WO2024028884A1 - A non-metal based metal passivator additive composition for fccu feed stocks - Google Patents
A non-metal based metal passivator additive composition for fccu feed stocks Download PDFInfo
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- WO2024028884A1 WO2024028884A1 PCT/IN2022/051109 IN2022051109W WO2024028884A1 WO 2024028884 A1 WO2024028884 A1 WO 2024028884A1 IN 2022051109 W IN2022051109 W IN 2022051109W WO 2024028884 A1 WO2024028884 A1 WO 2024028884A1
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- Prior art keywords
- additive composition
- metal
- glycol
- weight
- passivator
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 30
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052796 boron Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052759 nickel Inorganic materials 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 description 37
- 238000004231 fluid catalytic cracking Methods 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 238000004523 catalytic cracking Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- -1 nickel-porphyrin compound Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
Definitions
- a NON-METAL BASED METAL PASSIVATOR ADDITIVE COMPOSITION FOR FCCU FEED STOCKS FIELD OF THE INVENTION The present invention relates to a non-metal based metal passivator additive composition and a process for preparing the same.
- this invention relates to a non metal based nickel passivator additive composition comprising (i) 60-80% by weight of glycol as a solvent (ii) 20- 50% by weight of boron containing compound.
- the composition acts as a nickel passivator for Fluid Catalytic Cracking Unit (FCCU) feed stocks.
- FCCU Fluid Catalytic Cracking Unit
- FCC Fluid catalytic cracking
- the feedstock is heated to a high temperature and under moderate pressure, is brought into contact with a hot, powdered catalyst.
- the heated catalyst breaks the long-chain molecules of the high-boiling hydrocarbon liquids into much shorter molecules, which are collected as a vapor.
- FCC units operate either on maximum gasoline mode or the maximum distillate mode, which depends on seasonal product demand.
- FCCU feed Vauum Gas Oil
- FCCU feed have metals such as Nickel, Vanadium, Iron etc., which slowly get deposited on FCC catalysts.
- Cracking residue feeds in FCC units increase the level of contaminant Ni and V metals on cracking catalysts. Residue feeds contain higher content of nickel and vanadium. This results in decreasing catalytic activity and increasing undesirable dehydrogenation reaction in the reactor.
- WO2021017456A1 provides an anti-metal liquid yield booster for catalytic cracking and a preparation method therefor.
- the liquid yield booster is composed of a VPI-5 molecular sieve, and an antimony-based nickel passivator and a heteropoly acid together loaded in a pore channel thereof, wherein the mass fractions of the components are: 70-98% of a VPI-5 molecular sieve; 0.5-20% of an antimony-based nickel passivator; and 1-10% of heteropoly acid.
- a nickel-porphyrin compound can be concentrated in the pore channel of the VPI-5 for a cracking reaction, and the resulting metal nickel is controlled to remain in the pore channel of the VPI-5, such that the toxicity thereof to a catalytic cracking catalyst is reduced, and furthermore, the nickel element is more quickly exposed and reacted with the nickel passivator, and this is favorable for improving the reaction selectivity and reducing the generation of coke, and there is increased production of liquid products such as gasoline and diesel oil.
- FCC fluid catalytic cracking
- FCC catalyst compositions comprise particles containing a non-zeolitic component and one or more boron oxide components.
- the FCC catalyst composition contains a zeolite component and optionally a rare earth component and a transition alumina.
- FCC catalytic compositions may comprise a first particle type containing one or more boron oxide components and a first matrix component mixed with a second particle type containing a second matrix component, and a zeolite.
- the FCC catalyst compositions can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields.
- CN111686791A provides a catalytic cracking gasoline octane number auxiliary agent and a preparation method thereof, belonging to the field of catalyst preparation, and the method comprises the following steps: (1) preparing a ZSM-5 molecular sieve with a mesoporous- micro hierarchical pore structure: mixing and pulping a required boron-containing compound, a ZSM-5 molecular sieve and deionized water according to the mass ratio of the elemental boron to the deionized water of 0.005-0.05: 1: 5-50, continuously stirring at the temperature of 30-95 °C for ion exchange for 0.5-3 h, filtering, washing, roasting the obtained filter cake at the temperature of 400-800 °C for 1-3 h under the condition of 100% steam to obtain the ZSM- 5 zeolite molecular sieve with the mesoporous-microporous structure, (2) mixing and pulping the obtained ZSM-5 molecular sieve with the mesoporous-micropor
- boron-based catalysts show a superior selectivity toward olefins, excellent stability and atom-economy to valuable carbon- based products by minimizing CO2 emission, which are highly promising in future industrialization.
- the carbonaceous catalysts also exhibited impressive behavior in the ODH of light alkanes helped along by surface oxygen-containing functional groups.
- the prior art formulations include antimony which is a metal and currently antimony based formulations are already in use in refineries. Further, the prior arts disclose FCC catalyst compositions containing boron oxide. However, the use of metal passivating agent is independent of the catalyst usage.
- the purpose of adding nickel passivator in the FCC unit is to minimize the yield of hydrogen and dry gas and thus avoid its detrimental effect on the product yields. This is typically used when Ni on E-cat is more than 1000ppm or when H2/CH4 ratio in dry gas is more than 1.
- the present invention provides a metal passivator, preferably Ni Passivator. This will replace the import dependence as well as bring down the cost of the passivator significantly.
- the present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight a boron containing compound.
- the present invention also provides a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 0C.
- BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates graph for hydrogen reduction efficiencies of various formulations/composition.
- the term ‘hydrothermal deactivation’ used herein refers to deactivation of fresh FCC catalyst in presence of steam to equilibrate it to FCC unit aged catalyst.
- ACE studies used herein refers to cracking of hydrocarbon using ACE (Advanced cracking Evaluation) unit.
- the present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight of a boron containing compound.
- the glycol is selected from ethylene glycol and propylene glycol.
- the glycol is propylene glycol.
- the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid.
- the boron containing compound is boric acid.
- the boron containing compound in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight.
- the present invention also provides a process for preparation of non-metal based metal passivator additive composition
- a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 0C.
- the glycol is selected from ethylene glycol and propylene glycol.
- the glycol is propylene glycol.
- the boron containing compound in the process for preparation of non-metal based metal passivator additive composition, is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. In one of the preferred features of the present invention, the boron containing compound is boric acid. In one of the features of the present invention, in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight.
- a non metal based metal passivator additive composition containing (i) 60-80% by weight of propylene glycol as solvent (ii) 20-50% by weight of boric acid.
- the additive acts as metal passivator for nickel present in FCCU feed stocks.
- Example 1 Methodology: The metalation (Ni & V: 2000ppm each) of the catalyst and passivator loading was carried out using Mitchell’s method where components are artificially added onto the catalyst to simulate E-cat properties. Post impregnation, the catalyst was subjected to hydrogen reduction and hydrothermal deactivation (815 deg C/10hr). Subsequently the catalyst was calcined at 600 °C. Post impregnation the catalysts were utilized for ACE studies for base case data generation. Non-metal based metal passivator additive composition as prepared were loaded on the catalyst and calcined and then ACE studies were carried out for yield data generation.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a non-metal based metal passivator additive composition and a process for preparing the same. In particular, this invention relates to a non metal based nickel passivator additive composition comprising (i) 60-80% by weight of propylene glycol as a solvent (ii) 20-50% by weight of boric acid. The composition acts as a nickel passivator for FCCU feed stocks.
Description
A NON-METAL BASED METAL PASSIVATOR ADDITIVE COMPOSITION FOR FCCU FEED STOCKS FIELD OF THE INVENTION The present invention relates to a non-metal based metal passivator additive composition and a process for preparing the same. In particular, this invention relates to a non metal based nickel passivator additive composition comprising (i) 60-80% by weight of glycol as a solvent (ii) 20- 50% by weight of boron containing compound. The composition acts as a nickel passivator for Fluid Catalytic Cracking Unit (FCCU) feed stocks. BACKGROUND OF THE INVENTION Fluid catalytic cracking (FCC) is one of the most important conversion processes used in petroleum refineries. It is widely used to convert the high-boiling, high-molecular weight hydrocarbon fractions obtained from distillation of petroleum crude oils into more valuable streams that are routed to gasoline, LPG, diesel and other products. Cracking of petroleum hydrocarbons was originally done by thermal cracking, which has been almost completely replaced by catalytic cracking because it produces more gasoline with a higher octane rating. It also produces byproduct gases that have more carbon-carbon double bonds (i.e. more olefins), and hence more economic value, than those produced by thermal cracking. The feedstock to FCC is usually gas oil or residual feed stocks boiling above 370+ and an average molecular weight ranging from 200 to 600 or higher. In the FCC process, the feedstock is heated to a high temperature and under moderate pressure, is brought into contact with a hot, powdered catalyst. The heated catalyst breaks the long-chain molecules of the high-boiling hydrocarbon liquids into much shorter molecules, which are collected as a vapor. FCC units operate either on maximum gasoline mode or the maximum distillate mode, which depends on seasonal product demand. FCCU feed (Vacuum Gas Oil) have metals such as Nickel, Vanadium, Iron etc., which slowly get deposited on FCC catalysts. Cracking residue feeds in FCC units increase the level of contaminant Ni and V metals on cracking catalysts. Residue feeds contain higher content of nickel and vanadium. This results in decreasing catalytic activity and increasing undesirable dehydrogenation reaction in the reactor. This dehydrogenation reaction will increase in gas production in the form of higher hydrogen and coke yields.
WO2021017456A1 provides an anti-metal liquid yield booster for catalytic cracking and a preparation method therefor. The liquid yield booster is composed of a VPI-5 molecular sieve, and an antimony-based nickel passivator and a heteropoly acid together loaded in a pore channel thereof, wherein the mass fractions of the components are: 70-98% of a VPI-5 molecular sieve; 0.5-20% of an antimony-based nickel passivator; and 1-10% of heteropoly acid. With the anti-metal liquid yield booster of this prior art, a nickel-porphyrin compound can be concentrated in the pore channel of the VPI-5 for a cracking reaction, and the resulting metal nickel is controlled to remain in the pore channel of the VPI-5, such that the toxicity thereof to a catalytic cracking catalyst is reduced, and furthermore, the nickel element is more quickly exposed and reacted with the nickel passivator, and this is favorable for improving the reaction selectivity and reducing the generation of coke, and there is increased production of liquid products such as gasoline and diesel oil. US9895680B2 discloses fluid catalytic cracking (FCC) compositions, methods of manufacture and use. FCC catalyst compositions comprise particles containing a non-zeolitic component and one or more boron oxide components. The FCC catalyst composition contains a zeolite component and optionally a rare earth component and a transition alumina. FCC catalytic compositions may comprise a first particle type containing one or more boron oxide components and a first matrix component mixed with a second particle type containing a second matrix component, and a zeolite. The FCC catalyst compositions can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields. CN111686791A provides a catalytic cracking gasoline octane number auxiliary agent and a preparation method thereof, belonging to the field of catalyst preparation, and the method comprises the following steps: (1) preparing a ZSM-5 molecular sieve with a mesoporous- micro hierarchical pore structure: mixing and pulping a required boron-containing compound, a ZSM-5 molecular sieve and deionized water according to the mass ratio of the elemental boron to the deionized water of 0.005-0.05: 1: 5-50, continuously stirring at the temperature of 30-95 ℃ for ion exchange for 0.5-3 h, filtering, washing, roasting the obtained filter cake at the temperature of 400-800 ℃ for 1-3 h under the condition of 100% steam to obtain the ZSM- 5 zeolite molecular sieve with the mesoporous-microporous structure, (2) mixing and pulping the obtained ZSM-5 molecular sieve with the mesoporous-microporous structure, clay and binder according to the solid content of 10-30 wt% with the deionized water, and then carrying
out spray forming, washing, filtering and drying to obtain the octane number auxiliary agent of the catalytic cracking gasoline, wherein the octane number auxiliary agent of the catalytic cracking gasoline is used for catalytic cracking, has the characteristics of low liquefied gas yield and high gasoline octane number. Shaun Pan et al. in an article published in November 2015, titled “Creative Catalysis” discloses conventional Ni passivation techniques include the injection of antimony (Sb) and the incorporation of Ni trapping specialty alumina into the FCC catalyst. While antimony can be effective in reducing H2 and coke, it can also lead to increased NOX emissions due to its adverse effects on carbon monoxide (CO) promoters, and operational issues such as slurry heat exchanger fouling. Jian Sheng et al. in a Journal published in Chemical Society Reviews December 2020, titled “Oxidative dehydrogenation of light alkanes to olefins on metal-free catalysts” disclose Metal- free boron- and carbon-based catalysts have shown both great fundamental and practical value in oxidative dehydrogenation (ODH) of light alkanes. In particular, boron-based catalysts show a superior selectivity toward olefins, excellent stability and atom-economy to valuable carbon- based products by minimizing CO2 emission, which are highly promising in future industrialization. The carbonaceous catalysts also exhibited impressive behavior in the ODH of light alkanes helped along by surface oxygen-containing functional groups. The prior art formulations include antimony which is a metal and currently antimony based formulations are already in use in refineries. Further, the prior arts disclose FCC catalyst compositions containing boron oxide. However, the use of metal passivating agent is independent of the catalyst usage. The purpose of adding nickel passivator in the FCC unit is to minimize the yield of hydrogen and dry gas and thus avoid its detrimental effect on the product yields. This is typically used when Ni on E-cat is more than 1000ppm or when H2/CH4 ratio in dry gas is more than 1. Considering the above, the present invention provides a metal passivator, preferably Ni Passivator. This will replace the import dependence as well as bring down the cost of the passivator significantly.
SUMMARY OF THE INVENTION Accordingly, the present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight a boron containing compound. The present invention also provides a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 ⁰C. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates graph for hydrogen reduction efficiencies of various formulations/composition. DETAILED DESCRIPTION OF THE INVENTION While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims. The following description with reference to the accompanying drawings is provided to assist in a comprehensive understanding of exemplary embodiments of the invention. It includes various specific details to assist in that understanding but these are to be regarded as merely exemplary. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope of the invention. In addition, descriptions of well-known functions and constructions are omitted for clarity and conciseness. The terms and words used in the following description and claims are not limited to the bibliographical meanings, but, are merely used by the inventor to enable a clear and consistent
understanding of the invention. Accordingly, it should be apparent to those skilled in the art that the following description of exemplary embodiments of the present invention are provided for illustration purpose only and not for the purpose of limiting the invention as defined by the appended claims and their equivalents. It is to be understood that the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments. It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. The term ‘catalyst’ used herein refers to FCC catalyst. The term ‘passivator’ used herein refers to passivation of metal. The term ‘E-cat’ used herein refers to Equilibrium Catalyst of FCC unit. The term ‘hydrothermal deactivation’ used herein refers to deactivation of fresh FCC catalyst in presence of steam to equilibrate it to FCC unit aged catalyst. The term ‘ACE studies’ used herein refers to cracking of hydrocarbon using ACE (Advanced cracking Evaluation) unit. The present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight of a boron containing compound.
In one of the features of the present invention, in the non-metal based metal passivator additive composition the glycol is selected from ethylene glycol and propylene glycol. In one of the preferred features of the present invention, the glycol is propylene glycol. In yet another feature of the present invention, the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. In one of the preferred features of the present invention, the boron containing compound is boric acid. In one of the features of the present invention, in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight. The present invention also provides a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 ⁰C. In one of the features of the present invention, in the process for preparation of non-metal based metal passivator additive composition, the glycol is selected from ethylene glycol and propylene glycol. In one of the preferred features of the present invention, the glycol is propylene glycol. In one of the features of the present invention, in the process for preparation of non-metal based metal passivator additive composition, the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. In one of the preferred features of the present invention, the boron containing compound is boric acid. In one of the features of the present invention, in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight. In one of the features of the present invention, a non metal based metal passivator additive composition containing (i) 60-80% by weight of propylene glycol as solvent (ii) 20-50% by weight of boric acid.
The additive acts as metal passivator for nickel present in FCCU feed stocks. Examples: The present disclosure with reference to the accompanying examples describes the present invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. It is understood that the examples are provided for the purpose of illustrating the invention only and are not intended to limit the scope of the invention in any way. Example 1: Methodology: The metalation (Ni & V: 2000ppm each) of the catalyst and passivator loading was carried out using Mitchell’s method where components are artificially added onto the catalyst to simulate E-cat properties. Post impregnation, the catalyst was subjected to hydrogen reduction and hydrothermal deactivation (815 deg C/10hr). Subsequently the catalyst was calcined at 600 °C. Post impregnation the catalysts were utilized for ACE studies for base case data generation. Non-metal based metal passivator additive composition as prepared were loaded on the catalyst and calcined and then ACE studies were carried out for yield data generation. Alternate approach of spiking both Ni & V on the catalyst along with the VGO feed was studied for base case fresh catalyst deactivation and in case of non-metal based metal passivator additive composition of the present invention and commercial passivators were also spiked on the catalyst along with VGO feed to mimic actual commercial catalytic cracking process. Mitchell method: In Mitchell-type methods the FCC catalysts are metallated with vanadium and nickel naphthenates that are dissolved in an organic solvent. The metallation itself is performed by impregnating the FCC catalyst with solutions of the dissolved metal complexes. This artificial
deposition of contaminant metals on FCC catalysts is done by pore volume impregnation methods. Methodology: The Mitchell impregnation was performed using vanadium and nickel naphthenates. The FCC catalysts were impregnated with a volume of the impregnation solution that has the pore volume of the catalysts. The organic solvents were burned off with air at 550 °C for 3 h followed by passivator loading on the metallated catalyst and drying at 200 °C for 2 hr. Example 2 Preparation of non-metal based metal passivator additive composition: The formulations/composition were prepared using non-metallic components, with specific roles: Passivator: The active component for strong interaction with Ni and subsequently eliminating deleterious effects. Diluent: A stable solvent to solubilize the active ingredient for aiding in dosing. The above mentioned chemical components (the ingredients as mentioned in Table 1) were weighed in required proportions into a round bottom flask. These components were mixed using magnetic stirrer for about 3-4 hours between 60-120 ⁰C. It was ensured that a clear and homogeneous solution has formed at the end of the reaction. The transparent solution formed was stored and check for its phase stability overnight, before mixing with Ni and V doped catalyst was prepared for further main evaluation. ACE MAT Studies: ACE MAT studies were carried out with all homogeneous formulations/compositions. Primary parameters such as hydrogen yield and hydrogen reduction efficiency were monitored. The hydrogen reduction efficiencies were compared to the existing benchmark used in the refineries Results: Efficiency of the experiments is measured by monitoring the reduction in the hydrogen. To determine the same, hydrogen yields were used, and reduction efficiency was calculated using following formula.
The non-metal based metal passivator additive composition synthesized by the procedure of Example 2 have been tabulated in Table 1. Table 1
In addition to the hydrogen yields, the yields of distillates (LPG, Naphtha & Diesel) are given below in table 2: Table 2
The hydrogen reduction efficiencies of various formulations/composition are plotted in Graph- 1. Initial formulations from MP-4 to MP-12 reveal the efficiencies are below 60%. The efficiencies improve further upto 85% for MP-23. The best efficiency was shown by MP-25. The samples MP-25 to MP -30 are results pertaining to lower and higher dosage of the passivator with respect to the feed. Results for lower boron loading have been tabulated in Table 3: Table 3
With lower Boron chemical content in the formulation/composition, the activity is lower. Conclusion: The developed non-metal based metal passivator additive composition could effectively passivate Nickel. The reduction in hydrogen gas is more than 50%. The additives show excellent performance.
Claims
We claim: 1 A non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight a boron containing compound. 2. The composition as claimed in claim 1, wherein the glycol is selected from ethylene glycol and propylene glycol. 3. The composition as claimed in claim 1, wherein the glycol is propylene glycol. 4. The composition as claimed in claim 1, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. 5. The composition as claimed in claim 1, wherein the boron containing compound is boric acid. 6. A process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60-120 ⁰C. 7. The process as claimed in claim 6, wherein the glycol is selected from ethylene glycol and propylene glycol. 8. The process as claimed in claim 6, wherein the glycol is propylene glycol. 9. The process as claimed in claim 6, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. 10. The process as claimed in claim 6, wherein the boron containing compound is boric acid.
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