JP2021502243A - 流動接触分解(fcc)で使用する金属トラップ - Google Patents
流動接触分解(fcc)で使用する金属トラップ Download PDFInfo
- Publication number
- JP2021502243A JP2021502243A JP2020526027A JP2020526027A JP2021502243A JP 2021502243 A JP2021502243 A JP 2021502243A JP 2020526027 A JP2020526027 A JP 2020526027A JP 2020526027 A JP2020526027 A JP 2020526027A JP 2021502243 A JP2021502243 A JP 2021502243A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- organic acid
- fcc
- lanthanum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 238000005336 cracking Methods 0.000 title claims description 5
- 239000012530 fluid Substances 0.000 title description 2
- 239000004005 microsphere Substances 0.000 claims abstract description 76
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- -1 organic acid salts Chemical class 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims description 72
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 53
- 239000010457 zeolite Substances 0.000 claims description 43
- 229910021536 Zeolite Inorganic materials 0.000 claims description 40
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 39
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052720 vanadium Inorganic materials 0.000 claims description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000005995 Aluminium silicate Substances 0.000 claims description 19
- 235000012211 aluminium silicate Nutrition 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 150000007524 organic acids Chemical class 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 150000001447 alkali salts Chemical class 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 6
- UADULFIZHZKEOP-UHFFFAOYSA-K cerium(3+);triformate Chemical compound [Ce+3].[O-]C=O.[O-]C=O.[O-]C=O UADULFIZHZKEOP-UHFFFAOYSA-K 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 6
- PLOSEKHZRPLNLO-UHFFFAOYSA-K lanthanum(3+);triformate Chemical group [La+3].[O-]C=O.[O-]C=O.[O-]C=O PLOSEKHZRPLNLO-UHFFFAOYSA-K 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 8
- 159000000011 group IA salts Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 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 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 4
- 229960001633 lanthanum carbonate Drugs 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/635—0.5-1.0 ml/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- 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
- C10G2300/70—Catalyst aspects
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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Abstract
Description
2017年11月10日に出願されたアメリカ合衆国優先出願番号62/584244号は、明細書、図面、特許請求の範囲および要約を含み、その全体が参照により本明細書に組み込まれる。
一態様では、希土類元素の有機酸塩を含浸させた、事前に形成されたミクロスフェアを含む金属トラップが本明細書に開示される。
一態様では、希土類元素の有機酸塩を含浸させた、事前に形成されたミクロスフェアを含む金属トラップが提供される。金属トラップは、酸化物基準で、少なくとも約1重量%の希土類元素を含むことができる。これは、酸化物基準で、少なくとも約2重量%、少なくとも約5重量%、少なくとも約10重量%、少なくとも約15重量%、または少なくとも約20重量%の希土類元素を含み得る。これはまた、酸化物基準で、約1重量%〜約50重量%、約2重量%〜約25重量%、または約10重量%〜約20重量%の希土類元素を含み得る。
組成物を製造する方法に関して、活性ゼオライト成分は、2つの一般的な技術のうちの1つによって触媒のミクロスフェアに組み込むことができる。1つ目の技術では、ゼオライト成分は結晶化され、次いで別の工程でミクロスフェアに組み込まれる。2つ目の技術では、in−situ技術であり、ミクロスフェアが最初に形成され、次いでゼオライト成分をミクロスフェア自体で結晶化させて、ゼオライト成分および非ゼオライト成分の両方を含むミクロスフェアが提供される。
上記のFCC触媒および/または金属トラップはいずれも、金属を含有する炭化水素仕込み原料の接触分解に使用することができる。典型的な供給原料は、重質ガス油、または金属汚染物質が濃縮されている原油のより重質な留分である。
Claims (45)
- 希土類元素の有機酸塩を含浸させた、事前に形成されたミクロスフェアを含む金属トラップ。
- 前記事前に形成されたミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項1に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、か焼含水カオリンを含む、請求項2に記載の金属トラップ。
- 酸化物基準で、少なくとも1重量%の前記希土類元素を含む、請求項1〜3のいずれか一項に記載の金属トラップ。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項1〜4のいずれか一項に記載の金属トラップ。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項1〜5のいずれか一項に記載の金属トラップ。
- 前記有機酸塩が、ギ酸塩、酢酸塩、プロピオン酸塩、またはそれらの混合物である、請求項1〜6のいずれか一項に記載の金属トラップ。
- 前記有機酸塩が、ギ酸塩である、請求項7に記載の金属トラップ。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項7に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアを、前記希土類元素のアルカリ塩と有機酸との反応生成物と接触させることにより形成される、請求項1〜9のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、約40〜150ミクロンの粒子サイズを有する、請求項1〜10のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、約60〜100ミクロンの粒子サイズを有する、請求項1〜10のいずれか一項に記載の金属トラップ。
- 前記事前に形成されたミクロスフェアが、少なくとも約0.10cm3/グラムの細孔容積を有する、請求項1〜12のいずれか一項に記載の金属トラップ。
- 流動接触分解(FCC)触媒組成物であって、
第1のミクロスフェアを含むゼオライト成分と、
前記第1のミクロスフェアとは別に、希土類元素の有機酸塩を含浸させた、事前に形成された第2のミクロスフェアを含む非ゼオライト成分と、を含む、FCC触媒組成物。 - 前記事前に形成された第2のミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項14に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項14または15に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項14〜16のいずれか一項に記載のFCC触媒組成物。
- 前記有機酸塩が、ギ酸塩、酢酸塩、またはプロピオン酸塩、またはそれらの任意の2つ以上の混合物である、請求項14〜17のいずれか一項に記載のFCC組成物。
- 前記有機酸塩が、ギ酸塩である、請求項18に記載のFCC組成物。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項18に記載のFCC組成物。
- 前記希土類元素が、酸化物基準で、0.1重量%〜約20.0重量%の範囲で存在する、請求項14〜20のいずれか一項に記載のFCC触媒組成物。
- 金属トラップを調製する方法であって、事前に形成された第2のミクロスフェアを、希土類元素の有機酸塩と接触させることを含む、方法。
- 事前に形成された第2のミクロスフェアを希土類元素の前記有機酸塩との前記接触が、コーティング、噴霧乾燥、および含浸からなる群から選択される、請求項22に記載の方法。
- 前記希土類元素の前記有機酸塩が、前記有機酸を含む水性媒体中に含まれている、請求項22に記載の方法。
- 前記希土類元素のアルカリ塩を前記有機酸と反応させることにより、前記希土類元素の前記有機塩を調製することをさらに含む、請求項22〜24のいずれか一項に記載の方法。
- 前記希土類元素の前記アルカリ塩が、炭酸塩である、請求項25に記載の方法。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項22〜26のいずれか一項に記載の方法。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項27に記載の方法。
- 前記有機酸が、ギ酸、酢酸、プロピオン酸、またはそれらの任意の2つ以上の混合物である、請求項25に記載の方法。
- 前記有機酸が、ギ酸である、請求項29に記載の方法。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項29に記載の方法。
- 請求項14に記載のFCC触媒組成物を調製する方法であって、前記ゼオライト成分および前記非ゼオライト成分を配合することを含む、方法。
- 前記ゼオライト成分が、
非ゼオライト材料およびアルミナを含む、前駆体の第1のミクロスフェアを事前に形成することと、
前記事前に形成された第1のミクロスフェア上でゼオライトをその場で結晶化して前記ゼオライト成分を提供することと、を含む方法によって調製される、請求項32に記載の方法。 - 流動接触分解条件下で炭化水素供給物を分解する方法であって、前記炭化水素供給物を請求項14に記載のFCC触媒組成物と接触させることを含む、方法。
- FCCユニット床中の炭化水素油供給物由来の少なくとも1つの金属汚染物質を、不動態化および/または捕捉する方法であって、前記炭化水素油供給物を請求項14に記載のFCC触媒組成物と接触させることを含む、方法。
- 前記少なくとも1つの金属汚染物質が、バナジウムである、請求項34に記載の方法。
- 流動接触分解(FCC)触媒組成物であって、
第1のミクロスフェアを含む非分解成分と、
前記第1のミクロスフェアとは別に、希土類元素の有機酸塩を含浸させた、事前に形成された第2のミクロスフェアを含む非ゼオライト成分と、を含む、FCC触媒組成物。 - 前記事前に形成された第2のミクロスフェアが、カオリナイト、モンモリロナイト、ベントナイト、アタパルジャイト、カオリン、アモルファスカオリン、メタカオリン、ムライト、スピネル、含水カオリン、か焼含水カオリン、粘土、またはそれらの任意の2つ以上の混合物を含む、請求項37に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、イッテルビウム、ガドリニウム、イットリウム、ネオジム、またはそれらの任意の2つ以上の混合物である、請求項37または38に記載のFCC触媒組成物。
- 前記希土類元素が、ランタン、セリウム、またはそれらの混合物である、請求項37〜39のいずれか一項に記載のFCC触媒組成物。
- 前記有機酸塩が、ギ酸塩、酢酸塩、またはプロピオン酸塩、またはそれらの任意の2つ以上の混合物である、請求項37〜40のいずれか一項に記載のFCC組成物。
- 前記有機酸塩が、ギ酸塩である、請求項41に記載のFCC組成物。
- 前記希土類元素の前記有機酸塩が、ギ酸ランタン、酢酸ランタン、ギ酸セリウム、酢酸セリウム、またはそれらの任意の2つ以上の混合物である、請求項41に記載のFCC組成物。
- 前記希土類元素が、酸化物基準で、0.1重量%〜約20.0重量%の範囲で存在する、請求項37〜43のいずれか一項に記載のFCC触媒組成物。
- 請求項37に記載のFCC触媒組成物を調製する方法であって、前記非分解成分および前記非ゼオライト成分を配合することを含む、方法。
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PCT/US2018/059845 WO2019094603A1 (en) | 2017-11-10 | 2018-11-08 | A metal trap for use in fluid catalytic cracking (fcc) |
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