CA1280709C - Gasoline octane enhancement in fluid catalytic cracking process with split feed injection to riser reactor - Google Patents
Gasoline octane enhancement in fluid catalytic cracking process with split feed injection to riser reactorInfo
- Publication number
- CA1280709C CA1280709C CA000521691A CA521691A CA1280709C CA 1280709 C CA1280709 C CA 1280709C CA 000521691 A CA000521691 A CA 000521691A CA 521691 A CA521691 A CA 521691A CA 1280709 C CA1280709 C CA 1280709C
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- Prior art keywords
- riser
- feed
- riser reactor
- length
- gasoline
- Prior art date
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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
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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
ABSTRACT OF THE DISCLOSURE
A fluid catalytic cracking unit equipped with multiple feed injection points along the length of the riser is operated such that portions of the same fresh feed are charged to different feed injection points.
Preferably, the hydrocarbon fresh feed can be split into two or more non-distinct fractions, with one fraction charged to the bottom injection point along the length of the riser reactor, and the remaining fractions charged to injection points progressively higher up along the length of the riser reactor. Unconverted slurry oil boiling above 650°F can be recycled to one or more of the various injection points along the length of the riser. Steam in excess of levels typically employed for dispersion is used at the bottom of the riser to help lift the regenerated catalyst. Other inert gases can be used in place of, or in conjunction with, steam to accomplish lifting of the catalyst in the riser.
A fluid catalytic cracking unit equipped with multiple feed injection points along the length of the riser is operated such that portions of the same fresh feed are charged to different feed injection points.
Preferably, the hydrocarbon fresh feed can be split into two or more non-distinct fractions, with one fraction charged to the bottom injection point along the length of the riser reactor, and the remaining fractions charged to injection points progressively higher up along the length of the riser reactor. Unconverted slurry oil boiling above 650°F can be recycled to one or more of the various injection points along the length of the riser. Steam in excess of levels typically employed for dispersion is used at the bottom of the riser to help lift the regenerated catalyst. Other inert gases can be used in place of, or in conjunction with, steam to accomplish lifting of the catalyst in the riser.
Description
70~
o~
GASOLINE OCTANE ENHANCEMENT IN FLUID
CATALYTIC CRACKING PROCESS WITH SPLIT
FEED INJECTION TO RISER REACTOR
FIELD OF INVENTION
The invention relates generally to catalytic cracking of hydrocarbons. In one aspect 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.
Particularly, 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.
BACKGROUND OF THE INVENTION
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.
Typically, the octane number of the light distillate (gas-oline) 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. ~nfortunately, a limit on the maximum oper-ating temperature is set by reactor metallurgy, gascompressor 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 cata-lyst 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 ~ill generally involve substantially higher costs, be time consuming, and above all, lead to significant reductions in the yield of gasoline.
,, ~2~3~7~9 Therefore, with the current national emphasis on lead-free gasoline, and the need for increasing gasoline octane number by means other than the addition of lead, it is desir-able to have a modified cracking process available for increas-ing the octane number of the gasoline while minimizing the disadvan-tages associated with practices described in the prior art.
It is thus one object of this invention to provide a regenerated cracking process, and a further object of this invention to provide a process for increasing the octane number of the gasoline from the process. Another object of this invention is to achieve the increase in octane number of the gasoline by modifying -the me-thod of introduction of feed to the ! riser reactor in a fluid catalytic cracking process.
SUM~RY OE' THE INVENTIO~
In accordance with this invention, I have found that 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 Eeed to the bottom of the riser.
Thus, according to one aspect, the invention provides a process for the conversion of hydrocarbon feed in an FCC
riser reactor which comprises:
(a) splittiny the hydrocarbon feed and injecting at a plurality of positions along a length of said FCC riser re-actor;
(b) selecting the number of Eeed splits and selecting said positions along said length of said FCC riser reactor, to maximize the octane number of the gasoline;
(c) recycling regenerated catalys-t into the bottom of ~ .~
- 2a - ~ ~8~7~9 61936-1735 said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC riser reactor to sai~ injection position of said hydrocarbon oil feed with a flow of catalytically inert gas.
According to another aspect, the invention provides a process for the conversion of hydrocarbon feed in an FCC riser reactor which comprises:
(a) injecting said 'hydrocarbon feed at a plurali-ty of positions along a length of said FCC riser reactor;
(b) apportioning throughput -through said position along said leng-th of said FCC riser reactor to maximize octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC riser reactor to said injection position of said hydrocarbon oil feed wit'h a flow of catalytically inert gas.
~ .S. Patent No. 3,617,497 teac'hes segregation o-f 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 lengt'h 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'hydrocar'bon 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. In accordance with the process of the presen-t invention, a typical, full boiling range hydrocar'bon feed to a fluid catalytic craclcing process can be split into two or more non-distinct fractions, with one fraction charged -to the bottom of the riser reactor, and the ~'~
~,~, ...
37~3 ~1 -3-remaining fractions charged to upper injection points along the riser, to achieve the octane improvements.
S Thus, 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 ~U of gasoline, equivalent or higher yield of C3 and C4 olefins, and equivalent yields of coke and gas make.
Although 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 C3 and C4 olefins from the process) will be higher.
Although gasoline octane benefits accrue even when a majority of the feed is charged to upper injection points, and a minority to the bottom injector in accord-ance with the present invention, maximum improvements in gasoline octane and yields of desirable liquid products are achieved when a majority of the feed is charged to the bottom injector. Thus a preferred embodiment of the present invention is a modified fluid catalytic cracking ; ~S 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. The advantages associ-~ ated with practicing the teachings of the present invention will become clearer upon readiny the examples whi~.h are to follow.
DETAILED DESCRIPTION OF THE IMVENTION
The invention will be ~urther illustrated by way of a preferred embodiment and with reference to the accompanyincJ
drawinys in which:
Figure 1 represents a suitable reactor and regenerator system for performing the process accordiny to the invention.
The cracking occurs with a fluidized æeolitic catalyst in an elongated reactor tube 10, which is referred to as a riser. The riser has a lenyth to diameter ratio of above 20, or preferably above 25. Hydrocarbon oil feed in line 2 to be cracked can be charyed directly into the bottom of the riser through inlet line 14 or it can be charyed to upper injection points in the riser through lines 30A, 30B, or 30C or directly into ~he reactor vessel through line 30D. Steam is introduced into the lower feed injection point through line 18. Steam is also introduced independentl~ 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 in~ection points Ls introduced at about a 45 decJree upward angle lnto the riser through lines 30 and 32. Steam can be introduced into the upper feed in~ection inlet lines throuyh lines 34 and 36. Upper hydrocarbon feed injection lines 30 and 32 ~ach represent a plurali~y of similar lines spaced c:Lrcumferentially at the same heiyht 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 throu~h one of the lines designated as 38. The residence time of. hydrocarbon feed in ~3 -4a- 61936-1735 the riser can be varied by varying the amoun~s 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 430F to 1100F.
The feedstock to be cracked can also include appreciable amounts of virgin or hydrotreated residue having a boiling range of 900F to 1500F. The steam added to the riser amounts to about 2 wt% based on the oil J
~070~3 01 ~5~
charge, but the amount of steam can vary widely. The catalyst employed may be fluidized zeolitic aluminosili-05 cate and is preferably added to the bottom only of theriser. The type o$ 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 10 range is preferably about 900F to 1100F 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 hydro-carbon 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. Since no dense bed of catalyst is ordinarily permitted to build up within 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 ~.2~ 17~
Ol -6-catalyst to oil weight ratio between about 4:1 and 15:1, the weight ratio corresponding to the feed ratio.
05 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 ~6 so that discharge occurs through lateral slots 50 for proper dispersion. An instantaneous separation between hydro-carbon and catalyst occurs in the disengaging vessel. The hydrocarbon which separates Erom 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 cata-lyst separated from hydrocarbon in disengager 44 immedi-ately drops below the outlets o~ 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 bùrning is accomplished by introduction to the regenerator through line 66 of approxirnately the stoichiometrically required amount of air for combustion of the carbon deposits. The catalyst Erom the stripper enters the bottom section of the regenerator in a radial and downward direction througl trans~er line 62. Flue gas leaving the dense catalyst bed in regenerator 6~ flows through cyclones 72 wherein cata-lyst fines are separated rom flue gas permitting the fluegas to leave the regenerator through line 7~ and pass through a turbine 76 before leaving for a waste heat boiler, wherein any carbon monoxide contained in the flue gas is burned to carbon dioxide to accomplish heat recovery. Turbine 76 compresses atmospheric air in air ~7 ~1 -7-compressor 78 and this air is charged to the bottom of the regenerator through line 66.
05 The temperature throughout the dense catalyst bed in the regenerator is about 1250F. 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 stoichio-metric 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. In order to prevent excessively high temperatures in the regenerator flue gas due to afterburning, 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. Alternatively, CO oxidation promoters can be employed, as is now well known in the art, to oxidize the CO completely to CO2 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 1250F up to 1500F. 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 3~ required, steam is available through line 82 for cooling the reyenerator. Makeup catalyst may be added to the bottom of the regenerator through line 84. Hopper 86 i9 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.
Ol -8-TABLE I
FEEDSTOCK INSPECTIONS
Description Feed 1 Feed 2 API Gravity 22.8 26.7 Sulfur: Wt% 1.89 0.71 Nitrogen: Wt% 0.085 0.12 Hydrogen: Wt% 11.98 Carbon Residue: Wt% 0.39 1.74 Aniline Point: F 172.4 198.4 Viscosity @ 210F 45.2 Pour Point: ~F +95 15 Nickel: ppm 0.3 4.9 Vanadium: ppm 0.5 l.0 Distillation: D1160 10% 666 573 30% 740 717 50% 791 811 70% 856 928 90~ 943 1101 EP
Hydrocarbon Types: Mass Spec.
Aromatics 49.3 Mono 21.6 Di 14.8 Tri+ 7 0 Saturates 49.5 Alkanes 18.5 Cycloalkanes 31.0 Polar Compounds 1.2 Insolubles - -Volatiles EXAMPLES
To demonstrate the efficacy of my invention, a number of tests were conducted on a circulating pilot plant of the fluid catalytic cracking process using feedstocks described in Table I.
7~
01 _9_ Example I
Table II presents pilot plant data on cracking 05 of a gas oil feed using a conventional rare earth-exchanged Y zeolitic cracking catalyst in the pilotplant. Run No. 1 involved char~ing of all the fresh hydrocarbon feed to the bottom injector in the pilot plant. In Run No. 2, 75 volume percent of the fresh feed was charyed 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 lS research and motor octane numbers) of the gasoline are significantly higher with Run No. 2 which practiced the teachings of the present invention. In Run No. 3, only 25 volume percent of the fresh feed was charged to the bottom injector, with the remaining 75 volume percent was charged to the upper injection point. Comparing the results of Run Nos. 1, 2 and 3, it is obvious that while research octane number benefits are associated with both Run Nos. 2 and 3 compared to Run No. 1, the total yield of gasoline, and the motor octane number of the gasoline are highest for Run No. 2. Thus, while research octane numbers increase by apparently the same extent for both Run Nos. 2 and 3 compared to Run No. 1, best results are achieved when a majority of the feed is charged to the bottom injector, as in the case of Run No. 2. While the research octane number increase is the same for the two cases involving split feed injection shown in Table III (Run Nos. 2 and 3), it is important to note that mechanisms involved in achieving the increase are different in the two cases. As shown in Table II, the increase in research J~ octane number for Run No. 2, over Run No. 1, comes from an increase in the aromatic content of the gasoline; this explains why the motor octane number is also higher for Run No. 2 over Run No. 1. However, comparing the results of Run Nos. 1 and 3, it is obvious that the higher research octane number of the gasoline for Run No. 3 is due to the 3 2~3~)709 increase in the olefinic content of the gasoline, not the aromatic content. For those skilled in prior art, this 05 will also explain why the motor octane number of the gaso-line from Run No. 3 is not higher than that from Run No. l~
Example II
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. In 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.
7~;)9 TABLE II
05 Run Number 1 2 3 Chargestock <--------- Feed 1 ----------->
Catalyst ContainingConventional Rare Earth <--- Exchanged Y Zeolite ---->
lO Operating Conditions Riser Outlet Temp., F <----------- 980 ----------->
Riser Inlet Temp., F <----------- 1200 ----------->
Volume % Feed to Bottom Injector 100 75 25 Volume % Feed to Upper Injector 0 25 75 Conversion: Vol% FF81.9 81.6 78.7 Product Yields: Vol% FF
Total C3 12.0 13.9 12.4 C3= 10.1 11.7 10.5 tal C4 196 19 26 6 15 3 C4= 12.5 13.7 12.8 C5-430F Gasoline63.1 59.9 59.6 430-650F Light Catalytic Gas Oil 11.5 11.6 12.7 650F~ Decanted Oil6.6 6.8 8.6 2S C3~ Liquid 113.2 114.0 112.7 Total Gasoline + Alkylate 103.1 104.8 100.7 Product Yields: Wt% FF
C2 and Lighter 2.8 3.0 2.8 Coke 5.6 5.6 5.3 Gasoline API 57.1 55.7 56.6 Aromatics: Vol~ 27.5 31.1 26.5 Olefins: Vol~ 36.9 30.7 40.2 Saturates: Vol~35.5 38.3 33.3 Motor Octane Clear80.7 Bl.4 80.2 Research Octane Clear 93.9 95.1 95.2 0~3 TABLE III
Run Number 4 _ 5 Chargestock <-~ -- Feed 1 -------->
Catalyst Containing <---- ZSM-5 Zeolite ----->
Operating Conditions Riser Outlet Temp., F <--------- 980 --------->
Riser Inlet Temp., F<--------- 1200 ~ -->
Volume % Feed to Bottom Injector 100 60 Volume % Feed to Upper Injector 0 40 Conversion: Vol% FF 72.8 75.4 Product Yields: Vol% FF
Total C3 10.5 11.6 C3= 8.0 8.8 Total C4 15.6 17.5 iC4 5.8 6.4 C4= 8.3 9.3 C5-430F Gasoline 52.6 51.5 430-650F Light Catalytic Gas Oil 11.2 10.5 650F~ Decanted Oil 15.2 13.3 C3+ Liquid 105.9 105.2 Total Gasoline + Alkylate 99.4 101.4 Product Yields: Wt% FF
C2 and Lighter 3.4 3.7 Coke 6.0 5.9 Gasoline Motor Octane Clear 79.5 80.7 Research Octane Clear90.8 93.3 ~'~,8~17~
Example III
In this example, a feedstock containing a high ~5 boiling residual cornponent (boiling above 1000F) was cracked over conventional rare earth-exchanged Y zeolite containing catalyst in the fluid catalytic crac~ing pilot plant. Again, 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. In Run No. 7, 40 volume percent o~ 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. In ~un No. 8, 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. It is important to note that in all of the cases described in Table IV, the various feed fractions were identical in quality, in other words, the lower and upper injection feeds were not segregated according to molecular weight or boiling range or any other criterion. Comparing the results in the three columns in Table IV, the advantages associated with the teachings of the present invention, and in particular, charging a majority of the fresh feed to the bottom injector as in the case of Run No. 8, are obvious.
7~3 ~1 -14-TABLE IV
05 Run Number 6 7 8 Chargestock <------- - Feed 2 ~ ---->
Catalyst Containing Rare Earth <--- Exchanged Y Zeolite ---->
Operating Conditions Riser Outlet Temp., F <----------- 980 ----------->
l Riser Inlet Temp., F <----------- 1250 ----------->
Volume % Feed to Bottom lnjector 100 40 60 Volume % Feed to Upper Injector 0 60 40 lS Conversion: Vol% FF70.7 72.8 74.9 Product Yields: Vol% FF
Total C3 9.0 11.2 10.4 c3= 7.6 9.4 9.1 Total C4 13.8 16.0 16.7 iC~ 2.6 3.3 301 C4= 10.4 11.7 12.6 C5-430F Gasoline 56.6 55.2 58.5 430-650F Light Catalytic Gas Oil18.0 16.8 15.0 650F+ Decanted Oil11.3 10.4 10.2 C3+ Liquid Total Gasoline + Alkylate 88.4 92.5 97.0 Product Yields: Wt% FF
C2 and Lighter 3.1 3.6 3.0 Coke 4.2 4.3 4.2 Gasoline API 57.1 56.4 56.3 Aromatics: Vol~ 23.5 24.7 24.4 Olefins: Vol% 51.1 51.0 48.0 Saturates: Vol% 25.3 24.3 27.6 Motor Octane Clear77.4 77.5 78.8 Research Octane Clear 91.4 92.4 92.4 ~10
o~
GASOLINE OCTANE ENHANCEMENT IN FLUID
CATALYTIC CRACKING PROCESS WITH SPLIT
FEED INJECTION TO RISER REACTOR
FIELD OF INVENTION
The invention relates generally to catalytic cracking of hydrocarbons. In one aspect 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.
Particularly, 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.
BACKGROUND OF THE INVENTION
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.
Typically, the octane number of the light distillate (gas-oline) 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. ~nfortunately, a limit on the maximum oper-ating temperature is set by reactor metallurgy, gascompressor 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 cata-lyst 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 ~ill generally involve substantially higher costs, be time consuming, and above all, lead to significant reductions in the yield of gasoline.
,, ~2~3~7~9 Therefore, with the current national emphasis on lead-free gasoline, and the need for increasing gasoline octane number by means other than the addition of lead, it is desir-able to have a modified cracking process available for increas-ing the octane number of the gasoline while minimizing the disadvan-tages associated with practices described in the prior art.
It is thus one object of this invention to provide a regenerated cracking process, and a further object of this invention to provide a process for increasing the octane number of the gasoline from the process. Another object of this invention is to achieve the increase in octane number of the gasoline by modifying -the me-thod of introduction of feed to the ! riser reactor in a fluid catalytic cracking process.
SUM~RY OE' THE INVENTIO~
In accordance with this invention, I have found that 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 Eeed to the bottom of the riser.
Thus, according to one aspect, the invention provides a process for the conversion of hydrocarbon feed in an FCC
riser reactor which comprises:
(a) splittiny the hydrocarbon feed and injecting at a plurality of positions along a length of said FCC riser re-actor;
(b) selecting the number of Eeed splits and selecting said positions along said length of said FCC riser reactor, to maximize the octane number of the gasoline;
(c) recycling regenerated catalys-t into the bottom of ~ .~
- 2a - ~ ~8~7~9 61936-1735 said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC riser reactor to sai~ injection position of said hydrocarbon oil feed with a flow of catalytically inert gas.
According to another aspect, the invention provides a process for the conversion of hydrocarbon feed in an FCC riser reactor which comprises:
(a) injecting said 'hydrocarbon feed at a plurali-ty of positions along a length of said FCC riser reactor;
(b) apportioning throughput -through said position along said leng-th of said FCC riser reactor to maximize octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC riser reactor to said injection position of said hydrocarbon oil feed wit'h a flow of catalytically inert gas.
~ .S. Patent No. 3,617,497 teac'hes segregation o-f 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 lengt'h 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'hydrocar'bon 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. In accordance with the process of the presen-t invention, a typical, full boiling range hydrocar'bon feed to a fluid catalytic craclcing process can be split into two or more non-distinct fractions, with one fraction charged -to the bottom of the riser reactor, and the ~'~
~,~, ...
37~3 ~1 -3-remaining fractions charged to upper injection points along the riser, to achieve the octane improvements.
S Thus, 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 ~U of gasoline, equivalent or higher yield of C3 and C4 olefins, and equivalent yields of coke and gas make.
Although 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 C3 and C4 olefins from the process) will be higher.
Although gasoline octane benefits accrue even when a majority of the feed is charged to upper injection points, and a minority to the bottom injector in accord-ance with the present invention, maximum improvements in gasoline octane and yields of desirable liquid products are achieved when a majority of the feed is charged to the bottom injector. Thus a preferred embodiment of the present invention is a modified fluid catalytic cracking ; ~S 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. The advantages associ-~ ated with practicing the teachings of the present invention will become clearer upon readiny the examples whi~.h are to follow.
DETAILED DESCRIPTION OF THE IMVENTION
The invention will be ~urther illustrated by way of a preferred embodiment and with reference to the accompanyincJ
drawinys in which:
Figure 1 represents a suitable reactor and regenerator system for performing the process accordiny to the invention.
The cracking occurs with a fluidized æeolitic catalyst in an elongated reactor tube 10, which is referred to as a riser. The riser has a lenyth to diameter ratio of above 20, or preferably above 25. Hydrocarbon oil feed in line 2 to be cracked can be charyed directly into the bottom of the riser through inlet line 14 or it can be charyed to upper injection points in the riser through lines 30A, 30B, or 30C or directly into ~he reactor vessel through line 30D. Steam is introduced into the lower feed injection point through line 18. Steam is also introduced independentl~ 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 in~ection points Ls introduced at about a 45 decJree upward angle lnto the riser through lines 30 and 32. Steam can be introduced into the upper feed in~ection inlet lines throuyh lines 34 and 36. Upper hydrocarbon feed injection lines 30 and 32 ~ach represent a plurali~y of similar lines spaced c:Lrcumferentially at the same heiyht 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 throu~h one of the lines designated as 38. The residence time of. hydrocarbon feed in ~3 -4a- 61936-1735 the riser can be varied by varying the amoun~s 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 430F to 1100F.
The feedstock to be cracked can also include appreciable amounts of virgin or hydrotreated residue having a boiling range of 900F to 1500F. The steam added to the riser amounts to about 2 wt% based on the oil J
~070~3 01 ~5~
charge, but the amount of steam can vary widely. The catalyst employed may be fluidized zeolitic aluminosili-05 cate and is preferably added to the bottom only of theriser. The type o$ 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 10 range is preferably about 900F to 1100F 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 hydro-carbon 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. Since no dense bed of catalyst is ordinarily permitted to build up within 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 ~.2~ 17~
Ol -6-catalyst to oil weight ratio between about 4:1 and 15:1, the weight ratio corresponding to the feed ratio.
05 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 ~6 so that discharge occurs through lateral slots 50 for proper dispersion. An instantaneous separation between hydro-carbon and catalyst occurs in the disengaging vessel. The hydrocarbon which separates Erom 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 cata-lyst separated from hydrocarbon in disengager 44 immedi-ately drops below the outlets o~ 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 bùrning is accomplished by introduction to the regenerator through line 66 of approxirnately the stoichiometrically required amount of air for combustion of the carbon deposits. The catalyst Erom the stripper enters the bottom section of the regenerator in a radial and downward direction througl trans~er line 62. Flue gas leaving the dense catalyst bed in regenerator 6~ flows through cyclones 72 wherein cata-lyst fines are separated rom flue gas permitting the fluegas to leave the regenerator through line 7~ and pass through a turbine 76 before leaving for a waste heat boiler, wherein any carbon monoxide contained in the flue gas is burned to carbon dioxide to accomplish heat recovery. Turbine 76 compresses atmospheric air in air ~7 ~1 -7-compressor 78 and this air is charged to the bottom of the regenerator through line 66.
05 The temperature throughout the dense catalyst bed in the regenerator is about 1250F. 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 stoichio-metric 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. In order to prevent excessively high temperatures in the regenerator flue gas due to afterburning, 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. Alternatively, CO oxidation promoters can be employed, as is now well known in the art, to oxidize the CO completely to CO2 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 1250F up to 1500F. 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 3~ required, steam is available through line 82 for cooling the reyenerator. Makeup catalyst may be added to the bottom of the regenerator through line 84. Hopper 86 i9 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.
Ol -8-TABLE I
FEEDSTOCK INSPECTIONS
Description Feed 1 Feed 2 API Gravity 22.8 26.7 Sulfur: Wt% 1.89 0.71 Nitrogen: Wt% 0.085 0.12 Hydrogen: Wt% 11.98 Carbon Residue: Wt% 0.39 1.74 Aniline Point: F 172.4 198.4 Viscosity @ 210F 45.2 Pour Point: ~F +95 15 Nickel: ppm 0.3 4.9 Vanadium: ppm 0.5 l.0 Distillation: D1160 10% 666 573 30% 740 717 50% 791 811 70% 856 928 90~ 943 1101 EP
Hydrocarbon Types: Mass Spec.
Aromatics 49.3 Mono 21.6 Di 14.8 Tri+ 7 0 Saturates 49.5 Alkanes 18.5 Cycloalkanes 31.0 Polar Compounds 1.2 Insolubles - -Volatiles EXAMPLES
To demonstrate the efficacy of my invention, a number of tests were conducted on a circulating pilot plant of the fluid catalytic cracking process using feedstocks described in Table I.
7~
01 _9_ Example I
Table II presents pilot plant data on cracking 05 of a gas oil feed using a conventional rare earth-exchanged Y zeolitic cracking catalyst in the pilotplant. Run No. 1 involved char~ing of all the fresh hydrocarbon feed to the bottom injector in the pilot plant. In Run No. 2, 75 volume percent of the fresh feed was charyed 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 lS research and motor octane numbers) of the gasoline are significantly higher with Run No. 2 which practiced the teachings of the present invention. In Run No. 3, only 25 volume percent of the fresh feed was charged to the bottom injector, with the remaining 75 volume percent was charged to the upper injection point. Comparing the results of Run Nos. 1, 2 and 3, it is obvious that while research octane number benefits are associated with both Run Nos. 2 and 3 compared to Run No. 1, the total yield of gasoline, and the motor octane number of the gasoline are highest for Run No. 2. Thus, while research octane numbers increase by apparently the same extent for both Run Nos. 2 and 3 compared to Run No. 1, best results are achieved when a majority of the feed is charged to the bottom injector, as in the case of Run No. 2. While the research octane number increase is the same for the two cases involving split feed injection shown in Table III (Run Nos. 2 and 3), it is important to note that mechanisms involved in achieving the increase are different in the two cases. As shown in Table II, the increase in research J~ octane number for Run No. 2, over Run No. 1, comes from an increase in the aromatic content of the gasoline; this explains why the motor octane number is also higher for Run No. 2 over Run No. 1. However, comparing the results of Run Nos. 1 and 3, it is obvious that the higher research octane number of the gasoline for Run No. 3 is due to the 3 2~3~)709 increase in the olefinic content of the gasoline, not the aromatic content. For those skilled in prior art, this 05 will also explain why the motor octane number of the gaso-line from Run No. 3 is not higher than that from Run No. l~
Example II
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. In 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.
7~;)9 TABLE II
05 Run Number 1 2 3 Chargestock <--------- Feed 1 ----------->
Catalyst ContainingConventional Rare Earth <--- Exchanged Y Zeolite ---->
lO Operating Conditions Riser Outlet Temp., F <----------- 980 ----------->
Riser Inlet Temp., F <----------- 1200 ----------->
Volume % Feed to Bottom Injector 100 75 25 Volume % Feed to Upper Injector 0 25 75 Conversion: Vol% FF81.9 81.6 78.7 Product Yields: Vol% FF
Total C3 12.0 13.9 12.4 C3= 10.1 11.7 10.5 tal C4 196 19 26 6 15 3 C4= 12.5 13.7 12.8 C5-430F Gasoline63.1 59.9 59.6 430-650F Light Catalytic Gas Oil 11.5 11.6 12.7 650F~ Decanted Oil6.6 6.8 8.6 2S C3~ Liquid 113.2 114.0 112.7 Total Gasoline + Alkylate 103.1 104.8 100.7 Product Yields: Wt% FF
C2 and Lighter 2.8 3.0 2.8 Coke 5.6 5.6 5.3 Gasoline API 57.1 55.7 56.6 Aromatics: Vol~ 27.5 31.1 26.5 Olefins: Vol~ 36.9 30.7 40.2 Saturates: Vol~35.5 38.3 33.3 Motor Octane Clear80.7 Bl.4 80.2 Research Octane Clear 93.9 95.1 95.2 0~3 TABLE III
Run Number 4 _ 5 Chargestock <-~ -- Feed 1 -------->
Catalyst Containing <---- ZSM-5 Zeolite ----->
Operating Conditions Riser Outlet Temp., F <--------- 980 --------->
Riser Inlet Temp., F<--------- 1200 ~ -->
Volume % Feed to Bottom Injector 100 60 Volume % Feed to Upper Injector 0 40 Conversion: Vol% FF 72.8 75.4 Product Yields: Vol% FF
Total C3 10.5 11.6 C3= 8.0 8.8 Total C4 15.6 17.5 iC4 5.8 6.4 C4= 8.3 9.3 C5-430F Gasoline 52.6 51.5 430-650F Light Catalytic Gas Oil 11.2 10.5 650F~ Decanted Oil 15.2 13.3 C3+ Liquid 105.9 105.2 Total Gasoline + Alkylate 99.4 101.4 Product Yields: Wt% FF
C2 and Lighter 3.4 3.7 Coke 6.0 5.9 Gasoline Motor Octane Clear 79.5 80.7 Research Octane Clear90.8 93.3 ~'~,8~17~
Example III
In this example, a feedstock containing a high ~5 boiling residual cornponent (boiling above 1000F) was cracked over conventional rare earth-exchanged Y zeolite containing catalyst in the fluid catalytic crac~ing pilot plant. Again, 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. In Run No. 7, 40 volume percent o~ 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. In ~un No. 8, 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. It is important to note that in all of the cases described in Table IV, the various feed fractions were identical in quality, in other words, the lower and upper injection feeds were not segregated according to molecular weight or boiling range or any other criterion. Comparing the results in the three columns in Table IV, the advantages associated with the teachings of the present invention, and in particular, charging a majority of the fresh feed to the bottom injector as in the case of Run No. 8, are obvious.
7~3 ~1 -14-TABLE IV
05 Run Number 6 7 8 Chargestock <------- - Feed 2 ~ ---->
Catalyst Containing Rare Earth <--- Exchanged Y Zeolite ---->
Operating Conditions Riser Outlet Temp., F <----------- 980 ----------->
l Riser Inlet Temp., F <----------- 1250 ----------->
Volume % Feed to Bottom lnjector 100 40 60 Volume % Feed to Upper Injector 0 60 40 lS Conversion: Vol% FF70.7 72.8 74.9 Product Yields: Vol% FF
Total C3 9.0 11.2 10.4 c3= 7.6 9.4 9.1 Total C4 13.8 16.0 16.7 iC~ 2.6 3.3 301 C4= 10.4 11.7 12.6 C5-430F Gasoline 56.6 55.2 58.5 430-650F Light Catalytic Gas Oil18.0 16.8 15.0 650F+ Decanted Oil11.3 10.4 10.2 C3+ Liquid Total Gasoline + Alkylate 88.4 92.5 97.0 Product Yields: Wt% FF
C2 and Lighter 3.1 3.6 3.0 Coke 4.2 4.3 4.2 Gasoline API 57.1 56.4 56.3 Aromatics: Vol~ 23.5 24.7 24.4 Olefins: Vol% 51.1 51.0 48.0 Saturates: Vol% 25.3 24.3 27.6 Motor Octane Clear77.4 77.5 78.8 Research Octane Clear 91.4 92.4 92.4 ~10
Claims (10)
1. A process for the conversion of hydrocarbon feed in an FCC riser reactor which comprises:
(a) splitting the hydrocarbon feed and injecting at a plurality of positions along a length of said FCC riser reactor;
(b) selecting the number of feed splits and selecting said positions along said length of said FCC
riser reactor, to maximize the octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC
riser reactor to said injection position of said hydro-carbon oil feed with a flow of catalytically inert gas.
(a) splitting the hydrocarbon feed and injecting at a plurality of positions along a length of said FCC riser reactor;
(b) selecting the number of feed splits and selecting said positions along said length of said FCC
riser reactor, to maximize the octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC
riser reactor to said injection position of said hydro-carbon oil feed with a flow of catalytically inert gas.
2. The process of Claim 1 wherein 10 to 90 volume percent of the total feed is injected to the bottom of the riser reactor.
3. The process of Claim 2 wherein 10 to 90 volume percent of the total feed is injected into upper injection points along the riser.
4. The process of Claim 1 wherein one of the upper injection points is located in the reactor or stripper vessel.
5. A process for the conversion of hydrocarbon feed in an FCC riser reactor which comprises:
(a) injecting said hydrocarbon feed at a plurality of positions along a length of said FCC riser reactor;
(b) apportioning throughput through said position along said length of said FCC riser reactor to maximize octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC
riser reactor to said injection position of said hydro-carbon oil feed with a flow of catalytically inert gas.
(a) injecting said hydrocarbon feed at a plurality of positions along a length of said FCC riser reactor;
(b) apportioning throughput through said position along said length of said FCC riser reactor to maximize octane number of the gasoline;
(c) recycling regenerated catalyst into the bottom of said FCC riser reactor; and (d) lifting said regenerated catalyst up said FCC
riser reactor to said injection position of said hydro-carbon oil feed with a flow of catalytically inert gas.
6. The process of Claim 5 which further comprises:
recycling unconverted slurry oil to one or more injection positions along the length of the riser.
recycling unconverted slurry oil to one or more injection positions along the length of the riser.
7. The process of Claim 6 wherein said slurry oil comprises material boiling above 650°F.
8. The process of Claim 5 wherein said catalytically inert gas is steam.
9. The process of Claim 5 wherein said catalytically inert gas is recycled absorber gas.
10. The process of Claim 5 wherein said catalytically inert gas is gas selected from the group consisting of hydrogen, hydrogen sulfide, ammonia, methane, ethane, propane, and combinations thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79271885A | 1985-10-30 | 1985-10-30 | |
| US792,718 | 1991-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1280709C true CA1280709C (en) | 1991-02-26 |
Family
ID=25157845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000521691A Expired - Fee Related CA1280709C (en) | 1985-10-30 | 1986-10-29 | Gasoline octane enhancement in fluid catalytic cracking process with split feed injection to riser reactor |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0232587B1 (en) |
| JP (1) | JPS63501222A (en) |
| CA (1) | CA1280709C (en) |
| DE (1) | DE3668904D1 (en) |
| WO (1) | WO1987002695A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0302326A (en) * | 2003-06-03 | 2005-03-29 | Petroleo Brasileiro Sa | Fluid catalytic cracking process of mixed hydrocarbon fillers from different sources |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617496A (en) * | 1969-06-25 | 1971-11-02 | Gulf Research Development Co | Fluid catalytic cracking process with a segregated feed charged to separate reactors |
| 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 (en) * | 1972-05-20 | 1979-09-27 | ||
| US4218306A (en) * | 1979-01-15 | 1980-08-19 | Mobil Oil Corporation | Method for catalytic cracking heavy oils |
| US4405445A (en) * | 1981-08-24 | 1983-09-20 | Ashland Oil, Inc. | Homogenization of water and reduced crude for catalytic cracking |
-
1986
- 1986-10-29 CA CA000521691A patent/CA1280709C/en not_active Expired - Fee Related
- 1986-10-29 DE DE8686308420T patent/DE3668904D1/en not_active Expired - Fee Related
- 1986-10-29 EP EP19860308420 patent/EP0232587B1/en not_active Expired
- 1986-10-30 WO PCT/US1986/002329 patent/WO1987002695A1/en unknown
- 1986-10-30 JP JP61505909A patent/JPS63501222A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987002695A1 (en) | 1987-05-07 |
| JPS63501222A (en) | 1988-05-12 |
| EP0232587B1 (en) | 1990-02-07 |
| EP0232587A1 (en) | 1987-08-19 |
| JPH0471957B2 (en) | 1992-11-17 |
| DE3668904D1 (en) | 1990-03-15 |
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