WO2024069636A1 - A catalyst composition for catalytic cracking of paraffin rich feed into light olefins - Google Patents
A catalyst composition for catalytic cracking of paraffin rich feed into light olefins Download PDFInfo
- Publication number
- WO2024069636A1 WO2024069636A1 PCT/IN2022/051152 IN2022051152W WO2024069636A1 WO 2024069636 A1 WO2024069636 A1 WO 2024069636A1 IN 2022051152 W IN2022051152 W IN 2022051152W WO 2024069636 A1 WO2024069636 A1 WO 2024069636A1
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- WIPO (PCT)
- Prior art keywords
- zeolite
- zsm
- catalyst
- composition
- beta zeolite
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 24
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 18
- 238000004523 catalytic cracking Methods 0.000 title description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 119
- 238000005336 cracking Methods 0.000 claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 98
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 86
- 239000002002 slurry Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 19
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical group 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- RGROXIVYLKOHIY-UHFFFAOYSA-J dimagnesium;hydrogen phosphate Chemical compound [Mg+2].[Mg+2].OP([O-])([O-])=O.OP([O-])([O-])=O RGROXIVYLKOHIY-UHFFFAOYSA-J 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 239000003502 gasoline Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000007233 catalytic pyrolysis Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229940085991 phosphate ion Drugs 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- -1 ethylene, propylene Chemical group 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
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004227 thermal cracking Methods 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
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5 and beta zeolites. Specifically, the present invention relates to usage of the catalyst composition for cracking paraffin rich feed having boiling point in the range of 150-350°C to light olefins, gasoline products.
- AE alkaline earth
- kerosene fraction which is a paraffin rich feed. Part of this fraction is refined into Aviation Turbine Fuel (ATF) and the excess kerosene is blended into diesel stream.
- ATF Aviation Turbine Fuel
- kerosene is not fully absorbed into diesel stream.
- kerosene is also used as a fuel for heating and cooking. But when burning kerosene, it usually produces considerable smoke and an unpleasant odor. The smoke and odor not only reduce the heat efficiency but also pollute the air. Due to availability of more clean fuels the demand for kerosene is decreasing day by day. Accordingly, it is observed that the kerosene needs to be converted into more valuable products such as light olefins and gasoline.
- the catalytic cracking is employed to convert the heavier hydro feed into light olefins and gasoline.
- Catalytic cracking is a conversion process that can be applied to a variety of feedstocks ranging from gas oil to heavy crude oil and residue.
- the concept of catalytic cracking is basically the same as thermal cracking, but it differs by the use of a catalyst that is not consumed in the process, and it is one of several practical applications used in a refinery that employs a catalyst to improve process efficiency and product state.
- Catalytic cracking in the usual commercial process involves contacting a feedstock (usually a gas oil fraction) with a catalyst under suitable conditions of temperature, pressure, and residence time. By this means, a substantial part (>50%) of the feedstock is converted into gasoline and lower boiling products, usually in a single-pass operation.
- US20220081624 relates to methods for upgrading a hydrocarbon feed, the method includes introducing the hydrocarbon feed to a separation unit, where the separation unit separates the hydrocarbon feed to produce at least a greater boiling point effluent and a lesser boiling point effluent, and the greater boiling point effluent has an American Petroleum Institute gravity less than 30 degrees. Then passing the greater boiling point effluent to a first downflow fluid catalytic cracking unit downstream of the separation unit, where the first downflow fluid catalytic cracking unit contacts the greater boiling point effluent with a multicomponent catalyst.
- the contact results at least a portion of the greater boiling point effluent to undergo catalytic cracking and produce a first spent multicomponent catalyst and a first cracked effluent having one or more olefins.
- the multicomponent catalyst includes from 0 weight percent to 10 weight percent ZSM-5, from 10 weight percent to 40 weight percent zeolite Beta, and from 10 weight percent to 30 weight percent USY zeolite based on the total weight of the multicomponent catalyst, and where one or more transition metals are substituted into the framework of the USY zeolite.
- CN102019200B discloses a high-activity catalytic pyrolysis catalyst and a preparation method thereof, which is characterized in that: the catalytic pyrolysis catalyst is a solid composition which is formed by high-activity phosphorus modified ZSM-5 zeolite, high-activity rare earth modified Y zeolite, an alumina-based bonder, nickel tetracarbonyl vapor deposition modified porous silicide and filler clay, is in multiple pore diameter distribution and has different types of catalytic active centers; the catalytic pyrolysis catalyst has another important characteristic: the pore capacity provided by the mesoporous ZSM-5 zeolite in the catalytic pyrolysis catalyst should be approximately equal to the pore capacity provided by the macroporous Y zeolite, that is to say, the ratio is in a range of 0.9-1.1.
- the total amount of the zeolite is 30-60% of the total amount of the solid composition by weight; the alumina-based bonder formed by acidified pseudoboehmite and/or alumina sol is 5-30% of the total amount by weight; the porous silicide which is 0.01-0.5% of the nickel tetracarbonyl vapor deposition nickeliferous oxide by weight is 1-20% of the total amount by weight; and the balance is the filler clay.
- the slurry of the solid composition is spray-dried to form the microsphere catalytic pyrolysis catalyst which has extraordinarily high activity and selectivity when being used in a catalytic pyrolysis device and can effectively transform the heavy feeding and improve the yield of the low-carbon olefins such as ethylene, propylene and the like.
- US20220001362A1 discloses a fluid catalytic cracking catalyst composition (FCC catalyst composition) which includes a framework- substituted ultra-stable Y-type zeolite (USY zeolite) having one or more transition metals substituted into the framework of a USY zeolite and a FCC zeolite cracking additive.
- a method for upgrading a hydrocarbon feed includes contacting the hydrocarbon feed with the FCC catalyst composition of the present disclosure at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed.
- a method for upgrading a hydrocarbon feed includes passing the hydrocarbon feed to a fluid catalytic cracking unit, contacting the hydrocarbon feed with a FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracking reaction mixture comprising a used FCC catalyst composition and a cracked effluent comprising one or more olefins.
- KR101566185B1 discloses that gasoline and diesel oil are obtained in high yields, and at the same time provides a bottom-catalytic cracking, low-coke yield hydrocarbon catalytic cracking catalyst.
- the present invention relates to a catalyst composition
- a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites. Further, the catalyst composition is utilized for cracking kerosene molecule into light olefins and gasoline.
- the present invention provides a catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-30 wt.% of an ultra-stabilized Y-zeolite, (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
- AE alkaline earth
- the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
- the ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 2-3.5 wt.%.
- the alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
- the filler is clay, the binder is alumina and the beta zeolite have silicon to alumina ratio in a range of 30-50.
- the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline- earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite.
- AE alkaline- earth metal
- a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5- 30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
- the catalyst composition provides cracking of kerosene into valuable products like gasoline about >50%, liquefied petroleum gas (LPG) about >25% with higher C3+C4 olefin selectivity in LPG (>70%).
- LPG liquefied petroleum gas
- Pre-phosphate modification of ZSM-5 and combination with Beta zeolite stabilizes the zeolites framework as shape selective functionality to develop a composite catalyst.
- It is a primary objective of the present invention to provide a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites.
- the present invention relates to a catalyst composition
- a catalyst composition comprising: (a) 5-30 wt.% of an ultrastabilized Y-zeolite; (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5 zeolite and beta zeolite; (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
- AE alkaline earth
- the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
- AE alkaline earth
- the ultra-stabilized Y-zeolite is selected from rare earth exchanged USY (RE-USY) with RE content 1-3.5 wt.%.
- the alkaline earth (AE) metal ion modified phosphated ZSM-5/ Beta zeolites is selected from Mono Magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, Tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
- the silicon to alumina ratio of the ZSM-5 & beta zeolite is selected from 25-50.
- the filler is clay
- the binder is alumina
- the catalyst composition is utilized for cracking kerosene to light olefins.
- the process comprises cracking kerosene molecule with boiling range of 200-350°C in a temperature range of 540-650°C to convert into valuable products.
- the pre-phosphate modification of ZSM-5 stabilizes and combines with beta zeolite as shape selective functionality to develop a catalyst composition.
- the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite.
- AE alkaline-earth metal
- a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
- Preparing the modified magnesium hydrogen phosphate includes dissolving 256 g of magnesium nitrate hexahydrate with 800 g of demineralized water to get a solution. Adding 196 g of orthophosphoric acid to the solution, then adding 300 g of ammonium hydroxide under stirring at 30°C to obtain white precipitates. Filtering the white precipitates, washing the white precipitates with hot DM water for three times to remove excess ammonium, and drying the white precipitates.
- Preparing the alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite includes mixing 500 g of ZSM-5 zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Then filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Finally, drying the wet cake at 120°C for 10 hours and calcinating at 700°C for 3 hours.
- AE alkaline-earth metal
- Preparing the alkaline-earth metal (AE) ion modified phosphated Beta zeolite includes mixing 500 g of Beta zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Drying the wet cake at 120oC for 10 hours and calcinating at 700°C for 3 hours.
- AE alkaline-earth metal
- Preparing the ZSM-5/Beta zeolite composite catalyst includes mixing 85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium poly silicate and 69 g of alumina to prepare a uniform slurry, milling the uniform slurry with the help of a wet ball for 5 hours to get a milled slurry. Then mixing the milled slurry with 316 g of AE ion modified phosphated ZSM-5 zeolite and 112 g of AE ion modified phosphated Beta zeolite to produce a final slurry.
- spherical catalyst microspheres After spray drying the final slurry in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C to form spherical catalyst microspheres. Calcinating the spherical catalyst microspheres at 590°C for 4 hours to form a final composite ZSM-5/Beta zeolite catalyst.
- the spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
- the present invention also provides a process for cracking paraffin rich feed such as kerosene, naphtha, or VGO into light olefins by using the catalyst composition as discloses herein, wherein the process includes cracking paraffin rich feed with boiling range of 200-350°C in a temperature range of 540-650°C and maintaining the pressure in a range of 1.5-5 bar.
- alkaline earth metal ion based hydrogen phosphate salts were prepared with different AE/P ratios.
- the prepared phosphate salts were impregnated on the surface of zeolites and calcined at 500-700°C to establish the formation of stable Al-O-P with AE ion without affecting crystallinity of the zeolites.
- These P-modified zeolites were incorporated into the catalyst formulation with different composition along with binder, matrix components for shaping the catalyst to make microsphere of final catalyst.
- the final catalyst was calcined at temperature above 500°C and subjected for testing for cracking of kerosene.
- Example-2 Preparation of AE ion modified phosphated zeolites:
- 500 g of ZSM-5 (CBV-3024, Zeolyst) zeolite was mixed with above magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.%.
- 5000 g of DM water was added to the prepared zeolite mixer to get a zeolite slurry.
- the zeolite slurry was mixed and heated at 70°C for 3 hours. After 3 hours, zeolite slurry was filtered and washed with DM water for 2 times and a wet cake was obtained. The wet cake was dried at 120°C for 10 hours and calcined at 700°C for 3 hours.
- 500 g of beta zeolite CP814C, Zeolyst
- was treated with magnesium hydrogen phosphate was dried and calcined at 700°C for 3hours.
- Example -3 Preparation of ZSM-5/beta zeolite composite catalyst
- Example-4 Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification:
- 121 g of ortho-phosphoric acid, 411 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours.
- the milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry.
- the slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit.
- the spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
- Example-5 Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification with promoter:
- 121 g of ortho-phosphoric acid, 191 g of magnesium nitrate, 376 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours.
- the milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry.
- the slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit.
- the spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
- UOPK factor which signifies cracking potential of Kerosene stream
- VGO vacuum gas oil
- UOPK 11.44
- catalytic cracking experiments were carried out with Kerosene as feed in ACE R+MM unit using FCC E-CAT and in combination of ZSM-5 additive.
- Table 2 provides the list of the results of these experiments.
- the product yields from kerosene and VGO were compared and in presence of ZSM-5 additive kerosene molecules undergoes alkylation and form LCO range products.
- CLO from kerosene cracking the developed ZSM-5/beta zeolites composite catalyst was studied. During cracking of kero feedstock molecules, the molecules undergoes dimerization reaction, produces heavier molecules and increasing yield of LCO and CLO.
- Example 7 Catalyst composition with phosphate modification prepared from Example-3
- Table 3 discloses that the catalyst composition with phosphate modification provides higher C2- C4 olefins, lower LCO & CLO and higher conversion.
- the composite catalyst was evaluated at 600 and 630°C in different Cat/oil ratio. It was observed from the results, the modified catalyst composition provides higher conversion with minimum LCO and nil CLO.
- Example 8 Catalyst composition as prepared from Example-4 & 5 Table 4 discloses that the catalyst composition with no prephosphate modification of zeolites provides lower C2-C4 olefins.
- Catalyst composition with phosphate modification provides higher conversion rate with minimum LCO and nil CLO.
Abstract
The present invention discloses a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5/ Beta zeolites. Further, the catalyst composition is utilized for cracking paraffin rich feed into light olefins, wherein, the paraffin rich feed is selected from a kerosene, naphtha, or VGO.
Description
A CATALYST COMPOSITION FOR CATALYTIC CRACKING OF PARAFFIN RICH FEED INTO LIGHT OLEFINS
FIELD OF THE INVENTION:
The present invention relates to a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5 and beta zeolites. Specifically, the present invention relates to usage of the catalyst composition for cracking paraffin rich feed having boiling point in the range of 150-350°C to light olefins, gasoline products.
BACKGROUND OF THE INVENTION:
In a crude oil, 180-300°C fraction is considered as kerosene fraction which is a paraffin rich feed. Part of this fraction is refined into Aviation Turbine Fuel (ATF) and the excess kerosene is blended into diesel stream. With expected reducing demand in kerosene and other fossil fuels, kerosene is not fully absorbed into diesel stream. Further, it is well known that kerosene is also used as a fuel for heating and cooking. But when burning kerosene, it usually produces considerable smoke and an unpleasant odor. The smoke and odor not only reduce the heat efficiency but also pollute the air. Due to availability of more clean fuels the demand for kerosene is decreasing day by day. Accordingly, it is observed that the kerosene needs to be converted into more valuable products such as light olefins and gasoline. Generally, the catalytic cracking is employed to convert the heavier hydro feed into light olefins and gasoline.
Catalytic cracking is a conversion process that can be applied to a variety of feedstocks ranging from gas oil to heavy crude oil and residue. The concept of catalytic cracking is basically the same as thermal cracking, but it differs by the use of a catalyst that is not consumed in the process, and it is one of several practical applications used in a refinery that employs a catalyst to improve process efficiency and product state. Catalytic cracking in the usual commercial process involves contacting a feedstock (usually a gas oil fraction) with a catalyst under suitable conditions of temperature, pressure, and residence time. By this means, a substantial part (>50%) of the feedstock is converted into gasoline and lower boiling products, usually in a single-pass operation. Below are some of the prior know documents which discloses the catalytic conversion of different type of hydrocarbon feeds into more valuable and lighter hydrocarbon products.
US20220081624 relates to methods for upgrading a hydrocarbon feed, the method includes introducing the hydrocarbon feed to a separation unit, where the separation unit separates the hydrocarbon feed to produce at least a greater boiling point effluent and a lesser boiling point effluent, and the greater boiling point effluent has an American Petroleum Institute gravity less than 30 degrees. Then passing the greater boiling point effluent to a first downflow fluid catalytic cracking unit downstream of the separation unit, where the first downflow fluid catalytic cracking unit contacts the greater boiling point effluent with a multicomponent catalyst. The contact results at least a portion of the greater boiling point effluent to undergo catalytic cracking and produce a first spent multicomponent catalyst and a first cracked effluent having one or more olefins. Wherein, the multicomponent catalyst includes from 0 weight percent to 10 weight percent ZSM-5, from 10 weight percent to 40 weight percent zeolite Beta, and from 10 weight percent to 30 weight percent USY zeolite based on the total weight of the multicomponent catalyst, and where one or more transition metals are substituted into the framework of the USY zeolite.
CN102019200B discloses a high-activity catalytic pyrolysis catalyst and a preparation method thereof, which is characterized in that: the catalytic pyrolysis catalyst is a solid composition which is formed by high-activity phosphorus modified ZSM-5 zeolite, high-activity rare earth modified Y zeolite, an alumina-based bonder, nickel tetracarbonyl vapor deposition modified porous silicide and filler clay, is in multiple pore diameter distribution and has different types of catalytic active centers; the catalytic pyrolysis catalyst has another important characteristic: the pore capacity provided by the mesoporous ZSM-5 zeolite in the catalytic pyrolysis catalyst should be approximately equal to the pore capacity provided by the macroporous Y zeolite, that is to say, the ratio is in a range of 0.9-1.1. The total amount of the zeolite is 30-60% of the total amount of the solid composition by weight; the alumina-based bonder formed by acidified pseudoboehmite and/or alumina sol is 5-30% of the total amount by weight; the porous silicide which is 0.01-0.5% of the nickel tetracarbonyl vapor deposition nickeliferous oxide by weight is 1-20% of the total amount by weight; and the balance is the filler clay. The slurry of the solid composition is spray-dried to form the microsphere catalytic pyrolysis catalyst which has extraordinarily high activity and selectivity when being used in a catalytic pyrolysis device and
can effectively transform the heavy feeding and improve the yield of the low-carbon olefins such as ethylene, propylene and the like.
US20220001362A1 discloses a fluid catalytic cracking catalyst composition (FCC catalyst composition) which includes a framework- substituted ultra-stable Y-type zeolite (USY zeolite) having one or more transition metals substituted into the framework of a USY zeolite and a FCC zeolite cracking additive. A method for upgrading a hydrocarbon feed includes contacting the hydrocarbon feed with the FCC catalyst composition of the present disclosure at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed. A method for upgrading a hydrocarbon feed includes passing the hydrocarbon feed to a fluid catalytic cracking unit, contacting the hydrocarbon feed with a FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracking reaction mixture comprising a used FCC catalyst composition and a cracked effluent comprising one or more olefins.
KR101566185B1 discloses that gasoline and diesel oil are obtained in high yields, and at the same time provides a bottom-catalytic cracking, low-coke yield hydrocarbon catalytic cracking catalyst. A zeolite and a binder, and a catalyst composition B containing aluminum compound, a binder of 10 to 30% by weight of a catalyst composition A and zeolite, and a binder containing silica-based binder of 10 to 30% by weight of the weight of the catalyst composition by A W A, catalyst and the mass ratio (W A : W B ) of the composition B was set to W B in the range of 10:90 to 90: 10.
The above disclosed prior art documents provide catalytic process and catalyst to crack the different types of hydrocarbon feeds into lighter hydrocarbons. However, the prior art document does not disclose converting the paraffin rich feed such as kerosene, naphtha, or VGO into more valuable products like light olefins and gasoline. Further, the prior art does not provide any disclosure related to the catalyst which can be utilized to convert the kerosene into more valuable products. Accordingly, there is a need for a catalyst and a process for converting the kerosene into more valuable products such as light olefins, or gasoline products.
SUMMARY OF THE PRESENT INVENTION:
The present invention relates to a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites. Further, the catalyst composition is utilized for cracking kerosene molecule into light olefins and gasoline.
Specifically, the present invention provides a catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-30 wt.% of an ultra-stabilized Y-zeolite, (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
Specifically, the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder. The ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 2-3.5 wt.%. The alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate. The filler is clay, the binder is alumina and the beta zeolite have silicon to alumina ratio in a range of 30-50.
Further, the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline- earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite. Then preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5-
30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
TECHNICAL ADVANTAGES OF THE INVENTION:
The present invention has the following advantages over the cited prior arts:
(i) The catalyst composition provides cracking of kerosene into valuable products like gasoline about >50%, liquefied petroleum gas (LPG) about >25% with higher C3+C4 olefin selectivity in LPG (>70%).
(ii) It provides more than 90% conversion of kerosene during the cracking process.
(iii) It provides very low light cycle oil (LCO) and less than 1% heavier products of hydrocarbon with boiling point above 540°C.
(iv) Pre-phosphate modification of ZSM-5 and combination with Beta zeolite stabilizes the zeolites framework as shape selective functionality to develop a composite catalyst.
OBJECTIVES OF THE PRESENT INVENTION:
It is a primary objective of the present invention to provide a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites.
It is a further objective of the present invention to provide a catalyst composition for cracking kerosene molecule into light olefins and gasoline.
It is a further objective of the present invention to provide a process for preparation of the catalyst composition.
DESCRIPTION OF THE INVENTION:
Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such components of the composition, features of composition, referred to or indicated in this
specification, individually or collectively and any and all combinations of any or more of such components or features.
Definitions
For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have their meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.
The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as “consists of only”.
Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.
The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.
The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally equivalent products and processes are clearly within the scope of the disclosure, as described herein.
The present invention relates to a catalyst composition comprising: (a) 5-30 wt.% of an ultrastabilized Y-zeolite; (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5 zeolite and beta zeolite; (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
Specifically, the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
In yet another embodiment, the ultra-stabilized Y-zeolite is selected from rare earth exchanged USY (RE-USY) with RE content 1-3.5 wt.%.
In another embodiment, the alkaline earth (AE) metal ion modified phosphated ZSM-5/ Beta zeolites is selected from Mono Magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, Tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
In another embodiment, the silicon to alumina ratio of the ZSM-5 & beta zeolite is selected from 25-50.
In another embodiment, the filler is clay, and the binder is alumina.
In yet another embodiment, the catalyst composition is utilized for cracking kerosene to light olefins. The process comprises cracking kerosene molecule with boiling range of 200-350°C in a temperature range of 540-650°C to convert into valuable products. Further, the pre-phosphate
modification of ZSM-5 stabilizes and combines with beta zeolite as shape selective functionality to develop a catalyst composition.
In yet another embodiment, the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite. Then preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
Preparing the modified magnesium hydrogen phosphate includes dissolving 256 g of magnesium nitrate hexahydrate with 800 g of demineralized water to get a solution. Adding 196 g of orthophosphoric acid to the solution, then adding 300 g of ammonium hydroxide under stirring at 30°C to obtain white precipitates. Filtering the white precipitates, washing the white precipitates with hot DM water for three times to remove excess ammonium, and drying the white precipitates.
Preparing the alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite includes mixing 500 g of ZSM-5 zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Then filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Finally, drying the wet cake at 120°C for 10 hours and calcinating at 700°C for 3 hours.
Preparing the alkaline-earth metal (AE) ion modified phosphated Beta zeolite includes mixing 500 g of Beta zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Drying the wet cake at 120oC for 10 hours and calcinating at 700°C for 3 hours.
Preparing the ZSM-5/Beta zeolite composite catalyst includes mixing 85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium poly silicate and 69 g of alumina to prepare a uniform slurry, milling the uniform slurry with the help of a wet ball for 5 hours to get a milled slurry. Then mixing the milled slurry with 316 g of AE ion modified phosphated ZSM-5 zeolite and 112 g of AE ion modified phosphated Beta zeolite to produce a final slurry. Then spray drying the final slurry in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C to form spherical catalyst microspheres. Calcinating the spherical catalyst microspheres at 590°C for 4 hours to form a final composite ZSM-5/Beta zeolite catalyst. The spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
Specifically, the present invention also provides a process for cracking paraffin rich feed such as kerosene, naphtha, or VGO into light olefins by using the catalyst composition as discloses herein, wherein the process includes cracking paraffin rich feed with boiling range of 200-350°C in a temperature range of 540-650°C and maintaining the pressure in a range of 1.5-5 bar.
In the present invention, alkaline earth metal ion based hydrogen phosphate salts were prepared with different AE/P ratios. The prepared phosphate salts were impregnated on the surface of zeolites and calcined at 500-700°C to establish the formation of stable Al-O-P with AE ion without affecting crystallinity of the zeolites. These P-modified zeolites were incorporated into the catalyst formulation with different composition along with binder, matrix components for
shaping the catalyst to make microsphere of final catalyst. The final catalyst was calcined at temperature above 500°C and subjected for testing for cracking of kerosene.
Having described the important aspects of the present invention, the following non-limiting examples illustrate specific embodiments thereof. Those skilled in the art will appreciate that many modifications may be made in the invention without changing the essence of the invention.
EXAMPLES:
Example- 1: Preparation of magnesium hydrogen phosphate
256 g of magnesium nitrate hexahydrate was dissolved with 800 g of demineralized water. 196 g of ortho-phosphoric acid (50% concentration) was added to the solution. 300 g of ammonium hydroxide was added slowly under stirring at 30°C. The white precipitate was filtered and washed with hot DM water for three times to remove excess ammonium. The solid precipitate was dried used for modification of zeolites.
Example-2: Preparation of AE ion modified phosphated zeolites:
500 g of ZSM-5 (CBV-3024, Zeolyst) zeolite was mixed with above magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.%. 5000 g of DM water was added to the prepared zeolite mixer to get a zeolite slurry. The zeolite slurry was mixed and heated at 70°C for 3 hours. After 3 hours, zeolite slurry was filtered and washed with DM water for 2 times and a wet cake was obtained. The wet cake was dried at 120°C for 10 hours and calcined at 700°C for 3 hours. Similarly, 500 g of beta zeolite (CP814C, Zeolyst) was treated with magnesium hydrogen phosphate, dried and calcined at 700°C for 3hours.
Example -3: Preparation of ZSM-5/beta zeolite composite catalyst
85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with AE modified zeolites i.e., 316 g of ZSM-5 and 112 g of modified beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere having ABD above 0.9 g/cc and Attrition less than 6, average particle size of 75-80 micron in a co-current spray dryer
unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM- 5/Beta zeolite catalyst.
Example-4: Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification:
121 g of ortho-phosphoric acid, 411 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
Example-5: Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification with promoter:
121 g of ortho-phosphoric acid, 191 g of magnesium nitrate, 376 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
Example 6: Cracking experiment with kerosene
Table 1 below lists properties of Kerosene.
As can be seen from the Table 1 above, UOPK factor, which signifies cracking potential of Kerosene stream, is comparable to the typical vacuum gas oil (VGO) feedstock (UOPK = 11.44). Furthermore, catalytic cracking experiments were carried out with Kerosene as feed in ACE R+MM unit using FCC E-CAT and in combination of ZSM-5 additive. Table 2 provides the list of the results of these experiments. The product yields from kerosene and VGO were compared and in presence of ZSM-5 additive kerosene molecules undergoes alkylation and form LCO range products. In order to reduce the formation of LCO, CLO from kerosene cracking, the developed ZSM-5/beta zeolites composite catalyst was studied. During cracking of kero feedstock molecules, the molecules undergoes dimerization reaction, produces heavier molecules and increasing yield of LCO and CLO.
Table 2: Cracking experiments with kerosene and compared with VGO feedstock Catalyst: 50% FCC E-Cat+ 50% ZSM-5 additive
Example 7: Catalyst composition with phosphate modification prepared from Example-3
Table 3 discloses that the catalyst composition with phosphate modification provides higher C2- C4 olefins, lower LCO & CLO and higher conversion. The composite catalyst was evaluated at 600 and 630°C in different Cat/oil ratio. It was observed from the results, the modified catalyst composition provides higher conversion with minimum LCO and nil CLO.
Example 8: Catalyst composition as prepared from Example-4 & 5
Table 4 discloses that the catalyst composition with no prephosphate modification of zeolites provides lower C2-C4 olefins.
Accordingly, it is clear that the Catalyst composition with phosphate modification provides higher conversion rate with minimum LCO and nil CLO.
Claims
1. A catalyst composition for cracking of paraffin rich feed into light olefins, wherein the composition comprises:
(a) 5-30 wt.% of an ultra-stabilized Y-zeolite;
(b) 20-60 wt.% of an alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite;
(c) 20-40 wt.% of a filler; and
(d) 5-10 wt.% of a binder.
2. The catalyst composition as claimed in claim 1, wherein the composition comprises:
(a) 5-20 wt.% of an ultra-stabilized Y-zeolite;
(b) 20-50 wt.% of an alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite;
(c) 20-40 wt.% of a filler; and
(d) 5-10 wt.% of a binder.
3. The composition as claimed in claim 1, wherein the ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 1-3.5 wt.%.
4. The composition as claimed in claim 1, wherein the alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, trimagnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
5. The composition as claimed in claim 1, wherein the filler is clay.
6. The composition as claimed in claim 1, wherein the binder is alumina.
7. The composition as claimed in claim 1, wherein the beta zeolite comprises silicon to alumina ratio in a range of 30-50.
8. A process for preparation of the catalyst composition as claimed in claim 1, wherein the process comprises:
(i) preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide;
(ii) preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite;
(iii) preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with an AE ion modified phosphated Beta zeolite;
(iv) preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite;
(v) mixing the 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM- 5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina to get a slurry;
(vi) spray drying the slurry to form spherical catalyst microspheres, spray drying is performed in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C; and
(vii) calcinating the spherical catalyst microspheres at 590°C for 4 hours to get the catalyst composition.
9. The process as claimed in claim 8, wherein, the spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
10. A process for cracking a paraffin rich feed into light olefins by using the catalyst composition as claimed in claim 1-9, wherein the process comprises cracking the paraffin rich feed in a temperature range of 540-650°C and maintaining the pressure 1.5-5 bar.
11. The process as claimed in claim 10, wherein, the paraffin rich feed has a boiling point in a range of 200-540°C.
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EP0909582A1 (en) * | 1997-10-15 | 1999-04-21 | China Petro-Chemical Corporation | Cracking catalytic for the production of light olefins and its preparation |
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