CA2831537A1 - Catalyst for decomposition of hydrocarbon oil and method for decomposing hydrocarbon oil - Google Patents
Catalyst for decomposition of hydrocarbon oil and method for decomposing hydrocarbon oil Download PDFInfo
- Publication number
- CA2831537A1 CA2831537A1 CA2831537A CA2831537A CA2831537A1 CA 2831537 A1 CA2831537 A1 CA 2831537A1 CA 2831537 A CA2831537 A CA 2831537A CA 2831537 A CA2831537 A CA 2831537A CA 2831537 A1 CA2831537 A1 CA 2831537A1
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- Prior art keywords
- hydrocarbon oil
- cracking
- catalyst
- group
- oil
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 156
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 150
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 title abstract 5
- 125000001183 hydrocarbyl group Chemical group 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000005336 cracking Methods 0.000 claims description 87
- 239000010936 titanium Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 206010021143 Hypoxia Diseases 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 142
- 239000002244 precipitate Substances 0.000 description 20
- 239000002131 composite material Substances 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000004227 thermal cracking Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- BQXUPNKLZNSUMC-YUQWMIPFSA-N CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 Chemical compound CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 BQXUPNKLZNSUMC-YUQWMIPFSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000627951 Osteobrama cotio Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/755—Nickel
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B01J35/30—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
Abstract
The purpose of the present invention is to provide a catalyst for decomposition of a hydrocarbon oil capable of efficiently lightening a hydrocarbon oil at low cost and a method for decomposing a hydrocarbon oil. The catalyst for decomposition of a hydrocarbon oil of the present invention is used in decomposition of the hydrocarbon oil in the presence of water, and characterized by including an oxide with a perovskite structure or an oxide with a pseudobrookite structure, or a mixture thereof. The method for decomposing a hydrocarbon oil of the present invention is characterized by contacting a hydrocarbon oil with the catalyst for decomposition of a hydrocarbon oil in the presence of water to decompose the hydrocarbon oil.
Description
CA Application Wakes Ref 10549/00002 METHOD FOR DECOMPOSING HYDROCARBON OIL
100011 The present invention relates to a hydrocarbon oil cracking 6 catalyst and a method for cracking hydrocarbon oil, and in particular, to a 7 catalyst that is used in cracking hydrocarbon oil to produce lighter oil 8 without feeding hydrogen from the outside of the system, as well as a 9 method for cracking hydrocarbon oil by using the catalyst.
ii BACKGROUND ART
12 10002) Conventionally, hydrocracking, thermal cracking and fluid 13 catalytic cracking are known as methods for producing light hydrocarbon 14 oil which is useful as a feedstock for petrochemicals, fuel oil and so on, is and light hydrocarbon gas which is useful as fuel gas and so on, by cracking 16 heavy hydrocarbon oil to produce lighter oil.
17 00031 Here, hydrocracking is a process in which heavy hydrocarbon 18 oil is cracked to produce lighter oil by bringing the heavy hydrocarbon oil 19 into contact with a hydrogenation catalyst in a hydrogen atmosphere at 20 elevated temperature and pressure (see, for example, JP 2008-297452 A
21 (PIT I)). In addition, thermal cracking is a process used to produce lighter 22 oil from heavy hydrocarbon oil under an elevated temperature condition by 23 means of pyrolysis of hydrocarbon molecules without the aid of catalyst 24 (see, for example. JP 2009-102471 A (PTL 2)). Further, fluid catalytic 25 cracking is a process used to produce lighter oil from heavy hydrocarbon oil 26 by bringing the heavy hydrocarbon oil into contact with a fluidized catalyst 27 (see, for example, JP 8-269464 A (PTL 3)).
30 Patent Literature 31 100041 PTL 1: JP 2008-297452 A
32 PTL 2: JP 2009-102471 A
22447577,1 CA Application Blakes Ref :10549/00002 PTL 3: JP 8-.269464 A
4 (Technical Problem) 100051 The hydrocracking has a drawback, however, in that it uses a 6 large amount of high pressure hydrogen gas for cracking reaction and thus 7 requires large facilities for producing hydrogen gas, leading to increased 8 cost. The thermal cracking also has a drawback in that it produces a large 9 amount of coke with little aromatic ring cleavage, leading to inefficient manufacture of light hydrocarbon oil and inadequate cracking of heavy 11 hydrocarbon oil. Further, the fluid catalytic cracking has a drawback in 12 terms of high operational costs of devices, 13 [00061 Additionally, the hydrocracking requires proactive 14 desulfurization and denitrogenation of heavy hydrocarbon oil in order to prevent deterioration (poisoning) of a hydrogenated catalyst. Further, due 16 to little desulfurization and denitrogenation reaction of hydrocarbon oils, 17 both the thermal cracking and the fluid catalytic cracking require, as is the 18 case with the hydrocracking, proactive desulfurization and denitrogenation 19 of heavy hydrocarbon oils. That is, the hydrocracking, thermal cracking and fluid catalytic cracking have the disadvantage of the necessity of 21 pretreatment of heavy hydrocarbon oils.
22 100071 Therefore, an object of the present invention is to provide a 23 hydrocarbon oil cracking catalyst that allows efficient production of lighter 24 oil from hydrocarbon oil at low cost, without performing proactive desulfurization and denitrogenation of the hydrocarbon oil and without 26 using high pressure hydrogen gas, and a method for cracking hydrocarbon 27 oil.
28 (Solution to Problem) 29 [00081 The inventors of the present invention have made intensive studies to address the above-described problems and found that hydrocarbon 3 I oil can be cracked efficiently. without using hydrogen gas, in the presence 32 of water by using a catalyst composed of an oxide having a specific crystal 22447577.1 CA Application Blakes Ref: 10549100002 structure. The present invention has been completed based on this finding..
2 100091 That is, an object of the present invention is to advantageously 3 solve the above-described problems, and the present invention provides a 4 hydrocarbon oil cracking catalyst used in cracking hydrocarbon oil in the presence of water, the catalyst composed of an oxide having a perovskite-6 type structure or an oxide having a pseudobrookite-type structure, or a 7 mixture thereof.
8 (00101In the hydrocarbon oil cracking catalyst according to the 9 present invention, the oxide having a perovskite-type structure is preferably represented by the following general formula:
12 [where A is an element selected from the group consisting of a Group IA
13 element, a Group ILA element, a Group WA element and a Group VM
14 element, A' is at least one element selected from the group consisting of a IS Group VA element and a Group IIIB element, B is an element selected from 16 the group consisting of a Group 1113 element and a Group IVA element, and 17 B' is at least one element selected from the group consisting of a Group VA
IS element and a Group II1B element, in which A, A', B and B' are different 19 from one another, x is in the range of 0 5_ x 5_ 0.4, y is in the range of 0 y and 8 represents oxygen deficiency].
21 Additionally, with the hydrocarbon oil cracking catalyst according to the 22 present invention, it is further preferred that the A is nickel or cobalt, the B
23 is titanium, and the B' is aluminum or vanadium.
24 Moreover, with the hydrocarbon oil cracking catalyst according to the present invention, it is further preferred that x = 0.
26 100111 Furthermore, with the hydrocarbon oil cracking catalyst 27 according to the present invention, it is preferred that the oxide having a 28 pseudobrookite-type structure is Fe2Ti05.
29 100121 in addition, an object of the present invention is to advantageously solve the above-described problems, and the present 3 i invention provides a method for cracking hydrocarbon oil, including 32 bringing the hydrocarbon oil into contact with any of the hydrocarbon oil 22447577.1 CA Application Blakes Ref: 10549/00002 1 cracking catalysts according to the aforementioned aspects in the presence 2 of water to thereby crack the hydrocarbon oil.
3 (Effect of Invention) 4 10013] The hydrocarbon oil cracking catalyst and the method for cracking hydrocarbon oil according to the present invention enable efficient 6 production of lighter oil from hydrocarbon oil at low cost, without 7 performing proactive desulfurization and denitrogenation of the feedstock 8 hydrocarbon oil and without using high pressure hydrogen gas.
to BRIEF DESCRIPTION OF THE DRAWING
Ii 100141 FIG. I illustrates an X-ray diffraction spectrum of 12 NiTio,75A10.2502.875 baying a perovskite-type structure.
13 FIG. 2 illustrates an X-ray diffraction spectrum of NiTiO3 14 having a perovskite-type structure.
FIG. 3 illustrates an X-ray diffraction spectrum of 16 CoTi0.75V0,2503.125 having a perovskite-type structure.
I? FIG. 4 illustrates an X-ray diffraction spectrum of Fe2TiO5 18 having a pseudobrookite-type structure.
19 FIG. 5 illustrates an X-ray diffraction spectrum of a mixture of NiO and rutile-type 21 FIG. 6 illustrates an X-ray diffraction spectrum of a mixture of 22 Fe203, rutile-type TiO2 and anatase-type Ti02.
1001.5] Embodiments of the present invention will now be described in 26 detail below. A hydrocarbon oil cracking catalyst according to the present 27 invention is used in cracking hydrocarbon oil to produce lighter oil.
28 Additionally, a method for cracking hydrocarbon oil according to the 29 present invention involves bringing hydrocarbon oil into contact with hydrocarbon oil cracking catalyst in the presence of water, without feeding 3 i hydrogen from the outside of the reaction system, thereby cracking the 32 hydrocarbon oil to produce light hydrocarbon oil.
22447577.1 CA Application Blakes Ref 10549/00002 1 l0016] As used herein, examples of the hydrocarbon oil to be cracked 2 (to produce lighter oil therefrom) by using the hydrocarbon oil cracking 3 catalyst according to the present invention may be heavy hydrocarbon oils 4 including, but not limited to, atmospheric distillation residues and reduced-pressure distillation residues generated during petroleum refining. Specific 6 examples of the hydrocarbon oil to produce lighter oil therefrom by using 7 the hydrocarbon oil cracking catalyst may include hydrocarbon oil with a 8 vol /0 distillation temperature in atmospheric distillation (T50) of 150 C or 9 higher and 550 C or lower, a hydrocarbon oil with 150 of 200 C or higher and 550 C or lower, and a hydrocarbon oil with T50 of 250 C or higher ii and 550 C or lower.
12 10017-1 Additionally, the hydrocarbon oil cracking catalyst according to 13 the present invention composed of an oxide having a perovskite-type 14 structure, or an oxide having a pseudobrookite-type structure, or a mixture of an oxide having a perovskite-type structure and an oxide having a 16 pseudobrookite-type structure.
17 10018] It should be noted that the crystal structure of oxides may be 18 assessed by, for example, X-ray diffraction analysis. Specifically, whether 19 an oxide has a perovskite-type structure can be determined by whether peaks specific to the perovskite-type structure appears in the X-ray 21 diffraction spectrum. In addition, whether an oxide has a pseudobrookite-22 type structure can be determined by whether peaks specific to the 23 pseudobrookite-type structure appears in the X-ray diffraction spectrum.
24 100191 In this case, an oxide having a perovskite-type structure and an oxide having a .pseudobrookite-type structure are used as the hydrocarbon 26 oil cracking catalyst based on a novel finding revealed by the inventors of 27 the present invention that these Oxides allow, when used as the catalyst, 28 efficient cracking of hydrocarbon compounds using water as hydrogen 29 source. Although the mechanism by which hydrocarbon compounds can be efficiently decomposed with the use of these oxides as the catalyst is not 31 known, it is inferred that this is because an oxide having a perovskite-type 32 structure and an oxide having a pseudobrookite-type structure have a high 22447577.1 CA Application Blakes Ref: 10549/00002 1 ability to decompose water to produce oxygen and hydrogen because of 2 their high lattice oxygen supply rate. That is, it is inferred that this is 3 because, in cracking a hydrocarbon compound using water as hydrogen 4 source, a portion of the hydrocarbon compound is allowed to react with water as shown in the following reaction formula to thereby promote the 6 generation of hydrogen as hydrogen source:
100011 The present invention relates to a hydrocarbon oil cracking 6 catalyst and a method for cracking hydrocarbon oil, and in particular, to a 7 catalyst that is used in cracking hydrocarbon oil to produce lighter oil 8 without feeding hydrogen from the outside of the system, as well as a 9 method for cracking hydrocarbon oil by using the catalyst.
ii BACKGROUND ART
12 10002) Conventionally, hydrocracking, thermal cracking and fluid 13 catalytic cracking are known as methods for producing light hydrocarbon 14 oil which is useful as a feedstock for petrochemicals, fuel oil and so on, is and light hydrocarbon gas which is useful as fuel gas and so on, by cracking 16 heavy hydrocarbon oil to produce lighter oil.
17 00031 Here, hydrocracking is a process in which heavy hydrocarbon 18 oil is cracked to produce lighter oil by bringing the heavy hydrocarbon oil 19 into contact with a hydrogenation catalyst in a hydrogen atmosphere at 20 elevated temperature and pressure (see, for example, JP 2008-297452 A
21 (PIT I)). In addition, thermal cracking is a process used to produce lighter 22 oil from heavy hydrocarbon oil under an elevated temperature condition by 23 means of pyrolysis of hydrocarbon molecules without the aid of catalyst 24 (see, for example. JP 2009-102471 A (PTL 2)). Further, fluid catalytic 25 cracking is a process used to produce lighter oil from heavy hydrocarbon oil 26 by bringing the heavy hydrocarbon oil into contact with a fluidized catalyst 27 (see, for example, JP 8-269464 A (PTL 3)).
30 Patent Literature 31 100041 PTL 1: JP 2008-297452 A
32 PTL 2: JP 2009-102471 A
22447577,1 CA Application Blakes Ref :10549/00002 PTL 3: JP 8-.269464 A
4 (Technical Problem) 100051 The hydrocracking has a drawback, however, in that it uses a 6 large amount of high pressure hydrogen gas for cracking reaction and thus 7 requires large facilities for producing hydrogen gas, leading to increased 8 cost. The thermal cracking also has a drawback in that it produces a large 9 amount of coke with little aromatic ring cleavage, leading to inefficient manufacture of light hydrocarbon oil and inadequate cracking of heavy 11 hydrocarbon oil. Further, the fluid catalytic cracking has a drawback in 12 terms of high operational costs of devices, 13 [00061 Additionally, the hydrocracking requires proactive 14 desulfurization and denitrogenation of heavy hydrocarbon oil in order to prevent deterioration (poisoning) of a hydrogenated catalyst. Further, due 16 to little desulfurization and denitrogenation reaction of hydrocarbon oils, 17 both the thermal cracking and the fluid catalytic cracking require, as is the 18 case with the hydrocracking, proactive desulfurization and denitrogenation 19 of heavy hydrocarbon oils. That is, the hydrocracking, thermal cracking and fluid catalytic cracking have the disadvantage of the necessity of 21 pretreatment of heavy hydrocarbon oils.
22 100071 Therefore, an object of the present invention is to provide a 23 hydrocarbon oil cracking catalyst that allows efficient production of lighter 24 oil from hydrocarbon oil at low cost, without performing proactive desulfurization and denitrogenation of the hydrocarbon oil and without 26 using high pressure hydrogen gas, and a method for cracking hydrocarbon 27 oil.
28 (Solution to Problem) 29 [00081 The inventors of the present invention have made intensive studies to address the above-described problems and found that hydrocarbon 3 I oil can be cracked efficiently. without using hydrogen gas, in the presence 32 of water by using a catalyst composed of an oxide having a specific crystal 22447577.1 CA Application Blakes Ref: 10549100002 structure. The present invention has been completed based on this finding..
2 100091 That is, an object of the present invention is to advantageously 3 solve the above-described problems, and the present invention provides a 4 hydrocarbon oil cracking catalyst used in cracking hydrocarbon oil in the presence of water, the catalyst composed of an oxide having a perovskite-6 type structure or an oxide having a pseudobrookite-type structure, or a 7 mixture thereof.
8 (00101In the hydrocarbon oil cracking catalyst according to the 9 present invention, the oxide having a perovskite-type structure is preferably represented by the following general formula:
12 [where A is an element selected from the group consisting of a Group IA
13 element, a Group ILA element, a Group WA element and a Group VM
14 element, A' is at least one element selected from the group consisting of a IS Group VA element and a Group IIIB element, B is an element selected from 16 the group consisting of a Group 1113 element and a Group IVA element, and 17 B' is at least one element selected from the group consisting of a Group VA
IS element and a Group II1B element, in which A, A', B and B' are different 19 from one another, x is in the range of 0 5_ x 5_ 0.4, y is in the range of 0 y and 8 represents oxygen deficiency].
21 Additionally, with the hydrocarbon oil cracking catalyst according to the 22 present invention, it is further preferred that the A is nickel or cobalt, the B
23 is titanium, and the B' is aluminum or vanadium.
24 Moreover, with the hydrocarbon oil cracking catalyst according to the present invention, it is further preferred that x = 0.
26 100111 Furthermore, with the hydrocarbon oil cracking catalyst 27 according to the present invention, it is preferred that the oxide having a 28 pseudobrookite-type structure is Fe2Ti05.
29 100121 in addition, an object of the present invention is to advantageously solve the above-described problems, and the present 3 i invention provides a method for cracking hydrocarbon oil, including 32 bringing the hydrocarbon oil into contact with any of the hydrocarbon oil 22447577.1 CA Application Blakes Ref: 10549/00002 1 cracking catalysts according to the aforementioned aspects in the presence 2 of water to thereby crack the hydrocarbon oil.
3 (Effect of Invention) 4 10013] The hydrocarbon oil cracking catalyst and the method for cracking hydrocarbon oil according to the present invention enable efficient 6 production of lighter oil from hydrocarbon oil at low cost, without 7 performing proactive desulfurization and denitrogenation of the feedstock 8 hydrocarbon oil and without using high pressure hydrogen gas.
to BRIEF DESCRIPTION OF THE DRAWING
Ii 100141 FIG. I illustrates an X-ray diffraction spectrum of 12 NiTio,75A10.2502.875 baying a perovskite-type structure.
13 FIG. 2 illustrates an X-ray diffraction spectrum of NiTiO3 14 having a perovskite-type structure.
FIG. 3 illustrates an X-ray diffraction spectrum of 16 CoTi0.75V0,2503.125 having a perovskite-type structure.
I? FIG. 4 illustrates an X-ray diffraction spectrum of Fe2TiO5 18 having a pseudobrookite-type structure.
19 FIG. 5 illustrates an X-ray diffraction spectrum of a mixture of NiO and rutile-type 21 FIG. 6 illustrates an X-ray diffraction spectrum of a mixture of 22 Fe203, rutile-type TiO2 and anatase-type Ti02.
1001.5] Embodiments of the present invention will now be described in 26 detail below. A hydrocarbon oil cracking catalyst according to the present 27 invention is used in cracking hydrocarbon oil to produce lighter oil.
28 Additionally, a method for cracking hydrocarbon oil according to the 29 present invention involves bringing hydrocarbon oil into contact with hydrocarbon oil cracking catalyst in the presence of water, without feeding 3 i hydrogen from the outside of the reaction system, thereby cracking the 32 hydrocarbon oil to produce light hydrocarbon oil.
22447577.1 CA Application Blakes Ref 10549/00002 1 l0016] As used herein, examples of the hydrocarbon oil to be cracked 2 (to produce lighter oil therefrom) by using the hydrocarbon oil cracking 3 catalyst according to the present invention may be heavy hydrocarbon oils 4 including, but not limited to, atmospheric distillation residues and reduced-pressure distillation residues generated during petroleum refining. Specific 6 examples of the hydrocarbon oil to produce lighter oil therefrom by using 7 the hydrocarbon oil cracking catalyst may include hydrocarbon oil with a 8 vol /0 distillation temperature in atmospheric distillation (T50) of 150 C or 9 higher and 550 C or lower, a hydrocarbon oil with 150 of 200 C or higher and 550 C or lower, and a hydrocarbon oil with T50 of 250 C or higher ii and 550 C or lower.
12 10017-1 Additionally, the hydrocarbon oil cracking catalyst according to 13 the present invention composed of an oxide having a perovskite-type 14 structure, or an oxide having a pseudobrookite-type structure, or a mixture of an oxide having a perovskite-type structure and an oxide having a 16 pseudobrookite-type structure.
17 10018] It should be noted that the crystal structure of oxides may be 18 assessed by, for example, X-ray diffraction analysis. Specifically, whether 19 an oxide has a perovskite-type structure can be determined by whether peaks specific to the perovskite-type structure appears in the X-ray 21 diffraction spectrum. In addition, whether an oxide has a pseudobrookite-22 type structure can be determined by whether peaks specific to the 23 pseudobrookite-type structure appears in the X-ray diffraction spectrum.
24 100191 In this case, an oxide having a perovskite-type structure and an oxide having a .pseudobrookite-type structure are used as the hydrocarbon 26 oil cracking catalyst based on a novel finding revealed by the inventors of 27 the present invention that these Oxides allow, when used as the catalyst, 28 efficient cracking of hydrocarbon compounds using water as hydrogen 29 source. Although the mechanism by which hydrocarbon compounds can be efficiently decomposed with the use of these oxides as the catalyst is not 31 known, it is inferred that this is because an oxide having a perovskite-type 32 structure and an oxide having a pseudobrookite-type structure have a high 22447577.1 CA Application Blakes Ref: 10549/00002 1 ability to decompose water to produce oxygen and hydrogen because of 2 their high lattice oxygen supply rate. That is, it is inferred that this is 3 because, in cracking a hydrocarbon compound using water as hydrogen 4 source, a portion of the hydrocarbon compound is allowed to react with water as shown in the following reaction formula to thereby promote the 6 generation of hydrogen as hydrogen source:
7 CnHm + 2111120 nCO2 + (2n + (m/2)) H2 8 100201 Additionally, examples of the oxide having a perovskite-type 9 structure may include a composite oxide represented by a general formula:
ABO3, and a composite oxide with a portion of at least one of an A-site It element and a B-site element of the composite oxide ABO3 substituted by 12 other elements. Specific examples of the oxide having a perovskite-type 13 structure may include an oxide represented by the following general 14 formula (1):
A i_xtit xB _ylVy03-6 .. (1) 16 [where A is an element selected from the group consisting of a Group IA
17 element, a Group HA element, a Group IIIA element and a Group VIII
18 element, A' is at least one element selected from the group consisting of a 19 Group VA element and a Group IIIB element, B is an element selected from the group consisting of a Group MB element and a Group IVA element, and 21 B' is at least one element selected from the group consisting of a Group VA
22 element and a Group IIIB element, in which A, A'. B and B' are different 23 from one another, x is in the range of 0 x 0.4, y is in the range of 0 5. y 24 5Ø4, and 6 represents oxygen deficiency].
As used herein, the oxygen deficiency corresponds to a number which 26 makes the oxide represented by the general formula (1) electrically neutral.
27 100211 As mentioned above, the oxide having a iperovskite-type 28 structure may be a composite oxide with partial substitution of an A-site 29 element and a B-site element by other elements A' and or a composite oxide without substitution of an A-site element and a B-site element.
31 100221 in this regard, when an oxide with partial substitution of the A-32 site element and the B-site element by other elements A' and B' is used, the 22447577,1 .
CA Application Blakes Ref: 10549/00002 element A' preferably has an atomic ratio x of 0.4 or less (x 5. 0.4). and 2 more preferably x = 0 (i.e.. only the B-site element is substituted, while the 3 A-site element is not substituted). In addition, the element B' preferably 4 has an atomic ratio y of 0.4 or less (y 5 0.4). more preferably 0.35 or less (y .5 0.35), and particularly preferably 0.25 or less (y 5. 0.25). This is 6 because if the atomic ratio of these elements A' and B' is too large, the 7 perovskite-type structure may be difficult to maintain.
8 In addition, the B-site element is preferably an element selected from Group 9 IIIB elements when the A-site element is a Group IIIA element. Further, the B-site element is preferably an element selected from Group IVA
11 elements when the A-site element is a Group IA element, a Group hA
12 element or a Group VIII element.
13 100231 In the aforementioned oxide having a perovskite-type structure 14 represented by the general formula (I), particularly, the element A may be, for example, nickel. cobalt or barium. In addition, the element B may be, 16 for example, zirconium, cerium or titanium. Further, the element B' may 17 be, for example, aluminum or vanadium.
is 100241 In the aforementioned oxide having a perovskite-type structure 19 represented by the general formula (1), the element A is preferably, for example, nickel or cobalt. In addition, the element B is preferably, for 21 example, zirconium, cerium or titanium. Further, the element B' is 22 preferably, for example, aluminum or vanadium. The reason is that since 23 the hydrocarbon oil cracking catalyst according to the present invention is 24 used in the presence of water, the elements constituting the oxide are preferably such elements that have a low ionization tendency and are stable 26 in water; for example, transition metal elements.
27 100251 It should be noted that the oxide (composite oxide) having a 28 perovskite-type structure as mentioned earlier may be prepared by, without 29 any particular limitation, for example, a coprecipitation process in the following manner.
31 (i) Firstly, a compound containing an element A and a compound 32 containing an element B, and, optionally, a compound containing an element 22447577.1 CA Application Blakes Ref 10549/00002 A' and a compound containing an element B' are dissolved in ion-exchanged 2 water in amounts such that, for example, A'/A is in the range of 0 to 2./3 (in 3 molar ratio) and 11'/B is in the range of 0 to 2/3 (in molar ratio) to prepare 4 an aqueous solution containing the elements A and B as well as the optional elements A' and 6 (ii) Then, a coprecipitating agent, such as ammonia water and a sodium 7 carbonate solution, is added dropwise to the prepared aqueous solution 8 while adjusting the pH of the aqueous solution so as not to shift toward the 9 alkaline side (e.g., so that the pH is maintained at 5 to 8) to thereby form. a coprecipitate containing the elements A and B as well as the optional ti elements A' and B'.
12 (iii) Finally, the resulting precipitate is filtered and dried, and the dried 13 precipitate is calcined to obtain a composite oxide having a perovskite-type 14 structure.
In the above step (iii), the precipitate is preferably dried at a temperature 16 of 100 C or higher in terms of efficient evaporation of moisture therefrom.
17 Furthermore, the precipitate is preferably dried at a temperature of 160 C
18 or lower from the viewpoint of preventing rapid drying thereof. In 9 addition, the dried precipitate is preferably calcined at a temperature of 500 C.: or higher in terms of ensuring the structural stability of the produced 21 composite oxide (catalyst) (i.e.., reducing structural changes in the 22 composite oxide when used as the catalyst to crack hydrocarbon oil).
23 Furthermore, the precipitate is preferably calcined at a temperature of 24 C or lower from the viewpoint of alleviating the reduction of the surface area of the produced composite oxide.
26 100261 In addition, examples of the oxide having a pseudobrookite-type 27 structure as the hydrocarbon oil cracking catalyst according to the present 28 invention may include, without any particular limitation. Fe2Ti05, which is 29 a composite oxide.
100271 It should be noted that Fe2TiO5 having a pseudobrookite-type 31 structure may be prepared by, without any particular limitation, for 32 example, a coprecipitation process in the following manner.
22447577.1 CA Application Blakes Ref: 1050100002 1 (iv) Firstly, a compound containing Fe and a compound containing Ti are 2 dissolved in ion-exchanged water in amounts such that Fe:Ti = 2:1 (in molar 3 ratio) to prepare an aqueous solution containing Fe and Ti.
4 (v) Then, a coprecipitating agent, such as ammonia water and a sodium carbonate solution, is added dropwise to the prepared aqueous solution 6 while adjusting the pH of the aqueous solution so as not to shift toward the 7 alkaline side (e.g., so that the pH is maintained at 5 to 8) to thereby form a 8 c precipitate containing Fe and Ti.
9 (vi) Finally, the resulting precipitate is filtrated and dried, and the dried io precipitate is calcined to obtain Fe2TiO5 having a pseudobrookite-type 1 1 structure.
12 In the above step (vi), the precipitate is preferably dried at a temperature of 13 100 C or higher in terms of efficient evaporation of the water.
14 Furthermore. the precipitate is preferably dried at a temperature of 160 C
or lower from the viewpoint of preventing rapid drying of the precipitate.
16 in addition, the dried precipitate is preferably calcined at a temperature of 17 500 '12 or higher in terms of ensuring the structural stability of the 18 produced composite oxide (catalyst) (i.e., reducing structural changes in the 19 composite oxide when used as the catalyst to crack a hydrocarbon oil).
Furthermore, the precipitate is preferably calcined at a temperature of 900 21 C or lower from the viewpoint of alleviating the reduction of the surface 22 area of the produced composite oxide.
23 100281 In this regard, the aforementioned oxide having a perovskite-24 type structure and the aforementioned oxide having a. pseudobrookite-type structure may also be prepared by known methods other than the 26 coprecipitation process, such as a sol-gel process.
27 [00291 Additionally, a method for cracking hydrocarbon oil according 28 to the present invention involves bringing hydrocarbon oil into contact with 29 the aforementioned hydrocarbon oil cracking catalyst in the presence of water to thereby crack the hydrocarbon oil. Specifically, in the method for 31 cracking hydrocarbon oil according to the present invention, for example, a 32 mixture of hydrocarbon oil and water is allowed to flow into a reactor 22447577.1 CA Application Blakes Ref: 10549/00002 loaded with the catalyst. thereby causing the catalyst, the hydrocarbon oil 2 and the water to contact one another so as to crack the hydrocarbon oil.
3 [0030] In this process, water used in the cracking of the hydrocarbon 4 oil is utilized as hydrogen source when hydrocarbon compounds contained in the hydrocarbon oil with a high molecular weight are cracked to produce 6 hydrocarbon compounds with a lower molecular weight, i.e., when lighter 7 oil is produced from the hydrocarbon oil. Accordingly, it suffices to use 8 water in an amount sufficient to produce lighter oil from hydrocarbon oil.
9 For example, it is desirable that water is added by 5 parts by mass to parts by mass, preferably by I 0 parts by mass to 1000 parts by mass, and ii more preferably by 10 parts by mass to 500 parts by mass, per 100 parts by 12 mass of the hydrocarbon oil. This is because if water is added by less than 13 5 parts by mass per 100 parts by mass of the hydrocarbon oil, it may not be 14 possible to produce lighter oil from the hydrocarbon oil sufficiently due to the shortage of hydrogen source. On the other hand, if water is added by 16 more than 2000 parts by mass, a greater amount of water may fail to 17 contribute to the production of lighter oil from hydrocarbon oil, resulting in 18 an increase in cost and a reduction in the cracking efficiency of the 19 hydrocarbon oil (i.e., production efficiency of light hydrocarbon oil).
[00311 Additionally, in the method for cracking hydrocarbon oil 21 according to the present invention, the conditions under which the mixture 22 of the hydrocarbon oil and water is brought into contact with the catalyst in 23 the reactor may be changed appropriately.
24 Specifically, the mixture and the catalyst may be brought into contact with each other at a relatively low temperature, e.g., at 300 C to 600 C, 26 preferably at 350 C to 550 C, and more preferably at 400 C to 500 C.
If 27 the temperature is lower than 300 C, the cracking reaction of the 28 hydrocarbon oil may not proceed sufficiently due to activation energy 29 insufficient for the reaction. Alternatively, if the temperature is higher than 600 C, unnecessary gases (such as methane and ethane) may be 31 produced in large amounts, reducing the cracking efficiency of the 32 hydrocarbon oil.
22447577.1 CA Application Blakes Ref 10549/00002 In addition, the mixture and the catalyst may be brought into contact with 2 each other at a pressure of, for example, 0.1 MPa to 40 MPa, preferably 0.1 3 MPa to 35 MPa, and more preferably 0.1 MPa to 30 MPa. if the pressure is 4 less than 0.1 MPa, it may be difficult to allow the hydrocarbon oil and water to flow into the reactor smoothly. Alternatively, if the pressure is 6 more than 40 MPa, the reactor may be more costly to manufacture.
7 Further, the mixture may be allowed to flow into the reactor loaded with the 8 catalyst at a liquid hourly space velocity (LHSV) of, for example, 0.01 9 to 10 WI, preferably 0.05 ICI to 5 WI, and more preferably 0.1 11-1 to 2 WI.
JO One reason is that when the liquid hourly space velocity is less than 0.01 h-t 1 , unnecessary gases may be produced predominantly, resulting in a 12 reduction in the cracking efficiency of the hydrocarbon oil. Another reason 13 is that when the liquid hourly space velocity is more than 10 11-1. the 14 reaction time may be too short to allow the cracking reaction of the hydrocarbon oil to proceed sufficiently.
16 100321 As mentioned above, in the method for cracking hydrocarbon oil 17 according to the present invention, hydrogen that is necessary for the 18 cracking reaction of the hydrocarbon oil may be supplied from the water 19 present in the system. Accordingly, in the method for cracking hydrocarbon oil according to the present invention, there is no need to add hydrogen 21 from the outside of the system, where a molar ratio of the amount of 22 hydrogen to be added from the outside of the system to the supply amount 23 of the hydrocarbon oil to be cracked (the addition amount of hydrogen I
the 24 supply amount of the hydrocarbon oil) may be 0.1 or less, and preferably 0.
Therefore, according to the method for cracking hydrocarbon oil of the 26 present invention using the hydrocarbon oil cracking catalyst of the present 27 invention, it is possible to crack hydrocarbon oil at low cost in an efficient 28 manner to obtain light hydrocarbon, without using high pressure hydrogen 29 gas.
100331 Specifically, according to the method for cracking hydrocarbon 31 oil of the present invention, for example, heavy hydrocarbon oil that is 32 composed of a mixture of various hydrocarbon compounds including a 22447577.1 CA Application Blakes Ref: 10549/00002 1 condensed polycyclic-aromatic compound, such as 1-methylnaphthalene, 2 quinoline, anthracene and phenanthrene. and a non-condensed polycyclic-3 aromatic compound, such as dibenzothiophene and biphenyl, may be cracked 4 to obtain light hydrocarbon oil with a weight-average molecular weight which is half or less of, preferably a third or less of that of the heavy.
6 hydrocarbon oil. That is, light hydrocarbon oil may be produced by causing 7 cleavage of aromatic rings of the hydrocarbon compounds in the heavy 8 hydrocarbon oil with a very high probability to obtain monoaromatic 9 compounds. As used herein, the weight-average molecular weight refers to ia a weight-average molecular weight in terms of polystyrene as measured by it gel permeation chromatography (CiPC).
12 100341 In addition, since the hydrocarbon oil cracking catalyst of the 13 present invention is less prone to deterioration, according to the method for 14 cracking hydrocarbon oil of the present invention using this catalyst, there is no need to perform proactive desulfurization and denitrogenation of the 16 feedstock hydrocarbon oil to be cracked.
17 100351 While the embodiments of the present invention have been 18 described, the hydrocarbon oil cracking catalyst and the method for 19 cracking hydrocarbon oil according to the present invention are not limited to the disclosed embodiments, and numerous changes may be made thereto 21 as appropriate.
24 100361 The present invention will be described in more detail below with reference to examples thereof in a non-limiting way.
26 100371 (Example 1) 27 A catalyst composed of an oxide having a perovskite-type structure with an 28 element A of nickel, an element B of titanium and an element IV of 29 aluminum was prepared. Specifically. at first, nickel nitrate hexahydrate, titanium sulfate and aluminum nitrate were dissolved in ion-exchanged 31 water with Ni:Ti:Al = 1:0.75:0.25 (in molar ratio) to obtain an aqueous 32 solution. Then, a sodium carbonate solution was added dropwise to the 22447577.1 CA Application Makes Ref: 10549100002 1 obtained aqueous solution while adjusting the pH of the aqueous solution so 2 as not to exceed 7 to produce a precipitate. Finally, the resulting 3 precipitate was allowed to be aged (stand still for one hour), then filtered 4 and dried (at 150 ( for one hour), after which the dried precipitate was calcined at a temperature of 800 C to prepare a catalyst composed of a 6 composite oxide.
7 Meanwhile, the resulting composite oxide was analyzed by an X-ray 8 diffractometer, and the obtained results are as shown in an X-ray diffraction 9 spectrum as illustrated in FIG. 1 with diffraction peaks specific to 0 NiTi0.75A10.2502.875 having a perovskite-type structure (as indicated by 11 arrows in the figure). That is, it was found that the prepared catalyst is 12 NiTi0.75A10.2502.875 having a perovskite-type structure.
13 Then, the prepared catalyst was loaded into a stainless reactor (with inner 14 volume of 10 .mL) with a bulk density of 0.908 gicm3. Then, the interior of the reactor loaded with the catalyst was heated and pressurized to a 16 temperature of 470 C and a pressure of 0.10 MPaG, while feeding ion-17 exchanged water into the reactor at a flow rate of 0.1 mLimin.
]8 Subsequently, without feeding hydrogen, heavy hydrocarbon oil having 19 characteristics as shown in Table 1 (oils distilled from a thermal cracker) and ion-exchanged water were allowed to continuously flow into the reactor 21 (for both the ion-exchanged water and the heavy hydrocarbon oil, the flow 22 rate was 0.1 mL/min and LHSV was 0.6 h-1). Then, after two hours from 23 the start of oil-flowing, the effluents from the reactor (the cracking reaction 24 products) were collected over three hours to calculate the cracking rate of the heavy hydrocarbon oil as described below. The results thereof are 26 shown in Table 2.
22447577.1 CA Application Makes Ref: 10549/00002 1 [0038] [Table 1]
Characteristics Analysis Method Density (at 15 C) [g/cm3] 0.9737 JIS K 2249 Sulfur Content [mass%] 2.4 JIS K 2541 I
Nitrogen Content imass%1 0.19 JIS K 2609 Kinematic Viscosity (at 50 C) 11.7 JIS K 2283 [mm2/s) Kinematic Viscosity (at 100 'C.) 3.338 =
:mm2/s._ 105% _________________________________ 109 5% 344 10% 364 _______ 20 % 388 Distillation 30 % 406 = Characteristics 40 % 422 JIS K
[ C] 50 % 439 60% 458 70% 479 80% 508 90% 582 3 [0039] <Calculation of Cracking Rate>
4 The cracking rate Cv of fractions having a boiling point of 380 C._ or higher contained in the supplied heavy hydrocarbon oil was calculated using the 6 following equation, where "Coke" was measured by a combustion ultraviolet 7 fluorescence method:
R + Coke0 Cv = 1¨ __________________ xl 00 \s.
9 Cv: cracking rate [mass%] of fractions with a boiling point of 380 to C or higher in the heavy hydrocarbon oil ii F: amount [g/h] of fractions with a boiling point of 380 C. or 12 higher in the supplied heavy hydrocarbon 13 R: amount [g/h] of fractions with a boiling point of 380 C. or 14 higher in the cracking reaction product Coke: amount of carbonaceous deposits on the catalyst [0]
22447577.1 CA Application B lakes Ref: 10549100002 2 100401 (Example 2) 3 A catalyst was prepared in the same manner as described in Example 1, 4 except that the B site was not substituted, i.e., aluminum nitrate was not added. Additionally, following the same procedure as described in Example 6 1, the heavy hydrocarbon oil was cracked to calculate the cracking rate 7 thereof. The results thereof are shown in Table 2.
8 Meanwhile, the resulting catalyst was analyzed in the same manner as 9 described in Example I, and the obtained results are as shown in an X-ray diffraction spectrum illustrated in FIG. 2 with diffraction peaks specific to 11 N1TiO3 having a perovskite-type structure (as indicated by arrows in the 12 figure). That is, it was found that the prepared catalyst is NiTiO3 having a 13 perovskite-type structure.
ABO3, and a composite oxide with a portion of at least one of an A-site It element and a B-site element of the composite oxide ABO3 substituted by 12 other elements. Specific examples of the oxide having a perovskite-type 13 structure may include an oxide represented by the following general 14 formula (1):
A i_xtit xB _ylVy03-6 .. (1) 16 [where A is an element selected from the group consisting of a Group IA
17 element, a Group HA element, a Group IIIA element and a Group VIII
18 element, A' is at least one element selected from the group consisting of a 19 Group VA element and a Group IIIB element, B is an element selected from the group consisting of a Group MB element and a Group IVA element, and 21 B' is at least one element selected from the group consisting of a Group VA
22 element and a Group IIIB element, in which A, A'. B and B' are different 23 from one another, x is in the range of 0 x 0.4, y is in the range of 0 5. y 24 5Ø4, and 6 represents oxygen deficiency].
As used herein, the oxygen deficiency corresponds to a number which 26 makes the oxide represented by the general formula (1) electrically neutral.
27 100211 As mentioned above, the oxide having a iperovskite-type 28 structure may be a composite oxide with partial substitution of an A-site 29 element and a B-site element by other elements A' and or a composite oxide without substitution of an A-site element and a B-site element.
31 100221 in this regard, when an oxide with partial substitution of the A-32 site element and the B-site element by other elements A' and B' is used, the 22447577,1 .
CA Application Blakes Ref: 10549/00002 element A' preferably has an atomic ratio x of 0.4 or less (x 5. 0.4). and 2 more preferably x = 0 (i.e.. only the B-site element is substituted, while the 3 A-site element is not substituted). In addition, the element B' preferably 4 has an atomic ratio y of 0.4 or less (y 5 0.4). more preferably 0.35 or less (y .5 0.35), and particularly preferably 0.25 or less (y 5. 0.25). This is 6 because if the atomic ratio of these elements A' and B' is too large, the 7 perovskite-type structure may be difficult to maintain.
8 In addition, the B-site element is preferably an element selected from Group 9 IIIB elements when the A-site element is a Group IIIA element. Further, the B-site element is preferably an element selected from Group IVA
11 elements when the A-site element is a Group IA element, a Group hA
12 element or a Group VIII element.
13 100231 In the aforementioned oxide having a perovskite-type structure 14 represented by the general formula (I), particularly, the element A may be, for example, nickel. cobalt or barium. In addition, the element B may be, 16 for example, zirconium, cerium or titanium. Further, the element B' may 17 be, for example, aluminum or vanadium.
is 100241 In the aforementioned oxide having a perovskite-type structure 19 represented by the general formula (1), the element A is preferably, for example, nickel or cobalt. In addition, the element B is preferably, for 21 example, zirconium, cerium or titanium. Further, the element B' is 22 preferably, for example, aluminum or vanadium. The reason is that since 23 the hydrocarbon oil cracking catalyst according to the present invention is 24 used in the presence of water, the elements constituting the oxide are preferably such elements that have a low ionization tendency and are stable 26 in water; for example, transition metal elements.
27 100251 It should be noted that the oxide (composite oxide) having a 28 perovskite-type structure as mentioned earlier may be prepared by, without 29 any particular limitation, for example, a coprecipitation process in the following manner.
31 (i) Firstly, a compound containing an element A and a compound 32 containing an element B, and, optionally, a compound containing an element 22447577.1 CA Application Blakes Ref 10549/00002 A' and a compound containing an element B' are dissolved in ion-exchanged 2 water in amounts such that, for example, A'/A is in the range of 0 to 2./3 (in 3 molar ratio) and 11'/B is in the range of 0 to 2/3 (in molar ratio) to prepare 4 an aqueous solution containing the elements A and B as well as the optional elements A' and 6 (ii) Then, a coprecipitating agent, such as ammonia water and a sodium 7 carbonate solution, is added dropwise to the prepared aqueous solution 8 while adjusting the pH of the aqueous solution so as not to shift toward the 9 alkaline side (e.g., so that the pH is maintained at 5 to 8) to thereby form. a coprecipitate containing the elements A and B as well as the optional ti elements A' and B'.
12 (iii) Finally, the resulting precipitate is filtered and dried, and the dried 13 precipitate is calcined to obtain a composite oxide having a perovskite-type 14 structure.
In the above step (iii), the precipitate is preferably dried at a temperature 16 of 100 C or higher in terms of efficient evaporation of moisture therefrom.
17 Furthermore, the precipitate is preferably dried at a temperature of 160 C
18 or lower from the viewpoint of preventing rapid drying thereof. In 9 addition, the dried precipitate is preferably calcined at a temperature of 500 C.: or higher in terms of ensuring the structural stability of the produced 21 composite oxide (catalyst) (i.e.., reducing structural changes in the 22 composite oxide when used as the catalyst to crack hydrocarbon oil).
23 Furthermore, the precipitate is preferably calcined at a temperature of 24 C or lower from the viewpoint of alleviating the reduction of the surface area of the produced composite oxide.
26 100261 In addition, examples of the oxide having a pseudobrookite-type 27 structure as the hydrocarbon oil cracking catalyst according to the present 28 invention may include, without any particular limitation. Fe2Ti05, which is 29 a composite oxide.
100271 It should be noted that Fe2TiO5 having a pseudobrookite-type 31 structure may be prepared by, without any particular limitation, for 32 example, a coprecipitation process in the following manner.
22447577.1 CA Application Blakes Ref: 1050100002 1 (iv) Firstly, a compound containing Fe and a compound containing Ti are 2 dissolved in ion-exchanged water in amounts such that Fe:Ti = 2:1 (in molar 3 ratio) to prepare an aqueous solution containing Fe and Ti.
4 (v) Then, a coprecipitating agent, such as ammonia water and a sodium carbonate solution, is added dropwise to the prepared aqueous solution 6 while adjusting the pH of the aqueous solution so as not to shift toward the 7 alkaline side (e.g., so that the pH is maintained at 5 to 8) to thereby form a 8 c precipitate containing Fe and Ti.
9 (vi) Finally, the resulting precipitate is filtrated and dried, and the dried io precipitate is calcined to obtain Fe2TiO5 having a pseudobrookite-type 1 1 structure.
12 In the above step (vi), the precipitate is preferably dried at a temperature of 13 100 C or higher in terms of efficient evaporation of the water.
14 Furthermore. the precipitate is preferably dried at a temperature of 160 C
or lower from the viewpoint of preventing rapid drying of the precipitate.
16 in addition, the dried precipitate is preferably calcined at a temperature of 17 500 '12 or higher in terms of ensuring the structural stability of the 18 produced composite oxide (catalyst) (i.e., reducing structural changes in the 19 composite oxide when used as the catalyst to crack a hydrocarbon oil).
Furthermore, the precipitate is preferably calcined at a temperature of 900 21 C or lower from the viewpoint of alleviating the reduction of the surface 22 area of the produced composite oxide.
23 100281 In this regard, the aforementioned oxide having a perovskite-24 type structure and the aforementioned oxide having a. pseudobrookite-type structure may also be prepared by known methods other than the 26 coprecipitation process, such as a sol-gel process.
27 [00291 Additionally, a method for cracking hydrocarbon oil according 28 to the present invention involves bringing hydrocarbon oil into contact with 29 the aforementioned hydrocarbon oil cracking catalyst in the presence of water to thereby crack the hydrocarbon oil. Specifically, in the method for 31 cracking hydrocarbon oil according to the present invention, for example, a 32 mixture of hydrocarbon oil and water is allowed to flow into a reactor 22447577.1 CA Application Blakes Ref: 10549/00002 loaded with the catalyst. thereby causing the catalyst, the hydrocarbon oil 2 and the water to contact one another so as to crack the hydrocarbon oil.
3 [0030] In this process, water used in the cracking of the hydrocarbon 4 oil is utilized as hydrogen source when hydrocarbon compounds contained in the hydrocarbon oil with a high molecular weight are cracked to produce 6 hydrocarbon compounds with a lower molecular weight, i.e., when lighter 7 oil is produced from the hydrocarbon oil. Accordingly, it suffices to use 8 water in an amount sufficient to produce lighter oil from hydrocarbon oil.
9 For example, it is desirable that water is added by 5 parts by mass to parts by mass, preferably by I 0 parts by mass to 1000 parts by mass, and ii more preferably by 10 parts by mass to 500 parts by mass, per 100 parts by 12 mass of the hydrocarbon oil. This is because if water is added by less than 13 5 parts by mass per 100 parts by mass of the hydrocarbon oil, it may not be 14 possible to produce lighter oil from the hydrocarbon oil sufficiently due to the shortage of hydrogen source. On the other hand, if water is added by 16 more than 2000 parts by mass, a greater amount of water may fail to 17 contribute to the production of lighter oil from hydrocarbon oil, resulting in 18 an increase in cost and a reduction in the cracking efficiency of the 19 hydrocarbon oil (i.e., production efficiency of light hydrocarbon oil).
[00311 Additionally, in the method for cracking hydrocarbon oil 21 according to the present invention, the conditions under which the mixture 22 of the hydrocarbon oil and water is brought into contact with the catalyst in 23 the reactor may be changed appropriately.
24 Specifically, the mixture and the catalyst may be brought into contact with each other at a relatively low temperature, e.g., at 300 C to 600 C, 26 preferably at 350 C to 550 C, and more preferably at 400 C to 500 C.
If 27 the temperature is lower than 300 C, the cracking reaction of the 28 hydrocarbon oil may not proceed sufficiently due to activation energy 29 insufficient for the reaction. Alternatively, if the temperature is higher than 600 C, unnecessary gases (such as methane and ethane) may be 31 produced in large amounts, reducing the cracking efficiency of the 32 hydrocarbon oil.
22447577.1 CA Application Blakes Ref 10549/00002 In addition, the mixture and the catalyst may be brought into contact with 2 each other at a pressure of, for example, 0.1 MPa to 40 MPa, preferably 0.1 3 MPa to 35 MPa, and more preferably 0.1 MPa to 30 MPa. if the pressure is 4 less than 0.1 MPa, it may be difficult to allow the hydrocarbon oil and water to flow into the reactor smoothly. Alternatively, if the pressure is 6 more than 40 MPa, the reactor may be more costly to manufacture.
7 Further, the mixture may be allowed to flow into the reactor loaded with the 8 catalyst at a liquid hourly space velocity (LHSV) of, for example, 0.01 9 to 10 WI, preferably 0.05 ICI to 5 WI, and more preferably 0.1 11-1 to 2 WI.
JO One reason is that when the liquid hourly space velocity is less than 0.01 h-t 1 , unnecessary gases may be produced predominantly, resulting in a 12 reduction in the cracking efficiency of the hydrocarbon oil. Another reason 13 is that when the liquid hourly space velocity is more than 10 11-1. the 14 reaction time may be too short to allow the cracking reaction of the hydrocarbon oil to proceed sufficiently.
16 100321 As mentioned above, in the method for cracking hydrocarbon oil 17 according to the present invention, hydrogen that is necessary for the 18 cracking reaction of the hydrocarbon oil may be supplied from the water 19 present in the system. Accordingly, in the method for cracking hydrocarbon oil according to the present invention, there is no need to add hydrogen 21 from the outside of the system, where a molar ratio of the amount of 22 hydrogen to be added from the outside of the system to the supply amount 23 of the hydrocarbon oil to be cracked (the addition amount of hydrogen I
the 24 supply amount of the hydrocarbon oil) may be 0.1 or less, and preferably 0.
Therefore, according to the method for cracking hydrocarbon oil of the 26 present invention using the hydrocarbon oil cracking catalyst of the present 27 invention, it is possible to crack hydrocarbon oil at low cost in an efficient 28 manner to obtain light hydrocarbon, without using high pressure hydrogen 29 gas.
100331 Specifically, according to the method for cracking hydrocarbon 31 oil of the present invention, for example, heavy hydrocarbon oil that is 32 composed of a mixture of various hydrocarbon compounds including a 22447577.1 CA Application Blakes Ref: 10549/00002 1 condensed polycyclic-aromatic compound, such as 1-methylnaphthalene, 2 quinoline, anthracene and phenanthrene. and a non-condensed polycyclic-3 aromatic compound, such as dibenzothiophene and biphenyl, may be cracked 4 to obtain light hydrocarbon oil with a weight-average molecular weight which is half or less of, preferably a third or less of that of the heavy.
6 hydrocarbon oil. That is, light hydrocarbon oil may be produced by causing 7 cleavage of aromatic rings of the hydrocarbon compounds in the heavy 8 hydrocarbon oil with a very high probability to obtain monoaromatic 9 compounds. As used herein, the weight-average molecular weight refers to ia a weight-average molecular weight in terms of polystyrene as measured by it gel permeation chromatography (CiPC).
12 100341 In addition, since the hydrocarbon oil cracking catalyst of the 13 present invention is less prone to deterioration, according to the method for 14 cracking hydrocarbon oil of the present invention using this catalyst, there is no need to perform proactive desulfurization and denitrogenation of the 16 feedstock hydrocarbon oil to be cracked.
17 100351 While the embodiments of the present invention have been 18 described, the hydrocarbon oil cracking catalyst and the method for 19 cracking hydrocarbon oil according to the present invention are not limited to the disclosed embodiments, and numerous changes may be made thereto 21 as appropriate.
24 100361 The present invention will be described in more detail below with reference to examples thereof in a non-limiting way.
26 100371 (Example 1) 27 A catalyst composed of an oxide having a perovskite-type structure with an 28 element A of nickel, an element B of titanium and an element IV of 29 aluminum was prepared. Specifically. at first, nickel nitrate hexahydrate, titanium sulfate and aluminum nitrate were dissolved in ion-exchanged 31 water with Ni:Ti:Al = 1:0.75:0.25 (in molar ratio) to obtain an aqueous 32 solution. Then, a sodium carbonate solution was added dropwise to the 22447577.1 CA Application Makes Ref: 10549100002 1 obtained aqueous solution while adjusting the pH of the aqueous solution so 2 as not to exceed 7 to produce a precipitate. Finally, the resulting 3 precipitate was allowed to be aged (stand still for one hour), then filtered 4 and dried (at 150 ( for one hour), after which the dried precipitate was calcined at a temperature of 800 C to prepare a catalyst composed of a 6 composite oxide.
7 Meanwhile, the resulting composite oxide was analyzed by an X-ray 8 diffractometer, and the obtained results are as shown in an X-ray diffraction 9 spectrum as illustrated in FIG. 1 with diffraction peaks specific to 0 NiTi0.75A10.2502.875 having a perovskite-type structure (as indicated by 11 arrows in the figure). That is, it was found that the prepared catalyst is 12 NiTi0.75A10.2502.875 having a perovskite-type structure.
13 Then, the prepared catalyst was loaded into a stainless reactor (with inner 14 volume of 10 .mL) with a bulk density of 0.908 gicm3. Then, the interior of the reactor loaded with the catalyst was heated and pressurized to a 16 temperature of 470 C and a pressure of 0.10 MPaG, while feeding ion-17 exchanged water into the reactor at a flow rate of 0.1 mLimin.
]8 Subsequently, without feeding hydrogen, heavy hydrocarbon oil having 19 characteristics as shown in Table 1 (oils distilled from a thermal cracker) and ion-exchanged water were allowed to continuously flow into the reactor 21 (for both the ion-exchanged water and the heavy hydrocarbon oil, the flow 22 rate was 0.1 mL/min and LHSV was 0.6 h-1). Then, after two hours from 23 the start of oil-flowing, the effluents from the reactor (the cracking reaction 24 products) were collected over three hours to calculate the cracking rate of the heavy hydrocarbon oil as described below. The results thereof are 26 shown in Table 2.
22447577.1 CA Application Makes Ref: 10549/00002 1 [0038] [Table 1]
Characteristics Analysis Method Density (at 15 C) [g/cm3] 0.9737 JIS K 2249 Sulfur Content [mass%] 2.4 JIS K 2541 I
Nitrogen Content imass%1 0.19 JIS K 2609 Kinematic Viscosity (at 50 C) 11.7 JIS K 2283 [mm2/s) Kinematic Viscosity (at 100 'C.) 3.338 =
:mm2/s._ 105% _________________________________ 109 5% 344 10% 364 _______ 20 % 388 Distillation 30 % 406 = Characteristics 40 % 422 JIS K
[ C] 50 % 439 60% 458 70% 479 80% 508 90% 582 3 [0039] <Calculation of Cracking Rate>
4 The cracking rate Cv of fractions having a boiling point of 380 C._ or higher contained in the supplied heavy hydrocarbon oil was calculated using the 6 following equation, where "Coke" was measured by a combustion ultraviolet 7 fluorescence method:
R + Coke0 Cv = 1¨ __________________ xl 00 \s.
9 Cv: cracking rate [mass%] of fractions with a boiling point of 380 to C or higher in the heavy hydrocarbon oil ii F: amount [g/h] of fractions with a boiling point of 380 C. or 12 higher in the supplied heavy hydrocarbon 13 R: amount [g/h] of fractions with a boiling point of 380 C. or 14 higher in the cracking reaction product Coke: amount of carbonaceous deposits on the catalyst [0]
22447577.1 CA Application B lakes Ref: 10549100002 2 100401 (Example 2) 3 A catalyst was prepared in the same manner as described in Example 1, 4 except that the B site was not substituted, i.e., aluminum nitrate was not added. Additionally, following the same procedure as described in Example 6 1, the heavy hydrocarbon oil was cracked to calculate the cracking rate 7 thereof. The results thereof are shown in Table 2.
8 Meanwhile, the resulting catalyst was analyzed in the same manner as 9 described in Example I, and the obtained results are as shown in an X-ray diffraction spectrum illustrated in FIG. 2 with diffraction peaks specific to 11 N1TiO3 having a perovskite-type structure (as indicated by arrows in the 12 figure). That is, it was found that the prepared catalyst is NiTiO3 having a 13 perovskite-type structure.
14 (Example 3) 5 A catalyst was prepared in the same manner as described in Example 1, 16 except that the element A was cobalt, cobalt nitrate hexa.hydrate was added 17 in place of nickel nitrate hexahydrate with Co:Ti = 1:0.75 (in molar ratio), IS the element B was vanadium, and vanadium oxide sulfate was added in 19 place of aluminum nitrate with Ti:V = 0.75:0.25 (in molar ratio).
Additionally, following the same procedure as described in Example 1, the 21 heavy hydrocarbon oil was cracked to calculate the cracking rate thereof.
22 The results thereof are shown in Table 2.
23 Meanwhile, the resulting catalyst was analyzed in the same manner as 24 described in Example I. and the obtained results are as shown in an X-ray diffraction spectrum as illustrated in FIG. 3 with diffraction peaks specific 26 to CoTi0.75V0.2503.125 having a perovskite-type structure (as indicated by 27 arrows in the figure). That is, it was found that the prepared catalyst is 28 CoTi0.75V0.2503, 115 having a perovskite-type structure.
29 100411 (Example 4) A catalyst composed of an oxide having a pseudobrookite-type structure was 31 prepared. Specifically, at first, iron nitrate and titanium sulfate were 32 dissolved in ion-exchanged water with Fe:Ti = 2:1 (in molar ratio) to obtain 22447577,1 CA Application Blakes Ref: 10549/00002 an aqueous solution. Then, a sodium carbonate solution was added 2 dropwise to the obtained aqueous solution while adjusting the pH of the 3 aqueous solution so as not to exceed 7 to produce a precipitate. Finally, the 4 resulting precipitate was allowed to be aged (stand still for one hour), then filtered and dried (at 150 C for one hour), after which the dried precipitate 6 was calcined at a temperature of 800 C to prepare a catalyst composed of a 7 composite oxide.
8 Meanwhile, the resulting composite oxide was analyzed by an X-ray 9 diffractometer, and the obtained results are as shown in an X-ray diffraction io spectrum illustrated in FIG. 4 with diffraction peaks specific to Fe2TiO5 Ii having a pseudobrookite-type structure (as indicated by arrows in the 12 figure). That is, it was found that the prepared catalyst is Fe2TiO5 having a 13 pseudobrookite-type structure.
14 Then, the prepared catalyst was loaded into a stainless reactor (with inner volume of 10 ml.,) with a bulk density of 0.904 g/cm3. Then, the interior of 16 the reactor loaded with the catalyst was heated and pressurized to a 17 temperature of 470 C and a pressure of 15 MPa, while feeding ion-18 exchanged water into the reactor at a flow rate of 0.1 mUmin.
19 Subsequently, without feeding hydrogen, a heavy hydrocarbon oil having characteristics as shown in Table 1 (an oil distilled from a thermal cracker) 21 and ion-exchanged water were allowed to continuously flow into the reactor 22 (for both the ion-exchanged water and the heavy hydrocarbon oil, the flow 23 rate was 0.1 mlimin and LHSV was 0.75 h-1). Then. after two hours from 24 the start of oil-flowing, the effluents from the reactor (cracking reaction products) were collected over three hours to calculate the cracking rate of 26 the heavy hydrocarbon oil in the same manner as described in Example 1.
27 The results thereof are shown in Table 2.
28 100421 (Comparative Example 1) 29 Heavy hydrocarbon oil was cracked in the same manner as described in Example 1, except for the use of a catalyst obtained by calcining, at a 3 i temperature of 500 C, the titanium oxide powder with nickel nitrate 32 supported thereon with Ti:Ni = 1:1 (in molar ratio). Additionally.
following 22447577.1 CA Application B lakes Ref: 10549/00002 the same procedure as described in Example 1, the cracking rate of the 2 heavy hydrocarbon oil was calculated. The results thereof are shown in 3 Table 2.
4 Meanwhile, the resulting catalyst was analyzed by an X-ray diffractometer, and the obtained results are as shown in an X-ray diffraction spectrum 6 illustrated in FIG. 5 with diffraction peaks specific to NiO (as indicated by 7 solid arrows in the figure) and diffraction peaks specific to rutile-type 8 (as indicated by broken arrows in the figure). That is, it was found that the 9 prepared catalyst is a mixture of NiO and rutile-type Ti02.
(Comparative Example 2) 11 Heavy hydrocarbon oil was cracked in the same manner as described in 12 Example 4, except for the use of a catalyst obtained by calcining, at a 13 temperature of 500 C, the titanium oxide powder with iron nitrate 14 supported thereon with Ti:Fe = 1:2 (in molar ratio). Additionally, following the same procedure as described in Example 4, the cracking rate of the 16 heavy hydrocarbon oil was calculated. The results thereof are shown in 17 Table 2.
18 Meanwhile, the resulting catalyst was analyzed by an X-ray diffractom.eter, 19 and the obtained results are as shown in an X-ray diffraction spectrum illustrated in FIG, 6 with diffraction peaks specific to Fe203 (hematite) (as 21 indicated by solid arrows in the figure), diffraction peaks specific to rutile-22 type TiO2 (as indicated by broken arrows in the figure), and diffraction 23 peaks specific to anatase-type TiO2 (indicated by dotted arrows in the 24 figure). That is, it was found that the resulting catalyst is a mixture of Fe203 (hematite), rutile-type TiO2 and anatase-type 22447577.1 CA Application Blakes Ref: 10549/00002 100431 [Table 2]
Comparative Example 1 Example 2 Example 3 Comparative Example 4 Example 1 Example 2 Catalyst Perovskite Pseudobrookite Mixture Perovskite Type Perovskite Type Mixture =NiO, TiO2 NiTio 75Alo 2502.875 = Type CoTio 75Vo ,503.1 25 Fe203. TiO2 Type NiT103 Fe2TiO5 Cracking Rate 21.8 38.1 35.5 ; 40.9 44.5 52.7 I [massVol co Ul CA Application Slakes Ref 10549/00002 i 100441 it can be seen from Table 2 that the catalysts of Examples 1 to 3 2 each exhibit a higher cracking rate than that of the catalyst of Comparative 3 Example 1. It can also be understood that the catalyst of Example 4 4 exhibits a higher cracking rate than that of the catalyst of Comparative Example 2.
6 100451 To evaluate the deterioration resistance of the catalysts, in 7 Example 4 and Comparative Example .2, the cracking of the heavy 8 hydrocarbon oil was continued for 14 days and more. After 14 days from 9 the start of oil-flowing, the effluents from the reactor were collected over two hours to calculate the cracking rate of the heavy hydrocarbon oil in the 1 same manner as described in Example 1. Table 3 shows the cracking rate of 12 the heavy hydrocarbon oil after 6 hours from the start of oil-flowing and the 13 cracking rate of the heavy hydrocarbon oil after 14 days from the start of 14 oil-flowing.
100461 [Table 3]
Comparative Example 4 Example 2 Cracking rate after 6 hours from 44.5 52.7 start of oil-flowing [mass%]
Cracking rate after 14 days from 33.2 50.5 start of oil-flowing [mass%[
17 10 0 4 71 It can be seen from Table 3 that there is not much difference 18 between the cracking rates after 6 hours and after 14 days from the start of 19 oil-flowing in Example 4, whereas in Comparative Example 2 a considerable drop is observed in the cracking rate after 14 days from the start of oil-21 flowing. Thus, it can be understood that the deterioration of the catalyst is 22 alleviated in Example 4.
100481 The present invention may provide a hydrocarbon oil cracking 26 catalyst that enables efficient production of lighter oil from hydrocarbon oil 27 at low cost, without performing proactive desulfurization and 22447577.1 CA Application Blakes Ref 10549/00002 1 denitrogenation of the feedstock hydrocarbon oil and without using high pressure hydrogen gas. The present invention may also provide a method 3 for cracking hydrocarbon oil using the hydrocarbon oil cracking catalyst.
22447577.1
Additionally, following the same procedure as described in Example 1, the 21 heavy hydrocarbon oil was cracked to calculate the cracking rate thereof.
22 The results thereof are shown in Table 2.
23 Meanwhile, the resulting catalyst was analyzed in the same manner as 24 described in Example I. and the obtained results are as shown in an X-ray diffraction spectrum as illustrated in FIG. 3 with diffraction peaks specific 26 to CoTi0.75V0.2503.125 having a perovskite-type structure (as indicated by 27 arrows in the figure). That is, it was found that the prepared catalyst is 28 CoTi0.75V0.2503, 115 having a perovskite-type structure.
29 100411 (Example 4) A catalyst composed of an oxide having a pseudobrookite-type structure was 31 prepared. Specifically, at first, iron nitrate and titanium sulfate were 32 dissolved in ion-exchanged water with Fe:Ti = 2:1 (in molar ratio) to obtain 22447577,1 CA Application Blakes Ref: 10549/00002 an aqueous solution. Then, a sodium carbonate solution was added 2 dropwise to the obtained aqueous solution while adjusting the pH of the 3 aqueous solution so as not to exceed 7 to produce a precipitate. Finally, the 4 resulting precipitate was allowed to be aged (stand still for one hour), then filtered and dried (at 150 C for one hour), after which the dried precipitate 6 was calcined at a temperature of 800 C to prepare a catalyst composed of a 7 composite oxide.
8 Meanwhile, the resulting composite oxide was analyzed by an X-ray 9 diffractometer, and the obtained results are as shown in an X-ray diffraction io spectrum illustrated in FIG. 4 with diffraction peaks specific to Fe2TiO5 Ii having a pseudobrookite-type structure (as indicated by arrows in the 12 figure). That is, it was found that the prepared catalyst is Fe2TiO5 having a 13 pseudobrookite-type structure.
14 Then, the prepared catalyst was loaded into a stainless reactor (with inner volume of 10 ml.,) with a bulk density of 0.904 g/cm3. Then, the interior of 16 the reactor loaded with the catalyst was heated and pressurized to a 17 temperature of 470 C and a pressure of 15 MPa, while feeding ion-18 exchanged water into the reactor at a flow rate of 0.1 mUmin.
19 Subsequently, without feeding hydrogen, a heavy hydrocarbon oil having characteristics as shown in Table 1 (an oil distilled from a thermal cracker) 21 and ion-exchanged water were allowed to continuously flow into the reactor 22 (for both the ion-exchanged water and the heavy hydrocarbon oil, the flow 23 rate was 0.1 mlimin and LHSV was 0.75 h-1). Then. after two hours from 24 the start of oil-flowing, the effluents from the reactor (cracking reaction products) were collected over three hours to calculate the cracking rate of 26 the heavy hydrocarbon oil in the same manner as described in Example 1.
27 The results thereof are shown in Table 2.
28 100421 (Comparative Example 1) 29 Heavy hydrocarbon oil was cracked in the same manner as described in Example 1, except for the use of a catalyst obtained by calcining, at a 3 i temperature of 500 C, the titanium oxide powder with nickel nitrate 32 supported thereon with Ti:Ni = 1:1 (in molar ratio). Additionally.
following 22447577.1 CA Application B lakes Ref: 10549/00002 the same procedure as described in Example 1, the cracking rate of the 2 heavy hydrocarbon oil was calculated. The results thereof are shown in 3 Table 2.
4 Meanwhile, the resulting catalyst was analyzed by an X-ray diffractometer, and the obtained results are as shown in an X-ray diffraction spectrum 6 illustrated in FIG. 5 with diffraction peaks specific to NiO (as indicated by 7 solid arrows in the figure) and diffraction peaks specific to rutile-type 8 (as indicated by broken arrows in the figure). That is, it was found that the 9 prepared catalyst is a mixture of NiO and rutile-type Ti02.
(Comparative Example 2) 11 Heavy hydrocarbon oil was cracked in the same manner as described in 12 Example 4, except for the use of a catalyst obtained by calcining, at a 13 temperature of 500 C, the titanium oxide powder with iron nitrate 14 supported thereon with Ti:Fe = 1:2 (in molar ratio). Additionally, following the same procedure as described in Example 4, the cracking rate of the 16 heavy hydrocarbon oil was calculated. The results thereof are shown in 17 Table 2.
18 Meanwhile, the resulting catalyst was analyzed by an X-ray diffractom.eter, 19 and the obtained results are as shown in an X-ray diffraction spectrum illustrated in FIG, 6 with diffraction peaks specific to Fe203 (hematite) (as 21 indicated by solid arrows in the figure), diffraction peaks specific to rutile-22 type TiO2 (as indicated by broken arrows in the figure), and diffraction 23 peaks specific to anatase-type TiO2 (indicated by dotted arrows in the 24 figure). That is, it was found that the resulting catalyst is a mixture of Fe203 (hematite), rutile-type TiO2 and anatase-type 22447577.1 CA Application Blakes Ref: 10549/00002 100431 [Table 2]
Comparative Example 1 Example 2 Example 3 Comparative Example 4 Example 1 Example 2 Catalyst Perovskite Pseudobrookite Mixture Perovskite Type Perovskite Type Mixture =NiO, TiO2 NiTio 75Alo 2502.875 = Type CoTio 75Vo ,503.1 25 Fe203. TiO2 Type NiT103 Fe2TiO5 Cracking Rate 21.8 38.1 35.5 ; 40.9 44.5 52.7 I [massVol co Ul CA Application Slakes Ref 10549/00002 i 100441 it can be seen from Table 2 that the catalysts of Examples 1 to 3 2 each exhibit a higher cracking rate than that of the catalyst of Comparative 3 Example 1. It can also be understood that the catalyst of Example 4 4 exhibits a higher cracking rate than that of the catalyst of Comparative Example 2.
6 100451 To evaluate the deterioration resistance of the catalysts, in 7 Example 4 and Comparative Example .2, the cracking of the heavy 8 hydrocarbon oil was continued for 14 days and more. After 14 days from 9 the start of oil-flowing, the effluents from the reactor were collected over two hours to calculate the cracking rate of the heavy hydrocarbon oil in the 1 same manner as described in Example 1. Table 3 shows the cracking rate of 12 the heavy hydrocarbon oil after 6 hours from the start of oil-flowing and the 13 cracking rate of the heavy hydrocarbon oil after 14 days from the start of 14 oil-flowing.
100461 [Table 3]
Comparative Example 4 Example 2 Cracking rate after 6 hours from 44.5 52.7 start of oil-flowing [mass%]
Cracking rate after 14 days from 33.2 50.5 start of oil-flowing [mass%[
17 10 0 4 71 It can be seen from Table 3 that there is not much difference 18 between the cracking rates after 6 hours and after 14 days from the start of 19 oil-flowing in Example 4, whereas in Comparative Example 2 a considerable drop is observed in the cracking rate after 14 days from the start of oil-21 flowing. Thus, it can be understood that the deterioration of the catalyst is 22 alleviated in Example 4.
100481 The present invention may provide a hydrocarbon oil cracking 26 catalyst that enables efficient production of lighter oil from hydrocarbon oil 27 at low cost, without performing proactive desulfurization and 22447577.1 CA Application Blakes Ref 10549/00002 1 denitrogenation of the feedstock hydrocarbon oil and without using high pressure hydrogen gas. The present invention may also provide a method 3 for cracking hydrocarbon oil using the hydrocarbon oil cracking catalyst.
22447577.1
Claims (6)
1. A hydrocarbon oil cracking catalyst used in cracking hydrocarbon oil in the presence of water, the catalyst comprising an oxide having a perovskite-type structure or an oxide having a pseudobrookite-type structure, or a mixture thereof.
2. The hydrocarbon oil cracking catalyst according to claim 1, wherein the oxide having a perovskite-type structure is represented by the following general formula:
A1-x A'x B1-y B' y O3-.delta. ..... (1) [where A is an element selected from the group consisting of a Group IA
element, a Group HA element, a Group IIIA element and a Group VIII
element, A' is at least one element selected from the group consisting of a Group VA element and a Group IIIB element, B is an element selected from the group consisting of a Group IIIB element and a Group IVA element, and B' is at least one element selected from the group consisting of a Group VA
element and a Group IIIB element. in which A, A', B and B' are different from one another, x is in the range of 0 <= x <= 0.4, y is in the range of 0 <= y <= 0.4, and .delta. represents oxygen deficiency].
A1-x A'x B1-y B' y O3-.delta. ..... (1) [where A is an element selected from the group consisting of a Group IA
element, a Group HA element, a Group IIIA element and a Group VIII
element, A' is at least one element selected from the group consisting of a Group VA element and a Group IIIB element, B is an element selected from the group consisting of a Group IIIB element and a Group IVA element, and B' is at least one element selected from the group consisting of a Group VA
element and a Group IIIB element. in which A, A', B and B' are different from one another, x is in the range of 0 <= x <= 0.4, y is in the range of 0 <= y <= 0.4, and .delta. represents oxygen deficiency].
3. The hydrocarbon oil cracking catalyst according to claim 2, wherein the A is nickel or cobalt, the B is titanium. and the B' is aluminum or vanadium.
4. The hydrocarbon oil cracking catalyst according to claim 2 or 3, wherein x = 0.
5. The hydrocarbon oil cracking catalyst according to any one of claims 1 to 4, wherein the oxide having a pseudobrookite-type structure is Fe2TiO5.
6. A method for cracking hydrocarbon oil, comprising bringing the hydrocarbon oil into contact with the hydrocarbon oil cracking catalyst according to any one of claims 1 to 5 in the presence of water to thereby crack the hydrocarbon oil.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-080439 | 2011-03-31 | ||
| JP2011080439A JP5687941B2 (en) | 2011-03-31 | 2011-03-31 | Hydrocarbon oil cracking catalyst and hydrocarbon oil cracking method |
| PCT/JP2012/001920 WO2012132318A1 (en) | 2011-03-31 | 2012-03-21 | Catalyst for decomposition of hydrocarbon oil and method for decomposing hydrocarbon oil |
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| CA2831537A1 true CA2831537A1 (en) | 2012-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2831537A Abandoned CA2831537A1 (en) | 2011-03-31 | 2012-03-21 | Catalyst for decomposition of hydrocarbon oil and method for decomposing hydrocarbon oil |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5687941B2 (en) |
| CA (1) | CA2831537A1 (en) |
| WO (1) | WO2012132318A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5434998B2 (en) * | 2011-09-15 | 2014-03-05 | トヨタ自動車株式会社 | Negative electrode active material, negative electrode and battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269464A (en) * | 1995-04-03 | 1996-10-15 | Japan Energy Corp | Catalytic cracking method for hydrocarbon oil |
| CA2281123A1 (en) * | 1998-09-03 | 2000-03-03 | Gaz De France | Thermally stable, highly active perovskite catalysts for complete oxidation at high temperatures, and the process for their preparation |
| JP4780273B2 (en) * | 2004-06-29 | 2011-09-28 | メタウォーター株式会社 | Method for producing catalyst for lightening heavy oil |
| JP5396008B2 (en) * | 2007-05-31 | 2014-01-22 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing alkylbenzenes |
| JP5196396B2 (en) * | 2007-10-22 | 2013-05-15 | Ｊｘ日鉱日石エネルギー株式会社 | Method for pyrolysis of heavy oil |
| JP5221997B2 (en) * | 2008-03-28 | 2013-06-26 | Ｊｘ日鉱日石エネルギー株式会社 | Decomposition method of hydrocarbon oil |
-
2011
- 2011-03-31 JP JP2011080439A patent/JP5687941B2/en active Active
-
2012
- 2012-03-21 WO PCT/JP2012/001920 patent/WO2012132318A1/en active Application Filing
- 2012-03-21 CA CA2831537A patent/CA2831537A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP5687941B2 (en) | 2015-03-25 |
| WO2012132318A1 (en) | 2012-10-04 |
| JP2012213706A (en) | 2012-11-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |
Effective date: 20170306 |
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| FZDE | Discontinued |
Effective date: 20190321 |