EP1046696B1 - Procédé de conversion catalytique pour la production d'essence enrichie en isobutane et en isoparaffines - Google Patents

Procédé de conversion catalytique pour la production d'essence enrichie en isobutane et en isoparaffines Download PDF

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Publication number
EP1046696B1
EP1046696B1 EP20000108032 EP00108032A EP1046696B1 EP 1046696 B1 EP1046696 B1 EP 1046696B1 EP 20000108032 EP20000108032 EP 20000108032 EP 00108032 A EP00108032 A EP 00108032A EP 1046696 B1 EP1046696 B1 EP 1046696B1
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reaction
reaction zone
zone
catalyst
process according
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EP1046696A2 (fr
EP1046696A3 (fr
Inventor
Youhao Xu
Jiushun Zhang
Yinan Yang
Jun Long
Xieqing Wang
Zaiting Li
Ruichi Zhang
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Priority claimed from CN99105904A external-priority patent/CN1076751C/zh
Priority claimed from CN99109193A external-priority patent/CN1081222C/zh
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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

  • This invention relates to a process for catalytic, conversion of hydrocarbon feedstock in the absence of added hydrogen. More particularly, the present invention relates to a catalytic conversion process for producing isobutane and isoparaffin-enriched gasoline.
  • the mixture of isoparaffins possessing high octane number, low octane sensitivity, appropriate volatility and clean burning is an ideal blending components for aviation gasoline and motor gasoline.
  • the mixture of isoparaffins can be obtained by propylene polymerization or alkylation reaction of isobutane and olefins.
  • the conventional fluidized catalytic cracking (FCC) technology is used for producing gasoline with a yield of up to 50wt%.
  • FCC fluidized catalytic cracking
  • the phase down of leaded gasoline forced the catalytic cracking technology to go forward to the production of high octane gasoline.
  • the changing market demands have resulted in a great change in technology and catalyst types.
  • the advance in technological development is to increase reaction temperature, shorten reaction time, intensify reaction severity, suppress hydrogen transfer reaction and overcracking reaction and improve the contacting efficiency between feedstock and hot catalyst at the bottom of a riser reactor.
  • catalyst development the catalysts containing USY zeolite supported on an inert or active matrix or containing different typed zeolites have been put into commercial use.
  • FCC technology has been advanced to meet octane blending requirement, whether it is by means of changing in process parameters or using novel catalysts for increasing gasoline octane number, it results in an increase in olefin content of FCC gasoline.
  • FCC liquid petroleum gas (LPG) has an olefin content of up to 70wt%, in which butylenes is several times as much as the yield of isobutane, so it is not fit to be used as feedstock for alkylation.
  • USP5,154,818 discloses a method for the fluidized catalytic cracking of plural hydrocarbon feedstocks in a riser reactor to produce more gasoline of high octane number.
  • the process generally comprises two reaction zones. A relatively light hydrocarbon feedstock contacts with spent catalyst in a first reaction zone located in the bottom of conventional riser where aromatization and oligomerization take place. All of the first reaction zone effluent, the regenerated catalyst and heavy hydrocarbon feedstock are introduced into the second reaction zone where heavy hydrocarbon feedstock is cracked to desired reaction products. The reaction products and spent catalyst then pass through disengager for removal of entrained catalyst before the hydrocarbon vapors pass into a separation system. Spent catalyst passes into stripper and is divided into two parts, one is introduced into regenerator for burning off coke, the other part is recycled to the first reaction zone.
  • USP4,090,948 discloses a catalytic cracking process for producing the desired conversion of hydrocarbon feedstock of inferior quality (having higher contents of basic nitrogen and carbon residue) to obtain higher yields of the desired products in a riser reactor.
  • the process generally comprises contacting the hydrocarbon feedstock containing the highly reactive nitrogen and carbon residue with a recycled spent catalyst in the first reaction zone where the highly reactive nitrogen and carbon residue will deposit on the spent catalyst and then contacting the resultant mixture with freshly regenerated catalyst in the second reaction zone.
  • the reaction products and spent catalyst then pass through disengager for removal of entrained catalyst before the hydrocarbon vapors pass into a separation system.
  • Spent catalyst passes into stripper and is divided into two parts, one is introduced into regenerator for burning off coke and then returned to the second reaction zone, and the other part is recycled without regeneration to the first reaction zone.
  • An object of the present invention is to provide a catalytic conversion process for producing isobutane and isoparaffin-enriched gasoline to meet the requirement for blending components of the RFG, i.e. limiting the olefin content on the premise of maintaining higher gasoline octane number.
  • EP-A-0 369 536 discloses a process for selectively maximizing product production in fluidized catalytic cracking of hydrocarbons.
  • the process provided by the present invention is to contact the preheated hydrocarbon feedstock with hot regenerated catalyst in the lower part of a reactor with the result that hydrocarbon cracking reaction takes place at higher reaction temperature and shorter reaction time, and then the resultant mixture is up-flowed and enters into a suitable reaction environment with the result that isomerization and hydrogen transfer reaction take place at lower reaction temperature and longer reaction time.
  • the reaction products and spent catalyst then pass through disengager for removal of entrained catalyst.
  • the reaction products flow into subsequent separation system. Spent catalyst is stripped with steam, and then flow into the regenerator for regeneration, and thereafter the hot regenerated catalyst is recycled to the lower part of the reactor.
  • the process provided by the present invention employs a reactor to carry on two different reactions under different operating conditions, said reactor is preferably selected from the group consisting of an iso-diameter riser, an iso-linear velocity riser, a multi-cascade riser, a fluidized bed or a combination reactor of an iso-diameter riser and a fluidized bed.
  • olefins produced by catalytic cracking reaction can be selectively converted into isoparaffins and aromatics or isoparaffins and coke under specific reaction conditions and with specific catalysts.
  • the invention is a process comprising: the preheated hydrocarbon feedstock is atomized with injection steam and charged into the bottom of a conventional iso-diameter riser, and then mixed with hot regenerated catalyst with the result that feedstock is vaporized and cracked.
  • the product vapors and the coke deposited catalyst are up-flowed and are mixed with cooled regenerated catalyst with the result that isomerization and hydrogen transfer reaction take place.
  • the reaction vapors and catalyst flow into disengager where entrained catalyst is separated and dropped into the catalyst stripper.
  • the reaction vapors are separated into products in subsequent separation system.
  • Spent catalyst is stripped and introduced into regenerator for regeneration. Regenerated catalyst is divided into two parts, one is recycled into the prelift zone of the riser, and the other part is cooled in catalyst cooler and then recycled into the second reaction zone.
  • this invention is a process comprising: the preheated hydrocarbon feedstock is atomized with injection steam and charged into the bottom of a conventional iso-diameter riser, and then mixed with hot regenerated catalyst with the result that the feedstock is vaporized and cracked.
  • the product vapors and the coke deposited catalyst are up-flowed and are mixed with cooled semi-regenerated catalyst with the result that isomerization and hydrogen transfer reaction take place.
  • the reaction vapors and catalyst flow into disengager where entrained catalyst is separated and dropped into the catalyst stripper.
  • the reaction vapors are separated into products in subsequent separation system.
  • Spent catalyst is stripped and introduced into the primary regenerator for regeneration.
  • Semi-regenerated catalyst is divided into two parts, one flows into the secondary regenerator for regeneration, and then is recycled into the prelift zone of the riser, and the other part is cooled in catalyst cooler and then recycled into the second reaction zone.
  • this invention is a process comprising: the preheated hydrocarbon feedstock is atomized with injection steam and charged into the bottom of the riser in a combination reactor of an iso-diameter riser and a fluidized bed, and then mixed with hot regenerated catalyst with the result that the feedstock is vaporized and cracked.
  • the product vapors and the coke deposited catalyst in the riser flow upward and are mixed with cooled regenerated catalyst with the result that isomerization and hydrogen transfer reaction take place in the fluidizied bed.
  • the reaction vapors and catalyst flow into disengager where entrained catalyst is separated and dropped into the catalyst stripper.
  • the reaction vapors are separated into products in subsequent separation system.
  • Spent catalyst is stripped and introduced into regenerator for regeneration. Regenerated catalyst is divided into two parts, one is recycled into the prelift zone of the riser, and the other part is cooled in catalyst cooler and then recycled into the fluidized bed.
  • this invention comprises that the preheated hydrocarbon feedstock is atomized with injection steam and charged into the bottom of the first reaction zone in a multi-cascade riser, and then mixed with hot regenerated large particle size distribution catalyst containing USY zeolite with the result that feedstock is vaporized and cracked, providing the lifting force to carry the product vapors and the coke deposited catalyst in the first reaction zone into the second reaction zone where the effluents are mixed with the cooled regenerated small particle size distribution catalyst containing rare-earth Y zeolite with the result that isomerization and hydrogen transfer reaction take place.
  • the reaction vapors and catalyst flow into disengager where entrained catalyst is separated and dropped into the catalyst stripper.
  • reaction vapors are separated into products in subsequent separation system.
  • Spent catalyst is stripped and introduced into regenerator for regeneration.
  • Regenerated catalyst is divided into the large particle size distribution catalyst and the small particle size distribution catalyst, the large particle size distribution catalyst is recycled into the prelift zone of the riser, and the small particle size distribution catalyst is cooled in catalyst cooler and then recycled into the second reaction zone.
  • the process of the present invention comprises the steps as follows:
  • the process provided by the present invention employs a reactor to carry on two different reactions under different operating conditions; it is preferably selected from the group consisting of an iso-diameter riser, an iso-linear velocity riser, a multi-cascade riser, a fluidized bed or a combination of an iso-diameter riser and a fluidized bed.
  • the iso-diameter riser or iso-linear velocity riser is divided into a prelift zone, a first reaction zone, a second reaction zone from bottom to top, while the fluidized bed reactor comprises only a first reaction zone and a second reaction zone.
  • the height ratio of the first reaction zone to the second reaction zone is 10 ⁇ 40:90-60.
  • quenching mediums is set up at the bottom of the second reaction zone, and/or a heat remover having a height of 50% ⁇ 90% of that of the second reaction zone is located in the second reaction zone for adjusting the reaction temperature and time in the reaction zone.
  • said quenching medium is generally one or more selected from the group consisting of quenching liquid, cooled regenerated catalyst, cooled semi-regenerated catalyst or fresh catalyst or the mixtures thereof, in which quenching liquid is preferably selected from the group consisting of LPG, naphtha, stabilized gasoline, light cycle oil (LCO), heavy cycle oil (HCO) or water or the mixtures thereof.
  • LPG, naphtha and gasoline having high olefin content can not only act as quenching mediums, but also participate in reaction.
  • the cooled regenerated and semi-regenerated catalysts are obtained by cooling catalyst through catalyst cooler after the primary stage and secondary stage regeneration respectively.
  • said regenerated catalyst refers to catalyst that has a residual carbon content of below 0.1 wt%, more preferably below 0.05wt%
  • said semi-regenerated catalyst refers to catalyst that has a residual carbon content of from 0.1 wt% to 0.9wt%, more preferably from 0.15wt% to 0.7wt%.
  • the process of the present invention is carried out in a combination reactor of an iso-diameter riser and a fluidized bed, wherein the lower iso-diameter riser refers to the first reaction zone, the upper fluidized bed refers to the second reaction zone.
  • One inlet or multi-inlets of quenching mediums is set up at the bottom of the second reaction zone and/or a heat remover having a height of 50% ⁇ 90% of that of the second reaction zone is located in the second reaction zone for adjusting the reaction temperature and time in the reaction zone.
  • said quenching medium is generally one or more selected from the group consisting of quenching liquid, cooled regenerated catalyst , cooled semi-regenerated catalyst or fresh catalyst or the mixtures thereof, in which quenching liquid is preferably selected from the group consisting of LPG, naphtha, stabilized gasoline, light cycle oil (LCO), heavy cycle oil (HCO) or water or the mixtures thereof.
  • LPG, naphtha and gasoline having high olefin content can not only act as quenching mediums, but also participate in reaction.
  • the cooled regenerated and semi-regenerated catalysts are obtained by cooling catalyst through catalyst cooler after the primary stage and secondary stage regeneration respectively.
  • said regenerated catalyst refers to catalyst that has a residual carbon content of below 0.1 wt%, more preferably below 0.05wt%
  • said semi-regenerated catalyst refers to catalyst that has a residual carbon content of from 0.1wt% to 0.9wt%, more preferably from 0.15wt% to 0.7wt%.
  • the riser consists of a prelift zone a, a first reaction zone b, a second reaction zone with enlarged diameter c, the outlet zone with reduced diameter d from bottom to top along the coaxial direction.
  • the end of outlet zone is connected to a horizontal tube e.
  • the conjunct section between the first reaction zone and the second reaction zone is a circular truncated cone whose vertical section isotrapezia vertex angle ⁇ is generally 30° ⁇ 80°.
  • the conjunct section between the second reaction zone and the outlet zone is a circular truncated cone whose vertical section isotrapezia base angle ⁇ is generally 45° ⁇ 85°.
  • the total height of the riser is generally from 10 meters to 60 meters.
  • the diameter of the prelift zone is the same as that of a conventional iso-diameter riser and generally from 0.02 meter to 5 meters.
  • the height of the prelift zone is about 5% ⁇ 10% of the total height of the riser.
  • the function of this zone is to lift regenerated catalyst upward and to improve initial feed and catalyst contacting with the aid of a prelift medium that is selected from steam or dry gas same as that used in a conventional iso-diameter riser reactor.
  • the structure of the first reaction zone of the riser is similar to the lower section of a conventional iso-diameter riser. Its diameter is equal to or greater than that of the prelift zone. The diameter ratio of the former to the latter is generally from 1:1 to 2:1. The height of the first reaction zone is 10% ⁇ 30% of the total height of the riser.
  • the preheated feedstocks are atomized with injection steam and charged into this section, and then mixed with hot regenerated catalyst with result that cracking reaction takes place at higher reaction temperature and C/O ratio and shorter reaction time.
  • the diameter of the second reaction zone is greater than that of the first reaction zone.
  • the diameter ratio of the former to the latter is generally from 1.5:1 to 5:1.
  • the height of the second reaction zone is 30 ⁇ 60% of the total height of the riser.
  • the function of this zone is to reduce the velocity of vapors and catalyst and the reaction temperature in order to suppress cracking reaction and increase isomerization reaction and hydrogen transfer reaction.
  • the method of controlling the second reaction temperature is to inject quenching mediums at the conjunct section between the first reaction zone and the second reaction zone and/or to install a heat remover in the zone.
  • the height of the heat remover is generally from 50% to 90% of that of the second reaction zone.
  • the zone temperature is from about 420°C to about 530°C.
  • the contacting time of vapor and catalyst is generally from about 2 seconds to about 30 seconds.
  • said quenching medium is generally one or more selected from the group consisting of quenching liquid, cooled regenerated catalyst , cooled semi-regenerated catalyst or fresh catalyst or the mixtures thereof, in which quenching liquid is preferably selected from the group consisting of LPG, naphtha, stabilized gasoline, light cycle oil (LCO), heavy cycle oil (HCO) or water or the mixtures thereof LPG, naphtha and gasoline having high olefin content can not only act as quenching mediums, but also participate in reaction.
  • the cooled regenerated and semi-regenerated catalysts are obtained by cooling catalyst through catalyst cooler after the primary stage and secondary stage regeneration respectively.
  • said regenerated catalyst refers to catalyst that has a residual carbon content of below 0.1 wt%, more preferably below 0.05wt%
  • said semi-regenerated catalyst refers to catalyst that has a residual carbon content of from 0.1 wt% to 0.9wt%, more preferably from 0.15wt% to 0.7wt%.
  • the structure of the outlet zone is similar to that of a conventional iso-diameter riser.
  • the diameter ratio of the outlet zone to the first reaction zone is generally 0.8:1 to 1.5:1.
  • the height of this zone is generally 0 ⁇ 20% of total height of the riser.
  • the function of this zone is to increase effluent velocity and to suppress overcracking reaction.
  • One end of the horizontal tube is connected to the outlet zone and the other end is connected to the disengager.
  • one end of the horizontal tube is connected to the second reaction zone and the other end is connected to the disengager.
  • the function of the horizontal tube is to link the outlet zone with the disengager.
  • Feedstocks suitable for the process of the present invention include distillate having different boiling ranges, residue and crude. More specifically, the feedstocks are selected from the group consisting of atmospheric gas oil, naphtha, catalytic gasoline, diesel, vacuum gas oil (VGO), atmospheric residue (AR) or vacuum residue (VR), coker gas oil (CGO), deasphalted oil (DAO), hydrotreated residue, hydrocracked residue, shale oil or the mixtures thereof.
  • the processes of the present invention uses amorphous silica-alumina catalysts and zeolite catalysts with the active components preferably selected from the group consisting of Y, HY, USY or ZSM-5 series or any other zeolites typically employed in the cracking of hydrocarbons with or without rare earth and/or phosphor or the mixtures thereof.
  • the different reaction zones in the processes of the present invention are adaptable for use with the different type catalysts, including large and small particle size distribution catalysts or high and low apparent bulk density catalysts with the active components preferably selected from the group consisting of Y, HY, USY or ZSM-5 series or any other zeolites typically employed in the cracking of hydrocarbons with or without rare earth and/or phosphor or mixtures thereof.
  • Large and small particle size distribution catalysts or high and low apparent bulk density catalysts flow into different reaction zone respectively.
  • the large particle size distribution catalyst with USY zeolite flows into the first reaction zone for increasing cracking reaction
  • the small particle size distribution catalyst with rare earth Y zeolite flows into the second reaction zone for increasing hydrogen transfer reaction.
  • the mixed large and small particle size distribution catalysts are stripped in a stripper and are combusted in a regenerator, and then are separated into large particle size distribution catalyst and small particle size distribution catalyst.
  • the large and small particle size distribution catalyst are partitioned within the range of 30-40 ⁇ m.
  • the high and low apparent bulk density catalyst are partitioned within the range of 0.6 ⁇ 0.7g/cm 3 .
  • Fig.2 shows the schematic flow diagram used to produce isobutane and isoparaffin enriched gasoline in a multi-cascade riser.
  • the shape and size of the apparatus and pipelines are not limited in the attached diagram but depend on specific embodiments.
  • the prelift steam is introduced into prelift zone 2 via conduit 1.
  • Hot regenerated catalyst flow into prelift zone 2 via regenerated catalyst standpipe 16 and is lifted by prelift steam.
  • the preheated feedstock via conduit 4 is mixed with atomized steam via conduit 3 in proportion to form a mixture.
  • the mixture is charged into prelift zone, and then is contacted with hot regenerated catalyst, flowing into the first reaction zone 5 where cracking reaction takes place under certain reaction conditions.
  • the effluent is mixed with quenching mediums via conduit 6, flowing into the second reaction zone 7 with the result that isomerization and hydrogen transfer reaction take place under certain reaction conditions.
  • the reacted effluent flows into outlet zone 8 where the effluent is accelerated, and then passes through disengager 9, where entrained catalyst is separated and dropped into the catalyst stripper 12.
  • Residual catalyst is separated from the reaction vapors in a set of cyclones 10 located in the upper section of the reactor.
  • the reaction vapors pass to subsequent separation system via conduit 11.
  • Spent catalyst is contacted with stripping steam via conduit 13 to remove heavy hydrocarbons on the catalyst.
  • the catalyst flows to the spent catalyst standpipe 14 to the regenerator 15, where the spent catalyst is contacted with air via conduit 17 with the result that catalyst regeneration takes place to burn off coke. Flue gas is discharged from the regenerator via conduit 18.
  • the hot regenerated catalyst is recycled into the bottom of the riser via regenerated catalyst standpipe 16.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a conventional pilot plant iso-diameter riser in accordance with the present invention.
  • the preheated hydrocarbon feedstock D listed in table 1 was charged into the riser and contacted with hot regenerated catalyst D listed in table 2 in the presence of steam with the result that some reactions took place.
  • the reaction products were separated into isobutane enriched LPG, isoparaffin enriched gasoline and other products.
  • Spent catalyst flowed into regenerator via stripping. After regeneration, the regenerated catalyst was recycled for use.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a combination reactor of an iso-diameter riser and a fluidized bed in accordance with the present invention
  • the preheated hydrocarbon feedstock D listed in table 1 was charged into the riser and contacted with hot regenerated catalyst D listed in table 2 in the presence of steam with the result that some reactions took place.
  • the reaction products were separated into isobutane enriched LPG, isoparaffin enriched gasoline and other products.
  • Spent catalyst flowed into regenerator via stripping. After regeneration, regenerated catalyst was recycled for use.
  • the Comparative example was conducted in a conventional pilot plant iso-diameter riser reactor.
  • the catalyst and feedstock used were the same as that in example 2.
  • Operating conditions, product slate and gasoline properties were listed in table 5.
  • Table 5 showed that 32.80wt% of LPG was propylene, 7.76wt% of LPG was isobutane, and that the gasoline had an isoparaffin content of 17.30wt%, and an olefin content of 45.30wt%.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a multi-cascade riser reactor in accordance with the present invention.
  • the total height of the multi-cascade riser is 15 meters in which the height of the prelift zone with a diameter of 0.025 meter is 1.5meters, the height of the first reaction zone with a diameter of 0.025 meter is 4 meters, the height of the second reaction zone with a diameter of 0.1 meter is 6.5 meters, and the height of the outlet zone with a diameter of 0.025 meter is 3 meters.
  • the isotrapezia vertex angle ⁇ of the vertical section of the conjunct section between the first reaction zone and the second reaction zone is about 45°
  • the isotrapezia base angle ⁇ of the vertical section of the conjunct section between the second reaction zone and the outlet zone is about 60°.
  • the preheated hydrocarbon feedstock B listed in table 1 was charged into the riser and contacted with hot regenerated catalyst C listed in table 2 in the presence of steam with the result that some reactions took place.
  • the reaction products were separated into isobutane enriched LPG, isoparaffin enriched gasoline and other products.
  • Spent catalyst flowed into regenerator via stripping. After regeneration, regenerated catalyst was recycled for use.
  • the comparative example was conducted in a conventional pilot plant iso-diameter riser reactor.
  • the catalyst and feedstock used were the same as that in example 3.
  • Operating conditions and product slate were listed in table 6.
  • Gasoline properties were listed in table 7.
  • Table 6 showed that 15.74wt% of LPG was isobutane.
  • Table 7 showed that the gasoline had an isoparaffin content of 11.83wt%, and an olefin content of 56.49wt%.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline over different type catalysts in a pilot plant multi-cascade riser reactor in accordance with the present invention.
  • the reactor used in the example was the same as that in example 3.
  • the feedstocks used were the mixture of 80wt% of VGO A and 20wt% of CGO C, and AR D, whose properties were listed in table 1.
  • Operating conditions, catalyst types, product slate and Gasoline properties were listed in table 8.
  • Table 8 showed that about 28 ⁇ 32wt% of LPG was isobutane, and the gasoline had an isoparaffin content of about 33 ⁇ 39wt% and an olefin content of 16.0 ⁇ 27.0wt%.
  • hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a pilot plant multi-cascade riser reactor wherein gasoline with higher olefin content acted as quenching medium in accordance with the present invention.
  • the reactor, catalyst and feedstock were the same as those used in example 3.
  • the gasoline with higher olefin content acting as quenching medium was that obtained in comparative example 3.
  • the gasoline was injected into the bottom of the second reaction zone, other operating conditions were similar to these of example 2.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a pilot plant multi-cascade riser reactor in accordance with the present invention.
  • the total height of the multi-cascade riser is 15 meters in which the height of the prelift zone with a diameter of 0.025 meter is 1.5 meters, the height of the first reaction zone with a diameter of 0.025 meter is 4.5 meters, and the height of the second reaction zone with a diameter of 0.05 meter is 9 meters.
  • the isotrapezia vertex angle a of the vertical section of the conjunct section between the first reaction zone and the second reaction zone is about 45°.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a pilot plant multi-cascade riser reactor in accordance with the present invention.
  • the reactor used was the same as that in example 3.
  • the preheated hydrocarbon feedstock E listed in table 1 was charged into the first reaction zone and contacted with hot regenerated catalyst C listed in table 2 in the presence of steam with the result that cracking reaction took place, then the resultant mixture flowing into the second reaction zone was mixed with cooled regenerated catalyst via cooler.
  • the reaction products were separated into isobutane enriched LPG, isoparaffin enriched gasoline and other products.
  • Spent catalyst flowed into regenerator via stripping. After regeneration, the regenerated catalyst was divided into two parts. one was returned into the bottom of the first reaction zone, and the other part was cooled in catalyst cooler and recycled into the bottom of the second reaction zone for use.
  • the example showed that hydrocarbon feedstock was converted to produce isobutane and isoparaffin enriched gasoline in a pilot plant multi-cascade riser reactor in accordance with the present invention.

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Claims (19)

  1. Procédé de conversion catalytique de matière première hydrocarburée pour la production d'essence enrichie en isobutane et d'isoparaffine comprenant les étapes suivantes :
    (a) la matière première est contactée avec du catalyseur chaud régénéré dans la partie inférieure d'un réacteur avec le résultat qu'une réaction de craquage catalytique se déroule, lesdites conditions de réaction de craquage catalytique comprennent une température réactionnelle dans la gamme de 550 °C à 620 °C, un temps réactionnel dans la gamme de 0,5 secondes à 2,0 secondes et un rapport pondéral C/O dans la gamme de 3 : 1 à 15 : 1 ;
    (b) le mélange de catalyseur déposé sur des vapeurs et de coke s'écoule vers le haut et entre dans un environnement réactionnelle approprié avec le résultat que la réaction d'isomérisation et de transfert d'hydrogène se déroule, lesdites conditions de réaction d'isomérisation et de transfert d'hydrogène comprennent une température réactionnelle dans la gamme de 420 °C à 530 °C, une temps réactionnel dans la gamme de 3 secondes à 30,0 secondes et un rapport pondéral C/O dans la gamme de 3:1 à 18:1;
    (c) les produits de réaction sont séparées et le catalyseur épuisé est enlevé et régénéré pour le recyclage, dans lequel les catalyseurs sont les catalyseurs silice-alumine amorphes ou les catalyseurs zéolite.
  2. Procédé selon la revendication 1, dans lequel les conditions de réaction de craquage comprennent une température réactionnelle dans la gamme de 550 °C à 600 °C, un temps réactionnel dans la gamme de 0,8 secondes à 1,5 secondes, un rapport pondéral C/O dans la gamme de 4 : 1 à 12 : 1 ; et les conditions de réaction de transfert d'hydrogène et d'isomérisation comprennent une température réactionnelle dans la gamme de 460 °C à 510 °C, une temps réactionnel dans la gamme de 3 secondes à 15 secondes et un rapport pondéral C/O dans la gamme de 4 : 1 à 15 : 1.
  3. Procédé selon la revendication 1, dans lequel lesdits réacteurs comprennent une colonne montante iso-diamètrique, une colonne montante à vélocité iso-linéaire, une colonne montante à multi-cascade ou un lit fluidisé ou un réacteur de combinaison d'une colonne montante iso-diamètrique et d'un lit fluidisé.
  4. Procédé selon la revendication 3, dans lequel ladite colonne montante iso-diamètrique ou ladite colonne montante à vélocité iso-linéaire est divisée en une zone de pré-levage, une première zone réactionnelle, dans laquelle la réaction de craquage catalytique se déroule, et une deuxième zone réactionnelle, dans laquelle la réaction de transfert d'hydrogène et la réaction d'isomérisation se déroulent du bas vers le haut, et ledit lit fluidisé est divisé en une première zone dans laquelle la réaction de craquage catalytique se déroule, et une deuxième zone réactionnelle, dans laquelle la réaction de transfert d'hydrogène et la réaction d'isomérisation se déroulent du bas vers le haut, dans laquelle le rapport hauteur de la première zone réactionnelle à la deuxième zone réactionnelle est 10~40 : 90-60.
  5. Procédé selon la revendication 4, dans lequel un orifice d'entrée ou des orifices d'entrée multiples des milieux de quench sont installés en bas de la deuxième zone réactionnelle et/ou un dispositif de décapage de chaleur est arrangé dans la deuxième zone réactionnelle, la hauteur dudit dispositif de décapage de chaleur est 50 %~90 % de la hauteur de la deuxième zone réactionnelle.
  6. Procédé selon la revendication 3, dans lequel la partie inférieure dudit réacteur de combinaison est une colonne montante iso-diamètrique qui fonctionne en tant que première zone réactionnelle dans laquelle la réaction de craquage catalytique se déroule, et la partie supérieure de celui-ci est un lit fluidisé, qui fonctionne en tant que deuxième zone réactionnelle dans laquelle la réaction de transfert et la réaction d'isomérisation se déroulent.
  7. Procédé selon la revendication 6, dans lequel un orifice d'entrée ou des orifices d'entrées multiples des milieux de quench sont installés en bas de la deuxième zone réactionnelle et/ou un dispositif de décapage de chaleur est arrangé dans la deuxième zone réactionnelle, la hauteur dudit dispositif de décapage de chaleur est 50 %~90 % de la hauteur de la deuxième zone réactionnelle.
  8. Procédé selon la revendication 3, dans lequel le réacteur de colonne multi-cascade avec la hauteur de 10 mètres à 60 mètres consiste en une zone de pré-levage, une première zone réactionnelle, dans laquelle la réaction de craquage catalytique se déroule, une deuxième zone réactionnelle avec diamètre agrandi, dans laquelle la réaction de transfert d'hydrogène et la réaction d'isomérisation se déroulent, une zone de sortie avec diamètre réduit du bas vers le haut le long de la direction coaxiale, et le bout de la zone de sortie est lié au désengageur avec un tube horizontal.
  9. Procédé selon la revendication 8, dans lequel le rapport diamétrique de la première zone réactionnelle à la zone de prélèvement est 1~2: 1 et la hauteur de la première zone réactionnelle est 10 %~30 % de la hauteur de la colonne montante, et le diamètre de ladite zone de prélèvement est 0,02-5 mètres.
  10. Procédé selon la revendication 8, dans lequel le rapport diamétrique de ladite deuxième zone réactionnelle à ladite première zone réactionnelle est 1,5~5,0 : 1 et la hauteur de la deuxième zone réactionnelle est 30 %~60 % de la hauteur de la colonne montante.
  11. Procédé selon la revendication 8, dans lequel la partie conjointe entre la première zone réactionnelle et la deuxième zone réactionnelle est un cône circulaire tronqué dont l'angle α trapézoïde de la partie verticale au sommet est en générale 30°~80°, et la partie conjointe entre la deuxième zone réactionnelle et la zone de sortie est un cône circulaire tronqué dont l'angle ß trapézoïde de la partie verticale à la base est en générale 45°~85°.
  12. Procédé selon la revendication 11, dans lequel un orifice d'entrée ou des orifices d'entrée multiples des milieux de quench sont installés à la partie conjointe entre la première zone réactionnelle et la deuxième zone réactionnelle et/ou un dispositif de décapage de chaleur est arrangé dans la deuxième zone réactionnelle, la hauteur dudit dispositif de décapage de chaleur est 50 %~90 % de la hauteur de la deuxième zone réactionnelle.
  13. Procédé selon les revendications 5, 7 ou 12, dans lequel lesdits milieux de quench sont en général sélectionnés parmi le groupe consistant en le liquide de quench ou le catalyseur refroidi régénéré ou le catalyseur refroidi semi-régénéré ou le catalyseur frais ou les mélanges de ceux-ci dans un rapport arbitraire.
  14. Procédé selon la revendication 13, dans lequel ledit liquide de quench est préférablement sélectionné parmi le groupe consistant en le LPG, le naphta, l'essence stabilisée, l'huile de cycle légère, l'huile de cycle lourde ou l'eau ou les mélanges de ceux-ci dans un rapport arbitraire.
  15. Procédé selon la revendication 14, dans lequel ledit LPG, le naphta, et l'essence stabilisée enrichie en oléfine participent à la réaction.
  16. Procédé selon la revendication 13, dans lequel lesdits catalyseurs refroidis régénérés et sont obtenus par le refroidissement du catalyseur par un refroidisseur de catalyseur après l'étape de régénération primaire et l'étape de régénération secondaire, respectivement.
  17. Procédé selon la revendication 1, dans lequel la matière première hydrocarburée est les huiles de gaz atmospheriques, le naphta, l'essence catalytique, le diesel, l'huile de gaz de vide, les résidus atmosphériques ou les résidus de vide, l'huile de gaz de coke, l'huile desasphaltée, le résidu hydrotraité, le résidu hydrocraqué, l'huile de schiste ou les mélanges de ceux-ci.
  18. Procédé selon la revendication 1, dans lequel les catalyseurs sont des catalyseurs zéolite avec des constituants actives préférablement sélectionnés parmi le groupe consistant en la série Y, HY, USY, ou ZSM-5 ou un autre des zéolites typiquement employés pour le craquage d'hydrocarbures avec de terre rare et/ou du phosphore ou des mélanges de ceux-ci ou non.
  19. Procédé selon la revendication 1, 13 ou 16, dans lequel les catalyseurs entrant au sein des zones de réaction différentes, respectivement, peuvent être de la même espèce ou de différentes espèces.
EP20000108032 1999-04-23 2000-04-20 Procédé de conversion catalytique pour la production d'essence enrichie en isobutane et en isoparaffines Expired - Lifetime EP1046696B1 (fr)

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CN99105904 1999-04-23
CN99105904A CN1076751C (zh) 1999-04-23 1999-04-23 一种制取异丁烷和富含异构烷烃汽油的催化转化方法
CN99109193 1999-06-23
CN99109193A CN1081222C (zh) 1999-06-23 1999-06-23 一种降低液化气和汽油中烯烃含量的催化转化方法

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US6869521B2 (en) 2002-04-18 2005-03-22 Uop Llc Process and apparatus for upgrading FCC product with additional reactor with thorough mixing
US20030127358A1 (en) 2002-01-10 2003-07-10 Letzsch Warren S. Deep catalytic cracking process
US6866771B2 (en) 2002-04-18 2005-03-15 Uop Llc Process and apparatus for upgrading FCC product with additional reactor with catalyst recycle
FR2894849B1 (fr) * 2005-12-20 2008-05-16 Inst Francais Du Petrole Nouveau reacteur a deux zones reactionnelles fluidisees avec systeme de separation gaz/solide integre
CN1986505B (zh) * 2005-12-23 2010-04-14 中国石油化工股份有限公司 一种增产低碳烯烃的催化转化方法
JP5879038B2 (ja) * 2008-03-13 2016-03-08 中国石油化工股▲ふん▼有限公司 低品質の原料から軽質燃料を得るための方法
WO2012062173A1 (fr) 2010-11-11 2012-05-18 Shi Baozhen Procédé et appareil de craquage catalytique
CN102465006B (zh) * 2010-11-11 2014-01-29 石宝珍 一种催化裂化方法及装置
CN102477311A (zh) * 2010-11-28 2012-05-30 石宝珍 一种催化裂化方法及装置
CN102485841B (zh) * 2010-12-01 2014-02-26 石宝珍 一种催化裂化方法及装置
CN102485840B (zh) * 2010-12-01 2014-03-05 石宝珍 一种催化裂化方法及装置
CN102277193B (zh) * 2011-03-18 2014-04-02 青岛京润石化设计研究院有限公司 一种催化裂化方法及装置
CN102391889B (zh) * 2011-10-10 2013-12-18 石宝珍 一种催化转化方法
CN102399579B (zh) * 2011-10-14 2014-03-05 石宝珍 一种催化裂化方法
CA3202492A1 (fr) * 2020-12-16 2022-06-23 Dow Global Technologies Llc Systemes et procedes de production d'olefines

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JP2000336374A (ja) 2000-12-05

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