WO1994000236A1 - Regeneration de catalyseur destine au craquage en lit fluidise - Google Patents

Regeneration de catalyseur destine au craquage en lit fluidise Download PDF

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Publication number
WO1994000236A1
WO1994000236A1 PCT/US1992/005312 US9205312W WO9400236A1 WO 1994000236 A1 WO1994000236 A1 WO 1994000236A1 US 9205312 W US9205312 W US 9205312W WO 9400236 A1 WO9400236 A1 WO 9400236A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
coke
coke combustor
regenerated catalyst
bed
Prior art date
Application number
PCT/US1992/005312
Other languages
English (en)
Inventor
Mark Sheldon Ross
Original Assignee
Mobil Oil Corporation
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 US07/657,781 external-priority patent/US5143874A/en
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AU23034/92A priority Critical patent/AU2303492A/en
Priority to PCT/US1992/005312 priority patent/WO1994000236A1/fr
Publication of WO1994000236A1 publication Critical patent/WO1994000236A1/fr

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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
    • C10G11/182—Regeneration
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
    • B01J38/36—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed and with substantially complete oxidation of carbon monoxide to carbon dioxide within regeneration zone

Definitions

  • This invention relates to the regeneration of fluidized catalytic cracking catalyst.
  • hydrocarbon feed contacts particulate catalyst in a reactor at 425°C-600 ⁇ 'C, usually 460 o C-560°C, whereby the hydrocarbons are cracked and carbonaceous hydrocarbons or coke are deposited on the catalyst.
  • the cracked products are separated from the coked catalyst and the coked catalyst is stripped of volatiles, usually with steam, and then regenerated.
  • the catalyst regenerator the coke is burned from the catalyst with oxygen containing gas, usually air so as to restore catalyst activity and simultaneously heat the catalyst to, e.g., 500°C-900°C, usually 600°C-750°C.
  • the regenerated catalyst is then recycled to the cracking reactor.
  • H.E.R. High Efficiency Regenerator
  • the invention resides in a process for regenerating a coke-contaminated fluidized catalytic cracking catalyst comprising contacting a first dense bed of the coke-contaminated fluidized catalytic cracking catalyst with an oxygen-containing regeneration gas in a coke combustor having a sidewall portion and a base portion to produce at least partially regenerated catalyst and carbon monoxide, discharging from the coke combustor the at least partially regenerated catalyst and gas into a dilute phase transport riser, burning in the transport riser carbon monoxide to CO- and discharging from the dilute phase transport riser regenerated catalyst, which is collected in a second dense bed of hot regenerated catalyst, and flue gas which is removed from the process, the improvement comprising heating said spent catalyst in said coke combustor by maintaining the base portion and at least a portion of the sides of the coke combustor immersed within, and in a heat exchange relationship with, the second dense bed of regenerated catalyst.
  • Figure 1 is a simplified, cross-sectional view of a conventional, single dense bed regenerator
  • Figure 2 is a simplified, cross-sectional view of a regenerator according to one embodiment of the present invention.
  • the conventional regenera ⁇ tor shown therein comprises a regenerator shell 1 containing a bubbling dense bed 50 of hot, regenerated catalyst.
  • Spent catalyst from an FCC reactor stripper (not shown) is passed via line 40 into bubbling dense bed 50.
  • Combustion air is added via line 10, and distributed in a lower portion of bed 50 via air grid 25.
  • Hot regenerated catalyst is withdrawn for reuse in the cracking process via line 30.
  • Flue gas, with entrained catalyst rises above bed 50 and passes through cyclone 51.
  • Recovered catalyst is discharged back into bed 50 via dipleg 52, which is sealed by immersion in bed 50. Flue gas is discharged from the cyclone via outlet 53 to plenum 60 and flue gas exit line 70.
  • Figure 2 represents an existing FCC regenerator such as that shown in Figure 1, which has been modified to provide an H.E.R. design according to the present invention.
  • Elements common to both Figures have the same reference numerals, e.g., shell 1 is the same in both Figure 1 and Figure 2.
  • the main modification provided to produce the Figure 2 embodiment is an internal combustion chamber or coke combustor 301 which is located within the shell 1 and which receives spent catalyst from the line 40 via a baffled opening 315.
  • the coke combustor 301 maintains the catalyst as a relatively dense phase fluidized bed 450, but one which is much more active than the old bubbling bed 50 in the prior art design.
  • the coke combustor 301 receives combustion air from line 10 via dome air grid 325 to begin coke combustion.
  • the coke combustor includes an inwardly tapering transition section 305 connecting the coke combustor to a dilute phase transport riser 302. Regenerated catalyst is discharged from riser 302 and deflected by deflector 320 through opening 310 to collect as a second dense bed of catalyst 350 in the annular space betewwen the shell 1 and the coke combustor 301.
  • the base and at least a portion of the side walls of the coke combustor are immersed in, and in heat exchange relationship with, the second dense bed 350, which will usually be a bubbling bed, i.e., fairly similar in fluidization regime to that existing in the prior art single dense bed 50.
  • a fluffing ring 111 is supplied with fluffing air via lines 110 to keep hot regenerated catalyst in bed 350 in an aerated state. Regenerated catalyst is withdrawn from regenerator 1 via regenerated catalyst standpipe 30 for reuse in the catalytic cracking process.
  • the coke combustor 301 is heated to some extent by immersion in the bed 350 of hot, regenerated catalyst. There is also a limited amount of preheating of spent catalyst in line 40 and a modest amount of preheating of combustion air added via line 10.
  • a CO combustion promoter is present to enhance the efficiency of coke combustion within coke combustor 301, and to augment afterburning of carbon monoxide to carbon dioxide within dilute phase transport riser 302.
  • the unit operates as shown in Figure 2, i.e., with heat exchange, but no catalyst recycle, from the second dense bed to the coke combustor.
  • Operation with generous amounts of CO combustion promoter e.g., on the order of 1-10 ppm wt. will ensure rapid and complete coke combustion within the coke combustor, and relatively complete CO combustion in dilute phase transport riser 302.
  • catalyst exiting riser outlet 310 will have a very low carbon level, on the order of 0.05 wt. % carbon or less.
  • the present invention allows the highest temperatures to be confined to the coke combustor and the transport riser, especially to the transport riser outlet.
  • a heat exchange means such as a coil or heat exchanger tubes (not shown) can be used to remove heat from second dense bed 350, and achieve complete CO combustion without having much of the metallurgy of the regenerator vessel exposed to the high temperatures associated with complete CO combustion.
  • the Figure 2 embodiment works especially well when combined with a hot stripper, in which spent catalyst is mixed with some hot regenerated catalyst to heat the spent catalyst.
  • Hot stripping removes more strippable materials from the spent catalyst which reduces the burning load in the regenerator, and also provides hotter spent catalyst for use in the regenerator.
  • Hot catalyst strippers are known in the art, and a suitable design is shown in U.S. 4,820,404.
  • the spent catalyst temperature will usually be in the range 480 to 590°C (900 to 1100°F) , preferably 495 to 565°C (925 to 1050°F) .
  • the regeneration conditions include a certain amount of air preheat, typically to about 180°c (350 ⁇ F) .
  • the temperature of the catalyst at the regenerator inlet in a typical unit will be about 520°C (960°F).
  • the catalyst particle density will typically be about 1440 kg/m 3 (90 lbs/ft3) , and the average parti.cle diameter will be about 64 microns.
  • the carbon on spent catalyst will typically be around 0.8 wt%, and the hydrogen on coke will be about 8.5 %.
  • the superficial gas velocity at the top of the fast fluidized bed will preferably be about 100 cm/second (3.5 feet/second), while the superficial gas velocity in the dilute phase transport riser will be about 300 cm/second (10.5 feet/second) .
  • intense fluidization is achieved by designing the internal chamber so the dense bed of catalyst 450 is maintained as a fast fluidized bed.
  • Such beds are characterized by very small "bubbles'* or voids.
  • the bed will be relatively low in density, as compared to the density of the conventional dense phase fluidized beds used in single stage regenerators.
  • Conditions in the second dense bed of regenerated catalyst, bed 350 in the Figure 2 embodiment will typically include a dense bed temperature of around 700°C (1300T), for the spent catalyst and regeneration conditions used in the coke combustor as described above.
  • the bed density will be about 560 kg/ 3 (35
  • the second dense bed will be fluidized with air, but only about 1.0% of the combustion air will be added to the second dense bed, primarily for fluffing, and to maintain the bed active so that efficient heat exchange with the coke combustor can be achieved.
  • the most important factor in determining the effectiveness of heat transfer with the coke combustor 301 is geometry, i.e., having the bottom and sides of the coke combustor immersed in and in a heat exchange relationship with the second fluidized bed holding regenerated catalyst. Sufficient heat transfer can be obtained for many units merely by relying on heat transfer through the conventional vessel walls of the coke combustor. However, several steps can be taken to improve heat transfer further.
  • a conductive refractory, or use of more steel and less or no refractory will improve heat transfer.
  • a dimpled or rippled or ridged surface can be applied to the inner, or outer, or both walls of the coke combustor vessel to increase surface area.
  • Conventional heat exchange fins can be used to increase surface area.
  • Heat pipes are another effective means of increasing heat transfer from the bubbling or second fluidized bed to the coke combustor.
  • Heat pipes are a mechanical apparatus well known in the heat transfer arts. They comprise an outer sealed cylindrical conduit which retains a small amount of working fluid which may be vaporized and condensed at the tempera ⁇ tures of the heat source and heat sink, respectively. The working fluid is vaporized in the bubbling dense bed of the catalyst regenerator and condensed in the coke combustor. A wick is provided to transfer the condensed fluid from the fast fluidized bed coke combustor side back to the bubbling dense bed side of the regenerator.
  • Heat pipes work best when vertical, which means they are especially well suited for use in heating a coke combustor immersed in, but above the base of, a bubbling dense bed catalyst regenerator. Heat pipes have heretofore been proposed for use in removing heat from FCC regenerators, by transferring the heat to boil water and make steam, and heat pipes of similar design may be used herein.
  • the heat pipes should be made of metals which can withstand the harsh erosive environment within FCC regenerators and strippers, so use of heavy guage materials, such as thick stainless steel for the pipes is preferred. Standard references describe working fluids which are suitable, and conventional high temperature working fluids such as sodium, potassium, cesium or mercury can be considered for use herein.
  • a working fluid should be selected which will do the least amount of damage to the FCC catalyst inventory.
  • Sodium is a poison of sorts for FCC catalyst, but a well known one, which can be tolerated in relatively large amounts, so this may be a preferred working fluid.
  • heat pipes having on outer diameter of 2.5-12.7 cm (1-5 inch), and a length of 1.5-3 m (5-10 feet).
  • the heat pipes may be used in bundles or evenly distributed about or under the coke combustor.
  • the spent catalyst is heated at least about 10°C (20°F) by indirect heat exchange in the coke combustor, and most preferably at least 17°C (30°F).
  • the spent catalyst in the coke combustor is heated more than 22°C (40°F) , e.g., by 28-56°C (50-100°F) .
  • the bubbling dense bed of catalyst 350 will be spaced from the sidewalls and the bottom of the coke combustor by at least 0.3 m (1 ft), to allow adequate catalyst circulation, and preferably by a least 0.6 m (2 ft), and most preferably by 0.8-1.5 m (2.5-5 ft) .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

On décrit un procédé très efficace pour régénérer un catalyseur usé destiné au craquage en lit fluidisé, effectué dans un régénérateur existant à lit unique et dense, conçu pour ce type de catalyseur. Le catalyseur usé est introduit dans un brûleur de coke (301) immergé dans le lit de catalyseur du réacteur de régénération existant (1). Une conduite montante de transport (302) de la phase diluée située au-dessus du brûleur de coke (301) et reliée à celui-ci, évacue un mélange de catalyseur régénéré et de gaz de combustion. Le catalyseur régénéré est recueilli autour et en dessous du brûleur de coke. L'entrée du catalyseur usé (40) et l'entrée de l'air de combustion (10) sont de préférence immergées dans le lit de catalyseur régénéré chaud (350), de manière à permettre un échange thermique. Le fait de chauffer le brûleur de coke (301) par échange thermique indirect plutôt que par recyclage de catalyseur régénéré chaud diminue les émissions particulaires et économise l'énergie nécessaire à la régénération du cataylseur dans le régénérateur.
PCT/US1992/005312 1990-01-12 1992-06-23 Regeneration de catalyseur destine au craquage en lit fluidise WO1994000236A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU23034/92A AU2303492A (en) 1992-06-23 1992-06-23 Regeneration of fluidized catalytic cracking catalyst
PCT/US1992/005312 WO1994000236A1 (fr) 1990-01-12 1992-06-23 Regeneration de catalyseur destine au craquage en lit fluidise

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US46406890A 1990-01-12 1990-01-12
US07/657,781 US5143874A (en) 1990-01-12 1991-02-19 Catalyst regenetation in high efficiency regenerator heated by indirect heat exchange
PCT/US1992/005312 WO1994000236A1 (fr) 1990-01-12 1992-06-23 Regeneration de catalyseur destine au craquage en lit fluidise

Publications (1)

Publication Number Publication Date
WO1994000236A1 true WO1994000236A1 (fr) 1994-01-06

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100383379B1 (ko) * 2000-11-24 2003-05-12 (주) 바임래버러토리즈 무궁화 원료 추출 방법
FR2909907A1 (fr) * 2006-12-13 2008-06-20 Inst Francais Du Petrole Nouveau dispositif permettant de diminuer les emissions de nox des fumees de fcc
EP2334760A2 (fr) * 2008-09-30 2011-06-22 Uop Llc Dispositif et procédé pour mélanger un catalyseur régénéré et carbonisé
CN113423496A (zh) * 2019-02-15 2021-09-21 环球油品有限责任公司 用于催化剂再生器的改进的密封设备
CN114829010A (zh) * 2019-12-13 2022-07-29 环球油品有限责任公司 利用补充燃料再生催化剂的方法和设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2401739A (en) * 1941-08-25 1946-06-11 Standard Oil Co Cocurrent-countercurrent regenerator
US3919115A (en) * 1972-06-08 1975-11-11 Universal Oil Prod Co Fluidized catalyst regeneration process
US3923686A (en) * 1972-05-30 1975-12-02 Universal Oil Prod Co Fluidized catalyst regeneration by oxidation in a dense phase bed and a dilute phase transport riser
US4448753A (en) * 1982-02-12 1984-05-15 Mobil Oil Corporation Apparatus for regenerating cracking catalyst
US5143874A (en) * 1990-01-12 1992-09-01 Mobil Oil Corporation Catalyst regenetation in high efficiency regenerator heated by indirect heat exchange

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2401739A (en) * 1941-08-25 1946-06-11 Standard Oil Co Cocurrent-countercurrent regenerator
US3923686A (en) * 1972-05-30 1975-12-02 Universal Oil Prod Co Fluidized catalyst regeneration by oxidation in a dense phase bed and a dilute phase transport riser
US3919115A (en) * 1972-06-08 1975-11-11 Universal Oil Prod Co Fluidized catalyst regeneration process
US4448753A (en) * 1982-02-12 1984-05-15 Mobil Oil Corporation Apparatus for regenerating cracking catalyst
US5143874A (en) * 1990-01-12 1992-09-01 Mobil Oil Corporation Catalyst regenetation in high efficiency regenerator heated by indirect heat exchange

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100383379B1 (ko) * 2000-11-24 2003-05-12 (주) 바임래버러토리즈 무궁화 원료 추출 방법
FR2909907A1 (fr) * 2006-12-13 2008-06-20 Inst Francais Du Petrole Nouveau dispositif permettant de diminuer les emissions de nox des fumees de fcc
US7767177B2 (en) 2006-12-13 2010-08-03 Institut Francais Du Petrole Device permitting the reduction of NOX emissions from FCC fumes
EP2334760A2 (fr) * 2008-09-30 2011-06-22 Uop Llc Dispositif et procédé pour mélanger un catalyseur régénéré et carbonisé
EP2334760B1 (fr) * 2008-09-30 2014-10-29 Uop Llc Dispositif et procédé pour mélanger un catalyseur régénéré et carbonisé
CN113423496A (zh) * 2019-02-15 2021-09-21 环球油品有限责任公司 用于催化剂再生器的改进的密封设备
CN113423496B (zh) * 2019-02-15 2023-10-20 环球油品有限责任公司 用于催化剂再生器的改进的密封设备
CN114829010A (zh) * 2019-12-13 2022-07-29 环球油品有限责任公司 利用补充燃料再生催化剂的方法和设备

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