an ABOx structure.
- a or B is independently selected from the group consisting of sodium, magnesium, manganese, yttrium, zirconium, indium, antimony, cerium, tungsten, and bismuth.
- the oxygen carrier material is Bi 2 O 3 , Sb 2 O 4 , In 2 O 3 , CeO 2 , WO x , ZrO 2 -Y 2 O 3 , Na 2 WO 4 or Mg 6 MnO 8 or their It is preferably a mixture.
- the dehydrogenation catalyst is preferably an active metal oxide is supported on the support.
- the carrier includes alumina and an auxiliary carrier component.
- the auxiliary supporting component includes at least one selected from zirconium, alkali metals and alkaline earth metals.
- the alkali metal may be lithium, sodium, potassium, etc.
- the alkaline earth metal may be magnesium, etc., and will be apparent to those skilled in the art.
- zirconium is particularly preferred, and the zirconium is preferably present in a molar fraction of (Zr:Al) 0.01 to 0.1 with respect to aluminum in the alumina.
- the catalyst according to the present invention improves durability by an auxiliary supporting component, and has an excellent function of exciting C-H bonds of paraffin raw materials compared to when only alumina is used as a carrier. Thereby, the hydrocarbon conversion rate and olefin yield are excellent, and the olefin selectivity is also improved.
- zirconium serves to improve the durability of the alumina carrier.
- auxiliary supporting component in particular zirconium
- the characteristics of the durability improving effect are not exhibited, and if it exceeds 0.1, the surface area of the alumina carrier is rapidly reduced and polydispersed active metal components cannot be dispersed.
- the alumina carrier preferably has a ⁇ - ⁇ phase at a production temperature of 550 to 850°C above the dehydrogenation reaction temperature, and has a surface area of 80 to 300 m 2 /g in this range.
- the carrier When the carrier is prepared at a temperature lower than the dehydrogenation reaction temperature, thermal deformation of the catalyst may occur during the dehydrogenation reaction, and when prepared at a temperature above 850° C., it has a low catalyst surface area due to crystallization of the carrier, which is in contact with the reactants. It inhibits the mass transfer for catalytic activity.
- the active metal component is chromium, lanthanum, strontium, niobium, vanadium, gallium, cobalt, zirconium, tungsten, zinc, nickel-phosphorus, molybdenum-carbide, palladium, platinum, platinum-tin, platinum-gallium, platinum-copper, It is more preferable to include at least one selected from platinum-manganese, alkali metal and alkaline earth metal.
- the active metal component contains chromium as an essential, but non-chromium based vanadium, gallium, cobalt, zirconium, tungsten, zinc, niobium, nickel-phosphorus, molybdenum-carbide, palladium, platinum, platinum-tin, platinum -Gallium, platinum-copper, platinum-manganese, and the like.
- the active metal oxide is NaCrO X , KCrO X , CaCrO X , MgCrO X , LaCrO 3 , La 0.8 Sr 0.2 CrO 3 , La 0 . 7 Ca 0 .
- Particular preference is given to at least one selected from the group consisting of 3 CrO 3 , NbCrO 4 and SrCrO 4 .
- the metal oxide In order to increase the dispersion degree of the metal oxide, it was prepared by dissolving metal nitrate hydrate in citric acid and ethylene glycol (EG) solution. After dissolving 22.2 g of La(NO 3 ) 3 ⁇ 6H 2 O (lanthanum nitrate hexahydrate) in 46 g of water and stirring for 30 minutes, dissolve 20.52 g of Cr(NO 3 ) 3 ⁇ 9H 2 O (chromium nitrate hexahydrate) 30 Stir for minutes. 63.64 g of citric acid was added to the aqueous metal nitrate hydrate solution, stirred for 1 hour, dissolved, and then 18.724 g of ethylene glycol was added and stirred for 1 hour.
- EG ethylene glycol
- Oxygen carrier material selectively reacts only hydrogen and performs H 2 -TPR (TPR, Temperature-Programmed Reduction), C 3 H 8 -TPRxn experiment to confirm the reactivity to propane, and the results are shown. It is shown schematically in 2.
- the H 2 -TPR experiment was carried out as follows to measure the reducing power of the material for hydrogen. First, 0.1-0.4 g oxygen carrier material was injected into a U-shaped reactor, oxidized at 650° C. for 1 hour in an air atmosphere, and then lowered to 200° C. Thereafter, oxygen adsorbed on the reactor and the catalyst is removed for 1 hour using helium gas, and then a 10% H 2 /Ar mixed gas is injected at a flow rate of 50 mL/min to raise the temperature to 850°C at a rate of 10°C/min. Thus, the behavior of hydrogen consumption was detected through a thermal conductivity detector (TCD).
- TCD thermal conductivity detector
- a propane-TPRxn experiment was performed to confirm the reactivity of the oxygen carrier material to propane.
- the temperature was lowered to 200° C. after being oxidized at 640° C. for 1 hour in an air atmosphere. Thereafter, oxygen adsorbed on the reactor and the catalyst is removed for 1 hour using helium gas, and then 50% C 3 H 8 /N 2 mixed gas is injected at a flow rate of 110 mL/min to increase the temperature to 700 at a rate of 10°C/min.
- the temperature was raised to °C to confirm the reactivity to propane.
- Mg 6 MnO 8 decreases the amount of hydrogen from 500° C.
- the ZrO 2 -Y 2 O 3 material starts to react with lattice oxygen Lattice Oxygen in the catalyst from 500° C. and 580° C., respectively, through a decrease in the amount of hydrogen from 580° C.
- ZrO 2 -Y 2 O 3 is not reactive up to 600°C for propane, so it can be applied in a wide temperature range, but the amount of lattice oxygen is considered to be relatively small, and Mg 6 MnO 8 material is very rich in lattice oxygen.
- Mg 6 MnO 8 Further studies were conducted to increase the reduction temperature for hydrogen and propane by introducing an additional substance (Na 2 WO 4 ) into the substance.
- Mn(NO 3 ) 2 manganesium oxide
- MgO magnesium oxide
- the resulting slurry was dried at 120° C. for 15 hours, and then filtered through a mortar with a pestle bowl to collect a catalyst having a size smaller than 200 ⁇ m.
- the recovered catalyst was calcined at 200° C. for 4 hours to thermally decompose nitric acid groups.
- the peak of the crystal plane was observed while injecting 10% H 2 /N 2 mixed gas at a temperature range of 300 to 800° C. using an In-situ XRD instrument. As a result, it was observed that all the peaks moved at a low angle around 600°C, and the peak of the main peak, 42.9°, was moved at a low angle to 42.6°, as shown in FIG. 5. This is the result of confirming that the lattice oxygen of the prepared material is used by hydrogen because the oxygen in the lattice escapes as it reacts with hydrogen and the distance between the lattices increases (d-spacing).
- red is data obtained by mixing PDH catalyst and OCM
- blue is data when only PDH catalyst is present.
- FIG. 7 is a result showing the activity of a dehydrogenation catalyst (DH: 0.25% Na 2 WO 4 -15% Cr/Al 2 O 3 ) and a dehydrogenation catalyst/oxygen carrier material (OCM) complex in a propane dehydrogenation reaction.
- DH 0.25% Na 2 WO 4 -15% Cr/Al 2 O 3
- OCM oxygen carrier material
- non-OCM non-oxygen carrier material
- propane consumption/propylene production rate is reduced by about 5% Did.
- oxygen carrier materials of ZrO 2 -Y 2 O 3 (ZrY) and Na 2 WO 4 -Mg 6 MnO 8 (NW-MgMn)
- the propane consumption rate of 33% and 46%, respectively, was formed by complexing with the main catalyst. Showed an increase. This is due to the nature of the oxygen carrier, which makes the equilibrium reaction a more positive reaction by selectively converting the generated hydrogen to water.
- the propylene production rate showed a decrease of 48% and 38%, respectively, which not only selectively converts hydrogen, but also participates in the secondary reaction of the produced propylene when complexed with a dehydrogenation catalyst. Therefore, it is judged to produce side reactions.
- the present invention relates to a catalyst for the production of olefins with improved selectivity and conversion rate, including an oxygen carrier material.
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Abstract
Description
Claims (11)
- 산소 캐리어 물질 및 탈수소 촉매를 포함하는 올레핀 제조용 촉매.
- 제 1 항에 있어서, 상기 산소 캐리어 물질이 격자 구조내에 산소를 포함하는, 올레핀 제조용 촉매.
- 제 1 항에 있어서, 상기 산소 캐리어 물질이 ABOx 구조를 갖는 올레핀 제조용 촉매.
- 제 3 항에 있어서, 상기 ABOx 구조에서 A 또는 B가 나트륨, 마그네슘, 망간, 이트륨, 지르코늄, 인듐, 안티몬, 세륨, 텅스텐 및 비스무스로 구성된 군으로부터 독립적으로 선택되는 올레핀 제조용 촉매.
- 제 1 항에 있어서, 상기 산소 캐리어 물질이 Bi2O3, Sb2O4, In2O3, CeO2, WOx, ZrO2-Y2O3, Na2WO4 또는 Mg6MnO8 또는 이들의 혼합물인, 올레핀 제조용 촉매.
- 제 1 항에 있어서, 상기 탈수소 촉매는 활성금속 산화물이 담지체에 담지된 것인, 올레핀 제조용 촉매.
- 제 6 항에 있어서, 상기 담지체가 알루미나와 보조 담지성분을 포함하는, 올레핀 제조용 촉매.
- 제 7 항에 있어서, 상기 보조 담지성분이 지르코늄, 알칼리금속 및 알칼리토금속 중에서 선택되는 하나 이상을 포함하는, 올레핀 제조용 촉매.
- 제 6 항에 있어서, 상기 활성금속 성분이 크롬, 란타넘, 스트론튬, 니오븀, 바나듐, 갈륨, 코발트, 지르코늄, 텅스텐, 아연, 니켈-인, 몰리브덴-카바이드, 팔라듐, 백금, 백금-주석, 백금-갈륨, 백금-구리, 백금-망간, 알칼리금속 및 알칼리토금속 중에서 선택되는 하나 이상을 포함하는, 올레핀 제조용 촉매.
- 제 9 항에 있어서, 상기 활성금속 성분이 크롬을 필수로 포함하는, 올레핀 제조용 촉매.
- 제 6 항에 있어서, 상기 활성금속 산화물이 NaCrOx, KCrOx, CaCrOx, MgCrOx, LaCrO3, La0.8Sr0.2CrO3, La0 . 7Ca0 . 3CrO3, NbCrO4 및 SrCrO4로 구성된 군으로부터 선택된 하나 이상인, 올레핀 제조용 촉매.
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CN115350652A (zh) * | 2022-08-04 | 2022-11-18 | 西南化工研究设计院有限公司 | 一种使用脱氢催化剂的流化床丙烷脱氢装置及其工艺 |
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KR102585580B1 (ko) | 2023-10-05 |
CN113226540A (zh) | 2021-08-06 |
KR20200082080A (ko) | 2020-07-08 |
US20210354113A1 (en) | 2021-11-18 |
CN113226540B (zh) | 2024-03-26 |
US11865514B2 (en) | 2024-01-09 |
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