EP0212007A1 - Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen - Google Patents

Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen Download PDF

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Publication number
EP0212007A1
EP0212007A1 EP85201308A EP85201308A EP0212007A1 EP 0212007 A1 EP0212007 A1 EP 0212007A1 EP 85201308 A EP85201308 A EP 85201308A EP 85201308 A EP85201308 A EP 85201308A EP 0212007 A1 EP0212007 A1 EP 0212007A1
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EP
European Patent Office
Prior art keywords
solids
separator
cracking
hydrocarbon
inlet
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP85201308A
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English (en)
French (fr)
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EP0212007B1 (de
Inventor
Robert J. Gartside
Axel R. Johnson
Joseph L. Ross
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Stone and Webster Engineering Corp
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Stone and Webster Engineering Corp
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Publication date
Priority to US06/587,952 priority Critical patent/US4552645A/en
Application filed by Stone and Webster Engineering Corp filed Critical Stone and Webster Engineering Corp
Priority to EP19850201308 priority patent/EP0212007B1/de
Priority to DE8585201308T priority patent/DE3574987D1/de
Publication of EP0212007A1 publication Critical patent/EP0212007A1/de
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Publication of EP0212007B1 publication Critical patent/EP0212007B1/de
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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural parallel stages only

Definitions

  • This invention relates to the production of olefins and liquid hydrocarbon fuels from heavy hydro­carbons. More particularly, the invention relates to the production of olefins in a thermal cracking environment.
  • lighter molecular weight and lower boiling naturally occurring hydrocarbons such as gas oils
  • the lighter hydrocarbons typically contain fewer contaminants than heavy hydrocarbons.
  • Residual oils are customarily identified as residual, reduced crude oils, atmospheric tower bottoms, vacuum residual oils topped crudes and most hydrocarbons heavier than gas oils.
  • the problem with the residual oils is that the residual oils contain contaminants, such as sulfur and metals.
  • Heavy metals are particularly troublesome in catalytic cracking operations.
  • the heavy hydrocarbons also contain a greater abundance of coke precursors (asphaltenes, polynuclear aromatics, etc.). These coke precursors tend to convert to coke during the cracking operation and tend to foul the equipment and catalyst or inert particles used in the cracking process.
  • Solvent de­asphalting, fluid or delayed coking or hydrotreating are residual feed pretreating processes.
  • the solvent de­asphalting, fluid or delayed coking processes are essentially carbon rejection processes which result in a substantial loss of feedstock.
  • Hydrotreating typically takes a very heavy toll on the economics of the pro­cessing by virtue of the poisonuous effect of the con­taminants on the catalyst and on the consumption of hydrogen.
  • the process of the present invention proceeds essentially in a thermal cracking process.
  • the feed i.e., atmospheric tower bottom, is separated in a vacuum tower into a vacuum gas oil and vacuum resid.
  • the vacuum gas oil is delivered to a thermal cracking reactor and passed through with particulate solids at high temperatures, i.e., 1500°F and low residence times, i.e., 0.05 to 0.40 seconds to crack the hydrocarbon into olefins.
  • the olefins are separated from the particles in a separator and taken overhead from the separator.
  • the solids are delivered to a coker stripper.
  • the vacuum resid from the bottom of the vacuum tower is delivered to the coker stripper and therein cracked and to a great extent converted to coke.
  • the particulate solids are regenerated by combusting coke made in the cracking process and returned to the thermal cracking reactor for repetitive cracking.
  • the process of the present invention is direc­ted to producing olefins and liquid fuels from a heavy hydrocarbon feed.
  • Atmospheric tower bottoms are well suited for processing by the process of the present invention.
  • any heavy feed that can be separa­ted into a light and heavy stream can be processed by the present invention.
  • the system is com strictlyprised essentially of a vacuum tower 2 and a thermal regenerative cracking assembly.
  • the thermal regenera­tive cracking assembly is comprised of a thermal regenerative cracking reactor 6, a reactor feeder 4, a separator 8 and a coke stripper vessel 10.
  • the system also includes means for regenerating solids particles separated from the cracked product after the reaction.
  • the system shows illustratively an entrained bed heater 16, a transport line 12 and a fluid bed vessel 14 in which the solids can be regenerated.
  • atmospheric tower bottoms are delivered through line 3 to a conventional vacuum tower 2 (operated at about 20 millimeters) wherein the atmospheric tower bottoms (ATB) are separated into a light overhead vacuum oil stream and a heavier bottoms vacuum resid.
  • the vacuum gas oil is condensed and then passed through line 20 to the thermal regenerative cracking reactor 6.
  • the vacuum gas oil is delivered to the reactor 6 with hot solids particles that are passed through the reactor feeder 4 (best seen in FIGURE 2). Immediate intimate mixing of the hot solids and the vacuum gas oil occurs in the reactor and cracking proceeds immediately.
  • the temperature of the solids entering the reactor is in the range of 1750°F.
  • the vacuum gas oil is delivered to the reactor at approximately 700°F.
  • the solids to feed weight ratio is 5 to 60, and the reaction proceeds at 1500°F for a residence time of about 0.05 to 0.40 seconds, preferably form 0.20 to 0.30.
  • the product gases are separated from the solids in separator 8 (best seen in FIGURE 3) and the product gases pass overhead through a line 22 and are immediately quenched with typical quench oil that is delivered to line 22 through line 36.
  • the quenched product is passed through a cyclone 24 where entrained solids are removed and delivered through line 44 to the coker stripper 10.
  • the separated solids leave the separator 8 through line 26 and pass to the stripper coker 10.
  • vacuum resid from line 22 is delivered to the stripper coker 10 and is cracked by the solids which are now at a temperature of approximately 1300°F to 1600°F.
  • the weight ratio of solids to vacuum resid in the stripper coker ranges from 5 to 1 to 60 to 1.
  • the vacuum resid is elevated to a temperature of 950°F-­1250°F.
  • the vaporized product from the vacuum resid is taken overhead through line 30 and either delivered for processing in line 34 or taken directly out of the system through line 42.
  • the solids which have accumulated coke in both the tubular reactor 6 and the stripper coker 10 are passed to the entrained bed heater 16 and combusted with air delivered to the system through line 44 to provide the heat necessary for thermal regenerative cracking in the reactor 6.
  • the reactor feeder of the TRC processing sys­tem is particularly well suited for use in the system due to the capacity to rapidly admix hydrocarbon feed and particulate solids.
  • the reactor feeder 4 delivers particulate solids from a solids re­ceptacle 70 through vertically disposed conduits 72 to the reactor 6 and simultaneously delivers hydrocarbon feed to the reactor 6 at an angle into the path of the particulate solids discharging form the conduits 72.
  • An annular chamber 74 to which hydrocarbon is fed by 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 particulate solids.
  • 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 stream from the chamber 74 is angularly injected into the mixing zone and intercepts the solids phase flowing from conduits 78.
  • a projection of the gas flow would form a cone shown by dotted lines 77, the vortex of which is beneath the flow path of the solids.
  • ratio of shear surface to flow area (S/A) of infinity defines perfect mixing; 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 L/D of the mixing zone. A plug creates an effectively re­duced diameter D in a constant 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 low.
  • 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.
  • the separator 8 of the TRC system seen in FIGURE 3, can also be relied on for rapid and discrete separation of cracked product and particulate solids discharging from the reactor 6.
  • the inlet to the separator 8 is directly above a right angle corner 90 at which a mass of particulate solids 92 collect.
  • a weir 94 downstream from the corner 90 facilitates accumula­tion of the mass of solids 92.
  • the gas outlet 22 of the separator 8 is oriented 180° from the separator gas-­solids inlet 96 and the solids outlet 26 is directly opposed in orientation to the gas outlet 22 and down­stream of both the gas outlet 22 and the weir 94.
  • centrifugal force propels the solid particles 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.
  • 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 outlet 97 is, there­fore, not affected adversely by high inlet velocities, up to 150 ft./sec., and the separator 8 is operable over a wide range of dilute phase densities, preferably between 0.1 and 10.0 lbs./ft3.
  • the separator 8 of the present invention achieves efficiencies of about 80%, although the preferred embodiment, can obtain over 90% removal of solids.
  • separator efficiency is dependent upon separator geometry, and more particularly, the flow path must be essentially rectangular, and there is an optimum relationship between the height H and the sharpness of the U-bend in the gas flow.
  • the height of flow path H should be at least equal to the value of D i or 4 inches in height, whichever is greater.
  • Practice teaches that if H is less than D i or 4 inches the incoming stream is apt to disturb the bed solids 92 thereby re­entraining solids in the gas product leaving through outlet 97.
  • 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 an H eventually merely increases residence time without sub­stantive increases in efficiency.
  • the width W 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 .
  • Outlet 97 may be of any inside diameter. How­ever, velocities greater than 75 ft./sec. can cause erosion because of residual solids entrained in the gas.
  • the inside diameter of outlet 97 should be sized so that a pressure differential between the stripping vessel 10 shown in FIG. 1 and the separator 8 exist such that a static height of solids is formed in solids outlet line 26.
  • the static height of solids in line 26 forms a positive seal which prevents gases from entering the stripping vessel 10.
  • the magnitude of the pressure differential between the stripping vessel 10 and the separator 8 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 line 26. As the differential increases the net flow of gas to the stripping vessel 10 decreases. Solids, having gravitational momentum, over­come the differential, while gas preferentially leaves through the gas outlet.
  • FIG. 4 shows a cutaway view of a the separator along section 4-4 of FIG. 3. It is essential that long­itudinal side walls 101 and 102 should be rectilinear, or slightly arcuate as indicated by the dotted lines 101a and 102a.
  • the flow path through the separator 8 is essentially rectangular in cross section having a height H and width W as shown in FIG. 4.
  • the embodiment shown in FIG. 4 defines the geometry of the flow path by adjustment of the lining width for walls 101 and 102.
  • baffles, inserts, weirs or other means may be used.
  • the configuration of walls 103 and 104 transverse to the flow path may be similarly shaped, although this is not essential.
  • the separator shell and manways are preferably lined with erosion resistent linings 105, which may be required if solids at high velocities are encountered.
  • Typical commercially available materials for erosion resistent lining include Carborundum Precast Carbofrax D, Carborundum Precast Alfrax 201 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 resistent linings when the separator is to be used in high temperatures service. Thus, process temperatures above 1500°F. (870°C) can be used.
  • An atmospheric tower bottoms (ATB) having essentially 44° vacuum resid and 56% vacuum gas oil has the following composition:
  • the 27,600 pounds per hour of vacuum resid is delivered to the coker 10 at approximately 650°F. Therein 2760 pounds per hour of coke is produced. The total coke produced in the system is 3778 pounds. The over all combined yield from the process is:

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP19850201308 1984-03-09 1985-08-13 Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen Expired EP0212007B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US06/587,952 US4552645A (en) 1984-03-09 1984-03-09 Process for cracking heavy hydrocarbon to produce olefins and liquid hydrocarbon fuels
EP19850201308 EP0212007B1 (de) 1985-08-13 1985-08-13 Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen
DE8585201308T DE3574987D1 (de) 1985-08-13 1985-08-13 Verfahren zum kracken von schweren kohlenwasserstoffen fuer die erzeugung von olefinen und fluessigen kohlenwasserstoffbrennstoffen.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19850201308 EP0212007B1 (de) 1985-08-13 1985-08-13 Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen

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EP0212007A1 true EP0212007A1 (de) 1987-03-04
EP0212007B1 EP0212007B1 (de) 1989-12-27

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EP19850201308 Expired EP0212007B1 (de) 1984-03-09 1985-08-13 Verfahren zum Kracken von schweren Kohlenwasserstoffen für die Erzeugung von Olefinen und flüssigen Kohlenwasserstoffbrennstoffen

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871183A (en) * 1954-09-21 1959-01-27 Exxon Research Engineering Co Conversion of hydrocarbons
US3019272A (en) * 1956-08-02 1962-01-30 Basf Ag Process of thermally cracking a petroleum oil
US3172840A (en) * 1965-03-09 Light ends
FR2247527A1 (en) * 1973-10-12 1975-05-09 Inst Pererabotke Nefti Thermal cracking of petroleum fractions in coke fluidised beds - to produce unsaturates, aromatics, coke and fuel fractions
EP0026674A2 (de) * 1979-10-02 1981-04-08 Stone & Webster Engineering Corporation Apparat und Verfahren zum thermisch regenerativen Kracken
US4552645A (en) * 1984-03-09 1985-11-12 Stone & Webster Engineering Corporation Process for cracking heavy hydrocarbon to produce olefins and liquid hydrocarbon fuels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172840A (en) * 1965-03-09 Light ends
US2871183A (en) * 1954-09-21 1959-01-27 Exxon Research Engineering Co Conversion of hydrocarbons
US3019272A (en) * 1956-08-02 1962-01-30 Basf Ag Process of thermally cracking a petroleum oil
FR2247527A1 (en) * 1973-10-12 1975-05-09 Inst Pererabotke Nefti Thermal cracking of petroleum fractions in coke fluidised beds - to produce unsaturates, aromatics, coke and fuel fractions
EP0026674A2 (de) * 1979-10-02 1981-04-08 Stone & Webster Engineering Corporation Apparat und Verfahren zum thermisch regenerativen Kracken
US4552645A (en) * 1984-03-09 1985-11-12 Stone & Webster Engineering Corporation Process for cracking heavy hydrocarbon to produce olefins and liquid hydrocarbon fuels

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Publication number Publication date
EP0212007B1 (de) 1989-12-27
DE3574987D1 (de) 1990-02-01

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