WO2010113174A1 - Procede de craquage catalytique en lit fluidise - Google Patents

Procede de craquage catalytique en lit fluidise Download PDF

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Publication number
WO2010113174A1
WO2010113174A1 PCT/IN2010/000191 IN2010000191W WO2010113174A1 WO 2010113174 A1 WO2010113174 A1 WO 2010113174A1 IN 2010000191 W IN2010000191 W IN 2010000191W WO 2010113174 A1 WO2010113174 A1 WO 2010113174A1
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Prior art keywords
catalyst
heavy metal
fluidized catalytic
poisoned
spent
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PCT/IN2010/000191
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English (en)
Inventor
Saravanan Subramani
Debasis Bhattacharyya
Karthikeyani Arumugam Velayutham
Pankaj Kumar Kasliwal
Krishnan Venkatachalam
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Indian Oil Corporation Limited
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Application filed by Indian Oil Corporation Limited filed Critical Indian Oil Corporation Limited
Priority to US13/260,919 priority Critical patent/US20120024748A1/en
Priority to CN201080020809.0A priority patent/CN102439121B/zh
Publication of WO2010113174A1 publication Critical patent/WO2010113174A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/187—Controlling or regulating
    • 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
    • B01J29/80—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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
    • C10G2300/701—Use of spent catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity.
  • the present invention also relates to the use of heavy metal poisoned FCC/RFCC spent catalyst for maintaining the activity of the composite circulating catalyst and as a sulfur reducing agent in fluid catalytic cracking process for reduction of sulfur in products of catalytic cracking.
  • Background of the invention Fluid catalytic cracking process is a well known since 1942. The history and the evolution of FCC process at various generations are detailed in the book "Fluid Catalytic Cracking Handbook by Reza Sadeghbeigi, Gulf publishing company", ''Fluid catalytic cracking by Wilson, and various other literatures.
  • cracking is defined as breaking down, hydrocarbons of higher molecular weight into lower molecular weight hydrocarbons. It can be carried out thermally or catalytically.
  • the catalyst is a fluidizable fine particle in the size range of 5-150 microns.
  • the steps involved in the conventional FCC process are described below: a) Hydrocarbon feedstock is preheated to a temperature range of 150-400 0 C to enhance the atomization/ vaporization of feed. b) The preheated feed is mixed with the steam at particular ratio and passed through a nozzle to disperse the feed into fine droplets inside an up-fiow riser.
  • FCC process is termed as a cyclic process where the reaction and regeneration takes place continuously in a riser - reactor and regenerator respectively.
  • a particular amount of fresh catalyst is added to the circulating inventory in order to maintain the activity of the catalyst at same level while keeping the inventory at constant level.
  • the regeneration of catalyst mentioned above only removes the coke that is deposited on the catalyst not the heavy metal poisons.
  • the heavy metals present in the feedstock finally ends up in the coke which in turn deposits on the catalyst during reaction step.
  • Each metal has its own effect on the FCC unit performance. Vanadium particularly deactivates the catalyst permanently by destructing the zeolite structure. Nickel promotes the dehydrogenation reactions facilitating the production of hydrogen and coke. Iron reduces the catalyst bottom cracking characteristics. It also increases SO x emission and coke on regenerated catalyst (CRC) in partial burn units. As the cycle of FCC operation continues, these metals continuously deposits on the surface of catalyst and enhances its detrimental effects. Due to incremental deactivation by deposition of heavy metals on catalyst, addition of proportionately higher amount of catalyst is needed in order to maintain the activity of the circulating catalyst inventory. In order to keep the catalyst inventory at the desired level, a part of the catalyst is required to be withdrawn through which a portion of the heavy metals is disposed off from the circulating inventory.
  • Lam Effect of vanadium on the deactivation of FCC catalysts, Braz.Chem.Engg, VoI 15, No.2, June 1998, O'Connor et al, Deactivation and testing of hydrocarbon processing catalysts, ACS symposium series, 571(1995), etc.).
  • the destruction of zeolite structure due to vanadium, increased dehydrogenation activity of nickel and iron poisoning make the catalyst less active affecting the unit performance owing to loss in conversion and product selectivity.
  • Deactivation of catalyst by coke is a temporary phenomenon.
  • the activity of catalyst is restored by burning the coke on catalyst with the aid of air or any oxygen containing gas in regenerator.
  • deactivation of catalyst by heavy metals is considered to be permanent processes in which the activity of catalyst cannot be restored within the reactor-regenerator section.
  • the use of additives to trap the heavy metals within the reactor regenerator section has limited success, as it cannot rejuvenate the activity of the catalyst completely (See Kuei-Jung Chao et al, Vanadium Passivation of cracking catalysts by using secondary ion mass spectrometry, Appl.
  • the only way to maintain particular activity of catalyst in circulating inventory is to remove a portion of equilibrium catalyst from the inventory and add the equivalent amount of fresh catalyst.
  • equivalent amount of fresh catalyst is added in the circulating inventory in order to maintain the regenerator inventory level and also unit catalyst activity at constant values.
  • the spent catalyst removed from the circulating inventory of the unit is disposed for landfill operation and / or used as a raw material in the cement industries.
  • vanadium compound was selected from the group comprising vanadium oxalate, vanadium sulfate, vanadium naphthanate, vanadium halides and mixtures thereof.
  • the hydrocarbon feedstock contains organosulfur compounds as one of the impurities.
  • organosulfur compounds which are non-thiophenic get converted into H 2 S and removed along with product vapour.
  • the distribution of sulfur compounds in the liquid products depends upon many parameters.
  • the present invention relates to a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity.
  • the process involves adding a heavy metal poisoned spent catalyst to an equilibrium catalyst in an amount to maintain the activity of the circulating catalyst and obtaining a fluidized catalytic cracked product.
  • the present invention also relates to a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity, said process comprising: adding a heavy metal poisoned spent catalyst to an equilibrium catalyst to obtain a composite circulating catalyst, wherein the heavy metal poisoned spent catalyst is added in an amount to maintain the activity of the circulating catalyst, catalytically cracking a hydrocarbon feed in a reactor operating at catalytic cracking conditions with the circulating catalyst in a circulating inventory to obtain a reactor effluent, separating the reactor effluent into a vapour rich phase containing fluidized catalytic cracked product and a solid rich phase containing coke laden catalyst, and removing the vapour rich phase and fractionating the vapour rich phase to obtain fluidized catalytic cracked product.
  • the present invention further relates fluidized catalytic cracked product obtained by the process of the present invention.
  • the present invention provides a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity, said process comprising: adding a heavy metal poisoned spent catalyst to an equilibrium catalyst to obtain a composite circulating catalyst, wherein the metal poisoned spent catalyst is added in an amount to maintain the activity of the circulating catalyst; and obtaining a fluidized catalytic cracked product.
  • An embodiment of the present invention is the fluidized catalytic cracking process, wherein the hydrocarbon feed is selected from a group consisting of straight run hydrocarbon fractions and cracked hydrocarbon fractions or mixture thereof having carbon number 5 to 120 comprising at least one organo-sulfur compound.
  • the heavy metal poisoned spent catalyst comprises one or more metals selected from Pt, V, Ni, Fe, Co and Mo.
  • Another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal poisoned spent catalyst has metal concentration not less than 500 ppm.
  • Yet another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal poisoned spent catalyst has metal concentration in the range of 500 ppm to 35,000 ppm.
  • Yet another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal concentration in the equilibrium catalyst is less than 20,000 ppm.
  • the present invention is the fluidized catalytic cracking process, wherein the metal concentration in the equilibrium catalyst is in the range of 0 ppm to 20,000 ppm.
  • the present invention also provides a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity, said process comprising: adding a heavy metal poisoned spent catalyst to an equilibrium catalyst to obtain a composite circulating catalyst, wherein the heavy metal poisoned spent catalyst is added in an amount to maintain the activity of the composite circulating catalyst, catalytically cracking a hydrocarbon feed in a reactor operating at catalytic cracking conditions with the composite circulating catalyst in a circulating inventory to obtain a reactor effluent, separating the reactor effluent into a vapour rich phase containing fluidized catalytic cracked product and a solid rich phase containing coke laden catalyst, and removing the vapour rich phase and fractionating the vapour rich phase to obtain fluidized catalytic cracked product.
  • An embodiment of the present invention is the fluidized catalytic cracking process, wherein the hydrocarbon feed is selected from a group consisting of straight run hydrocarbon fractions and cracked hydrocarbon fractions or mixture thereof having carbon number 5 to 120 comprising at least one organo-sulfur compound.
  • Another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal poisoned spent catalyst comprises one or more metals selected from Pt, V, Ni, Fe, Co, Mo etc,.
  • Yet another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal poisoned spent catalyst has heavy metal concentration not less than 500 ppm.
  • Another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal poisoned spent catalyst has the metal concentration in the range of 500 ppm to 35,000ppm.
  • Another embodiment of the present invention is the fluidized catalytic cracking process, wherein the heavy metal concentration in the equilibrium catalyst is less than 20,000 ppm.
  • the present invention provides fluidized catalytic cracked product obtained by the process of the present invention.
  • the present invention provides fluidized catalytic cracked product, wherein sulfur content is reduced by more than 20 % (wt/wt) when the cut point of the fluidized catalytic cracked product is C5-250°C.
  • the fluidized catalytic cracked products having carbon number in the range of C5 to C15 the sulfur content is reduced by more than 20 % (wt/wt).
  • the fluidized catalytic cracked products having carbon number in the range of C5 to Cl 5 the sulfur content is reduced by more than 20 % (wt/wt) and upto 50% (wt/wt).
  • the fluidized catalytic cracked products having cut point in the range of C5-250°C having the Research Octane Number (RON) increases by more than 1 unit.
  • the "Research octane number (RON)" is a parameter used to estimate the antiknocking characteristics of a fuel at low engine speeds (@600 rpm and 12O 0 F (49 0 C) air temperature).
  • An embodiment of the present invention the added heavy metal poisoned spent catalyst improves the propylene yield by more than 0.25 wt% depending on the feed characteristics, host catalyst property and the process conditions.
  • the present invention provides a fluidized catalytic cracking process for cracking hydrocarbon feed having organo-sulfur compound as an impurity, said process comprising, adding a requisite amount of heavy metal poisoned spent catalyst to the circulating catalyst inventory in such concentration to maintain the activity of the circulating catalyst even with the increase in heavy metal concentration and obtaining fluidized catalytic cracked products.
  • the feedstock used in the fluidized catalytic cracking process of present invention is any hydrocarbon feedstock, which contains atleast one organosulfur compounds.
  • Some of the examples of the conventional FCC feedstocks are vacuum gas oil, hydrocracker bottoms, heavy vacuum gas oil, vacuum slop, cycle oils, slurry oils, atmospheric residue, vacuum residue, light straight run naphtha, heavy naphtha, coker gas oil, coker naphtha, etc. and mixtures thereof.
  • the feed explained above may also contain the impurities like basic nitrogen, vanadium, nickel, iron, sulfur, etc. The impurities concentration may vary depending upon the source of crude.
  • Heavy metal poisoned spent FCC/RFCC catalyst and the actual host catalyst are mixed in different proportions and tested in the laboratory.
  • the effect of present invention is to remove the sulfur from cracked products, primarily gasoline by increasing the metal concentration of the circulating inventory without increasing the metal concentration on the actual host catalyst particles.
  • the amount of the fresh catalyst to be added to the circulating catalyst is reduced by the addition of an equivalent amount of heavy metal poisoned spent catalyst.
  • Still another embodiment of the present invention is to provide a fluidized catalytic cracking process wherein the metal concentration in the circulatory catalyst inventory without adding a requisite amount of heavy metal poisoned spent catalyst is less than the metal concentration of the metal poisoned spent catalyst.
  • the continuous circulating catalyst inventory in the FCC/RFCC unit is referred as equilibrium catalyst (E-cat).
  • E-cat equilibrium catalyst
  • spent catalyst The spent catalyst referred here is completely different from that of spent catalyst mentioned earlier, i.e., the coke laden fluidizable catalyst, which is transferred to regenerator through spent catalyst standpipe and spent catalyst slide valve.
  • the preferred spent catalyst for the present invention is the heavy metal poisoned spent catalyst normally withdrawn from the unit inventory and disposed thereof.
  • an improved FCC/RFCC process where the spent heavy metal poisoned FCC/RFCC catalyst with higher concentration of heavy metals particularly vanadium and nickel is added separately or along with the fresh catalyst into the FCC/RFCC unit catalyst inventory, which has lower metal concentration.
  • the addition provides the increase in heavy metal concentration in the composite circulating catalyst without increasing the host heavy metal concentration, which in turn reduces the sulfur content of the cracked products and also enhances the conversion and selectivity of the valuable products.
  • the heavy metal poisoned FCC/RFCC catalyst can also be blended with any of the commercial FCC/RFCC catalyst cum additive system with desired concentration and can be added in FCCU/RFCCU.
  • Examples of the said commercial additives are ZSM-5, SOx, NOx, Bottom cracking additive, Gasoline sulfur reduction additive, etc.
  • the base catalyst and heavy metal poisoned FCC/RFCC catalyst used in the process is obtained from different refineries and also simulated in laboratories.
  • Yet another embodiment of the present invention is that there is an increase in C5- 220 ⁇ C conversion with increased LPG and light olefins yield. It may be due to the effect of heavy metal poisoned catalyst, which has the ability to crack the feed components, which is not possible using commercial additive aiming towards gasoline sulfur reduction or incorporation of vanadium as liquid along with the feed. It is important to note here that the increased heavy metal concentration in the FCCU catalyst inventory does not lead to the host catalyst deactivation. This can be further explained in the following examples.
  • the term activity means ASTM 3907 MAT activity
  • conversion means the sum of yields of gas products, liquid products with final true boiling point up to 22O 0 C and coke.
  • An embodiment of the present invention is that the added external spent heavy metal poisoned FCC/RFCC catalyst reduces the sulfur content in the cracked products, primarily gasoline.
  • Another embodiment of the present invention is the reduction in sulfur content up to 50 wt% in the cracked products, primarily gasoline.
  • Another embodiment of the present invention is utilization of spent heavy metal poisoned FCC/RFCC catalyst, which is to be disposed off.
  • Yet another embodiment of the present invention is the addition of foreign spent heavy metal poisoned FCC/RFCC catalyst will not inhibit the host equilibrium catalyst in the circulating catalyst inventory of FCCU/RFCCU process.
  • Further embodiment of the present invention relates to addition of the spent catalyst to the host FCC unit circulating catalyst inventory, which can be performed independently through a separate line or by mixing with fresh host catalyst or by mixing with specific additives like ZSM-5, BCA, SOx and NOx additives, etc. Addition in all these cases can be in either intermittent or continuous.
  • Yet another embodiment of the present invention is that the reduction of metal concentration on spent heavy metal poisoned FCC/RFCC spent catalyst due to its addition to FCCU/RFCC unit inventory having low metal concentration, which makes the mixture catalyst less hazardous and enables its acceptance as raw materials in cement industry.
  • the addition of heavy metal poisoned FCC/RFCC catalyst in to the equilibrium catalyst inventory is unit specific.
  • unit specific means the quantity of the addition depends upon various constraints/variables like system metal concentration, wet gas compressor capacity, unit-operating conditions, amount of sulfur to be removed, feed sulfur, coke burning capacity of the regenerator, etc.
  • the spent catalyst can be mixed with host equilibrium catalyst by separate addition or by mixing with fresh catalyst or in combination with different additive system as stated earlier.
  • the fluidized catalytic cracking (FCC) process in accordance to the present invention was tested in a fixed fluidized bed catalyst ACE unit.
  • the catalyst in the reactor is fluidized with a stream of nitrogen of 1 OOcc/min flow rate.
  • the catalyst to oil ratio was varied by changing the amount of catalyst added.
  • the feed rate and time on stream were kept constant.
  • the catalyst was stripped by nitrogen.
  • the quantity of gaseous product was measured by water displacement method.
  • Coke on catalyst was determined by in-situ regeneration with fluidized air.
  • the gaseous product obtained from ACE unit was analyzed by an online gas chromatographic technique.
  • the liquid product was analyzed by using Simdist analyzer.
  • the products in the process of the present invention are Dry gas (DG comprising Hydrogen disulfide, hydrogen and Cl & C2 hydrocarbons), Liquefied petroleum gas (LPG comprising C3 & C4 hydrocarbons), Gasoline (C5 tol 50°C), HCN (Heavy Cracked Naphtha, 150-220 0 C), Light Cycle Oil (LCO: 220-370 0 C) and Clarified oil (CLO: 370°C+). Carbon was analyzed by online Infra red analyzer.
  • the catalyst used in this experiment comprises 90 wt% Catalyst-A, the E-Cat from FCC unit-A and 10 wt% of Catalyst-C which is a heavy metal poisoned spent catalyst from FCC unit-C.
  • the results of the experiment in fluidized based ACE unit using Feed-A are shown in Table-3.
  • the catalyst used in this experiment comprises 90 wt% Catalyst-B and 10 wt% of Catalyst-C.
  • the feed for this experiment was changed corresponding to the unit and it is designated as Feed B.
  • the results of the experiment in fluidized based ACE Micro-reactor unit are shown in Table-3.
  • Eixternal heavy metal poisoned spent catalyst from a FCC unit was directly used to test its effect on FCC unit performance.
  • the catalyst used in this experiment comprises a mixture of 60 wt%, equilibrium catalyst having nickel and vanadium concentration of 3500 and 7000 ppm respectively and 40 wt% of spent heavy metal poisoned catalyst having nickel and vanadium concentration of 3400 and 9000 ppm respectively.
  • the results of the experiment in fluidized based ACE unit using Feed-A are shown in Table-4.
  • the catalyst used in this experiment comprises a mixture of 70 wt% equilibrium catalyst (E-Cat) having nickel and vanadium concentration of 3000 and 12000 ppm respectively and 30 wt% of heavy metal poisoned spent catalyst having nickel and vanadium concentration of 3000 and 20000 ppm respectively .
  • E-Cat equilibrium catalyst
  • the results of the experiment in fluidized based ACE unit using Feed-A are shown in Table-5.
  • the purpose of this example is to verify whether the vanadium from the external heavy metal poisoned spent catalyst being directly included in the equilibrium catalyst inventory is migrating to the host FCC/RFCC equilibrium catalyst and thereby causing incremental destruction of zeolite leading to catalyst deactivation.
  • Catalyst-A was subjected to calcination followed by hydrothermal deactivation at 810 0 C for 5 hours in presence of saturated steam under fluidized conditions.
  • Catalyst-C was calcined and hydro-thermally deactivated under same conditions and a mixture was prepared comprising 90 wt% of hydro-thermally deactivated Catalyst-A and 10 wt% of hydro-thermally deactivated Catalyst-C. It is to be noted that in this case, the hydrothermal deactivation using steam was carried out separately. The performance of the above catalyst / catalyst mixture was tested using Feed-A at specified operating conditions and the results are shown in Table-6. TabIe-6
  • Fresh FCC catalyst corresponding to Catalyst-C in the commercial unit was doped with the vanadium and nickel actuates.
  • the amount of nickel and vanadium actuates was in accordance with the metal concentration on actual Catalyst-C. Therefore, the said fresh catalyst was doped with 8400 ppm of Vanadium and 2500 ppm of nickel.
  • the metal concentration was measured using XRF technique.
  • the metal doped catalyst was subjected to one cycle of hydrogen reduction and subsequently, it was steam deactivated to simulate the characteristics of actual spent catalyst.
  • Fresh FCC catalyst corresponding to Catalyst-A in the commercial unit was steam deactivated at 81O 0 C for 5 hrs using saturated steam in a fluidized bed tubular reactor to simulate the characteristics of actual Catalyst-A. This is referred to as 'Simulated Catalyst- A'.
  • Experiments were conducted by using a catalyst mixture comprising 90 wt% of 'Simulated Catalyst-A' thus obtained in the laboratory and 10 wt% of Catalyst-C using Feed-A and the results are compared with those obtained with Catalyst-A at same operating conditions in Table-9.
  • the percentage reduction of gasoline sulfur when compared to the base catalyst was found to be 29.4 wt%. In this case also, yields of LPG and propylene increase with incorporation of external heavy metal poisoned spent catalyst. Similarly, it is clear that there is no synergy or contribution by any other additive in the host equilibrium catalyst.
  • Catalyst-C was replaced by Catalyst-D obtained from other source in the above experiment, the result of which is included in the same Table-8.
  • the result again follows the same trend as obtained with that of catalyst-C.
  • the FCC performance effect of addition of heavy metal poisoned spent catalyst does not depend upon the spent catalyst source and type.
  • the heavy metal present in the spent catalyst is responsible for sulfur reduction.
  • the performance in regard to the yield pattern may vary depending upon the type of spent catalyst. Table-10
  • the performance with 100% host catalyst-A is considered as base.
  • 10 wt% of total circulating inventory was replaced by Catalyst-C subsequently.
  • Feed-A is processed continuously with the composite circulating catalyst inventory for about 170 hrs.
  • the yield pattern obtained during these run are compared with base in Table- 1 1.
  • the liquid samples collected from both the runs were fractionated to separate out the gasoline.
  • the results of analysis of gasoline for both the runs are shown in Table-12.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de craquage catalytique en lit fluidisé pour le craquage d'une charge d'hydrocarbures comprenant un composé organo-soufré en tant qu'impureté, ledit procédé comprenant : l'ajout d'un catalyseur de métal lourd épuisé empoisonné à un catalyseur d'équilibre pour obtenir un catalyseur composite en circulation, le catalyseur de métal lourd épuisé empoisonné étant ajouté en une quantité pour maintenir l'activité du catalyseur en circulation ; et l'obtention d'un produit de craquage catalytique en lit fluidisé. La présente invention concerne également le produit de craquage catalytique en lit fluidisé obtenu par le procédé selon la présente invention. La teneur en soufre du produit de craquage catalytique en lit fluidisé, principalement de l'essence dont le point d'ébullition est compris entre C5 et 250°C réduit par plus de 20% en poids et le nombre d'Octane Recherche du produit de craquage catalytique fluidisé est augmenté par plus d'une unité.
PCT/IN2010/000191 2009-03-30 2010-03-29 Procede de craquage catalytique en lit fluidise WO2010113174A1 (fr)

Priority Applications (2)

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US13/260,919 US20120024748A1 (en) 2009-03-30 2010-03-29 Fluidized catalytic cracking process
CN201080020809.0A CN102439121B (zh) 2009-03-30 2010-03-29 流化催化裂化方法

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IN647/DEL/2009 2009-03-30
IN647DE2009 2009-03-30

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WO2010113174A1 true WO2010113174A1 (fr) 2010-10-07

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KR102321624B1 (ko) * 2014-05-23 2021-11-04 에스케이이노베이션 주식회사 디젤 수율을 극대화할 수 있는 rfcc 공정용 접촉분해촉매 및 이의 제조방법
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DK3167026T3 (da) * 2014-07-07 2019-07-01 Albemarle Europe Sprl Alkyleringsfremgangsmåde der anvender en katalysator, som omfatter sjælden jord rigt på cerium, der indeholder zeolitter og et hydrogeneringsmetal.
CN108031545B (zh) * 2015-06-30 2020-12-08 安耐罗技术股份有限公司 具有杂质去除的改善的催化快速热解方法
US10633596B2 (en) * 2016-06-17 2020-04-28 Basf Corporation FCC catalyst having alumina derived from crystalline boehmite
US9981888B2 (en) * 2016-06-23 2018-05-29 Saudi Arabian Oil Company Processes for high severity fluid catalytic cracking systems
CN107868675B (zh) * 2016-09-23 2019-11-15 中国石油化工股份有限公司 一种催化裂化的方法和催化裂化惰性载体助剂
CN110573594B (zh) * 2017-03-01 2022-10-25 雅宝欧洲有限责任公司 具有改进的辛烷值的烷基化工艺
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US20120024748A1 (en) 2012-02-02
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