EP1043384A2 - Fluidkatalytisches Krackverfahren mit einen Katalysator mit verbessertem Widerstand gegen Metalle - Google Patents

Fluidkatalytisches Krackverfahren mit einen Katalysator mit verbessertem Widerstand gegen Metalle Download PDF

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Publication number
EP1043384A2
EP1043384A2 EP00610038A EP00610038A EP1043384A2 EP 1043384 A2 EP1043384 A2 EP 1043384A2 EP 00610038 A EP00610038 A EP 00610038A EP 00610038 A EP00610038 A EP 00610038A EP 1043384 A2 EP1043384 A2 EP 1043384A2
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EP
European Patent Office
Prior art keywords
catalyst
regeneration
vanadium
residual oil
majority
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Application number
EP00610038A
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English (en)
French (fr)
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EP1043384A3 (de
Inventor
David B. Bartholic
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Bar-Co Processes Joint Venture
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Bar-Co Processes Joint Venture
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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
    • C10G11/182—Regeneration

Definitions

  • This invention relates to an improved fluid catalytic cracking (FCC) process for processing residual oils, in which the FCC unit (FCCU) design and operating conditions enable operating the FCCU with a level of metals on equilibrium catalyst which is increased over and above the current state of the art.
  • FCC fluid catalytic cracking
  • the major objective in refining crude petroleum oil has always been to produce the maximum quantities of the highest value added products and to minimize the production of low value products.
  • the highest value added products of oil refining with the largest market have been transportation fuels, such as gasoline, jet fuel and diesel fuels, and Number 2 home heating oil.
  • the lower value products have been associated with the residual oil, defined as the portion of the crude oil boiling above about 1000°F or 538°C.
  • the refining industry has striven to find a cost effective method for conversion of the residual oil portion of the crude oil to the higher value products and has had success by employing non-catalytic processes such as visbreaking, coking (delayed and fluid), and solvent deasphatting.
  • Catalyst poisons accelerate the deactivation of catalyst, reduce catalyst selectivity, and increase the catalyst and other operating costs so that these residual oil processing methods have only been made economical, in most cases, by limiting the proportion of residual oil in the feed relative to other feedstock components containing less catalyst poisons.
  • FCCU fluid catalytic cracking
  • FCCU is a very cost effective sulfur removal process in that it converts about 50% of the feed sulfur to H 2 S without hydrogen addition.
  • the amount of residual oil that a refiner has been able to economically convert in the FCC process has been limited by the cost of replacement catalyst required as a result of catalyst deactivation, which results from the metals, especially vanadium and sodium, contained in the residual oil feedstock.
  • the buildup of other catalyst poisons on the catalyst, such as the coke precursors, nitrogen and sulfur can be effectively controlled by using catalyst coolers to negate the effect of coke formation from the asphaltene compounds, using the MSCC process to overcome the problems associated with riser coking and vaporization in a riser type FCC, using regenerator flue gas and product treating to negate the environmental effects of feed sulfur, and using the MSCC process to negate the effects of feed nitrogen and nickel.
  • Equilibrium catalyst is FCC catalyst which has been circulated in the FCCU between the reactor and regenerator over a number of cycles.
  • the amount of fresh catalyst addition required. or the catalyst replacement rate is determined by the catalyst loss rate and the replacement rate necessary to maintain the desired equilibrium catalyst activity and selectivity to produce the optimum yield structure.
  • Catalyst activity is reduced, and selectivity for gasoline and light olefins is diminished.
  • This catalyst deactivation mechanism requires that the vanadium be fully oxidized, i.e., in the pentoxide form (not in the di-, tri-, or tetra-oxide form). Therefore, some oxidation of the vanadium can take place without resulting in such catalyst deactivating. It is believed that the mechanism for catalyst deactivation by sodium is similar to that for vanadium.
  • the present process is contrary to the philosophies employed by the major users of FCC technology. That is, the current FCC design philosophy used in several FCC processes is the so-called two stage regenerator, which regenerates the catalyst in two stages, with the second stage having a high temperature, typically greater than 1 300°F (704°C), and an oxidizing atmosphere. In another process the spent catalyst is distributed across the top of the regenerator bed so that the lower part of the fluidized bed where the combustion air is injected into the bed contacts the hottest catalyst with the highest oxygen concentration. All of the above are contrary to the principles of the present invention and do not permit satisfactory operation of an FCCU on a residual oil feedstock.
  • a primary objective of this invention is an FCC process enabling economical processing of residual oil feeds having greater than 30 ppm of metals (Ni+V) in the feed. Another objective is to reduce the detrimental effect of vanadium on catalyst activity. Another objective is to reduce the detrimental effect of sodium on catalyst activity. Still another objective of the invention is to reduce the FCC fresh catalyst replacement rate required to compensate for the catalyst deactivation effect caused by vanadium and sodium, which will reduce fresh catalyst costs, transportation costs, equilibrium catalyst disposal costs, and unit catalyst losses. Other objects of the invention will become apparent from the following description and/or practice of the invention.
  • an improved residual oil fluid catalytic cracking process for reducing catalyst deactivation caused by vanadium and/or sodium deposited on circulating catalyst used in the process from a residual oil feed, which process includes the steps of; contacting a residual oil feed in a fluid catalytic cracking reactor with hot regenerated cracking catalyst under hydrocarbon cracking conditions to convert the residual oil feed into lower molecular weight hydrocarbon product vapors and form a spent catalyst containing carbonaceous deposits including vanadium and/or sodium; separating a majority of the lower molecular weight hydrocarbon product vapors from the spent cracking catalyst to form separated product vapors and separated spent catalyst containing entrained hydrocarbon vapors; processing the separated product vapors into desired product fractions; subjecting the separated spent catalyst to stripping to remove therefrom a majority of the entrained hydrocarbon vapors; contacting the resulting stripped spent catalyst in a regenerator with an oxygen-containing regeneration gas under catalyst regeneration conditions which include a combination of a regeneration temperature
  • the present invention employs an FCC process design which incorporates a regenerator design and method of operation that maintains a less than complete oxidation atmosphere and/or reducing atmosphere in the regenerator and/or a regenerator temperature below 1300°F (704°C).
  • a less than complete oxidation atmosphere is defined as process conditions in the regenerator that results in at least 0.08 wt. % carbon on regenerated catalyst. That is, when processing residual oil feedstocks containing vanadium and/or sodium, it has been determined that the catalyst deactivation caused by vanadium and sodium can be substantially prevented by maintaining a less than complete oxidation atmosphere and/or a reducing atmosphere in the regenerator. This will retard the formation of vanadic acid and vanadium pentoxide and low melting point sodium compounds, and therefore, as discussed above, reduce the adverse effects of vanadium and sodium on catalyst activity.
  • regenerator temperature below 1300°F (704°C), and more preferably below 1250°F (677°C), that one can also reduce, even when utilizing an excess of oxygen for regeneration, the effect of vanadium and sodium on catalyst activity.
  • FCCU can be designed to operate the regenerator in a reducing atmosphere and/or at a temperature less than 1300°F (704°C) to minimize the catalyst deactivation by vanadium and sodium, combining both these processing conditions will result in the least catalys deactivation.
  • the feedstock employed in the present process contains residual oil, which may be in admixture with other lower-boiling hydrocarbons such as one or more gas oils or the like.
  • the proportion of residual oil in the feed may vary, depending upon the nature of the feedstock components.
  • the residual oil feed will contain from about 5 to 90 vol. % residual oil, with the remainder being one or more gas oils, for example, a vacuum gas oil, atmospheric gas oil, recycle, or the like.
  • residual oil refers to a crude oil fraction boiling above about 1000°F (538°C). Among the above-mentioned catalyst poisons, the residual oil will contain vanadium, sodium, or both.
  • a “residual oil” may contain sodium and vanadium in the metallic form and/or in the form of any various inorganic or organometallic compounds of these metals.
  • sodium and vanadium When said sodium and vanadium are deposited on the circulating catalyst such deposits may be in the form of a metal or one or more compounds thereof, e.g., sulfur compound or organometallic compound.
  • vanadium used sodium deposits refers any of various types of vanadium- and sodium- containing deposits formed on the catalyst as metals or as compounds thereof.
  • a residual oil feed supplied via line 1 is mixed with regenerated catalyst supplied via line 2 in a reactor 4 of an FCC type reaction system.
  • FCC reaction systems are well known, and need not be described in detail herein. Any type of FCC reaction system can be employed. However, the aforementioned MSCC system is preferred because of the reasons stated above.
  • the flow of regenerated catalyst in line 2 from regenerator vessel 8 is regulated by regenerated catalyst slide valve 3 to control the outlet temperature of product vapors exiting the reactor 4 via line 10.
  • the resultant reactor vapors flowing in line 10 are separated from the now spent catalyst.
  • the separated spent catalyst and entrained hydrocarbon vapors flow downward through reactor 4 into stripper section 15, where, in a preferred method, it is mixed with hot regenerated catalyst regulated by slide valve 16 to control the stripper temperature at a higher temperature than that of the reactor vapors in line 10.
  • the now elevated temperature mixture of spent and regenerated catalyst is subjected to steam stripping in stripper 15 to remove as much hydrocarbon as possible before exiting reactor 4 through spent catalyst slide valve 5, which controls the catalyst level in the reactor stripper 15.
  • vapors of the residual oil feedstock intimately contact the catalyst therein under cracking conditions to produce lower molecular weight hydrocarbon product vapors, while at the same time there is formed spent catalyst having formed thereon carbonaceous deposits and metal deposits, including vanadium and sodium deposits, which typically are in form of sulfides or other metal-containing compounds.
  • the spent catalyst 14 Downstream of spent catalyst slide valve 5, the spent catalyst 14 is mixed with an oxygen-containing combustion gas, e.g., air, supplied via line 7 in combustor riser 6, wherein the mixture flows upwardly and into the regenerator vessel 8.
  • the rate of combustion air used to burn the carbon from the spent catalyst is regulated to control the oxygen in regenerator flue gas, which exits the regenerator via line 9, at less than 1 mole%, more preferably less than 0.5 mole%, and still more preferably less than 0. 1 mole%.
  • the carbon burning rate As the temperature of the outlet of combustion riser 6 is lowered, the carbon burning rate is decreased so that it is possible to maintain the level of carbon on regenerated catalyst using a less than complete oxidizing atmosphere or a reducing atmosphere, with oxygen exiting combustion riser 6.
  • This method, use of a combustor riser, of regeneration is preferred over a conventional fluidized bed regenerator, or a fast fluid regenerator, as it minimizes backmixing and minimizes oxygen partial pressure as the carbon on regenerated catalyst decreases and exposes the metals on the surface of the catalyst to possible oxidation.
  • a high velocity preferably greater than 10 ft. per second
  • a short residence time preferably less than 20 seconds, and more preferably less than 15 seconds.
  • the regenerator temperature must be lowered to reduce the oxidation-potential of the vanadium and sodium.
  • the combustion air is and spent catalyst are mixed, the combustion of the carbonaceous deposits on the spent catalyst is initiated.
  • the oxygen is consumed as the carbon is burned off the surface. This reduces the oxygen partial pressure which has the effect of limiting the oxidation driving force for burning the carbon or oxidizing the metals. Since the metals are mainly on the surface of the catalyst and the carbon deposited in reactor 4 covers these metals, the metals become exposed and can only be oxidized once they are uncovered and while at high temperature.
  • regenerator when operated in accordance with these teachings, can be used to reduce the catalyst deactivating effects of sodium and vanadium.
  • the outlet temperature of combustion riser 6 is controlled at less than 1300°F (704°C) and more preferably at less that 1250°F (677°C), to maintain a carbon level on regenerated catalyst, preferably of less than 0.4, preferably 0.3, wt%, but more than 0.08 wt.%. This is accomplished by mixing regenerated catalyst that has been cooled by catalyst cooler 11 with the upwardly flowing spent catalyst and combustion air at a point in combustion riser 6 where the temperature of the resulting mixture is less than 1250°F (677°C) and preferably less than 1200°F (649°C) to minimize the oxidation of metals and carbon burning from the surface of the cooled regenerated catalyst flowing in line 13.
  • the rate of cooled regenerated catalyst is regulated by slide valve 12 to control the regenerated catalyst temperature at less that 1300° F (704°C), and more preferably below 1250°F (677°C).
  • regenerator vessel 8 the products of combustion (the flue gas in line 9) and the regenerated catalyst plus cooled regenerated catalyst are separated.
  • the regenerator flue gas can be further processed for heat recovery and treated for particulate and SOx control before being exhausted to the atmosphere.
  • the regenerated catalyst is returned to reactor 4 to vaporize and contact the residual oil feed in reactor 4 and recycled through catalyst cooler 11 and slide valve 5 to combustion riser 6 to control the regenerated catalyst temperature.
  • the spent catalyst regeneration conditions in the regenerator i.e. in the combustor riser 6 and the regenerator vessel 8 are maintained so that they are effective to burn a majority of the carbonaceous deposits from the spent catalyst while leaving a majority of the vanadium and sodium deposits in the non-oxidized or lower oxidation state.
  • the regenerated catalyst has a carbon level of not more than about 0.4 wt.%, but at least about 0.08 wt.%, and oxidation of the vanadium and sodium deposits is substantially prevented. This can be accomplished by controlling the regenerator temperatures and atmosphere as described herein.

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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)
  • Catalysts (AREA)
EP00610038A 1999-04-09 2000-04-06 Fluidkatalytisches Krackverfahren mit einen Katalysator mit verbessertem Widerstand gegen Metalle Withdrawn EP1043384A3 (de)

Applications Claiming Priority (2)

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US288665 1988-12-19
US28866599A 1999-04-09 1999-04-09

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EP1043384A2 true EP1043384A2 (de) 2000-10-11
EP1043384A3 EP1043384A3 (de) 2001-05-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1306420A2 (de) * 2001-10-24 2003-05-02 Bar-Co Processes Joint Venture Verfahren zum Regeln der Oxidation von Stickstoff und Metallen in einem Wirbelbettverfahren
CN1333044C (zh) * 2003-09-28 2007-08-22 中国石油化工股份有限公司 一种烃油裂化方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0905257B1 (pt) * 2009-12-28 2018-04-17 Petroleo Brasileiro S.A. - Petrobras Processo de craqueamento catalítico fluido com emissão reduzida de dióxido de carbono
JP7108570B2 (ja) * 2019-04-01 2022-07-28 出光興産株式会社 流動接触分解ガソリンの製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377470A (en) * 1981-04-20 1983-03-22 Ashland Oil, Inc. Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
EP0152845A1 (de) * 1984-02-08 1985-08-28 Air Products And Chemicals, Inc. Methode zur Kontrolle der Temperatur und Fliessgeschwindigkeit eines FCC-Regenerators mittels Carbondioxids
US5077252A (en) * 1990-07-17 1991-12-31 Mobil Oil Corporation Process for control of multistage catalyst regeneration with partial co combustion
EP0511071A1 (de) * 1991-04-26 1992-10-28 Institut Français du Pétrole Verfahren und Vorrichtung für Wärmeaustausch von festen Teilchen für Regenerierung in katalytischem Cracken
EP0702077A2 (de) * 1994-09-13 1996-03-20 Bar-Co Processes Joint Venture Wirbelschichtverfahren zum Abziehen und Kühlen von verbrauchten Feststoffen
EP0724009A1 (de) * 1995-01-30 1996-07-31 Exxon Research And Engineering Company Katalytischer Krackverfahren und Vorrichtung dazu
WO1997008269A1 (en) * 1995-08-30 1997-03-06 Mobil Oil Corporation Fcc nox reduction by turbulent/laminar thermal conversion
EP0801126A2 (de) * 1996-04-11 1997-10-15 Exxon Research And Engineering Company Regenerierung von verbrauchtem FCC-Katalysator

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377470A (en) * 1981-04-20 1983-03-22 Ashland Oil, Inc. Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
EP0152845A1 (de) * 1984-02-08 1985-08-28 Air Products And Chemicals, Inc. Methode zur Kontrolle der Temperatur und Fliessgeschwindigkeit eines FCC-Regenerators mittels Carbondioxids
US5077252A (en) * 1990-07-17 1991-12-31 Mobil Oil Corporation Process for control of multistage catalyst regeneration with partial co combustion
EP0511071A1 (de) * 1991-04-26 1992-10-28 Institut Français du Pétrole Verfahren und Vorrichtung für Wärmeaustausch von festen Teilchen für Regenerierung in katalytischem Cracken
EP0702077A2 (de) * 1994-09-13 1996-03-20 Bar-Co Processes Joint Venture Wirbelschichtverfahren zum Abziehen und Kühlen von verbrauchten Feststoffen
EP0724009A1 (de) * 1995-01-30 1996-07-31 Exxon Research And Engineering Company Katalytischer Krackverfahren und Vorrichtung dazu
WO1997008269A1 (en) * 1995-08-30 1997-03-06 Mobil Oil Corporation Fcc nox reduction by turbulent/laminar thermal conversion
EP0801126A2 (de) * 1996-04-11 1997-10-15 Exxon Research And Engineering Company Regenerierung von verbrauchtem FCC-Katalysator

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1306420A2 (de) * 2001-10-24 2003-05-02 Bar-Co Processes Joint Venture Verfahren zum Regeln der Oxidation von Stickstoff und Metallen in einem Wirbelbettverfahren
EP1306420A3 (de) * 2001-10-24 2003-10-08 Bar-Co Processes Joint Venture Verfahren zum Regeln der Oxidation von Stickstoff und Metallen in einem Wirbelbettverfahren
CN1333044C (zh) * 2003-09-28 2007-08-22 中国石油化工股份有限公司 一种烃油裂化方法

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EP1043384A3 (de) 2001-05-30
JP2000319667A (ja) 2000-11-21

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