EP0232587A1 - Gasolin-Oktanzahl-Steigerung in einem katalytischen Flüssigcrackprozess mit Split-Einspeisung des Rohmaterials in einen Steigrohrreaktor - Google Patents

Gasolin-Oktanzahl-Steigerung in einem katalytischen Flüssigcrackprozess mit Split-Einspeisung des Rohmaterials in einen Steigrohrreaktor Download PDF

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Publication number
EP0232587A1
EP0232587A1 EP19860308420 EP86308420A EP0232587A1 EP 0232587 A1 EP0232587 A1 EP 0232587A1 EP 19860308420 EP19860308420 EP 19860308420 EP 86308420 A EP86308420 A EP 86308420A EP 0232587 A1 EP0232587 A1 EP 0232587A1
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EP
European Patent Office
Prior art keywords
riser
feed
riser reactor
length
catalyst
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.)
Granted
Application number
EP19860308420
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English (en)
French (fr)
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EP0232587B1 (de
Inventor
Ashok S. Krishna
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.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
Chevron Research Co
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Publication date
Application filed by Chevron Research and Technology Co, Chevron Research Co filed Critical Chevron Research and Technology Co
Publication of EP0232587A1 publication Critical patent/EP0232587A1/de
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Publication of EP0232587B1 publication Critical patent/EP0232587B1/de
Expired legal-status Critical Current

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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

Definitions

  • the invention relates generally to catalytic cracking of hydrocarbons.
  • the invention relates to a change in the method of introduction of the feed, thereby creating an advantageous increase in the octane number of the gasoline produced in the process.
  • the invention relates to splitting the hydrocarbon feed and charging a portion of the total feed near the bottom of an elongated riser reactor, and the remaining portions progressively further up the riser.
  • Feedstocks containing higher molecular weight hydrocarbons are cracked by contacting the feedstocks under elevated temperatures with a cracking catalyst whereby light and middle distillates are produced.
  • the octane number of the light distillate is dependent upon the riser temperature, conversion level of operation or the catalyst type. Therefore, to increase the octane number of the gasoline, conversion of the hydrocarbon feed to lighter products must be increased by preferably raising the temperature of operation, or by increasing other operating variables such as catalyst to oil ratio.
  • a limit on the maximum operating temperature is set by reactor metallurgy, gas compressor constraint or other operating constraints. Increasing conversion by other means may also result in poor selectivity to desired products.
  • the octane number of the gasoline may be increased by switching from a catalyst containing rare earth-exchanged Y zeolite to one containing ultrastable Y zeolite or ZSM-5, as is well known in prior art; however, such a switch will generally involve substantially higher costs, be time consuming, and above all, lead to significant reductions in the yield of gasoline.
  • a desirable way to advantageously increase the octane number of the gasoline produced in the process is to charge some of the fresh hydrocarbon feed to upper injection points along the length of the riser while charging a majority of-the fresh feed to the bottom of the riser.
  • U.S. Patent No. 3,617,497 teaches segregation of hydrocarbon feeds to a fluid catalytic cracking process into low and high boiling fractions, and charging of the different fractions at different locations along the length of the riser reactor in order to improve the yield of gasoline from the process.
  • An important aspect of the present invention is that segregation of hydrocarbon feed according to molecular weight, boiling range or any other criterion is not required to achieve the gasoline octane improvements associated with the process of the present invention.
  • a typical, full boiling range hydrocarbon feed to a fluid catalytic cracking process can be split into two or more non-distinct fractions, with one fraction charged to the bottom of the riser reactor, and the remaining fractions charged to upper injection points along the riser, to achieve the octane improvements.
  • costly equipment associated with segregation of hydrocarbon feed into various distinct fractions is avoided, and simple piping and valving arrangements will permit practicing of the teachings of the present invention.
  • the distribution of feed between lower and upper injection points can cover a wide range, with between 10 and 90 volume percent of the total feed charged to bottom injector, and between 90 and 10 volume percent of total feed charged to upper injection points.
  • Typical yield shifts associated with the process of the present invention, as compared to prior art practices of charging all the feed to the bottom injector in the riser, include: equivalent or higher conversion of the hydrocarbon feed to gasoline and lighter components, equivalent or lower yield of gasoline, equivalent or higher yield of C 3 and C 4 olefins, and equivalent yields of coke and gas make.
  • the yield of gasoline from the process can be lower, the octane number of the gasoline will be higher, and the yield of total gasoline (gasoline plus potential alkylate from alkylation of the C 3 and C 4 olefins from the process) will be higher.
  • a preferred embodiment of the present invention is a modified fluid catalytic cracking process wherein the hydrocarbon feed is split into several non-distinct fractions, and a major portion of the feed is charged to the lowest injection point in a riser reactor, and the remaining fractions progressively higher up along the length of the riser reactor.
  • a suitable reactor-regenerator system for performing this invention is described in reference to FIG. 1.
  • the cracking occurs with a fluidized zeolitic catalyst in an elongated reactor tube 10, which is referred to as a riser.
  • the riser has a length to diameter ratio of above 20, or preferably above 25.
  • Hydrocarbon oil feed in line 2 to be cracked can be charged directly into the bottom of the riser through inlet line 14 or it can be charged to upper injection points in the riser through lines 30A, 30B, or 30C or directly into the reactor vessel through line 30D.
  • Steam is introduced into the lower feed injection point through line 18.
  • Steam is also introduced independently to the bottom of the riser through line 22 to help carry upwardly into the riser regenerated catalyst which flows to the bottom of the riser through transfer line 26.
  • Feed to the upper injection points is introduced at about a 45 degree upward angle into the riser through lines 30 and 32.
  • Steam can be introduced into the upper feed injection inlet lines through lines 34 and 36.
  • Upper hydrocarbon feed injection lines 30 and 32 each represent a plurality of similar lines spaced circumferentially at the same height of the riser. Any recycle hydrocarbon can be admitted to the lower section of the riser through one of the inlet lines designated as 20, or to the upper section of the riser through one of the lines designated as 38.
  • the residence time of hydrocarbon feed in the riser can be varied by varying the amounts or positions of introduction of the feed.
  • the full range oil charge to be cracked in the riser is a gas oil having a boiling range of about 430°F to 1100°F.
  • the feedstock to be cracked can also include appreciable amounts of virgin or hydrotreated residua having a boiling range of 900°F to 1500°F.
  • the steam added to the riser amounts to about 2 wt% based on the oil charge, but the amount of steam can vary widely.
  • the catalyst employed may be fluidized zeolitic aluminosilicate and is preferably added to the bottom only of the riser.
  • the type of zeolite in the catalyst can be a rare earth-exchanged X or Y, hydrogen Y, ultrastable Y, super- stable Y or ZSM-5 or any other zeolite typically employed in the cracking of hydrocarbons.
  • the riser temperature range is preferably about 900°F to 1100°F and is controlled by measuring the temperature of the product from the risers and then adjusting the opening of valve 40 by means of temperature controller 42 which regulates the inflow of hot regenerated catalyst to the bottom of the riser.
  • the temperature of the regenerator catalyst should be above the control temperature in the riser so that the incoming catalyst contributes heat to the cracking reaction.
  • the riser pressure should be between about 10 and 35 psig. Between about 0 and 10% of the oil charge to the riser is recycled with the fresh oil feed to the bottom of the riser.
  • the residence time of both hydrocarbon and catalyst in the riser is very small and preferably ranges from 0.5 to 5 seconds.
  • the velocity throughout the riser is about 35 to 65 feet per second and is sufficiently high so that there is little or no slippage between the hydrocarbon and catalyst flowing through the riser. Therefore, no bed of catalyst is permitted to build up within the riser, whereby the density within the riser is very low.
  • the density within the riser ranges from a maximum of about 4 pounds per cubic foot at the bottom of the riser and decreases to about 2 pounds per cubic foot at the top of the riser.
  • the space velocity through the riser is usually high and ranges between 100 or 120 and 600 weight of hydrocarbon per hour per instantaneous weight of catalyst in the reactor. No significant catalyst buildup within the reactor should be permitted to occur and the instantaneous catalyst inventory within the riser is due to a flowing catalyst to oil weight ratio between about 4:1 and 15:1, the weight ratio corresponding to the feed ratio.
  • each riser The hydrocarbon and catalyst exiting from the top of each riser is passed into a disengaging vessel 44.
  • the top of the riser is capped at 46 so that discharge occurs through lateral slots 50 for proper dispersion.
  • An instantaneous separation between hydrocarbon and catalyst occurs in the disengaging vessel.
  • the hydrocarbon which separates from the catalyst is primarily gasoline together with middle distillate and heavier components and some lighter gaseous components.
  • the hydrocarbon effluent passes through cyclone system 54 to separate catalyst fines contained therein and is discharged to a fractionator through line 56.
  • the catalyst separated from hydrocarbon in disengager 44 immediately drops below the outlets of the riser so that there is no catalyst level in the disengager but only in a lower stripper section 58. Steam is introduced into catalyst stripper section 58 through sparger 60 to remove any entrained hydrocarbon in the catalyst.
  • Catalyst leaving stripper 58 passes through transfer line 62 to a regenerator 64.
  • This catalyst contains carbon deposits which tend to lower its cracking activity and as much carbon as possible must be burned from the surface of the catalyst.
  • the burning is accomplished by introduction to the regenerator through line 66 of approximately the stoichiometrically required amount of air for combustion of the carbon deposits.
  • the catalyst from the stripper enters the bottom section of the regenerator in a radial and downward direction through transfer line 62.
  • Turbine 76 compresses atmospheric air in air compressor 78 and this air is charged to the bottom of the regenerator through line 66.
  • the temperature throughout the dense catalyst bed in the regenerator is about 1250°F.
  • the temperature of the flue gas leaving the top of the catalyst bed in the regenerator can rise due to afterburning of carbon monoxide to carbon dioxide.
  • Approximately a stoichiometric amount of oxygen is charged to the regenerator in order to minimize afterburning of carbon monoxide to carbon dioxide above the catalyst bed, thereby avoiding injury to the equipment, since at the temperature of the regenerator flue gas some afterburning does occur.
  • the temperature of the regenerator flue gas is controlled by measuring the temperature of the flue gas entering the cyclones and then venting some of the pressurized air otherwise destined to be charged to the bottom of the regenerator through vent line 80 in response to this measurement.
  • CO oxidation promoters can be employed, as is now well known in the art, to oxidize the CO completely to C0 2 in the regenerator dense bed thereby eliminating any problems due to afterburning in the dilute phase. With complete CO combustion, regenerator temperatures can be in excess of 1250°F up to 1500°F.
  • the regenerator reduces the carbon content of the catalyst from about 1.0 wt% to 0.2 wt%, or less for the maximum gasoline mode of operation. If required, steam is available through line 82 for cooling the regenerator. Makeup catalyst may be added to the bottom of the regenerator through line 84. Hopper 86 is disposed at the bottom of the regenerator for receiving regenerated catalyst to be passed to the bottom of the reactor riser through transfer line 26.
  • Table II presents pilot plant data on cracking of a gas oil feed using a conventional rare earth-exchanged Y zeolitic cracking catalyst in the pilot plant.
  • Run No. 1 involved charging of all the fresh hydrocarbon feed to the bottom injector in the pilot plant.
  • Run No. 2 75 volume percent of the fresh feed was charged to the bottom injector and the remaining 25 volume percent was charged to an injection point higher up in the riser reactor. Comparing the results from Run No. 1 and Run No. 2, it is evident that the yield of total gasoline plus alkylate, and the octane numbers (both research and motor octane numbers) of the gasoline are significantly higher with Run No. 2 which practiced the teachings of the present invention.
  • Run No. 1 involved charging of all the fresh hydrocarbon feed to the bottom injector in the pilot plant.
  • 75 volume percent of the fresh feed was charged to the bottom injector and the remaining 25 volume percent was charged to an injection point higher up in the riser reactor. Comparing the results from Run No. 1 and Run No. 2, it is evident
  • Table III shows pilot plant data on a high octane-producing catalyst containing the rare earth-exchanged Y zeolite and the ZSM-5 zeolite.
  • Run No. 4 corresponds to a conventional fluid catalytic cracking process wherein all the fresh feed is charged to the bottom of the riser reactor.
  • Run No. 5 60 volume percent of the fresh feed is charged to the bottom of the riser, and the remaining 40 volume percent to an upper injection point along the length of the riser. Comparing the results from the two runs, the higher octane numbers and higher total gasoline yield advantages associated with Run No. 5, in accordance with the present invention, are obvious.
  • a feedstock containing a high boiling residual component (boiling above 1000°F) was cracked over conventional rare earth-exchanged Y zeolite containing catalyst in the fluid catalytic cracking pilot plant.
  • Run No. 6 corresponds to a conventional fluid catalytic cracking process wherein all the fresh feed is charged to the bottom of the riser reactor.
  • Run No. 7 40 volume percent of the fresh feed was charged to the bottom of the riser, and the remaining 60 volume percent to an upper injection point in the riser.
  • 60 volume percent of the fresh feed was charged to the bottom of the riser while the remaining 40 volume percent was charged to the upper injection point.

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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)
EP19860308420 1985-10-30 1986-10-29 Gasolin-Oktanzahl-Steigerung in einem katalytischen Flüssigcrackprozess mit Split-Einspeisung des Rohmaterials in einen Steigrohrreaktor Expired EP0232587B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79271885A 1985-10-30 1985-10-30
US792718 1991-11-15

Publications (2)

Publication Number Publication Date
EP0232587A1 true EP0232587A1 (de) 1987-08-19
EP0232587B1 EP0232587B1 (de) 1990-02-07

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Application Number Title Priority Date Filing Date
EP19860308420 Expired EP0232587B1 (de) 1985-10-30 1986-10-29 Gasolin-Oktanzahl-Steigerung in einem katalytischen Flüssigcrackprozess mit Split-Einspeisung des Rohmaterials in einen Steigrohrreaktor

Country Status (5)

Country Link
EP (1) EP0232587B1 (de)
JP (1) JPS63501222A (de)
CA (1) CA1280709C (de)
DE (1) DE3668904D1 (de)
WO (1) WO1987002695A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0302326A (pt) * 2003-06-03 2005-03-29 Petroleo Brasileiro Sa Processo de craqueamento catalìtico fluido de cargas mistas de hidrocarbonetos de diferentes origens

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1266068A (de) * 1969-06-25 1972-03-08
US4218306A (en) * 1979-01-15 1980-08-19 Mobil Oil Corporation Method for catalytic cracking heavy oils

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617497A (en) * 1969-06-25 1971-11-02 Gulf Research Development Co Fluid catalytic cracking process with a segregated feed charged to the reactor
JPS5429967B2 (de) * 1972-05-20 1979-09-27
US4405445A (en) * 1981-08-24 1983-09-20 Ashland Oil, Inc. Homogenization of water and reduced crude for catalytic cracking

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1266068A (de) * 1969-06-25 1972-03-08
US4218306A (en) * 1979-01-15 1980-08-19 Mobil Oil Corporation Method for catalytic cracking heavy oils

Also Published As

Publication number Publication date
JPH0471957B2 (de) 1992-11-17
EP0232587B1 (de) 1990-02-07
JPS63501222A (ja) 1988-05-12
CA1280709C (en) 1991-02-26
DE3668904D1 (de) 1990-03-15
WO1987002695A1 (en) 1987-05-07

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