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EP1076680A1 - Procede de craquage catalytique fluide permettant de transformer plusieurs charges d'alimentation - Google Patents

Procede de craquage catalytique fluide permettant de transformer plusieurs charges d'alimentation

Info

Publication number
EP1076680A1
EP1076680A1 EP99914279A EP99914279A EP1076680A1 EP 1076680 A1 EP1076680 A1 EP 1076680A1 EP 99914279 A EP99914279 A EP 99914279A EP 99914279 A EP99914279 A EP 99914279A EP 1076680 A1 EP1076680 A1 EP 1076680A1
Authority
EP
European Patent Office
Prior art keywords
feed
feeds
riser
differ
fccu
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99914279A
Other languages
German (de)
English (en)
Inventor
Teh Chung Ho
Shun Chong Fung
Gordon Frederick Stuntz
Robert Charles William Welch
Daniel Paul Leta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/231,697 external-priority patent/US6123832A/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1076680A1 publication Critical patent/EP1076680A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C10G11/14—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

Definitions

  • This invention relates to Fluid Catalytic Cracking (FCC) for producing liquid fuels and light olefins from liquid hydrocarbon mixtures such as petroleum fractions. More specifically, it relates to an improved FCC process, especially for converting hydrocarbon mixtures by taking advantage of a process nonlinearity.
  • FCC Fluid Catalytic Cracking
  • FCC has been, and will remain for quite some time, the primary conversion process in oil refining.
  • a liquid feed mixture is atomized through a nozzle to form small droplets at the bottom of a riser.
  • the droplets contact hot regenerated catalyst and are vaporized and cracked to lighter products and coke.
  • the vaporized products rise through the riser.
  • the catalyst is separated out from the hydrocarbon stream through cyclones. Once separated, the catalyst is stripped in a steam stripper of adsorbed hydrocarbons and then fed to a regenerator where coke is burned off.
  • the products are sent to a fractionator for fractionation into several products.
  • the catalyst once regenerated, is then fed back into the riser.
  • the riser-regenerator assembly is heat balanced in that heat generated by the coke burn is used for feed vaporization and cracking.
  • the most common FCC feeds by far are gas oils or vacuum gas oils (VGO) which are hydrocarbon mixtures boiling above about 650°F.
  • VGO vacuum gas oils
  • refiners need to convert heavy, or highly contaminated oils such as resids, they usually blend a small amount of such heavy oils with the gas oil feeds. Due to a dwindling supply of high-quality crudes, the trend in the petroleum industry is that FCC will have to convert more and more heavy, dirty feeds.
  • Such feeds contain a high level of contaminants such as nitrogen, sulfur, metals, polynuclear aromatics, and Conradson Carbon Residue (CCR, a measure of asphaltene content).
  • CCR Conradson Carbon Residue
  • heavy component is used to include such highly contaminated hydrocarbons as resids, deasphalted oils, lube extracts, tar sands, coal liquids, and the like.
  • Such heavy components are added to other feeds containing less heavy components to obtain an FCC feed. These heavy components will become a significant portion of FCC feeds in years to come.
  • FCC feed injectors typically consist of rings around the riser wall with 6 to 10 nozzles. These nozzles can be at the same elevation or in two rows one above the other.
  • the standard practice has been to premix the heavy component with gas oil and inject the resulting mixture through all of the nozzles.
  • a major effort in FCC has been directed toward the improvement of the spray pattern to minimize the variation in the catalyst-to-oil ratio over the riser cross-section. For this reason, feed nozzles that produce a flat fan of liquid are gaining wide acceptance these days (see R. J.
  • U.S. Patent No. 3,993,556 cracked heavy and light gas oils in separate risers to improve yields of high octane naphtha.
  • U.S. Patent No. 3,928,172 proposed to crack a gas oil feed and heavy naphtha and/or virgin naphtha fraction in separate cracking zones.
  • U.S. Patent No. 3,801,493 cracked virgin gas oil, topped crude and the like, and slack wax in separate risers to recover a light cycle gas oil fraction for furnace oil use and a high octane naphtha fraction suitable for use in motor fuel, respectively.
  • the present invention provides an improved FCC process and feed injection method for cracking FCC feeds containing heavy components.
  • One embodiment 4 of the invention is to use at least one nozzle in the unit for injecting a first feed and use the remaining nozzles for injecting a second feed of different quality.
  • Another embodiment is to use two separate risers to convert the two feeds individually.
  • Still another embodiment is to partition the riser into two zones for separate cracking of said feeds at least in a portion of the riser.
  • the present invention gives a higher overall liquid yield and lower coke selectivity.
  • the benefit when using at least one feed having Conradson Carbon Residue stems from the fact that the lower CCR feed increases the conversion to a much greater extent than the conversion loss due to the higher CCR containing feed.
  • the present invention is directed to a Fluid Catalytic Cracking process conducted in a fluid catalytic cracking unit (FCCU) comprising one or more risers, each of said risers having a plurality of injection nozzles therein and at least one reaction zone therein comprising the steps of spatially nonuniformly injecting a plurality of feeds wherein said plurality of feeds comprises at least one feed ( ⁇ ) and at least another feed ( ⁇ ), wherein said feeds ( ⁇ ) and ( ⁇ ) : (a) differ in Conradson Carbon Residue by at least about 2 wt% points or (b) differ in hydrogen content by at least about 0.2 wt%; or (c) differ in API gravities by at least about 2 points; or (d) differ in nitrogen content by at least about 50 ppm; or (e) differ in carbon-to-hydrogen ratio by at least about 0.3; or (f) differ in mean boiling point by at least about 200°F; and wherein said spatially nonuniform injection is accomplished by
  • said feeds are substantially non-paraffinic feeds.
  • Such operation can result in a higher overall conversion and a lower coke selectivity.
  • the benefit can translate into a higher heavy component-containing feed cracking capacity at constant liquid yield.
  • the invention is likewise directed to a method for selecting two feeds ⁇ and ⁇ for use in a Fluid Catalytic Cracking process in a fluid catalytic cracking unit (FCCU) to obtain a predetermined increase in liquid yield and a predetermined decrease in coke make wherein said process comprises nonuniformly injecting said feeds ⁇ and ⁇ , said spatially nonuniform injection being accomplished by
  • said selection is accomplished by generating a plot of conversion and a plot of coke make versus a feed quality index and selecting from the plots two feeds which exhibit an increase in liquid yield and a decrease in coke make equal to said predetermined increase and decrease as shown by D minus F and G minus E on Figures la and lb, respectively, and wherein said feeds ( ⁇ ) and ( ⁇ ) : (a) differ in Conradson Carbon Residue by at least about 2 wt% points or (b) differ in hydrogen content by at least about 0.2 wt%; or (c) differ in API gravities by at least about 2 points; or (d) differ in nitrogen content by at least about 50 ppm; 6 or (e) differ in carbon-to-hydrogen ratio by at least about 0.3; or (f) differ in mean boiling point by at least about 200°F.
  • the invention is likewise directed to a Fluid Catalytic Cracking process conducted in a fluid catalytic cracking unit (FCCU) comprising one or more risers, each of said risers having a plurality of injection nozzles therein and at least one reaction zone therein comprising the steps of spatially nonuniformly injecting a plurality of feeds wherein said plurality of feeds comprises at least one feed ( ⁇ ) and at least another feed ( ⁇ ), wherein said feeds ( ⁇ ) and ( ⁇ ): (a) differ in Conradson Carbon Residue by at least about 2 wt% points or (b) differ in hydrogen content by at least about 0.2 wt%; or (c) differ in API gravities by at least about 2 points; or (d) differ in nitrogen content by at least about 50 ppm; or (e) differ in carbon-to-hydrogen ratio by at least about 0.3; or (f) differ in mean boiling point by at least about 200°F; and wherein said spatially nonuniform injection is accomplished by
  • feeds ( ⁇ ) and ( ⁇ ) are selected by generating a plot of conversion and a plot of coke make versus a feed quality index and selecting from the plots two feeds which exhibit an increase in liquid yield and a decrease in coke make equal to said predetermined increase and decrease as shown by D minus F and G minus E on Figures la and lb, respectively.
  • said predetermined increase in liquid yield and predetermined decrease in coke make are an increase or decrease over what would be achieved if the two feeds were mixed prior to injection into the riser of said FCC unit.
  • Figure la Conversion as a function of wt% resid in total feed.
  • Figure lb Coke yield as a function of wt% resid in total feed.
  • Figure 2a Coke-free kinetic conversion to ⁇ 430°F products vs. wt% resid in feed; 515°C, 8 C/O.
  • Figure 2b Coke-free kinetic conversion to ⁇ 650°F products vs. wt% resid in feed; 515°C, 8 C/O.
  • Figure 2c Coke selectivity vs. wt% resid in feed; 515°C, 8 C/O.
  • Figure 3a Conversion to ⁇ 430°F products vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst A.
  • Figure 3b Conversion to ⁇ 430°F products vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst B.
  • Figure 3 c Coke yield vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst C.
  • Figure 3d Propylene yield vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst B.
  • Figure 3e Distillate yield vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst C.
  • Figure 3g Bottoms yield vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst C.
  • Figure 3h Butylene yield vs. wt% feed hydrogen; 496°C, 6.5 C/O; catalyst C.
  • Figure 1 depicts qualitatively the nonlinear dependencies of conversion and coke yield on the concentration of the resid in the feed.
  • the curve for conversion is convex, whereas that for coke yield is concave.
  • an FCC unit's coke burning capacity is such that the maximum permissible concentration of the resid is 10 wt%
  • the instant invention uses an entirely different approach.
  • the invention calls for a spatially nonuniform injection scheme.
  • One embodiment of the present invention is to use a number of the nozzles of the FCC unit for injecting a heavy component-rich feed and the remaining nozzles for injecting a heavy component-lean feed.
  • the rich feed is that having the higher Conradson Carbon number.
  • a hypothetical FCC riser having ten nozzles.
  • the feeds are selected from the nonlinear curves of conversion and coke make versus a feed quality index such as wt% resid as shown in Figures la and lb, or wt% feed hydrogen as shown in Figure 3b.
  • a feed quality index such as wt% resid as shown in Figures la and lb, or wt% feed hydrogen as shown in Figure 3b.
  • such plots can be obtained a priori in small scale routine experiments. Knowing the FCC unit's resid capacity then helps the skilled artisan to select two feeds ( ⁇ ) and ( ⁇ ) for utilization in the instant invention. For example, if one predetermined that a 3% increase in liquid yield was desired, any two feeds which give the 3% increase [see e.g.
  • the increase in liquid yield will be at least about 0.5 wt % on feed, and the decrease in coke make will be at least about 0.2 wt % on feed.
  • the wt% decrease in coke yield would be represented by G minus E on Figure lb.
  • substantially non-paraffinic feeds may be used in any of the injection schemes (i) to (iii).
  • substantially non-paraffinic means feeds having a Watson K factor of less than 12.2.
  • injection schemes (i) and (ii), which utilize a single riser, will be used.
  • the feed injection rate for the two sets of nozzles are adjusted to give a desired overall resid concentration, e.g., 10 wt%.
  • the local catalyst-to-oil 10 ratio for the two streams will be different, allowing cracking of each stream to be individually optimized.
  • the nozzles will be chosen such that feed ( ⁇ ) will be injected via adjacent nozzles and feed ( ⁇ ) will be injected via adjacent nozzles.
  • feed ( ⁇ ) will be injected via adjacent nozzles
  • feed ( ⁇ ) will be injected via adjacent nozzles.
  • the two feed streams can be injected into two reaction zones in the riser achieved by partitioning at least the bottom of the riser.
  • the instant invention can be applied to any feed pair whenever the feed properties are sufficiently different.
  • the feed pair may comprise a naphtha-rich stock and naphtha-lean stock.
  • Nonlimiting examples of feed properties yardsticks for feeds that have a CCR difference of less than 2 wt% or do not contain CCR, including heavy component-containing feeds having no CCR, are hydrogen content (differing by at least about 0.2 wt%), carbon-to- hydrogen ratio (differing by at least about 0.3), API gravity (differing by at least about 2 points), nitrogen content (differing by at least about 50 ppm), mean boiling point (differing by at least about 200°F), etc.
  • the criterion of the instant invention is satisfied if that feed has a CCR content of about 2 wt% points or higher than the other feed which has no CCR or any of the other criteria are met.
  • the feeds will preferably differ in API gravities by at least about 3 points. Preferably, only two feeds will be utilized.
  • the cracking experiments were conducted in an FCC pilot unit at 515°C and a catalyst-to-oil (C/O) ratio of 8.
  • the catalyst is metered from a regenerated catalyst hopper into a riser using a screw feeder.
  • the hot catalyst contacts incoming oil and gaseous nitrogen and is carried up the riser where the oil is cracked.
  • the spent catalyst and reactor products enter a separation zone.
  • the gases continue overhead to a product recovery system and the catalyst drops down a stripper and into a spent 12 catalyst hopper.
  • the gaseous products are cooled to produce a C 5 + liquid product and a C 5 " gas product.
  • Figures 2a and 2b show, respectively, the coke-free kinetic conversions to ⁇ 430°F and ⁇ 650°F products as functions of the resid content of the total feed.
  • Figure 2c depicts a similar plot for coke yield. From these plots one can determine the average kinetic conversion and coke selectivity. It follows from Figures 2a to 2c that ⁇ (for conversions to ⁇ 430°F and ⁇ 650°F products) are higher than those obtained from the 16% VR-in-VGO feed, while S is lower. Each data point is the average of two or three runs. Specifically, the 430 and 650 coke-free kinetic conversions were improved by 5.3% and 7.5%, respectively. That is, in the case of 430 coke-free kinetic conversion, the ratio of ⁇ to ⁇ (for the 16% VR-in- VGO feed) is 1.053. And the coke selectivity is lowered by 12.2%.
  • the catalyst was the same as in Example 1 except that it was not impregnated with Ni. Cracking conditions are 5 C/O and 515°C. The 430 and 650 kinetic conversions were improved by 8.9% and 10.7%, respectively, with the coke selectivity being decreased by 4.4%. The propylene yield was improved by 6.5%.
  • the feed components used in this example are a hydrotreated VGO (HTGO) and a butane-deasphalted resid (DAO).
  • HTGO hydrotreated VGO
  • DAO butane-deasphalted resid Table 2 lists the compositions and properties of the feed blends.
  • a vacuum gas oil was separated into different fractions having varying hydrogen contents via solvent extraction. These resulting fractions were each cracked at 496°C, 6.5 C/O, and 80 g/m oil rate over several commercial catalysts, designated as catalysts A, B, and C. Table 3 lists the properties of these catalysts.
  • the hydrogen content of the feed was used as the feed quality measure. The data shown in Figures 3 a to 3 h were obtained for 14

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

Abstract

Cette invention concerne un procédé de craquage catalytique fluide qui se déroule dans une unité de craquage catalytique fluide (UCCF) comprenant une ou plusieurs colonnes montantes. Chaque colonne montante comprend plusieurs buses d'injection et au moins une zone de réaction. Ce procédé consiste à injecter de manière non uniforme et tridimensionnelle plusieurs charges d'alimentation, à savoir au moins une charge (α) et au moins une autre charge (β). Les deux charges (α) et (β) se distinguent l'une de l'autre en ce que: (a) soit leurs résidus Conradson diffèrent d'au moins 2 points de % en poids environ; (b) soit leurs teneurs en hydrogène diffèrent d'au moins 0,2 % en poids environ; (c) soit leurs gravités API diffèrent d'au moins 2 points environ; (d) soit leurs teneurs en azote diffèrent d'au moins 50 mg/l environ; (e) soit les rapports carbone-hydrogène diffèrent d'au moins 0,3 environ; ou (f), soit leurs points d'ébullition moyens diffèrent d'au moins 200 °F environ. L'injection non uniforme tridimensionnelle se fait de la manière suivante: (i) on injecte simultanément, dans une seule zone de réaction d'une seule et même colonne montante, la charge (α) par au moins une buse d'injection ainsi que la charge (β) par les autres buses de cette colonne; (ii) on injecte la charge (α) dans au moins une des zones de réaction de la colonne montante de l'UCCF et l'on injecte simultanément la charge (β) dans une autre zone de réaction de ladite colonne montante; ou (iii) on injecte la charge (α) dans au moins une colonne montante de l'UCCF tandis que l'on injecte simultanément la charge (β) dans une seconde colonne montante de l'UCCF. Lorsque l'injection non uniforme tridimensionnelle se fait selon le procédé décrit en (iii), les charges d'alimentation consistent essentiellement en des charges non paraffiniques.
EP99914279A 1998-04-28 1999-03-30 Procede de craquage catalytique fluide permettant de transformer plusieurs charges d'alimentation Withdrawn EP1076680A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US231697 1988-08-12
US6786998A 1998-04-28 1998-04-28
US09/231,697 US6123832A (en) 1998-04-28 1999-01-14 Fluid catalytic cracking process for converting hydrocarbon mixtures
PCT/US1999/006928 WO1999055801A1 (fr) 1998-04-28 1999-03-30 Procede de craquage catalytique fluide permettant de transformer plusieurs charges d'alimentation
US67869 2002-02-08

Publications (1)

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EP1076680A1 true EP1076680A1 (fr) 2001-02-21

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EP99914279A Withdrawn EP1076680A1 (fr) 1998-04-28 1999-03-30 Procede de craquage catalytique fluide permettant de transformer plusieurs charges d'alimentation

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EP (1) EP1076680A1 (fr)
JP (1) JP2003517491A (fr)
CA (1) CA2328088A1 (fr)
WO (1) WO1999055801A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100404644C (zh) * 2005-10-24 2008-07-23 中国石油大学(北京) 一种加工焦化蜡油的方法及装置
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
CN101993710A (zh) * 2009-08-25 2011-03-30 中国石油大学(北京) 一种焦化蜡油分区催化裂化的方法和装置

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US3424672A (en) * 1967-01-09 1969-01-28 Phillips Petroleum Co Fluid catalytic stripping
US3617496A (en) * 1969-06-25 1971-11-02 Gulf Research Development Co Fluid catalytic cracking process with a segregated feed charged to separate reactors
US3993556A (en) * 1972-12-11 1976-11-23 Texaco Inc. Method of catalytic cracking of hydrocarbons
US3928172A (en) * 1973-07-02 1975-12-23 Mobil Oil Corp Catalytic cracking of FCC gasoline and virgin naphtha
US4435279A (en) * 1982-08-19 1984-03-06 Ashland Oil, Inc. Method and apparatus for converting oil feeds
FR2625509B1 (fr) * 1987-12-30 1990-06-22 Total France Procede et dispositif de conversion d'hydrocarbures en lit fluidise
CA1327177C (fr) * 1988-11-18 1994-02-22 Alan R. Goelzer Procede permettant de maximiser de facon selective la distribution d'hydrocarbures dans une installation de craquage catalytique a lit fluidise
US5009769A (en) * 1989-02-06 1991-04-23 Stone & Webster Engineering Corporation Process for catalytic cracking of hydrocarbons
US5098554A (en) * 1990-03-02 1992-03-24 Chevron Research Company Expedient method for altering the yield distribution from fluid catalytic cracking units

Non-Patent Citations (1)

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Title
See references of WO9955801A1 *

Also Published As

Publication number Publication date
WO1999055801A1 (fr) 1999-11-04
CA2328088A1 (fr) 1999-11-04
JP2003517491A (ja) 2003-05-27

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