EP0381870B1 - Procédé de production d'oléfines - Google Patents

Procédé de production d'oléfines Download PDF

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Publication number
EP0381870B1
EP0381870B1 EP89200285A EP89200285A EP0381870B1 EP 0381870 B1 EP0381870 B1 EP 0381870B1 EP 89200285 A EP89200285 A EP 89200285A EP 89200285 A EP89200285 A EP 89200285A EP 0381870 B1 EP0381870 B1 EP 0381870B1
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EP
European Patent Office
Prior art keywords
solids
catalyst
cracking
reactor
process according
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EP89200285A
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German (de)
English (en)
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EP0381870A1 (fr
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Robert J. Gartside
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Stone and Webster Engineering Corp
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Stone and Webster Engineering Corp
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Priority to DE8989200285T priority Critical patent/DE68906529T2/de
Priority to EP89200285A priority patent/EP0381870B1/fr
Priority to EP19920200692 priority patent/EP0490886A3/fr
Priority to AT89200285T priority patent/ATE89308T1/de
Publication of EP0381870A1 publication Critical patent/EP0381870A1/fr
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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
    • 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

Definitions

  • This invention relates to the production of olefins from hydrocarbon feedstocks. More particularly, the invention relates to the production of olefins by catalytically cracking alone or cracking and dehydrogenating a hydrocarbon. Most particularly the invention relates to a process for cracking hydrocarbons in the presence of an entrained stream of catalytic heat carrying solids at short residence times to preferentially produce olefins having three or more carbon atoms It has long been known that naturally occurring hydrocarbons can be cracked at high temperatures to produce valuable olefinic materials, such as ethylene and propylene.
  • the growth in the propylene based plastics market relative to the ethylene based plastics market has made it desirable to improve the propylene yield when cracking hydrocarbons to olefins.
  • C4 olefins are important precursors for providing high octane blending components, i.e., C4's are precursors to MTBE production and alkylation.
  • radical initiation takes place by homolysis of a carbon - carbon bond. Once initiated the free radicals undergo two principal reactions. They are (1) scission at the beta position of the radical and (2) abstraction of a hydrogen, resulting in termination of the reaction.
  • One effort at producing increased production of C3 and higher olefins is directed to subjecting a light hydrocarbon comprising at least one alkane to cracking conditions in the presence of hydrogen sulfide and a solid contact material comprising silica (US-A-4 471 151 (Kolts)).
  • the contact material employed such as silica gel, preferably has a high surface area i.e. at least 50 m2/g. Typical H2S concentrations of 0.1 to 10 mole percent based on the alkane feed are employed in the process. It is theorized in Kolts that the improvement in cracking is due to the high surface area material which acts as a catalyst to decompose H2S. The result is increased conversion levels with improved selectivity to desired products. However, the improved selectivity to propylene was demonstrated only when cracking n-butane.
  • the solid contact material employed in Kolts is suitable only for fixed bed operations and not for fluidized bed environments due to its very low mechanical stability.
  • the solid catalyst of Kolts continues to have the drawbacks of typical catalytic dehydrogenation catalysts designed for fixed beds. These are larger size, diffusion limited catalysts incapable of continuous regeneration in a circulating loop system.
  • a fluidized catalytic cracking (FCC) unit may also be employed to catalytically produce C3 and higher compounds.
  • the FCC unit uses acidic cracking catalysts to increase the production of C3 to C7 compounds through a carbonium ion mechanism compared to the free radical pyrolysis reaction mechanism.
  • the acidic cracking activity of the catalysts in addition to promoting cracking and isomerization, promotes rapid hydrogen transfer resulting in high yields of paraffins rather than olefins.
  • the nature of the catalytic cracking unit itself favors the shift to paraffins.
  • the typical definition of residence time in a catalytic cracking operation is the time the feedstock is in contact with the catalyst itself. This definition is acceptable if the temperatures are low such that thermal reactions do not occur to any appreciable extent. However, thermal and catalytic reactions proceed in parallel. While catalyst separation will terminate the catalytic portion of the reaction, the thermal reactions (pyrolysis) will continue until the temperature is reduced to a level where the rate of reaction is insignificant (quench). In this situation, the total kinetic residence time can be defined as the time from the introduction of the hydrocarbon into the system to the quenching of the effluent including the separation of the solids from the reaction. Total conversion is thus the summation of the catalytic reaction (time in contact with the catalyst) and the thermal reactions (time at the reaction temperature).
  • the typical FCC reaction environment has relatively long residence times including time for solids separation (normally greater than one second) and does not include a quench. Cracking takes place at lower temperatures under these longer residence times. Conversion is achieved at these lower temperatures due to the extended contact with the catalyst. Thermal reactions are minimized at these lower temperatures thus eliminating the need for quenching the effluent. While increased C3 and higher compounds are produced in comparison to pyrolysis, the effluent will have a disproportionately high concentration of paraffins due to the increased hydrogen transfer activity.
  • the favored conditions for olefin production, specifically higher temperatures and shorter residence times, are difficult to achieve especially when processing light feedstocks such as LPG and naphthas which require proportionately higher temperatures to initiate and sustain the reaction (either catalytic or thermal).
  • US-A-2 906 695 discloses a high-temperature, short-time hydrocarbon conversion process in which the hydrocarbon feed is contacted with fluidized particulate solids at a temperature of from 538°C to 649°C in the initial section of a reactor, the resultant reaction mixture is caused to flow rapidly through the reaction zone and receives a strong rotational motion about the axis of the flow, additional highly heated particulate solids being introduced immediately thereafter in the central portion of the fluid mixture so as to heat the mixture to a temperature of from 677°C to 982°C.
  • GB-A-2 048 299 discloses a catalytic cracking process in which hydrocarbons having a boiling point above 220°C are converted into lower boiling hydrocarbon products of improved octane rating with the aid of a particulate crystalline catalyst having pore opening and maximum cage dimensions of 55 nm to 70 nm, an active dehydrogenating metal being disposed within the interior of the crystals.
  • EP-A-0 26 674 discloses an improved sequential Thermal Regenerative Cracking (TRC) process, together with an improved solids quench procedure, an improved preheat vaporization system and an improved fuel gas generation system.
  • TRC sequential Thermal Regenerative Cracking
  • the present invention relates generally to a process for preferentally cracking hydrocarbons to obtain olefins, preferably C3 to C5 olefins, at the acid sites of catalyst solids and catalytically dehydrogenating the resulting paraffin isomers to thereby produce olefins
  • This invention now provides a process for catalytically cracking a hydrocarbon feedstock to selectively produce C3 to C5 olefins, comprising the steps of:
  • Acidic catalytic cracking of hydrocarbons proceeds by a carbonium ion mechanism unlike the free radical mechanism of thermal cracking.
  • the carbonium ion is formed by the abstraction of a hydride ion from the carbon - hydrogen bond.
  • the abstraction of the hydride ion and the creation of a carbonium ion is catalyzed by the acid sites on the catalyst solids.
  • Carbonium ion cracking also occurs at the beta position thereby leading to the formation of an olefin and a primary carbonium ion.
  • the primary carbonium ion undergoes a rapid ionic shift (isomerization) to produce a secondary or tertiary carbonium ion.
  • This coupled with the beta cracking rule leads to the formation of propylene in high yields without the concurrent production of significant amounts of ethylene. Any ethylene found in the product is the result of the competitive free radical cracking route.
  • the acidic sites on the catalyst promote hydrogen transfer.
  • thermodynamic equilibrium conditions at the temperatures contemplated in the invention favor olefins over paraffins
  • the increased hydrogen transfer activity may result in a disproportionately high paraffin yield.
  • branched isomers such as isobutylene.
  • the yield distribution can be shifted toward the thermodynamic equilibrium and higher concentrations of the desired olefins can be obtained.
  • the kinetic residence time is defined as the total time from the point where the hydrocarbon is introduced to the reactor zone to the point where the cracked products are quenched, including the intermediate separation step. This distinguishes the present process from other processes where measurement of the residence time is terminated prior to the point of separation and quench. This is especially important since the catalytic cracking of hydrocarbons always proceeds in parallel with pyrolysis.
  • the extent to which products are formed catalytically or thermally is a function of catalyst activity, catalyst loading, catalyst residence time, reaction temperature profile, and the total kinetic residence time in the thermal-catalytic environment.
  • mild acidic catalytic activity at higher temperatures could be used to shift diolefin production to paraffins and olefins without substantially altering the ratio of the carbon products obtained by pyrolysis.
  • very highly active acidic cracking catalysts could be used at significantly lower temperatures to minimize the thermal route and maximize the acidic catalyst product distribution.
  • catalytic dehydrogenation catalysts can be used in combination with the acidic cracking catalysts to shift the reaction in favor of olefin production.
  • the present invention is particularly well suited for cracking hydrocarbon feedstocks such as C4-C7 paraffins, naphthas, and light gas oils to higher order olefins, i.e., having three to five carbon atoms.
  • hydrocarbon feedstocks such as C4-C7 paraffins, naphthas, and light gas oils
  • higher order olefins i.e., having three to five carbon atoms.
  • the process has general applications for cracking the entire range of hydrocarbons from light distillates to heavy resids.
  • the process of the present invention proceeds by delivering a preheated hydrocarbon feedstock and steam to the top of a downflow tubular reactor. Simultaneously, hot catalyst solids are introduced to the top of the reactor and the combined stream of hydrocarbon, steam and catalyst solids pass through the reactor zone, a separation zone, and a quench zone where the hydrocarbon undergoes cracking at low severity and short residence times and the effluent is stabilized to prevent product degradation.
  • the tubular reactor is operated at a temperature of 482°C to 816°C (900°F to 1500°F), preferably 538°C to 704°C (1000°F to 1300°F) and at a pressure of 0,69 bar to 6,9 bar (10 to 100 psia) with a total kinetic residence time of about 0.05 to 2.0 s, preferably about 0.10 to 0.5 s.
  • the catalyst solids are stripped of residual hydrocarbon, regenerated and reheated in a transfer line and returned to the tubular reactor to continue the cracking process.
  • the present invention is particularly well adapted foruse in a short residence time fluidized solids cracking apparatus and in a short residence time separation apparatus, as described in US-A-4 370 303 (Woebcke et al), US-A-4 433 984 (Gartside et al).
  • the specific catalyst solids and the catalyst to hydrocarbon ratio are chosen based on the feedstock characteristics and the product distribution desired.
  • Catalyst activity and catalyst loading will define operating temperatures at the short residence times employed in the present invention and thus determine the split between the catalytic and thermal reactions.
  • the catalyst type either acidic cracking alone or in combination with noble metal oxide dehydrogenation, will further determine the product distribution between olefins and paraffins.
  • the process of the present invention is directed to a means for cracking hydrocarbon feedstocks in the presence of catalytically active heat carrying solids for the purpose of producing olefins with a high selectivity towards C3 to C5 olefins.
  • hydrocarbons contemplated as feedstocks include the high boiling distillate gas oils, atmospheric gas oils, naphthas, and C4-C7 paraffins.
  • the process has general applications for catalytically cracking a wide range of hydrocarbons to produce the desired olefins.
  • the process of the present invention can be performed in a short residence time fluidized solids cracking system 1, hereinafter QC system, incorporating a tubular reactor 2, a reactor feeder 4, a separator 6, a quench means 24 and a solids stripper 8.
  • the system 1 also includes means for regenerating the catalyst solids separated from the cracked product after the reaction.
  • the system shown illustratively includes an entrained bed heater 10 wherein the catalyst solids can be regenerated and reheated, a transport line 12 and a fluid bed vessel 14 wherein the solids are stripped of combustion gases and again distributed to the reactor 2.
  • hot catalyst solids from the fluid bed vessel 14 enter the reactor feeder 4 and are admixed with steam entering through a line 16.
  • the hydrocarbon feed is delivered through a line 18 to a preheater 20, then through a line 22 to the upper region of the tubular reactor 2.
  • the preheated hydrocarbon feed along with the catalyst solids and steam from the reactor feeder 4 are passed through the tubular reactor 2. Intimate mixing of the hot catalyst solids, steam and preheated hydrocarbon occurs in the reactor and cracking proceeds immediately.
  • the cracked hydrocarbon effluent and steam are immediately separated from the catalyst solids in the separator 6 and the cracked effluent product passes overhead through the quench area 24 where the cracked product is immediately quenched with steam or a light hydrocarbon delivered to the quench area 24 through a quench line 26.
  • the cracked product exiting the tubular reactor 2 and separated from the catalyst solids in the separator 6 may be quenched by passing the entire mixture over a bed of solids with catalytic (dehydrogenation) activity. Since dehydrogenation is an endothermic reaction, the flowing mixture will be cooled as the reaction proceeds. This can be used with the introduction of steam to improve the reaction conditions.
  • the preferred method of quenching in this manner includes the use of a catalyst reactor 25, in which the bed of the catalytic solids are contained, located immediately downstream of the separator 6, where quenching occurs in the previous embodiment.
  • the quenched product is passed through a cyclone 28 where small amounts of entrained catalyst solids are removed and delivered through a line 30 to the solids stripper 8 where they are combined with the bulk of the stripped solids delivered from the separator 6 through a line 32.
  • the catalyst solids are striped of residual hydrocarbon by steam, nitrogen or other inert gases delivered to the solids stripper 8 through a line 34.
  • the catalyst solids, which have accumulated carbon or coke deposits from the tubular reactor 2 are then passed to the entrained bed heater 10.
  • Air delivered to the heater 10 through a line 36 is mixed with the stripped catalyst solids in the heater 10 and the mixture is fed into the transport line 12 for conveying the catalyst solids back to the fluid bed vessel 14.
  • the carbon deposits on the catalyst solids are removed by combustion to provide the heat necessary for the cracking reaction. If additional fuel is required it may be added into the entrained heater 10 from a fuel source (not shown).
  • the process of the present invention is conducted by delivering a hydrocarbon such as naphtha, atmospheric gas oil or mixtures thereof, through the line 13 to the preheater 20 wherein the temperature of the hydrocarbon is elevated to 427°C to 482°C (800-900°F).
  • catalyst solids from the fluid bed vessel 14 are delivered to the reactor feeder 4 (best seen in FIGURE 2) where they are admixed with steam supplied through the line 16 and delivered to the reactor at a temperature in the range of 1000-1600°F.
  • the catalyst solids to the hydrocarbon feed ratio ranges from 1 to 60:1 based on weight depending on the particular catalyst utilized.
  • the water vapor/hydrocarbon feed ratio is in the range of 0 to 1.0, preferably 0.0 to 0.3.
  • the catalytic cracking process may be initiated by injecting an alkane such as ethane into the tubular reactor 2, via injection line 16, to form olefins and free radicals.
  • an alkane such as ethane
  • injection line 16 to form olefins and free radicals.
  • alkanes are added just upstream of the hydrocarbon feed 22.
  • a suitable catalyst solids for the present invention may be one of the generally available supports having acid properties such as, silica gel, alumina, clays, etc.
  • the catalyst system employed is a conventional zeolitic FCC catalyst or one of the high activity ZSM-5 or rare earth zeolitic catalysts, including a dehydrogenation catalyst consisting of one of the noble metal oxides such as the oxides of iron, chromium, platinum, etc. on a suitable support such as silica alumina.
  • the catalyst could be a mixture of the aforementioned catalysts to achieve specific yield distributions.
  • the composite hydrocarbon feedstock is elevated to 427°C to 593°C (800 to 1100°F). and the catalyst solids are heated to 649°C to 927°C (1200 to 1700°F) in the tubular reactor 2.
  • the ratio of solids to hydrocarbon is set by heat balance and desired solids catalytic activity.
  • the cracked effluent product and catalyst solid effluent from the tubular reactor 2 flow directly into separator 6 (best seen in FIGURE 3) where a separation into a gas product phase and a catalyst solid phase is effected.
  • the gas product is removed via the line 24, while the catalyst solids enter the solids stripper 8 through the line 32.
  • An in-line quench of the gas product is provided in quench area 24 through the quench line 26.
  • Cold solids, water, steam, light hydrocarbons, and recycle oils are examples of suitable quench materials.
  • quenching takes place in the catalyst reactor 25 (see FIGURE 5) by passing the product over a catalyst bed, the additional reaction being without the presence of solids.
  • the total residence time from the point of hydrocarbon introduction to the tubular reactor 2 to the point of quench in the quench area 24, optionally comprising a catalyst reactor 25, is preferably about 0.1 to 0.3 seconds.
  • the catalyst solids are stripped of gas impurities by a stream of steam, nitrogen or inert gas delivered through the line 34. Vapors are removed from the solids stripper 8 through the line 30.
  • the stripped catalyst solids are removed from the stripper 8 through a line 38.
  • the catalyst solids which have accumulated carbon from the tubular reactor 2 are passed to the entrained bed heater 10 where air is delivered through a line 36 to provide the necessary atmosphere for regenerating the catalyst solids.
  • the catalyst solids are entrained in the heater 10 and returned to the fluid bed vessel 14 through the transport line 12 where the catalyst solids continue to regenerate.
  • the regeneration of the catalyst solids raises the temperature of the catalyst solids to 649°C to 927°C (1200 to 1700°F) prior to delivery of the catalyst to the fluid bed vessel 14.
  • the reactor feeder 4 has the capability of rapidly admixing hydrocarbon feed and catalyst solids.
  • the reactor feeder 4 delivers catalyst solids from a solids receptacle or fluid bed vessel 70 through vertically disposed conduits 72 to the tubular reactor 2 and simultaneously delivers hydrocarbon feed to the tubular reactor 2 at an angle into the path of the catalyst solids being discharged from the conduits 72.
  • An annular chamber 74 to which hydrocarbon is fed by a single entry comprising a toroidal feed line 76 terminates in angled openings 78.
  • a mixing baffle or plug 80 also assists in effecting rapid and intimate mixing of the hydrocarbon feed and the catalyst solids.
  • the edges 79 of the angled openings 78 are preferably convergently beveled, as are the edges 79 at the reactor end of the conduits 72.
  • the gaseous hydrocarbon stream from the chamber 74 is angularly injected into the mixing zone and intercepts the catalyst solids phase flowing from the conduits 72.
  • a projection of the gas would form a cone shown by dotted lines 77, the vortex of which is beneath the flow path of the solids.
  • the mixing of a solid phase with a gaseous phase is a function of the shear surface between the solids and gas phases, and the flow area.
  • a ratio of shear surface to flow area (S/A) of infinity defines perfect mixing while poorest mixing occurs when the solids are introduced at the wall of the reaction zone.
  • the gas stream is introduced annularly to the solids which ensures high shear surface.
  • penetration of the phases is obtained and even faster mixing results.
  • Mixing is also a known function of the length to diameter ratio of the mixing zone. A plug creates an effectively reduced diameter D in a constant length L, thus increasing mixing.
  • the plug 80 reduces the flow area and forms discrete mixing zones.
  • the combination of annular gas addition around each solids feed point and a confined discrete mixing zone greatly enhances the conditions for mixing.
  • the time required to obtain an essentially homogenous reaction phase in the reaction zone is quite short.
  • this preferred method of gas and solids addition can be used in reaction systems having a residence time below 1 second, and even below 100 milliseconds. Because of the environment of the tubular reactor 2 and the reactor feeder 4, the walls are lined with an inner core 81 of ceramic material.
  • the separator 6 of the QC system can also be relied on for rapid and discrete separation of product and catalyst solids discharging from the tubular reactor 2.
  • the inlet to the separator 6 is directly above a right angle corner 90 at which a mass of catalyst solids 92 collect within a chamber 93.
  • An optional weir 94 downstream from the right angle corner 90 facilitates accumulation of the mass of solids 92 especially when run on small scale rather than commercial scale production.
  • the gas outlet 24 of the separator 6 is oriented 180° from a separator gas-solids inlet 96 and the solids outlet line 32 is directly opposed in orientation to the gas outlet 24 and downstream of both the gas outlet line 24 and the weir 94.
  • centrifugal force propels the catalyst solids to the wall opposite inlet 96 of the chamber 93 while the gas portion having less momentum, flows through the vapor space of the chamber 93.
  • catalyst solids impinge on the wall opposite the inlet 96 but subsequently accumulate to form a static bed of solids 92 which ultimately form in a surface configuration having a curvilinear arc of approximately 90° of a circle.
  • Solids impinging upon the bed 92 are moved along the curvilinear arc to the solids outlet 95, which is preferably oriented for downflow of solids by gravity.
  • the exact shape of the arc is determined by the geometry of the particular separator and the inlet stream parameters such as velocity, mass flowrate, bulk density, and particle size.
  • separator efficiency defined as the removal of solids from the gas phase leaving through the outlet 97, is therefore, not affected adversely by high inlet velocities, up to 45,75 m/s (150 ft./sec.), and the separator 6 is operable over a wide range of dilute phase densitites, preferably between 0,016 to 0,16 g/cm3 (0.1 and 10.0 lbs./ft.3)
  • the separator 6 of the present invention achieves efficiencies of about 90%, although the preferred embodiment, can obtain over 97% removal of catalyst solids.
  • the efficiency of the separator 6 increases as the flow path decreases and, hence, residence time decreases.
  • the distance CL between the centerlines of the inlet 96 and the outlet 97 is preferably not greater than 4.0(D i ), while the most preferred distance between said centerlines is between 1.5 and 2.5(D i ). Below 1.5(D i ) better separation is obtained but difficulty in fabrication makes this embodiment less attractive in most instances. Should this latter embodiment be desired, the separator 6 may require a unitary casting design because the inlet 96 and the outlet 97 would be too close to one another to allow welded fabrication.
  • the height H should be at least equal to the value of 1.5 x D i or 10,16 cm (4 inches) in height, whichever is greater. Practice teaches that if H is less than D i or 10,16 cm (4 inches) the incoming stream is apt to disturb the bed solids 92 thereby reentraining solids in the gas product leaving through the outlet 97. Preferably the height H is on the order of twice D i to obtain even greater separation efficiency. While not otherwise limited, it is apparent that too large a height H eventually merely increases residence time without substantive increases in efficiency.
  • the width W shown in FIGURE 4 of the flow path is preferably between 0.75 and 1.25 times D i , most preferably between 0.9 and 1.10 (D i ).
  • the outlet 97 may be of any inside diameter (Dog). However, velocities greater than 23 m/s (75 ft./sec). can cause erosion because of residual solids entrained in the gas.
  • the inside diameter Dog of the outlet 97 should be sized so that a pressure differential between the solids stripper 8 shown in FIGURE 1 and the separator 6 exists such that a static height of solids is formed in the solids outlet line 32.
  • the static height of solids in the solids outlet line 32 forms a positive seal which prevents gases from entering the solids stripper 8.
  • the magnitude of the pressure differential between the solids stripper 8 and the separator 6 is determined by the force required to move the solids in bulk flow to the solids outlet 95 as well as the height of solids in the line 32.
  • the inside diameter Dog of the gas outlet 97 is the same as the inside diameter of the inlet 96, when one outlet is employed, to provide outlet velocity less than or equal to inlet velocity.
  • FIGURE 4 shows a cutaway view of the separator 6 along section 4-4 of FIGURE 3. It is essential that longitudinal side walls 101 and 102 be rectilinear, or slightly arcuate as indicated by the dotted lines 101a and 102a. Thus, the flow path through the separator 6 is essentially rectangular in cross-section having a height H and width W as shown in FIGURE 4.
  • the embodiment shown in FIGURE 4 defines the geometry of the flow path by adjustment of the lining width for the walls 101 and 102.
  • baffles, inserts, weirs or other means may be used.
  • the configuration of the walls 103 and 104 transverse to the flow path may be similarly shared, although this is not essential.
  • the separator shell and manways are preferably lined with erosion resistant linings 105, which may be required if solids at high velocities are encountered.
  • erosion resistant linings include Carborundum Precast Carbofrax D (Reg. Trade Mark), Carborundum Precast Alfrax 201 (Reg. Trade Mark) or their equivalent.
  • a thermal insulation lining 106 may be placed between the shell and the lining 105 and between the manways and their respective erosion resistant linings when the separator 6 is to be used in high temperatures service.
  • a system 202 comprising a reactor system 204, a solids regeneration assembly 208 and a solids delivery system 210.
  • the reactor system 204 includes a convergent mixing section 211, an elongated reaction section 212, a divergent section 213 downstream of the elongated reaction section 212, a separator 206 and a quench system 207 (shown in FIGURE 8).
  • the mixing sections 211 are formed with a plug section 214 shown in cross-section as having an arcuate lower surface 215.
  • a horizontally disposed plate 217 is arranged over the plug section 214 in spaced-relationship with the plug section 214 to form solids inlet passages 219 to the interior of the mixing section 211.
  • the solids inlet passages 219 are configured in cross-section with a right angle turn and terminate in a reactangular openings 225 through which the particulate solids enter the mixing section 211, in the form a curtain of solids 226.
  • the horizontal openings 225 are directly above each hydrocarbon feed inlet.
  • Venturi configured passages 203 extend from the solids inlet passages 219 to the hydrocabon feed inlets 228.
  • Steam plenums are arranged along each longitudinal edge of the horizontal opening 225 to deliver pre-acceleration gas (steam) through nozzles (not shown) into the curtain of solids 226 passing through the horizontal openings 225.
  • a gas delivery line (not shown) is provided to deliver gas, usually steam or light hydrocarbon, under pressure to the nozzles.
  • the nozzles are arranged at a downward angle of 45° to the horizontal.
  • the pre-acceleration gas is delivered to the plenums at pressures of 3 to 5 psi above the pressure in the reactor and discharges through the nozzles at the same relative pressure at a velocity of about 150 feet per second.
  • the pre-acceleration gas accelerates the flow of solids through the horizontal openings 225 from a nominal three to six feet per second to approximately 50 feet per second for the mix of solids and pre-acceleration gas.
  • the hydrocarbon feed inlets 228 are located on the reactor wall arranged either normal to the solids curtain 226 or at an angle upwardly of 30° into the solids curtain 226.
  • the hydrocarbon feed is delivered to a manifold 223 through a line 224.
  • the feed inlet nozzles 228 are fed with hydrocarbon from the manifold 223. As seen in FIGURE 7, the feed inlet nozzles 228 are diametrically opposed from each other in the same horizontal plane.
  • the mixing zone 211 of the reactor is rectangular with the configuration making a transition to a tubular reactor at the elongated reaction section 212.
  • the feedstock entering the mixing zone 211 through nozzles 228 immediately impinge the solids curtains 226 and the desired mixing of feed and hot particulate solids occurs.
  • the opposing feed jets and entrained solids from the solids curtain 226 will be directed by the arcuate contour 215 of the plug section 214 and impact with each other at approximately the vertical centerline of the mixing zone 211.
  • the nozzles 228 are arranged at an angle normal or 90° to the solids curtain 226.
  • the hydrocarbon feed is a gas
  • the nozzles 228 are arranged at an upwardly directed angle of 30° into the solids curtain.
  • the quantity of solids entering the mixing zone 211 of the reactor system 204 through the horizontal inlets 219 is controlled in large part by the pressure differential between the mixing zone 211 of the reactor system 204 and the chamber 231a above the solids reservoir 218 in a solids control hopper 231 directly above the horizontal inlets 219.
  • Pressure probes 233 and 235 are located respectively in the mixing zone 211 of the reactor system 204 and the control hopper chamber 231a to measure the pressure differential.
  • Gas (steam) under pressure is delivered through a line 230 to the control hopper chamber 231a to regulate the pressure differential between the mixing zone 211 of the reactor system 204 and the control hopper chamber 231a to promote or interrupt flow of the solids from the solids control hopper 231 to the mixing zone 211.
  • the separator 206 is comprised of a mixed phase inlet 232, a horizontal chamber section 234, a plurality of cracked gas outlets 236 and particulate solids outlets 238.
  • the basic principles relating to relative diameters (Di, Dog, Dos), chamber height (H) and length (L) recited in the first embodiment described herein are applicable herein.
  • the separator 206 is arranged in combination with the elongated cracking zone 212 and divergent section 213 of the reactor system 204.
  • the divergent section 213 terminates in the separator mixed phase inlet 232 which is centrally disposed at the top of the horizontal section 234.
  • a solids bed 242 develops on the floor 240 of the horizontal section 234 with the cross-sectional profile 243 of the bed 242 forming a curvilinear arc over which the mixed phase gas and solids travel.
  • the expansion of solids and cracked gas in the divergent section 213 enhances heat transfer and limits the velocity of the solids-gas mixture entering the separator 206.
  • the solids are sent to the lateral ends 246 of the horizontal section 234 and discharge downwardly through the solids outlets 238.
  • the cracked gases follow a 180° path and after separation from the solids discharge through gas outlets 236 that are located on the top of the horizontal section 234 intermediate the lateral ends 246.
  • the plurality of solids outlets 238 and gas outlets 236 provide simultaneously for both minimum time in the separation zone and maximum solids-gas separation.
  • the separation or quench system 207 also includes a conventional cyclone separator 250 directly downstream of each gas outlet 236, as best seen in FIGURE 8.
  • the entry line 254 to each cyclone separator 250 is arranged at an angle of 90° to the gas outlet 236 with the cyclone separator 250 vertically disposed in the system.
  • the cyclone separators 250 serve to collect the remaining entrained particulate solids from the cracked gas discharged from the separator 206.
  • a dipleg line 249 returns the particulate solids to the regeneration assembly 208 and the cracked gas is sent for downstream processing through the gas outlet 251.
  • Each cyclone entry line 254 extending from the cracked gas outlet 236 to the cyclone 250 is provided with a direct quench line 252.
  • Quench oil usually the 38°C-204°C (100-400°F) cut from a downstream distillation tower is introduced into the cyclone 250 through the direct quench line 252 to terminate the reactions of the cracked gas.
  • the regeneration assembly 208 is comprised of a stripper 253, control hopper 255, entrained bed heater 258, a lift line 257, and a rengerated solids vessel 260.
  • the stripper 253 is a tubular vessel into which the particulate solids from the separator 206 are delivered through solids outlet legs extending from the separator solids outlets 238 and from the cyclone diplegs 249.
  • a ring 262 having nozzle openings 264 is provided at the bottom of the stripper 253.
  • a stripping gas, typically steam is delivered to the ring 262 for discharge through the nozzles 264.
  • the stripping steam passes upwardly through the bed of particulate solids to remove impurities from the surface of the particulate solids.
  • the stripping steam and entrained impurities pass upwardly through the particulate solids in the stripper 253 and discharge through a vent line (not shown) to the cracked gas line.
  • the stripped solids are accumulated in the control hopper 255 for eventual delivery to the entrained bed heater 258.
  • the control hopper 255 is a collection vessel in which solids enter through a standpipe 266 and from which an outlet line 273 extends to deliver solids to the entrained bed heater 258.
  • the assembly of the control hopper 255 and the standpipe 266 provides for a slumped bed solids transport system.
  • the pressure differential maintained between the slumped bed surface 268 in the control hopper 255 and the exit 270 of the outlet line 273 determine the solids flow rate between the control hopper 255 and the entrained bed heater 258.
  • a line 272 is provided to selectively introduce steam under pressure into the control hopper 255 to regulate the pressure differential.
  • Probes 267 and 269 are placed respectively in the control hopper 255 and entrained bed heater 258 to monitor the pressure differential and regulate a valve 265 in the steam line 272.
  • the entrained bed heater 258 is essentially tubular in configuration.
  • An array of distinct fuel nozzles 261 fed by fuel lines 263 are arranged essentially symmetrically on the lower inclined surface 275 of the entrained bed heater 258.
  • Pressurized air enters the entrained bed heater 258 through a nozzle 277 arranged to direct the air axially upwardly through the entrained bed heater 258.
  • the air jet provides both the motive force to lift the solids particles upwardly through the entrained bed heater 258 to the rengerated solids vessel 260 and the air necessary for combustion.
  • the fuel is ignited by contact with the solids in the presence of air.
  • the combustion gas/solids mixture moving upwardly through lift line 257 enters the regenerated solids vessel 260 tangentially, preferably, perpendicular to the lift line to separate the combustion gases from the solids.
  • the vessel 260 has a distube 285 in the gas outlet nozzle 286 to provide cyclonic movement which improves the separation efficiency of the system.
  • the regenerated solids vessel 260 is a cylindrical vessel provided with a standpipe 271, seen in FIGURE 7, extending to the reactor hopper 231. Again the structure of the regenerated solids vessel 260 provides for accumulation of a slumped bed 281, seen in FIGURE 9 above which pressure can be regulated to enable controlled delivery of the regenerated particulate solids to the reactor hopper 231.
  • the upper solids collection vessel 260 seen in FIGURES 6, 7 and 9 contains a stripping section as the lower portion with a stripping ring 279 and form a part of the solids deliver system 210.
  • the solids Above ring 279, the solids are fluidized; below the ring 279 the solids slump and are fed to the standpipe 271 shown in FIGURE 7.
  • the standpipe 271 feeds the slumped bed in the control hopper 231 as best seen in FIGURE 7. Solids flow into the reactor hopper 231 through the standpipe 271 to replace solids that have flowed into the reactor 204. Unaerated solids (slumped solids) will not continue to flow into the reactor hopper 231 once the entrance 282 to the hopper 231 has been covered.
  • the position of the entrance 282 defines the solids level in hopper 231.
  • the entrance 282 is uncovered allowing additional solids to flow into the hopper 231.
  • FIGURE 1 One embodiment of the process of the present invention as shown in the accompanying FIGURE 1 is illustrated by the following comparative example (Table I) wherein a light FCC naphtha is cracked employing conventional tubular pyrolysis, conventional catalytic cracking at typical FCC residence times of greater than 1 second using moderately active catalysts, catalytic cracking with high activity catalysts at short residence times for FCC units (0.9 seconds), and very short residence time cracking plus quench (QC system) with a similar high activity catalyst. Two cases employing the high activity catalyst are shown to illustrate the effect of residence time on olefin yields.
  • Table I comparative example
  • Example A illustrates the yields obtainable using conventional pyrolysis operated at typical thermal cracking temperatures and residence times.
  • Example B illustrates a conventional catalytic riser reactor employing typically longer residence times and lower temperatures than the pyrolysis Example A.
  • the conventional catalytic conversions are substantially lower than those obtained in the pyrolysis Example A.
  • the lower conversion is a result of the lower temperature operation (565°C vs. 816°C) with insufficient catalytic activity for this relatively light feedstock.
  • the total C3 and C4 compounds are high relative to the pyrolysis case as a result of the carbonium ion mechanism.
  • the ratio of C3 paraffins to C3 olefins is substantially increased due to hydrogen transfer activity of the acidic cracking catalyst.
  • Example C illustrates the product yields which will be obtained by employing high activity acidic catalysts at low FCC residence times or high QC residence times without quenching.
  • the selected operating conditions of Example C will result in a suppression of the methane and ethylene yields compared to the pyrolysis system of Example A.
  • the conversion is increased relative to Example B even at lower temperatures (510°C vs. 565°C) due to the increased activity.
  • due to the longer residence times there is a significant amount of hydrogen transfer as evidenced by the unacceptably high C3 paraffin to olefin ratio compared to either Example A or B.
  • Example D illustrates the dramatic improvement in olefin yields that will be obtained by employing the process of the present invention in a very short residence time QC system.
  • the reactor temperature is increased about 30°C and the total kinetic residence time, i.e., cracking reaction plus separation plus quench, is reduced to about 0.15 seconds.
  • the paraffins to olefin ratio is reduced to less than half that obtained in the longer residence time Example C.
  • the paraffin to olefin ratio for this case is higher than for the pyrolysis case at a similar residence time as a result of the hydrogen transfer activity of the catalyst.
  • the methane yield is further suppressed below the lower level of Example C and the C4 yields are improved by almost 100% indicating less secondary cracking due to the quenching and short residence time reaction.
  • a dehydrogenation catalyst is combined with an acidic cracking catalyst.
  • Table II uses a Minas naphtha feedstock and compares cracking both catalytically and thermally.
  • the catalytic case requires a lower temperature to achieve the given conversion thus will have in this case only 75% of the thermal products (C1 and C2 compounds).
  • the carbonium ion cracking will shift the yield spectrum to favor C3 and C4 compounds.
  • the isobutylene production from the same feed is increased by a factor of over 3 and the normal butene by a factor of over 2.
  • the use of mixed catalyst systems provides an additional product distribution flexibility for the catalytic process. Rather than admix the dehydrogenation catalyst with the acidic cracking catalyst and follow the mix reaction with a quench, using steam for example, the dehydrogenation catalyst can be located in a packed bed within a catalyst reactor 25 located downstream of the primary separation in separator 6. The paraffins formed by contact with the acidic catalyst will be dehydrogenated to their olefin counterpart.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Claims (11)

  1. Procédé de craquage catalytique d'une charge d'hydrocarbures, pour la production sélective d'oléfines en C₃ à C₅, comprenant les étapes consistant à :
    (a) introduire la charge d'hydrocarbures dans un réacteur de craquage,
    (b) introduire simultanément des produits solides chauds, constitués de catalyseur de craquage acide, à activité très élevée, dans le réacteur de craquage,
    (c) effectuer le craquage catalytique et thermique de la charge d'hydrocarbures, grâce à la chaleur fournie par les produits solides chauds, constitués de catalyseur acide à activité très élevée, pour former un produit craqué,
    (d) séparer le produit craqué des produits solides chauds, constitués de catalyseur, et
    (e) tremper le produit craqué séparé,
    caractérisé en ce que le temps de séjour cinétique total de la charge d'hydrocarbures, depuis l'étape (a) jusqu'à l'étape (e), est de 0,05 s à 2,0 s, la température de la réaction de craquage est de 482°C à 815°C, la pression du réacteur de craquage est de 0,69 bar à 6,9 bars (10 psi à 100 psi), le rapport en poids des produits solides constitués de catalyseur à la charge d'hydrocarbures est de 1:1 à 60:1, et le catalyseur de craquage acide, à activité très élevée, est un catalyseur zéolithique, associé à un catalyseur de déshydrogénation, constitué d'un oxyde métallique choisi parmi les oxydes de fer, de chrome, d'étain et de platine, fixé sur un support inerte.
  2. Procédé selon la revendication 1, dans lequel le temps de séjour est de 0,05 s à 0,5 s.
  3. Procédé selon la revendication 1, comprenant en outre les étapes consistant à :
    (f) introduire les produits solides constitués de catalyseur, séparés, dans un purificateur, pour éliminer les produits gazeux craqués résiduels,
    (g) effectuer la combustion des produits solides constitués de catalyseur, séparés, pour éliminer des dépôts de carbone et chauffer les produits solides constitués de catalyseur, purifiés, afin de former des produits solides constitués de catalyseur, régénérés, et
    (h) amener les produits solides constitués de catalyseur, régénérés, au réacteur de craquage.
  4. Procédé selon la revendication 1, dans lequel la température de la réaction de craquage catalytique est de 537°C (1000°F) à 704,4°C (1300°F) et le temps de séjour est de 0,1 s à 0,3 s.
  5. Procédé selon la revendication 1, dans lequel la charge d'hydrocarbures est choisie parmi les paraffines en C₄ à C₇, les naphtas et les gazoles légers.
  6. Procédé selon la revendication 1, dans lequel le catalyseur acide à activité très élevée est un support de catalyseur, choisi parmi le gel de silice, l'alumine et l'argile.
  7. Procédé selon la revendication 1, dans lequel le catalyseur acide à activité très élevée est un catalyseur choisi parmi les catalyseurs de craquage catalytique, fluidisés, zéolithiques, la zéolithe ZSM-5 à activité élevée et les zéolithes de terres rares.
  8. Procédé selon la revendication 1, dans lequel le support pour le catalyseur de déshydrogénation est choisi parmi le gel de silice, les mélanges silice-alumine, les argiles et les mélanges de n'importe lesquels des composés précédents.
  9. Procédé selon la revendication 1, dans lequel le courant de charge d'hydrocarbures et les produits solides chauds, constitués de catalyseur, sont introduits dans un réacteur de craquage thermique régénérateur, tubulaire, par l'intermédiaire d'un dispositif d'alimentation de réacteur, présentant des passages verticaux communiquant avec le réacteur de craquage régénérateur, tubulaire, et avec les produits solides contenus dans un récipient à produits solides chauds, une fluidisation localisée des produits solides est assurée au-dessus des passages verticaux, et la charge d'hydrocarbures pénètre dans le réacteur thermique régénérateur, tubulaire, en faisant un angle avec le trajet des produits solides, constitués de catalyseur, entrant dans le réacteur thermique régénérateur, tubulaire.
  10. Procédé selon la revendication 1, dans lequel les produits solides chauds, constitués de catalyseur, et les produits gazeux craqués à séparer, entrent dans un séparateur par une entrée de séparateur, subissent un changement de direction de 90°, après lequel les produits gazeux subissent un autre changement de direction de 90° pour effectuer un changement de direction de 180° par rapport à la direction d'entrée, les produits solides, constitués de catalyseur, poursuivant leur route dans la direction faisant un angle de 90° avec l'entrée du séparateur et le trajet des produits solides, constitués de catalyseur, étant finalement dirigé vers le bas, et les produits gazeux séparés sont trempés.
  11. Procédé selon la revendication 1, dans lequel les produits solides, constitués de catalyseur, et les gaz craqués sont séparés dans un séparateur comprenant une chambre permettant d'ôter rapidement 80 % des produits solides, constitués de catalyseur, du courant entrant, constitué d'une phase mixte, ladite chambre ayant des parois latérales longitudinales pratiquement rectilignes, formant un chemin d'écoulement de hauteur H et de largeur W, et une entrée de phase mixte, de largeur intérieure Di, une sortie de gaz et une sortie de produits solides, ladite entrée étant à une extrémité de la chambre et étant disposée perpendiculairement au chemin d'écoulement de hauteur H qui est égale à au moins Di ou à 10,2 cm (4 pouces), selon celle de ces valeurs qui est la plus grande, la largeur W étant de 0,75 Di à 1,25 Di, ladite sortie de produits solides étant à l'extrémité opposée de la chambre et disposée de façon à permettre un écoulement vers le bas, par gravité, des produits solides évacués, ladite sortie de gaz étant située entre les deux, à une distance de l'entrée ne dépassant pas 4 Di, ladite distance étant mesurée entre les axes respectifs, et étant orientée de façon à réaliser un changement de 180° de la direction du gaz, ce qui fait que les forces centrifuges résultantes dirigent les produits solides, constitués de catalyseur, présents dans le courant entrant, vers une paroi de la chambre, opposée à l'entrée, où ils forment et maintiennent un lit, pratiquement statique, de produits solides, la surface du lit définissant un chemin curviligne correspondant à un arc de cercle de 90°, pour l'écoulement des produits solides vers la sortie de produits solides.
EP89200285A 1989-02-08 1989-02-08 Procédé de production d'oléfines Expired - Lifetime EP0381870B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE8989200285T DE68906529T2 (de) 1989-02-08 1989-02-08 Verfahren zur herstellung von olefinen.
EP89200285A EP0381870B1 (fr) 1989-02-08 1989-02-08 Procédé de production d'oléfines
EP19920200692 EP0490886A3 (fr) 1989-02-08 1989-02-08 Procédé de production sélective d'éthylène et d'aromatiques par craquage catalytique
AT89200285T ATE89308T1 (de) 1989-02-08 1989-02-08 Verfahren zur herstellung von olefinen.

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EP89200285A EP0381870B1 (fr) 1989-02-08 1989-02-08 Procédé de production d'oléfines

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* Cited by examiner, † Cited by third party
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US7122493B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122495B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122494B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122492B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7125817B2 (en) 2003-02-20 2006-10-24 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0381870B1 (fr) 1989-02-08 1993-05-12 Stone & Webster Engineering Corporation Procédé de production d'oléfines
US4980051A (en) * 1989-11-21 1990-12-25 Mobil Oil Corporation Process and apparatus for preheating heavy feed to a catalytic cracking unit
CA2017116C (fr) * 1990-03-26 1996-11-12 James Francis Mosby Craquage catalytique avec capacite de refroidissement
US5626741A (en) * 1990-03-26 1997-05-06 Amoco Corporation Catalytic cracking with quenching
US5391289A (en) * 1990-09-04 1995-02-21 Chevron Research And Technology Company FCC process with rapid separation of products
US5254788A (en) * 1991-09-10 1993-10-19 Stone And Webster Engineering Corporation Process for the production of olefins from light paraffins
US5846402A (en) * 1997-05-14 1998-12-08 Indian Oil Corporation, Ltd. Process for catalytic cracking of petroleum based feed stocks
EP0909804B1 (fr) * 1997-10-15 2010-09-08 China Petro-Chemical Corporation Procédé de production d'éthylène et de propylène par pyrolyse catalytique d'hydrocarbures lourds
CN1056595C (zh) 1997-10-20 2000-09-20 中国石油化工总公司 多种进料烃类直接转化制烯烃方法
EP1734098A4 (fr) * 2004-03-08 2012-04-04 China Petroleum & Chemical Processus de production d'olefines inferieures et d'elements aromatiques
BRPI0803718A2 (pt) * 2008-08-29 2010-06-15 Petroleo Brasileiro Sa método para produção de olefinas leves em unidades de craqueamento catalìtico com deficiência energética
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
US9284495B2 (en) 2009-03-20 2016-03-15 Uop Llc Maintaining catalyst activity for converting a hydrocarbon feed
CN111065714A (zh) * 2017-08-28 2020-04-24 沙特阿拉伯石油公司 用于催化烃裂化的化学回环工艺
CN108300507B (zh) * 2018-04-17 2023-11-21 中国石油大学(华东) 基于低分子烃活化强化的重油下行床固体热载体毫秒热解装置
EP3623043A1 (fr) 2018-09-13 2020-03-18 INDIAN OIL CORPORATION Ltd. Composition de catalyseur pour améliorer le rendement d'oléfines dans un processus de craquage catalytique fluide (fcc)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2906695A (en) * 1956-08-07 1959-09-29 Exxon Research Engineering Co High temperature short time hydrocarbon conversion process
US4359378A (en) * 1979-04-16 1982-11-16 Chevron Research Company Catalytic cracking process for improved octane
US4433984A (en) 1979-07-06 1984-02-28 Stone & Webster Engineering Corp. Low residence time solid-gas separation device and system
US4288235A (en) 1979-07-06 1981-09-08 Stone & Webster Engineering Corporation Low residence time solid-gas separation device and system
EP0026674A3 (fr) * 1979-10-02 1982-01-20 Stone & Webster Engineering Corporation Appareillage et procédé de craquage thermique régénérateur
US4338187A (en) 1979-10-22 1982-07-06 Stone & Webster Engineering Corporation Solids feeding device and system
US4370303A (en) 1980-07-03 1983-01-25 Stone & Webster Engineering Corp. Thermal regenerative cracking (TRC) apparatus
EP0381870B1 (fr) 1989-02-08 1993-05-12 Stone & Webster Engineering Corporation Procédé de production d'oléfines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7122493B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122495B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122494B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122492B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7125817B2 (en) 2003-02-20 2006-10-24 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking

Also Published As

Publication number Publication date
DE68906529T2 (de) 1993-09-23
EP0490886A2 (fr) 1992-06-17
EP0381870A1 (fr) 1990-08-16
DE68906529D1 (de) 1993-06-17
EP0490886A3 (fr) 1992-07-08
ATE89308T1 (de) 1993-05-15

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