EP3277778A1 - Fluid catalytic cracking catalyst additive composition and process for preparation thereof - Google Patents
Fluid catalytic cracking catalyst additive composition and process for preparation thereofInfo
- Publication number
- EP3277778A1 EP3277778A1 EP15887376.0A EP15887376A EP3277778A1 EP 3277778 A1 EP3277778 A1 EP 3277778A1 EP 15887376 A EP15887376 A EP 15887376A EP 3277778 A1 EP3277778 A1 EP 3277778A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- group
- zeolite
- total weight
- promoter
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 239000000654 additive Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 27
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000546 pharmaceutical excipient Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010603 pastilles Nutrition 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229940048084 pyrophosphate Drugs 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 5
- 239000002184 metal Substances 0.000 claims 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 229910021478 group 5 element Inorganic materials 0.000 abstract description 13
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- -1 flakes Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/40—
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
Definitions
- the present disclosure relates to a fluid catalytic cracking (FCC) catalyst additive composition and its process of preparation.
- FCC fluid catalytic cracking
- Fluid Catalytic Cracking is a process which employs specialized catalysts known as FCC catalysts to facilitate the catalytic cracking of heavy hydrocarbon feedstock, such as vacuum gas oil, to lighter products, such as naphtha and other distillate range fractions.
- One of the significant objectives of carrying out the afore-stated cracking process is to convert the left-over heavy fraction obtained during the derivatization of crude oil into low molecular weight beneficial chemicals such as propylene, light cycle oil, liquefied petroleum gas, gasoline, olefinic gases and the like. After isolation, these products are recycled in the industry; which not only makes the industrial processes economical but also satisfies the ever increasing demand of the afore-stated chemicals.
- zeolites are used as FCC catalysts.
- Zeolites that are used in the FCC units are typically crystalline alumino- silicates which have a uniform crystal structure characterized by a large number of regular microlevel cavities interconnected by a large number of smaller channels.
- These catalysts act as molecular sieves resulting in selective absorption of molecules having sizes below a defined value and rejection of molecules of larger sizes.
- a sastisfactory yield of the desirable products is not achieved.
- there is felt need for developing a catalyst system that is capable of achieving optimum benefits of the FCC process.
- An object of the present disclosure is to provide a fluid catalytic cracking (FCC) catalyst additive composition.
- Another object of the present disclosure is to provide a FCC catalyst additive composition having a wide spectrum of industrial applicability.
- Another object of the present disclosure is to provide a process for the preparation of the FCC catalyst additive composition.
- the present disclosure provides a fluid catalytic cracking (FCC) catalyst additive composition
- FCC fluid catalytic cracking
- zeolite in an amount ranging from 30 to 50% of the total weight of the composition
- Group V element in an amount ranging from 0.1 to 5 % of the total weight of the zeolite
- promoter in an amount ranging from 1 to 3 % of the total weight of the zeolite and optionally, at least one excipient in an amount ranging from 50 to 70% of the total weight of the composition.
- the Group V element is phosphorus.
- the promoter is at least one element selected from the group consisting of magnesium, calcium, strontium, barium, copper, iron, nickel, zinc, gallium, indium, thallium and the lanthanide series.
- the present disclosure further provides a process for the preparation of the FCC catalyst additive comprising admixing at least one pre-dried zeolite with at least one promoter precursor and at least one Group V element precursor to obtain a slurry; agitating said slurry for a time period ranging from 2 to 4 hours to form a thick slurry; heating said thick slurry at a temperature ranging from 50 to 100 °C under vacuum to obtain a dried mass; calcining said dried mass at a temperature ranging from 500 °C to 750 °C at a time period ranging from 4 to 6 hours to obtain a calcined mass; grinding said calcined mass to obtain a ground mass and processing said ground mass to obtain the FCC catalyst additive composition.
- the present disclosure provides an FCC catalyst additive composition consisting of at least one zeolite, at least one Group V element, at least one promoter and optionally at least one excipient.
- the zeolite which is the center of the catalytic activity, is included in the composition in an amount ranging from 30 to 50% of the total weight of the composition.
- the zeolite is at least one selected from the group consisting of ZSM-5, ZSM-11, ZSM- 12, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-44, MCM-22, an intergrowth of ZSM-11, zeolite Y and Beta.
- the zeolite is ZSM-5 with silica to alumina (S1O2/A2O 3 ) molar ratio of 23.
- the Group V element is phosphorus and is included in the composition in an amount ranging from 0.1 to 5 % of the total weight of the zeolite.
- the afore-stated range has been obtained on the basis of optimization data.
- the Group V elements are included in the composition to boost the catalytic activity.
- inclusion of the Group V element in the composition in the afore-stated quantity aids in effecting passivation of the highly active acid sites which in turn results in lower crackability, lesser production of dry gas and increase in the liquid yield.
- the promoter like the Group V element, enhances the catalytic activity and performance of the zeolite.
- the promoter included in the composition of the present disclosure is at least one element selected from the group consisting of magnesium, calcium, strontium, barium, copper, iron, nickel, zinc, gallium, indium, thallium and the lanthanide series and is included in the composition in an amount ranging from 1 to 3 % of the total weight of the zeolite.
- the promoter when included in the afore-stated range, modifies the acidity of the active sites and provides stability.
- the promoter is at least one selected from the group consisting of magnesium, calcium, strontium and barium.
- the promoter is a combination of zinc and gallium.
- the composition optionally, includes at least one excipient in an amount ranging from 50 to 70% of the total weight of the composition.
- the excipient is at least one selected from the group consisting of binder, filler and matrix.
- the binder is pseudoboehmite. Pseudoboehmite functions both as a binder and as matrix.
- the filler is alpha alumina.
- the present disclosure provides a process for the preparation of the FCC catalyst additive composition. Initially, at least one zeolite, in a pre-determined amount, is admixed with a pre-determined amount of at least one Group V element precursor and a pre-determined amount of at least one promoter precursor to obtain slurry.
- the zeolite is pre-dried.
- the Group V element precursor is selected from the group consisting of phosphoric acid, phosphates, phosphorous acid, phosphites, pyrophosphoric acid, pyrophosphate, polymeric phosphoric acid, polyphosphates, metaphosphoric acid and metaphosphates.
- the promoter precursor is selected from the group consisting of a chloride of the promoter, a fluoride of the promoter, a bromide of the promoter, an oxalate of the promoter, sulfate of the promoter, acetate of the promoter, a carbonate of the promoter and an oxide of the promoter.
- the promoter precursor is a nitrate of the promoter.
- the promoter precursor is admixed in pre-determined quantity of water before it is admixed with the Group V element and the zeolite.
- At least one excipient is also admixed to form the slurry.
- the addition of the excipient is accompanied by stirring for a time period ranging from 2 to 4 hours and is optionally followed by admixing aqueous nitric acid having concentration ranging from 40 to 60 % to adjust the pH.
- the resulting slurry is agitated for a time period ranging from 2 to 4 hours at an agitation speed of 1 to 250 rpm to form a thick slurry.
- the thick slurry is heated at a temperature ranging from 50 to 100 °C under vacuum to obtain a dried mass.
- the dried mass is calcined at a temperature ranging from 500 °C to 750 °C at a time period ranging from 4 to 6 hours to obtain a calcined mass.
- the calcined mass is ground to obtain a ground mass and the ground mass is further processed to obtain the FCC catalyst additive composition.
- the step of processing is at least one selected from the group that includes but is not limited to pelletizing, pastilling, extruding, granulating and spray drying.
- the resulting composition is in at least one form selected from the group that includes but is not limited to extrudates, pellets, pastilles, beads, flakes, granules and powder.
- the composition is in the form of a spray dried powder.
- the afore-stated ingredients are admixed in pre-determined quantities so as to have the eventual composition comprise at least one zeolite in an amount ranging from 30 to 50% of the total weight of the composition; at least one Group V element in an amount ranging from 0.1 to 5 % of the total weight of the zeolite; at least one promoter in an amount ranging from 1 to 3 % of the total weight of the zeolite and optionally, at least one excipient in an amount ranging from 50 to 70% of the total weight of the composition.
- Examples 2 - 10 As in Example 1 , catalyst additives were prepared containing different promoters such as calcium, strontium, barium, nickel, iron, copper, lanthanum and cerium.
- promoters such as calcium, strontium, barium, nickel, iron, copper, lanthanum and cerium.
- extrudates were also prepared using strontium nitrate as the precursor.
- the metal nitrates were dissolved in water independently and then admixed together to form a promoter pool; the resulting additive composition is in the form of granules of average size 700 microns and contains 40% zeolite and 60% pseudoboehmite
- the catalyst additive of the present disclosure has a wide spectrum of applications in various fields such as polymer, metallurgy and petrochemicals.
Abstract
Description
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PCT/IB2015/055542 WO2016156938A1 (en) | 2015-03-31 | 2015-07-22 | Fluid catalytic cracking catalyst additive composition and process for preparation thereof |
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US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
US8137534B2 (en) * | 2009-04-23 | 2012-03-20 | Uop Llc | Catalyst compositions for improved fluid catalytic cracking (FCC) processes targeting propylene production |
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