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
• • 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
  • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
  • C10G51/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural parallel stages only
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
• • 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
• • 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
  • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
  • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4093—Catalyst stripping
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins

Definitions

• This invention relates to increasing the production of lighter hydrocarbons, such as ethylene, propylene and the butylenes, and gasoline in conjunction with the operation of a fluidized catalytic cracking process.
• Propylene is second in importance only to ethylene as a petrochemical raw material building block.
• Propylene has traditionally been obtained as a byproduct from steam cracking to produce ethylene and from refinery fluidized catalytic cracking processes to produce gasoline.
• the projected growth in demand for propylene has started to exceed that of ethylene so that existing processes cannot satisfy the future propylene demand.
• a catalytic paraffmic naphtha cracking process can be utilized.
• Fluidized catalytic cracking is a well-known and widely practiced process for converting heavy hydrocarbons, gasoils and residues into lighter hydrocarbon fractions.
• the process for the cracking of hydrocarbon feedstocks relies on contact with heated fluidized catalytic particles in a reaction zone maintained at appropriate temperatures and pressures.
• carbonaceous deposits commonly referred to as coke
• the deactivated, or spent, catalyst is separated from the cracked products, stripped of removable hydrocarbons and passed to a regeneration vessel where the coke is burned from the catalyst in the presence of air to produce a substantially regenerated catalyst.
• the combustion products are removed from the vessel as flue gas.
• the heated regenerated catalyst is then recycled to the reaction zone in the FCC unit.
• Various methods and apparatus have been proposed for increasing or enhancing the output of particular product streams from the FCC unit.
• ancillary reactors and other treatment vessels have been provided to treat a particular fraction or reaction product stream.
• multiple reactors are provided, each with a different feed, in order to derive a particularly desired product stream.
• USP 4,090,949 describes a method for upgrading poor quality olefinic gasoline using two reactor risers, one of which receives a typical gas feedstream, while the second is used to crack a feedstream consisting primarily of low quality olefinic gasoline.
• the reactor temperature is from 450° F to 900° F and the catalyst-to-olefinic gasoline ratio is in the range of from 1 to 40, with a residence time in the range of from 1 to 30 seconds.
• a process employing multiple cracking zones in either a fluidized bed or in parallel riser reactors is disclosed in USP 3,856,659.
• paraffmic naphtha feed from the crude unit is mixed with recycled cracked naphtha (olefinic) and fed to one of the riser reactors.
• Typical operating temperatures range from 900° F to 1,300° F with a catalyst/oil ratio of from 3 to 20 and a residence time of from 1 to 10 seconds.
• a process using separate multiple fluidized reactors with upward direction in elongated transfer lines, or risers is disclosed in USP 4,297,203. Cracked naphtha feedstock from the first riser reactor is recovered and recycled to the second riser along with another hydrocarbon feedstream. Reactor temperatures are somewhat lower than in the prior example.
• a method for upgrading or cracking virgin naphtha is disclosed in USP 4,830,728 using a single catalyst of the Y zeolite type, or a combination of Y zeolite ZSM-5. In this process, ethylene is mixed with the virgin naphtha in the riser reactor. This process mentions upgrading straight run naphtha, which is mixed with recycled cracked material and injected into a separate upflow riser reactor.
• a method is described in USP 5,372,704 that employs spent catalyst in a re-cracking reactor for limited conversion of FCC naphtha or other thermally produced olefinic naphtha to light products with an increase in the product naphtha octane rating.
• the operating conditions for this process are relatively mild with temperatures in the 800° F to 1,100° F range and a residence time of from. 1 to 100 seconds.
• Yet another object of the invention is to provide a novel process for efficiently cracking a paraffinic naphtha feedstock to produce a lighter hydrocarbon product stream consisting of ethylene, propylene, butylenes and gasoline, which reaction product stream can either be recovered separately and further fractionated to recover the individual components or combined with an effluent stream from the FCC unit for further fractionation.
• the term "paraffinic naphtha feed” shall be understood to include any hydrocarbon charge stock boiling in the range of pentane (C 5 ) hydrocarbons up to about 450° F that contains 40% to 80% by weight of paraffinic components with very little olefin components. The remaining components will be naphthenes, aromatics and olefins in descending order of composition.
• paraffinic naphtha feed usually comes from crude or other atmospheric fractionation columns, but can also be derived from other processes which produce paraffinic-containing hydrocarbons.
• hydrotreater processes known in the refining and petrochemical art will produce paraffinic hydrocarbons from olefinic and aromatic type feed streams that can be used in the practice of the invention.
• the term "paraffinic naphtha” will also be understood to include light straight run (LSR) naphtha, or virgin naphtha, such as that obtained from a crude distillation unit, and will also include high paraffinic naphtha feedstreams resulting from extraction processes, all of which are known in the art.
• LSR light straight run
• a downward flow fluidized catalyst reactor is added as an ancillary reactor to the existing FCC process unit operation.
• the ancillary downflow reactor system utilizes the same hot regenerated catalyst as is used in the FCC unit.
• the regenerated catalyst and a virgin paraffinic naphtha feedstream derived from a source that is independent of the FCC unit are introduced and thoroughly mixed in an upper portion of the downflow reactor that is above the reaction zone.
• the mixture passes through the reaction zone with a residence time of 0.1 seconds to 5 seconds, and preferably in a range of 0.2 seconds to 2 seconds, where the reaction zone operating temperature is from 900° F to 1,200° F.
• the ratio of catalyst-to-naphtha, also referred to as the catalyst-to-oil ratio, in the reaction zone is in the range of from 10 percent to 80 percent by weight, with a preferred operating range of from 20 percent to 50 percent by weight.
• the determination of the catalyst-to-oil ratio is an indication of operating severity and its determination is well known to the art.
• the efficient operation of this process is dependent upon the introduction of a single feedstream consisting of a virgin paraff ⁇ nic naphtha feed.
• the relatively low residence times and higher catalyst-to-oil ratios of 20 to 50 percent by weight are specific to the paraffmic naphtha feedstream.
• the introduction of other hydrocarbons into the feedstream of the secondary downflow reactor will adversely affect the yields of the desired lighter hydrocarbon reaction products.
• the downfiow reactor provides several advantages including the relative ease of separating the desired end products from other components.
• the improved process of the invention can be utilized with prior art FCC units, whether they employ riser cracking in an upward or downward flow reaction scheme, or bed cracking to catalytically convert naphthas to the desired lighter hydrocarbons.
• Any existing FCC catalyst can be employed in the practice of the improved process of the invention.
• Typical FCC catalysts with or without catalyst additives are suitable for use in this process improvement.
• FIG. 1 is a simplified schematic illustration of a typical FCC apparatus and process of the prior art.
• FIG. 2 is a simplified schematic illustration of an embodiment of the apparatus and process of the present invention.
• the method and apparatus of the present invention can be employed with any number of FCC process units known to the prior art.
• a typical prior art FCC process is schematically illustrated.
• the reactor vessel (10) receives the hydrocarbon, or oil, feedstock (12) that is admitted into the lower end of reactor riser (14) where it is mixed with fresh and/or regenerated catalyst that is transferred by a conduit (22).
• a conduit (22) for the purpose of this simplified schematic illustration and description, the numerous valves, temperature sensors, electronic controllers and the like that are customarily employed and well known to those of ordinary skill in the art are not included.
• the mixture of catalyst and FCC reactor feedstream proceed upward through the riser into a reaction zone in which the temperature, pressure and residence time are controlled again within ranges that
• reaction product is withdrawn through conduit (16) for recovery and/or further processing in the refinery.
• the spent catalyst from the FCC unit is withdrawn via transfer line (18) for delivery to the lower portion of regeneration vessel (20), most conveniently located in relatively close proximity to FCC unit (10).
• the spent catalyst entering through transfer line (18) is contacted by at least a stream of air admitted through conduit (24) for controlled combustion of any accumulated coke.
• the flue gases are removed from the regenerator via conduit (26), and the temperature of the regenerated catalyst is raised to provide heat for the endothermic cracking reaction in the reactor vessel (10).
• Feedline (32) introduces a parafflnic naphtha feedstream from a source other than the FCC unit for mixing with the incoming regenerated catalyst from regenerator (20).
• the mixture of naphtha and catalyst passes into a reaction zone (34) that is maintained at a temperature that ranges from 900° F to 1,200° F.
• the ratio of the catalyst-to- naphtha is in the range from 20 percent to 50 percent by weight
• the residence time of the mixture in the reaction zone is from about 0.2 seconds to about 2 seconds.
• the same catalyst used in the main FCC unit is also employed in the catalytic cracking of the paraffinic naphtha feedstream in downflow reactor (30).
• zeolite catalysts of the Y type be used alone or in combination with ZSM-5 catalysts.
• catalysts additives can also be used with either of these systems. The choice of the catalyst(s) system does not form a part of the present invention.
• the light hydrocarbon reaction product stream containing ethylene, propylene, butylenes, gasoline, and any other by-products from the cracking reactions is withdrawn and can be either recovered separately in a segregated recovery section (not shown) or combined with the reaction product stream from the FCC unit for further fractionation and eventual recovery.
• Stripping steam is admitted through line (36) to drive off any removable hydrocarbons from the spent catalyst.
• gases are discharged from the downflow reactor (30) and introduced into the upper portion of the stripper vessel (37) where these combined gases, or vapors, pass through cyclone separators (39) and out of the stripper vessel via line (34) for product recovery in accordance with methods known to the art.
• the spent catalyst from the downflow reactor (30) is discharged through transfer line (40) and admitted to the lower end of the diptube, or lift riser, (29) which extends from the lower portion of the modified catalyst regenerator (20).
• air is introduced below the spent catalyst transfer line (40) at the end of diptube or lift riser (29) via pressurized air line (25).
• the present invention broadly comprehends a method of producing a product stream consisting primarily of the light olefins ethylene, propylene and butylenes, and of gasoline in conjunction with the processing of a petroleum feedstock in a fluidized catalytic cracking (FCC) unit containing a catalyst of specified composition, the FCC and associated downflow reactor catalyst feed being regenerated from spent catalyst, and the method including the steps of: a.
• FCC fluidized catalytic cracking
• the hot regenerated catalyst at approximately 1250° F to 1500° F is transferred from the regenerator vessel (20) of the FCC process by conventional means, e.g., through a downwardly directed conduit or pipe (28), commonly referred to as a transfer line or standpipe, to a withdrawal well or hopper (31) at the top of the downflow reactor above the reaction zone (33) where the hot catalyst flow is allowed to stabilize. in order to be uniformly directed into the mix zone or feed injection portion of the reaction zone (33).
• a pressure stabilization line (38) connects the top of the withdrawal well (31) to the existing regenerator (20).
• the naphtha feedstock is injected into the mixing zone through feed injection nozzles (32a) placed in the immediate vicinity of the point of introduction of the regenerated catalyst into the downflow reactor (30). These multiple injection nozzles (32a) result in the catalyst and oil mixing thoroughly and uniformly. Once the paraffinic naphtha feedstock contacts the hot catalyst the cracking reactions occur. The reaction vapor of hydrocarbon cracked products and unreacted naphtha feed and catalyst mixture quickly flows through the remainder of the downflow reactor and into a rapid separation section (35) at the bottom portion of the reactor. The residence time of the mixture in the reaction zone is controlled in accordance with apparatus and procedures known to the art.
• a quench injection (50) is provided for the naphtha feed, recycle cracked naphtha or other light olefinic hydrocarbon near the bottom of the reaction zone (33) immediately before the separator. This quench injection quickly reduces or stops the cracking reactions and can be utilized for controlling cracking severity and allows for added process flexibility.
• the reaction temperature i.e., the outlet temperature of the downflow reactor
• the reaction temperature is controlled by opening and closing a catalyst slide valve (not shown) that controls the flow of regenerated catalyst from the withdrawal well (31) and into the mix zone.
• the heat required for the endothermic cracking reaction is supplied by the regenerated catalyst.
• the rapid separator (35) along with the end portion of the downflow reactor (30) is housed in the upper section of a large vessel referred to as the catalyst stripper (37). The rapid separator directs the reaction vapor and catalyst directly into the top part the stripper vessel (37).
• the reactor vapor stream moves upward from the rapid separator outlet into the stripper, combines with stripped hydrocarbon product vapors and stripping gas from the catalyst stripping section of this vessel and passes through conventional separating means such as cyclones (39), which further separate any entrained catalyst particles from the vapors.
• the catalyst from the separator that is captured in the cyclones is directed to the bottom of the stripper vessel (37) through a cyclone dipleg for discharge into the bed of catalyst that was recovered from the rapid separator in the stripping section.
• a conduit or pipe commonly referred to as a reactor vapor line (34) to a conventional product recovery section known in the FCC art.
• the catalyst from the rapid separator and cyclone diplegs flows to the lower section of the stripper reactor vessel (37) that includes a catalyst stripping section into which a suitable stripping gas, such as steam, is introduced through streamline (36).
• a suitable stripping gas such as steam
• the stripping section is provided with several baffles or structured packing (not shown) over which the downwardly flowing catalyst passes counter-currently to the flowing stripping gas.
• the upwardly flowing stripping gas which is typically steam, is used to "strip" or remove any additional hydrocarbons that remain in the catalyst pores or between catalyst particles.
• the stripped catalyst is transported by the combustion air stream (25) through a lift riser (29) that terminates in the existing regenerator (20) in a typical FCC process to burn off any coke that is a by-product of the naphtha cracking process.
• the regenerator the heat produced from the combustion of the by-product coke produced in the first reaction zone (10 and 14) of a typical FCC process from cracking heavy hydrocarbons and from the naphtha cracking in zone (33) of the downflow reactor (30) is transferred to the catalyst.
• the regenerator vessel (20) can be of any conventional previously known design and can be used with the enhanced process and downflow reaction zone of this invention.
• the placement of the regenerator-to-reactor conduit (28) or regenerated catalyst transfer line for the regenerator will be such that it insures a steady and continuous flow of a substantial quantity of regenerated catalyst that is needed to meet the maximum design requirements of the downflow reactor.
• the catalyst requirements for the process of the invention can be determined in conjunction with any catalyst conventionally used in FCC processes, e.g., zeolites, silica-alumina, carbon monoxide burning promoter additives, bottoms cracking additives, light olefin-producing additives and any other catalyst additives routinely used in the FCC process.
• the preferred cracking zeolites in the FCC process are zeolites Y, REY, USY, and RE-USY.
• a preferred shaped selective catalyst additive typically used in the FCC process to produce light olefins and increase FCC gasoline octane is ZSM-5 zeolite crystal or other pentasil type catalyst structure.
• This ZSM-5 additive is mixed with the cracking catalyst zeolites and matrix structures in conventional FCC catalyst and is preferably used in the method of the invention to maximize and optimize the paraffinic naphtha cracking in the downflow reactor.
• a particular advantage of this invention as an enhancement to an existing FCC process for typical FCC heavy hydrocarbon feedstocks is the amount on coke produced from these cracking reactions.
• the overall unit operational efficiency is adversely effected by the limited amount of coke produced during the cracking reactions.
• the amount of coke produced is not sufficient to produce enough heat during catalyst regeneration to allow for the paraffinic naphtha cracking reactions to occur in the downflow reactor.
• the coke produced during the heavy oil or gasoil cracking in the typical FCC process is more than adequate to provide the required heat to the downflow reactor.
• this heat is transferred from the regenerator to the downflow reactor by the regenerated catalyst by mixing the spent catalysts from the two sources during the regeneration processing in vessel (20).
• a further advantage of the present invention as an enhancement to existing FCC processes for co-processing paraffinic naphtha is that the products can be recovered in the existing recovery section of the unit.
• the unconverted paraffinic naphtha can be recycled with the olefinic naphtha in the FCC process to produce additional light olefins from cracking the olefinic naphtha or for use as a blending stock in finished gasoline.
• the process has the advantage of providing for the separate recovery of the naphthas from each reactor for further separate downstream processing, with the alternative of combining the two streams for partial recycling to the FCC unit or for gasoline blending. Examples
• a bench scale pilot plant was used to determine the operating conditions for obtaining desired product yields from cracking a typical paraffinic naphtha feedstock.
• a pilot plant unit was used to represent the cracking conditions in the downflow reactor.
• two catalyst systems are utilized to demonstrate the potential for cracking paraffmic naphtha to produce light olefin yields.
• One catalyst was a typical low rare earth, low hydrogen transfer USY zeolite catalyst that is commercially available.
• the second catalyst system was the same commercially available USY zeolite cracking catalyst blended with a shape selective ZSM-5 zeolite type cracking catalyst additive.
• the term "Selectivity" is defined as the ratio of the amount of a particular Component to the Total Gas, e.g., Propylene/Total Gas.

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