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EP1170355B1 - Verfahren und Einrichtung zum Cracken von Kohlenwasserstoffen in zwei aufeinanderfolgenden Reaktionstufen - Google Patents

Verfahren und Einrichtung zum Cracken von Kohlenwasserstoffen in zwei aufeinanderfolgenden Reaktionstufen Download PDF

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Publication number
EP1170355B1
EP1170355B1 EP01401737A EP01401737A EP1170355B1 EP 1170355 B1 EP1170355 B1 EP 1170355B1 EP 01401737 A EP01401737 A EP 01401737A EP 01401737 A EP01401737 A EP 01401737A EP 1170355 B1 EP1170355 B1 EP 1170355B1
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EP
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Prior art keywords
effluents
chamber
reaction chamber
fractional distillation
reaction
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English (en)
French (fr)
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EP1170355A1 (de
Inventor
Marcellin Espeillac
Pierre Crespin
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TotalEnergies Marketing Services SA
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TotalFinaElf France SA
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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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique

Definitions

  • the present invention relates to the cracking of hydrocarbons in the presence of heat transfer particles, catalytic or not, circulating in the fluidized phase. It relates more particularly to a cracking process in a fluidized bed, in which heat-transfer particles circulate in two successive reaction chambers, in each of which they are brought into contact with one or more cuts of hydrocarbons to be cracked.
  • the invention also relates to a device designed for implementing the method according to the invention.
  • the hydrocarbon charge In this type of process, the hydrocarbon charge, generally sprayed in the form of fine droplets, is brought into contact with heat-carrying particles at high temperature and which circulate in the reactor in the form of a fluidized bed, that is to say in suspension more or less dense within a gaseous fluid ensuring or assisting their transport.
  • the charge On contact with hot particles, the charge vaporizes, followed by cracking of the hydrocarbon molecules.
  • the cracking reaction is of the thermal type, when the particles have only a heat transfer function.
  • reaction effluents are separated from the particles.
  • the latter deactivated due to the coke which is deposited on their surface, are generally stripped in order to recover the entrained hydrocarbons, then regenerated by combustion of the coke, and finally brought back into contact with the charge to be cracked.
  • reactors used are most often vertical reactors of the tubular type, in which the charge and the particles move in an essentially ascending flow (the reactor is then called “riser”) or in an essentially descending flow (the reactor is then called “Dropper” or “downer”).
  • a major difficulty in such methods consists in carrying out a cracking which is both complete and selective of the charge, that is to say to succeed in cracking the entire charge, so as to obtain a maximum amount of it. recoverable hydrocarbons, while minimizing the quantity of undesirable by-products.
  • This objective is all the more difficult to achieve since the charges to be cracked have relatively wide boiling intervals, and are made up of very diverse compounds which crack under significantly different conditions to lead to various products.
  • a first solution consists in recycling all or part of these products in the cracking reactor, so as to subject them to a second cracking step.
  • a measure proves not only ineffective, but also harmful, insofar as such recycling often has the effect of appreciably affecting the quality of the cracking of the fresh charge.
  • a second solution consists in increasing the severity of the cracking, in order to crack the charge injected further and convert all the types of hydrocarbons present.
  • such measure if it makes it possible to increase the conversion rate of the charge, on the other hand favors overcracking phenomena, which result in a reduction in the selectivity of the conversion: an increased production of dry gases and coke is observed to the detriment intermediate hydrocarbons sought.
  • US Patent No. 2,488,713 proposes a catalytic cracking process using two successive reactors, in each of which circulate catalytic particles.
  • a heavy recycle cut (residue from the fractionation of cracked effluents, of the type known as a “slurry”) is cracked on contact with the catalytic particles coming from the regenerator.
  • a fresh charge as well as an intermediate recycle cut of the distillate type are cracked on contact with the particles coming from the first reactor.
  • the hydrocarbon effluents are separated from the particles, then are combined and directed to a conventional fractionation column.
  • the first drawback of such a process is that the fresh charge is treated, in the second reactor, in the presence of particles which have already been largely coked and deactivated in the first reactor, in contact with the heavy recycle charge, which is particularly rich in refractory polyaromatic compounds.
  • the heavy recycle charge which is particularly rich in refractory polyaromatic compounds.
  • a second disadvantage comes from the fact that the heavy recycle cut progressively enriches itself with the most refractory heavy compounds, which, even recycled in the first reactor, do not crack or crack in an incomplete manner, and "go around in circles" in the unit. . This exacerbates the problems described above of premature coking of the particles in the first reactor. A purge planned on the recycling line does not solve the problem satisfactorily.
  • the purge not only extracts only part of the most refractory compounds that are desired eliminate from the unit, but additionally extracts a fraction of compounds directly originating from the fresh charge, which were not converted during their passage through the second reactor, but which could have been cracked in the first reactor in contact with regenerated particles.
  • the poor selectivity of this purge system thus induces an additional loss of yield in desired products.
  • patent EP No. 573316 describes a catalytic cracking process in which the reaction takes place in two successive reactors, the first reactor being in downward flow, and the second being in upward flow (riser).
  • the charge to be cracked is brought into contact with the regenerated particles at the inlet of the downflow reactor, at the bottom of which the charge / particle mixture is transferred into the upflow reactor.
  • the charge therefore flows in contact with the particles in two successive reactors, which makes it possible to increase the overall yield of cracked hydrocarbons.
  • this process is absolutely not selective: the hydrocarbons already converted in the first reactor continue to crack in the second reactor, resulting in an overcracking phenomenon generating increased production of dry gases and coke, to the detriment of intermediate cuts sought.
  • the present invention relates to a process for cracking in a fluidized bed a hydrocarbon feedstock in which heat-carrying particles, optionally catalytic, circulate in two successive reaction chambers? in each of which they are brought into contact with at least one section of hydrocarbons, and the reaction effluents from each of said chambers are directed to the same fractionation unit.
  • This process is characterized in that the effluents from each of the reaction chambers are partially fractionated separately in the same partially partitioned fractionation column, and in that that at least one section resulting from the separate fractionation of the effluents from one of the two reaction chambers is, in whole or in part, reinjected into the other chamber.
  • reaction chamber designates any enclosure provided with means for introducing heat-transfer particles (catalytic or not), means for injecting one or more cuts of hydrocarbons to be cracked, a reaction zone of cracking and means for separating cracking effluents and particles.
  • This term includes in particular any type of thermal or catalytic cracking reactor in a fluidized bed, whatever its operating mode (ascending or descending).
  • hydrocarbons are cracked in a first reaction chamber, in contact with fully active particles coming from the regenerator.
  • the effluents are separated from the particles, and the latter continue their journey in a second reaction chamber in which their residual activity is used to crack an additional quantity of hydrocarbons.
  • the process according to the invention allows a more thorough and more selective conversion of the charge to be cracked. It allows the refiner to re-inject low-value products obtained during a first conventional cracking step, so as to subject these products to a second cracking step.
  • the fact that the recycling of said products takes place in a different reactor has the advantage, on the one hand, of being able to carry out this second cracking under appropriate conditions and, on the other hand, of avoiding affecting the quality of the first step of cracking the load.
  • the method according to the invention makes it possible to subject the hydrocarbons constituting the charge to separate cracking circuits, perfectly adapted to the various natures of these hydrocarbons, so as to obtain a maximum quantity of recoverable products.
  • the charge to be cracked undergoes a first conversion, as a result of which the undesirable products obtained are fractionated separately from the effluents of the other reactor, in a compartment of the partitioned zone of the fractionation column.
  • These products are then reinjected into a separate reactor, in which they undergo a second cracking step, under conditions specifically suited to their nature.
  • the effluents resulting from this second cracking are then fractionated in the same column as the effluents from the first cracking, and the partitioned fractionation system of this column makes it possible to prevent the residual undesirable compounds, not converted after passing through the two reactors (in particularly compounds that are particularly refractory to cracking), are not recycled a second time and "go around in circles" in the unit. Indeed, such compounds are recovered, in the fractionation column, in the compartmentalized fractionation compartment of the effluents from the second cracking step. These compounds are thus recovered separately from the effluents from the first cracking step, and they can for example be eliminated from the unit.
  • This system makes it possible to reinject into one of the reaction chambers only hydrocarbons coming exclusively from the other chamber. This avoids any phenomenon of enrichment of the recycled cuts in refractory compounds, which would gradually degrade the quality of the cracking of said cuts, while causing excessive coking of the particles circulating in the unit.
  • the method according to the invention makes it possible to make the most of undesirable products originating from a first conventional cracking step, in order to produce an additional quantity of products with greater added value.
  • it offers the refiner the possibility of carrying out a cracking that is both more complete and more selective in favor of the type of products he wishes to obtain.
  • the profitability of the unit is significantly improved.
  • the present invention therefore also relates to a cracking device in a fluidized bed of a hydrocarbon feedstock, using two reaction chambers connected to each other by means of transfer of the heat-carrying particles, a fractionation column and supply lines for the hydrocarbon effluents from each of the two chambers at said fractionation column.
  • a first advantage of the device according to the invention is linked to the fact that the hydrocarbon effluents from the two reaction chambers are partly treated separately, but in a single fractionation column. This system makes it possible to avoid having to use two separate columns, therefore to have a compact unit and to limit investments.
  • a second advantage of this device is linked to the fact that it allows optimal implementation of the method according to the invention.
  • said partitioned fractionation zone is advantageously dimensioned as a function of the boiling ranges of the undesirable products to which the refiner wishes to subject a second cracking step.
  • the common fractionation zone is used for the fractionation of products for which the refiner does not wish to differentiate those from each of the two reaction chambers, for example because these are directly recoverable products, which he does not wish to reverse.
  • first and second reaction chamber The two reaction chambers involved in the invention are designated in the present description by "first" and “second” reaction chamber, it being understood that this order is adopted by reference to the direction of circulation of the heat-carrying particles from the regenerator.
  • the injection of hydrocarbons can be done co-current and / or against the current of the flow of heat-transfer particles.
  • reaction chambers can in particular be made up of any type of downward (or downward) or riser (riser) flow reactors.
  • the two chambers can completely be identical, the method according to the invention is all the more advantageous when said chambers are different. This makes it possible in particular to make different operating conditions prevail in these two chambers, adapted to the type of hydrocarbons injected into each.
  • the residence time of the hydrocarbons injected into the first reaction chamber is less than the residence time of the hydrocarbons injected into the second reaction chamber.
  • the cracking in the first reaction chamber takes place in the presence of particles coming directly from the regenerator, therefore at particularly high temperature and maximum activity.
  • the cracking takes place under milder conditions, since the particles have partly cooled, or even deactivated, during their passage through the first reaction chamber. Consequently, it has proved advantageous to prolong the contact there between the particles and the hydrocarbons, so as to allow a sufficiently complete cracking of the latter.
  • the residence time of the hydrocarbons injected into the first reaction chamber is between 0.05 and 5 seconds, preferably between 0.1 and 1 seconds.
  • the residence time of the hydrocarbons injected into the second reaction chamber it is advantageously between 0.1 and 10 seconds, preferably between 0.4 and 5 seconds.
  • the flow of the charge and the catalyst in the first reaction chamber takes place in an essentially descending direction.
  • Said reaction chamber can then consist of a substantially vertical downward flow reactor of the type known under the name of "downer", as described for example in international patent application WO 98/12279.
  • this type of reactor allows a particularly short contact time between the hydrocarbons and the fluidized bed of particles.
  • the flow of the charge and the catalyst in the second reaction chamber takes place in an essentially ascending direction.
  • Said reaction chamber can then consist of a substantially vertical reactor with upward flow, of the type known under the name of "riser". Indeed, this type of reactor allows access to longer contact times between the hydrocarbons and the fluidized bed of particles.
  • the present invention presents numerous modes of implementation, among which the refiner will be able to choose the one which is the most adapted to the types of products he wishes to obtain, taking into account the type of fillers available.
  • a first particularly advantageous embodiment consists in partitioning the fractionation of the heavy part of the effluents from the two reactors.
  • the heaviest effluents from each of the two reaction chambers are fractionated separately, while the lightest effluents are combined.
  • said cut resulting from the separate fractionation of the effluents from one of the reaction chambers and which is, in whole or in part, reinjected into the other chamber comprises slurry and / or a heavy distillate of the HCO type.
  • HCO from the English term "heavy cycle oil”
  • HCO is usually used to designate a heavy fraction whose boiling range can extend from an initial point generally between 320 and 400 ° C. up to an end point generally between 450 and 480 ° C. It is a poorly recoverable product, rich in sulfur and aromatic compounds, which is generally used as a diluent for heavy fuels.
  • the product commonly called “slurry”
  • slurry it consists of the fractionation residue from the cracked effluents. It is a very heavy, very viscous product, the initial cutting point of which is generally between 450 and 480 ° C.
  • This residue is all the more difficult to develop as it is particularly rich in polyaromatic compounds, and that it comprises an appreciable proportion of fines, that is to say dust from the erosion of the heat-carrying particles circulating in unit.
  • a second particularly advantageous embodiment consists in partitioning the fractionation of the light part of the effluents from the two reactors.
  • the lightest effluents from each of the two reaction chambers are fractionated separately while the heaviest effluents are combined.
  • said cut resulting from the separate fractionation of the effluents from one of the reaction chambers and which is, in whole or in part, reinjected into the other chamber comprises gasoline.
  • cuts are designated by essence whose boiling range can extend from an initial point generally greater than or equal to 20 ° C up to an end point generally between 140 and 220 ° C. It can be particularly advantageous for the refiner to subject a second cracking step to this type of product, insofar as this increases the production of light olefins such as, for example, propenes and butenes, which are very sought after products, in particular for uses in petrochemicals.
  • At least one section resulting from the separate fractionation of the effluents from one of the reaction chambers is, in whole or in part, reinjected into the other chamber.
  • the reinjected proportions depend in particular on the nature (more or less dense, more or less difficult to crack, ...) of the cuts concerned. These proportions must also take into account the operating conditions prevailing in the reactor in which such cuts are reinjected, so as to ensure complete vaporization and cracking of the recycled hydrocarbons.
  • the proportion reinjected advantageously comprises from 10 to 100% of the flow of said cut. More preferably, this proportion is between 50 and 100%.
  • each of the reinjected cuts can be, prior to this reinjection, combined with other cuts of hydrocarbons.
  • the diluent can, for example, include fresh feed, in particular conventional fillers such as diesel or distillates.
  • the diluent can moreover comprise for example light recycling oils ("light cycle oils", LCO) or heavy recycling oils ("heavy cycle oils", HCO).
  • each of the reinjected sections can, before this reinjection, be subjected to one or more intermediate treatments.
  • an intermediate treatment includes a hydrotreatment, such as for example a hydrogenation, a hydrodearomatization, a hydrodesulfurization, a hydrodenitrogenation.
  • Such treatments are usually carried out in the presence of catalysts known to those skilled in the art, and which generally comprise, deposited on a refractory mineral oxide support, one or more metals from Group VIII of the Periodic Table of the Elements, sometimes associated with other metals such as those of Group VI of the Periodic Table of the Elements.
  • the cracking of the hydrocarbons is carried out in the presence of the heat-transfer particles coming from the first chamber, in which they have been partially coked, or even deactivated, in contact with the charge injected into this first chamber.
  • a particularly advantageous variant of the invention consists in introducing upstream of this second reaction chamber, in addition to the particles coming from the first reaction chamber, an addition of particles coming from the regenerator. This variant is particularly beneficial when the heat provided by the particles from said first chamber is insufficient to vaporize the hydrocarbons injected into the second reaction chamber. Adding regenerated particles then makes it possible to provide an additional quantity of heat, and to control the temperature prevailing in said second chamber.
  • this system has the additional advantage of introducing into the second chamber an addition of fully active catalytic sites, so as to optimize the cracking reactions of the hydrocarbons injected into this second chamber.
  • the addition of particles is introduced between the zone where the separation of the particles and effluents takes place from the first reaction chamber and the zone where the injection of the hydrocarbon fractions takes place in the second reaction chamber.
  • Said make-up is advantageously introduced so as to ensure a homogeneous mixture with the particles coming from the first reactor.
  • a system for homogenizing the fluidized beds of particles as described in patent application EP No. 99.401112 in the name of the Applicant may prove to be particularly useful.
  • the invention uses a specific fractionation column. Indeed, this must allow the simultaneous distillation of the effluents from the two reactors, and be arranged so that the fractionation of these two types of effluents is carried out partly separately, partly in common.
  • This partial segregation of the effluents from the two reactors is carried out using a partitioning disposed inside the column, which partitioning separates part of said column into two compartments which constitute said partitioned fractionation zone.
  • This partially partitioned fractionation column can be arranged in many ways, depending on the part of the effluents for which it is desired that the fractionation be carried out separately.
  • the partitioned fractionation zone corresponds to the lower part of the fractionation column.
  • different modes of partitioning can be envisaged for the device according to the present invention.
  • the partitioned fractionation zone is separated into two compartments by means of a substantially vertical separation means, extending from the bottom of the fractionation column over part of the height thereof. It may for example be a flat vertical wall. It may also be a cylindrical vertical wall whose axis of revolution is parallel to the longitudinal axis of the fractionating column.
  • the partitioned fractionation zone is separated into two compartments by means of a substantially horizontal separation means, for example consisting of a tray extending over a horizontal section of the column, and provided with one or more several chimneys allowing the passage upwards, towards the common fractionation zone, of light effluents from the lower compartment to said tray.
  • a substantially horizontal separation means for example consisting of a tray extending over a horizontal section of the column, and provided with one or more several chimneys allowing the passage upwards, towards the common fractionation zone, of light effluents from the lower compartment to said tray.
  • the partitioned fractionation zone corresponds to the upper part of the fractionation column.
  • the partitioned fractionation zone is separated into two compartments by means of a substantially vertical separation, extending from the head of the fractionation column over a part of the height thereof, such as for example a flat vertical wall or a vertical cylindrical wall whose axis of revolution is parallel to the longitudinal axis of the fractionating column.
  • the partitioned fractionation zone is separated into two compartments by means of a substantially horizontal separation means, for example consisting of a tray extending over a horizontal section of the column, and provided with one or more several chimneys allowing the passage downwards, towards the common fractionation zone, of the heavy effluents coming from the upper compartment to said tray.
  • a substantially horizontal separation means for example consisting of a tray extending over a horizontal section of the column, and provided with one or more several chimneys allowing the passage downwards, towards the common fractionation zone, of the heavy effluents coming from the upper compartment to said tray.
  • each of the two reaction chambers operates can vary. They are preferably different in each of these two chambers, taking into account the different natures of the hydrocarbons which are injected there. In general, these operating conditions include a reaction temperature between 450 and 900 ° C, and a pressure close to atmospheric pressure. A person skilled in the art knows perfectly how to optimize these conditions according to the type of petroleum cuts to be cracked.
  • the hydrocarbon charges liable to be cracked in the context of the present invention can be extremely diverse. They include in particular, but are not limited to, the usual fillers for cracking processes, such as for example distillates and / or gas oils obtained from atmospheric or vacuum distillation, distillates and / or visbreaking gas oils, deasphalted residues.
  • the process according to the invention is, moreover, perfectly suited to the conversion of heavier feedstocks, containing fractions normally boiling up to 700 ° C. and more, which may contain high quantities of asphaltenes and have a Conradson carbon content. up to 4% and beyond.
  • the feed can include heavy distillates, atmospheric distillation residues, or even vacuum distillation residues.
  • the injected fillers may if necessary have received a preliminary treatment such as, for example, a hydrotreatment in the presence of an appropriate catalyst, for example a catalyst based on cobalt and molybdenum deposited on a porous refractory oxide.
  • a preliminary treatment such as, for example, a hydrotreatment in the presence of an appropriate catalyst, for example a catalyst based on cobalt and molybdenum deposited on a porous refractory oxide.
  • the charge to be cracked can moreover be diluted by one or more lighter cuts, which can include intermediate cuts coming from the fractionation zone of the cracking effluents.
  • the LCOs or HCOs mentioned above can constitute excellent diluents.
  • FIG. 1 represents a catalytic cracking unit comprising two successive reaction chambers, the first with downward flow and the second with upward flow.
  • This unit comprises a first reaction chamber consisting of a tubular reactor 1 with downflow, known as name of "downer”.
  • This reactor is connected in its upper part to an enclosure 2, from which it is fed by a flow of regenerated catalyst particles, with a flow rate regulated by means of a valve 3.
  • the charge to be cracked is conveyed by line 4 and injected into reactor 1 by means of injectors 5.
  • the catalyst particles and the hydrocarbons then flow from top to bottom in reactor 1.
  • the mixture emerges in enclosure 6, in the upper part of which a separator, not shown, separates the catalyst particles from the reaction effluents, which are directed to the fractionation zone by line 7.
  • a separator not shown, separates the catalyst particles from the reaction effluents, which are directed to the fractionation zone by line 7.
  • the particles are stripped, by means of water vapor brought by the line 8 to the diffuser 9.
  • the particles are then evacuated via line 10 out of the enclosure 6, and transferred to the base of the second reaction chamber.
  • the latter consists of a reactor 16 in the form of a column, of a type known per se, known as a load elevator, or riser.
  • the reactor 16 is supplied at its base by the conduit 10 with particles of catalyst.
  • a riser gas for example water vapor
  • a riser gas for example water vapor
  • a charge comprising a substantial proportion of a cut resulting from the separate fractionation of heaviest effluents from the first reactor 1
  • a charge comprising a substantial proportion of a cut resulting from the separate fractionation of heaviest effluents from the first reactor 1
  • the catalyst particles and the hydrocarbons then flow from bottom to top in the reactor 16 .
  • the column 16 opens at its top in an enclosure 15, which is for example concentric and in which the separation of the cracked charge takes place and the stripping of the deactivated particles of catalyst.
  • the particles are separated from the charge treated by means of a cyclone 17, which is housed in the enclosure 15, at the top of which is provided a discharge line 18 for the effluents from the second reactor 16, which are routed to the fractionation zone.
  • the deactivated particles move by gravity towards the base of the enclosure 15.
  • a line 20 supplies stripping fluid, generally steam, to injectors or diffusers 21 of fluidizing gas regularly arranged at the base of the pregnant 15.
  • the particles are then evacuated at the base of the enclosure 15 to a regenerator 23, via the conduit 22.
  • the regenerator 23 the coke deposited on the particles is burned using air or a another oxygen-rich gas, injected at the base of the regenerator 23 by a line 24, which feeds regularly spaced injectors or diffusers 25.
  • the particles entrained by the combustion gas are separated by cyclones 26, and the combustion gas is evacuated by a line 27, while the particles flow towards the base of the enclosure 23, from where they are recycled by the conduit 28 towards the enclosure 2 supplying the first reactor 1.
  • the reaction effluents from each of reactors 1 and 16 are routed respectively by lines 7 and 18 to the fractionation column 12.
  • the latter consists of two zones: a lower zone 40 for partitioned fractionation, and an upper zone 41 for fractionation common.
  • the partitioned fractionation zone 40 is divided into two compartments 38 and 39 by a separation means 37, consisting of a flat vertical wall, extending from the bottom of the column 12 over part of the height thereof. .
  • the lines 7 and 18 for supplying the effluents from the two reactors open on either side of the separation means 37, into the respective compartments 39 and 38, in which the corresponding heavy products are fractionated separately.
  • These products correspond to distillation residues or "slurry", the initial cutting point of which is preferably chosen at a value between 450 and 480 ° C.
  • the two compartments 38 and 39 communicate with the common fractionation zone 41, located in the upper part of the column 12, and in which the lighter products contained in the combined effluents from the two reactors 1 and 16 are carried out.
  • fractionation zone can perfectly comprise conventional additional columns, not shown, coupled to column 12, in which part of the fractionation of the common effluents described above and / or subsequent fractionations can be carried out.
  • the condensed residues in compartments 38 and 39 are drawn off respectively by lines 42 and 13.
  • the section drawn off by line 13, which corresponds to the slurry resulting from the separate fractionation of the effluents from the first reaction chamber 1, is, in accordance with invention, recycled to the second reaction chamber 16.
  • line 47 makes it possible to dilute this bottom fraction by a less viscous cut, for example all or part of the HCO cut drawn off by line 46.
  • the line 48 makes it possible to withdraw part of said bottom fraction, so as to inject only a given proportion into the reactor 16.
  • section drawn off by line 42 corresponds to the slurry resulting from the separate fractionation of the effluents from the second reaction chamber 16.
  • This section which comprises particularly refractory compounds which are not converted after successive cracking in each of the two reactors, can be by example removed from the unit.
  • FIG. 2 in which the members already described in relation to FIG. 1 are designated by the same reference numbers, shows a first alternative embodiment of the fractionation column 12, which shows another means of partitioning the lower part 40 of said column.
  • the column 12 comprises a separation means consisting, as in FIG. 1, of a substantially vertical partitioning, extending from the bottom of the column 12.
  • this partitioning element here consists of a cylindrical vertical wall 37 ′ whose axis of revolution is parallel to the longitudinal axis of the column 12.
  • This cylindrical element is disposed internally and concentrically with the wall of the column 12, and it extends from the bottom of this over a sufficient height, thus dividing the partitioned fractionation zone 40 into two compartments 39 and 38, into which lead respectively the line 7 for conveying effluents from the first reaction chamber 1, and the line 18 for conveying effluents from the second reaction chamber 16.
  • the two compartments 38 and 39 are therefore concentric.
  • Each compartment 38 and 39 communicates directly with the common fractionation zone 41 situated above, in which is carried out, in a conventional manner, the fractionation of the lighter products contained in the combined effluents of the two reactors.
  • the partition element 37 extends over a greater height of the column 12, so as to also cover the distillation zone of HCO type cuts. Furthermore, the HCO is not separated from the slurry, so that the residues, drawn off by lines 42 and 13 in the bottom of each of the two respective compartments 38 and 39, consist of a mixture of these two types of products. .
  • the residue drawn off by line 13 consisting of a mixture of HCO and slurry from the separate fractionation of heavy effluents from the first reaction chamber 1, is, in accordance with the invention, recycled in whole or in part to the second reaction chamber 16.
  • supply lines 7 and 18 can completely be inverted, provided that the two lines 13 and 42 for drawing off the corresponding products are also inverted.
  • FIG. 3 in which the members already described in relation to FIG. 1 are again designated by the same reference numbers, represents a second alternative embodiment of the fractionation column 12 of this FIG. 1, in which the means 37 " for separating the lower partitioned partitioning zone 40 is of the horizontal type.
  • the zone 40 comprises an internal partitioning constituted by a horizontal plate 37 ", which is dimensioned so as to cover the entire cross section of the column 12 and to be in sealed contact with the internal vertical wall of that -this.
  • This partitioning delimits a first upper compartment 39, into which opens the line 7 for transporting the effluents from the first reaction chamber 1, and a second lower compartment 38, into which opens the line 18 for transporting the effluents from the second reaction chamber. 16.
  • the two compartments 38 and 39 are therefore arranged one above the other.
  • Each compartment, 38, 39 communicates directly with the common fractionation zone 41 situated above.
  • the tray 37 is provided with at least one chimney 50, which allows the passage upwards, towards said common fractionation zone 41, of the vaporized products coming from the compartment 38 below the tray 37".
  • the lightest effluents from the second reaction chamber 16 rise via this chimney towards the common area 41, where they are fractionated and drawn off by lines 43, 44 and 45, in mixture with the light effluents from first reaction chamber 1.
  • the chimney 50 is surmounted by a cap 51, for example conical, which makes it possible to prevent hydrocarbons from passing from the upper compartment 39 to the lower compartment 38. This system therefore ensures perfect segregation of the heavy effluents from the two reactors 1 and 16.
  • the section drawn off by line 13 of the compartment 39 for partitioning heavy effluents from the first reaction chamber 1 is, in accordance with the invention, recycled in whole or in part to the second reaction chamber 16.
  • the supply lines 7 and 18 can be inverted (the separate fractionation of the heavy effluents from the first reactor 1 is then carried out in the lower compartment 38, while the separate fractionation of the effluents heavy of the second reactor 16 is carried out in the upper compartment 39), provided that the two lines 13 and 42 for drawing off the corresponding products are also reversed.
  • FIG. 4 also represents a catalytic cracking unit comprising, like that presented in FIG. 1, a first reaction chamber 1 with downward flow and a second reaction chamber 16 with upward flow.
  • This unit has many elements common to the unit shown in Figure 1 and designated by the same reference numerals, so that only the different elements will be described below.
  • the process illustrated in this FIG. 4 corresponds to an embodiment of the invention, in which the lightest effluents from each of the two reactors 1 and 16 are fractionated separately, in order to reinject into one of them products light from the other.
  • the fractionation column 12 comprises an upper zone 40 for partitioned partitioning of light effluents, and a lower zone 41 for common fractionation of heavy effluents.
  • the partitioned fractionation zone 40 is divided into two compartments 38 and 39 by a separation means 37, consisting of a flat vertical wall extending downwards from the head of the column 12, over part of the height of it.
  • the gasoline fraction removed through line 44 is separated after splitting of the lightest effluents from the second reaction chamber, is fed to injectors 5, from which it is fed back into the first reaction chamber 1.
  • injectors 5 from which it is fed back into the first reaction chamber 1.
  • the fresh charge can be wholly or partly injected into the second reactor 16. For this purpose, it is sent to the injectors 14 via the line 52.
  • FIG. 5 where the members already described in relation to FIG. 4 are designated by the same reference numerals, represents an alternative embodiment of the fractionation column 12 of this FIG. 4, in which the means 37 "for separating the upper zone 40 of partitioned fractionation is of horizontal type.
  • the zone 40 comprises an internal partitioning constituted by a horizontal plate 37 ", dimensioned so as to cover the entire cross section of column 12 and be in leaktight contact with the internal vertical wall of that.
  • This partitioning delimits a first upper compartment 39, into which opens the line 7 for transporting the effluents from the first reaction chamber 1, and a second lower compartment 38, into which opens the line 18 for transporting the effluents from the second reaction chamber. 16.
  • Each compartment 38, 39 communicates directly with the common fractionation zone 41 located below.
  • the tray 37 is provided with at least one chimney 50, which allows the passage downward, towards said common fractionation zone 41, of the heavy products coming from the compartment 39 above the tray 37".
  • the heaviest effluents from the first reaction chamber 1 descend via this path to the common area 41, where they are fractionated and drawn off by lines 45, 46 and 53, mixed with the heavy effluents from the second reaction chamber 16.
  • the chimney 50 is provided with a baffle 51, for example conical, which makes it possible to prevent hydrocarbons from passing from the lower compartment 38 to the upper compartment 39. This system therefore makes it possible to ensure perfect segregation of the light effluents from the two reactors 1 and 16.
  • the gasoline section drawn off by line 44 a from the compartment 38 for partitioning partitioned light effluents from the second reaction chamber 16 is, in accordance with the invention, recycled in whole or in part to the first reaction chamber 1.
  • the first test was carried out in an experimental catalytic cracking unit in accordance with that shown in Figure 1, which comprises two successive reaction chambers (1; 16), the first (1) with downflow (“downer”), and the second (16) with upward flow (“riser”).
  • the catalyst used is a conventional commercial catalyst, of the zeolitic type.
  • the effluents from each of these two reaction chambers are directed to the same fractionation column (12), partitioned in its lower part (40) by a flat vertical wall (37).
  • the fresh charge is injected into the first reaction chamber (1), while in the second reaction chamber (16) a section is recycled from the separate fractionation of the effluents from the first chamber (1).
  • test No. 2 a comparative test was carried out under the same conditions, but by replacing the partially partitioned fractionation column (12) with a conventional column, in which the effluents from each of the two chambers (1; 16 ) are combined and split in the traditional way.
  • the fresh charge is injected into the first reaction chamber (1), while in the second reaction chamber (16) a section is recycled from the fractionation of the combined effluents from the two chambers.
  • the fraction recycled in the second reaction chamber (16) corresponds to a heavy distillate or HCO, with a boiling range extending from 380 ° C. to 480 ° C.
  • test 1 all of the HCO from the partitioned fractionation of the effluents from the first reaction chamber (1) is injected into the second reaction chamber (16).
  • the recycling rate ratio of the amount of HCO recycled in the second reaction chamber to the total amount of HCO produced in the unit is 0.8.
  • the recycled HCO cut contains only hydrocarbons from a first cracking of the fresh charge, while in the second case it also contains hydrocarbons from the second chamber, not converted after passing through the two successive reactors, therefore particularly refractory to cracking, and which "go around in circles" in the unit.
  • the elimination of such compounds by means of the partitioned fractionation system notably improves the quality of the cracking in the second reaction chamber. It can be seen that this conversion is both more complete (10-point increase in the conversion rate), and more selective (sharp reduction in yield of slurry, which is a particularly undesirable product, in favor of an increase in yields sought intermediate products, such as gasolines and LPG).
  • This example therefore illustrates the fact that, in the process according to the invention, the qualities of the recycle cut are higher, which contributes to better yields, better selectivity and better quality of the products obtained during the cracking of this cut. in the second reaction chamber 16.
  • an experimental catalytic cracking unit conforming to that shown in FIG. 4 which comprises two successive reaction chambers (1; 16), the first (1) with downward flow, and the second (16) upward flow ("riser").
  • the catalyst used is a conventional commercial catalyst, of the zeolitic type.
  • a first test (test No. 5) is carried out in accordance with the invention: the effluents from each of these two reaction chambers are directed to the same fractionation column (12), partitioned in its upper part (40) by a vertical wall plane (37). The fresh charge is injected into the second reaction chamber (16), while in the first reaction chamber (1) a section is recycled from the separate fractionation of the effluents from the second chamber (16).
  • test no. 6 a comparative test was carried out under the same conditions, but by replacing the partially partitioned fractionation column (12) with a conventional column, in which the effluents from each of the two chambers (1; 16 ) are combined and split in the traditional way.
  • the fresh charge is injected into the second reaction chamber (16), while in the first reaction chamber (1) a section is recycled from the fractionation of the combined effluents from the two chambers.
  • the cut recycled in the first reaction chamber (1) is a light gasoline (with a boiling range extending from 20 ° C. to 220 ° C.).
  • test 5 all of the petrol coming from the partitioned fractionation of the effluents from the second reaction chamber (16) is injected into the first reaction chamber (1).
  • the recycling rate ratio of the quantity of petrol recycled in the first reaction chamber to the total quantity of petrol produced in the unit is 0.8.
  • the above examples perfectly illustrate some of the many advantages provided by the present invention.
  • they show that the invention makes it possible to optimally recycle certain hydrocarbon fractions resulting from a first step of cracking the fresh charge, which makes it possible to substantially increase the total conversion efficiency of this charge. , with increased selectivity in favor of the specific products sought.

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Claims (28)

  1. Verfahren zum Cracken einer Beladung von Kohlenwasserstoffen im Fließbett, bei dem
       wärmeübertragende, eventuell katalytische Partikel in zwei aufeinanderfolgenden Reaktionskammern (1, 16) zirkulieren, in jeder von denen sie in Kontakt gebracht werden mit zumindest einem Verschnitt von Kohlenwasserstoffen, und
       die von jeder dieser Kammern abgegebenen Reaktionsausflüsse zu derselben Fraktioniereinheit geleitet werden,
       dadurch gekennzeichnet, dass
       die Ausflüsse jeder der Reaktionskammern (1, 16) teilweise getrennt in derselben Fraktioniersäule fraktioniert werden, die teilweise unterteilt ist, und
       zumindest ein Verschnitt (13, 44a) der von der getrennten Fraktionierung der Ausflüsse einer der zwei Reaktionskammern (1, 16) abgegeben wird, ganz oder teilweise in die andere Kammer zurückinjiziert wird.
  2. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass die Aufenthaltsdauer der in die erste Reaktionskammer (1) eingespritzten Kohlenwasserstoffe kleiner ist als die Aufenthaltsdauer der in die zweite Reaktionskammer (16) eingespritzten Kohlenwasserstoffe.
  3. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass die Aufenthaltsdauer der in die erste Reaktionskammer (1) eingespritzten Kohlenwasserstoffe zwischen 0,05 und 5 Sekunden liegt, vorzugsweise zwischen 0,1 und 1 Sekunde.
  4. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass die Aufenthaltsdauer der in die zweite Reaktionskammer (16) eingespritzten Kohlenwasserstoffe zwischen 0,1 und 10 Sekunden liegt, vorzugsweise zwischen 0,4 und 5 Sekunden.
  5. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass das Strömen der Beladung und der Partikel in der ersten Reaktionskammer (1) in einer im Wesentlichen absteigenden Richtung erfolgt.
  6. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass das Strömen der Beladung und der Partikel in der zweiten Reaktionskammer (16) in einer im Wesentlichen aufsteigenden Richtung erfolgt.
  7. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass in der teilweise unterteilten Fraktioniersäule (12) die schwersten von jeder der zwei Reaktionskammern abgegebenen Ausflüsse getrennt fraktioniert werden, während die leichtesten Ausflüsse zusammengeführt werden.
  8. Verfahren nach dem vorigen Anspruch, dadurch gekennzeichnet, dass der Verschnitt (13), der von der getrennten Fraktionierung der Ausflüsse einer der Reaktionskammern abgegeben wird und der ganz oder teilweise in die andere Kammer zurückinjiziert wird, Abschlämmung und/oder ein schweres Destillat vom Typ des HCO und/oder einen Verschnitt vom Gasöl-Typ wie z.B. LCO enthält.
  9. Verfahren nach einem Ansprüche 7 und 8, dadurch gekennzeichnet, dass zumindest ein Verschnitt (13), der von der getrennten Fraktionierung der schwersten Ausflüsse der ersten Reaktionskammer (1) abgegeben wird, ganz oder teilweise in die zweite Reaktionskammer (16) zurückinjiziert wird.
  10. Verfahren nach einem Ansprüche 1 bis 6, dadurch gekennzeichnet, dass in der teilweise unterteilten Fraktioniersäule (12) die leichtesten von jeder der zwei Reaktionskammern abgegebenen Ausflüsse getrennt fraktioniert werden, während die schwersten Ausflüsse zusammengeführt werden.
  11. Verfahren nach dem vorigen Anspruch, dadurch gekennzeichnet, dass der Verschnitt (44a), der von der getrennten Fraktionierung der Ausflüsse einer der Reaktionskammern abgegeben wird und der ganz oder teilweise in die andere Kammer zurückinjiziert wird, Benzin enthält.
  12. Verfahren nach einem Ansprüche 10 und 11, dadurch gekennzeichnet, dass zumindest ein Verschnitt (44a), der von der getrennten Fraktionierung der leichtesten Ausflüsse der zweiten Reaktionskammer (16) abgegeben wird, ganz oder teilweise in die erste Reaktionskammer (1) zurückinjiziert wird.
  13. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass der Verschnitt (13, 44a), der von der getrennten Fraktionierung der Ausflüsse einer der Reaktionskammern abgegeben wird und die ganz oder teilweise in die andere Kammer zurückinjiziert wird, vor der Rückführung mit anderen Verschnitten von Kohlenwasserstoffen zusammengeführt wird.
  14. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass der Verschnitt (13, 44a), der von der getrennten Fraktionierung der Ausflüsse einer der Reaktionskammern abgegeben wird und der ganz oder teilweise in die andere Kammer zurückinjiziert wird, vor der Rückführung einer oder mehreren Zwischenbehandlungen unterzogen wird.
  15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Zwischenbehandlung eine Hydrobehandlung enthält wie z.B. eine Hydrierung, eine Hydroaromatisierung, eine Hydroentschwefelung, eine Hydrodenitrierung.
  16. Verfahren nach einem der vorigen Ansprüche, dadurch gekennzeichnet, dass stromaufwärts von der zweiten Reaktionskammer (16) zusätzlich zu den von der ersten Reaktionskammer (1) abgegebenen Partikeln ein Zusatz von Partikeln zugeführt wird, die aus einem Regenerator kommen.
  17. Vorrichtung zum Cracken einer Beladung von Kohlenwasserstoffen im Fließbett durch Inbetriebnahme von
       zwei Reaktionskammern (1, 16), die untereinander durch ein Mittel (10) zum Transportieren wärmeübertragender Partikel verbunden sind,
       einer Fraktioniersäule (12), und
       Leitungen (7, 18) zum Zuführen der von jeder der beiden Kammern (1, 16) abgegebenen Kohlenwasserstoffausflüsse zu der Fraktioniersäule (12),
       dadurch gekennzeichnet, dass
       die Fraktioniersäule (12) in ihrem Inneren zumindest zwei verschiedene Zonen aufweist: eine erste Zone (40) der unterteilten Fraktionierung, die aus zwei Abteilungen (38, 39) besteht, von denen jede mit einer zweiten Zone (41) der gemeinsamen Fraktionierung in Verbindung steht,
       die Leitungen (7, 18) zum Zuführen der von der ersten und der zweiten Reaktionskammer (1, 16) abgegebenen Ausflüsse jeweils in der ersten bzw. in der zweiten Abteilung (39, 38) der Zone (40) der unterteilten Fraktionierung münden,
       Mittel (13, 44a) vorgesehen sind zum Wiederverwenden und Zuführen zu einer der Reaktionskammern (1, 16) zumindest eines der Abteilung der unterteilten Fraktionierung entnommenen Verschnitts der Ausflüsse der anderen Reaktionskammer.
  18. Vorrichtung nach dem vorigen Anspruch, dadurch gekennzeichnet, dass die Reaktionskammern (1, 16) verschieden sind.
  19. Vorrichtung nach einem der Ansprüche 17 und 18, dadurch gekennzeichnet, dass die erste Reaktionskammer (1) aus einem im Wesentlichen vertikalen Reaktor mit absteigender Strömung des unter der Bezeichnung "Downer" bekannten Typs besteht.
  20. Vorrichtung nach einem der Ansprüche 17 bis 19, dadurch gekennzeichnet, dass die zweite Reaktionskammer (16) aus einem im Wesentlichen vertikalen Reaktor mit aufsteigender Strömung des unter der Bezeichnung "Riser" bekannten Typs besteht.
  21. Vorrichtung nach einem der Ansprüche 17 bis 20, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung dem unteren Abschnitt der Fraktioniersäule (12) entspricht.
  22. Vorrichtung nach Anspruch 21, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung in zwei Abteilungen (38, 39) unterteilt ist durch ein im Wesentlichen vertikales Trennelement (37, 37'), das sich von dem Grund der Fraktioniersäule (12) aus über einen Teil ihrer Höhe erstreckt.
  23. Vorrichtung nach Anspruch 21, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung in zwei Abteilungen (38, 39) unterteilt ist durch ein im Wesentlichen horizontales Trennelement, das aus einer Platte (37") besteht, die sich über einen horizontalen Abschnitt der Säule (12) erstreckt und mit einem oder mehreren Schloten (50) versehen ist, die den Durchgang der von der Abteilung (38) unterhalb der Platte (37") abgegebenen leichten Ausflüsse nach oben zu der Zone (41) der gemeinsamen Fraktionierung ermöglichen.
  24. Vorrichtung nach einem der Ansprüche 17 bis 20, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung dem oberen Abschnitt der Fraktioniersäule (12) entspricht.
  25. Vorrichtung nach Anspruch 24, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung in zwei Abteilungen (38, 39) unterteilt ist durch ein im Wesentlichen vertikales Trennelement (37, 37'), das sich von dem Kopfende der Fraktioniersäule (12) aus über einen Teil ihrer Höhe erstreckt.
  26. Vorrichtung nach Anspruch 24, dadurch gekennzeichnet, dass die Zone (40) der unterteilten Fraktionierung in zwei Abteilungen (38, 39) unterteilt ist durch ein im Wesentlichen horizontales Trennelement, das aus einer Platte (37") besteht, die sich über einen horizontalen Abschnitt der Säule (12) erstreckt und mit einem oder mehreren Schloten (50) versehen ist, die den Durchgang der von der Abteilung (39) oberhalb der Platte (37") abgegebenen schweren Ausflüsse nach unten zu der Zone (41) der gemeinsamen Fraktionierung ermöglichen.
  27. Vorrichtung nach einem der Ansprüche 22 oder 25, dadurch gekennzeichnet, dass das Trennelement aus einer vertikalen ebenen Wand besteht.
  28. Vorrichtung nach einem der Ansprüche 22 oder 25, dadurch gekennzeichnet, dass das Trennelement aus einer vertikalen zylindrischen Wand besteht (37'), deren Drehachse parallel zu der Längsachse der Fraktioniersäule (12) ist.
EP01401737A 2000-07-05 2001-06-29 Verfahren und Einrichtung zum Cracken von Kohlenwasserstoffen in zwei aufeinanderfolgenden Reaktionstufen Expired - Lifetime EP1170355B1 (de)

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ATE286107T1 (de) 2005-01-15

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